CN117659812A - High throwing power electrophoretic paint and preparation method and application thereof - Google Patents
High throwing power electrophoretic paint and preparation method and application thereof Download PDFInfo
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- CN117659812A CN117659812A CN202311611599.8A CN202311611599A CN117659812A CN 117659812 A CN117659812 A CN 117659812A CN 202311611599 A CN202311611599 A CN 202311611599A CN 117659812 A CN117659812 A CN 117659812A
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- 239000003973 paint Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000049 pigment Substances 0.000 claims abstract description 62
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000003822 epoxy resin Substances 0.000 claims abstract description 43
- 229920000647 polyepoxide Polymers 0.000 claims abstract description 43
- 238000002156 mixing Methods 0.000 claims abstract description 39
- 239000006087 Silane Coupling Agent Substances 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000003756 stirring Methods 0.000 claims abstract description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000000126 substance Substances 0.000 claims abstract description 20
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 19
- 239000011248 coating agent Substances 0.000 claims abstract description 18
- 238000000576 coating method Methods 0.000 claims abstract description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims abstract description 15
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 15
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 claims abstract description 10
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 14
- PTBDIHRZYDMNKB-UHFFFAOYSA-N 2,2-Bis(hydroxymethyl)propionic acid Chemical compound OCC(C)(CO)C(O)=O PTBDIHRZYDMNKB-UHFFFAOYSA-N 0.000 claims description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 13
- 229910021389 graphene Inorganic materials 0.000 claims description 13
- 229910052751 metal Inorganic materials 0.000 claims description 13
- 239000002184 metal Substances 0.000 claims description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 11
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 11
- -1 polydimethylsiloxane Polymers 0.000 claims description 11
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 7
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 7
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 claims description 7
- 239000004842 bisphenol F epoxy resin Substances 0.000 claims description 7
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- 239000003963 antioxidant agent Substances 0.000 claims description 6
- 230000003078 antioxidant effect Effects 0.000 claims description 6
- 239000004841 bisphenol A epoxy resin Substances 0.000 claims description 6
- PXKLMJQFEQBVLD-UHFFFAOYSA-N bisphenol F Chemical compound C1=CC(O)=CC=C1CC1=CC=C(O)C=C1 PXKLMJQFEQBVLD-UHFFFAOYSA-N 0.000 claims description 6
- 239000004408 titanium dioxide Substances 0.000 claims description 6
- 239000002518 antifoaming agent Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000004094 surface-active agent Substances 0.000 claims description 4
- 239000006097 ultraviolet radiation absorber Substances 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 3
- 229940083957 1,2-butanediol Drugs 0.000 claims description 2
- ZXDDPOHVAMWLBH-UHFFFAOYSA-N 2,4-Dihydroxybenzophenone Chemical compound OC1=CC(O)=CC=C1C(=O)C1=CC=CC=C1 ZXDDPOHVAMWLBH-UHFFFAOYSA-N 0.000 claims description 2
- JKIJEFPNVSHHEI-UHFFFAOYSA-N Phenol, 2,4-bis(1,1-dimethylethyl)-, phosphite (3:1) Chemical compound CC(C)(C)C1=CC(C(C)(C)C)=CC=C1OP(OC=1C(=CC(=CC=1)C(C)(C)C)C(C)(C)C)OC1=CC=C(C(C)(C)C)C=C1C(C)(C)C JKIJEFPNVSHHEI-UHFFFAOYSA-N 0.000 claims description 2
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 2
- BMRWNKZVCUKKSR-UHFFFAOYSA-N butane-1,2-diol Chemical compound CCC(O)CO BMRWNKZVCUKKSR-UHFFFAOYSA-N 0.000 claims description 2
- ZQBAKBUEJOMQEX-UHFFFAOYSA-N phenyl salicylate Chemical compound OC1=CC=CC=C1C(=O)OC1=CC=CC=C1 ZQBAKBUEJOMQEX-UHFFFAOYSA-N 0.000 claims description 2
- PNGBYKXZVCIZRN-UHFFFAOYSA-M sodium;hexadecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCCCCCS([O-])(=O)=O PNGBYKXZVCIZRN-UHFFFAOYSA-M 0.000 claims description 2
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- 239000010960 cold rolled steel Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- 238000004070 electrodeposition Methods 0.000 description 5
- 238000001962 electrophoresis Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 3
- 239000007888 film coating Substances 0.000 description 3
- 238000009501 film coating Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 125000005373 siloxane group Chemical group [SiH2](O*)* 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4473—Mixture of polymers
-
- 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
