CN101368057A - High-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint - Google Patents
High-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint Download PDFInfo
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- CN101368057A CN101368057A CNA2008101987621A CN200810198762A CN101368057A CN 101368057 A CN101368057 A CN 101368057A CN A2008101987621 A CNA2008101987621 A CN A2008101987621A CN 200810198762 A CN200810198762 A CN 200810198762A CN 101368057 A CN101368057 A CN 101368057A
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- epoxy
- polyurethane
- electrophoretic paint
- cathode electrophoretic
- performance
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- 239000003973 paint Substances 0.000 title claims abstract description 38
- 239000004814 polyurethane Substances 0.000 title claims abstract description 32
- 229920002635 polyurethane Polymers 0.000 title claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 150000001768 cations Chemical class 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 9
- -1 innoxious drier Substances 0.000 claims abstract description 9
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 7
- 239000004593 Epoxy Substances 0.000 claims description 44
- 229920005989 resin Polymers 0.000 claims description 36
- 239000011347 resin Substances 0.000 claims description 36
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000008367 deionised water Substances 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000009413 insulation Methods 0.000 claims description 17
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 16
- 239000000839 emulsion Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 13
- 231100000252 nontoxic Toxicity 0.000 claims description 11
- 230000003000 nontoxic effect Effects 0.000 claims description 11
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 10
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 10
- 150000002576 ketones Chemical class 0.000 claims description 10
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- 150000002170 ethers Chemical class 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 7
- 150000008431 aliphatic amides Chemical class 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920001228 polyisocyanate Polymers 0.000 claims description 6
- 239000005056 polyisocyanate Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 4
- 150000002391 heterocyclic compounds Chemical class 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 125000002091 cationic group Chemical group 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 150000001868 cobalt Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical group [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims 1
- 238000009472 formulation Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000010422 painting Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 6
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 239000003822 epoxy resin Substances 0.000 abstract description 3
- 239000000049 pigment Substances 0.000 abstract description 3
- 229920000647 polyepoxide Polymers 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 239000003513 alkali Substances 0.000 abstract description 2
- 239000000945 filler Substances 0.000 abstract 1
- 238000001962 electrophoresis Methods 0.000 description 17
- 239000002585 base Substances 0.000 description 9
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 8
- 238000004070 electrodeposition Methods 0.000 description 7
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 4
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical class COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000004922 lacquer Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229920001451 polypropylene glycol Polymers 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 241000237502 Ostreidae Species 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000020636 oyster Nutrition 0.000 description 2
- TZMFJUDUGYTVRY-UHFFFAOYSA-N pentane-2,3-dione Chemical compound CCC(=O)C(C)=O TZMFJUDUGYTVRY-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- CUDYYMUUJHLCGZ-UHFFFAOYSA-N 2-(2-methoxypropoxy)propan-1-ol Chemical compound COC(C)COC(C)CO CUDYYMUUJHLCGZ-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 206010021703 Indifference Diseases 0.000 description 1
- WRQNANDWMGAFTP-UHFFFAOYSA-N Methylacetoacetic acid Chemical compound COC(=O)CC(C)=O WRQNANDWMGAFTP-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical class CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 235000019445 benzyl alcohol Nutrition 0.000 description 1
- 229960004217 benzyl alcohol Drugs 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
- 238000007665 sagging Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 229960004418 trolamine Drugs 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Paints Or Removers (AREA)
Abstract
The invention discloses a high performance 150 DEG C dried bi-component epoxy-polyurethane cathode electrophoretic paint, which comprises aqueous cation epoxide resin, pigments and fillers, innoxious drier, dispersant, emulsifying agent, acid and so on. The thermostability and the breakdown voltage of the tank liquor involved in the invention are high; the content of working solvents is low; the tank liquor is friendly to the environment and energy-saving. The high performance 150 DEG C dried bi-component epoxy-polyurethane cathode electrophoretic paint has the excellent overall properties of salt-mist-resistance, chemical resistance, alkali resistance, and water resistance of cathode electrophoretic paint. The high performance 150 DEG C dried bi-component epoxy-polyurethane cathode electrophoretic paint can be widely applied as bottom anticorrosion painting in the metal anticorrosion industries of automobiles, components and fittings, engineering machinery, farm trucks, motorcycles, hardware, white goods and so on, which can be manufactured into transparent and chromatic cathode electrophoretic paints meeting the requirement for primer-topcoat coating of white goods, indoor hardware and so on.
