CN102337073B - Water-soluble nonluminous anionic electrophoretic coating and preparation method and application thereof - Google Patents
Water-soluble nonluminous anionic electrophoretic coating and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a water-soluble nonluminous anionic electrophoretic coating and a preparation method and application thereof. The electrophoretic coating is prepared from 39-51 parts of acrylic ester polymer, 5-9 parts of nonionic polyurethane surfactant, 18-25 parts of enclosed isocyanate crosslinking agent, 0.2-0.3 part of initiator, 0.04-0.06 part of chain transfer agent, 3-7.2 parts of alkaline compound and 120-250 parts of water. No organic solvent is used in the preparation process of the water-soluble nonluminous anionic electrophoretic coating, so that the pollution of the coating on the environment is lowered; and after the electrophoretic coating is subjected to electrophoretic painting, the coating glossiness is low, the scar covering power is high, the curing temperature is low (120 DEG C), and energy is saved. Due to the adoption of the electrophoretic coating, the defects of high coating curing temperature (140-170 DEG C), insufficient mold scar covering power, pollution caused by the use of organic solvents and the like existing in the prior art are overcome.
Description
Technical field
The invention belongs to the material engineering field, be specifically related to a kind of metallic surface electrophoresis coating, particularly a kind of Water-soluble nonluminous anionic electrophoretic coating and preparation method thereof and application.
Background technology
Aluminium is lightweight, and easily processing, and good corrosion resistance, be widely used as the material relevant to building materials.But the rust-preventing characteristic of aluminium own, wear resistant, chemical proofing are poor, therefore, after generally aluminium being carried out to anodic oxidation treatment, utilize the anion electrophoresis coating of delustring to carry out re-using after electrophoretic coating last layer matt film to it.
The extinction electrophoresis coating used as the aluminum products coating method, always carrying out various research.The anion electrophoresis coating " Unexamined Patent 10-46065 communique " that utilizes two kinds of different acrylic resins of solubility parameter and do not have the melamine resin of consistency to be dispersed in water with these resins is arranged; In addition, the resin that will possess in addition water dispersible mixes with melamine resin, utilizes the poor unglazed coating " JP 2001-131494 communique " that obtains of the SP value of resin.But the coating of above-mentioned two inventions must be in baking more than 170 ℃, and easily making to film produces be full of cracks, and film performance is exerted an influence; Its consumed energy increases in addition, can cause loss economically.
In addition, the resin used containing carboxyl and hydroxyl is arranged, the electrophoretic paint that the blocked polyisocyanates compound is manufactured, have low the filming of excellent performance, gloss that obtains 140 ℃ of baking-curings, but its covering property of mould scar inadequate " Unexamined Patent 8-41380 communique ".
In addition, by the method for microgel in the insoluble particle of resin formation, as imported the alcoxyl silyl in binder resin, by the condensation reaction of alcoxyl silyl, form microgel in insoluble particle in copolymer resin in electrophoretic paint.As JP 59-67398 communique, JP 64-14281 communique, Unexamined Patent 05-263296 communique, CN1329460C all reported similar technology, but when by change application condition variation gloss, easily be subject to the impact of matting after electrophoresis, easily become the condition of restriction coating decoration.
As all the other ways of interior microgel, as utilized the carboxyl existed in resin, cooperation can form with the functional group of this carboxyl reaction the method for microgel.This class functional group is just like epoxy group(ing) (JP 59-138278 communique, special open 2-12511 communique), oxazolinyl (Unexamined Patent 6-25568 communique) etc.These class methods, need in manufacturing processed to form microgel in particle by reacting by heating, and the preparation method is cumbersome.
Mostly adopt solution polymerization process in the above-mentioned method medium vinyl resin manufacture process of mentioning, need in manufacturing processed in a large number with an organic solvent, coating easily is subject to the impact of solvent, and the electrophoretic paint environmental-protecting performance that contains a large amount of solvents reduces.Therefore, someone proposes to carry out letex polymerization by synthetic anionic polyurethane surfactant and acrylic resin polymkeric substance and prepares extinction electrophoresis coating (CN 102115526A), and according to its preparation method, 60 ℃ of gloss can't reach below 10.
Summary of the invention
For the shortcoming and deficiency that overcome prior art, primary and foremost purpose of the present invention is to provide a kind of can solidify at low temperatures, and stability in storage is good, and or not containing organic solvent, 60 ℃ of lower gloss do not reach the Water-soluble nonluminous anionic electrophoretic coating below 10.