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4457—Polyepoxides containing special additives, e.g. pigments, polymeric particles
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of paint, and discloses a high throwing power electrophoretic paint, and a preparation method and application thereof. The preparation method comprises the following steps: mixing epoxy resin, dihydroxypolydimethylsiloxane, adamantane, a silane coupling agent, an alcohol substance and water under stirring, adding a modified pigment and an auxiliary agent, and mixing to prepare the electrophoretic coating; the preparation process of the modified pigment comprises the following steps: and (3) stirring and mixing the pigment, polyethylene glycol, a silane coupling agent, 2-dimethylolpropionic acid, sodium dodecyl sulfonate and water to obtain the modified pigment. The electrophoretic paint has throwing power exceeding 66.0% and even 71.1%, and the paint film formed with the electrophoretic paint has impact strength exceeding 58kg cm.
Description
Technical Field
The invention belongs to the technical field of paint, and particularly relates to a high throwing power electrophoretic paint, and a preparation method and application thereof.
Background
The cathode electrophoretic paint belongs to a common paint, is often coated on the surface of metal parts, and has attractive effect, and also has the remarkable anti-corrosion protection effect on the metal parts. However, the existing metal parts often have irregular shapes, and generally have uneven surfaces, such as convex, concave, slit, and the like. Because of the irregular shape of the metal parts, the existing electrophoretic paint forms uneven film on the surfaces of the metal parts (such as thicker film forming at some parts, thinner film forming at some inner cavities and even difficult film forming at some places), which is mainly attributed to poor throwing power of the electrophoretic paint. The electrophoretic paint with poor throwing power easily causes huge corrosion resistance difference of different positions of the same metal part, and causes adverse effect on the service life of the metal part. Uneven film formation also causes poor appearance of the metal parts.
In the existing electrophoretic paint, the film forming problem is also improved, however, the complex modification of the epoxy resin is often required, which clearly increases the manufacturing cost of the electrophoretic paint. In addition, the throwing power of the prepared electrophoretic paint is difficult to exceed 66.0 percent (tested by a four-box method), and the impact strength of the film layer is always only about 52kg cm, which is difficult to meet the further requirements of industry.
Therefore, there is a need to provide a new electrodeposition coating material which has good throwing power and good film formation appearance.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. Therefore, the invention provides the high throwing power electrophoretic paint, and the preparation method and the application thereof. The electrophoretic paint has throwing power of over 66.0% and even 71.1%, and the paint film formed with the electrophoretic paint has impact strength over 58kg cm.
The invention is characterized in that: the electrophoretic coating is prepared by directly using epoxy resin, dihydroxy polydimethylsiloxane, adamantane, a silane coupling agent, an alcohol substance, a modified pigment, an auxiliary agent and water. According to the invention, epoxy resin, dihydroxyl polydimethylsiloxane and adamantane are used as film forming basic components of the coating, and as the dihydroxyl polydimethylsiloxane is introduced, not only is siloxane groups introduced, but also the dihydroxyl structure is easier to act with other components to form a more stable network structure, and the unique dry skeleton structure of adamantane further improves the space of the coating after film forming, so that the compatibility and dispersion uniformity of modified pigment and film forming substances are facilitated. The pigment is modified by polyethylene glycol, a silane coupling agent and 2, 2-dimethylolpropionic acid, and the obtained pigment surface is grafted with a hydroxyl structure, so that not only is the dispersion stability of the pigment improved, but also the compatibility of the modified pigment and a film-forming substance is obviously improved, and the throwing power and impact resistance of the electrophoretic coating are improved. In the process of preparing the electrophoretic paint, graphene oxide is further added, and due to the special two-dimensional electronic structure of the graphene oxide, the graphene oxide has electronic interaction with the pigment and adamantane, so that the throwing power of the electrophoretic paint is further improved.
