CN112430420B - Scratch-resistant tin-free cathode electrophoretic coating and preparation method thereof - Google Patents
Scratch-resistant tin-free cathode electrophoretic coating and preparation method thereof Download PDFInfo
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- 230000003678 scratch resistant effect Effects 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- 238000000576 coating method Methods 0.000 title claims abstract description 28
- 239000011248 coating agent Substances 0.000 title claims abstract description 25
- 238000002156 mixing Methods 0.000 claims abstract description 80
- 238000010438 heat treatment Methods 0.000 claims abstract description 78
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 66
- 239000000839 emulsion Substances 0.000 claims abstract description 54
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 44
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000003973 paint Substances 0.000 claims abstract description 27
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 claims abstract description 22
- 229930195725 Mannitol Natural products 0.000 claims abstract description 22
- 239000000679 carrageenan Substances 0.000 claims abstract description 22
- 229940113118 carrageenan Drugs 0.000 claims abstract description 22
- 235000010418 carrageenan Nutrition 0.000 claims abstract description 22
- 229920001525 carrageenan Polymers 0.000 claims abstract description 22
- 239000000594 mannitol Substances 0.000 claims abstract description 22
- 235000010355 mannitol Nutrition 0.000 claims abstract description 22
- UHVMMEOXYDMDKI-JKYCWFKZSA-L zinc;1-(5-cyanopyridin-2-yl)-3-[(1s,2s)-2-(6-fluoro-2-hydroxy-3-propanoylphenyl)cyclopropyl]urea;diacetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O.CCC(=O)C1=CC=C(F)C([C@H]2[C@H](C2)NC(=O)NC=2N=CC(=CC=2)C#N)=C1O UHVMMEOXYDMDKI-JKYCWFKZSA-L 0.000 claims abstract description 22
- 235000015165 citric acid Nutrition 0.000 claims abstract description 20
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000003822 epoxy resin Substances 0.000 claims description 101
- 229920000647 polyepoxide Polymers 0.000 claims description 101
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 57
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 40
- 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 claims description 36
- 238000003756 stirring Methods 0.000 claims description 34
- 239000012948 isocyanate Substances 0.000 claims description 30
- 150000002513 isocyanates Chemical class 0.000 claims description 30
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 29
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 29
- 238000001816 cooling Methods 0.000 claims description 29
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 20
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 20
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 claims description 14
- 150000004658 ketimines Chemical class 0.000 claims description 14
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 12
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 10
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 10
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 10
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 claims description 10
- 235000019253 formic acid Nutrition 0.000 claims description 10
- WHIVNJATOVLWBW-UHFFFAOYSA-N n-butan-2-ylidenehydroxylamine Chemical compound CCC(C)=NO WHIVNJATOVLWBW-UHFFFAOYSA-N 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims description 10
- 239000005995 Aluminium silicate Substances 0.000 claims description 7
- 235000012211 aluminium silicate Nutrition 0.000 claims description 7
- REKWPXFKNZERAA-UHFFFAOYSA-K bismuth;2-carboxyphenolate Chemical compound [Bi+3].OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O.OC1=CC=CC=C1C([O-])=O REKWPXFKNZERAA-UHFFFAOYSA-K 0.000 claims description 7
- 239000006229 carbon black Substances 0.000 claims description 7
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 239000004576 sand Substances 0.000 claims description 4
- 229910052810 boron oxide Inorganic materials 0.000 abstract description 3
- 150000001868 cobalt Chemical class 0.000 abstract description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 150000003606 tin compounds Chemical class 0.000 abstract description 2
- 239000004566 building material Substances 0.000 abstract 1
- 238000013329 compounding Methods 0.000 abstract 1
- 239000000047 product Substances 0.000 description 12
- 239000004593 Epoxy Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 239000012043 crude product Substances 0.000 description 4
- 238000001962 electrophoresis Methods 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 238000006748 scratching Methods 0.000 description 4
- 230000008961 swelling Effects 0.000 description 4
- 230000006378 damage Effects 0.000 description 3
- 150000002009 diols Chemical class 0.000 description 3
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 229960002887 deanol Drugs 0.000 description 2
- 239000012972 dimethylethanolamine Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920001610 polycaprolactone Polymers 0.000 description 2
- 239000004632 polycaprolactone Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007542 hardness measurement Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001453 quaternary ammonium group Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides a scratch-resistant tin-free cathode electrophoretic coating and a preparation method thereof, wherein resin emulsion of the electrophoretic coating contains scratch-resistant agent modified alumina, and the preparation method of the modified alumina comprises the following steps: mixing ethylene glycol and water, adding Co (NO)3)2·6H2O and B2O3Adding nano-alumina into the mixture, heating to 40-50 ℃, preserving heat for 1-3 hours at 40-50 ℃, adding a mixture of citric acid, mannitol and carrageenan, heating to 53-57 ℃, preserving heat for 4-8 hours, drying the product at 75-85 ℃, and crushing to obtain the product. The electrophoretic coating disclosed by the invention is added with the modified alumina scratch resistance agent, and the cobalt salt, the boron oxide, the citric acid, the mannitol and the carrageenan are used for compounding and modifying the alumina, so that the coating has a good scratch resistance effect, does not contain heavy metal tin compounds, and has the advantages of environmental friendliness, good paint film flexibility, good leveling property, high glossiness, good corrosion resistance and the like. Can be widely applied to the fields of automobile industry, building materials, hardware industry, household appliance industry and the like.
Description
Technical Field
The invention relates to the technical field of electrophoretic coatings, in particular to a scratch-resistant tin-free cathode electrophoretic coating and a preparation method thereof.