Description
Technical field
The present invention relates to Chemicals and preparation method field, particularly a kind of bi-component epoxy-polyurethane cathode electrophoretic paint.
Background technology
Epoxy-polyurethane two-pack cathode electrophoresis dope is at present at painting dressing automobiles, and industries such as agricultural vehicle, motorcycle, engineering machinery, household electrical appliance, five metals have been used widely, and have replaced the anode coating process substantially.Along with the top large-scale coatings enterprises in the world such as U.S. PPG company, German BASF AG.Japan's Northwest coating has been set up individual proprietorship or joint venture in succession in China, also promoted the technical progress of domestic anode electrophoresis dope and application greatly, but still there is a certain distance in China's cathode electrophoresis dope technology and world standard.Cathode electrophoresis dope is with its utilization efficiency of coatings height, the film performance excellence, and safety, environmental protection is fit to numerous advantages such as industrial automation production and is used widely, and is not described further at this piece of writing.
The present cathode electrophoresis dope technology of China mainly shows following several aspect with the gap of external advanced level:
(1) tank liquor thermostability and advanced level gap are big.The independently developed electrophoretic paint tank liquor temperature of China generally all is controlled at below 30 ℃ at present, surpasses 30 ℃ of electrodeposited paint film plumpnesses, and the Stability of Bath Solution extreme difference.And U.S. PPG company ability cathode electrophoresis paint bath temperature 35 ℃ still stable and under this temperature electrodeposited paint film even.
(2) domestic cathode electrodip painting tank liquor breakdown potential is forced down, and general film-type voltage breakdown is at 280V-320V, even middle thick film is also only about 350V.And international most advanced level has up to more than the 600V.The throwing power sign electrocoating paint of electrocoating paint is to the size of the coating ability of complex part inner chamber, and the height voltage that breaks indicates that to a great extent it is by force the throwing power height that electrocoating paint applies ability to the complex part inner chamber.
(3) domestic electrocoating paint hopper liquid solvent is generally between 2-6%, and international most advanced level reaches≤and 1.5%.
Summary of the invention
For solving or improving the problems referred to above, the purpose of this invention is to provide a kind of high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint, the thermostability height of its tank liquor, voltage breakdown height, the low and more environmental protection of work solvent.
The object of the present invention is achieved like this: a kind of high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint, it is characterized in that: it is composed of the following components to calculate tank liquor by mass parts: 1 part of water dispersible mill base, emulsion 2-3 part, deionized water 3-4 part; Described water dispersible mill base is by waterborne cation Resins, epoxy 20-40 part, color stuffing 10-40 part, solvent 10-20 part, nontoxic siccative 0.5-1.5 part, dispersion agent 0.5-2 part, deionized water 20-50 part; Described emulsion is by waterborne cation Resins, epoxy 40-60 part, nontoxic siccative 0.5-1 part, and solvent 0.5-5 part, emulsifying agent 0.1-2 part, sour 0.1-2 part, deionized water 30-50 part is formed.
Waterborne cation Resins, epoxy calculates by mass parts, and prescription comprises following component: modified epoxy 50-70 part, type semienclosed and/or blocked polyurethane curing agent 10-30 part, neutralizing agent 5-30 part, deionized water 5-20 part.
Described modified epoxy calculates by mass parts, and prescription comprises following component: pure ethers and ketones solvent 10-30 part, Resins, epoxy 20-35 part, aliphatic amide 0.5-2 part, ketoimine resin 10-25 part.Ketoimine resin wherein calculates by mass parts, and prescription comprises following component: polyetheramine or polyamide 6 0-80 part, butanone or methyl iso-butyl ketone (MIBK) 20-40 part.
