CN1548488A - Composition for electrode deposition painting and method of preparing corresponding aquatic resin - Google Patents
Composition for electrode deposition painting and method of preparing corresponding aquatic resin Download PDFInfo
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- CN1548488A CN1548488A CNA031224008A CN03122400A CN1548488A CN 1548488 A CN1548488 A CN 1548488A CN A031224008 A CNA031224008 A CN A031224008A CN 03122400 A CN03122400 A CN 03122400A CN 1548488 A CN1548488 A CN 1548488A
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Abstract
The composition for electrode deposition painting includes monomer with unsaturated vinyl bond and capable of emulsion polymerizing 15-40 weight portions; cationic polymer emulsifier 15-60 weight portions; completely closed isocyanate as cross-linking agent 10-30 weight portions; polymerization initiator 0.10-4.5 weight portions; and water 100 weight portions. The composition for electrode deposition painting may be emulsion polymerized at 50-100 deg.c to obtain water-thinned resin, and the water-thinned resin may be diluted to form stable emulsion for electrode depositing painting to obtain deposited film with excellent performance.
Description
Technical field
The present invention relates to a kind of electrodeposition application prepares water-base resin with composition and use said composition method; Be particularly related to seal fully type isocyanate crosslinking and cationic high-molecular emulsifying agent in the presence of, make the polymerisable monomer that contains the vinyl unsaturated link(age) carry out emulsion polymerization, and obtain having the method for the water-base resin of crosslinkable.
Background technology
Electrodeposition application (electrodeposition coating) method can be described as combining of baking vanish and electro-plating method.During application, it utilizes similar galvanized principle, and water-borne coatings is plated on the metallic surface, is toasted dry again.
Cation type polymer emulsion (cationic polymer dispersion) can be used as the electrodeposition application.U.S.Patent No.4,683, a kind of preparation method of acryl emulsion is disclosed in 173, it is will have amino acryl monomer mixture, traditional low molecule-type emulsifying agent (as Triton X-405), contain acid neutralizing agent (as phosphoric acid), seal isocyanate-based linking agent fully mixes, and carries out letex polymerization then.Though this emulsion after dilution, can carry out electrodeposition and baking is dry, yet the emulsifying agent of the low non-response type of molecule has detrimentally affect for the performance of electrodeposition film.
U.S.Patent No.4, disclose a kind of emulsion polymerization product in 304,703, its preparation method is: utilize solution polymerization process to synthesize acryl cation resin earlier, be used as emulsifying agent with this acryl cation resin then, further make the monomer that does not contain linking agent carry out letex polymerization.Then, with linking agent (melamine formaldehyde resin) that the emulsion of letex polymerization gained is crosslinked again.Yet, utilize the Combination of this method institute synthetic emulsion and linking agent poor, stability is bad, and hardening effect is not good, bathes so be difficult to prepare the available electrodeposition.
Summary of the invention
Purpose of the present invention is for providing a kind of electrodeposition application composition, and it can be used for preparing electrodeposition application use resin; This water-base resin forms stable emulsion after diluting, can be used for the electrodeposition application, and the electrodeposition film properties is good.
In order to reach above-mentioned purpose, electrodeposition application of the present invention comprises with composition:
The polymerisable monomer that contains the vinyl unsaturated link(age) of 10～50 weight parts;
The cationic high-molecular emulsifying agent of 10～75 weight parts;
The type of sealing the fully isocyanate crosslinking of 5～40 weight parts;
0.02 the polymerization starter of～6 weight parts; And
The water of 100 weight parts,
Wherein, this polymerisable monomer comprise have can with the functional group's of this linking agent reaction monomer, and the monomer that contains this functional group accounts for 5～60 weight percents of whole polymerisable monomers.
Preferably, electrodeposition application of the present invention comprises with composition:
The polymerisable monomer that contains the vinyl unsaturated link(age) of 15～40 weight parts;
The cationic high-molecular emulsifying agent of 15～60 weight parts;
The type of sealing the fully isocyanate crosslinking of 10～30 weight parts;
0.1 the polymerization starter of～4.5 weight parts; And
The water of 100 weight parts,
Wherein, this polymerisable monomer comprise have can with the functional group's of this linking agent reaction monomer, and the monomer that contains this functional group accounts for 5～60 weight percents of whole polymerisable monomers.