Background
The cathode electrophoretic coating is rapidly developed in recent years, and gets the attention of many enterprises, particularly in the field of automobile decoration and protection. In order to realize the large-scale production of the cathode electrophoretic paint and meet the higher quality requirement of the coated product, the formula and the synthesis process of the cathode electrophoretic paint are continuously optimized and upgraded at home and abroad. Most of electrophoretic coatings play a role in catalytic crosslinking by adding organic tin products in the processes of main resin synthesis and product curing, and the temperature of the products is generally required to be reduced in order to improve the crosslinking effect, so that most of electrophoretic coatings have the problems of baking temperature, coating performance and the like, and finally formed coating films and waste liquid contain organic tin, thereby having great harm to human bodies and environment. At present, the tin-free electrophoretic paint is one of the research directions. In addition, parts after electrophoretic coating processing usually need other production links such as packaging, transportation, assembly and the like, so that how to continuously improve the scratch resistance of paint films is also one of the important points of research.
Disclosure of Invention
In view of the defects of the prior art, the invention aims to provide a scratch-resistant tin-free cathode electrophoretic paint.
The scratch-resistant tin-free cathode electrophoretic coating comprises epoxy resin emulsion and color paste, wherein the epoxy resin emulsion contains a scratch-resistant agent, the scratch-resistant agent is modified aluminum oxide, and the preparation method comprises the following steps:
Mixing 6-10 parts of ethylene glycol and 45-55 parts of water uniformly, and adding 1-3 parts of Co (NO)3) 2 ·6H2O and B2O3Adding 2-5 parts of nano-alumina into the mixture, heating to 40-50 ℃, preserving heat for 1-3 hours at 40-50 ℃, adding 5-10 parts of a mixture of citric acid, mannitol and carrageenan, heating to 53-57 ℃, preserving heat for 4-8 hours at 53-57 ℃, drying and crushing the product at 75-85 ℃ to obtain the modified alumina.
The grain size of the nano-grade alumina is 50-100 nm.
According to the invention, the nano-alumina is compositely modified by using cobalt salt and boron oxide as inorganic modifiers and citric acid, mannitol and carrageenan as organic modifiers, and the nano-alumina has good scratch-resistant and scratch-resistant effects when being used for electrophoretic paint.
As a preferred embodiment of the present invention, the Co (NO) is3) 2 ·6H2O and B2O3The mass ratio of (1-5): (1-2). Further, the Co (NO)3) 2 ·6H2O and B2O3The mass ratio of (1-3): 1.
in a preferred embodiment of the present invention, the mass ratio of the citric acid, the mannitol and the carrageenan is (1-3): (1-3): (1-5).
The preparation method of the epoxy resin emulsion comprises the following steps:
mixing modified epoxy resin and ethylene glycol butyl ether, heating to 93-97 ℃, adding triethanolamine, diethanolamine and ketimine, heating to 112-117 ℃, keeping the temperature for 1-4 h, cooling to 90-95 ℃, adding an isocyanate curing agent, keeping the temperature for 1-3 h at 90-95 ℃, cooling to 35-45 ℃, adding water, acetic acid and formic acid, uniformly mixing, stirring for 1-4 h at 35-45 ℃, adding modified aluminum oxide and ethylene glycol butyl ether, stirring for 20-50 min at 35-45 ℃, adding water, stirring for 2-5 h at 35-45 ℃, adding cerium acetate, and uniformly mixing to obtain an epoxy resin emulsion.
As a preferred embodiment of the present invention, the epoxy resin emulsion is prepared as follows:
mixing 115-123 g of modified epoxy resin and 8-13 g of ethylene glycol butyl ether, heating to 93-97 ℃, adding 2-3 g of triethanolamine, 1-3 g of diethanolamine and 6-8 g of ketimine, heating to 112-117 ℃, keeping the temperature for 1-4 h, cooling to 90-95 ℃, adding 58-62 g of isocyanate curing agent, keeping the temperature for 1-3 h at 90-95 ℃, cooling to 35-45 ℃, adding 110-130 g of water, 2-5 g of acetic acid and 0.2-0.7 g of formic acid, uniformly mixing, stirring for 1-4 h at 35-45 ℃, adding 7-15 g of modified alumina and 0.7-2.1 g of ethylene glycol butyl ether, stirring for 20-50 min at 35-45 ℃, adding 160-200 g of water, stirring for 2-5 h at 35-45 ℃, adding 0.4-1 g of cerium acetate, uniformly mixing, and obtaining the epoxy resin emulsion. The preparation method of the ketimine comprises the following steps: mixing methyl isobutyl ketone and m-xylylenediamine according to a molar ratio of (1-2): 1, reacting at 128-132 ℃ for 3-4 hours to obtain a crude product, and distilling the crude product at 85-95 ℃ and a vacuum degree of 0.05-0.08 MPa under reduced pressure until no distillate is distilled out to obtain ketimine.
The preparation method of the isocyanate curing agent comprises the following steps:
mixing diphenylmethane diisocyanate and methyl isobutyl ketone, heating to 38-42 ℃, adding methyl ethyl ketoxime, and reacting at 42-46 ℃ for 2-4 h; adding ethylene glycol monobutyl ether, heating to 98-102 ℃, preserving the temperature for 0.5-1.5 hours at 98-102 ℃, adding methyl isobutyl ketone, and uniformly mixing to obtain the isocyanate curing agent.
As a preferred embodiment of the present invention, the method for preparing the isocyanate-based curing agent comprises the steps of:
mixing 48-53 g of diphenylmethane diisocyanate and 8-13 g of methyl isobutyl ketone, heating to 38-42 ℃, adding 28-32 g of methyl ethyl ketoxime, and reacting at 42-46 ℃ for 2-4 h; adding 8-12 g of butyl cellosolve, heating to 98-102 ℃, keeping the temperature at 98-102 ℃ for 0.5-1.5 hours, adding 2-4 g of methyl isobutyl ketone, and uniformly mixing to obtain the isocyanate curing agent.
