CN110982383B - Emulsion for cathode electrophoretic paint and preparation method thereof - Google Patents
Emulsion for cathode electrophoretic paint and preparation method thereof Download PDFInfo
- Publication number
- CN110982383B CN110982383B CN201911344835.8A CN201911344835A CN110982383B CN 110982383 B CN110982383 B CN 110982383B CN 201911344835 A CN201911344835 A CN 201911344835A CN 110982383 B CN110982383 B CN 110982383B
- Authority
- CN
- China
- Prior art keywords
- parts
- epoxy resin
- mass ratio
- emulsion
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003973 paint Substances 0.000 title claims abstract description 43
- 239000000839 emulsion Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000003822 epoxy resin Substances 0.000 claims abstract description 48
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 48
- FDIPWBUDOCPIMH-UHFFFAOYSA-N 2-decylphenol Chemical compound CCCCCCCCCCC1=CC=CC=C1O FDIPWBUDOCPIMH-UHFFFAOYSA-N 0.000 claims abstract description 41
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 21
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 18
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000003756 stirring Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000007599 discharging Methods 0.000 claims abstract description 13
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 238000004945 emulsification Methods 0.000 claims abstract description 4
- 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 32
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 31
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 26
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 24
- 239000004593 Epoxy Substances 0.000 claims description 21
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims description 21
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 18
- XXBDWLFCJWSEKW-UHFFFAOYSA-N dimethylbenzylamine Chemical compound CN(C)CC1=CC=CC=C1 XXBDWLFCJWSEKW-UHFFFAOYSA-N 0.000 claims description 16
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 15
- RWNUSVWFHDHRCJ-UHFFFAOYSA-N 1-butoxypropan-2-ol Chemical compound CCCCOCC(C)O RWNUSVWFHDHRCJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 239000004310 lactic acid Substances 0.000 claims description 12
- 235000014655 lactic acid Nutrition 0.000 claims description 12
- 239000004814 polyurethane Substances 0.000 claims description 10
- 229920002635 polyurethane Polymers 0.000 claims description 10
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 9
- 238000004070 electrodeposition Methods 0.000 claims description 8
- 230000003472 neutralizing effect Effects 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- 238000006386 neutralization reaction Methods 0.000 claims description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 abstract description 16
- 238000000576 coating method Methods 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 12
- 150000003839 salts Chemical class 0.000 abstract description 6
- 238000006243 chemical reaction Methods 0.000 description 36
- 230000004048 modification Effects 0.000 description 9
- 238000012986 modification Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000004132 cross linking Methods 0.000 description 8
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 8
- 230000001804 emulsifying effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 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 description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 4
- FZERHIULMFGESH-UHFFFAOYSA-N N-phenylacetamide Chemical compound CC(=O)NC1=CC=CC=C1 FZERHIULMFGESH-UHFFFAOYSA-N 0.000 description 4
- 239000002981 blocking agent Substances 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- UPGSWASWQBLSKZ-UHFFFAOYSA-N 2-hexoxyethanol Chemical compound CCCCCCOCCO UPGSWASWQBLSKZ-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 239000005057 Hexamethylene diisocyanate Substances 0.000 description 3
- 239000006229 carbon black Substances 0.000 description 3
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- RRAMGCGOFNQTLD-UHFFFAOYSA-N hexamethylene diisocyanate Chemical compound O=C=NCCCCCCN=C=O RRAMGCGOFNQTLD-UHFFFAOYSA-N 0.000 description 3
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 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 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 229960001413 acetanilide Drugs 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 2
- 229940043237 diethanolamine Drugs 0.000 description 2
- 238000001962 electrophoresis Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 150000004658 ketimines Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- OSWPMRLSEDHDFF-UHFFFAOYSA-N methyl salicylate Chemical compound COC(=O)C1=CC=CC=C1O OSWPMRLSEDHDFF-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- YXRKNIZYMIXSAD-UHFFFAOYSA-N 1,6-diisocyanatohexane Chemical compound O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O.O=C=NCCCCCCN=C=O YXRKNIZYMIXSAD-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- YEYKMVJDLWJFOA-UHFFFAOYSA-N 2-propoxyethanol Chemical compound CCCOCCO YEYKMVJDLWJFOA-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-O N-dimethylethanolamine Chemical compound C[NH+](C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-O 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 150000004985 diamines Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229920000831 ionic polymer Polymers 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- NIMLQBUJDJZYEJ-UHFFFAOYSA-N isophorone diisocyanate Chemical compound CC1(C)CC(N=C=O)CC(C)(CN=C=O)C1 NIMLQBUJDJZYEJ-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229960001047 methyl salicylate Drugs 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006011 modification reaction Methods 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
- 239000000080 wetting agent 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
- C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
-
- 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
- C09D5/4453—Polyepoxides characterised by the nature of the curing agent
-
- 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
- C09D5/4465—Polyurethanes
-
- 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
- C09D5/4473—Mixture of polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
The invention provides an emulsion for cathode electrophoretic paint and a preparation method thereof. The preparation method of the emulsion for the cathode electrophoretic paint comprises the following steps: mixing the decylphenol-modified epoxy resin with methylethanolamine and monoethanolamine, carrying out amination reaction for 2-5 h at 100-120 ℃, adding a cross-linking agent and an auxiliary agent, stirring for 0.5-2 h, and discharging the neutralized product into water for emulsification to obtain the epoxy resin emulsion. According to the preparation method, the epoxy resin is modified by the decylphenol, and a specific aminating agent is used for amination reaction, so that the salt fog resistance and throwing power of the cathode electrophoretic paint prepared from the emulsion are effectively improved, and the electrophoretic coating productivity is improved.
