CN115746617B - Microgel for cathode electrophoretic coating and preparation method thereof - Google Patents
Microgel for cathode electrophoretic coating and preparation method thereof Download PDFInfo
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- CN115746617B CN115746617B CN202211470129.XA CN202211470129A CN115746617B CN 115746617 B CN115746617 B CN 115746617B CN 202211470129 A CN202211470129 A CN 202211470129A CN 115746617 B CN115746617 B CN 115746617B
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- 238000000576 coating method Methods 0.000 title claims abstract description 46
- 239000011248 coating agent Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 239000003973 paint Substances 0.000 claims abstract description 21
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 15
- 239000000126 substance Substances 0.000 claims abstract description 14
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 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 abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 5
- 150000001412 amines Chemical class 0.000 claims abstract description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000003822 epoxy resin Substances 0.000 claims abstract description 4
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 4
- 239000004593 Epoxy Substances 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001962 electrophoresis Methods 0.000 claims description 9
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 7
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 6
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 4
- SYBYTAAJFKOIEJ-UHFFFAOYSA-N 3-Methylbutan-2-one Chemical compound CC(C)C(C)=O SYBYTAAJFKOIEJ-UHFFFAOYSA-N 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 4
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 4
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 claims description 4
- 150000004658 ketimines Chemical class 0.000 claims description 4
- 150000002576 ketones Chemical class 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920000768 polyamine Polymers 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 4
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 claims description 3
- -1 aminoethyl aminoethoxy aminopropyl trimethoxysilane Chemical compound 0.000 claims description 3
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- OTARVPUIYXHRRB-UHFFFAOYSA-N diethoxy-methyl-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](C)(OCC)CCCOCC1CO1 OTARVPUIYXHRRB-UHFFFAOYSA-N 0.000 claims description 3
- 238000004945 emulsification Methods 0.000 claims description 3
- 239000004310 lactic acid Substances 0.000 claims description 3
- 235000014655 lactic acid Nutrition 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 2
- HXLAEGYMDGUSBD-UHFFFAOYSA-N 3-[diethoxy(methyl)silyl]propan-1-amine Chemical compound CCO[Si](C)(OCC)CCCN HXLAEGYMDGUSBD-UHFFFAOYSA-N 0.000 claims description 2
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 claims description 2
- 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 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 2
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- QLBRROYTTDFLDX-UHFFFAOYSA-N [3-(aminomethyl)cyclohexyl]methanamine Chemical compound NCC1CCCC(CN)C1 QLBRROYTTDFLDX-UHFFFAOYSA-N 0.000 claims description 2
- FDLQZKYLHJJBHD-UHFFFAOYSA-N [3-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=CC(CN)=C1 FDLQZKYLHJJBHD-UHFFFAOYSA-N 0.000 claims description 2
- 229960000583 acetic acid Drugs 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 229960002887 deanol Drugs 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 239000012972 dimethylethanolamine Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000012362 glacial acetic acid Substances 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 2
- KOVKEDGZABFDPF-UHFFFAOYSA-N n-(triethoxysilylmethyl)aniline Chemical compound CCO[Si](OCC)(OCC)CNC1=CC=CC=C1 KOVKEDGZABFDPF-UHFFFAOYSA-N 0.000 claims description 2
- VNBLTKHUCJLFSB-UHFFFAOYSA-N n-(trimethoxysilylmethyl)aniline Chemical compound CO[Si](OC)(OC)CNC1=CC=CC=C1 VNBLTKHUCJLFSB-UHFFFAOYSA-N 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 2
- 150000003512 tertiary amines Chemical class 0.000 claims description 2
- JXUKBNICSRJFAP-UHFFFAOYSA-N triethoxy-[3-(oxiran-2-ylmethoxy)propyl]silane Chemical compound CCO[Si](OCC)(OCC)CCCOCC1CO1 JXUKBNICSRJFAP-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000005260 corrosion Methods 0.000 abstract description 25
- 230000007797 corrosion Effects 0.000 abstract description 25
- 230000000694 effects Effects 0.000 abstract description 6
- 239000008367 deionised water Substances 0.000 abstract description 2
- 229910021641 deionized water Inorganic materials 0.000 abstract description 2
- 239000000839 emulsion Substances 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 10
- 238000012360 testing method Methods 0.000 description 6
