CN105969056A - High-throwing-power cathodic electrophoretic paint - Google Patents
High-throwing-power cathodic electrophoretic paint Download PDFInfo
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- CN105969056A CN105969056A CN201610382585.7A CN201610382585A CN105969056A CN 105969056 A CN105969056 A CN 105969056A CN 201610382585 A CN201610382585 A CN 201610382585A CN 105969056 A CN105969056 A CN 105969056A
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- epoxy resin
- throwing power
- resin
- power cathode
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- 239000003973 paint Substances 0.000 title abstract description 22
- 239000003822 epoxy resin Substances 0.000 claims abstract description 65
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 65
- 239000002904 solvent Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000839 emulsion Substances 0.000 claims abstract description 30
- 239000008367 deionised water Substances 0.000 claims abstract description 29
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 29
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 28
- 150000001412 amines Chemical class 0.000 claims abstract description 23
- 239000004593 Epoxy Substances 0.000 claims abstract description 22
- 229920005749 polyurethane resin Polymers 0.000 claims abstract description 21
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims abstract description 20
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 19
- 229920005989 resin Polymers 0.000 claims abstract description 16
- 239000011347 resin Substances 0.000 claims abstract description 16
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 10
- 231100000252 nontoxic Toxicity 0.000 claims abstract description 10
- 230000003000 nontoxic effect Effects 0.000 claims abstract description 10
- 229920005570 flexible polymer Polymers 0.000 claims abstract description 6
- 239000004014 plasticizer Substances 0.000 claims abstract description 6
- 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 60
- 238000001962 electrophoresis Methods 0.000 claims description 39
- 229940106691 bisphenol a Drugs 0.000 claims description 30
- -1 alcohol ethers Chemical class 0.000 claims description 24
- 238000005576 amination reaction Methods 0.000 claims description 22
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 19
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 229920000570 polyether Polymers 0.000 claims description 15
- 150000002118 epoxides Chemical class 0.000 claims description 14
- 239000002585 base Substances 0.000 claims description 13
- 150000002576 ketones Chemical class 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- 229920002635 polyurethane Polymers 0.000 claims description 10
- 239000004814 polyurethane Substances 0.000 claims description 10
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 9
- 150000001768 cations Chemical class 0.000 claims description 9
- 239000002270 dispersing agent Substances 0.000 claims description 9
- 150000002334 glycols Chemical class 0.000 claims description 8
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 235000011054 acetic acid Nutrition 0.000 claims description 6
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 claims description 6
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 5
- 239000004952 Polyamide Substances 0.000 claims description 5
- 238000009472 formulation Methods 0.000 claims description 5
- 229920002647 polyamide Polymers 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical class NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- QCOGKXLOEWLIDC-UHFFFAOYSA-N N-methylbutylamine Chemical compound CCCCNC QCOGKXLOEWLIDC-UHFFFAOYSA-N 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 4
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001228 polyisocyanate Polymers 0.000 claims description 4
- 239000005056 polyisocyanate Substances 0.000 claims description 4
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- 229920002292 Nylon 6 Polymers 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims description 2
- 238000000576 coating method Methods 0.000 claims description 2
- 150000004985 diamines Chemical class 0.000 claims description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 2
- 150000002009 diols Chemical class 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000004310 lactic acid Substances 0.000 claims description 2
- 235000014655 lactic acid Nutrition 0.000 claims description 2
- DUWWHGPELOTTOE-UHFFFAOYSA-N n-(5-chloro-2,4-dimethoxyphenyl)-3-oxobutanamide Chemical compound COC1=CC(OC)=C(NC(=O)CC(C)=O)C=C1Cl DUWWHGPELOTTOE-UHFFFAOYSA-N 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 abstract description 9
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000003795 chemical substances by application Substances 0.000 abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000004841 bisphenol A epoxy resin Substances 0.000 abstract 1
- 125000002091 cationic group Chemical group 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 239000004210 ether based solvent Substances 0.000 abstract 1
- 239000000945 filler Substances 0.000 abstract 1
- 150000004658 ketimines Chemical class 0.000 abstract 1
- 239000005453 ketone based solvent Substances 0.000 abstract 1
- 239000000049 pigment Substances 0.000 abstract 1
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 80
- 238000003756 stirring Methods 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 12
- 238000002360 preparation method Methods 0.000 description 9
- 239000003643 water by type Substances 0.000 description 6