Described semiclosed or blocked polyurethane curing agent calculates by mass parts, prescription comprises following component: aromatic polyisocyanate 5-20 part, alcohol ether compound, heterocyclic compound one of them or two or more mixing 3-30 part, polyethers or PCDL 0-80 part, ketones solvent 0-40 part.
The preparation method of above-mentioned emulsion, its feature may further comprise the steps: disperse cylinder A at 900-1500 rev/min of following high speed dispersion 1-2 hour waterborne cation Resins, epoxy, nontoxic siccative, innoxious solvent input; Simultaneously deionized water, acid, emulsifying agent were dropped into the B cylinder at 1100-1500 rev/min of following high speed dispersion 10-40 minute; Thereafter under 1300-1500 rev/min, A cylinder mixture slowly is added drop-wise in the B cylinder, drips and finish the thick emulsion components that under this rotating speed, continues to disperse promptly to get in 1-2 hour.
The preparation method of above-mentioned mill base component, may further comprise the steps: waterborne cation Resins, epoxy, color stuffing, non-ionic dispersing agent, solvent, deionized water, siccative are dropped into dispersion pot, leave standstill more than 8 hours after the dispersion down at 700-1100 rev/min, disperse to advance sand mill in 20-40 minute down at 600-800 rev/min again and grind, to fineness≤15 μ.
The invention has the advantages that the advantage of having concentrated the existing many cathode electrophoresis dopes in market is as the thermostability height of tank liquor (the tank liquor electrophoresis temperature is between 35-38 ℃); Tank liquor voltage breakdown height (voltage breakdown 〉=380V); Tank liquor work solvent low (solvent is lower than at 1.5% o'clock, does not influence electrophoresis); Electrocoating paint does not contain any noxious solvent such as ethylene glycol monomethyl ether, ethylene glycol ethyl ether aspect environmental protection, glycol ethers content is extremely low, and electrocoating paint is not leaded, tin class siccative and toxic heavy metal; 150 ℃ of drying-types are more energy-conservation than 175 ℃ of drying-type electrocoating paints, and the salt spray resistance of cathode electrodip painting, chemicals-resistant, excellent comprehensive performance universal succession in product of the present invention such as alkaline-resisting, water-fast.The present invention can be widely used in the bottom anticorrosive coating of anti-corrosion of metal industries such as automobile and spare and accessory parts, engineering machinery, agricultural vehicle, motorcycle, five metals, household electrical appliance, also can be satisfying to require aspect the bottom surfaces unification applications such as household electrical appliance, indoor five metals and make transparent color and color cathode electrophoretic paint.
Embodiment
Electrophoretic paint is the water-borne coatings kind of developing the earliest, and with other water-borne coatings ratios, the tank liquor solvent is low, helps environmental protection, and security is good, and electrophoresis wet film solvent still less, is not easy to produce disadvantages such as sagging orange peel, long-pending lacquer in drying course; The antiseptic power of filming is strong, and the cathode electrophoresis dope of especially high throwing power has significant raising to the rotproofness at the inner chamber of workpiece, weld seam, edge; Utilization efficiency of coatings is high, and electrophoretic painting can be realized mechanize, automatization fully in addition, raises labour productivity greatly; Temperature is dried electrophoretic paint than 175 ℃ of high bake electrophoretic paints in 150 ℃, but save energy reduces loss on heating.
The present invention is a kind of high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint, it is characterized in that: it is composed of the following components to calculate tank liquor by mass parts: 1 part of water dispersible mill base, emulsion 2-3 part, deionized water 3-4 part.
Described water dispersible mill base is by waterborne cation Resins, epoxy 20-40 part, color stuffing 10-40 part, solvent 10-20 part, nontoxic siccative 0.5-1.5 part, dispersion agent 0.5-2 part, deionized water 20-50 part.
