CN100582173C - Method for preparing bottom surface unification cathode electrophoresis dope - Google Patents
Method for preparing bottom surface unification cathode electrophoresis dope Download PDFInfo
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- CN100582173C CN100582173C CN200710035454A CN200710035454A CN100582173C CN 100582173 C CN100582173 C CN 100582173C CN 200710035454 A CN200710035454 A CN 200710035454A CN 200710035454 A CN200710035454 A CN 200710035454A CN 100582173 C CN100582173 C CN 100582173C
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Abstract
Production of cathodic electrophoresis combined with back surface is carried out by: adding into solvent, agitating, heating, dripping into methyl methyl-acrylate monomer and evocating agent solution to obtain cationic acrylic anhydride resin, chain extending for epoxy resin, ring-opening for epoxy resin by ammonia and ketoimine, preparing isocyanate in semi-closed environment, graft reacting, preparing cross-linking agent, preparing half-finished product into emulsion and color paste and coating. It costs low, has less energy-resource consumption and VOC discharge, and shorter process flow path. It can be used to coat chassis of vehicles, work pieces, toys, light ornaments and hardware products.
Description
Technical field
The present invention relates to a kind of preparation method of coating, especially a kind of preparation method of bottom surface unification cathode electrophoresis dope.
Background technology
Cathode electrophoresis dope is many to be main film forming matter with Resins, epoxy (mostly being bisphenol A-type), because it has very high sticking power and excellent Corrosion Protection, is commonly used for priming paint and antifouling paste.Resins, epoxy films that outdoor weatherability is poor, easily efflorescence, loss of gloss, and the fullness ratio of filming is bad, should not be as high-quality outdoor paint and high-decoration with lacquer.Commercially available cathode electrophoresis dope has remarkable xanthochromia when baking-curing, so the color of coating is only limited to black and grey, is mainly used in priming paint.Coating weatherability is poor, and tangible efflorescence just appears in outdoor exposure 1 wheat harvesting period, and the artificial ageing resistance performance has only 100h, only as priming paint and the disposable application of low-grade coated article.Acrylate type resin has obtained using widely in various coating with its excellent weathering resistance and good guarantor's look, gloss retention, can play effect anticorrosion in short-term and that decorate.By using the disposable application of bottom surface unification cathode electrophoresis dope, the performance of integrated application epoxypaint and acrylate paint, can make workpiece reach requirement anticorrosion and that decorate, the 1C/1B novel process of employing " electrophoresis/oven dry " has replaced the 2C/2B traditional technology of " electrophoretic primer/oven dry/topcoating/oven dry ", technical process is shortened, save facility investment, artificial, energy consumption, the VOC total release reduces more than 70%, is suitable for the application of devices such as automobile chassis, component, toy, lamp decoration, five metals.
Patent of invention (notification number CN1757683A) discloses a kind of preparation method of weather ability cathode electrophoresis coatings.It is to be main film forming substance by Resins, epoxy, add weathering resistance properties-correcting agent, be made for the single component cathode electrophoresis dope through mechanical dispersion again, performances such as its stability, throwing power, preservative property are poorer than the two-pack cathode electrophoresis dope, only rely on Resins, epoxy and add the antiultraviolet auxiliary agent, reach the weather resistance of 250 hours ultraviolet light and aging loss of gloss rate≤10%, be difficult to satisfy the requirement of coating bottom surface unification type coating high-weatherability.
Summary of the invention
At above-mentioned situation, the purpose of this invention is to provide and a kind ofly can satisfy coating bottom surface unification and have the high-weatherability energy and decoration and anticorrosion taking into account and the preparation method of energy-saving and cost-reducing bottom surface unification cathode electrophoresis dope.