Another object of the present invention is to provide the preparation method of above-mentioned Water-soluble nonluminous anionic electrophoretic coating.
A further object of the present invention is to provide the purposes of above-mentioned Water-soluble nonluminous anionic electrophoretic coating.
Purpose of the present invention is achieved through the following technical solutions:
A kind of Water-soluble nonluminous anionic electrophoretic coating is that the composition by following parts by weight prepares:
Acrylic ester polymer: 39-51 part
Nonionic Polyurethane Surfactants: 5-9 part
Blocked isocyanate linking agent: 18-25 part
Initiator: 0.2-0.3 part
Chain-transfer agent: 0.04-0.06 part
Basic cpd: 3-7.2 part
Water: 120-250 part;
Described acrylic ester polymer is by the unsaturated monomer that contains carboxyl, hydroxyl unsaturated monomer and other free-radical polymerised unsaturated basic monomer composition;
The acid number of described acrylic ester polymer is 15-150mg KOH/g, preferably 40-100mg KOH/g; Hydroxyl value is 30-150mg KOH/g, preferably 40-100mg KOH/g; Second-order transition temperature is 10-40 ℃, preferably 15-30 ℃; Molecular weight is 10000-100000, preferably the scope of 20000-60000; Molecular weight distribution is 1～5;
Preferably, described acrylic ester polymer is comprised of acrylate or vinyl compound base monomer;
Described acrylate or vinyl compound base monomer are for having general formula CH
2=C (R
1) COOR
2acrylic ester monomer, or the mixture of multiple such monomer; Wherein, R
1for-H or-CH
3, R
2for the carbonatoms alkyl that is 1-18;
More preferably, described acrylic ester polymer is grouped into by the one-tenth of following parts by weight:
Methyl methacrylate: 8.8-13 part
Hydroxyethyl methylacrylate: 6.4-9.5 part
Methacrylic acid: 4.2-6.4 part
Butyl acrylate: 15-22 part
Vinylbenzene: 5-8.1 part;
All the other monomers of vinylformic acid not mentioned above, as β-dimethyl-aminoethylmethacrylate, n propyl methacrylate, vinyl cyanide, acrylamide, lauryl methacrylate(LMA), Hydroxyethyl acrylate, N methacrylamide etc., and vinyl compound all can add the formula of acrylate copolymer, in order to sticking power, snappiness, water tolerance, solvent resistance and the wear resistance of improving final coating.
Under the effect of water soluble starter and non-ionic polyurethane tensio-active agent, following copolyreaction occurs in the monomer methacrylic acid in the acroleic acid polymerization composition formula, hydroxyethyl methylacrylate, methacrylic methyl esters, butyl acrylate, vinylbenzene:
Described Nonionic Polyurethane Surfactants is aromatics, fatty compounds, alicyclic ring kind isocyanate and the polyether glycol urethane that polymerization obtains under catalyst action; Described polyether glycol content (referring to account for the massfraction of synthetic urethane) is 10-50%, preferably 25-45%; Polyether glycol number-average molecular weight used is 200-5000, preferably 500-2000; The synthesis of polyurethane molecular weight is 1000～7000 (preferably 2000～5000); Preferred aliphat or alicyclic urethane;
Described Nonionic Polyurethane Surfactants can be obtained by common polyaddition reaction, and its molecular weight can be controlled by regulating the poly glycol monomethyl ether molecular weight;
Described Nonionic Polyurethane Surfactants is prepared by following steps: get hexamethylene diisocyanate trimer (HDI tripolymer) and mix with poly glycol monomethyl ether, add catalyzer dibutyl tin laurate, acetone, stir, back flow reaction in 80 ℃ of waters bath with thermostatic control, with the dibutylamine method measure in product containing free-during NCO, cooling down, extract acetone, and, in 30 ℃ of lower vacuum-dryings, make Nonionic Polyurethane Surfactants;
The mol ratio of described hexamethylene diisocyanate trimer and poly glycol monomethyl ether is 1: 3;
The molecular weight of described poly glycol monomethyl ether is 500～2000;
Described Nonionic Polyurethane Surfactants or prepared by following steps: get isophorone diisocyanate and mix with glyceryl monostearate, add catalyzer dibutyl laurate, acetone, stir lower back flow reaction in 80 ℃ of waters bath with thermostatic control, with in dibutylamine method assaying reaction system-after nco value reaches preset value, add poly glycol monomethyl ether to continue reaction 2～3h, cooling down, extract acetone, and obtain Nonionic Polyurethane Surfactants in 30 ℃ of lower vacuum-dryings;
Described isophorone diisocyanate, poly glycol monomethyl ether, glyceryl monostearate three's mol ratio is 2: 2: 1;
The molecular weight of described poly glycol monomethyl ether is 500～2000.