Described emulsion is by waterborne cation Resins, epoxy 40-60 part, nontoxic siccative 0.5-1 part, and solvent 0.5-5 part, emulsifying agent 0.1-2 part, sour 0.1-2 part, deionized water 30-50 part is formed.
Waterborne cation Resins, epoxy calculates by mass parts, and prescription comprises following component: modified epoxy 50-70 part, type semienclosed and/or blocked polyurethane curing agent 10-30 part, neutralizing agent 5-30 part, deionized water 5-20 part.Neutralizing agent, acid are organic acid, preferable formic acid, acetate, propionic acid, lactic acid, the aqueous solution of oxalic acid etc.Modified epoxy calculates by mass parts, and prescription comprises following component: pure ethers and ketones solvent 10-30 part, Resins, epoxy 20-35 part, aliphatic amide 0.5-2 part, ketoimine resin 10-25 part.Wherein, pure ethers and ketones solvent can be propylene glycol first/second/butyl ether, 2-hydroxyl first/second/butyl ether, phenylcarbinol, dipropylene glycol methyl ether, butanols, Virahol, butanone, ring ethyl ketone, methyl iso-butyl ketone (MIBK); Resins, epoxy can be that epoxy equivalent (weight) is the bisphenol A type epoxy resin between the 180-1000, phenol aldehyde modified Resins, epoxy; The amine value of polymeric amide is between 80-380; The molecular weight of polyetheramine is between 1000-3000.Semiclosed or blocked polyurethane curing agent calculates by mass parts, prescription comprises following component: aromatic polyisocyanate 5-20 part, alcohol ether compound, heterocyclic compound one of them or two or more mixing 3-30 part, polyethers or PCDL 0-80 part, ketones solvent 0-40 part.Wherein, aromatic polyisocyanate can be TDI, MDI; The alcohol ether compound can be butyl glycol ether, Diethylene Glycol first/second/butyl ether, 2-hydroxyl first/second/butyl ether, propylene glycol first/second/butyl ether; Heterocyclic compound can be N-methylpyrrole alkanol, tetrahydrofurfuryl alcohol, methyl ethyl diketone, methyl aceto acetate etc.; Polyethers can be polypropylene glycol ether, the polyglycol ether of molecular weight between 400-3000, or admixtured polyether; The molecular weight of PCDL is between 1000-3000; Aliphatic amide can be Mono Methyl Ethanol Amine, dimethylethanolamine, diethylamine, diethanolamine, trolamine, dipropyl amine, Di-n-Butyl Amine; Ketones solvent can be butanone, ring ethyl ketone, methyl iso-butyl ketone (MIBK).
Pigment can be titanium dioxide, carbon black, red iron oxide, process white, water-washed kaoline etc.
Nontoxic siccative is various bismuth salt, rare earth drier, cobalt salt siccative.
Dispersion agent is non-ionic dispersing agent or cationic dispersing agent.
The preparation method of above-mentioned emulsion, its feature may further comprise the steps: disperse cylinder A at 900-1500 rev/min of following high speed dispersion 1-2 hour waterborne cation Resins, epoxy, nontoxic siccative, innoxious solvent input; Simultaneously deionized water, acid, emulsifying agent were dropped into the B cylinder at 1100-1500 rev/min of following high speed dispersion 10-40 minute; Thereafter under 1300-1500 rev/min, A cylinder mixture slowly is added drop-wise in the B cylinder, drips and finish the thick emulsion components that under this rotating speed, continues to disperse promptly to get in 1-2 hour.
The preparation method of above-mentioned mill base component, may further comprise the steps: waterborne cation Resins, epoxy, color stuffing, non-ionic dispersing agent, solvent, deionized water, siccative are dropped into dispersion pot, leave standstill more than 8 hours after the dispersion down at 700-1100 rev/min, disperse to advance sand mill in 20-40 minute down at 600-800 rev/min again and grind, to fineness≤15 μ.