The preparation method of the modified epoxy resin comprises the following steps:
after mixing bisphenol A epoxy resin, bisphenol A and butyl cellosolve, heating to 105-110 ℃ under the protection of nitrogen, adding N, N-dimethylbenzylamine, continuously heating to 157-162 ℃, reacting for 3-6 hours, cooling to 55-65 ℃, and adding diethanolamine to obtain the modified epoxy resin.
As a preferred embodiment of the present invention, the method for preparing the modified epoxy resin comprises the steps of:
after 68-73 g of bisphenol A epoxy resin (with epoxy equivalent of 225-235 g/equivalent), 25-30 g of bisphenol A and 4-6 g of butyl cellosolve are mixed, the temperature is raised to 105-110 ℃ under the protection of nitrogen, 2-5 g N, N-dimethylbenzylamine is added, the temperature is raised to 157-162 ℃ continuously, the reaction is carried out for 3-6 hours, the temperature is lowered to 55-65 ℃, and 5-8 g of diethanolamine is added, so that the modified epoxy resin is obtained.
The color paste comprises the following components: 28-33 parts of quaternary ammonium salt dispersed epoxy resin, 2-5 parts of bismuth salicylate, 11-15 parts of kaolin, 13-17 parts of carbon black, 3-6 parts of propylene glycol methyl ether, 1.5-4 parts of methyl isobutyl ketone, 5-9 parts of acetic acid and 35-42 parts of water.
As a preferred embodiment of the present invention, the method for preparing the quaternary ammonium salt-dispersed epoxy resin comprises the steps of:
mixing 870-920 g of epoxy resin (epoxy equivalent 210-230 g/equivalent), 380-420 g of bisphenol A, 215-230 g of polycaprolactone diol (number average molecular weight 1600-2000) and 0.1-0.3 g of dimethylbenzylamine, reacting at 128-132 ℃ for 5-6.5 hours, adding 120-140 g of dimethylethanolamine and 68-75 g of acetic acid, and reacting at 118-122 ℃ for 3-6 hours to obtain the quaternary ammonium salt dispersed epoxy resin.
The preparation method of the color paste comprises the following steps: weighing the raw materials according to the weight parts, sequentially adding the weighed quaternary ammonium salt dispersed epoxy resin, bismuth salicylate, propylene glycol methyl ether, methyl isobutyl ketone, acetic acid and water into a reaction container, stirring and mixing uniformly, adding kaolin and carbon black, dispersing for 2-5 hours at 1500-4500 rpm, and then grinding by a sand mill until the fineness is less than or equal to 12 mu m.
The invention also aims to provide a preparation method of the scratch-resistant tin-free cathode electrophoretic paint, which comprises the following steps:
Adding quaternary ammonium salt dispersed epoxy resin, bismuth salicylate, propylene glycol methyl ether, methyl isobutyl ketone, acetic acid and water into a reaction vessel, stirring and mixing uniformly, adding kaolin and carbon black, dispersing for 2-5 hours at 1500-4500 rpm, and grinding by using a sand mill to obtain color paste; uniformly mixing the epoxy resin emulsion, the color paste and water according to the proportion of (3-6) to (1) to (4-7) to obtain the scratch-resistant tin-free cathode electrophoretic paint. The fineness of the color paste is less than or equal to 12 mu m.
The invention has the beneficial effects that:
the electrophoretic coating disclosed by the invention is added with the modified alumina scratch-resistant agent, and the nano-alumina is compositely modified by using the cobalt salt, the boron oxide, the citric acid, the mannitol and the carrageenan, so that the coating has a good scratch-resistant effect, does not contain heavy metal tin compounds, and has the advantages of environmental friendliness, good flexibility of a paint film, good leveling property, high glossiness, good corrosion resistance and the like.
Detailed Description
Exemplary embodiments that embody features and advantages of the invention are described in detail below in the specification.
It is to be understood that the invention is capable of modification in various embodiments without departing from the scope of the invention, and that the description is intended to be illustrative in nature and not to limit the invention.
Unless otherwise specified, "parts" in the present invention are all parts by weight.
The preparation method of the ketimine used in examples 1 to 5, comparative example 1, and comparative example 2 was as follows: mixing methyl isobutyl ketone and m-xylylenediamine according to a molar ratio of 2:1, reacting at 130 ℃ for 3.5 hours to obtain a crude product, and distilling the crude product at 90 ℃ under a vacuum degree of 0.07MPa under reduced pressure until no distillate is distilled out to obtain ketimine.
Example 1
The embodiment provides a scratch-resistant tin-free cathode electrophoretic coating, which comprises an epoxy resin emulsion and color paste. The epoxy resin emulsion contains scratch-resistant agent modified alumina.
