CN102337073A - 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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- CN102337073A CN102337073A CN2011102371110A CN201110237111A CN102337073A CN 102337073 A CN102337073 A CN 102337073A CN 2011102371110 A CN2011102371110 A CN 2011102371110A CN 201110237111 A CN201110237111 A CN 201110237111A CN 102337073 A CN102337073 A CN 102337073A
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- Prior art keywords
- water
- soluble
- lightless
- monomethyl ether
- glycol monomethyl
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- 238000000576 coating method Methods 0.000 title claims abstract description 60
- 239000011248 coating agent Substances 0.000 title claims abstract description 56
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 125000000129 anionic group Chemical group 0.000 title abstract description 4
- 239000004814 polyurethane Substances 0.000 claims abstract description 29
- 229920002635 polyurethane Polymers 0.000 claims abstract description 29
- 229920006222 acrylic ester polymer Polymers 0.000 claims abstract description 21
- 239000012948 isocyanate Substances 0.000 claims abstract description 20
- 150000002513 isocyanates Chemical class 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003999 initiator Substances 0.000 claims abstract description 15
- 239000012986 chain transfer agent Substances 0.000 claims abstract description 7
- 238000010422 painting Methods 0.000 claims abstract description 6
- 238000001962 electrophoresis Methods 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 34
- 150000001450 anions Chemical class 0.000 claims description 33
- 239000013543 active substance Substances 0.000 claims description 25
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 24
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 22
- 229920000151 polyglycol Polymers 0.000 claims description 22
- 239000010695 polyglycol Substances 0.000 claims description 22
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 19
- 239000005057 Hexamethylene diisocyanate Substances 0.000 claims description 12
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- -1 neopentyl alcohol amine Chemical class 0.000 claims description 11
- VBICKXHEKHSIBG-UHFFFAOYSA-N 1-monostearoylglycerol Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC(O)CO VBICKXHEKHSIBG-UHFFFAOYSA-N 0.000 claims description 10
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 claims description 10
- 239000013638 trimer Substances 0.000 claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 229920002554 vinyl polymer Polymers 0.000 claims description 9
- 239000003643 water by type Substances 0.000 claims description 8
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 claims description 7
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 7
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 6
- 239000000839 emulsion Substances 0.000 claims description 6
- 239000000284 extract Substances 0.000 claims description 6
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 5
- 239000005058 Isophorone diisocyanate Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 5
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical group CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 5
- 229940075507 glyceryl monostearate Drugs 0.000 claims description 5
- 238000009413 insulation Methods 0.000 claims description 5
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000001788 mono and diglycerides of fatty acids Substances 0.000 claims description 5
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 4
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 4
- 229960004418 trolamine Drugs 0.000 claims description 4
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 3
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 3
- 229960002887 deanol Drugs 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- LVTYICIALWPMFW-UHFFFAOYSA-N diisopropanolamine Chemical compound CC(O)CNCC(C)O LVTYICIALWPMFW-UHFFFAOYSA-N 0.000 claims description 3
- 239000012972 dimethylethanolamine Substances 0.000 claims description 3
- POULHZVOKOAJMA-UHFFFAOYSA-M dodecanoate Chemical compound CCCCCCCCCCCC([O-])=O POULHZVOKOAJMA-UHFFFAOYSA-M 0.000 claims description 3
- 239000008393 encapsulating agent Substances 0.000 claims description 3
- 229940070765 laurate Drugs 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- BKMMTJMQCTUHRP-UHFFFAOYSA-N 2-aminopropan-1-ol Chemical compound CC(N)CO BKMMTJMQCTUHRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000004160 Ammonium persulphate Substances 0.000 claims description 2
- 229910000737 Duralumin Inorganic materials 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- 239000004159 Potassium persulphate Substances 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001412 amines Chemical class 0.000 claims description 2
- 235000019395 ammonium persulphate Nutrition 0.000 claims description 2
- 230000001143 conditioned effect Effects 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- 229940043279 diisopropylamine Drugs 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 2
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Substances CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 claims description 2