Description
Technical Field
The invention relates to the technical field of coatings, and particularly relates to an emulsion for a cathode electrophoretic paint and a preparation method thereof.
Background
Electrophoretic paints, also known as electrocoats. Electrophoresis is one of the most effective methods for coating metal workpieces. The electrophoretic coating is a special coating method which comprises the steps of immersing an object to be coated with electric conductivity into an electrophoretic coating tank which is filled with water and diluted and has relatively low concentration to be used as an anode (or a cathode), arranging a cathode (or an anode) corresponding to the object in the tank, and depositing a uniform, fine and water-insoluble coating film on the surface of the object to be coated after direct current is conducted between the two electrodes for a period of time. The electrophoretic coating uses water-soluble or water-dispersible ionic polymer as a film forming material, and the coated workpiece can be an anode or a cathode. Electrophoretic paints can be classified into anodic electrophoretic paints and cathodic electrophoretic paints (also called cathodic electrophoretic paints) according to the work pieces to be coated. Wherein, the cathode electrophoretic paint can be divided into: epoxy electrophoretic paints, acrylic electrophoretic paints and polyurethane electrophoretic paints. The epoxy electrophoretic paint has super strong salt spray performance and deep hole throwing power, the salt spray performance on a phosphorized substrate can reach more than 1000 hours, and the main mature products mainly comprise bright black, elegant black, dark gray and light gray.
A paint film formed by the cathodic electrophoretic paint has excellent corrosion resistance and mechanical properties, is suitable for automatic coating, and is rapidly popularized in the automobile industry. Because the shapes of automobile bodies and parts are complex and contain a plurality of concave bodies, cavities, gaps and the like, the thickness of a paint film on the inner surface and the outer surface of a coated workpiece is uneven due to the fact that an electric shielding phenomenon is often generated in the electrophoretic coating process, and the corrosion resistance of the whole workpiece (the automobile industry or the workpiece with the concave bodies, the cavities and the gaps on the surface) is seriously influenced. The index for judging whether the cathode electrophoretic paint enables the concave depth, the gap or the shielded part of the coated workpiece to be uniformly coated with the paint film is the throwing power, wherein the higher the throwing power is, the more uniform the thickness of the paint film coated on the coated workpiece is, and the higher the overall corrosion resistance of the workpiece is. In addition, the throwing power is improved, the consumption of the coating can be effectively reduced, and the cost is saved. In cathodic electrocoating, resin emulsions are one of the key factors in determining the performance of paint films. The resin emulsion for the cathode electrophoretic coating disclosed in the prior art has poor throwing power and cannot meet the requirements of coating industry in certain industries.
Disclosure of Invention
The first object of the present invention is to provide a method for preparing an emulsion for a cathodic electrodeposition paint. According to the preparation method, decyl phenol modified epoxy resin is used for amination and crosslinking, and the prepared emulsion can be used for obtaining the cathode electrophoretic coating with strong electrophoretic capacity.
The preparation method of the emulsion for the cathode electrophoretic paint comprises the following steps: mixing decyl phenol modified epoxy resin with methylethanolamine and monoethanolamine, carrying out amination reaction for 2-5 h at 100-120 ℃, adding a cross-linking agent and an auxiliary agent, stirring for 0.5-2 h, neutralizing, and discharging the obtained product into water for emulsification to obtain the emulsion.
In the art, amination can generally be carried out using monoamines such as monoethanolamine, diethanolamine, methyl monoethanolamine, N-dimethylethanolamine, and the like, or diamines such as polyamide or ketimine. Through a great deal of research and invention, compared with other combinations, the performance of the obtained emulsion can be effectively improved by carrying out amination reaction on decyl phenol modified epoxy resin, methylethanolamine and monoethanolamine.
In a preferred embodiment of the invention, the weight ratio of the decylphenol to the epoxy resin in the decylphenol-modified epoxy resin is 1 (15-30), preferably 1 (20-25).