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000004576 sand Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- JQVDAXLFBXTEQA-UHFFFAOYSA-N dibutylamine Chemical compound CCCCNCCCC JQVDAXLFBXTEQA-UHFFFAOYSA-N 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000010422 painting Methods 0.000 description 2
- FDPIMTJIUBPUKL-UHFFFAOYSA-N pentan-3-one Chemical compound CCC(=O)CC FDPIMTJIUBPUKL-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- OXHNLMTVIGZXSG-UHFFFAOYSA-N 1-Methylpyrrole Chemical compound CN1C=CC=C1 OXHNLMTVIGZXSG-UHFFFAOYSA-N 0.000 description 1
- PTTPXKJBFFKCEK-UHFFFAOYSA-N 2-Methyl-4-heptanone Chemical compound CC(C)CC(=O)CC(C)C PTTPXKJBFFKCEK-UHFFFAOYSA-N 0.000 description 1
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 239000001089 [(2R)-oxolan-2-yl]methanol Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229960002887 deanol Drugs 0.000 description 1
- 239000012972 dimethylethanolamine Substances 0.000 description 1
- WEHWNAOGRSTTBQ-UHFFFAOYSA-N dipropylamine Chemical compound CCCNCCC WEHWNAOGRSTTBQ-UHFFFAOYSA-N 0.000 description 1
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- BSYVTEYKTMYBMK-UHFFFAOYSA-N tetrahydrofurfuryl alcohol Chemical compound OCC1CCCO1 BSYVTEYKTMYBMK-UHFFFAOYSA-N 0.000 description 1
- 238000005303 weighing Methods 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
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Paints Or Removers (AREA)
Abstract
The invention relates to the field of paint, in particular to high-throwing-power cathodic electrophoretic paint. The paint is prepared from, by mass, 2-3 parts of mill base, 4-6 parts of emulsion and 5-7 parts of deionized water. The mill base is prepared from 20-40 parts of water-borne cationic epoxy resin, 10-40 parts of pigment filler, 10-20 parts of solvent, 05-1.5 parts of non-toxic drying catalyst, 0.5-2 parts of dispersion agent and 20-50 parts of deionized water. The emulsion is prepared from 40-50 parts of aminated modified epoxy resin, 10-20 parts of epoxy polyurethane resin, 10-30 parts of cross-linking agent, 0.1-2 parts of emulsifying agent, 0.1-2 parts of neutralizer and 30-50 parts of deionized water. The aminated modified epoxy resin is prepared from 40-60 parts of bisphenol A epoxy resin, 8-16 parts of solvent methyl isobutyl ketone, 4-16 parts of plasticizer, 10-35 parts of flexible polymer and 3-8 parts of single molecule amine. The epoxy polyurethane resin is prepared from 10-30 parts of alcohol ether and ketone solvents, 20-35 parts of epoxy resin, 0.5-2 parts of aliphatic amine and 10-25 parts of ketimine resin.
Description
Technical field
The present invention relates to paint field, be specifically related to a kind of high throwing power cathode electrophoresis dope.
Background technology
Come out from cathode electrophoresis dope, because its paint film formed has the corrosion resistance of excellence, mechanical performance, be suitable for again automation paint, the most quickly popularized.Owing to body of a motor car and parts are complex-shaped, containing many concave volumes, cavity and gap.Usually because producing electric screen phenomenon during electrophoretic painting, making to be coated the paint film became uneven of workpiece surfaces externally and internally, inner surface paint film is relatively thin, has a strong impact on the Corrosion Protection of whole workpiece.Can make to be coated at the recessed depths of workpiece, gap or be uniformly coated with paint film by shielding, becoming the important indicator i.e. throwing power weighing cathode electrophoresis dope quality.Throwing power is the highest, and the film thickness coated by painting workpiece surfaces externally and internally is the most uniform, and workpiece entirety Corrosion Protection is the highest.Along with the fast development of auto industry, the cathode electrophoresis dope preparing high throwing power is the most very urgent.
Summary of the invention
The purpose of the present invention, is the problem in order to solve in background technology, it is provided that a kind of high throwing power cathode electrophoresis dope.
The above-mentioned technical purpose of the present invention has the technical scheme that
A kind of high throwing power cathode electrophoresis dope, including in parts by mass, mill base 2-3 part, emulsion 4-6 part and deionized water 5-7 part；
Described paste formula includes, waterborne cation epoxy resin 20-40 part, color stuffing 10-40 part, solvent 10-20 part, nontoxic drier 0.5-1.5 part, dispersant 0.5-2 part, deionized water 20-50 part；
Described emulsion formulations includes, amination modifying epoxy resin 40-50 part, epoxy polyurethane resin 10-20 part, cross-linking agent 10-30 part, emulsifying agent 0.1-2 part, nertralizer 0.1-2 part and deionized water 30-50 part；
Described amination modifying Formulaion of epoxy resin includes, bisphenol A type epoxy resin 40-60 part, solvent methylisobutyl ketone 8-16 part, plasticizer 4-16 part, flexible polymer 10-35 part and unimolecule amine 3-8 part；
Described epoxy polyurethane resin formula includes, alcohol ethers and ketones solvent 10-30 part, epoxy resin 20-35 part, fatty amine 0.5-2 part, ketimide resin 10-25 part；
Described ketimide resin formula includes, polyetheramine or polyamide 6 0-80 part, butanone or methyl iso-butyl ketone (MIBK) 20-40 part；
Described cross-linking agent is type semienclosed and/or blocked polyurethane includes, aromatic polyisocyanate 5-20 part, alcohol ether compound, heterocycle compound one of them or two or more mixing 3-30 part, polyethers or PCDL 0-80 part, ketones solvent 0-40 part.