Described blocked isocyanate linking agent can be: the isocyanate group of current known polyisocyanate compound is carried out to the polyisocyanate compound that end-blocking obtains with end-capping reagent; Can be also: by aromatics, fatty compounds, alicyclic ring kind isocyanate and polyether glycol, under catalyst action, add the end-capping reagent polymerization to obtain the blocked polyisocyanates solidifying agent; Wherein, described polyether glycol content (referring to account for the massfraction of synthetic urethane) is 10-50%, preferably 25-45%; Polyether glycol number-average molecular weight used is 200～5000, preferably 500～3000; Described blocked polyisocyanates crosslinking agent molecule amount is 2000～10000, preferably 3000～7000;
The end-capping reagent of described blocked polyisocyanates crosslinking agent has phenolic compound, alcohol compound, oxime compounds, active methylene group compounds, lactam analog compound, aminated compounds, glyoxaline compound, urea compound, amino formate compounds etc.; Preferred oxime compounds; More preferably methyl ethyl ketoxime;
Described blocked isocyanate linking agent preferred aliphat or alicyclic polyisocyanates.
Prepared by the following method by described blocked isocyanate linking agent:
Hexamethylene diisocyanate trimer (HDI tripolymer) is mixed with poly glycol monomethyl ether, add the catalyzer dibutyl tin laurate, then be warming up to 80 ℃ of reaction 3～5h; Add the encapsulant methyl ethyl ketoxime, react 2～2.5h until in reaction system-the NCO group seals fully, with vinyl acetic monomer, reduces system viscosity, then is cooled to 20-30 ℃ and add water to shear to disperse, finally obtain the blocked isocyanate linking agent;
The mol ratio of described hexamethylene diisocyanate trimer and poly glycol monomethyl ether is 1: 1;
The molecular weight of described poly glycol monomethyl ether is 500～3000;
The mol ratio of described methyl ethyl ketoxime and hexamethylene diisocyanate trimer is 2: 1.
Described initiator is a kind of in Potassium Persulphate, Sodium Persulfate or ammonium persulphate;
Described chain-transfer agent is sulfur alcohol compound, preferably lauryl mercaptan;
Described basic cpd is a kind of in ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol, diethylamine, triethylamine, Isopropylamine, Diisopropylamine, tri-isopropyl amine, diethanolamine, diisopropanolamine (DIPA), trolamine, dimethylethanolamine, diethylethanolamine, amine water, sodium hydroxide or potassium hydroxide; Consider from over-all properties, select thanomin best; The neutralization ratio reached by these alkaline matters is advisable with 30%～100%, especially better with 60%～90%;
The preferred deionized water of described water.
The preparation method of above-mentioned Water-soluble nonluminous anionic electrophoretic coating comprises the following steps:
Under the protection of nitrogen, water intaking, chain-transfer agent, 1/3 acrylic ester polymer, 1/3 initiator and Nonionic Polyurethane Surfactants mix, and at 75-85 ℃ of reaction 0.5-1.5h, make seed emulsion; Then drip remaining acrylic ester polymer and initiator, time for adding is controlled at 3-5h, after dropwising, at 75-85 ℃ of insulation 1-3h, adds the blocked isocyanate linking agent, and add basic cpd conditioned reaction system pH to 8.0-9.0, obtain Water-soluble nonluminous anionic electrophoretic coating.
The preparation of Lightless anion electrophoresis coating of the present invention is that Extinction Characteristic, paint stability, curability at low temperatures, the feature of environmental protection and the physicochemical property each side from coating considers, contradiction between balance various factors, design all good products of coating performance and workability, control the second-order transition temperature of polymkeric substance by the ratio between the soft or hard monomer, by mercaptan, control polymericular weight and distribution thereof; By hydroxy radical content reasonable in design, so that suitable hydroxyl value to be provided; Introduce appropriate methacrylic acid and reach suitable acid number; Introduce styrene monomer, make coating possess resistance to crocking and water tolerance, reduce the consistency between coating.By whole design, make synthetic emulsion possess satisfactory stability and physicochemical property.