In a preferred embodiment of the present invention, the epoxy resin of the present invention may be one or more selected from E-54 (epoxy value of 0.52 to 0.56), E-51 (epoxy value of 0.48 to 0.54), E-44 (epoxy value of 0.41 to 0.47), E-20 (epoxy value of 0.18 to 0.22), E-12 (epoxy value of 0.08 to 0.12), and E-10 (epoxy value of 0.04 to 0.07), preferably a mixture of E-54, E-51, E-44, and E-20, and more preferably E-20 and E-51; wherein the mass ratio of E-20 to E-51 is preferably (5-10): 1, and more preferably (7-8): 1.
In a preferred embodiment of the present invention, the method for preparing the decylphenol-modified epoxy resin comprises the steps of: epoxy resin, bisphenol A, decyl phenol, dimethylbenzylamine and xylene are mixed and react at 130-140 ℃. Wherein the mass ratio of the epoxy resin, the bisphenol A, the decylphenol, the dimethylbenzylamine and the dimethylbenzene is preferably (15-30): 1-5): 1 (0.01-0.1): 1-5), and more preferably (20-25): 2-4): 1 (0.05-0.8): 2-4). Wherein the reaction temperature is preferably 105-115 ℃. In this modification reaction, it is preferable to carry out the next reaction when the epoxy value of the system is 0.1.
In a preferred embodiment of the invention, the mass ratio of the decyl phenol, the epoxy resin, the methyl ethanolamine and the monoethanolamine is 1 (15-30): (1-5): 0.2-1, preferably 1 (20-25): 1-2): 0.5-0.8. Wherein, in the amination reaction, the reaction solvent is one or more of propylene glycol butyl ether, xylene and methyl isobutyl ketone, and the preferred reaction solvent is propylene glycol butyl ether and methyl isobutyl ketone. Wherein, the mass ratio of the propylene glycol butyl ether to the methyl isobutyl ketone is preferably 1: 1. the addition amount of the reaction solvent is 20-25 wt% of the solvent in the reaction system. The temperature of the amination reaction is 85-95 ℃.
That is, in a preferred embodiment of the present invention, the method for preparing the emulsion for a cathodic electrodeposition paint comprises the steps of: the preparation method of the decyl phenol modified epoxy resin comprises the following steps: mixing epoxy resin, bisphenol A, decylphenol, dimethylbenzylamine and xylene, reacting at 130-140 ℃, adding propylene glycol butyl ether and methyl isobutyl ketone when the epoxy value of a system is 0.1, adding methylethanolamine at 85-95 ℃, reacting for 1-1.5 h, adding monoethanolamine, and reacting for 1-3.5 h at 105-115 ℃.
In a preferred embodiment of the invention, the mass ratio of the decyl phenol to the cross-linking agent to the auxiliary agent is 1 (8-15): (0.05-0.15), preferably 1 (9-10): 0.08-0.09.
In a preferred embodiment of the invention, the cross-linking agent is a blocked polyurethane. In the present invention, the isocyanate used for the blocked polyurethane is one or more of Toluene Diisocyanate (TDI), Hexamethylene Diisocyanate (HDI), hexamethylene diisocyanate trimer (HDI trimer), isophorone diisocyanate (IPDI), or diphenylmethane diisocyanate (MDI). The used blocking agent can be one or more of methyl salicylate, 3, 5-dimethylpyrazole, acetanilide, phenol, caprolactam, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether and ethylene glycol monohexyl ether. The preferable cross-linking agent is blocked polyurethane obtained by reacting toluene diisocyanate with a blocking agent of ethylene glycol monobutyl ether under the action of methyl isobutyl ketone or blocked polyurethane prepared by using diphenylmethane diisocyanate and a blocking agent of ethylene glycol monohexyl ether.
In a preferred embodiment of the present invention, the process for the preparation of the preferred crosslinkers of the present invention, i.e. the blocked polyurethanes, preferably comprises the steps of:
mixing toluene diisocyanate and methyl isobutyl ketone, heating to 50-60 ℃, adding glycerol, detecting NCO percent of 14-15%, heating to 70-80 ℃, adding ethylene glycol monobutyl ether, and detecting NCO<8*10-3Percent; wherein the mass ratio of the toluene diisocyanate to the methyl isobutyl ketone to the glycerol to the ethylene glycol monobutyl ether is (5-6) to (2-3) to (3.5-4.5).
In a preferred embodiment of the present invention, the auxiliary agent is one or more of BYK110, BYK425, BYK410, TEGO110, TEGO120, TEGO130, TEGO140, TEGO410, TEGO440, TEGO450, TEGO500, TEGO650, OP-4, OP-7, OP-9, OP-10, OP-13, OP-15, OP-20, preferably BYK425, TEGO130 and OP-4, and further preferably: the mass ratio of BYK425 to TEGO130 to OP-4 is 1:1 (2-3).
In the preparation method, a neutralizer is added for neutralization, the neutralizer can be one or more of formic acid, acetic acid, butyric acid and lactic acid, preferably acetic acid and lactic acid, and the mass ratio of the acetic acid to the lactic acid is preferably 1 (2-5), and more preferably 1 (3-4). The mass ratio of decylphenol to neutralising agent is preferably 1: 2. In the neutralization reaction, the reaction temperature is preferably 50 to 70 ℃, and more preferably 60 ℃.