The preparation method of the epoxy resin emulsion comprises the following steps:
(1) preparing modified alumina: mixing 8 parts ofThe diol was mixed with 50 parts of water and 1.5 parts of Co (NO) was added3) 2 ·6H2O and B2O3Adding 3 parts of alumina (with the particle size of 80 nm), heating to 45 ℃, preserving heat for 2 hours at 45 ℃, adding 7 parts of a mixture of citric acid, mannitol and carrageenan, heating to 55 ℃, preserving heat for 6 hours at 55 ℃, and drying a product at 80 ℃ to obtain modified alumina; wherein said Co (NO)3) 2 ·6H2O and B2O3The mass ratio of (A) to (B) is 3: 1, the mass ratio of the citric acid to the mannitol to the carrageenan is 1: 3: 1
(2) Preparing an isocyanate curing agent: mixing 50g of diphenylmethane diisocyanate and 11g of methyl isobutyl ketone, heating to 40 ℃, adding 30g of methyl ethyl ketoxime, and reacting at 44 ℃ for 3 hours; adding 10g of ethylene glycol butyl ether, heating to 100 ℃, preserving the temperature for 1 hour at 100 ℃, adding 2.5g of methyl isobutyl ketone, and uniformly mixing to obtain an isocyanate curing agent;
(3) Preparing modified epoxy resin: mixing 70g of bisphenol A type epoxy resin (the epoxy equivalent is 228 g/equivalent), 28g of bisphenol A and 5.5g of butyl cellosolve, heating to 108 ℃ under the protection of nitrogen, adding 3.5g N, N-dimethylbenzylamine, continuously heating to 159 ℃, reacting for 4.5 hours, cooling to 60 ℃, and adding 6g of diethanolamine to obtain modified epoxy resin;
(4) preparing an epoxy resin emulsion: mixing 120g of modified epoxy resin and 11g of ethylene glycol butyl ether, heating to 95 ℃, adding 2.2g of triethanolamine, 2g of diethanolamine and 7g of ketimine, heating to 115 ℃, keeping the temperature for 2 hours, cooling to 92 ℃, adding 60g of isocyanate curing agent, keeping the temperature at 92 ℃ for 1.5 hours, cooling to 40 ℃, adding 120g of water, 3g of acetic acid and 0.5g of formic acid, uniformly mixing, stirring at 40 ℃ for 2 hours, adding 10g of modified alumina and 1.2g of ethylene glycol butyl ether, stirring at 40 ℃ for 30 minutes, adding 180g of water, stirring at 40 ℃ for 3 hours, adding 0.6g of cerium acetate, and uniformly mixing to obtain an epoxy resin emulsion.
The preparation method of the color paste comprises the following steps:
(1) preparing quaternary ammonium salt dispersed epoxy resin:
890g of epoxy resin (epoxy equivalent 220 g/equivalent), 400g of bisphenol A, 225g of polycaprolactone diol (number average molecular weight is 1800) and 0.22g of dimethylbenzylamine are mixed, and then the mixture is reacted at 130 ℃ for 5.5 hours, 130g of dimethylethanolamine and 72g of acetic acid are added, and the reaction is carried out at 120 ℃ for 4.5 hours, so as to obtain the quaternary ammonium salt dispersed epoxy resin.
(2) Preparing color paste: the color paste comprises 30 parts of quaternary ammonium salt dispersed epoxy resin, 3 parts of bismuth salicylate, 13 parts of kaolin, 15 parts of carbon black, 4.5 parts of propylene glycol methyl ether, 2.5 parts of methyl isobutyl ketone, 7.5 parts of acetic acid and 37 parts of water. Weighing the raw materials according to the weight parts, sequentially adding the weighed quaternary ammonium salt dispersed epoxy resin, bismuth salicylate, propylene glycol methyl ether, methyl isobutyl ketone, acetic acid and water into a reaction vessel, stirring and mixing uniformly, adding kaolin and carbon black, dispersing for 3 hours at 3000 r/min, and then grinding by a sand mill until the fineness is less than or equal to 12 mu m.
Uniformly mixing the epoxy resin emulsion, the color paste and the water according to the ratio of 4: 1: 5 to obtain the scratch-resistant tin-free cathode electrophoretic paint.
Example 2
The embodiment provides a scratch-resistant tin-free cathode electrophoretic coating, which comprises an epoxy resin emulsion and color paste. The epoxy resin emulsion contains aluminum oxide modified by an anti-scratching agent.
The preparation method of the epoxy resin emulsion comprises the following steps:
(1) preparing modified alumina: 8 parts of ethylene glycol and 51 parts of water are mixed homogeneously, 1.5 parts of Co (NO) are added3) 2 ·6H2O and B2O3Adding 3 parts of alumina (with the particle size of 80 nm), heating to 45 ℃, preserving heat for 2 hours at 45 ℃, adding 7 parts of a mixture of citric acid, mannitol and carrageenan, heating to 55 ℃, preserving heat for 6 hours at 55 ℃, and drying a product at 80 ℃ to obtain modified alumina; wherein said Co (NO) 3) 2 ·6H2O and B2O3The mass ratio of (1): 1, wherein the mass ratio of citric acid to mannitol to carrageenan is 1: 3: 1
(2) Preparing an isocyanate curing agent: mixing 50g of diphenylmethane diisocyanate and 11.2g of methyl isobutyl ketone, heating to 40 ℃, adding 30.5g of methyl ethyl ketoxime, and reacting at 44 ℃ for 3 hours; adding 10g of ethylene glycol butyl ether, heating to 100 ℃, preserving the temperature for 1 hour at 100 ℃, adding 2.5g of methyl isobutyl ketone, and uniformly mixing to obtain an isocyanate curing agent;
(3) preparing modified epoxy resin: mixing 71g of bisphenol A type epoxy resin (the epoxy equivalent is 228 g/equivalent), 28g of bisphenol A and 5.5g of butyl cellosolve, heating to 108 ℃ under the protection of nitrogen, adding 3.5g N, N-dimethylbenzylamine, continuously heating to 159 ℃, reacting for 4.5 hours, cooling to 60 ℃, and adding 6g of diethanolamine to obtain modified epoxy resin;
(4) preparing an epoxy resin emulsion: mixing 120g of modified epoxy resin and 11g of ethylene glycol butyl ether, heating to 95 ℃, adding 2.3g of triethanolamine, 2g of diethanolamine and 7.1g of ketimine, heating to 115 ℃, keeping the temperature for 2 hours, cooling to 92 ℃, adding 60g of isocyanate curing agent, keeping the temperature at 92 ℃ for 1.5 hours, cooling to 40 ℃, adding 120g of water, 3g of acetic acid and 0.5g of formic acid, uniformly mixing, stirring at 40 ℃ for 2 hours, adding 10g of modified alumina and 1.2g of ethylene glycol butyl ether, stirring at 40 ℃ for 30 minutes, adding 180g of water, stirring at 40 ℃ for 3 hours, adding 0.6g of cerium acetate, and uniformly mixing to obtain an epoxy resin emulsion.