The first aspect of the invention provides a preparation method of the high throwing power electrophoretic paint.
In particular to a preparation method of an electrophoretic paint with high throwing power, which comprises the following steps:
mixing epoxy resin, dihydroxypolydimethylsiloxane, adamantane, a silane coupling agent, an alcohol substance and water under stirring, adding a modified pigment and an auxiliary agent, and mixing to obtain the electrophoretic coating;
the preparation process of the modified pigment comprises the following steps: and (3) stirring and mixing the pigment, polyethylene glycol, a silane coupling agent, 2-dimethylolpropionic acid, sodium dodecyl sulfonate and water to obtain the modified pigment.
Preferably, the weight ratio of the epoxy resin to the dihydroxy polydimethylsiloxane to the adamantane to the silane coupling agent to the alcohol substances to the water to the modified pigment is 50: (8-15): (0.3-3): (5-15): (3-15): (50-120): (40-80); further preferably 50: (10-15): (0.5-1.5): (6-12): (5-12): (60-100): (40-80). The reasonable relation of the dosage of each component is favorable for obtaining the electrophoretic coating with good performance.
Preferably, the preparation process of the modified pigment comprises the following steps: according to the weight portions, 10 portions of pigment, 10 to 20 portions of polyethylene glycol, 8 to 20 portions of silane coupling agent, 1 to 5 portions of 2, 2-dimethylolpropionic acid, 3 to 10 portions of sodium dodecyl sulfate and 50 to 100 portions of water are stirred and mixed to obtain the modified pigment.
Further preferably, the preparation process of the modified pigment comprises the following steps: according to parts by weight, 10 parts of pigment, 10-20 parts of polyethylene glycol, 8-20 parts of silane coupling agent, 1-5 parts of 2, 2-dimethylolpropionic acid, 3-10 parts of sodium dodecyl sulfate and 50-100 parts of water are stirred and mixed for 1-3 hours at 60-90 ℃ to obtain the modified pigment.
Preferably, the epoxy resin is selected from bisphenol a type epoxy resin and/or bisphenol F type epoxy resin; further preferably, the epoxy resin is bisphenol A epoxy resin and bisphenol F epoxy resin, and the weight ratio of the epoxy resin to the bisphenol F epoxy resin is 1: (0.8-1.2). At this ratio, the resulting electrocoat performs better.
Preferably, the alcohol is at least one selected from ethanol, 1, 2-butanediol or glycerol.
Preferably, the pigment is selected from any one of titanium dioxide and ferric oxide.
Preferably, the auxiliary agent comprises at least one of a curing agent, a surfactant, a defoaming agent, an antioxidant and an ultraviolet absorber.
Preferably, the curing agent is at least one selected from diethylenetriamine, allyl ether and phthalic anhydride.
Preferably, the surfactant is selected from at least one of sodium dodecyl sulfonate or sodium hexadecyl sulfonate.
Preferably, the defoaming agent is silicone oil.
Preferably, the antioxidant is selected from at least one of antioxidant 1010 or antioxidant 168.
Preferably, the ultraviolet absorber comprises at least one of phenyl orthohydroxybenzoate or 2, 4-dihydroxybenzophenone.
Preferably, the solvent is water, more preferably deionized water.
Preferably, the silane coupling agent is selected from at least one of KH550 or KH 560.