In a preferred embodiment of the present invention, a method for preparing an emulsion for a cathodic electrophoretic paint, comprises the steps of:
mixing epoxy resin, bisphenol A, decyl phenol, dimethylbenzylamine and xylene, and reacting at 130-140 ℃; wherein the mass ratio of the epoxy resin, the bisphenol A, the decyl phenol, the dimethylbenzylamine and the dimethylbenzene is preferably (15-30): (1-5): 1 (0.01-0.1): 1-5);
when the epoxy value of the system is 0.1, adding propylene glycol butyl ether and methyl isobutyl ketone, adding methylethanolamine at the temperature of 85-95 ℃, reacting for 1-1.5 h, adding monoethanolamine, and reacting for 1-3.5 h at the temperature of 105-115 ℃; the mass ratio of the decyl phenol to the epoxy resin to the methyl ethanolamine to the monoethanolamine is 1 (15-30) to 1-5 to 0.2-1;
cooling to 90 ℃, adding a cross-linking agent, cooling to 70-75 ℃, adding an auxiliary agent, stirring for 1-1.5 h, adding a neutralizing agent for neutralization at 50-70 ℃, and discharging the obtained product into water for emulsification to obtain an emulsion; the auxiliary agents are BYK425, TEGO130 and OP-4; the neutralizing agent is acetic acid and lactic acid; the mass ratio of the decyl phenol to the cross-linking agent to the auxiliary agent is 1 (8-15) to 0.05-0.15.
Wherein the epoxy resin is preferably E-20 and E-51, and the mass ratio of the E-20 to the E-51 is (5-10): 1.
The cross-linking agent is blocked polyurethane obtained by reacting toluene diisocyanate with a blocking agent of ethylene glycol monobutyl ether under the action of methyl isobutyl ketone.
It is another object of the present invention to provide an emulsion for a cathodic electrodeposition paint obtained by the above preparation method.
The emulsion containing the decylphenol-modified epoxy resin is mixed with color paste in the field, water is added to prepare a bath solution, and the electrophoretic penetration of a paint film obtained by electrophoretic production after curing is effectively improved to be up to 23.8 mm.
According to the invention, a large number of researches show that the salt spray resistance and the throwing power of the cathode electrophoretic paint prepared from the emulsion are effectively improved by modifying the epoxy resin with decyl phenol and carrying out amination reaction by using a specific aminating agent, so that the productivity of electrophoretic coating is improved.
Detailed Description
The following examples are given to further illustrate the embodiments of the present invention. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Unless otherwise specified, the technical means used in the examples are conventional means well known to those skilled in the art, and the raw materials used are commercially available.
In the present invention, the parts by weight may be in the units of μ g, mg, g, kg, etc. known in the art, or may be multiples thereof, such as 1/10, 1/100, 10, 100, etc.
The preparation method of the cross-linking agent 1 comprises the following steps: putting 522 parts of TDI and 242 parts of methyl isobutyl ketone into a reaction kettle, heating to 50 ℃, dropwise adding 92 parts of glycerol, keeping the temperature at 50-55 ℃, detecting NCO percent of 14.72 +/-0.1%, heating to 70 ℃, dropwise adding 354 parts of ethylene glycol monobutyl ether, keeping the temperature at 70-80 ℃, detecting NCO<8*10-3Percent, packaging and discharging.
The preparation method of the cross-linking agent 2 comprises the following steps: putting 250 parts of MDI and 133 parts of butanone into a reaction kettle, heating to 50 ℃, adding 108 parts of acetanilide by 5 times, heating to 70 ℃, dropwise adding 175 parts of ethylene glycol monohexyl ether, heating to 105-110 ℃ after dropwise adding, and detecting NCO<8*10-3Percent, packaging and discharging.
Example 1
This example provides an emulsion for a cathodic electrophoretic paint, the preparation method comprising the steps of:
modification of epoxy resins with decyl phenol: 1750 parts of epoxy resin E-20, 250 parts of E-51, 200 parts of bisphenol A, 100 parts of decyl phenol, 200 parts of dimethylbenzene and 5 parts of dimethylbenzylamine are added into a reaction kettle, and the reaction is carried out at 135 +/-5 ℃.
Amination: when the epoxy value is 0.1, 315 parts of propylene glycol butyl ether and 315 parts of methyl isobutyl ketone are added, the temperature is reduced to 90 ℃, 150 parts of methylethanolamine is added, the reaction is carried out for 1 hour at 90 ℃, 75 parts of monoethanolamine is added, and the reaction is carried out for 3 hours at 110 +/-5 ℃.
And (3) crosslinking: cooling to 90 ℃, and adding 1000 parts of cross-linking agent 1; cooling to 70 ℃, adding 2 parts of BYK425, 5 parts of OP-4 and 2 parts of TEGO130, stirring for 1 hour, adding 50 parts of acetic acid and 150 parts of lactic acid at 60 ℃, and stirring for 0.5 hour. Discharging the obtained product into 5000 parts of water, emulsifying, and removing the solvent to obtain the emulsion.