In Lightless anion electrophoresis coating of the present invention, can add as required pigment, dyestuff, linking agent, defoamer, stablizer etc. to be regulated, further optimize the performance of filming.
The electrophoretic paint that the present invention is made, as required can be with after the deionized water dilution, supplying electrophoretic painting.When using Lightless anion electrophoresis coating of the present invention, the solid of application tank liquor minute concentration is that 4-15% (massfraction) is suitable, is preferably 10%.
Coating process of the present invention, be that coated article is first passed through to oil removing, anodic oxidation, and the coated article of usining carries out electrophoretic painting as anode, and the voltage of application is 30-300V, the 50-120V optimum.Conduction time 0.5-7min, 2-3min is better.Coated article after application is through washing, and then under 100-130 ℃, heating 15-40min acquisition is finally filmed, and thickness is 16-22um.
The coated article that is applicable to electrophoresis coating method of the present invention, as long as have electroconductibility.While adopting aluminium alloy to carry out electrophoresis, can obtain filming of even level and smooth, 60 ° of gloss below 10, excellent performance.
The present invention has following advantage and effect with respect to prior art:
(1) make Lightless anion electrophoresis coating by non-ionic polyurethane tensio-active agent and carboxylic acrylic resin polymkeric substance single step reaction, operation is simple; Not with an organic solvent, reduced the pollution of coating to environment in the coating preparation process.
(2) the Lightless anion coating obtained by non-ionic polyurethane tensio-active agent and acrylic resin polymer reaction, opacifying property good, low 120 ℃ of the solidification value of low, the scar of coating gloss after electrophoretic painting, save the energy.
(3) the non-ionic polyurethane tensio-active agent is insensitive to ionogen, and the paint stability of preparation is better, and raw material sources are extensive, and cost is low, so application prospect is extensive.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of preparation method of Water-soluble nonluminous anionic electrophoretic coating comprises the following steps:
(1) prepare Nonionic Polyurethane Surfactants: add 0.05molHDI tripolymer and 0.15mol poly glycol monomethyl ether (molecular weight 500), 1～2 catalyzer dibutyl tin laurate, 50ml acetone in reactor, stir, back flow reaction 5h in 80 ℃ of waters bath with thermostatic control, with the dibutylamine method measure in product containing free-during NCO, cooling down, extract acetone, and, in 30 ℃ of lower vacuum-dryings, make Nonionic Polyurethane Surfactants (molecular weight 2000);
(2) prepare the blocked isocyanate linking agent: 0.05molHDI tripolymer, 0.05mol poly glycol monomethyl ether (molecular weight 2000) are joined in reactor, add 1～2 dibutyl tin laurate, react 4h after being warming up to 80 ℃; Slowly add again 0.1mol encapsulant methyl ethyl ketoxime, reaction 2～2.5h until in reaction system-the NCO group seals fully, add the 50ml vinyl acetic monomer to reduce system viscosity, be cooled to 25 ℃ and add deionized water shear to disperse, finally obtain blocked isocyanate linking agent (molecular weight 3000);
(3) 5 parts of methacrylic acids, 8 parts of hydroxyethyl methylacrylates, 12 parts of methyl methacrylates, 20 parts of butyl acrylates, 5 parts of vinylbenzene are mixed and obtain acrylic ester polymer, standby;
(4) under the protection of nitrogen, the Nonionic Polyurethane Surfactants of 5 parts of steps (1) (molecular weight 2000) is dissolved in 180 parts of deionized waters, then add in the four-hole round-bottomed flask that agitator, reflux condensing tube, thermometer and separating funnel are housed, 1.6 parts of initiator potassium persulfate solution that add 17 parts of acrylic ester polymers, 0.05 part of lauryl mercaptan, 5% (massfraction), be warming up to 80 ℃ in the rapid stirring process, after reaction 1h, make seed emulsion; Drip 3.2 parts of the initiator potassium persulfate solution of 34 parts of acrylic ester polymers and 5% (massfraction) from dropping funnel, in 4h, drip off, continuation is at 80 ℃ of insulation 1h, after reaction finishes, carry out blending dispersion, the blocked isocyanate linking agent (molecular weight 3000) that adds 18 parts of steps (2), and regulate pH to 8.5 with 5.8 parts of triethylamines, can obtain milky, solid content at 21.3% Water-soluble nonluminous anionic electrophoretic coating A;
Described umber is weight fraction.