By using, the amination modifying epoxy resin of mixing and epoxy polyurethane resin are as emulsion main material, make electrophoretic paint have stronger throwing power and electrophoretic paint tank liquor has higher breakdown voltage, the heat stability of tank liquor is the highest, and the salt spray resistance of this electrophoretic paint, chemicals-resistant, alkaline-resisting, water resistance is outstanding.
As preferably, described aromatic polyisocyanate is TDI or MDI；Alcohol ether compound is butyl glycol ether, diethylene glycol first/second/butyl ether, 2-hydroxyl first/second/butyl ether or propylene glycol first/second/butyl ether；Heterocycle compound is N-methylpyrrole alkanol, tetrahydrofurfuryl alcohol, acetylacetone,2,4-pentanedione or ethyl acetoacetate；Polyethers is molecular weight polypropylene glycol ether between 400-3000, polyglycol ether or admixtured polyether；The molecular weight of PCDL is between 1000-3000；Ketones solvent is butanone, ring ethyl ketone or methyl iso-butyl ketone (MIBK).
As preferably, described unimolecule amine at least contains the one in the ketimide of aminoethyl ethanolamine or the diketimine of diethylenetriamines, its consumption at least accounts for the 50% of the total consumption of unimolecule amine, and other compositions in unimolecule amine are one or more in butylamine, octylame, diethylamine, methylbutylamine, monoethanolamine, diethanolamine or N-methylethanolamine.
As preferably, the epoxide equivalent of described bisphenol A type epoxy resin is 200～1000.
As preferably, described flexible polymer is polyether Glycols, polyester diol or polyethers diamine, and its number-average molecular weight is 400～1500.
As preferably, the number-average molecular weight of described amination modifying epoxy resin is 1500～3500.
As preferably, described plasticizer is bisphenol A polyethenoxy ether or bisphenol-A polyethenoxy ether.
As preferably, described epoxy resin be epoxide equivalent be the bisphenol A type epoxy resin between 180-1000 or phenol aldehyde modified epoxy resin, described fatty amine is methylethanolamine, dimethylethanolamine, diethylamine, diethanolamine, triethanolamine, di-n-propylamine or di-n-butylamine.
As preferably, the amine number of described polyamide is 80-380, and molecular weight is 1000-3000.
As preferably, described nertralizer is formic acid, acetic acid, propanoic acid, lactic acid, oxalic acid or other organic acid.
The preparation technology of this programme coating, comprises the following steps:
Prepared by A mill base, by waterborne cation epoxy resin 20-40 part, color stuffing 10-40 part, solvent 10-20 part, nontoxic drier 0.5-1.5 part, dispersant 0.5-2 part, deionized water 20-50 part, puts into dispersion pot, stands more than 8 hours under 700-1100 rev/min after dispersion, disperse 20-40 minute under 600-800 rev/min again, enter sand mill and be ground to fineness≤15 μm；
Prepared by B emulsion, 1. prepare amination modifying epoxy resin；2. epoxy polyurethane resin is prepared；3., after amination modifying epoxy resin 40-50 part and epoxy polyurethane resin 10-20 part being stirred mixing, it is heated to 100-120 DEG C；4. drip or be dividedly in some parts cross-linking agent 10-30 part, be incubated 1.5-2.5 hour；5. cool to 70-90 DEG C, add emulsifying agent 0.1-2 part and nertralizer 0.1-2 part, dispersed with stirring 30-60 minute；6. cool to 30-70 DEG C, add deionized water 30-50 part, continue stirring and obtain emulsion in 30-60 minute；
C electrophoretic paint is allocated, and adds 2-3 part deionized water and 2-3 part emulsion, start circulation mixing pump, both are circulated mixing in electrophoresis tank；In premix groove, put into 2-3 part emulsion start stirring, the most slowly put into 2-3 part mill base, after stirring 30 minutes, premix groove mixed liquor is the most uniformly inputted in electrophoresis tank；Throwing the water after 3-4 part deionized water cleans premix groove and will clean again and the most uniformly pump into electrophoresis tank, in constantly circulation, tank liquor transconversion into heat i.e. obtained carrying out the electrophoretic paint of application after 48 hours.
As preferably, described amination modifying epoxy resin preparation method is, by bisphenol A type epoxy resin that epoxide equivalent is 200～1000 and solvent methylisobutyl ketone, it is heated to 110 DEG C together, until bisphenol A type epoxy resin is the most melted, cool to 90 DEG C subsequently, add flexible polymer, be heated to 120 DEG C carry out chain extending reaction or heating catalyst in the presence of carry out chain extending reaction, be incubated 2 hours；It is cooled to 100 DEG C, after adding appropriate plasticizer and solvent mix homogeneously, adds unimolecule amine, continue mixing 2 hours.