Example 2
This example provides an emulsion for a cathodic electrophoretic paint, the preparation method comprising the steps of:
modification of epoxy resins with decyl phenol: adding 2223 parts of epoxy resin E-20, 227 parts of E-51, 400 parts of bisphenol A, 100 parts of decyl phenol, 400 parts of dimethylbenzene and 8 parts of dimethylbenzylamine into a reaction kettle, and carrying out heat preservation reaction at 135 +/-5 ℃.
Amination: when the epoxy value is 0.1, 414 parts of propylene glycol butyl ether and 414 parts of methyl isobutyl ketone are added, the temperature is reduced to 90 ℃, 100 parts of methylethanolamine is added, the reaction is carried out for 1 hour at 90 ℃, 50 parts of monoethanolamine is added, and the reaction is carried out for 3 hours at 110 +/-5 ℃.
And (3) crosslinking: cooling to 90 ℃, and adding 900 parts of cross-linking agent 1; cooling to 70 ℃, adding 2 parts of BYK110, 5 parts of OP-7 and 2 parts of TEGO500, stirring for 1 hour, adding 50 parts of formic acid and 150 parts of lactic acid at 60 ℃, and stirring for 0.5 hour. Discharging the obtained product into 5000 parts of water, emulsifying, and removing the solvent to obtain the emulsion.
Example 3
This example provides an emulsion for a cathodic electrophoretic paint, the preparation method comprising the steps of:
modification of epoxy resins with decyl phenol: 1312.5 parts of epoxy resin E-20, 187.5 parts of E-51, 100 parts of bisphenol A, 100 parts of decyl phenol, 100 parts of dimethylbenzene and 1 part of dimethylbenzylamine are added into a reaction kettle, and the reaction is carried out at 135 +/-5 ℃.
Amination: when the epoxy value is 0.1, 225 parts of propylene glycol butyl ether and 225 parts of methyl isobutyl ketone are added, the temperature is reduced to 90 ℃, 100 parts of methylethanolamine is added, the reaction is carried out for 1 hour at 90 ℃, 20 parts of monoethanolamine is added, and the reaction is carried out for 3 hours at 110 +/-5 ℃.
And (3) crosslinking: cooling to 90 ℃, and adding 800 parts of cross-linking agent 1; cooling to 70 ℃, adding 2 parts of BYK425, 5 parts of OP-4 and 2 parts of TEGO130, stirring for 1 hour, adding 40 parts of acetic acid and 160 parts of lactic acid at 60 ℃, and stirring for 0.5 hour. And discharging the obtained product into 4000 parts of water, emulsifying, and removing the solvent to obtain the emulsion.
Example 4
This example provides an emulsion for a cathodic electrophoretic paint, the preparation method comprising the steps of:
modification of epoxy resins with decyl phenol: 2667 parts of epoxy resin E-20, 333 parts of E-51, 500 parts of bisphenol A, 100 parts of decyl phenol, 500 parts of dimethylbenzene and 5 parts of dimethylbenzylamine are added into a reaction kettle, and the reaction is carried out at 135 +/-5 ℃.
Amination: when the epoxy value is 0.1, 500 parts of propylene glycol butyl ether and 500 parts of methyl isobutyl ketone are added, the temperature is reduced to 90 ℃, 200 parts of methylethanolamine is added, the reaction is carried out for 1 hour at 90 ℃, 80 parts of monoethanolamine is added, and the reaction is carried out for 3 hours at 110 +/-5 ℃.
And (3) crosslinking: cooling to 90 ℃, and adding 1500 parts of cross-linking agent 1; cooling to 70 ℃, adding 2 parts of BYK425, 5 parts of OP-4 and 2 parts of TEGO130, stirring for 1 hour, adding 50 parts of acetic acid and 150 parts of lactic acid at 60 ℃, and stirring for 0.5 hour. Discharging the obtained product into 5000 parts of water, emulsifying, and removing the solvent to obtain the emulsion.
Example 5
This example provides an emulsion for a cathodic electrophoretic paint, the preparation method comprising the steps of:
modification of epoxy resins with decyl phenol: adding 2000 parts of epoxy resin E-51, 200 parts of bisphenol A, 100 parts of decyl phenol, 200 parts of dimethylbenzene and 5 parts of dimethylbenzylamine into a reaction kettle, and carrying out heat preservation reaction at 135 +/-5 ℃.
Amination: when the epoxy value is 0.1, 251 parts of propylene glycol butyl ether and 250 parts of methyl isobutyl ketone are added, the temperature is reduced to 90 ℃, 150 parts of methylethanolamine is added, the reaction is carried out for 1 hour at 90 ℃, 75 parts of monoethanolamine is added, and the reaction is carried out for 3 hours at 110 +/-5 ℃.