The preparation method of above-mentioned waterborne cation Resins, epoxy, its feature may further comprise the steps:
(1) preparation of modified epoxy: with Resins, epoxy 20-35 part, pure ethers, ketones solvent 10-30 part input reactor add aliphatic amide 0.5-2 part 50 ℃ of-80 ℃ of following stirring and dissolving and reacted 2-3 hour down at 80 ℃-90 ℃ after 1 hour; After reaction is finished, drip 10-25 part ketoimine resin down at 75 ℃-90 ℃ and go into reactor and be incubated 1.5-2.5 hour, get modified epoxy;
(2) preparation of solidifying agent: aromatic polyisocyanate 5-20 part is dropped into reactor, add in batches or drip pure ethers monohydroxy compound or heterocyclic hydroxy-containing compounds 3-30 part at 20-50 ℃, polyethers or PCDL 0-80 part (if PCDL or polyethers need in advance through dissolution with solvents); Thereafter be warming up to 70 ℃-90 ℃ insulations 1.5-3 hour after 0.5-2 hour again 30-80 ℃ of insulation, solubilizing agent 0-40 part promptly gets semiclosed or blocked polyurethane curing agent;
(3) modified epoxy 50-70 part is heated to 70-90 ℃, drips or add semiclosed or blocked curing agent 10-30 part in batches, and add deionized water 5-20 part after 1.5-2.5 hour 70-90 ℃ of insulation 40-80 minute in insulation under this temperature; Thereafter being cooled to 25-70 ℃ adds neutralizing agent 5-30 part and stirs and hour promptly to get waterborne cation Resins, epoxy half an hour to 1.
Embodiment 1
76 parts of TDI are dropped into reactors, open and stir and, be warming up to 80 ℃ of insulations 2 hours again, promptly get semiclosed polyurethane curing agent add 46 parts of tetrahydrofurfuryl alcohols below 50 ℃ in batches 50 ℃ of insulation half an hour.
Embodiment 2
In reactor, drop into 33.4 parts of methyl ethyl diketones, 55.3 parts of TDI, 1 part of dimethylethanolamine, 80 parts of solvent butanone, heated and stirred is warming up to 85 ℃ of reactions in insulation under 70 ℃ and promptly got blocked polyurethane curing agent in 4 hours after 30 minutes.
Embodiment 3
To gather 25 parts of input reactors of semiclosed solidifying agent that 110 parts of carbon ester dibasic alcohol (molecular weight 2000), 15 parts of butanone solvents, embodiment 1 make, open to stir and be warming up to 120 ℃ of reactions after 2 hours, be cooled to 80 ℃, drip TDI10 part, be warming up to 110 ℃ of insulations after dripping off and promptly got semi-enclosed polyurethane curing agent in 1 hour.
Embodiment 4
81 parts of E20 Resins, epoxy, 39.4 parts of propylene glycol monomethyl ethers, 19.8 parts of input reactors of butanone were dissolved 1 hour 50 ℃-80 ℃ following heated and stirred; Add 19.7 parts of 2.2 parts of dimethylethanolamines, 9.1 parts of diethanolamine, Virahol afterwards 80 ℃-85 ℃ insulations 2 hours; Drip 49.2 parts in ketoimine mixture (this ketoimine mixture is 2000 2.8 parts of polyetheramines by the molecular weight with butanone sealing and is that 300 polyamide is formed for 46.4 parts with the amine value of methyl iso-butyl ketone (MIBK) sealing) then and 85 ℃ of insulations after 1 hour down, be warming up to 90 ℃ of insulations 2 hours again, promptly get modified epoxy.
Embodiment 5
17.6 parts in the semiclosed solidifying agent that 80 parts of input reactors of modified epoxy that embodiment 4 is made make at 75 ℃ of-80 ℃ of following agitation and dropping embodiment 1, then add 11.3 parts of the blocked polyurethane curing agents that embodiment 2 makes in three batches, and 80 ℃ down insulation add water after 2 hours and continue insulation 1 hour for 6 parts, cool to and add neutralizing agent below 50 ℃ and stir for 6 parts and promptly got the cationic water epoxy resin in 30 minutes.