- 235000019394 potassium persulphate Nutrition 0.000 claims description 2
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 abstract description 8
- 239000003960 organic solvent Substances 0.000 abstract description 5
- 231100000241 scar Toxicity 0.000 abstract description 5
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- 239000004094 surface-active agent Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 239000003973 paint Substances 0.000 description 11
- 229920005989 resin Polymers 0.000 description 10
- 239000011347 resin Substances 0.000 description 10
- 239000004721 Polyphenylene oxide Substances 0.000 description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 6
- 229920000570 polyether Polymers 0.000 description 6
- 239000005056 polyisocyanate Substances 0.000 description 6
- 229920001228 polyisocyanate Polymers 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N Acrylic acid Chemical compound OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 5
- 239000004411 aluminium Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000004640 Melamine resin Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- OMIGHNLMNHATMP-UHFFFAOYSA-N 2-hydroxyethyl prop-2-enoate Chemical compound OCCOC(=O)C=C OMIGHNLMNHATMP-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- KGWDUNBJIMUFAP-KVVVOXFISA-N Ethanolamine Oleate Chemical compound NCCO.CCCCCCCC\C=C/CCCCCCCC(O)=O KGWDUNBJIMUFAP-KVVVOXFISA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229920000538 Poly[(phenyl isocyanate)-co-formaldehyde] Polymers 0.000 description 1
- 229920006387 Vinylite Polymers 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- RQGNEYFWHWFECS-UHFFFAOYSA-N amino formate Chemical class NOC=O RQGNEYFWHWFECS-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229920006026 co-polymeric resin Polymers 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- GMSCBRSQMRDRCD-UHFFFAOYSA-N dodecyl 2-methylprop-2-enoate Chemical compound CCCCCCCCCCCCOC(=O)C(C)=C GMSCBRSQMRDRCD-UHFFFAOYSA-N 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007720 emulsion polymerization reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical compound CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 1
- HZVOZRGWRWCICA-UHFFFAOYSA-N methanediyl Chemical class [CH2] HZVOZRGWRWCICA-UHFFFAOYSA-N 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 125000005968 oxazolinyl group Chemical group 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000010734 process oil Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- NHARPDSAXCBDDR-UHFFFAOYSA-N propyl 2-methylprop-2-enoate Chemical compound CCCOC(=O)C(C)=C NHARPDSAXCBDDR-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
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 and use coating, particularly a kind of water-soluble Lightless anion electrophoresis coating and preparation method thereof and application.
Background technology
Aluminium is in light weight, and processing easily, and good corrosion resistance is widely used as the material relevant with building materials.But the rust-preventing characteristic of aluminium own, wear resistant, chemical proofing are poor, so after generally aluminium being carried out anodize, utilize the anion electrophoresis coating of delustring that it is carried out re-using behind the electrophoretic coating last layer matt film.
As the employed delustring electrophoretic paint of aluminum products coating method, always carrying out various researchs.Have and utilize two kinds of different acrylic resins of solubility parameter and do not have the melamine resin of consistency to be dispersed in the anion electrophoresis coating " spy opens flat 10-46065 communique " in the water with these resins; In addition, the resin that will possess water dispersible in addition mixes with melamine resin, utilizes the difference of the SP value of resin to obtain unglazed coating " spy opens the 2001-131494 communique ".But the coating of above-mentioned two inventions must be in baking more than 170 ℃, and making easily films produces be full of cracks, and film performance is exerted an influence; Its consumed energy increases in addition, can cause loss economically.
In addition, have and use the resin that contains carboxyl and hydroxyl, the electrophoretic paint that the blocked polyisocyanates compound is made has low the filming of excellent performance, gloss that obtains 140 ℃ of baking-curings, but its covering property of mould scar not enough " spy opens flat 8-41380 communique ".
In addition, in electrophoretic paint,,,, in copolymer resin, form microgel in the insoluble particle through the condensation reaction of alcoxyl silyl as in binder resin, importing the alcoxyl silyl with the method for microgel in the insoluble particle of resin formation.Open clear 59-67398 communique, spy like the spy and open that clear 64-14281 communique, spy are opened flat 05-263296 communique, CN1329460C all reported similar technology; But when the time through change application condition variation gloss; Receive the influence of matting behind the electrophoresis easily, be prone to become the condition of restriction coating decoration property.