And (3) crosslinking: cooling to 90 ℃, and adding 1000 parts of cross-linking agent 2; cooling to 70 ℃, adding 2 parts of BYK410, 5 parts of OP-4 and 2 parts of TEGO500, stirring for 1 hour, adding 50 parts of butyric acid and 150 parts of lactic acid at 60 ℃, and stirring for 0.5 hour. Discharging the obtained product into 5000 parts of water, emulsifying, and removing the solvent to obtain the emulsion.
Comparative example 1
This comparative example provides an emulsion for cathodic electrodeposition paint, the preparation method comprising the steps of:
modification of epoxy resins with decyl phenol: 1750 parts of epoxy resin E-20, 250 parts of E-51, 200 parts of bisphenol A, 100 parts of nonyl phenol, 200 parts of dimethylbenzene and 5 parts of dimethylbenzylamine are added into a reaction kettle, and the reaction is carried out at 135 +/-5 ℃.
Amination: when the epoxy value is 0.1, 300 parts of propylene glycol butyl ether and 300 parts of methyl isobutyl ketone are added, the temperature is reduced to 90 ℃, 150 parts of diethanol amine is added, the reaction is carried out for 1 hour at the temperature of 90 ℃, 75 parts of monoethanolamine is added, and the reaction is carried out for 3 hours at the temperature of 110 +/-5 ℃.
And (3) crosslinking: cooling to 90 ℃, and adding 1000 parts of cross-linking agent 1; the temperature is reduced to 70 ℃, 2 parts of byk425, 5 parts of op-4 and 2 parts of tego130 are added and stirred for 1 hour, and at 60 ℃, 50 parts of acetic acid and 150 parts of lactic acid are added and stirred for 0.5 hour. Discharging the obtained product into 5000 parts of water, emulsifying, and removing the solvent to obtain the emulsion.
Comparative example 2
This comparative example provides an emulsion for cathodic electrodeposition paint, the preparation method comprising the steps of:
modification of epoxy resins with decyl phenol: 1750 parts of epoxy resin E-20, 250 parts of E-51, 200 parts of bisphenol A, 100 parts of decyl phenol, 200 parts of dimethylbenzene and 5 parts of dimethylbenzylamine are added into a reaction kettle, and the reaction is carried out at 135 +/-5 ℃.
Amination: when the epoxy value is 0.1, 315 parts of propylene glycol butyl ether and 315 parts of methyl isobutyl ketone are added, the temperature is reduced to 90 ℃, 150 parts of methyl ethanolamine is added, the reaction is carried out for 1 hour at the temperature of 90 ℃, 75 parts of ketimine is added, and the reaction is carried out for 3 hours at the temperature of 110 +/-5 ℃.
And (3) crosslinking: cooling to 90 ℃, and adding 1000 parts of cross-linking agent 2; cooling to 70 ℃, adding 2 parts of BYK425, 5 parts of OP-4 and 2 parts of TEGO130, stirring for 1 hour, adding 50 parts of acetic acid and 150 parts of lactic acid at 60 ℃, and stirring for 0.5 hour. Discharging the obtained product into 5000 parts of water, emulsifying, and removing the solvent to obtain the emulsion.
Experimental example 1
The color paste 1 used was a commercially available unmodified epoxy resin color paste available from the Hubei Copponda technologies, Inc.
The color paste 2 is color paste modified by decyl phenol, and the preparation method comprises the following steps:
modification of epoxy resins with decyl phenol: adding 500 parts of epoxy resin e-54 (0.52-0.56), 125 parts of epoxy resin e-51 (0.48-0.54), 63 parts of bisphenol A, 125 parts of decylphenol, 70 parts of xylene and 5 parts of dimethylbenzylamine into a reaction kettle in sequence, reacting at 130 ℃, detecting the epoxy value in a reaction system, cooling to 90 ℃ when the epoxy value is 0.16, adding 100 parts of methyl isobutyl ketone, adding 45 parts of N-methylethanolamine, reacting at 90 ℃ for 1 hour, adding 30 parts of monoethanolamine, reacting at 110 +/-5 ℃ for 3 hours, and removing a solvent to obtain the modified epoxy resin. Uniformly mixing 20 parts of modified epoxy resin, 5 parts of butyl cellosolve, 5 parts of ethylene glycol and 3 parts of butanol to obtain a mixed solution, and adding 1 part of cabot M700 type carbon black into the mixed solution to soak for 12 hours to obtain carbon black color paste; uniformly stirring carbon black color paste, 10 parts of hydroxy cellulose, 3 parts of ferric oxide, 0.1 part of dispersing aid TEGO740W, 0.8 part of acetic acid, 15 parts of high titanium dioxide and 0.1 part of base material wetting agent TEGO280, grinding to the fineness of 15 mu m, pouring deionized water, and adjusting the solid content to 40% to obtain the cathode electrophoretic paint color paste.