Preferably, the preparation method of the high throwing power electrophoretic paint comprises the following steps:
mixing epoxy resin, dihydroxypolydimethylsiloxane, adamantane, a silane coupling agent, an alcohol substance and water under stirring, wherein the temperature of the stirring and mixing is 60-80 ℃, the time of the stirring and mixing is 30-60 minutes, and then adding a modified pigment and an auxiliary agent, wherein the weight ratio of the epoxy resin to the dihydroxypolydimethylsiloxane to the adamantane to the silane coupling agent is 50: (8-15): (0.3-3): (5-15): (3-15): (50-120): (40-80), the weight ratio of the epoxy resin to the auxiliary agent is 50: (3-20), mixing (the mixing stirring speed is 800-1500 rpm, and the mixing time is 20-40 minutes) to obtain the electrophoretic paint;
the preparation process of the modified pigment comprises the following steps: according to parts by weight, 10 parts of pigment, 10-20 parts of polyethylene glycol, 8-20 parts of silane coupling agent, 1-5 parts of 2, 2-dimethylolpropionic acid, 3-10 parts of sodium dodecyl sulfate and 50-100 parts of water are stirred and mixed for 1-3 hours at 60-90 ℃ to obtain the modified pigment.
Preferably, when the epoxy resin is added, graphene oxide is also added. For example, 0.1 to 1 part of graphene oxide is added. The addition of the graphene oxide is beneficial to improving the throwing power of the electrophoretic paint.
In a second aspect, the present invention provides a high throwing power electrophoretic paint.
In particular to a preparation method of the high throwing power electrophoretic paint.
Preferably, the electrocoat has a throwing power exceeding 66.0%, such as a throwing power of 67.0-71.0%, and even 71.1%.
Preferably, the electrodeposition coating composition forms a paint film having an impact resistance exceeding 58kg cm, for example, 59 to 65kg cm.
A third aspect of the present invention provides the use of a high throwing power electrophoretic coating.
A metal device comprises a film layer formed by the electrophoretic paint.
Preferably, the metal device is a metal device containing iron, aluminum or copper. Such as metal parts in appliances.
Compared with the prior art, the invention has the following beneficial effects:
(1) The electrophoretic coating is prepared by directly using epoxy resin, dihydroxy polydimethylsiloxane, adamantane, a silane coupling agent, an alcohol substance, a modified pigment, an auxiliary agent and water. According to the invention, epoxy resin, dihydroxyl polydimethylsiloxane and adamantane are used as film forming basic components of the coating, and as the dihydroxyl polydimethylsiloxane is introduced, not only is siloxane groups introduced, but also the dihydroxyl structure is easier to act with other components to form a more stable network structure, and the unique dry skeleton structure of adamantane further improves the space of the coating after film forming, so that the compatibility and dispersion uniformity of modified pigment and film forming substances are facilitated. The pigment is modified by polyethylene glycol, a silane coupling agent and 2, 2-dimethylolpropionic acid, and the obtained pigment surface is grafted with a hydroxyl structure, so that not only is the dispersion stability of the pigment improved, but also the compatibility of the modified pigment and a film-forming substance is obviously improved, and the throwing power and impact resistance of the electrophoretic coating are improved.
(2) In the process of preparing the electrophoretic paint, graphene oxide is further added, and due to the special two-dimensional electronic structure of the graphene oxide, the graphene oxide has electronic interaction with the pigment and adamantane, so that the throwing power of the electrophoretic paint is further improved.
Detailed Description
In order to make the technical solutions of the present invention more apparent to those skilled in the art, the following examples will be presented. It should be noted that the following examples do not limit the scope of the invention.
The starting materials, reagents or apparatus used in the following examples are all available from conventional commercial sources or may be obtained by methods known in the art unless otherwise specified.
Example 1: preparation of electrophoretic paint
A preparation method of the high throwing power electrophoretic paint comprises the following steps:
epoxy resin (bisphenol A epoxy resin and bisphenol F epoxy resin in a weight ratio of 1:1), dihydroxypolydimethylsiloxane, adamantane, silane coupling agent KH560, alcohol substance (glycerol) and water are stirred and mixed at a temperature of 70 ℃ for 40 minutes, then modified pigment and auxiliary agent (diethylenetriamine 1 part, allyl ether 2 part, phthalic anhydride 2 part, sodium dodecyl sulfonate 1.5 part and silicone oil 1.5 part) are added, and the weight ratio of epoxy resin, dihydroxypolydimethylsiloxane, adamantane, silane coupling agent, alcohol substance, water and modified pigment is 50:10:1:8:10:80:70, the weight ratio of the epoxy resin to the auxiliary agent is 50:8, mixing (the mixing stirring speed is 1000 rpm, and the mixing time is 30 minutes) to prepare the electrophoretic paint;
the preparation process of the modified pigment comprises the following steps: 10 parts of titanium dioxide, 15 parts of polyethylene glycol, 10 parts of silane coupling agent KH560, 4 parts of 2, 2-dimethylolpropionic acid, 5 parts of sodium dodecyl sulfate and 55 parts of water are stirred and mixed for 2.5 hours at 80 ℃ to obtain the modified pigment.