As preferably, described epoxy polyurethane process for preparing resins is, by epoxy resin 20-35 part, alcohol ethers and ketones solvent 10-30 part stirring and dissolving at 50 DEG C-80 DEG C, is subsequently added fatty amine 0.5-2 part, reacts 2-3 hour at 80 DEG C-90 DEG C；After having reacted, at 75 DEG C-90 DEG C, drip ketimide resin 10-25 part, be incubated 1.5-2.5 hour.
As preferably, described cross-linking agent preparation method is, aromatic polyisocyanate 5-20 part is put into reaction pot, is dividedly in some parts or drips alcohol ether compound or heterocycle compound 3-30 part, polyethers or PCDL 0-80 part at 20-50 DEG C；It is warming up to 70 DEG C-90 DEG C again after being incubated 0.5-2 hour at 30-80 DEG C subsequently and is incubated 1.5-3 hour, add ketones solvent 0-40 part, obtain type semienclosed and/or blocked polyurethane curing agent；Wherein, described alcohol ether compound is alcohol ethers monohydroxy compound, and described heterocycle compound is heterocyclic hydroxy-containing compounds.
In sum, beneficial effects of the present invention:
①
Breakdown voltage >=the 380V of a kind of high throwing power cathode electrophoresis dope of the present invention, Ford box method records throwing power >=22cm, strong to the inner chamber film ability of workpiece.
②
One of the present invention high throwing power cathode electrophoresis dope, the heat stability of tank liquor is high, and tank liquor electrophoresis temperature >=35 DEG C, electrodeposited paint film uniformity is good.
③
One of the present invention high throwing power cathode electrophoresis dope, solidification temperature is 160 DEG C of energy-conserving and environment-protective, when tank liquor working solvent content is less than 1.5%, still can normal film.
Detailed description of the invention
Specific examples below is only explanation of the invention; it is not limitation of the present invention; the present embodiment can be made after reading this specification by those skilled in the art as required does not has the amendment of creative contribution, but as long as all being protected by Patent Law in scope of the presently claimed invention.
Below in conjunction with specific embodiment, the present invention is described in detail.
Embodiment 1:
A kind of high throwing power cathode electrophoresis dope, including in parts by mass, mill base 2 parts, emulsion 6 parts and deionized water 5 parts；
Described paste formula includes, waterborne cation epoxy resin 20 parts, color stuffing 40 parts, solvent 10 parts, nontoxic drier 0.5 part, dispersant 0.5 part, deionized water 50 parts；
Described emulsion formulations includes, number-average molecular weight is amination modifying epoxy resin 40 parts, epoxy polyurethane resin 10 parts, cross-linking agent 30 parts, emulsifying agent 0.1 part, acetic acid 0.5 part and the deionized water 40 parts of 2500；
Described amination modifying Formulaion of epoxy resin includes, polyether Glycols 10 parts and the unimolecule amine 8 parts that bisphenol A type epoxy resin 60 parts that epoxide equivalent is 200～1000, solvent methylisobutyl ketone 12 parts, bisphenol A polyethenoxy ether 8 parts, number-average molecular weight are 1400；Wherein unimolecule amine is made up of the diketimine 4 parts of methylethanolamine 4 parts He diethylenetriamines；
Described epoxy polyurethane resin formula includes, alcohol ethers and ketones solvent 15 parts, and epoxide equivalent is the bisphenol A type epoxy resin 20 parts of 400, diethanolamine 0.5 part, ketimide resin 10 parts；Described ketimide resin formula includes, amine number is 80-380, and molecular weight is the polyamide 80 parts of 1000-3000, methyl iso-butyl ketone (MIBK) 20 parts；
Described cross-linking agent is that blocked polyurethane formula includes, TDI20 part, butyl glycol ether 15 parts, PCDL 50 parts, methyl iso-butyl ketone (MIBK) 30 parts.