Embodiment 2
A kind of preparation method of Water-soluble nonluminous anionic electrophoretic coating comprises the following steps:
(1) prepare Nonionic Polyurethane Surfactants: 0.05mol isophorone diisocyanate and 0.025mol glyceryl monostearate are added in reactor, add 1～2 catalyzer dibutyl laurate, 50ml acetone, stir lower back flow reaction 3h in 80 ℃ of waters bath with thermostatic control, with in dibutylamine method assaying reaction system-after nco value reaches preset value, add 0.05mol poly glycol monomethyl ether (molecular weight 1500) to continue reaction 2.5h, after cooling, extract acetone, and obtain Nonionic Polyurethane Surfactants (molecular weight 4000) in 30 ℃ of lower vacuum-dryings;
(2) preparation method of blocked isocyanate linking agent is with embodiment 1 step (2);
(3) 4.2 parts of methacrylic acids, 6.4 parts of hydroxyethyl methylacrylates, 8.8 parts of methyl methacrylates, 15 parts of butyl acrylates, 5.6 parts of vinylbenzene are mixed and obtain acrylic ester polymer, standby;
(4) under the protection of nitrogen, the Nonionic Polyurethane Surfactants of 7 parts of steps (1) (molecular weight 4000) is dissolved in 120 parts of deionized waters, then add in the four-hole round-bottomed flask that agitator, reflux condensing tube, thermometer and separating funnel are housed, 1.35 parts of initiator Sodium Persulfate solution that add 13 parts of acrylic ester polymers, 0.04 part of lauryl mercaptan, 5% (massfraction), be warming up to 75 ℃ in the rapid stirring process, after reaction 1.5h, make seed emulsion; Drip 2.7 parts of the initiator Sodium Persulfate solution of 26 parts of acrylic ester polymers and 5% (massfraction) from dropping funnel, in 5h, drip off, continuation is at 75 ℃ of insulation 3h, after reaction finishes, carry out blending dispersion, the blocked isocyanate linking agent (molecular weight 3000) that adds 25 parts of steps (2), add 7.2 parts of trolamines to regulate pH to 9.0, can obtain milky, solid content at 20.6% Water-soluble nonluminous anionic electrophoretic coating B;
Described umber is weight fraction.
Embodiment 3
A kind of preparation method of Water-soluble nonluminous anionic electrophoretic coating comprises the following steps:
(1) preparation method of Nonionic Polyurethane Surfactants is with embodiment 1 step (1);
(2) preparation method of blocked isocyanate linking agent is with embodiment 1 step (2);
(3) 6.4 parts of methacrylic acids, 9.5 parts of hydroxyethyl methylacrylates, 13 parts of methyl methacrylates, 22 parts of butyl acrylates, 8.1 parts of vinylbenzene are mixed and obtain acrylic ester polymer, standby;
(4) under the protection of nitrogen, the Nonionic Polyurethane Surfactants of 9 parts of steps (1) (molecular weight 2000) is dissolved in the 250g deionized water, then add in the four-hole round-bottomed flask that agitator, reflux condensing tube, thermometer and separating funnel are housed, 2 parts of initiator ammonium persulfate solutions that add 16 parts of acrylic ester polymers, 0.06 part of lauryl mercaptan, 5% (massfraction), be warming up to 85 ℃ in the rapid stirring process, after reaction 0.5h, make seed emulsion; Drip 4 parts of the initiator ammonium persulfate solutions of 32 parts of acrylic ester polymers and 5% (massfraction) from dropping funnel, in 3h, drip off, continuation is at 85 ℃ of insulation 2h, after reaction finishes, carry out blending dispersion, the blocked isocyanate linking agent (molecular weight 3000) that adds 21 parts of steps (2), add 3 parts, sodium hydroxide to regulate pH to 8.0, can obtain milky, solid content at 20.8% Water-soluble nonluminous anionic electrophoretic coating C;
Described umber is weight fraction.