The present invention also provides a kind of method for preparing electrodeposition application use resin, comprises above-mentioned electrodeposition application is carried out letex polymerization with composition under 50～100 ℃.Principal character of the present invention for seal fully type isocyanate crosslinking and cationic high-molecular emulsifying agent in the presence of, make the polymerisable monomer that contains the vinyl unsaturated link(age) carry out letex polymerization, and obtain the water-base resin of tool crosslinkable.
In the polymerisable monomer that contains the vinyl unsaturated link(age) that the present invention is used, have 15～45 weight percents that can preferably account for whole polymerisable monomers with the functional group's who seals the reaction of type isocyanate crosslinking fully monomer.
Be applicable to that the polymerisable monomer that contains the vinyl unsaturated link(age) of the present invention comprises the acryl monomer, also can further comprise being selected from aromatic vinyl base system monomer, C
2-C
12Aliphatic olefin class, C
6-C
16In alicyclic alkene class, vinylchlorid or the vinyl acetate one or more.The acryl monomer can be acrylic acid or the like, esters of acrylic acid, methacrylic and methyl acrylic ester; Be preferably vinylformic acid, methacrylic acid, vinylformic acid C
1-C
8Alkyl ester or methacrylic acid C
1-C
8Alkyl ester.Concrete acryl examples of monomers comprises vinylformic acid, methacrylic acid, ethyl propenoate, butyl acrylate, Octyl acrylate, methyl methacrylate, reaches butyl methacrylate.
Polymerisable monomer had among the present invention can with the functional group of this linking agent reaction, can be hydroxyl, carboxyl or active amino.For example, the polymerisable monomer that is fit to can be the acryl monomer of hydroxyl, or carboxylic acryl monomer.The monomeric object lesson of hydroxyl acryl comprises Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate and Rocryl 410.
The weight-average molecular weight of cationic macromolecule emulsifier can be 2,000～200 among the present invention, 000g/mole.The cationic high-molecular emulsifying agent that is suitable for can be cationic acryl resin, cationic Resins, epoxy and cationic polyamide resin.The cationic high-molecular emulsifying agent preferably passes through ammonification, i.e. ammonification acryl resin, ammonification Resins, epoxy, and ammonification polyamide resin.Wherein amino content is preferably 0.3～3.5meq/g in the ammonification acryl resin.
The cationic high-molecular emulsifying agent also can have hydroxyl, and hydroxy radical content is preferably 0.1～4.0meq/g.
Be applicable to the type isocyanate crosslinking of sealing fully of the present invention, can seal fully with alcohols or oximes.The example of alcohols can be C
1-C
18Alkanol or C
6-C
20Alicyclic ring alcohol is as butanols.The example of oximes can be C
3-C
12Aliphatics oxime or C
6-C
16Alicyclic oxime is as Diacetylmonoxime.
Embodiment
Below by several embodiment illustrating further method of the present invention, feature and advantage, but be not to be used for limiting the scope of the invention, protection scope of the present invention should be as the criterion with the scope of claims.
Use the meaning of abbreviation representative as follows among the embodiment:
2-EHA=2-ethylhexyl acrylate, 2-EHA
MMA=methyl methacrylate, methyl methacrylate
N-BMA=n-butyl methacrylate, n-BMA
2-HEMA=2-hydroxyethyl methacrylate, 2-hydroxyethyl methacrylate
DMAEMA=2-(dimethylamino) ethyl methacrylate, methacrylic acid 2-(dimethylamino) ethyl ester
EtAc=ethyl acetate, ethyl acetate
AIBN=azobis (isobutyronitrile), azobis isobutyronitrile
IPDI=isophorone diisocyanate, the isophorone vulcabond
The preparation of cationic high-molecular emulsifying agent
Preparation embodiment 1: contain the synthetic of amino and hydroxyl acryl resin
In capacity is 1 liter four neck reaction flasks, the 200 gram EtAc solvents of packing into earlier, logical nitrogen is heated to reflux temperature, uses pump of constant delivery type, and monomer solution was added in 2 hours in the reaction flask of continuously stirring successively, carries out solution polymerization.Monomer solution comprises 67.8 gram 2-EHA, 113.8 gram MMA, 113.8 gram n-BMA, 67.4 gram 2-HEMA, 90.9 gram DMAEMA, 200 gram EtAc solvents, and 4.0 gram AIBN radical initiators.After the monomer solution charging finishes, continue under reflux temperature, to keep 1 hour.Then, will contain EtAc solution 150 grams of 1.0 gram AIBN, in 0.5 hour, add successively in the reaction flask, proceed polyreaction.After the radical initiator solution feed finishes, continue under reflux temperature, to keep 1 hour.Cool off blanking then.The solids content (120 ℃ * 1.5 hours) that gained contains the acryl resin of amino and hydroxyl is 59.0wt%, the amino equivalent number is 0.818meq/g, the hydroxyl equivalent number is 0.708meq/g, and weight-average molecular weight is 19080g/mole, and number-average molecular weight is 7310g/mole (GPC records).