Above-mentioned high throwing power cathode electrophoresis dope preparation technology, comprises the following steps:
Prepared by A mill base, by waterborne cation epoxy resin 20 parts, color stuffing 40 parts, solvent 10 parts, nontoxic drier 0.5 part, dispersant 0.5 part, deionized water 50 parts, puts into dispersion pot, stands more than 8 hours under 700-1100 rev/min after dispersion, disperse 30 minutes under 600-800 rev/min again, enter sand mill and be ground to fineness≤15 μm；
Prepared by B emulsion, 1. amination modifying epoxy resin is prepared, by bisphenol A type epoxy resin 60 parts that epoxide equivalent is 200～1000 and solvent methylisobutyl ketone 12 parts, it is heated to 110 DEG C together, until bisphenol A type epoxy resin is the most melted, cool to 90 DEG C subsequently, add the polyether Glycols 10 parts that number-average molecular weight is 1400, be heated to 120 DEG C carry out chain extending reaction or heating catalyst in the presence of carry out chain extending reaction, be incubated 2 hours；It is cooled to 100 DEG C, after adding bisphenol A polyethenoxy ether 8 parts and solvent mix homogeneously, adds the diketimine 4 parts of methylethanolamine 4 parts and diethylenetriamines, continue mixing 2 hours；2. prepare epoxy polyurethane resin, by epoxy resin 20 parts, alcohol ethers and ketones solvent 10-30 part stirring and dissolving at 50 DEG C-80 DEG C, be subsequently added diethanolamine 0.5 part, react 2-3 hour at 80 DEG C-90 DEG C；After having reacted, at 75 DEG C-90 DEG C, drip ketimide resin 10 parts, be incubated 1.5 hours；3. by after amination modifying epoxy resin 40 parts and epoxy polyurethane resin 10 parts stirring mixing, it is heated to 100-120 DEG C；4. dripping or be dividedly in some parts cross-linking agent 30 parts, be incubated 1.5-2.5 hour, described cross-linking agent preparation method is, 20 parts of TDI is put into reaction pot, is dividedly in some parts butyl glycol ether 3-30 part, PCDL 50 parts at 20-50 DEG C；It is warming up to 70 DEG C-90 DEG C again after being incubated 0.5-2 hour at 30-80 DEG C subsequently and is incubated 1.5-3 hour, methylate isobutyl ketone 30 parts, obtain blocked polyurethane curing agent；5. cool to 70-90 DEG C, add emulsifying agent 0.1-2 part and nertralizer 0.1-2 part, dispersed with stirring 30-60 minute；6. cool to 30-70 DEG C, add deionized water 30-50 part, continue stirring and obtain emulsion in 30-60 minute；
C electrophoretic paint is allocated, and adds 2 parts of deionized waters and 3 parts of emulsions, start circulation mixing pump, both are circulated mixing in electrophoresis tank；In premix groove, put into 3 parts of emulsions start stirring, the most slowly put into 2 parts of mill bases, after stirring 30 minutes, premix groove mixed liquor is the most uniformly inputted in electrophoresis tank；Throwing the water after 3 parts of deionized waters clean premix groove and will clean again and the most uniformly pump into electrophoresis tank, in constantly circulation, tank liquor transconversion into heat i.e. obtained carrying out the electrophoretic paint of application after 48 hours.
Embodiment 2:
A kind of high throwing power cathode electrophoresis dope, including in parts by mass, mill base 2 parts, emulsion 4 parts and deionized water 6 parts；
Described paste formula includes, waterborne cation epoxy resin 30 parts, color stuffing 30 parts, solvent 10 parts, nontoxic drier 0.5 part, dispersant 0.5 part, deionized water 40 parts
Described emulsion formulations includes, number-average molecular weight is 2000 amination modifying epoxy resin 50 parts, epoxy polyurethane resin 10 parts, cross-linking agent 20 parts, emulsifying agent 0.5 part, acetic acid 0.1 part and deionized water 50 parts；
Described amination modifying Formulaion of epoxy resin includes, epoxide equivalent be 200～1000 bisphenol A type epoxy resin 50 parts, solvent methylisobutyl ketone 16 parts, bisphenol-A polyethenoxy ether 8 parts, number-average molecular weight be polyether Glycols 10 parts and the unimolecule amine 5 parts of 1000；Wherein unimolecule amine is made up of the ketimide 4 parts of diethanolamine 4 parts He aminoethyl ethanolamine；
Described epoxy polyurethane resin formula includes, alcohol ethers and ketones solvent 30 parts, and epoxide equivalent is the bisphenol A type epoxy resin 30 parts of 400, diethanolamine 0.5-2 part, ketimide resin 20 parts；Described ketimide resin formula includes, molecular weight is the polyamide 60 part of 1000-3000, butanone 40 parts；
Described cross-linking agent is that type semienclosed polyurethane includes, TDI20 part, diethylene glycol ether 20 parts, PCDL 40 parts, butanone 30 parts.