Embodiment 6
32.6 parts of waterborne cation Resins, epoxy, 15.4 parts of 1250 order calcined kaolins, 1.1 parts of high-carbon black pigments, 0.7 part of non-ionic dispersing agent, 6 parts of propylene glycol monomethyl ethers, 7.8 parts of Virahols, 38.6 parts of deionized waters, organo-bismuth siccative are dropped into dispersion pot for 0.76 part, after disperseing 1 hour under 700-1100 rev/min, left standstill 8 hours, disperseing to advance sand mill in 30 minutes down at 700 rev/mins again grinds, to fineness≤15 μ be qualified packing, electrophoretic paint mill base component.
Embodiment 7
123.4 parts of waterborne cation Resins, epoxy, 1.8 parts of propylene glycol monomethyl ethers, rare earth drier are dropped into dispersion cylinder A for 7.1 parts to be disperseed 1.5 hours down at 1300 rev/mins; In disperseing cylinder B, drop into simultaneously 131.5 parts of deionized waters, 2 parts of 20% acetic acid, 2.8 parts of 20% nonionic emulsifying agents, 1500 rev/mins of following high speed dispersion 30 minutes; Under 1500 rev/mins of high speed dispersion with A cylinder material with slowly evenly adding the B cylinder in 1.5 hours; Material adds the two-pack cathode electrophoresis dope is continued to disperse promptly to get in 1.5 hours in the back under this rotating speed another component---emulsion.
Embodiment 8
In clean electrophoresis chamber, drop into 2 parts of ionized waters, start the circulation mixing pump, and in groove, drop into 1.5 parts of emulsions, continue circulation; In the premix groove, drop into 1.5 parts of emulsions and start stirring, under agitation slowly drop into 1.5 parts of mill bases, stir and slowly evenly squeezed in the electrophoresis chamber premix groove mixed solution afterwards in 30 minutes; The water of throwing again after 2 parts of washed with de-ionized water premix grooves also will clean slowly evenly pumps into electrophoresis chamber.The tank liquor thermalization can work be carried out the workpiece electrophoretic painting after 48 hours in constantly circulating.
Detected result
One, former lacquer index
| Project | The mill base component | Measured value | Emulsion components | Measured value | Detection method |
| Outward appearance | Grey, the layering of nothing caking | There is not the caking layering | Oyster white | Oyster white | Range estimation |
| Fineness μ m | ≤15 | ≤15 | —— | —— | GB/T1742 |
| Admittedly contain % | Ash 50 ± 2% black 41 ± 2% | 52.3 | 35±2％ | 34.5 | GB/T6751 |
| The pH value | 5.4±0.3 | 5.3 | 6.7±0.3 | 6.71 | PH meter |
| Specific conductivity us/cm | 1200±300 | 1370 | 900±300 | 952 | HB/T3335 |
Two, tank liquor performance
| Project | Design load | Measured value | Detection method |
| Solids content % | 19±1％ | 20.48 | GB/T6751 |
| The pH value | 6.5±0.3 | 6.35 | PH meter |
| Specific conductivity us/cm | 1000±300 | 1139 | HG/T3335 |
| Ash % | The black 0.95-2.09 of ash 3.42-4.56 | 4.3 | GB/T1747 |
| Solvent | ≤1.5 | Do not survey | Gas-chromatography |
| The MEQ value | 30±4 | Do not survey | A4 in the TB/T10242 appendix A |
| Throwing power % | ≥85 | Do not survey | A10 in the TB/T10242 appendix A |
| The storehouse colour efficiency | ≥25 | Do not survey | HG/T3337 |
| Voltage V breaks | ≥380 | >380 | A3 in the TB/T10242 appendix A |
| The L effect | Horizontal vertical and do not have significant difference | Indifference | A6 in the TB/T10242 appendix A |
| Dissolution rate % again | ≤10 | 8 | A2 in the TB/T10242 appendix A |
Three, film performance