Preparation embodiment 2: the preparation of the acryl resin emulsifying agent of amino-contained and hydroxyl
After the lactic acid thorough mixing that the acryl resin of preparation 1 synthetic amino-contained of embodiment and hydroxyl and amino equivalent is several 1.1 times is even, place vacuum drying oven with 50 ℃ of dryings 24 hours, can obtain solid-state acryl resin emulsifying agent, its weight-average molecular weight is 21270g/mole, and number-average molecular weight is 8030g/mole (GPC records).
Seal the preparation of type isocyanate crosslinking fully
Preparation embodiment 3: propyl carbinol is sealed the preparation of type IPDI fully
At first with 192.6 gram propyl carbinols, 0.20 gram T-12 (dibutyl tin laurate) adds in the four neck reaction flasks with 57.6 gram toluene, under 22 ℃ of water-baths and mechanical stirring state, the mixed solution with 277.9 gram IPDI and 60.0 gram toluene added in the reaction flask with pump of constant delivery type in 1 hour.In regular turn in 26 ℃ and 50～60 ℃ of water-baths, continue reaction 1.2 hours and 2.8 hours again, cool off blanking then.Blanking amount 570.1 grams, productive rate 96.9%.Its solids content (100 ℃ * 1.5 hours) is 78.7wt%, and viscosity is 600cps, seals the NCO base fully and is 4.30meq/g.
Preparation embodiment 4:Diacetylmonoxime is sealed the preparation of type IPDI fully
At first with 675.6 gram Diacetylmonoximes (2-butoxime), 0.61 gram T-12 (dibutyl tin laurate) adds in the four neck reaction flasks with 170 gram toluene, under 22 ℃ of water-baths and mechanical stirring state, mixed solution with 835.2 gram IPDI and 200 gram toluene added in the reaction flask with pump of constant delivery type in 3.2 hours.In regular turn 30～35 ℃ and 45～55 ℃ of water-baths, continue reaction 1.3 hours and 2.3 hours again, cool off blanking then.Blanking amount 1803.9 grams, productive rate 95.9%.Its solids content (100 ℃ * 1.5 hours) is 79.2wt%, and viscosity is 880cps, seals the NCO base fully and is 4.12meq/g.
The preparation and the assessment of electrodeposition application use resin
Comparing embodiment 1
In capacity is 1 liter four neck reaction flasks, at first add 200 gram water, 45 and restrain to be equipped with prepared acryl resin emulsifying agent among the embodiment 2, and the monomer mixed solution of 5.0 grams, this monomer mixed solution gets for being mixed by monomers such as 24.8 gram n-BMA, 9.0 gram 2-EHA and 11.3 gram 2-HEMA.After stirring, logical nitrogen is heated to 70 ℃, keeps 10 minutes.Then, once adding 20.7 gram concentration is the peroxidation sulfuric acid aqueous ammonium of 3.3wt%, continues to be heated to 80 ℃, keeps 10 minutes.In 40 minutes, all the other 40.1 gram monomer mixed solutions are added in the reaction flask then.Under 80 ℃, continued to keep 0.85 hour.Then, once add 3 tertbutyl peroxides (t-BHP) once again, continue to keep 90 minutes at 80 ℃.Cool off blanking then.Products therefrom is stablizes newborn attitude, and its viscosity (23 ℃) is 28cps, and solids content (120 ℃ * 1.5 hours) is 24.5wt%.Mn (number-average molecular weight) is 11,500, and Mw (weight-average molecular weight) is 22,600, Mw/Mn=1.96.