Above-mentioned high throwing power cathode electrophoresis dope preparation technology, comprises the following steps:
Prepared by A mill base, by waterborne cation epoxy resin 30 parts, color stuffing 30 parts, solvent 10 parts, nontoxic drier 0.5 part, dispersant 0.5 part, deionized water 40 parts, puts into dispersion pot, stands more than 8 hours under 700-1100 rev/min after dispersion, disperse 20-40 minute under 600-800 rev/min again, enter sand mill and be ground to fineness≤15 μm；
Prepared by B emulsion, 1. amination modifying epoxy resin is prepared, by bisphenol A type epoxy resin 50 parts that epoxide equivalent is 200～1000 and solvent methylisobutyl ketone 16 parts, it is heated to 110 DEG C together, until bisphenol A type epoxy resin is the most melted, cool to 90 DEG C subsequently, add the polyether Glycols 10 parts that number-average molecular weight is 1000, be heated to 120 DEG C carry out chain extending reaction or heating catalyst in the presence of carry out chain extending reaction, be incubated 2 hours；It is cooled to 100 DEG C, after adding bisphenol-A polyethenoxy ether 8 parts and solvent mix homogeneously, adds the ketimide 4 parts of diethanolamine 4 parts and aminoethyl ethanolamine, continue mixing 2 hours；2. prepare epoxy polyurethane resin, by epoxy resin 30 parts, alcohol ethers and 30 parts of stirring and dissolving at 50 DEG C-80 DEG C of ketones solvent, be subsequently added diethanolamine 0.5-2 part, react 2-3 hour at 80 DEG C-90 DEG C；After having reacted, at 75 DEG C-90 DEG C, drip ketimide resin 20 parts, be incubated 2 hours；3. by after amination modifying epoxy resin 50 parts and epoxy polyurethane resin 10 parts stirring mixing, it is heated to 100-120 DEG C；4. dripping or be dividedly in some parts cross-linking agent 20 parts, be incubated 1.5-2.5 hour, described cross-linking agent preparation method is, 20 parts of TDI is put into reaction pot, is dividedly in some parts or diethylene glycol ether 20 parts at 20-50 DEG C, PCDL 40 parts；It is warming up to 70 DEG C-90 DEG C again after being incubated 0.5-2 hour at 30-80 DEG C subsequently and is incubated 1.5-3 hour, butanone 30 parts, obtain type semienclosed polyurethane curing agent；5. cool to 70-90 DEG C, add emulsifying agent 0.5 part and acetic acid 0.1 part, dispersed with stirring 30-60 minute；6. cool to 30-70 DEG C, add deionized water 50 parts, continue stirring and obtain emulsion in 30-60 minute；
C electrophoretic paint is allocated, and adds 3 parts of deionized waters and 2 parts of emulsions, start circulation mixing pump, both are circulated mixing in electrophoresis tank；In premix groove, put into 2 parts of emulsions start stirring, the most slowly put into 2 parts of mill bases, after stirring 30 minutes, premix groove mixed liquor is the most uniformly inputted in electrophoresis tank；Throwing the water after 3 parts of deionized waters clean premix groove and will clean again and the most uniformly pump into electrophoresis tank, in constantly circulation, tank liquor transconversion into heat i.e. obtained carrying out the electrophoretic paint of application after 48 hours.
Embodiment 3:
A kind of high throwing power cathode electrophoresis dope, including in parts by mass, mill base 3 parts, emulsion 4 parts and deionized water 6 parts；
Described paste formula includes, waterborne cation epoxy resin 30 parts, color stuffing 40 parts, solvent 20 parts, nontoxic drier 1 part, dispersant 1 part, deionized water 35 parts
Described emulsion formulations includes, number-average molecular weight is 3000 amination modifying epoxy resin 45 parts, epoxy polyurethane resin 20 parts, cross-linking agent 25 parts, emulsifying agent 1 part, acetic acid 0.5 part and deionized water 50 parts；
Described amination modifying Formulaion of epoxy resin includes, epoxide equivalent be 200～1000 bisphenol A type epoxy resin 45 parts, solvent methylisobutyl ketone 10 parts, bisphenol A polyethenoxy ether 10 parts, number-average molecular weight be polyether Glycols 20 parts and the unimolecule amine 7 parts of 800；Wherein unimolecule amine is made up of the ketimide 4 parts of diethanolamine 4 parts He aminoethyl ethanolamine；
Described epoxy polyurethane resin formula includes, alcohol ethers and ketones solvent 20 parts, and epoxide equivalent is the bisphenol A type epoxy resin 35 parts of 600, diethanolamine 1 part, ketimide resin 20 parts；Described ketimide resin formula includes, molecular weight is the polyamide 60 part of 1000-3000, butanone 40 parts；
Described cross-linking agent is that type semienclosed polyurethane includes, TDI20 part, diethylene glycol ether 20 parts, PCDL 40 parts, butanone 30 parts.