| Index name | Design load | Measured value | Detection method |
| Outward appearance | Smooth smooth, no shrinkage cavity | Smooth smooth, no shrinkage cavity | Range estimation |
| Voltage thickness V/um | 280-330/(21±2) | 300/19 | —— |
| Gloss 60% | ≥60 | 75 | GB/T9754 |
| Shock strength Kgcm | 50 | Qualified | GB/T1732 |
| Cupping mm | ≥5 | 6.8 | GB/T9753 |
| Sticking power level (1mm * 1mm, 100/100) | 0 | 0 | GB/T9286 |
| Pencil hardness | H | 2H | GB/T6739 |
| Snappiness (mm) | 1 | 1 | GB/T1731 |
| Alkali resistance (5%) | ≥48h | >120h | GB/T1763 |
| Acid resistance (0.05mol) | ≥48h | Qualified | GB/T1763 |
| Water tolerance (40 ℃) | 360h | Qualified | GB-5209 |
| (3%) 25 ℃ of salt water resistance | 360h | Qualified | GB-1763 |
| Salt-fog test phosphatization plate 21 ± 2 μ | 800h | Qualified | GB/T1771 |
| Anti-gasoline (93#) | 48h | >240h | GB/T1734 |
Advantage of the present invention is as follows:
(1) heat endurance of tank liquor is high, and the tank liquor electrophoresis temperature is between 35-38 ℃;
(2) height of breakdown voltage reflects electrophoretic coating to the ability of filming of workpiece lumen height, i.e. permeability ratio height, so high-breakdown-voltage proves the high-performance of lacquer from the side, and tank liquor breakdown voltage 〉=380V of the present invention (35-38 ℃);
When (3) tank liquor work solvent is lower than 1.5%, still can the electrophoresis qualified products, solvent is low to be one of electrophoretic coating developing direction;
(4) do not contain any toxic solvent such as EGME, ethylene glycol ethyl ether, gylcol ether content is extremely low, and simultaneously not leaded, tin class drier and toxic heavy metal belong to environmentally friendly;
(5) solidification temperature be 150 ℃ have than common 175 ℃ of drying-type ratios energy-conservation, the low advantage such as hot driving that adds;
(6) find that by making sheet this product is good to coated workpieces edge coverage ability;
(7) owing to be middle low-temperature bake, paint film toasts nondiscolouring, and therefore xanthochromia not can be used as light electrophoretic painting.
Claims (10)
1. a high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint is characterized in that: composed of the following components by mass parts calculating tank liquor: 1 part of water dispersible mill base, emulsion 2-3 part, deionized water 3-4 part; Described water dispersible paste formula is by waterborne cation Resins, epoxy 20-40 part, color stuffing 10-40 part, solvent 10-20 part, nontoxic siccative 0.5-1.5 part, dispersion agent 0.5-2 part, deionized water 20-50 part; Described emulsion formulations is by waterborne cation Resins, epoxy 40-60 part, nontoxic siccative 0.5-1 part, and solvent 0.5-5 part, emulsifying agent 0.1-2 part, sour 0.1-2 part, deionized water 30-50 part is formed.
2. high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint according to claim 1, it is characterized in that: described waterborne cation Resins, epoxy calculates by mass parts, prescription comprises following component: modified epoxy 50-70 part, type semienclosed and/or blocked polyurethane curing agent 10-30 part, neutralizing agent 5-30 part, deionized water 5-20 part.
3. high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint according to claim 2, it is characterized in that: described modified epoxy calculates by mass parts, prescription comprises following component: pure ethers and ketones solvent 10-30 part, Resins, epoxy 20-35 part, aliphatic amide 0.5-2 part, ketoimine resin 10-25 part.