The emulsion that this comparing embodiment is made adds the preparation embodiment 3 or the 4 prepared type of sealing the fully IPDI curing agent solutions of equivalent, and a small amount of agglutination phenomenon is arranged after the mixing.After thin up becomes the electrodeposition of 10wt% to bathe, can't form stable emulsion.Therefore, can't prepare and contain the electrodeposition of sealing type IPDI solidifying agent fully and bathe.
Embodiment 1
In capacity is 1 liter four neck reaction flasks, at first add 200 gram water, 45 and restrain to be equipped with prepared acryl resin emulsifying agent among the embodiment 2, and 5.0 gram monomer mixed solutions, this monomer mixed solution gets for being mixed by 24.8 gram n-BMA, 9.0 gram 2-EHA and 11.3 monomers such as gram 2-HEMA etc.After stirring, logical nitrogen is heated to 70 ℃, keeps 10 minutes.Then, once adding 20.7 gram concentration is the peroxidation sulfuric acid aqueous ammonium of 3.3wt%, continues to be heated to 80 ℃, keeps 10 minutes.In 15 minutes, 20.0 gram monomer mixed solutions are added in the reaction flask then.Under 80 ℃, continued to keep 0.5 hour.Then in 30 minutes, all the other 20.1 gram monomer mixed solutions and 32.6 are restrained be equipped with alcohol radical prepared among the embodiment 3 and seal fully in the type IPDI curing agent solution adding reaction flask.Under 80 ℃, continued to keep 1 hour.At last, the tertbutyl peroxide (t-BHP) that a charging once again is 3 continues to keep 60 minutes at 80 ℃.Cool off blanking then.Products therefrom is stablizes newborn attitude, its blanking amount 336 grams, and productive rate 97.1%, viscosity (23 ℃) is 34cps, solids content (120 ℃ * 1.5 hours) is 30.6wt%.Mn (number-average molecular weight) is 23,400, and Mw (weight-average molecular weight) is 71,800, Mw/Mn=3.07.
The direct thin up of the above-mentioned emulsion that present embodiment is prepared becomes the electrodeposition of 8.0wt% to bathe.Its pH is 3.80, and conductance is 979 μ S/cm.At normal temperature, with the electrodeposition condition of 25V * 80 second and 25V * 110 second, stainless steel substrates is carried out the cathode electrode deposition test respectively.After the deposition, the electrodeposition film was through 160 ℃ * 30 minutes baking-curings.Its result shows: the initial current of (1) two kind of electrodeposition condition is all greater than 0.25A, and its ultimate current is 0.03A and 0.01A in regular turn.(2) the about 10 μ m of electrodeposition film thickness, glossiness (60 °) is 37, and pencil hardness is 2B, and hundred lattice densities are 100/100, and the electrodeposition film properties is good.
Embodiment 2
In capacity is 1 liter four neck reaction flasks, at first add 200 gram water, 45 and restrain to be equipped with prepared acryl resin emulsifying agent among the embodiment 2, and 5.0 gram monomer mixed solutions, this monomer mixed solution gets for being mixed by 24.8 gram n-BMA, 9.0 gram 2-EHA and 11.3 monomers such as gram 2-HEMA etc.After stirring, logical nitrogen is heated to 70 ℃, keeps 10 minutes.Then, once adding 20.7 gram concentration is the peroxidation sulfuric acid aqueous ammonium of 3.3wt%, continues to be heated to 80 ℃, keeps 10 minutes.In 15 minutes, 20.0 gram monomer mixed solutions are fed in the reaction flask then.Under 80 ℃, continued to keep 0.5 hour.Then in 30 minutes, all the other 20.1 gram monomer mixed solutions and 34.0 are restrained be equipped with oximido prepared among the embodiment 4 and seal fully in the type IPDI stiffening agent solution adding reaction flask.Under 80 ℃, continued to keep 1 hour.At last, once add 3 tertbutyl peroxide (t-BHP) once again, continue to keep 60 minutes at 80 ℃.Cool off blanking then.Products therefrom is stablizes newborn attitude, its blanking amount 332 grams, and productive rate 95.6%, viscosity (23 ℃) is 76cps, solids content (120 ℃ * 1.5 hours) is 34.8wt%.Mn (number-average molecular weight) is 10,800, and Mw (weight-average molecular weight) is 43,600, Mw/Mn=4.03.