As all the other ways of interior microgel, as be utilized in the carboxyl that exists in the resin, cooperation can form the method for microgel with the functional group of this carboxyl reaction.(spy opens clear 59-138278 communique, special open 2-12511 communique) 、 oxazolinyl (spy opens flat 6-25568 communique) etc. to this type functional group just like epoxy group(ing).These class methods need in the manufacturing processed to form microgel in the particle through reacting by heating, and the preparation method is cumbersome.
Adopt solution polymerization process in the above-mentioned method of mentioning in the Vinylite manufacturing processed mostly, need in a large number with an organic solvent in the manufacturing processed, coating receives the influence of solvent easily, and contains the electrophoretic paint environmental-protecting performance reduction of high amounts of solvents.Therefore, the someone proposes to carry out emulsion polymerization prepared delustring electrophoretic paint (CN 102115526A) through synthetic anionic polyurethane surfactant and vinyl resin polymkeric substance, 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, does not contain organic solvent, and 60 ℃ of following gloss reach the water-soluble Lightless anion electrophoresis coating below 10.
Another object of the present invention is to provide the preparation method of above-mentioned water-soluble Lightless anion electrophoresis coating.
A purpose more of the present invention is to provide the purposes of above-mentioned water-soluble Lightless anion electrophoresis coating.
The object of the invention is realized through following technical proposals:
A kind of water-soluble Lightless anion electrophoresis coating is to be prepared by following compositions in portion by weight:
Acrylic ester polymer: 39-51 part
Nonionic polyurethane tensio-active agent: 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 become by the unsaturated monomer that contains carboxyl, hydroxyl unsaturated monomer and other free-radical polymerised unsaturated basic set of monomers;
The acid number of said acrylic ester polymer is 15-150mg KOH/g, preferred 40-100mg KOH/g; Hydroxyl value is 30-150mg KOH/g, preferred 40-100mg KOH/g; Second-order transition temperature is 10-40 ℃, preferred 15-30 ℃; Molecular weight is 10000-100000, the scope of preferred 20000-60000; MWD is 1～5;
Preferably, described acrylic ester polymer is made up of propenoate or vinyl compound base monomer;
Described propenoate or vinyl compound base monomer are for having general formula CH
2=C (R
1) COOR
2Acrylic ester monomer, or multiple such monomeric mixture; Wherein, R
1For-H or-CH
3, R
2For carbonatoms is the alkyl of 1-18;
More preferably, described acrylic ester polymer is made up of following compositions in portion by weight:
TEB 3K: 8.8-13 part
Rocryl 400: 6.4-9.5 part
Methylacrylic acid: 4.2-6.4 part
Bing Xisuandingzhi: 15-22 part
Vinylbenzene: 5-8.1 part;
Above-mentioned all the other monomers of the vinylformic acid of not mentioning; Like Jia Jibingxisuanyizhi, n propyl methacrylate, vinyl cyanide, acrylic amide, lauryl methacrylate(LMA), Hydroxyethyl acrylate, N methacrylamide etc.; And vinyl compound all can add the prescription of XPA, in order to improve final ADHESION OF PAINTS power, snappiness, water tolerance, solvent resistance and wear resistance.
Under water soluble starter and non-ionic polyurethane influence of surfactant, following copolyreaction takes place in the monomer methylacrylic acid in the acroleic acid polymerization composition formula, Rocryl 400, methacrylic methyl esters, Bing Xisuandingzhi, vinylbenzene:
Described nonionic polyurethane tensio-active agent 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%, preferred 25-45%; Used polyether glycol number-average molecular weight is 200-5000, preferred 500-2000; The synthesis of polyurethane molecular weight is 1000～7000 (preferred 2000～5000); Aliphatic or alicyclic urethane;
Described nonionic polyurethane tensio-active agent can be obtained by common polyaddition reaction, and its molecular weight can be controlled through regulating the poly glycol monomethyl ether molecular weight;
Described nonionic polyurethane tensio-active agent 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; Measure when not containing free-NCO in the product with the dibutylamine method, the cooling cooling extracts acetone; And, make the nonionic polyurethane tensio-active agent in 30 ℃ of following vacuum-dryings;
The mol ratio of said hexamethylene diisocyanate trimer and poly glycol monomethyl ether is 1: 3;
The molecular weight of said poly glycol monomethyl ether is 500～2000;
Described nonionic polyurethane tensio-active agent is perhaps prepared by following steps: get isophorone diisocyanate and mix with glyceryl monostearate; Add catalyzer dibutyl laurate, acetone; In 80 ℃ of waters bath with thermostatic control, stir the refluxed reaction; With in the dibutylamine method assaying reaction system-after nco value reaches preset value, add poly glycol monomethyl ether and continue reaction 2～3h, the cooling cooling; Extract acetone, and obtain the nonionic polyurethane tensio-active agent in 30 ℃ of following vacuum-dryings;
Said isophorone diisocyanate, poly glycol monomethyl ether, glyceryl monostearate three's mol ratio is 2: 2: 1;
The molecular weight of said poly glycol monomethyl ether is 500～2000.