The Water-soluble nonluminous anionic electrophoretic coating of embodiment 1-3 is made into to the electrophoresis groove liquid (tank liquor A, B, C correspond respectively to coating A, B, C) of 10% (massfraction), the aluminium sheet that electrophoresis is used first passes through oil removing, anodic oxidation, then electrophoresis 1min under the voltage of 60V, wherein aluminium sheet is made anode, and insoluble conductor is negative electrode.
Insoluble paint film after electrophoresis, after washing is dried, is solidified under 120 ℃ * 30min condition.Paint film property is pressed tank liquor A～C as table 1:
Electrophoretic paint performance that table 1 negatively charged ion is unglazed (after electrophoresis)
As can be seen from Table 1, Water-soluble nonluminous anionic electrophoretic coating of the present invention does not form gel or tackify in preserving or using, therefore possess good preservation stability, after electrophoretic painting, can obtain opacifying property good, 60 ° of gloss smooth the filming below 10 of mould scar.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.
Claims (2)
1. a Water-soluble nonluminous anionic electrophoretic coating it is characterized in that being prepared by the composition of following parts by weight:
Acrylate mixture: 39-51 part
Nonionic Polyurethane Surfactants: 5-9 part
Blocked isocyanate linking agent: 18-25 part
Initiator: 0.2-0.3 part
Chain-transfer agent: 0.04-0.06 part
Basic cpd: 3-7.2 part
Water: 120-250 part;
Described acrylate mixture is grouped into by the one-tenth of following parts by weight:
Methyl methacrylate: 8.8-13 part
Hydroxyethyl methylacrylate: 6.4-9.5 part
Methacrylic acid: 4.2-6.4 part
Butyl acrylate: 15-22 part
Vinylbenzene: 5-8.1 part;
Described Nonionic Polyurethane Surfactants is prepared by following methods:
Getting hexamethylene diisocyanate trimer mixes with poly glycol monomethyl ether, add catalyzer dibutyl tin laurate, acetone, stir, back flow reaction in 80 ℃ of waters bath with thermostatic control, with the dibutylamine method measure in product containing free-during NCO, cooling down, extract acetone, and, in 30 ℃ of lower vacuum-dryings, make Nonionic Polyurethane Surfactants;
The mol ratio of described hexamethylene diisocyanate trimer and poly glycol monomethyl ether is 1:3;
The molecular weight of described poly glycol monomethyl ether is 500～2000;
Described Nonionic Polyurethane Surfactants or prepared by following methods:
Getting isophorone diisocyanate mixes with glyceryl monostearate, add catalyzer dibutyl laurate, acetone, stir lower back flow reaction in 80 ℃ of waters bath with thermostatic control, with in dibutylamine method assaying reaction system-after nco value reaches preset value, add poly glycol monomethyl ether to continue reaction 2～3h, cooling down, extract acetone, and obtain Nonionic Polyurethane Surfactants in 30 ℃ of lower vacuum-dryings;
Described isophorone diisocyanate, poly glycol monomethyl ether, glyceryl monostearate three's mol ratio is 2:2:1;
The molecular weight of described poly glycol monomethyl ether is 500～2000;
Described blocked isocyanate linking agent is prepared by following methods:
Hexamethylene diisocyanate trimer is mixed with poly glycol monomethyl ether, add the catalyzer dibutyl tin laurate, then be warming up to 80 ℃ of reaction 3～5h; Add the encapsulant methyl ethyl ketoxime, react 2～2.5h until in reaction system-the NCO group seals fully, with vinyl acetic monomer, reduces system viscosity, then is cooled to 20-30 ℃ and add water to shear to disperse, finally obtain the blocked isocyanate linking agent;
The mol ratio of described hexamethylene diisocyanate trimer and poly glycol monomethyl ether is 1:1;
The molecular weight of described poly glycol monomethyl ether is 500～3000;
The mol ratio of described methyl ethyl ketoxime and hexamethylene diisocyanate trimer is 2:1.
2. Water-soluble nonluminous anionic electrophoretic coating according to claim 1 is characterized in that: described initiator is a kind of in Potassium Persulphate, Sodium Persulfate or ammonium persulphate.
3, Water-soluble nonluminous anionic electrophoretic coating according to claim 1 is characterized in that: described chain-transfer agent is lauryl mercaptan.