And (3) respectively mixing the emulsions in the examples 1-5 and the comparative examples 1-2 with color paste 1 and color paste 2 according to the mass ratio of 4:1, adding deionized water to prepare a bath solution with the solid content of 20%, curing for 48 hours, and carrying out electrophoresis production to obtain the coated cathode electrophoretic paint. The throwing power of the resulting cathodic electrophoretic paint was measured using the ford box method and the salt spray time was measured using the standard salt spray test, and the results are given in table 1 below.
TABLE 1 Performance results for cathodic electrodeposition paints
Finally, the method of the present invention is only a preferred embodiment and is not intended to limit the scope of the present invention. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (8)
1. A preparation method of emulsion for cathode electrophoretic paint is characterized by comprising the following steps:
mixing epoxy resin, bisphenol A, decyl phenol, dimethylbenzylamine and xylene, and reacting at 130-140 ℃; wherein the mass ratio of the epoxy resin, the bisphenol A, the decyl phenol, the dimethylbenzylamine and the dimethylbenzene is (15-30): 1-5): 1, (0.01-0.1): 1-5);
when the epoxy value of the system is 0.1, adding propylene glycol butyl ether and methyl isobutyl ketone, adding methylethanolamine at the temperature of 85-95 ℃, reacting for 1-1.5 h, adding monoethanolamine, and reacting for 1-3.5 h at the temperature of 105-115 ℃; the mass ratio of the decyl phenol to the epoxy resin to the methyl ethanolamine to the monoethanolamine is 1 (15-30) to 1-5 to 0.2-1;
cooling to 90 ℃, adding a cross-linking agent, cooling to 70-75 ℃, adding an auxiliary agent, stirring for 1-1.5 h, adding a neutralizing agent for neutralization at 50-70 ℃, and discharging the obtained product into water for emulsification to obtain an emulsion; the auxiliary agents are BYK425, TEGO130 and OP-4; the mass ratio of the BYK425 to the TEGO130 to the OP-4 is 1:1 (2-3); the neutralizing agent is acetic acid and lactic acid; the mass ratio of the decyl phenol to the cross-linking agent to the auxiliary agent is 1 (8-15) to 0.05-0.15;
wherein the epoxy resin is E-20 and E-51, and the mass ratio of the E-20 to the E-51 is (5-10) to 1; the cross-linking agent is blocked polyurethane.
2. The method according to claim 1, wherein the weight ratio of the decylphenol to the epoxy resin is 1 (20-25).
3. The method according to claim 1, wherein the mass ratio of the epoxy resin to the bisphenol A to the decyl phenol to the dimethylbenzylamine is (20-25): 2-4): 1, (0.05-0.08): 2-4).
4. The preparation method according to claim 1, wherein the mass ratio of E-20 to E-51 is (7-8): 1.
5. The method according to claim 1, wherein the mass ratio of the decylphenol to the epoxy resin to the methylethanolamine to the monoethanolamine is 1 (20-25): 1-2: 0.5-0.8.
6. The preparation method of claim 1, wherein the mass ratio of the decyl phenol to the cross-linking agent to the auxiliary agent is 1 (9-10) to (0.08-0.09).
7. The method for preparing a blocked polyurethane according to claim 1, wherein the method for preparing a blocked polyurethane preferably comprises the steps of:
mixing toluene diisocyanate and methyl isobutyl ketone, heating to 50-60 ℃, adding glycerol, detecting NCO percent of 14-15%, heating to 70-80 ℃, adding ethylene glycol monobutyl ether, and detecting NCO<8*10-3Percent; wherein the mass ratio of the toluene diisocyanate to the methyl isobutyl ketone to the glycerol to the ethylene glycol monobutyl ether is (5-6) to (2-3) to (3.5-4.5).