Described blocked isocyanate linking agent can for: the NCO of present known polyisocyanate compound is carried out the polyisocyanate compound that end-blocking obtains with end-capping reagent; Also can for:, under catalyst action, add the end-capping reagent polymerization and obtain the blocked polyisocyanates solidifying agent by aromatics, fatty compounds, alicyclic ring kind isocyanate and polyether glycol; Wherein, described polyether glycol content (referring to account for the massfraction of synthetic urethane) is 10-50%, preferred 25-45%; Used polyether glycol number-average molecular weight is 200～5000, preferred 500～3000; Described blocked polyisocyanates crosslinking agent molecule amount is 2000～10000, preferred 3000～7000;
The end-capping reagent of described blocked polyisocyanates crosslinking agent has phenolic cpd, alcohol compound, oxime compounds, active methylene radical 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 aliphatic or alicyclic POLYMETHYLENE POLYPHENYLISOCYANATE.
Described blocked isocyanate linking agent is prepared by following method:
Hexamethylene diisocyanate trimer (HDI tripolymer) is mixed with poly glycol monomethyl ether, add the catalyzer dibutyl tin laurate, be warming up to 80 ℃ of reaction 3～5h then; Add the encapsulant methyl ethyl ketoxime, reaction 2～2.5h in reaction system-NCO group complete closed, reduce system viscosity with vinyl acetic monomer, be cooled to 20-30 ℃ and add entry and shear and disperse then, obtain the blocked isocyanate linking agent at last;
The mol ratio of said hexamethylene diisocyanate trimer and poly glycol monomethyl ether is 1: 1;
The molecular weight of said poly glycol monomethyl ether is 500～3000;
The mol ratio of said methyl ethyl ketoxime and hexamethylene diisocyanate trimer is 2: 1.
Described initiator is a kind of in Potassium Persulphate, Sodium Persulfate or the ammonium persulphate;
Described chain-transfer agent is a sulfur alcohol compound, preferred 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, diethylolamine, HSDB 338, trolamine, dimethylethanolamine, diethylethanolamine, amine water, sodium hydroxide or the Pottasium Hydroxide; Consider from over-all properties, select thanomin best; Neutralization ratio through these alkaline matters reach is advisable with 30%～100%, and is better with 60%～90% especially;
The preferred deionized water of described water.
The preparation method of above-mentioned water-soluble Lightless anion electrophoresis coating may further comprise the steps:
Under protection of nitrogen gas, water intaking, chain-transfer agent, 1/3 acrylic ester polymer, 1/3 initiator and nonionic polyurethane tensio-active agent mix, and at 75-85 ℃ of reaction 0.5-1.5h, make seed emulsion; Drip remaining acrylic ester polymer and initiator then; The dropping time is controlled at 3-5h, dropwises the back 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 Lightless anion electrophoresis 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 is taken all factors into consideration; Contradiction between the balance various factors; Design the equal good quality production of coating performance and workability; Come the second-order transition temperature of controlling polymers through the ratio between the soft or hard monomer, come controlling polymers molecular weight and distribution thereof through mercaptan; Through hydroxy radical content reasonable in design, so that suitable hydroxyl value to be provided; Introduce an amount of methylacrylic acid and reach suitable acid number; Introduce styrene monomer, make coating possess resistance to crocking and water tolerance, reduce the consistency between the coating.Through the design of integral body, make the synthetic emulsion possess satisfactory stability property and physicochemical property.
In the Lightless anion electrophoresis coating of the present invention, can add pigment, dyestuff, linking agent, skimmer, stablizer etc. as required and regulate, further optimize the performance of filming.