4, Water-soluble nonluminous anionic electrophoretic coating according to claim 1 is characterized in that: described basic cpd is a kind of in ethamine, propylamine, butylamine, benzylamine, monoethanolamine, neopentyl alcohol amine, 2-aminopropanol, 3-aminopropanol, diethylamine, triethylamine, Isopropylamine, Diisopropylamine, tri-isopropyl amine, diethanolamine, diisopropanolamine (DIPA), trolamine, dimethylethanolamine, diethylethanolamine, amine water, sodium hydroxide or potassium hydroxide.
5, Water-soluble nonluminous anionic electrophoretic coating according to claim 1 is characterized in that: described basic cpd is a kind of in diethanolamine, diisopropanolamine (DIPA), trolamine, dimethylethanolamine or diethylethanolamine.
6, Water-soluble nonluminous anionic electrophoretic coating according to claim 1 is characterized in that: described water is deionized water.
7, the preparation method of the described Water-soluble nonluminous anionic electrophoretic coating of claim 1-6 any one, it is characterized in that comprising the following steps: under the protection of nitrogen, water intaking, chain-transfer agent, 1/3 acrylate mixture, 1/3 initiator and Nonionic Polyurethane Surfactants mix, at 75-85 ℃ of reaction 0.5-1.5h, make seed emulsion; Then drip remaining acrylate mixture and initiator, time for adding is controlled at 3-5h, after dropwising, at 75-85 ℃ of insulation 1-3h, adds the blocked isocyanate linking agent, and add basic cpd conditioned reaction system pH to 8.0-9.0, obtain Water-soluble nonluminous anionic electrophoretic coating.
8, the described Water-soluble nonluminous anionic electrophoretic coating of claim 1-6 any one is for the electrophoretic painting of aluminium alloy.
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| CN108329454B (en) * | 2018-03-05 | 2020-09-11 | 河南省科学院高新技术研究中心 | Polyurethane, preparation method thereof and drug-loaded micelle |
| CN108341923B (en) * | 2018-03-05 | 2020-11-03 | 河南省科学院高新技术研究中心 | Glyceryl monostearate- (polyethylene glycol)2Copolymer, preparation method and drug-loaded micelle |
| KR102076608B1 (en) * | 2018-08-03 | 2020-02-13 | 주식회사 케이씨씨 | Blocked polyisocyanate and aqueous paint composition comprising thereof |
| KR102599546B1 (en) * | 2021-04-14 | 2023-11-07 | 주식회사 케이씨씨 | Acrylic composition for electro-deposition coating |
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| CN1603366A (en) * | 2003-09-29 | 2005-04-06 | 关西涂料株式会社 | Extinction anion type electrophoresis paint |
| CN1618895A (en) * | 2003-11-20 | 2005-05-25 | 关西涂料株式会社 | Extinction anion electrophoresis film forming method and coating implement |
| CN1676553A (en) * | 2004-03-29 | 2005-10-05 | 关西涂料株式会社 | Lightless anion electrophoresis coating |
| CN1807528A (en) * | 2006-02-10 | 2006-07-26 | 冯国贤 | Acroleic acid/polyurethane transparent anode electrophoresis coating and its preparation method |
| CN101885829A (en) * | 2010-07-12 | 2010-11-17 | 中科院广州化学有限公司 | Alcohol end capping nonionic polyurethane cross-linking agent and preparation method and application thereof |
| CN102115526A (en) * | 2011-01-04 | 2011-07-06 | 中科院广州化学有限公司 | Extinction acrylic resin for anodic electrophoresis and preparation method thereof |
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2011
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1603366A (en) * | 2003-09-29 | 2005-04-06 | 关西涂料株式会社 | Extinction anion type electrophoresis paint |
| CN1618895A (en) * | 2003-11-20 | 2005-05-25 | 关西涂料株式会社 | Extinction anion electrophoresis film forming method and coating implement |
| CN1676553A (en) * | 2004-03-29 | 2005-10-05 | 关西涂料株式会社 | Lightless anion electrophoresis coating |
| CN1807528A (en) * | 2006-02-10 | 2006-07-26 | 冯国贤 | Acroleic acid/polyurethane transparent anode electrophoresis coating and its preparation method |
| CN101885829A (en) * | 2010-07-12 | 2010-11-17 | 中科院广州化学有限公司 | Alcohol end capping nonionic polyurethane cross-linking agent and preparation method and application thereof |
| CN102115526A (en) * | 2011-01-04 | 2011-07-06 | 中科院广州化学有限公司 | Extinction acrylic resin for anodic electrophoresis and preparation method thereof |
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