- 239000012224 working solution Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- 238000004062 sedimentation Methods 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- HQYALQRYBUJWDH-UHFFFAOYSA-N trimethoxy(propyl)silane Chemical compound CCC[Si](OC)(OC)OC HQYALQRYBUJWDH-UHFFFAOYSA-N 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 239000008199 coating composition Substances 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000001282 organosilanes Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XFSXUCMYFWZRAF-UHFFFAOYSA-N 2-(trityloxymethyl)oxirane Chemical compound C1OC1COC(C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 XFSXUCMYFWZRAF-UHFFFAOYSA-N 0.000 description 1
- 229910002808 Si–O–Si Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005562 fading Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007888 film coating Substances 0.000 description 1
- 238000009501 film coating Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000000518 rheometry Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002699 waste material Substances 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 microgel for cathode electrophoretic paint, which comprises the following components in parts by weight: 1000-2500 parts of epoxy resin, 353-884 parts of bisphenol A, 250-400 parts of ether substances, 0.2-10 parts of catalysts, 273-400 parts of amine substances, 60-100 parts of silane coupling agent A, 60-100 parts of silane coupling agent B, 200-550 parts of acid and 800-5000 parts of deionized water. The invention also discloses a preparation method of the microgel for the cathode electrophoretic coating. The microgel for the cathode electrophoretic coating has stable preparation process, and the prepared high-edge corrosion-resistant cathode electrophoretic coating can realize the high corner protection effect of a workpiece and has great effects of improving the corner corrosion resistance of the workpiece and leveling the appearance of a paint film.
Description
Technical Field
The invention relates to the technical field of paint, in particular to microgel for cathode electrophoretic paint and a preparation method thereof.
Background
In the coating of electrophoretic paint, various edges and sharp angles are often formed when automobile spare parts or some metal workpieces with complex shapes are processed and molded; before the coating is electrophoretically cured, the corner wrapping property is good; when in curing, the viscosity of the resin is reduced by high-temperature baking; the paint at the edge portion shrinks toward the middle due to the surface tension, the film thickness at the sharp edge portion decreases, the corner portion is exposed, the corner coverage is deteriorated, and serious corrosion is likely to occur. About 1/4 of automobile parts are corroded by corner rust every year worldwide, and great waste of materials is caused. Therefore, how to reduce or even avoid the corrosion of the corners becomes an important subject in the current automobile spare and accessory parts industry.
In recent years, high edge coating type cathode electrophoretic paint has been rapidly developed, and in order to solve the problem of corner corrosion, a Japanese oil company adds a high relative molecular weight resin as a regulator, and both the corner coating property of a coating film and the flatness of the coating film are achieved by a rheology control principle, so that the corner anti-rust type paint has been successfully developed. Development of high-corner corrosion-resistant cathode electrophoretic paint, and the sharp-edge corrosion resistance is improved by adding organic high polymer or inorganic additive. Typical varieties with edge coverage are ED681 of PPG, EC3000 of Herberts and TM6100 of AXATTA. The improvement of the edge coverage and the corner corrosion resistance of the electrophoretic paint has become one of the development directions of the electrophoretic paint. The high-edge corrosion-resistant cathode electrophoretic coating is favorable for environmental protection, energy conservation and high-edge protection, meets the requirement of time development, and has extremely wide application prospect.
Disclosure of Invention
Based on this, the object of the invention is: the microgel is matched with epoxy system emulsion to prepare high-edge corrosion-resistant cathode electrophoresis paint emulsion which has good storage stability, and the high-edge corrosion-resistant cathode electrophoresis paint emulsion is prepared with epoxy system color paste and water to form a film through cathode electrophoresis, so that the film coating leveling effect is good, and the corner corrosion resistance is good.
The technical scheme for realizing the aim of the invention is as follows: the microgel auxiliary agent for the cathode electrophoretic coating comprises the following components in parts by weight:
in one embodiment, the ether material is at least one of ethylene glycol butyl ether and diethylene glycol butyl ether.