For achieving the above object, a kind of preparation method of bottom surface unification cathode electrophoresis dope, it comprises that the following step poly-:
(1) preparation of cationic acrylate resin, modified epoxy and linking agent
I, the preparation of cationic acrylate resin is solvent to be added be furnished with agitator, in the reactor of reflux exchanger and thermometer, start stirring, after being heated to 75～85 ℃, begin to drip methyl methacrylate and 2-EHA and vinylformic acid 2-hydroxyl ethyl ester and dimethylaminoethyl acrylate methyl ammonia ethyl ester and vinylbenzene and initiator solution, be controlled in 2～4 hours and dropwise, kept insulation reaction 1～3 hour, add initiator solution, dropwised follow-up continuation of insurance temperature 2～3 hours, when treating that product is cooled to 50 ℃, add neutralizing agent, dilute with deionized water again, make the cationic acrylate resin, its solvent, the mass ratio of monomer and initiator is 1: 1～1.5: 0.01～0.03, and cationic acrylate resin number-average molecular weight is 2000～10000;
The preparation of ii, modified epoxy comprises following Resins, epoxy chain extending reaction, and amine and ketoimine react the ring-opening reaction of Resins, epoxy, the preparation of semiclosed isocyanic ester and grafted:
The first step is by molecular weight epoxy in low-molecular-weight epoxy resin and the bisphenol-a reaction preparation, its Resins, epoxy and dihydroxyphenyl propane mol ratio are 1～2.5: 1, temperature of reaction is 100～120 ℃, and the reaction times is 4～6 hours, and the resin number-average molecular weight of preparation is 1000～2000;
Second step was to carry out ring-opening reaction with the Resins, epoxy that diethanolamine, ketoimine and the above-mentioned the first step prepare, and the mol ratio of Resins, epoxy and diethanolamine, ketoimine is 1: 3～3.5: 1～0.5, and temperature of reaction is 80～90 ℃, and the reaction times is 4～6 hours;
The 3rd step was to prepare semiclosed isocyanic ester with isocyanic ester and sealing solvent reaction, and with the Resins, epoxy of the open loop of the above-mentioned second step preparation on the amino reaction, generate semiclosed isocyanic ester grafted amine-modified epoxy resin, the mol ratio of isocyanic ester and sealing solvent is 1: 1, temperature of reaction is 50～80 ℃, and the reaction times is 2～4 hours, and semiclosed isocyanic ester and amine-modified epoxy resin mol ratio are 1: 0.2～0.6, temperature of reaction is 60～90 ℃, and the reaction times is 2～4 hours;
The preparation of iii, linking agent is with the reactor heating, drying, feed nitrogen, drop into isocyanate-monomer and solvent, start stirring, be warming up to 50～70 ℃, be incubated 10～30 minutes, make the monomer dissolving, in 2～4 hours, drip the sealing solvent, be warming up to 60～90 ℃ again, be incubated 3～4 hours, with the completely dissolve of infrared measurement isocyanic ester base peak, add solvent or acid neutralization, cooling, discharging is standby, thereby makes linking agent, isocyanate-monomer is 1: 1～1.02 with sealing solvent mol ratio, and the solids content of linking agent is 60～90%;
(2) continue above-mentioned cationic acrylate resin, modified epoxy, the linking agent that makes is prepared into emulsion and mill base, it comprises that the following step poly-:
A, modified epoxy, solubility promoter, acid, emulsifying agent added in the reactor successively mix, temperature is controlled at below 40 ℃; Slowly add again and filled deionized water and the emulsification of organic acid reactor high speed 1 hour, emulsifying temperature is controlled at below 20 ℃, extracting ℃ is carried out to emulsion in elevated temperature to 40～60, extract the solvent in the emulsion, filter with strainer, make latex A, the latex A control indexes is: solids content 35 ± 2%, particle diameter≤0.20 μ m, pH value 7.0 ± 0.5;
B, cationic acrylate resin and linking agent thorough mixing, add solubility promoter and neutralizing agent, middling speed stirs, and adds the deionized water dilution again, preparation emulsion B, making its solids content is 30 ± 2%;
C, modified epoxy, solubility promoter, organic acid and deionized water are added in the container successively, start and mix, add pigment and curing catalysts high speed dispersion, grind with sand mill again, filter filters, and the mill base controlling index is: fineness≤15 μ m, and the pH value is 6.5 ± 0.5;
As further measure of the present invention, the preparation method of bottom surface unification cathode electrophoresis dope, it comprises that the following step poly-:
During Workpiece coating, add latex A, emulsion B, mill base and deionized water, coating working fluid solids content is adjusted to 10～35%, through parkerized workpiece as negative electrode, 25～35 ℃ of working fluid temperature, electrophoresis is 1～3 minute under the condition of voltage 100～300V, after rinsing well, toasted 5～10 minutes under 100～110 ℃ of temperature, toasted under 155～165 ℃ temperature 10～20 minutes, the electrophoresis that makes thickness and be 10～30 μ m is filmed.