Become the electrodeposition of 8.0wt% to bathe the direct thin up of the prepared above-mentioned emulsion of present embodiment.Its pH is 3.46, and conductance is 991 μ S/cm.At normal temperature, with the electrodeposition condition of 25V * 80 second and 25V * 100 second, stainless steel substrates is carried out the cathodic deposition test respectively.After the deposition, the electrodeposition film was through 140 ℃ * 30 minutes baking-curings.Its result shows: the initial current of (1) two kind of electrodeposition condition is all greater than 0.15A, and its ultimate current is 0.05A and 0.01A in regular turn.(2) the about 7 μ m of electrodeposition film thickness, glossiness (60 °) is 90, and pencil hardness is 2H, and hundred lattice densities are 100/100, and outward appearance and electrodeposition film properties are good.
Though the present invention with preferred embodiment openly as above; right its is not in order to qualification the present invention, any those of ordinary skill in the art, without departing from the spirit and scope of the present invention; can do to change and retouching, so protection scope of the present invention is as the criterion with claims.
Claims (16)
1. electrodeposition application composition, it comprises:
15～40 weight parts contain the vinyl unsaturated link(age), can carry out the monomer of letex polymerization;
The cationic high-molecular emulsifying agent of 15～60 weight parts;
The type of sealing the fully isocyanate crosslinking of 10～30 weight parts;
0.10 the polymerization starter of～4.5 weight parts; And
The water of 100 weight parts,
Wherein,
This monomer that can carry out letex polymerization comprise have can with the functional group's of this linking agent reaction monomer, and the monomer that contains this functional group accounts for monomeric 5～60 weight percents that all can carry out letex polymerization;
The monomer that this contains the vinyl unsaturated link(age), can carry out letex polymerization comprises and is selected from vinylformic acid, acrylate, methacrylic acid, or one or more acryl monomers in the methacrylic ester;
This cationic high-molecular emulsifying agent has hydroxyl, it is selected from ammonification acryl resin, ammonification Resins, epoxy or the ammonification polyamide resin one or more, its hydroxy radical content is 0.1～4.0meq/g, amino content is 0.3～3.5meq/g, weight-average molecular weight is 2,000～200,000g/mole.
2. composition as claimed in claim 1 is characterized in that, the monomer that describedly contain the vinyl unsaturated link(age), can carry out letex polymerization also comprises and is selected from aromatic vinyl monomer, C
2-C
12Aliphatic olefin, C
6-C
16One or more monomers in ester ring family alkene, vinylchlorid or the vinyl acetate.
3. composition as claimed in claim 1 or 2 is characterized in that, in the described monomer that carries out letex polymerization, has and can account for monomeric 15～45 weight percents that all can carry out letex polymerization with the functional group's of linking agent reaction monomer.
4. composition as claimed in claim 1 or 2 is characterized in that, described acryl monomer is selected from vinylformic acid, methacrylic acid, vinylformic acid C
1～C
8Alkyl ester and methacrylic acid C
1～C
8In the alkyl ester one or more.
5. composition as claimed in claim 1 or 2 is characterized in that, described carry out letex polymerization monomer had can be selected from hydroxyl, carboxyl or the active amino one or more with the functional group of this linking agent reaction.
6. composition as claimed in claim 5 is characterized in that, acryl monomer that the described monomer that carries out letex polymerization is a hydroxyl or carboxylic acryl monomer.
7. composition as claimed in claim 6 is characterized in that, the described monomer that carries out letex polymerization is the acryl monomer of hydroxyl.
8. composition as claimed in claim 7 is characterized in that, the acryl monomer of described hydroxyl is selected from one or more in Hydroxyethyl acrylate, Propylene glycol monoacrylate, hydroxyethyl methylacrylate or the Rocryl 410.
9. composition as claimed in claim 1 or 2 is characterized in that, described cationic high-molecular emulsifying agent is the ammonification acryl resin.