In one embodiment, the catalyst is at least one of benzylamine, tertiary amine, quaternary ammonium and triphenylphosphine.
In one embodiment, the amine substance is at least one of amino compounds di-n-butylamine, methylethanolamine, diethanolamine, triethanolamine, dimethylethanolamine, methyldiethanolamine or at least one of ketimine substances; the ketimine is prepared by condensation reaction of ketone and polyamine for dehydration.
In one embodiment, the polyamine is at least one of diethylenetriamine, m-phenylenediamine, m-xylylenediamine, 1, 3-bis (aminomethyl) cyclohexane;
the ketone is at least one of methyl isopropyl ketone, methyl isobutyl ketone and methyl ethyl ketone.
In one embodiment, the silane coupling agent a is at least one of aminopropyl triethoxysilane, aminopropyl trimethoxysilane, aminoethyl aminoethoxy aminopropyl trimethoxysilane, γ -aminopropyl methyldimethoxy silane, γ -aminopropyl methyldiethoxy silane, anilinomethyl trimethoxysilane, and anilinomethyl triethoxysilane.
In one embodiment, the silane coupling agent B is at least one of gamma-glycidoxypropyl triethoxysilane, 3-glycidoxypropyl methyldiethoxysilane and triphenylglycidoxymethane.
In one embodiment, the acid is at least one of sulfamic acid, formic acid, glacial acetic acid and lactic acid.
In one embodiment, the microgel for cathodic electrocoating has a rotational viscosity of 100 to 1000 centipoise.
In one embodiment, the microgel has a solids content of 25-30%; the pH value of the microgel is 4.8-6.0; the conductivity of the microgel is 3000-4000 mu s/cm.
The invention also provides a preparation method of the microgel for the cathode electrophoretic coating, which comprises the following steps:
mixing 1000-2500 parts of epoxy resin, 353-884 parts of bisphenol A and 250-400 parts of ether substances, heating to 100-120 ℃, uniformly stirring, adding 0.2-10 parts of catalyst, heating to 130-150 ℃, and preserving heat until the epoxy equivalent is enlarged to a required range; cooling to below 100 ℃, adding 273-400 parts of amine substances, heating to 100-120 ℃ and preserving heat for 2-3 hours; 60-100 parts of silane coupling agent A is added at 90-100 ℃, the temperature is kept at 100-120 ℃ for 2-3 hours, 60-100 parts of silane coupling agent B is added, the temperature is kept at 100-120 ℃ for 2-3 hours, the temperature is reduced to 70-80 ℃, 200-550 parts of acid is added, the mixture is stirred uniformly, 800-5000 parts of water is added for emulsification, the temperature is kept at 50-70 ℃ for 3-5 hours, the temperature is reduced, and the material is discharged, so that the microgel for the cathode electrophoresis coating is prepared.
In one embodiment, the until the epoxy equivalent is increased to the desired range means that the epoxy equivalent is increased to 600-800.
The invention has the technical effects that: the microgel for the cathode electrophoretic coating of the technical scheme of the invention is characterized in that a silane coupling agent is introduced into resin, an organosilane auxiliary agent is added in the hydrolysis and condensation process, and a grafting part generates a bridging effect through the effective chemical action between the silane coupling agent and the organosilane auxiliary agent, so that more hydrolysis and condensation sites are provided, and the hydrolysis and condensation efficiency is improved; meanwhile, due to the formation of Si-O-Si bonds, the adhesive force of a paint film and a substrate is increased under the action of chemical bonds such as hydrogen bonds. The high-edge corrosion-resistant cathode electrophoretic coating emulsion prepared by matching the microgel disclosed by the invention with the epoxy system emulsion has good storage stability, and is prepared into an electrophoretic working solution with epoxy system color paste and water, and a coating film obtained by cathode electrophoretic coating of the electrophoretic working solution has good leveling effect, excellent salt spray resistance and good salt spray corrosion resistance at corner parts.
Detailed Description
The invention is further described below with reference to examples, but is not limited thereto.