The present invention adopts monomers such as methyl methacrylate, butyl acrylate, 2-EHA, vinylformic acid 2-hydroxyl ethyl ester, dimethylaminoethyl acrylate methyl ammonia ethyl ester, vinylbenzene and initiator to prepare the cationic acrylate resin; To the Resins, epoxy chain extension, and adopt amine and ketoimine to epoxy addition, semiclosed isocyanic ester grafting prepares modified epoxy; Adopt isocyanate-monomer and sealing solvent, preparation blocked isocyanate resin is as linking agent; Thereby preparation cathode electrophoresis dope emulsion and mill base, the 2C/2B preparation method technical process that has overcome traditional technology " electrophoretic primer/oven dry/topcoating/oven dry " is longer, artificial input, energy consumption, facility investment and the bigger defective of VOC total release.
The beneficial effect that the present invention is produced compared to existing technology:
(1) weather resistance is higher, and prepared the resin-blocked isocyanate crosslinking of cationic acrylate and be applied in the cathode electrophoresis dope, the anti-artificial accelerated aging test 400 hours of filming, the loss of gloss rate is less than 10%;
(2) decoration and antiseptic property are more excellent, have prepared the semiclosed isocyanic ester grafted amine-modified epoxy resin of energy self cure, and the stability of Resins, epoxy and film anticorrosion ability obviously strengthen, and the salt-fog resistant test of filming was greater than 500 hours;
(3) it has disposable application and can satisfy the anticorrosion of workpiece and decorate requirement;
(4) it can replace the 2C/2B traditional technology of " electrophoretic primer/oven dry/topcoating/oven dry ", has technical process and shortens, and saves facility investment, artificial, energy consumption, and the VOC total release reduces more than 70%.
The bottom surface unification cathode electrophoresis dope of the inventive method preparation is suitable for the various anticorrosion utensils that require with decoration, is particularly suitable for the application of devices such as automobile chassis, component, toy, lamp decoration, five metals.
The present invention is further detailed explanation below in conjunction with embodiment.
Embodiment
Embodiment 1
(1) preparation of cationic acrylate resin, modified epoxy and linking agent
31 parts of Virahols and 9 parts of butyl glycol ethers addings is furnished with agitator, in the reactor of reflux exchanger and thermometer, start stirring, after being heated to 82～85 ℃, begin to drip 13.4 parts of methyl methacrylates, 22.2 part 2-EHA, 6.6 part vinylformic acid 2-hydroxyl ethyl ester, 9 parts of dimethylaminoethyl acrylate methyl ammonia ethyl esters, 9 parts of vinylbenzene and 0.6 part of azo two isobutyl are fine, be controlled in 2～4 hours and dropwise, kept insulation reaction 1～3 hour, it is fine to add 0.2 part of azo two isobutyl, dropwised follow-up continuation of insurance temperature 2～3 hours, treat that product is cooled to about 50 ℃, add 0.5 part of Glacial acetic acid, with 7.5 parts of deionized water dilutions, make the cationic acrylate resin again;