8. An emulsion for a cathodic electrodeposition paint prepared by the preparation method according to any one of claims 1 to 7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911344835.8A CN110982383B (en) | 2019-12-24 | 2019-12-24 | Emulsion for cathode electrophoretic paint and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911344835.8A CN110982383B (en) | 2019-12-24 | 2019-12-24 | Emulsion for cathode electrophoretic paint and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110982383A CN110982383A (en) | 2020-04-10 |
| CN110982383B true CN110982383B (en) | 2022-05-20 |
Family
ID=70076091
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911344835.8A Expired - Fee Related CN110982383B (en) | 2019-12-24 | 2019-12-24 | Emulsion for cathode electrophoretic paint and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110982383B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112812273A (en) * | 2021-02-26 | 2021-05-18 | 美高微球(南通)科技有限公司 | Polyepoxy quaternary ammonium salt emulsion for cathode electrophoretic coating and preparation method and application thereof |
| CN113527633A (en) * | 2021-07-27 | 2021-10-22 | 中国海洋石油集团有限公司 | Modified epoxy resin, resin emulsion and cathode electrophoretic coating for ultrahigh throwing power |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988281A (en) * | 1972-05-19 | 1976-10-26 | Shinto Paint Co., Ltd. | Water-dispersible thermosetting coating composition |
| GB2376905A (en) * | 2000-09-20 | 2002-12-31 | Kansai Paint Co Ltd | Multi-layer coating film-forming method |
| CN102344708A (en) * | 2010-07-27 | 2012-02-08 | 日本油漆株式会社 | Cured electrodeposition coating film and process for forming multi layered coating film |
| CN102942835A (en) * | 2012-11-21 | 2013-02-27 | 广东科德化工实业有限公司 | High throwing power cathode electrophoresis paint and preparation method and using method thereof |
| CN103497617A (en) * | 2013-09-09 | 2014-01-08 | 湖南工程学院 | Preparation method for self-emulsified cationic epoxy emulsion |
| CN107057525A (en) * | 2017-05-16 | 2017-08-18 | 枣阳市同邦达科技有限公司 | It is a kind of for emulsion of cathode electrodip painting and preparation method thereof |
| CN107216704A (en) * | 2017-05-16 | 2017-09-29 | 枣阳市同邦达科技有限公司 | A kind of cathodic electrodeposition paint emulsion and preparation method thereof |
-
2019
- 2019-12-24 CN CN201911344835.8A patent/CN110982383B/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3988281A (en) * | 1972-05-19 | 1976-10-26 | Shinto Paint Co., Ltd. | Water-dispersible thermosetting coating composition |
| GB2376905A (en) * | 2000-09-20 | 2002-12-31 | Kansai Paint Co Ltd | Multi-layer coating film-forming method |
| CN102344708A (en) * | 2010-07-27 | 2012-02-08 | 日本油漆株式会社 | Cured electrodeposition coating film and process for forming multi layered coating film |
| CN102942835A (en) * | 2012-11-21 | 2013-02-27 | 广东科德化工实业有限公司 | High throwing power cathode electrophoresis paint and preparation method and using method thereof |
| CN103497617A (en) * | 2013-09-09 | 2014-01-08 | 湖南工程学院 | Preparation method for self-emulsified cationic epoxy emulsion |
| CN107057525A (en) * | 2017-05-16 | 2017-08-18 | 枣阳市同邦达科技有限公司 | It is a kind of for emulsion of cathode electrodip painting and preparation method thereof |
| CN107216704A (en) * | 2017-05-16 | 2017-09-29 | 枣阳市同邦达科技有限公司 | A kind of cathodic electrodeposition paint emulsion and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110982383A (en) | 2020-04-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| KR101488692B1 (en) | Use of bismuth subnitrate in electro-dipping paints | |
| JPS6139351B2 (en) | ||
| CA2404930A1 (en) | Photodegradation-resistant electrodepositable coating compositions and processes related thereto | |
| CN110982383B (en) | Emulsion for cathode electrophoretic paint and preparation method thereof | |
| JP2011132607A (en) | Electrodeposition bath containing yttrium | |
| DE3002865C2 (en) | Aqueous dispersion and its use | |
| KR20040034738A (en) | Cathodic electrocoating compositions containing hydroxyl-carbonate blocked polyisocyanate crosslinking agent | |
| DE69802266T2 (en) | ANTI-SCRATCHING AGENTS CONTAINING CATHODICALLY DEPENDABLE ELECTRO-DIVING COMPOSITIONS | |
| EP0626000A1 (en) | Process for lacquering electroconductive substrates, aqueous electro-dipcoats, process for preparing an aqueous dispersion of crosslinked polymer microparticules and dispersions prepared according to this process. | |
| US20120222962A1 (en) | Cationic electrodeposition coating composition | |
| CA1083280A (en) | Cataphoretic electrodeposition baths containing water- soluble lead salts | |
| CN109161325B (en) | Electrophoretic paint and preparation method thereof | |
| EP0159363B1 (en) | Self-curing resin composition | |
| JPH09504327A (en) | Isocyanate-crosslinked microgels for cathodic electrolytic coating compositions | |
| JP6288846B2 (en) | How to apply cationic electrodeposition paint | |
| JP2793870B2 (en) | Low curing cathodic electrodeposition bath | |
| KR20100130194A (en) | Cathodic electrodeposition paint containing metal-organic compound | |
| KR20080078792A (en) | Lead-free cationic electrodeposition coating composition, and electrodeposition coating process | |
| CN104803885B (en) | Epoxy resin of cathode electrophoresis dope independent of circulation and preparation method thereof | |
| CN1900191A (en) | Resin containing biamide structure, cathode electrophoretic paint containing said resin and their preparing method | |
| CN111019441B (en) | Color paste for cathode electrophoretic paint and preparation method thereof | |
| CN116234883A (en) | Electrodeposition coating composition comprising alkoxylated polyethylenimine | |
| CN110804364B (en) | Preparation method of high throwing power emulsion | |
| WO2022014277A1 (en) | Cationic electrodeposition coating composition | |
| JP2015193684A (en) | cationic electrodeposition coating composition |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20220520 |