The raw materials used in the examples and comparative examples are commercial industrial products, unless otherwise specified, and are commercially available, wherein the epoxy system HED-3K emulsion and the epoxy system ZH30 black paste are both produced by Zhonghai oil Changzhou environmental protection paint Co.
EXAMPLE 1 preparation of microgel for cathode electrophoretic coating
(1) Preparation of the prepolymer
Adding 150g of epoxy resin 828, 57.6 parts of bisphenol A and 50g of ethylene glycol butyl ether mixed substance into a four-neck flask with a stirrer, a reflux condenser and a thermometer, heating to 100-120 ℃, uniformly stirring, adding 0.2g of N, N-dimethylbenzylamine, heating to 130-150 ℃, and preserving heat until the epoxy equivalent is enlarged to 700; cooling to below 100deg.C, adding 17.8g methylethanolamine, heating to 110-120deg.C, and maintaining for 2-3 hr; 13.0g of aminopropyl triethoxysilane A-1100 is added at 90-100 ℃, the temperature is raised to 100-120 ℃, and the temperature is kept for 2-3 hours.
(2) Microgel for preparing cathode electrophoretic paint
Taking 100g of the prepolymer prepared in the step (1), adding 4.5g of 3- (2, 3-glycidoxy) propyl trimethoxy silane serving as a component B of a silane coupling agent, heating to 100-120 ℃, preserving heat for 2-3 hours, adding 16.8g of lactic acid, uniformly stirring, adding 400g of deionized water for emulsification, preserving heat for 3-5 hours at 50-70 ℃, cooling and discharging to prepare the microgel for the cathode electrophoretic coating, wherein the solid content of the microgel is 30wt%.
EXAMPLE 2 preparation of microgel for cathode electrophoretic coating
Instead of 17.8g of methylethanolamine used in step (1) of example 1, 24.5g of diethanolamine was used, and the remaining amounts and specific preparation steps were the same as in example 1.
EXAMPLE 3 preparation of microgel for cathode electrophoretic coating
10.5g of aminopropyl trimethoxysilane was used instead of 13.0g of aminopropyl triethoxysilane used in step (1) of example 1, the remainder of the amounts and the specific preparation steps being identical to those of example 1.
EXAMPLE 4 preparation of microgel for cathode electrophoretic coating
4.7g of 3-glycidoxypropyl methyldiethoxysilane was used instead of 4.5g of 3- (2, 3-glycidoxypropyl) propyltrimethoxysilane used in step (2) of example 1, the remainder of the amounts and the specific preparation steps being identical to those of example 1.
Comparative example 1 preparation of microgel for cathode electrophoretic coating
The difference from example 1 is that: the silane coupling agent B component is not added in the step (2): 4.5g of 3- (2, 3-glycidoxy) propyltrimethoxysilane, the remainder of the amounts and the specific preparation steps being identical to those of example 1.
Comparative example 2 cathodic electrocoating composition
The existing epoxy system HED-3K emulsion, the epoxy system ZH30 black slurry and water are used for preparing the cathode electrophoretic coating composition.
Detection of film Properties
(1) Preparation of templates
Microgels for cathode electrophoretic coating prepared in the above examples 1 to 4 and comparative example 1 were compounded with epoxy system emulsion to prepare high-edge corrosion-resistant cathode electrophoretic coating emulsion according to the microgel: the epoxy system emulsion was 1: 13, and then preparing the high-edge corrosion-resistant cathode electrophoretic coating composition by matching the epoxy system ZH30 black paste and water.
The electrophoretic coating working solution is prepared according to the method, and the solid content of the working solution is 16-18 wt%. Forming an electrophoretic coating film on the sample plate by the existing electrophoretic coating method to prepare a detection sample plate, and storing the detection sample plate for later use;
(2) test method
Appearance of paint film
And visually observing whether orange peel exists or whether orange peel is flat and smooth. The evaluation criteria are: 4 is very good, 3 is good, 2 is bad, and 1 is very bad.
Curing time
And placing the template in a baking oven at 170 ℃ for 30 minutes, and wiping the fully cured coating solvent-resistant MEK back and forth for 50 times without fading and falling of the coating film.