In the four-hole boiling flask that condenser and nitrogen protection and reflux are arranged, drop into 11g isophorone diisocyanate and 0.2g hexone, heat up 50 ℃, drip methyl ethyl ketoxime 4.8g, be incubated 0.5 hour, be warmed up to 70 ℃, be incubated 2 hours, after mensuration isocyanide acid number was 120, it was standby to lower the temperature, and makes blocked isocyanate; In the four-hole boiling flask that condenser and nitrogen protection and reflux are arranged, drop into Resins, epoxy 25g, bisphenol a resin 13g, diethanolamine 0.5g, be warming up to 110～120 ℃; Drip propylene glycol monomethyl ether 10g and hexone 10g, dropwise in 2 hours, be incubated 3 hours, the measurement ring oxygen value is to be cooled to 70 ℃ after 1.6 ± 0.1; Drip diethanolamine 5g, Virahol 3g, be warmed up to 90 ℃, be incubated 2.5 hours, after mensuration amine value is 70 ± 5, drip ketoimine resin 16g, be incubated 2 hours, measuring the amine value is 100～120, is cooled to 75 ℃, drips semiclosed isocyanic ester, be incubated 2 hours, add deionized water 2g, be incubated 1 hour, measuring the amine value is 65～75, cooling filters and packages, and makes modified epoxy;
With the reactor heating, drying, feed nitrogen, drop into 1 part of ditane isocyanic ester and 0.3 part of methylethylketone, start stirring, be warming up to 50～55 ℃, be incubated 10～30 minutes, in 2～4 hours, drip 1.4 parts of ethylene glycol ethyl ethers, be warming up to 65～75 ℃ again, be incubated 3～4 hours, with the completely dissolve of infrared measurement isocyanic ester base peak, add 1.3 parts of methylethylketones, cooling, discharging is standby, thereby makes linking agent;
(2) preparation of cathode electrophoresis dope emulsion and grey mill base
42g modified epoxy, 0.4g polyethers PPG-2000,0.4g Glacial acetic acid, 0.3g OP-emulsifying agent, 0.7g butyl glycol ether added in the reactor successively stirred 30 minutes, temperature is controlled at below 40 ℃; Slowly add the reactor high speed emulsification 1 hour that fills 54.6g deionized water and 0.2g Glacial acetic acid again, emulsifying temperature is controlled at below 20 ℃, is warming up to 40～60 ℃ emulsion carried out extracting, extracts the solvent in the emulsion, makes latex A;
100g cationic acrylate resin and 25g linking agent thorough mixing, add butyl glycol ether 2g and 1g Glacial acetic acid, middling speed stirs, and adds the dilution of 129g deionized water again, makes emulsion B;
24.7g pigment dispersing resin, 3g diethylene glycol ether, 0.5g polyethers PPG-4000,0.8g Glacial acetic acid, 0.1gOP emulsifying agent and 39.6g deionized water added in the container successively stir, add 30g titanium dioxide, 1g carbon black and 1.5g Dibutyltin oxide high speed dispersion, grind with sand mill again, make grey mill base;
The coating of the present invention preparation is by mill base: latex A: emulsion B: deionized water is 1: 2: 1: 4 dispose electrophoresis groove liquids, and the electrophoresis test plate (panel) is 2 minutes under 200V voltage, films to have following performance:
Be coated with thickness, 20 μ m;
Pencil hardness, 2H;
Resistance to impact shock, 50cm;
Sticking power (cross-hatching), 0 grade;
Salt fog resistance (being coated with thickness 20 μ m, the phosphatization plate), 600 hours, cut wriggling≤1.5mm;
Weathering resistance (QUV temper(ing) experimental machine), 400 hours, loss of gloss rate≤10%.
