CN111073459A - Energy-saving and environment-friendly cathode electrophoretic coating - Google Patents
Energy-saving and environment-friendly cathode electrophoretic coating Download PDFInfo
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- CN111073459A CN111073459A CN201911413785.4A CN201911413785A CN111073459A CN 111073459 A CN111073459 A CN 111073459A CN 201911413785 A CN201911413785 A CN 201911413785A CN 111073459 A CN111073459 A CN 111073459A
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
- C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
- C08G59/4014—Nitrogen containing compounds
- C08G59/4028—Isocyanates; Thioisocyanates
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
- C09D5/10—Anti-corrosive paints containing metal dust
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- 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
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- 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
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/08—Metals
- C08K2003/0881—Titanium
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses an energy-saving and environment-friendly cathode electrophoretic coating, which comprises water, color paste, an auxiliary agent and an emulsion; the solid content of the electrophoretic coating is 20 wt%, and the ash content is 10 wt%; the emulsion comprises 100 parts by mass of amine modified epoxy resin, 20-30 parts by mass of a totally-enclosed curing agent, 2-3 parts by mass of a bismuth-zinc composite drier, 1.6-1.8 parts by mass of a neutralizer, 1.5 parts by mass of an auxiliary agent and 130 parts by mass of deionized water; the totally-enclosed curing agent is prepared by the reaction of m-xylylene diisocyanate, methyl isobutyl ketone, methyl ethyl ketone oxime and ethylene glycol hexyl ether. The epoxy cathode electrophoretic paint with ultralow temperature, no tin and high corrosion resistance is prepared by selecting a sealing agent of an isocyanate curing agent and the like.
Description
Technical Field
The invention relates to the field of ultralow-temperature coatings, in particular to an energy-saving and environment-friendly cathode electrophoretic coating.
Background
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 and the coating method are industrially applied after the 60 s in the 20 th century, a fully-closed circulating system can be operated by adopting the electrophoretic coating, and the utilization rate of the coating can reach about 95 percent. 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. The electrophoretic paint can be divided into anode electrophoretic paint and cathode electrophoretic paint according to the electrode of the workpiece to be coated; the anionic electrophoretic coating and the cationic electrophoretic coating can be classified according to the ionic form of the film-forming material in water. The cathode electrophoretic paint can be divided into a single-component electrophoretic paint and a two-component electrophoretic paint according to the water dispersion state; it can be divided into film type, medium thick film and thick film type cathode electrophoretic paint according to the thickness of the film. The cathodic electrophoretic paint can be divided into: epoxy electrophoretic paint, acrylic electrophoretic paint, and polyurethane electrophoretic paint. Epoxy electrophoretic paint: the salt spray performance on a phosphorized substrate can reach more than 1000 hours, and the main mature products are mainly bright black, dumb black, dark gray and light gray. The epoxy electrophoretic paint is a paint capable of covering a substrate, is mainly used for primer corrosion prevention, and can also be used as a finish paint for hardware workpieces with general requirements.
The baking temperature range of the common epoxy cathode electrophoretic coating is generally 160-180 ℃, and heavy metals such as lead, tin and the like are required to be used as catalytic deblocking agents. For some workpieces with special purposes, especially automobile parts and hardware parts with rubber, plastics and the like, the workpieces are easy to deform during high-temperature baking. And the traditional cathode electrophoretic paint drier is lead and tin, but the use of the traditional cathode electrophoretic paint drier is forbidden by China and European Union in sequence due to the environmental protection problem, so that an energy-saving and environment-friendly cathode electrophoretic paint needs to be designed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an energy-saving and environment-friendly cathode electrophoretic coating.
The invention is realized by the following scheme:
an energy-saving and environment-friendly cathode electrophoretic coating comprises water, color paste, an auxiliary agent and an emulsion; the solid content of the electrophoretic coating is 20 wt%, and the ash content is 10 wt%;
the emulsion comprises 100 parts by mass of amine modified epoxy resin, 20-30 parts by mass of a totally-enclosed curing agent, 2-3 parts by mass of a bismuth-zinc composite drier, 1.6-1.8 parts by mass of a neutralizer, 1.5 parts by mass of an auxiliary agent and 130 parts by mass of deionized water;
the totally-enclosed curing agent is prepared by the reaction of m-xylylene diisocyanate, methyl isobutyl ketone, methyl ethyl ketone oxime and ethylene glycol hexyl ether.
The color paste comprises, by mass, 20 parts of quaternary ammonium salt dispersion resin, 25 parts of deionized water, 15 parts of kaolin, 0.2-0.5 part of carbon black, 5 parts of an emulsifier, 20-25 parts of rutile titanium dioxide and 10-15 parts of titanium-based sodium rice paste.
The formula of the titanium-based sodium rice pulp comprises, by mass, 80 parts of metal nano titanium particles, 10 parts of epoxy resin, 3 parts of silane coupling agent and 10 parts of butanone.
The neutralizer comprises formic acid, acetic acid, lactic acid and maleic acid.
The auxiliary agent comprises isopropanol, sec-butyl alcohol, dipropylene glycol methyl ether and propylene glycol methyl ether.