The preparation method of the color paste is the same as that of the embodiment 1.
Uniformly mixing the epoxy resin emulsion, the color paste and the water according to the ratio of 4: 1: 5 to obtain the scratch-resistant tin-free cathode electrophoretic paint.
Example 3
The embodiment provides a scratch-resistant tin-free cathode electrophoretic coating, which comprises an epoxy resin emulsion and color paste. The epoxy resin emulsion contains aluminum oxide modified by an anti-scratching agent.
The preparation method of the epoxy resin emulsion comprises the following steps:
(1) preparing modified alumina: 8.2 parts of ethylene glycol and 51 parts of water are mixed homogeneously, 1.5 parts of Co (NO) are added3) 2 ·6H2O and B2O3Adding 3 parts of alumina (with the particle size of 80 nm), heating to 45 ℃, keeping the temperature at 45 ℃ for 2h, adding 7.2 parts of a mixture of citric acid, mannitol and carrageenan, heating to 55 ℃, keeping the temperature at 55 ℃ for 6h, and drying the product at 80 ℃ to obtain the modified productAlumina; wherein said Co (NO)3) 2 ·6H2O and B2O3The mass ratio of (A) to (B) is 3: 1, the mass ratio of the citric acid to the mannitol to the carrageenan is 1: 1: 3
(2) Preparing an isocyanate curing agent: mixing 50.5g of diphenylmethane diisocyanate and 11g of methyl isobutyl ketone, heating to 40 ℃, adding 30g of methyl ethyl ketoxime, and reacting at 44 ℃ for 3 hours; adding 10.2g of ethylene glycol butyl ether, heating to 100 ℃, keeping the temperature at 100 ℃ for 1 hour, adding 2.5g of methyl isobutyl ketone, and uniformly mixing to obtain an isocyanate curing agent;
(3) Preparing modified epoxy resin: mixing 70g of bisphenol A type epoxy resin (the epoxy equivalent is 228 g/equivalent), 28g of bisphenol A and 5.5g of butyl cellosolve, heating to 108 ℃ under the protection of nitrogen, adding 3.5g N, N-dimethylbenzylamine, continuously heating to 159 ℃, reacting for 4.5 hours, cooling to 60 ℃, and adding 6g of diethanolamine to obtain modified epoxy resin;
(4) preparing an epoxy resin emulsion: mixing 120g of modified epoxy resin and 11g of ethylene glycol butyl ether, heating to 95 ℃, adding 2.2g of triethanolamine, 2g of diethanolamine and 7g of ketimine, heating to 115 ℃, keeping the temperature for 2 hours, cooling to 92 ℃, adding 60g of isocyanate curing agent, keeping the temperature at 92 ℃ for 1.5 hours, cooling to 40 ℃, adding 122g of water, 3g of acetic acid and 0.6g of formic acid, uniformly mixing, stirring at 40 ℃ for 2 hours, adding 10g of modified alumina and 1.2g of ethylene glycol butyl ether, stirring at 40 ℃ for 30 minutes, adding 180g of water, stirring at 40 ℃ for 3 hours, adding 0.6g of cerium acetate, and uniformly mixing to obtain an epoxy resin emulsion.
The preparation method of the color paste is the same as that of the embodiment 1.
Uniformly mixing the epoxy resin emulsion, the color paste and the water according to the ratio of 4: 1: 5 to obtain the scratch-resistant tin-free cathode electrophoretic paint.
Example 4
The embodiment provides a scratch-resistant tin-free cathode electrophoretic coating which comprises an epoxy resin emulsion and color paste. The epoxy resin emulsion contains aluminum oxide modified by an anti-scratching agent.
The preparation method of the epoxy resin emulsion comprises the following steps:
(1) preparing modified alumina: 8 parts of ethylene glycol and 50 parts of water are mixed uniformly, and 1.5 parts of Co (NO) are added3) 2 ·6H2O and B2O3Adding 3 parts of alumina (with the particle size of 80 nm), heating to 45 ℃, preserving heat for 2 hours at 45 ℃, adding a mixture of 7 parts of citric acid, mannitol and carrageenan, heating to 55 ℃, preserving heat for 6 hours at 55 ℃, and drying a product at 80 ℃ to obtain modified alumina; wherein said Co (NO)3) 2 ·6H2O and B2O3The mass ratio of (A) to (B) is 3: 1, the mass ratio of citric acid to mannitol to carrageenan is 3: 1: 1
(2) Preparing an isocyanate curing agent: mixing 50g of diphenylmethane diisocyanate and 11g of methyl isobutyl ketone, heating to 40 ℃, adding 30g of methyl ethyl ketoxime, and reacting at 44 ℃ for 3 hours; adding 10.5g of ethylene glycol butyl ether, heating to 100 ℃, keeping the temperature at 100 ℃ for 1 hour, adding 2.4g of methyl isobutyl ketone, and uniformly mixing to obtain an isocyanate curing agent;
(3) preparing modified epoxy resin: mixing 70g of bisphenol A type epoxy resin (the epoxy equivalent is 228 g/equivalent), 28g of bisphenol A and 5.5g of butyl cellosolve, heating to 108 ℃ under the protection of nitrogen, adding 3.5g N, N-dimethylbenzylamine, continuously heating to 159 ℃, reacting for 4.5 hours, cooling to 60 ℃, and adding 6g of diethanolamine to obtain modified epoxy resin;
(4) Preparing epoxy resin emulsion: mixing 120g of modified epoxy resin and 11g of butyl cellosolve, heating to 95 ℃, adding 2.2g of triethanolamine, 2g of diethanolamine and 7g of ketimine, heating to 115 ℃, keeping the temperature for 2 hours, cooling to 92 ℃, adding 60.2g of isocyanate curing agent, keeping the temperature at 92 ℃ for 1.5 hours, cooling to 40 ℃, adding 120g of water, 3g of acetic acid and 0.5g of formic acid, uniformly mixing, stirring at 40 ℃ for 2 hours, adding 10g of modified alumina and 1.2g of butyl cellosolve, stirring at 40 ℃ for 30 minutes, adding 180g of water, stirring at 40 ℃ for 3 hours, adding 0.6g of cerium acetate, and uniformly mixing to obtain an epoxy resin emulsion.