Embodiment 2
(1) preparation of cationic acrylate resin, modified epoxy and linking agent
33.6g Virahol and the adding of 11g butyl glycol ether is furnished with agitator, in the reactor of reflux exchanger and thermometer, start stirring, after being heated to 82～85 ℃, begin to drip the 9.6g methyl methacrylate, 12.3g propenoic acid beta-hydroxy propyl ester, the 17g butyl acrylate, 20.9g dimethylaminoethyl acrylate methyl ammonia ethyl ester, 4.7g vinylbenzene and 0.6g azo two isobutyls are fine, be controlled in 2～4 hours and dropwise, kept insulation reaction 1～3 hour, it is fine to add 0.2g azo two isobutyls, dropwised follow-up continuation of insurance temperature 2～3 hours, treat that product is cooled to about 50 ℃, add the 1.25g Glacial acetic acid, with the dilution of 5g deionized water, make the cationic acrylate resin again;
Example 1 is seen in the preparation of modified epoxy;
With the reactor heating, drying, feed nitrogen, drop into 50g isophorone diisocyanate and 18g methyl iso-butyl ketone (MIBK), start stirring, be warming up to 60～70 ℃, be incubated 10～30 minutes, in 2～4 hours, drip the 40g dimethylethanolamine, be warming up to 80～90 ℃ again, be incubated 3～4 hours,, add the 51g lactic acid neutralization with the completely dissolve of infrared measurement isocyanic ester base peak, it is standby to lower the temperature, thereby makes linking agent;
(2) preparation of cathode electrophoresis dope emulsion and grey mill base
Example 1 is seen in the latex A preparation;
100g cationic acrylate resin and 34g linking agent thorough mixing, add butyl glycol ether 2g and 1.25g Glacial acetic acid, middling speed stirs, and adds the dilution of 148g deionized water again, makes emulsion B;
27.4g pigment dispersing resin, 4g diethylene glycol ether, 0.8g Glacial acetic acid, 0.8gNP-15 tensio-active agent and 30g deionized water added in the container successively stir, add 5g calcined kaolin, 10g titanium dioxide, 5g carbon black and 1.0g Dibutyltin oxide high speed dispersion, grind with sand mill again, make black slurry;
The coating of the present invention preparation is by mill base: latex A: emulsion B: deionized water is 1: 1.5: 1.5: 4 dispose electrophoresis groove liquids, and the electrophoresis test plate (panel) is 2 minutes under 200V voltage, films to have following performance:
Be coated with thickness, 22 μ m;
Pencil hardness, 2H;
Resistance to impact shock, 50cm;
Sticking power (cross-hatching), 0 grade;
Salt fog resistance (being coated with thickness 20 μ m, the phosphatization plate), 500 hours, cut wriggling≤1.5mm;
Weathering resistance (QUV temper(ing) experimental machine), 450 hours, loss of gloss rate≤10%.
Embodiment 3
(1) preparation of cationic acrylate resin, modified epoxy and linking agent
Example 1 is seen in the preparation of cationic acrylate resin;
In the four-hole boiling flask that condenser and nitrogen protection and reflux are arranged, drop into 6.1g and 0.8g hexone, heat up 50 ℃, drip diethylene glycol ether 7.1g, be incubated 0.5 hour, be warmed up to 70 ℃, be incubated 2 hours, after mensuration isocyanide acid number was 125 ± 5, it was standby to lower the temperature, and makes semiclosed isocyanic ester; In the four-hole boiling flask that condenser and nitrogen protection and reflux are arranged, drop into Resins, epoxy 28.3g, bisphenol a resin 10.1g, diethanolamine 0.5g, be warming up to 110～120 ℃; Drip propylene glycol monomethyl ether 12.1g and hexone 8.5g, dropwise in 2 hours, be incubated 3 hours, the measurement ring oxygen value is to be cooled to 70 ℃ after 1.5 ± 0.1; Drip diethanolamine 5.7g, Virahol 3.7g, be warmed up to 90 ℃, be incubated 2.5 hours, after mensuration amine value is 70 ± 5, drip ketoimine resin 15.5g, be incubated 2 hours, measuring the amine value is 110 ± 10, is cooled to 75 ℃, drips semiclosed isocyanic ester, be incubated 2 hours, add deionized water 1.5g, be incubated 1 hour, measuring the amine value is 75 ± 5, cooling filters and packages, and makes modified epoxy;
Example 2 is seen in the preparation of linking agent;
(2) preparation of cathode electrophoresis dope emulsion and mill base
40g modified epoxy, 0.4g polyethers PPG-2000,0.4g Glacial acetic acid, 0.7g butyl glycol ether added in the reactor successively stirred 30 minutes, temperature is controlled at below 40 ℃; Slowly add the reactor high speed emulsification 1 hour that fills 54.6g deionized water, 0.3g NP-15 tensio-active agent and 0.2g Glacial acetic acid again, emulsifying temperature is controlled at below 30 ℃, be warming up to 40～60 ℃ emulsion carried out extracting, extract the solvent in the emulsion, make latex A;
Example 1 is seen in the preparation of emulsion B;
Example 2 is seen in the preparation of black slurry;
The coating of the present invention preparation is by mill base: latex A: emulsion B: deionized water is 1: 1: 1.5: 3.5 dispose electrophoresis groove liquids, and the electrophoresis test plate (panel) is 2 minutes under 200V voltage, films to have following performance:
Be coated with thickness, 20 μ m;
Pencil hardness, 2H;
Resistance to impact shock, 50cm;
Sticking power (cross-hatching), 0 grade;
Salt fog resistance (being coated with thickness 20 μ m, the phosphatization plate), 500 hours, cut wriggling≤1.5mm;
Weathering resistance (QUV temper(ing) experimental machine), 500 hours, loss of gloss rate≤10%.