To the electrophoretic paint that the present invention makes, as required can be with deionized water dilution back power supply electrophoresis painting dressing.When using Lightless anion electrophoresis coating of the present invention, the solids constituent concentration of application tank liquor is that 4-15% (massfraction) is suitable, is preferably 10%.
Coating process of the present invention is with coated article process oil removing earlier, anodic oxidation, carries out electrophoretic painting with coated article as anode, and the voltage of application is 30-300V, and 50-120V is optimum.Conduction time 0.5-7min, 2-3min is better.Coated article after the application heats 15-40min down at 100-130 ℃ then and obtains finally to film through washing, and thickness is 16-22um.
The coated article that is fit to electrophoresis coating method of the present invention is as long as have electroconductibility.When adopting duraluminum to carry out electrophoresis, can obtain filming of evenly 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 through non-ionic polyurethane tensio-active agent and carboxylic vinyl resin polymkeric substance single step reaction, operation is simple; Coating prepares in the process not to be had not with an organic solvent, has reduced the pollution of coating to environment.
(2) the Lightless anion coating that obtains through non-ionic polyurethane tensio-active agent and vinyl resin polymer reaction, is saved the energy at opacifying property good, low 120 ℃ of the solidification value of low, the scar of coating gloss behind the electrophoretic painting.
(3) the non-ionic polyurethane tensio-active agent is insensitive to ionogen, and coatings formulated stability 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 embodiment of the present invention is not limited thereto.
Embodiment 1
A kind of preparation method of water-soluble Lightless anion electrophoresis coating may further comprise the steps:
(1) preparation nonionic polyurethane tensio-active agent: in reactor drum, add 0.05molHDI tripolymer and 0.15mol poly glycol monomethyl ether (molecular weight 500), 1～2 catalyzer dibutyl tin laurate, 50ml acetone; Stir, back flow reaction 5h in 80 ℃ of waters bath with thermostatic control measures when not containing free-NCO in the product with the dibutylamine method; The cooling cooling; Extract acetone, and, make nonionic polyurethane tensio-active agent (molecular weight 2000) in 30 ℃ of following vacuum-dryings;
(2) preparation blocked isocyanate linking agent: 0.05molHDI tripolymer, 0.05mol poly glycol monomethyl ether (molecular weight 2000) are joined in the reactor drum, add 1～2 dibutyl tin laurate, be warming up to 80 ℃ of afterreaction 4h; Slowly add 0.1mol encapsulant methyl ethyl ketoxime again; The reaction 2～2.5h in reaction system-NCO group complete closed; Add the 50ml vinyl acetic monomer and reduce system viscosity, be cooled to 25 ℃ and add deionized water and shear and disperse, obtain blocked isocyanate linking agent (molecular weight 3000) at last;
(3) 5 parts of methylacrylic acids, 8 parts of Rocryl 400s, 12 parts of TEB 3Ks, 20 parts of Bing Xisuandingzhis, 5 parts of vinylbenzene are mixed and obtain acrylic ester polymer, subsequent use;
(4) under protection of nitrogen gas; The nonionic polyurethane tensio-active agent (molecular weight 2000) of 5 parts of steps (1) is dissolved in 180 parts of deionized waters; Add then and be equipped with in the four-hole round-bottomed flask of whisking appliance, reflux condensing tube, TM and separating funnel, adds 1.6 parts of the initiator potassium persulfate solution of 17 parts of acrylic ester polymers, 0.05 part of lauryl mercaptan, 5% (massfraction), be warming up to 80 ℃ in the quick whipping process; Behind the reaction 1h, make seed emulsion; From tap funnel, drip 3.2 parts of the initiator potassium persulfate solution of 34 parts of acrylic ester polymers and 5% (massfraction); Drip off in the 4h, continue 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 Lightless anion electrophoresis coating A;
Said umber is a weight fraction.