4. high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint according to claim 3, it is characterized in that: described ketoimine resin calculates by mass parts, and prescription comprises following component: polyetheramine or polyamide 6 0-80 part, butanone or methyl iso-butyl ketone (MIBK) 20-40 part.
5. high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint according to claim 2, it is characterized in that: described semiclosed or blocked polyurethane curing agent calculates by mass parts, prescription comprises following component: aromatic polyisocyanate 5-20 part, alcohol ether compound, heterocyclic compound one of them or two or more mixing 3-30 part, polyethers or PCDL 0-80 part, ketones solvent 0-40 part.
6. high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint according to claim 1 and 2 is characterized in that: described acid, neutralizing agent are organic acid.
7. high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint according to claim 1 is characterized in that: described nontoxic siccative is bismuth salt siccative, rare earth drier or cobalt salt siccative; Described dispersion agent is non-ionic dispersing agent, cationic dispersing agent.
8. high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint according to claim 1, it is characterized in that: the preparation method of described emulsion, its feature may further comprise the steps: disperse cylinder A at 900-1500 rev/min of following high speed dispersion 1-2 hour waterborne cation Resins, epoxy, nontoxic siccative, innoxious solvent input; Simultaneously deionized water, acid, emulsifying agent were dropped into the B cylinder at 1100-1500 rev/min of following high speed dispersion 10-40 minute; Thereafter under 1300-1500 rev/min, A cylinder mixture slowly is added drop-wise in the B cylinder, drips and finish the thick emulsion components that under this rotating speed, continues to disperse promptly to get in 1-2 hour.
9. high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint according to claim 1, it is characterized in that: the preparation method of above-mentioned mill base component, may further comprise the steps: waterborne cation Resins, epoxy, color stuffing, non-ionic dispersing agent, solvent, deionized water, siccative are dropped into dispersion pot, leave standstill more than 8 hours after the dispersion down at 700-1100 rev/min, disperse to advance sand mill in 20-40 minute down at 600-800 rev/min again and grind, to fineness≤15 μ.
10. high-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint according to claim 1 is characterized in that: the preparation method of described waterborne cation Resins, epoxy, and its feature may further comprise the steps:
(1) preparation of modified epoxy: with Resins, epoxy 20-35 part, pure ethers, ketones solvent 10-30 part input reactor add aliphatic amide 0.5-2 part and reacted 2-3 hour down at 80 ℃-90 ℃ after 50 ℃ of-80 ℃ of following stirring and dissolving; After reaction is finished, drip 10-25 part ketoimine resin down at 75 ℃-90 ℃ and go into reactor and be incubated 1.5-2.5 hour, get modified epoxy;
(2) preparation of solidifying agent: aromatic polyisocyanate 5-20 part is dropped into reactor, add in batches or drip pure ethers monohydroxy compound or heterocyclic hydroxy-containing compounds 3-30 part, polyethers or PCDL 0-80 part at 20-50 ℃; Thereafter be warming up to 70 ℃-90 ℃ insulations 1.5-3 hour after 0.5-2 hour again 30-80 ℃ of insulation, solubilizing agent 0-40 part promptly gets semiclosed or blocked polyurethane curing agent;
(3) modified epoxy 50-70 part is heated to 75-85 ℃, drips or add type semienclosed and/or blocked curing agent 10-30 part in batches, and add deionized water 5-20 part after 1.5-2.5 hour 70-90 ℃ of insulation 40-80 minute in insulation under this temperature; Thereafter being cooled to 25-70 ℃ adds neutralizing agent 5-30 part and stirs and promptly to get waterborne cation Resins, epoxy in 0.5-1 hour.
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Application publication date: 20090218 Assignee: GUANGDONG KODEST CHEMICAL INDUSTRY Co.,Ltd. Assignor: Jiang Zeping|Chen Qinbin Contract record no.: 2012440000642 Denomination of invention: High-performance 150 DEG C oven dry type bi-component epoxy-polyurethane cathode electrophoretic paint Granted publication date: 20110914 License type: Exclusive License Record date: 20121206 |
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