Hardness of paint film
The hardness grade of the paint film is inspected by test detection according to GB/T6739-2006. The evaluation criteria are: 4H is very good; 3H is preferably; 2H is the difference; 1H is very poor.
Emulsion stability
The microgel (examples 1-4 and comparative example 1) is matched with epoxy system emulsion to prepare high-edge corrosion-resistant cathode electrophoretic coating emulsion, epoxy system HED-3K emulsion (comparative example 2) is placed in a 50 ℃ oven for standing, and then whether precipitation exists or not is observed. The evaluation criteria are: 4 is very good, and the sedimentation time is more than or equal to 6 months; 3, the sedimentation time is more than 3 months; 2 is the difference, the sedimentation time is less than or equal to 1 month and less than or equal to 3 months; 1. the sedimentation time was < 1 month for poor.
Corner corrosion resistance grade
The method for testing the corner corrosiveness of the electrophoretic paint comprises the following steps:
the edge and corner parts of the vehicle body are simulated by using an art designer blade, and the blade is subjected to electrophoresis after phosphating to test the edge and corner coverage of the electrophoretic paint.
(1) Selecting a blade with better phosphating performance for electrophoresis, wherein the blade faces one side of the electrode, and the surface of the blade with the groove faces the same direction, and the polar ratio is ensured to be 1 during electrophoresis: and 2, drying the blade after washing.
(2) The cutting edge is put upwards into a salt fog box, forms an included angle of 15-30 degrees with the vertical plane, and carries out a 168h neutral salt fog test according to GB/T10125-1997 to judge the corrosion condition.
(3) 3 blades were made in parallel and the test results taken as arithmetic averages.
TABLE 1 relationship between the number of rust points and the corrosion level of the blade
| Number of rust spots/number of rust spots | Corrosion grade/level |
| 1～10 | 1 |
| 11～30 | 2 |
| 31～50 | 3 |
| 51 or more | 4 |
TABLE 2 test results for examples 1-4 and comparative examples 1-2
As can be seen from the detection results in Table 2, the microgel (examples 1-4) for the cathode electrophoretic coating of the invention is matched with an epoxy system emulsion to prepare a high-edge corrosion-resistant cathode electrophoretic coating emulsion, and then is matched with a working solution prepared from an epoxy system ZH30 black slurry and water to prepare a sample plate through cathode electrophoresis, and each performance of the cured coating film is obviously superior to that of a comparative example 1 without adding a silane coupling agent B component, and meanwhile, examples 1-4 and comparative example 1 are obviously superior to that of a comparative example 2 without adding the microgel. The microgel of the invention is matched with epoxy system emulsion to prepare high-edge corrosion-resistant cathode electrophoretic coating emulsion, and then the high-edge corrosion-resistant cathode electrophoretic coating emulsion is mixed with epoxy system color paste and water to prepare electrophoretic working solution, and after electrophoretic coating, the appearance of a coating film is smooth and smooth, the hardness is high, the crosslinking density is high, and the corner corrosion resistance of the coating film is excellent.
It should be understood that the above examples are only preferred embodiments of the present invention and are intended to illustrate specific embodiments of the technical solution of the present invention, but not to limit the scope of the present invention. It should be noted that: modifications and substitutions for various equivalent forms of the invention herein after described may be made by those skilled in the art without departing from the principles of the present invention, which are intended to be within the scope of the invention as defined in the appended claims.