Embodiment 2
A kind of preparation method of water-soluble Lightless anion electrophoresis coating may further comprise the steps:
(1) preparation nonionic polyurethane tensio-active agent: 0.05mol isophorone diisocyanate and 0.025mol glyceryl monostearate are added in the reactor drum; Add 1～2 catalyzer dibutyl laurate, 50ml acetone; In 80 ℃ of waters bath with thermostatic control, stir refluxed reaction 3h; With in the dibutylamine method assaying reaction system-after nco value reaches preset value, add 0.05mol poly glycol monomethyl ether (molecular weight 1500) and continue reaction 2.5h, after the cooling; Extract acetone, and obtain nonionic polyurethane tensio-active agent (molecular weight 4000) in 30 ℃ of following vacuum-dryings;
(2) preparation method of blocked isocyanate linking agent is with embodiment 1 step (2);
(3) 4.2 parts of methylacrylic acids, 6.4 parts of Rocryl 400s, 8.8 parts of TEB 3Ks, 15 parts of Bing Xisuandingzhis, 5.6 parts of vinylbenzene are mixed and obtain acrylic ester polymer, subsequent use;
(4) under protection of nitrogen gas; The nonionic polyurethane tensio-active agent (molecular weight 4000) of 7 parts of steps (1) is dissolved in 120 parts of deionized waters; Add then and be equipped with in the four-hole round-bottomed flask of whisking appliance, reflux condensing tube, TM and separating funnel, adds 1.35 parts of the initiator Sodium Persulfate solution of 13 parts of acrylic ester polymers, 0.04 part of lauryl mercaptan, 5% (massfraction), be warming up to 75 ℃ in the quick whipping process; Behind the reaction 1.5h, make seed emulsion; From tap funnel, drip 2.7 parts of the initiator Sodium Persulfate solution of 26 parts of acrylic ester polymers and 5% (massfraction); Drip off in the 5h, continue 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) adds trolamine and regulates pH to 9.0 for 7.2 parts, can obtain milky, solid content at 20.6% water-soluble Lightless anion electrophoresis coating B;
Said umber is a weight fraction.
Embodiment 3
A kind of preparation method of water-soluble Lightless anion electrophoresis coating may further comprise the steps:
(1) preparation method of nonionic polyurethane tensio-active agent 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 methylacrylic acids, 9.5 parts of Rocryl 400s, 13 parts of TEB 3Ks, 22 parts of Bing Xisuandingzhis, 8.1 parts of vinylbenzene are mixed and obtain acrylic ester polymer, subsequent use;
(4) under protection of nitrogen gas; The nonionic polyurethane tensio-active agent (molecular weight 2000) of 9 parts of steps (1) is dissolved in the 250g deionized water; Add then and be equipped with in the four-hole round-bottomed flask of whisking appliance, reflux condensing tube, TM and separating funnel, adds 2 parts of the initiator ammonium persulfate solutions of 16 parts of acrylic ester polymers, 0.06 part of lauryl mercaptan, 5% (massfraction), be warming up to 85 ℃ in the quick whipping process; Behind the reaction 0.5h, make seed emulsion; From tap funnel, drip 4 parts of the initiator ammonium persulfate solutions of 32 parts of acrylic ester polymers and 5% (massfraction); Drip off in the 3h, continue 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) adds sodium hydroxide and regulates pH to 8.0 for 3 parts, can obtain milky, solid content at 20.8% water-soluble Lightless anion electrophoresis coating C;
Said umber is a weight fraction.
The water-soluble Lightless anion electrophoresis coating of embodiment 1-3 is made into 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 is earlier through oil removing, anodic oxidation; Electrophoresis 1min under the voltage of 60V then; Wherein aluminium sheet is made anode, and insoluble conductor is a negative electrode.
Insoluble paint film behind the electrophoresis after washing is dried, is solidified under 120 ℃ * 30min condition.Paint film property is pressed tank liquor A～C such as table 1:
Electrophoretic paint performance that table 1 negatively charged ion is unglazed (behind the electrophoresis)
Can find out from table 1; Water-soluble Lightless anion electrophoresis coating of the present invention does not form gel or tackify in preserving or using; Therefore possess good preservation stability, behind the electrophoretic painting, can get opacifying property good, 60 ° of gloss smooth the filming below 10 of mould scar.