The preparation method of the color paste is the same as that of the embodiment 1.
Uniformly mixing the epoxy resin emulsion, the color paste and the water according to the ratio of 4: 1: 5 to obtain the scratch-resistant tin-free cathode electrophoretic paint.
Example 5
The embodiment provides a scratch-resistant tin-free cathode electrophoretic coating, which comprises an epoxy resin emulsion and color paste. The epoxy resin emulsion contains scratch-resistant agent modified alumina.
The preparation method of the epoxy resin emulsion comprises the following steps:
(1) preparing modified alumina: 7.8 parts of ethylene glycol and 50 parts of water are mixed uniformly, and 1.5 parts of Co (NO) are added3) 2 ·6H2O and B2O3Adding 3 parts of alumina (with the particle size of 80 nm), heating to 45 ℃, preserving heat for 2 hours at 45 ℃, adding 7 parts of a mixture of citric acid, mannitol and carrageenan, heating to 55 ℃, preserving heat for 6 hours at 55 ℃, and drying a product at 80 ℃ to obtain modified alumina; wherein said Co (NO) 3) 2 ·6H2O and B2O3The mass ratio of (1): 2, the mass ratio of the citric acid to the mannitol to the carrageenan is 1: 3: 1
(2) Preparing an isocyanate curing agent: mixing 50g of diphenylmethane diisocyanate and 11.1g of methyl isobutyl ketone, heating to 40 ℃, adding 30g of methyl ethyl ketoxime, and reacting at 44 ℃ for 3 hours; adding 10g of ethylene glycol butyl ether, heating to 100 ℃, preserving the temperature for 1 hour at 100 ℃, adding 2.5g of methyl isobutyl ketone, and uniformly mixing to obtain an isocyanate curing agent;
(3) preparing modified epoxy resin: mixing 70g of bisphenol A epoxy resin (with the epoxy equivalent of 228 g/equivalent), 28.2g of bisphenol A and 5.6g of butyl cellosolve, heating to 108 ℃ under the protection of nitrogen, adding 3.4g N, N-dimethylbenzylamine, continuously heating to 159 ℃, reacting for 4.5 hours, cooling to 60 ℃, and adding 6g of diethanolamine to obtain modified epoxy resin;
(4) preparing an epoxy resin emulsion: mixing 119g of modified epoxy resin and 11g of ethylene glycol butyl ether, heating to 95 ℃, adding 2.2g of triethanolamine, 2g of diethanolamine and 7g of ketimine, heating to 115 ℃, keeping the temperature for 2 hours, cooling to 92 ℃, adding 60g of isocyanate curing agent, keeping the temperature at 92 ℃ for 1.5 hours, cooling to 40 ℃, adding 120g of water, 3g of acetic acid and 0.5g of formic acid, uniformly mixing, stirring at 40 ℃ for 2 hours, adding 10g of modified alumina and 1.2g of ethylene glycol butyl ether, stirring at 40 ℃ for 30 minutes, adding 181g of water, stirring at 40 ℃ for 3 hours, adding 0.6g of cerium acetate, and uniformly mixing to obtain an epoxy resin emulsion.
The preparation method of the color paste is the same as that of the embodiment 1.
Uniformly mixing the epoxy resin emulsion, the color paste and the water according to the ratio of 4: 1: 5 to obtain the scratch-resistant tin-free cathode electrophoretic paint.
Comparative example 1
The embodiment provides a scratch-resistant tin-free cathode electrophoretic coating, which comprises an epoxy resin emulsion and color paste. The epoxy resin emulsion contains scratch-resistant agent modified alumina.
The preparation method of the epoxy resin emulsion comprises the following steps:
(1) preparing modified alumina: 8.2 parts of ethylene glycol and 50 parts of water are mixed uniformly, and 1.5 parts of Co (NO) are added3) 2 ·6H2Adding 3 parts of alumina (with the particle size of 80 nm), heating to 45 ℃, preserving heat for 2h at 45 ℃, adding a mixture of 7 parts of citric acid, mannitol and carrageenan, heating to 55 ℃, preserving heat for 6h at 55 ℃, and drying a product at 80 ℃ to obtain modified alumina; wherein the mass ratio of the citric acid to the mannitol to the carrageenan is 1: 3: 1
(2) Preparing an isocyanate curing agent: mixing 50g of diphenylmethane diisocyanate and 11g of methyl isobutyl ketone, heating to 40 ℃, adding 30g of methyl ethyl ketoxime, and reacting at 44 ℃ for 3 hours; adding 10g of ethylene glycol butyl ether, heating to 100 ℃, preserving the temperature for 1 hour at 100 ℃, adding 2.5g of methyl isobutyl ketone, and uniformly mixing to obtain an isocyanate curing agent;
(3) Preparing modified epoxy resin: mixing 70g of bisphenol A type epoxy resin (the epoxy equivalent is 228 g/equivalent), 28g of bisphenol A and 5.5g of butyl cellosolve, heating to 108 ℃ under the protection of nitrogen, adding 3.5g N, N-dimethylbenzylamine, continuously heating to 159 ℃, reacting for 4.5 hours, cooling to 60 ℃, and adding 6g of diethanolamine to obtain modified epoxy resin;
(4) preparing an epoxy resin emulsion: mixing 120g of modified epoxy resin and 11g of ethylene glycol butyl ether, heating to 95 ℃, adding 2.1g of triethanolamine, 2.1g of diethanolamine and 7g of ketimine, heating to 115 ℃, keeping the temperature for 2 hours, cooling to 92 ℃, adding 60g of isocyanate curing agent, keeping the temperature for 1.5 hours at 92 ℃, cooling to 40 ℃, adding 120g of water, 3g of acetic acid and 0.5g of formic acid, uniformly mixing, stirring for 2 hours at 40 ℃, adding 10g of modified alumina and 1.2g of ethylene glycol butyl ether, stirring for 30 minutes at 40 ℃, adding 180g of water, stirring for 3 hours at 40 ℃, adding 0.6g of cerium acetate, and uniformly mixing to obtain the epoxy resin emulsion.