A kind of high throwing power cathode electrophoresis dope preparation technology, comprises the following steps:
Prepared by A mill base, by waterborne cation epoxy resin 30 parts, color stuffing 40 parts, solvent 20 parts, nontoxic drier 1 part, dispersant 1 part, deionized water 35 parts, puts into dispersion pot, stands more than 8 hours under 700-1100 rev/min after dispersion, disperse 20-40 minute under 600-800 rev/min again, enter sand mill and be ground to fineness≤15 μm；
Prepared by B emulsion, 1. amination modifying epoxy resin is prepared, by bisphenol A type epoxy resin 45 parts that epoxide equivalent is 200～1000 and solvent methylisobutyl ketone 10 parts, it is heated to 110 DEG C together, until bisphenol A type epoxy resin is the most melted, cool to 90 DEG C subsequently, add the polyether Glycols 20 parts that number-average molecular weight is 800, be heated to 120 DEG C carry out chain extending reaction or heating catalyst in the presence of carry out chain extending reaction, be incubated 2 hours；It is cooled to 100 DEG C, after adding bisphenol A polyethenoxy ether 10 parts and solvent mix homogeneously, adds the ketimide 4 parts of diethanolamine 4 parts and aminoethyl ethanolamine, continue mixing 2 hours；2. prepare epoxy polyurethane resin, by epoxy resin 35 parts, alcohol ethers and 20 parts of stirring and dissolving at 50 DEG C-80 DEG C of ketones solvent, be subsequently added diethanolamine 1 part, react 2-3 hour at 80 DEG C-90 DEG C；After having reacted, at 75 DEG C-90 DEG C, drip ketimide resin 20 parts, be incubated 2 hours；3. by after amination modifying epoxy resin 45 parts and epoxy polyurethane resin 20 parts stirring mixing, it is heated to 100-120 DEG C；4. dripping or be dividedly in some parts cross-linking agent 25 parts, be incubated 1.5-2.5 hour, described cross-linking agent preparation method is, 20 parts of TDI is put into reaction pot, is dividedly in some parts or diethylene glycol ether 20 parts at 20-50 DEG C, PCDL 40 parts；It is warming up to 70 DEG C-90 DEG C again after being incubated 0.5-2 hour at 30-80 DEG C subsequently and is incubated 1.5-3 hour, butanone 30 parts, obtain type semienclosed polyurethane curing agent；5. cool to 70-90 DEG C, add emulsifying agent 1 part and nertralizer 0.5 part, dispersed with stirring 30-60 minute；6. cool to 30-70 DEG C, add deionized water 50 parts, continue stirring and obtain emulsion in 30-60 minute；
C electrophoretic paint is allocated, and adds 3 parts of deionized waters and 2 parts of emulsions, start circulation mixing pump, both are circulated mixing in electrophoresis tank；In premix groove, put into 2 parts of emulsions start stirring, the most slowly put into 3 parts of mill bases, after stirring 30 minutes, premix groove mixed liquor is the most uniformly inputted in electrophoresis tank；Throwing the water after 3 parts of deionized waters clean premix groove and will clean again and the most uniformly pump into electrophoresis tank, in constantly circulation, tank liquor transconversion into heat i.e. obtained carrying out the electrophoretic paint of application after 48 hours.
Table 1 is the film performance table of 3 embodiments of the present invention
| Index embodiment | Embodiment 1 | Embodiment 2 | Embodiment 3 |
| Outward appearance | Flat smooth is without shrinkage cavity | Flat smooth is without shrinkage cavity | Flat smooth is without shrinkage cavity |
| Throwing power (Ford box method) | 22.4mm | 22.5mm | 22.3mm |
| Voltage thickness V/ μm | 310/20 | 312/20 | 308/20 |
| Gloss 60% | 80 | 82 | 79 |
| Impact strength Kg cm | ≥50 | ≥50 | ≥50 |
| Cupping mm | 6.8 | 6.8 | 6.8 |
| Adhesive force/level | 0 | 0 | 0 |
| Pencil hardness/H | 2 | 2 | 2 |
| Alkali resistance (5%) | >120h | >120h | >120h |
| Acid resistance (0.05mol) | >48h | >48h | >48h |
| Resistance to water (40 DEG C), 360h | Qualified | Qualified | Qualified |
| Salt water resistance (3%) 25 DEG C, 360h | Qualified | Qualified | Qualified |
| Salt spray test phosphatization plate 21 ± 2 μ, 800h | Qualified | Qualified | Qualified |
| Resistance to gasoline (93#) | >240h | >240h | >240h |
Claims (10)
1. a high throwing power cathode electrophoresis dope, including mill base, emulsion and deionized water, it is characterised in that in parts by mass, described electrophoretic coating includes, mill base 2-3 part, emulsion 4-6 part and deionized water 5-7 part；
Described emulsion formulations includes, amination modifying epoxy resin 40-50 part, epoxy polyurethane resin 10-20 part, cross-linking agent 10-30 part, emulsifying agent 0.1-2 part, nertralizer 0.1-2 part and deionized water 30-50 part；
Described amination modifying Formulaion of epoxy resin includes, bisphenol A type epoxy resin 40-60 part, solvent methylisobutyl ketone 8-16 part, plasticizer 4-16 part, flexible polymer 10-35 part and unimolecule amine 3-8 part；
Described epoxy polyurethane resin formula includes, alcohol ethers and ketones solvent 10-30 part, epoxy resin 20-35 part, fatty amine 0.5-2 part, ketimide resin 10-25 part；
Described ketimide resin formula includes, polyetheramine or polyamide 6 0-80 part, butanone or methyl iso-butyl ketone (MIBK) 20-40 part；
Described cross-linking agent is type semienclosed and/or blocked polyurethane includes, aromatic polyisocyanate 5-20 part, alcohol ether compound, heterocycle compound one of them or two or more mixing 3-30 part, polyethers or PCDL 0-80 part, ketones solvent 0-40 part.