Embodiment 4
(1) preparation of cationic acrylate resin, modified epoxy and linking agent
Example 2 is seen in the preparation of cationic acrylate resin;
Example 3 is seen in the preparation of modified epoxy;
With the reactor heating, drying, feed nitrogen, drop into 1,6-hexamethyl vulcabond 16.8g and hexone 0.8g start stirring, are warming up to 50～55 ℃, be incubated 10～30 minutes, in 2～4 hours, drip the 17.4g methyl ethyl ketoxime, be warming up to 65～75 ℃ again, be incubated 3～4 hours, with the completely dissolve of infrared measurement isocyanic ester base peak, add the 9g hexone, cooling, discharging is standby, thereby makes linking agent;
(2) preparation of cathode electrophoresis dope emulsion and mill base
Example 3 is seen in the latex A preparation;
100g cationic acrylate resin and 12.7g linking agent thorough mixing, add butyl glycol ether 2g and 1.25g Glacial acetic acid, middling speed stirs, and adds the dilution of 104g deionized water again, makes emulsion B;
Example 2 is seen in the preparation of black slurry;
The coating of the present invention preparation is by mill base: latex A: emulsion B: deionized water is 1: 1: 2: 4 dispose electrophoresis groove liquids, and the electrophoresis test plate (panel) is 2 minutes under 200V voltage, films to have following performance:
Be coated with thickness, 20 μ m;
Pencil hardness, 2H;
Resistance to impact shock, 50cm;
Sticking power (cross-hatching), 0 grade;
Salt fog resistance (being coated with thickness 20 μ m, the phosphatization plate), 500 hours, cut wriggling≤1.5mm;
Weathering resistance (QUV temper(ing) experimental machine), 500 hours, loss of gloss rate≤10%.
Below only be preferred embodiment of the present invention, according to above-mentioned design of the present invention, those skilled in the art also can make various modifications and conversion to this.For example, monomers such as methyl methacrylate, butyl acrylate, 2-EHA, vinylformic acid 2-hydroxyl ethyl ester, dimethylaminoethyl acrylate methyl ammonia ethyl ester, vinylbenzene, initiator prepares the cationic acrylate resin, to the Resins, epoxy chain extension, and adopt amine and ketoimine to epoxy addition, semiclosed isocyanic ester grafting prepares modified epoxy; Adopt isocyanate-monomer and sealing solvent, prepare the blocked isocyanate resin as raw materials such as linking agents, adjustment conversion of processing parameter, working method etc. or the like.Yet similar this conversion and modification all belong to essence of the present invention.