The preparation method of the color paste is the same as that of the embodiment 1.
Uniformly mixing the epoxy resin emulsion, the color paste and the water according to the ratio of 4: 1: 5 to obtain the scratch-resistant tin-free cathode electrophoretic paint.
Comparative example 2
The embodiment provides a scratch-resistant tin-free cathode electrophoretic coating which comprises an epoxy resin emulsion and color paste. The epoxy resin emulsion contains aluminum oxide modified by an anti-scratching agent.
The preparation method of the epoxy resin emulsion comprises the following steps:
(1) preparing modified alumina: mixing 8 parts of ethylene glycol with 50.5 parts of water uniformly, adding 1.5 parts of B2O3Adding 3 parts of alumina (with the particle size of 80 nm), heating to 45 ℃, preserving heat for 2 hours at 45 ℃, adding a mixture of 7 parts of citric acid, mannitol and carrageenan, heating to 55 ℃, preserving heat for 6 hours at 55 ℃, and drying a product at 80 ℃ to obtain modified alumina; wherein the mass ratio of the citric acid to the mannitol to the carrageenan is 1: 3: 1
(2) Preparing an isocyanate curing agent: mixing 50g of diphenylmethane diisocyanate and 11g of methyl isobutyl ketone, heating to 40 ℃, adding 30g of methyl ethyl ketoxime, and reacting at 44 ℃ for 3 hours; adding 10g of ethylene glycol butyl ether, heating to 100 ℃, preserving the temperature for 1 hour at 100 ℃, adding 2.5g of methyl isobutyl ketone, and uniformly mixing to obtain an isocyanate curing agent;
(3) preparing modified epoxy resin: mixing 70g of bisphenol A type epoxy resin (the epoxy equivalent is 228 g/equivalent), 28g of bisphenol A and 5.4g of butyl cellosolve, heating to 108 ℃ under the protection of nitrogen, adding 3.5g N, N-dimethylbenzylamine, continuously heating to 159 ℃, reacting for 4.5 hours, cooling to 60 ℃, and adding 6g of diethanolamine to obtain modified epoxy resin;
(4) Preparing epoxy resin emulsion: mixing 120g of modified epoxy resin and 11g of ethylene glycol butyl ether, heating to 95 ℃, adding 2.2g of triethanolamine, 2g of diethanolamine and 7g of ketimine, heating to 115 ℃, keeping the temperature for 2 hours, cooling to 92 ℃, adding 60g of isocyanate curing agent, keeping the temperature at 92 ℃ for 1.5 hours, cooling to 40 ℃, adding 120g of water, 3g of acetic acid and 0.5g of formic acid, uniformly mixing, stirring at 40 ℃ for 2 hours, adding 10.1g of modified alumina and 1.2g of ethylene glycol butyl ether, stirring at 40 ℃ for 30min, adding 180g of water, stirring at 40 ℃ for 3 hours, adding 0.6g of cerium acetate, and uniformly mixing to obtain an epoxy resin emulsion.
The preparation method of the color paste is the same as that of the embodiment 1.
Uniformly mixing the epoxy resin emulsion, the color paste and the water according to the ratio of 4: 1: 5 to obtain the scratch-resistant tin-free cathode electrophoretic paint.
Paint film preparation and Performance testing
The scratch-resistant tin-free cathode electrophoretic coating of the embodiments 1-5, the comparative examples 1 and 2 is prepared into an electrophoretic paint film, and the film preparation conditions are as follows: electrophoresis temperature: the electrophoresis time is 3min at 28 ℃, the voltage is 120V, and the electrophoresis is baked for 30min at 170 ℃ after the electrophoresis is finished. The thickness of the paint film is 20 um. Various indexes of the paint film are detected, and related tests are as follows:
1) gloss testing: reference is made to GB/T9754-1998 determination of 20 °, 60 ° and 85 ° specular gloss of pigmented paint films which are free of metallic pigments;
2) And (3) detecting the scratch resistance: a flat MEK-resistant wiping method is adopted, and reference is made to GB/T13448-2006;
3) and (3) testing impact strength: refer to GB1732-79 determination of paint film impact resistance;
4) and (3) hardness testing: refer to GB/T6739-1996 Pencil hardness test method for coating film;
5) testing the temperature resistance of the salt-resistant water: the cross-cut damage was cut into each paint film with a knife, and the cross-cut damage after 10 days of immersion in 5% saline at 55 ℃ was evaluated according to the following criteria:
first-stage: the maximum width of rust or swelling is less than 2.5mm (one side) from the cut; and (2) second stage: the maximum width of rust or swelling is 2.5mm or more and less than 3.0mm (one side) from the cut part; third-stage: the maximum width of rust or swelling is 3.0mm or more and less than 4mm (one side) from the cut part; and (4) fourth stage: the maximum width of rust or swelling is 4mm or more (one side) from the cut portion.