Claims (5)
1. A preparation method of microgel for cathode electrophoretic paint is characterized in that: the microgel comprises the following components in parts by weight,
the silane coupling agent A is at least one of aminopropyl triethoxysilane, aminopropyl trimethoxysilane, aminoethyl aminoethoxy aminopropyl trimethoxysilane, gamma-aminopropyl methyl dimethoxy silane, gamma-aminopropyl methyl diethoxy silane, phenylaminomethyl trimethoxysilane and phenylaminomethyl triethoxy silane,
the silane coupling agent B is at least one of gamma-glycidoxypropyl triethoxysilane and 3-glycidoxypropyl methyldiethoxysilane;
the preparation method comprises the following steps of,
mixing 1000-2500 parts of epoxy resin, 353-884 parts of bisphenol A and 250-400 parts of ether substances, heating to 100-120 ℃, uniformly stirring, adding 0.2-10 parts of catalyst, heating to 130-150 ℃, and preserving heat until the epoxy equivalent is enlarged to 600-800; cooling to below 100 ℃, adding 273-400 parts of amine substances, heating to 100-120 ℃ and preserving heat for 2-3 hours; 60-100 parts of silane coupling agent A is added at 90-100 ℃, the temperature is kept at 100-120 ℃ for 2-3 hours, 60-100 parts of silane coupling agent B is added, the temperature is kept at 100-120 ℃ for 2-3 hours, the temperature is reduced to 70-80 ℃, 200-550 parts of acid is added, the mixture is stirred uniformly, 800-5000 parts of water is added for emulsification, the temperature is kept at 50-70 ℃ for 3-5 hours, and the temperature is reduced and the material is discharged to obtain the microgel for the cathode electrophoresis coating.
2. The method for producing a microgel for a cathodic electrophoretic coating according to claim 1, wherein: the ether substance is at least one of ethylene glycol butyl ether and diethylene glycol butyl ether.
3. The method for producing a microgel for a cathodic electrophoretic coating according to claim 1, wherein: the catalyst is at least one of benzylamine, tertiary amine, quaternary ammonium and triphenylphosphine.
4. The method for producing a microgel for a cathodic electrophoretic coating according to claim 1, wherein: the amine substance is at least one of amino compounds di-n-butylamine, methylethanolamine, diethanolamine, triethanolamine, dimethylethanolamine and methyldiethanolamine or at least one of ketimine substances; the ketimine is prepared by condensation reaction of ketone and polyamine for dehydration; the polyamine is at least one of diethylenetriamine, m-phenylenediamine, m-xylylenediamine and 1, 3-bis (aminomethyl) cyclohexane; the ketone is at least one of methyl isopropyl ketone, methyl isobutyl ketone and methyl ethyl ketone.
5. The method for producing a microgel for a cathodic electrophoretic coating according to claim 1, wherein: the acid is at least one of sulfamic acid, formic acid or glacial acetic acid and lactic acid.
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| US5380781A (en) * | 1992-07-27 | 1995-01-10 | Kansai Paint Co., Ltd. | Cationically electrodepositable fine particles derived from alkoxysilane-modified epoxy resins and cationic electrodeposition paint composition comprising the same |
| CA2166604A1 (en) * | 1993-07-09 | 1995-01-19 | Peter W. Uhlianuk | Siloxane crosslinked microgel for cathodic electrocoating compositions |
| CN106905664A (en) * | 2017-04-10 | 2017-06-30 | 立邦涂料（中国）有限公司 | A kind of function polyamine modified microgel, preparation method and its usage |
| CN109504264A (en) * | 2018-12-02 | 2019-03-22 | 广州立邦涂料有限公司 | A kind of edge anti-corrosion electrodeposition coating composition, Preparation method and use |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5380781A (en) * | 1992-07-27 | 1995-01-10 | Kansai Paint Co., Ltd. | Cationically electrodepositable fine particles derived from alkoxysilane-modified epoxy resins and cationic electrodeposition paint composition comprising the same |
| CA2166604A1 (en) * | 1993-07-09 | 1995-01-19 | Peter W. Uhlianuk | Siloxane crosslinked microgel for cathodic electrocoating compositions |
| CN106905664A (en) * | 2017-04-10 | 2017-06-30 | 立邦涂料（中国）有限公司 | A kind of function polyamine modified microgel, preparation method and its usage |
| CN109504264A (en) * | 2018-12-02 | 2019-03-22 | 广州立邦涂料有限公司 | A kind of edge anti-corrosion electrodeposition coating composition, Preparation method and use |
| CN109679118A (en) * | 2018-12-02 | 2019-04-26 | 廊坊立邦涂料有限公司 | A kind of phosphate modified cationic microgel, Preparation method and use |
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