Claims (2)
1. the preparation method of a bottom surface unification cathode electrophoresis dope is characterized in that it may further comprise the steps:
(1) preparation of cationic acrylate resin, modified epoxy and linking agent
I, the preparation of cationic acrylate resin is solvent to be added be furnished with agitator, in the reactor of reflux exchanger and thermometer, start stirring, after being heated to 75～85 ℃, begin to drip methyl methacrylate and 2-EHA and vinylformic acid 2-hydroxyl ethyl ester and dimethylaminoethyl acrylate methyl ammonia ethyl ester and vinylbenzene and initiator solution, be controlled in 2～4 hours and dropwise, kept insulation reaction 1～3 hour, add initiator solution, dropwised follow-up continuation of insurance temperature 2～3 hours, when treating that product is cooled to 50 ℃, add neutralizing agent, dilute with deionized water again, make the cationic acrylate resin, its solvent, the mass ratio of monomer and initiator is 1: 1～1.5: 0.01～0.03, and cationic acrylate resin number-average molecular weight is 2000～10000;
The preparation of ii, modified epoxy comprises following Resins, epoxy chain extending reaction, and amine and ketoimine react the ring-opening reaction of Resins, epoxy, the preparation of semiclosed isocyanic ester and grafted:
The first step is by molecular weight epoxy in low-molecular-weight epoxy resin and the bisphenol-a reaction preparation, its Resins, epoxy and dihydroxyphenyl propane mol ratio are 1～2.5: 1, temperature of reaction is 100～120 ℃, and the reaction times is 4～6 hours, and the resin number-average molecular weight of preparation is 1000～2000;
Second step was to carry out ring-opening reaction with the Resins, epoxy that diethanolamine, ketoimine and the above-mentioned the first step prepare, and the mol ratio of Resins, epoxy and diethanolamine, ketoimine is 1: 3～3.5: 1～0.5, and temperature of reaction is 80～90 ℃, and the reaction times is 4～6 hours;
The 3rd step was to prepare semiclosed isocyanic ester with isocyanic ester and sealing solvent reaction, and with the Resins, epoxy of the open loop of the above-mentioned second step preparation on the amino reaction, generate semiclosed isocyanic ester grafted amine-modified epoxy resin, the mol ratio of isocyanic ester and sealing solvent is 1: 1, temperature of reaction is 50～80 ℃, and the reaction times is 2～4 hours, and semiclosed isocyanic ester and amine-modified epoxy resin mol ratio are 1: 0.2～0.6, temperature of reaction is 60～90 ℃, and the reaction times is 2～4 hours;
The preparation of iii, linking agent is with the reactor heating, drying, feed nitrogen, drop into isocyanate-monomer and solvent, start stirring, be warming up to 50～70 ℃, be incubated 10～30 minutes, make the monomer dissolving, in 2～4 hours, drip the sealing solvent, be warming up to 60～90 ℃ again, be incubated 3～4 hours, with the completely dissolve of infrared measurement isocyanic ester base peak, add solvent or acid neutralization, cooling, discharging is standby, thereby makes linking agent, isocyanate-monomer is 1: 1～1.02 with sealing solvent mol ratio, and the solids content of linking agent is 60～90%;
(2) continue above-mentioned cationic acrylate resin, modified epoxy, the linking agent that makes is prepared into emulsion and mill base, it may further comprise the steps:
A, modified epoxy, solubility promoter, acid, emulsifying agent added in the reactor successively mix, temperature is controlled at below 40 ℃; Slowly add again and filled deionized water and the emulsification of organic acid reactor high speed 1 hour, emulsifying temperature is controlled at below 20 ℃, extracting ℃ is carried out to emulsion in elevated temperature to 40～60, extract the solvent in the emulsion, filter with strainer, make latex A, the latex A control indexes is: solids content 35 ± 2%, particle diameter≤0.20 μ m, pH value 7.0 ± 0.5;
B, cationic acrylate resin and linking agent thorough mixing, add solubility promoter and neutralizing agent, middling speed stirs, and adds the deionized water dilution again, preparation emulsion B, making its solids content is 30 ± 2%;
C, modified epoxy, solubility promoter, organic acid and deionized water are added in the container successively, start and mix, add pigment and curing catalysts high speed dispersion, grind with sand mill again, filter filters, and the mill base controlling index is: fineness≤15 μ m, the pH value is 6.5 ± 0.5.
2, the preparation method of bottom surface unification cathode electrophoresis dope according to claim 1 is characterized in that it may further comprise the steps:
During Workpiece coating, add latex A, emulsion B, mill base and deionized water, coating working fluid solids content is adjusted to 10～30%, through parkerized workpiece as negative electrode, 25～35 ℃ of working fluid temperature, electrophoresis is 1～3 minute under the condition of voltage 100～300V, after rinsing well, toasted 5～10 minutes under 100～110 ℃ of temperature, toasted under 155～165 ℃ temperature 10～20 minutes, the electrophoresis that makes thickness and be 10～30 μ m is filmed.
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