Table 1: test result table
| Paint film appearance | 60 degree gloss | MEK-resistant plate wiping method | Impact strength | Hardness of | Salt and water resistance | |
| Example 1 | Is flat and smooth | 86% | 300 times (twice) | 60 kg/cm | ≥2H | First stage |
| Example 2 | Is flat and smooth | 84% | 290 times of | 58 kg/cm | ≥2H | First stage |
| Example 3 | Is flat and smooth | 84% | 275 times | 57 kg/cm | ≥2H | First stage |
| Example 4 | Is flat and smooth | 83% | 242 times (a) | 52kg/cm | ≥2H | Second stage |
| Example 5 | Is flat and smooth | 83% | 256 times | 54kg/cm | ≥2H | First stage |
| Comparative example 1 | Is flat and smooth | 82% | 214 times | 54kg/cm | ≥2H | First stage |
| Comparative example 2 | Is flat and smooth | 83% | 208 times (one time) | 53kg/cm | ≥2H | First stage |
Unless otherwise defined, all terms used herein have the meanings commonly understood by those skilled in the art.
The described embodiments are for illustrative purposes only and are not intended to limit the scope of the present invention, and various other substitutions, changes, and modifications within the scope of the present invention will be apparent to those skilled in the art.
Claims (3)
1. The scratch-resistant tin-free cathode electrophoretic coating is characterized by comprising an epoxy resin emulsion and color paste, wherein the epoxy resin emulsion contains a scratch-resistant agent, the scratch-resistant agent is modified aluminum oxide, and the preparation method comprises the following steps:
mixing 6-10 parts of ethylene glycol and 45-55 parts of water uniformly, and adding 1-3 parts of Co (NO)3)2·6H2O and B2O3Adding 2-5 parts of nano-grade alumina into the mixture, heating to 40-50 ℃, preserving heat for 1-3 hours at 40-50 ℃, adding 5-10 parts of a mixture of citric acid, mannitol and carrageenan, heating to 53-57 ℃, preserving heat for 4-8 hours at 53-57 ℃, drying and crushing the product at 75-85 ℃ to obtain modified alumina;
wherein said Co (NO)3)2·6H2O and B2O3The mass ratio of (1-3): 1, the mass ratio of the citric acid to the mannitol to the carrageenan is 1: (1-3): (1-5);
After mixing bisphenol A epoxy resin, bisphenol A and butyl cellosolve, heating to 105-110 ℃ under the protection of nitrogen, adding N, N-dimethylbenzylamine, continuously heating to 157-162 ℃, reacting for 3-6 hours, cooling to 55-65 ℃, and adding diethanolamine to obtain modified epoxy resin;
mixing modified epoxy resin and ethylene glycol butyl ether, heating to 93-97 ℃, adding triethanolamine, diethanolamine and ketimine, heating to 112-117 ℃, keeping the temperature for 1-4 h, cooling to 90-95 ℃, adding an isocyanate curing agent, keeping the temperature for 1-3 h at 90-95 ℃, cooling to 35-45 ℃, adding water, acetic acid and formic acid, uniformly mixing, stirring for 1-4 h at 35-45 ℃, adding modified alumina and ethylene glycol butyl ether, stirring for 20-50 min at 35-45 ℃, adding water, stirring for 2-5 h at 35-45 ℃, adding cerium acetate, uniformly mixing to obtain an epoxy resin emulsion; adding quaternary ammonium salt dispersed epoxy resin, bismuth salicylate, propylene glycol methyl ether, methyl isobutyl ketone, acetic acid and water into a reaction vessel, stirring and mixing uniformly, adding kaolin and carbon black, dispersing for 2-5 hours at 1500-4500 rpm, and grinding by using a sand mill to obtain color paste; uniformly mixing epoxy resin emulsion, color paste and water according to the proportion of (3-6) to 1 to (4-7) to obtain the scratch-resistant tin-free cathode electrophoretic paint;
The fineness of the color paste is less than or equal to 12 mu m.
2. The scratch-resistant tin-free cathode electrophoretic paint as claimed in claim 1, wherein the preparation method of the isocyanate curing agent comprises the following steps:
mixing diphenylmethane diisocyanate and methyl isobutyl ketone, heating to 38-42 ℃, adding methyl ethyl ketoxime, reacting for 2-4 h at 42-46 ℃, adding ethylene glycol butyl ether, heating to 98-102 ℃, keeping the temperature for 0.5-1.5 h at 98-102 ℃, adding methyl isobutyl ketone, and uniformly mixing to obtain the isocyanate curing agent.
3. The scratch-resistant tin-free cathode electrophoretic coating as claimed in claim 1, wherein the color paste comprises the following components: 28-33 parts of quaternary ammonium salt dispersed epoxy resin, 2-5 parts of bismuth salicylate, 11-15 parts of kaolin, 13-17 parts of carbon black, 3-6 parts of propylene glycol methyl ether, 1.5-4 parts of methyl isobutyl ketone, 5-9 parts of acetic acid and 35-42 parts of water.
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| CN113684511B (en) * | 2021-09-23 | 2022-08-16 | 中国计量大学 | Electrochemical preparation method of high-temperature self-repairing coating and product thereof |
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| CN112430420A (en) | 2021-03-02 |
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Denomination of invention: Scratch resistant Wuxi type cathodic electrophoretic coating and its preparation method Effective date of registration: 20231115 Granted publication date: 20220628 Pledgee: Bank of China Limited Shanghai Yangtze River Delta Integration Demonstration Zone Branch Pledgor: Shanghai Ruijun electrophoretic coating Co.,Ltd. Registration number: Y2023980065674 |
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