The foregoing description is a preferred implementation of the present invention; But embodiment of the present invention is not restricted to the described embodiments; Other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; All should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1. water-soluble Lightless anion electrophoresis coating is characterized in that it being to be prepared by following compositions in portion by weight:
Acrylic ester polymer: 39-51 part
Nonionic polyurethane tensio-active agent: 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 made up of following compositions in portion by weight:
TEB 3K: 8.8-13 part
Rocryl 400: 6.4-9.5 part
Methylacrylic acid: 4.2-6.4 part
Bing Xisuandingzhi: 15-22 part
Vinylbenzene: 5-8.1 part;
Described nonionic polyurethane tensio-active agent is prepared by following method:
Get hexamethylene diisocyanate trimer and mix, add catalyzer dibutyl tin laurate, acetone, stir with poly glycol monomethyl ether; Back flow reaction in 80 ℃ of waters bath with thermostatic control; Measure when not containing free-NCO in the product with the dibutylamine method, the cooling cooling extracts acetone; And, make the nonionic polyurethane tensio-active agent in 30 ℃ of following vacuum-dryings;
The mol ratio of said hexamethylene diisocyanate trimer and poly glycol monomethyl ether is 1: 3;
The molecular weight of said poly glycol monomethyl ether is 500～2000;
Described nonionic polyurethane tensio-active agent is perhaps prepared by following method:
Getting isophorone diisocyanate mixes with glyceryl monostearate; Add catalyzer dibutyl laurate, acetone, in 80 ℃ of waters bath with thermostatic control, stir the refluxed reaction, with in the dibutylamine method assaying reaction system-after nco value reaches preset value; Add poly glycol monomethyl ether and continue reaction 2～3h; The cooling cooling extracts acetone, and obtains the nonionic polyurethane tensio-active agent in 30 ℃ of following vacuum-dryings;
Said isophorone diisocyanate, poly glycol monomethyl ether, glyceryl monostearate three's mol ratio is 2: 2: 1;
The molecular weight of said poly glycol monomethyl ether is 500～2000.
2. water-soluble Lightless anion electrophoresis coating according to claim 1 is characterized in that: described blocked isocyanate linking agent is prepared by following method:
Hexamethylene diisocyanate trimer is mixed with poly glycol monomethyl ether, add the catalyzer dibutyl tin laurate, be warming up to 80 ℃ of reaction 3～5h then; Add the encapsulant methyl ethyl ketoxime, reaction 2～2.5h in reaction system-NCO group complete closed, reduce system viscosity with vinyl acetic monomer, be cooled to 20-30 ℃ and add entry and shear and disperse then, obtain the blocked isocyanate linking agent at last;
The mol ratio of said hexamethylene diisocyanate trimer and poly glycol monomethyl ether is 1: 1;
The molecular weight of said poly glycol monomethyl ether is 500～3000;
The mol ratio of said methyl ethyl ketoxime and hexamethylene diisocyanate trimer is 2: 1.
3. water-soluble Lightless anion electrophoresis coating according to claim 1 is characterized in that: described initiator is a kind of in Potassium Persulphate, Sodium Persulfate or the ammonium persulphate.
4. water-soluble Lightless anion electrophoresis coating according to claim 1 is characterized in that: described chain-transfer agent is a lauryl mercaptan.
5. water-soluble Lightless anion electrophoresis 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, diethylolamine, HSDB 338, trolamine, dimethylethanolamine, diethylethanolamine, amine water, sodium hydroxide or the Pottasium Hydroxide.
6. water-soluble Lightless anion electrophoresis coating according to claim 1 is characterized in that: described basic cpd is a kind of in diethylolamine, HSDB 338, trolamine, dimethylethanolamine or the diethylethanolamine.
7. water-soluble Lightless anion electrophoresis coating according to claim 1 is characterized in that: described water is deionized water.
8. the preparation method of each described water-soluble Lightless anion electrophoresis coating of claim 1-7; It is characterized in that may further comprise the steps: under protection of nitrogen gas; Water intaking, chain-transfer agent, 1/3 acrylic ester polymer, 1/3 initiator and nonionic polyurethane tensio-active agent mix; At 75-85 ℃ of reaction 0.5-1.5h, make seed emulsion; Drip remaining acrylic ester polymer and initiator then; The dropping time is controlled at 3-5h, dropwises the back 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 Lightless anion electrophoresis coating.
9. each described water-soluble Lightless anion electrophoresis coating of claim 1-7 is used for the electrophoretic painting of duraluminum.
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