One the most according to claim 1 high throwing power cathode electrophoresis dope, it is characterised in that described paste formula includes, waterborne cation epoxy resin 20-40 part, color stuffing 10-40 part, solvent 10-20 part, nontoxic drier 0.5-1.5 part, dispersant 0.5-2 part, deionized water 20-50 part.
One the most according to claim 2 high throwing power cathode electrophoresis dope, it is characterized in that, described unimolecule amine at least contains the one in the ketimide of aminoethyl ethanolamine or the diketimine of diethylenetriamines, its consumption at least accounts for the 50% of the total consumption of unimolecule amine, and other compositions in unimolecule amine are one or more in butylamine, octylame, diethylamine, methylbutylamine, monoethanolamine, diethanolamine or N-methylethanolamine.
One the most according to claim 3 high throwing power cathode electrophoresis dope, it is characterised in that the epoxide equivalent of described bisphenol A type epoxy resin is 200～1000.
One the most according to claim 4 high throwing power cathode electrophoresis dope, it is characterised in that described flexible polymer is polyether Glycols, polyester diol or polyethers diamine, its number-average molecular weight is 400～1500.
One the most according to claim 5 high throwing power cathode electrophoresis dope, it is characterised in that the number-average molecular weight of described amination modifying epoxy resin is 1500～3500.
One the most according to claim 6 high throwing power cathode electrophoresis dope, it is characterised in that described plasticizer is bisphenol A polyethenoxy ether or bisphenol-A polyethenoxy ether.
One the most according to claim 2 high throwing power cathode electrophoresis dope, it is characterised in that described epoxy resin be epoxide equivalent be the bisphenol A type epoxy resin between 180-1000 or phenol aldehyde modified epoxy resin.
One the most according to claim 8 high throwing power cathode electrophoresis dope, it is characterised in that the amine number of described polyamide is 80-380, molecular weight is 1000-3000.
One the most according to claim 9 high throwing power cathode electrophoresis dope, it is characterised in that described nertralizer is formic acid, acetic acid, propanoic acid, lactic acid, oxalic acid or other organic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108384308A (en) * | 2018-03-12 | 2018-08-10 | 镇江百胜千隆新材料科技有限公司 | A kind of aqueous cathode electrophoresis dope and its manufacture craft |
| CN108587413A (en) * | 2018-05-30 | 2018-09-28 | 安徽润晟建设有限公司 | A kind of exterior wall waterborne epoxy coatings |
| CN110105845A (en) * | 2019-05-27 | 2019-08-09 | 枣阳市旺前电泳涂料有限公司 | A kind of cathode epoxy electrophoretic paint and its production method |
| CN111088515A (en) * | 2019-12-31 | 2020-05-01 | 枣阳市旺前电泳涂料有限公司 | High-throwing-power electrophoretic paint mixing tank method |
| 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 |
| CN114736353A (en) * | 2022-03-01 | 2022-07-12 | 天津市新丽华色材有限责任公司 | Special toughening resin for cathode electrophoretic coating and preparation method and application thereof |
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| CN102838846A (en) * | 2012-09-26 | 2012-12-26 | 中国海洋石油总公司 | Resin emulsion for cathode electrophoretic coating with high throwing power and preparation method thereof |
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| CN101362919A (en) * | 2008-09-25 | 2009-02-11 | 江泽平 | Single-component cationoid water-soluble epoxy-polyurethane anticorrosion primer system drying at 150 DEG C |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108384308A (en) * | 2018-03-12 | 2018-08-10 | 镇江百胜千隆新材料科技有限公司 | A kind of aqueous cathode electrophoresis dope and its manufacture craft |
| CN108587413A (en) * | 2018-05-30 | 2018-09-28 | 安徽润晟建设有限公司 | A kind of exterior wall waterborne epoxy coatings |
| CN110105845A (en) * | 2019-05-27 | 2019-08-09 | 枣阳市旺前电泳涂料有限公司 | A kind of cathode epoxy electrophoretic paint and its production method |
| CN111088515A (en) * | 2019-12-31 | 2020-05-01 | 枣阳市旺前电泳涂料有限公司 | High-throwing-power electrophoretic paint mixing tank method |
| 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 |
| CN114736353A (en) * | 2022-03-01 | 2022-07-12 | 天津市新丽华色材有限责任公司 | Special toughening resin for cathode electrophoretic coating and preparation method and application thereof |
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