10. composition as claimed in claim 1 or 2 is characterized in that, the described type isocyanic ester of sealing is fully sealed fully with alcohols or oximes.
11. composition as claimed in claim 10 is characterized in that, described alcohols is C
1-C
18Alkanol or C
6-C
20Alicyclic ring alcohol.
12. composition as claimed in claim 11 is characterized in that, described alcohols is a butanols.
13. composition as claimed in claim 10 is characterized in that, described oximes is C
3-C
12Aliphatics oxime or C
6-C
16Alicyclic oxime.
14. composition as claimed in claim 13 is characterized in that, described oximes is a Diacetylmonoxime.
15. a method for preparing electrodeposition application use resin comprises:
Will comprise that but 15～40 weight parts contain the emulsion polymerization monomer of vinyl unsaturated link(age);
15～60 weight part cationic high-molecular emulsifying agents;
10～30 weight parts are sealed the type isocyanate crosslinking fully;
0.10～4.5 weight part polymerization starters; And
The composition of 100 weight parts waters carries out letex polymerization under 50～100 ℃,
Wherein,
This cationic high-molecular emulsifying agent and linking agent segmentation add;
This monomer that can carry out letex polymerization comprise have can with the functional group's of this linking agent reaction monomer, and the monomer that contains this functional group accounts for monomeric 5～60 weight percents that all can carry out letex polymerization;
The monomer that this contains the vinyl unsaturated link(age), can carry out letex polymerization comprises and is selected from vinylformic acid, acrylate, methacrylic acid, and one or more acryl monomers in the methacrylic ester;
This cationic high-molecular emulsifying agent has hydroxyl, it is selected from ammonification acryl resin, ammonification Resins, epoxy or the ammonification polyamide resin one or more, its hydroxy radical content is 0.1～4.0meq/g, amino content is 0.3～3.5meq/g, weight-average molecular weight is 2,000～200,000g/mole.
16. method as claimed in claim 15 is characterized in that, the monomer that describedly contain the vinyl unsaturated link(age), can carry out letex polymerization also comprises and is selected from aromatic vinyl monomer, C
2-C
12Aliphatic olefin, C
6-C
16Ester ring family alkene, vinylchlorid, and vinyl acetate in one or more monomers.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031224008A CN1548488A (en) | 2003-05-08 | 2003-05-08 | Composition for electrode deposition painting and method of preparing corresponding aquatic resin |
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|---|---|---|---|
| CNA031224008A CN1548488A (en) | 2003-05-08 | 2003-05-08 | Composition for electrode deposition painting and method of preparing corresponding aquatic resin |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585899B (en) * | 2008-05-23 | 2011-03-16 | 北京化工大学 | Cationic modified epoxy resin emulsion and preparation method and application thereof |
| CN102925042A (en) * | 2012-10-18 | 2013-02-13 | 铜陵市陵阳化工有限责任公司 | Preparation method of high-weather-resistant low-temperature-curing environment-friendly cation coating |
| CN103540249A (en) * | 2012-07-09 | 2014-01-29 | 纬创资通股份有限公司 | Water-based paint and method for forming object with smooth surface |
| CN111978818A (en) * | 2020-08-17 | 2020-11-24 | 上海金力泰化工股份有限公司 | Graphene oxide modified cathode electrophoresis primer and coating method thereof |
-
2003
- 2003-05-08 CN CNA031224008A patent/CN1548488A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585899B (en) * | 2008-05-23 | 2011-03-16 | 北京化工大学 | Cationic modified epoxy resin emulsion and preparation method and application thereof |
| CN103540249A (en) * | 2012-07-09 | 2014-01-29 | 纬创资通股份有限公司 | Water-based paint and method for forming object with smooth surface |
| CN103540249B (en) * | 2012-07-09 | 2016-06-08 | 纬创资通股份有限公司 | Water-based paint and method for forming object with smooth surface |
| CN102925042A (en) * | 2012-10-18 | 2013-02-13 | 铜陵市陵阳化工有限责任公司 | Preparation method of high-weather-resistant low-temperature-curing environment-friendly cation coating |
| CN111978818A (en) * | 2020-08-17 | 2020-11-24 | 上海金力泰化工股份有限公司 | Graphene oxide modified cathode electrophoresis primer and coating method thereof |
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