Example 2: preparation of electrophoretic paint
A preparation method of the high throwing power electrophoretic paint comprises the following steps:
mixing epoxy resin (bisphenol A epoxy resin and bisphenol F epoxy resin in a weight ratio of 1:0.8), dihydroxy polydimethylsiloxane, adamantane, silane coupling agent KH550, alcohol substances (glycerol) and water under stirring, wherein the temperature of the stirring and mixing is 75 ℃, the time of the stirring and mixing is 35 minutes, and then adding modified pigment and auxiliary agent (1 part of diethylenetriamine, 2 parts of allyl ether, 2 parts of phthalic anhydride, 1 part of sodium dodecyl sulfonate, 2 parts of silicone oil and 1010 0.5 part of antioxidant) in a weight ratio of 50:12:0.8:7:12:85:65, the weight ratio of the epoxy resin to the auxiliary agent is 50:8.5, mixing (the mixing stirring speed is 1200 rpm, and the mixing time is 40 minutes) to prepare the electrophoretic paint;
the preparation process of the modified pigment comprises the following steps: according to the parts by weight, 10 parts of titanium dioxide, 12 parts of polyethylene glycol, 11 parts of silane coupling agent KH550, 2 parts of 2, 2-dimethylolpropionic acid, 5 parts of sodium dodecyl sulfate and 50 parts of water are stirred and mixed for 2 hours at 85 ℃ to obtain the modified pigment.
Example 3: preparation of electrophoretic paint
A preparation method of the high throwing power electrophoretic paint comprises the following steps:
mixing epoxy resin (bisphenol A epoxy resin and bisphenol F epoxy resin in a weight ratio of 1:1.2), dihydroxy polydimethylsiloxane, adamantane, silane coupling agent KH550, alcohol substances (glycerol) and water under stirring, wherein the temperature of the stirring and mixing is 75 ℃, the time of the stirring and mixing is 35 minutes, and then adding modified pigment and auxiliary agent (1 part of diethylenetriamine, 2 parts of allyl ether, 2 parts of phthalic anhydride, 1 part of sodium dodecyl sulfonate, 2 parts of silicone oil and 1010 0.5 part of antioxidant) in a weight ratio of 50:11:0.9:8:12:85:65, the weight ratio of the epoxy resin to the auxiliary agent is 50:8.5, mixing (the mixing stirring speed is 1200 rpm, and the mixing time is 40 minutes) to prepare the electrophoretic paint;
the preparation process of the modified pigment comprises the following steps: 10 parts of ferric oxide, 17 parts of polyethylene glycol, 12 parts of a silane coupling agent KH550, 3 parts of 2, 2-dimethylolpropionic acid, 5 parts of sodium dodecyl sulfate and 50 parts of water are stirred and mixed for 2 hours at 85 ℃ to obtain a modified pigment.
Example 4: preparation of electrophoretic paint
A preparation method of the high throwing power electrophoretic paint comprises the following steps:
epoxy resin (bisphenol A epoxy resin and bisphenol F epoxy resin in a weight ratio of 1:1), graphene oxide, dihydroxypolydimethylsiloxane, adamantane, a silane coupling agent KH560, an alcohol substance (glycerol) and water are stirred and mixed for 40 minutes at a temperature of 70 ℃, and then modified pigment and auxiliary agent (1 part of diethylenetriamine, 2 parts of allyl ether, 2 parts of phthalic anhydride, 1.5 parts of sodium dodecyl sulfonate and 1.5 parts of silicone oil) are added, wherein the weight ratio of epoxy resin to dihydroxypolydimethylsiloxane to adamantane to the silane coupling agent to the alcohol substance to the water to the modified pigment is 50:10:1:8:10:80:70, the weight ratio of the epoxy resin to the graphene oxide is 50:0.2, the weight ratio of the epoxy resin to the auxiliary agent is 50:8, mixing (the mixing stirring speed is 1000 rpm, and the mixing time is 30 minutes) to prepare the electrophoretic paint;
the preparation process of the modified pigment comprises the following steps: 10 parts of titanium dioxide, 15 parts of polyethylene glycol, 10 parts of silane coupling agent KH560, 4 parts of 2, 2-dimethylolpropionic acid, 5 parts of sodium dodecyl sulfate and 55 parts of water are stirred and mixed for 2.5 hours at 80 ℃ to obtain the modified pigment.
Example 5: preparation of electrophoretic paint
A preparation method of the high throwing power electrophoretic paint comprises the following steps:
mixing epoxy resin (bisphenol A type epoxy resin), dihydroxypolydimethylsiloxane, adamantane, silane coupling agent KH560, alcohol substance (glycerol) and water under stirring, wherein the temperature of the stirring and mixing is 70 ℃, the stirring and mixing time is 40 minutes, and then adding modified pigment and auxiliary agent (1 part of diethylenetriamine, 2 parts of allyl ether, 2 parts of phthalic anhydride, 1.5 parts of sodium dodecyl sulfonate and 1.5 parts of silicone oil), wherein the weight ratio of epoxy resin, dihydroxypolydimethylsiloxane, adamantane, silane coupling agent, alcohol substance, water and modified pigment is 50:10:1:8:10:80:70, the weight ratio of the epoxy resin to the auxiliary agent is 50:8, mixing (the mixing stirring speed is 1000 rpm, and the mixing time is 30 minutes) to prepare the electrophoretic paint;
the preparation process of the modified pigment comprises the following steps: 10 parts of titanium dioxide, 15 parts of polyethylene glycol, 10 parts of silane coupling agent KH560, 4 parts of 2, 2-dimethylolpropionic acid, 5 parts of sodium dodecyl sulfate and 55 parts of water are stirred and mixed for 2.5 hours at 80 ℃ to obtain the modified pigment.
Comparative example 1
In comparison with example 1, comparative example 1 uses the same amount of dihydroxypolydimethylsiloxane instead of adamantane, and the rest of the components are the same as in example 1.
Comparative example 2
In comparison with example 1, the modified pigment of comparative example 2 was prepared without using 2, 2-dimethylolpropionic acid, and the remaining components and processes were the same as in example 1.
Comparative example 3
In comparison with example 1, the same amount of polyethylene glycol was used instead of dihydroxy polydimethylsiloxane in comparative example 1, and the remaining components were the same as in example 1.
Product effect test
The electrodeposition coating materials prepared in examples 1, 4 and 5 and comparative examples 1 to 3 were each subjected to electrodeposition coating. In the electrophoresis film coating process, the temperature of an electrophoresis tank is set to 25 ℃, an anode is a stainless steel container, a cathode is a cold-rolled steel plate (200 mm long, 80mm wide and 2mm thick) treated by zinc phosphate, electrophoresis is carried out for 3 minutes at 250V, the coated cold-rolled steel plate is taken out from the electrophoresis tank after film coating, water is used for washing 3 times, baking is carried out for 18 minutes at 160 ℃, and an electrophoresis film coating layer is formed on the cold-rolled steel plate. The appearance of the film layer on the surface of the cold-rolled steel sheet was then observed, and the throwing power performance was tested (see HG/T3334-2012, general test method for electrophoretic paint, 4.3.2, test for electrophoretic paint throwing power-four-box method), and the impact strength of the film layer was tested (see GB/T1732-79, test for impact resistance of paint film), and the results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the film-forming appearance, throwing power, and impact resistance of the electrodeposition coating materials prepared in examples were significantly superior to those of comparative examples 1 to 3.
From the results of example 1 and comparative examples 1-3, it can be seen that the use of dihydroxypolydimethylsiloxane, adamantane, 2 dimethylolpropionic acid has a great influence on the properties of the film layer. As can be seen from examples 1 and 4, the addition of graphene oxide helps to further improve the throwing power of the film layer; the epoxy resin in example 5 is bisphenol a type epoxy resin, thus resulting in a decrease in film properties relative to example 1, and it can be seen that the film properties obtained are better when a bisphenol a type epoxy resin and bisphenol F type epoxy resin compounding scheme is used.
The effects of the other embodiments described above are similar to those of embodiment 1.
In addition, taking the cold-rolled steel sheet corresponding to the embodiment 1 of the invention and the coated workpiece prepared in the embodiment 4 of CN109627951A, immersing the cold-rolled steel sheet in hydrochloric acid of 0.1mol/L at 40 ℃ to observe the appearance of the surface film layer, the result shows that the cold-rolled steel sheet corresponding to the embodiment 1 of the invention starts to have local pinholes at 36 hours, and the coated workpiece prepared in the embodiment 4 of CN109627951A has the local pinholes at 24 hours. Therefore, the film layer formed by the electrophoretic paint has better corrosion resistance.
Claims (11)
1. The preparation method of the electrophoretic paint is characterized by comprising the following steps:
mixing epoxy resin, dihydroxypolydimethylsiloxane, adamantane, a silane coupling agent, an alcohol substance and water under stirring, adding a modified pigment and an auxiliary agent, and mixing to obtain the electrophoretic coating;
the preparation process of the modified pigment comprises the following steps: and stirring and mixing the pigment, polyethylene glycol, a silane coupling agent, 2-dimethylolpropionic acid, sodium dodecyl sulfonate and water to obtain the modified pigment.
2. The preparation method according to claim 1, wherein the weight ratio of the epoxy resin, the dihydroxy polydimethylsiloxane, the adamantane, the silane coupling agent, the alcohol substance, the water and the modified pigment is 50: (8-15): (0.3-3): (5-15): (3-15): (50-120): (40-80).
3. The preparation method according to claim 1, wherein the preparation process of the modified pigment comprises the steps of: according to the weight portions, 10 portions of pigment, 10 to 20 portions of polyethylene glycol, 8 to 20 portions of silane coupling agent, 1 to 5 portions of 2, 2-dimethylolpropionic acid, 3 to 10 portions of sodium dodecyl sulfate and 50 to 100 portions of water are stirred and mixed to obtain the modified pigment.
4. The method according to claim 1, wherein the alcohol is at least one selected from ethanol, 1, 2-butanediol, and glycerol; and/or the pigment is selected from any one of titanium dioxide and ferric oxide.
5. The method according to claim 1, wherein the auxiliary agent comprises at least one of a curing agent, a surfactant, a defoaming agent, an antioxidant, and an ultraviolet absorber.
6. The method according to claim 5, wherein the epoxy resin is selected from bisphenol a type epoxy resin and/or bisphenol F type epoxy resin; and/or the curing agent is at least one selected from diethylenetriamine, allyl ether and phthalic anhydride.
7. The preparation method according to claim 6, wherein the epoxy resin is bisphenol a epoxy resin and bisphenol F epoxy resin in a weight ratio of 1: (0.8-1.2).
8. The method according to claim 5, wherein the surfactant is at least one selected from sodium dodecyl sulfonate and sodium hexadecyl sulfonate; and/or, the defoaming agent is silicone oil; and/or the antioxidant is selected from at least one of antioxidant 1010 or antioxidant 168; and/or the ultraviolet absorber comprises at least one of phenyl orthohydroxybenzoate or 2, 4-dihydroxybenzophenone.
9. The method according to claim 1, wherein graphene oxide is further added when the epoxy resin is added.
10. A method of preparing an electrophoretic coating, characterized in that it is prepared by the preparation method of any one of claims 1 to 9.
11. A metal device comprising a film layer formed from the electrocoat of claim 10.
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| CN202311611599.8A CN117659812A (en) | 2023-11-29 | 2023-11-29 | High throwing power electrophoretic paint and preparation method and application thereof |
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