The preparation method of the emulsion comprises the following steps: 100 parts of amine modified epoxy resin, 20-30 parts of totally-enclosed curing agent and 2-3 parts of bismuth-zinc composite drier are mixed and stirred uniformly, then 1.6-1.8 parts of neutralizer, 1.5 parts of auxiliary agent and 120-130 parts of deionized water are sequentially added and stirred uniformly, and emulsion is obtained after emulsification.
The preparation method of the totally-enclosed curing agent comprises the following steps: 188.2 parts of m-xylylene diisocyanate and 85.0 parts of methyl isobutyl ketone are weighed in parts by mass and added into a reaction vessel, stirring is started, condensed water is turned on, and N is introduced2Heating to 70 ℃, weighing 87.5 parts of methyl ethyl ketone oxime, adding the methyl ethyl ketone oxime into a constant pressure titration funnel, beginning to dropwise add the methyl ethyl ketone oxime into a reaction container, keeping the temperature of the reaction container at (70 +/-2) DEG C, finishing dropwise adding the methyl ethyl ketone oxime within 2-3 h, then preserving heat for 1-2 h at the temperature of (70 +/-2) DEG C, weighing 146.5 parts of HCS, adding the HCS into the constant pressure titration funnel when the-NCO content reaches a theoretical value, beginning to dropwise add ethylene glycol hexyl ether at (70 +/-2) DEG C, finishing dropwise adding within 2-3 h, preserving heat for 2-3 h at (70 +/-2) DEG C, and preparing the totally-closed curing agent with the solid content of 80 wt% when the-NCO content reaches the theoretical value again.
The invention has the beneficial effects that: the epoxy cathode electrophoretic paint with ultralow temperature, no tin and high corrosion resistance is prepared by selecting a sealing agent of an isocyanate curing agent and the like.
Detailed Description
The invention is further illustrated by the following specific examples:
an energy-saving and environment-friendly cathode electrophoretic coating comprises water, color paste, an auxiliary agent and an emulsion; the solid content of the electrophoretic coating is 20 wt%, and the ash content is 10 wt%;
the emulsion comprises 100 parts by mass of amine modified epoxy resin, 20-30 parts by mass of a totally-enclosed curing agent, 2-3 parts by mass of a bismuth-zinc composite drier, 1.6-1.8 parts by mass of a neutralizer, 1.5 parts by mass of an auxiliary agent and 130 parts by mass of deionized water;
the totally-enclosed curing agent is prepared by the reaction of m-xylylene diisocyanate, methyl isobutyl ketone, methyl ethyl ketone oxime and ethylene glycol hexyl ether.
The color paste comprises, by mass, 20 parts of quaternary ammonium salt dispersion resin, 25 parts of deionized water, 15 parts of kaolin, 0.2-0.5 part of carbon black, 5 parts of an emulsifier, 20-25 parts of rutile titanium dioxide and 10-15 parts of titanium-based sodium rice paste.
The formula of the titanium-based sodium rice pulp comprises, by mass, 80 parts of metal nano titanium particles, 10 parts of epoxy resin, 3 parts of silane coupling agent and 10 parts of butanone.
The neutralizer comprises formic acid, acetic acid, lactic acid and maleic acid.
The auxiliary agent comprises isopropanol, sec-butyl alcohol, dipropylene glycol methyl ether and propylene glycol methyl ether.
The preparation method of the emulsion comprises the following steps: 100 parts of amine modified epoxy resin, 20-30 parts of totally-enclosed curing agent and 2-3 parts of bismuth-zinc composite drier are mixed and stirred uniformly, then 1.6-1.8 parts of neutralizer, 1.5 parts of auxiliary agent and 120-130 parts of deionized water are sequentially added and stirred uniformly, and emulsion is obtained after emulsification.
The preparation method of the totally-enclosed curing agent comprises the following steps: 188.2 parts of m-xylylene diisocyanate and 85.0 parts of methyl isobutyl ketone are weighed in parts by mass and added into a reaction vessel, stirring is started, condensed water is turned on, and N is introduced2Heating to 70 ℃, weighing 87.5 parts of methyl ethyl ketoxime, adding the methyl ethyl ketoxime into a constant pressure titration funnel, beginning to dropwise add the methyl ethyl ketoxime into the reaction vessel, keeping the temperature of the reaction vessel at (70 +/-2) DEG C, and dropwise adding the methyl ethyl ketoxime within 2-3 hAnd after finishing, preserving heat for 1-2 h at the temperature of (70 +/-2) DEG C, when the-NCO content reaches a theoretical value, weighing 146.5 parts of HCS, adding the HCS into a constant pressure titration funnel, beginning to dropwise add ethylene glycol hexyl ether at the temperature of (70 +/-2) DEG C, completing dripping within 2-3 h, preserving heat for 2-3 h at the temperature of (70 +/-2) DEG C, and when the-NCO content reaches the theoretical value again, preparing the fully-closed curing agent, wherein the solid content of the fully-closed curing agent is 80 wt%.
In the present application, the isocyanate content is determined by the di-n-butylamine method. The theoretical value of the isocyanate content is known in the art and will not be described in detail here.
The present application is further illustrated with reference to the following specific examples:
example 1
An energy-saving and environment-friendly cathode electrophoretic coating comprises water, color paste, an auxiliary agent and an emulsion; the solid content of the electrophoretic coating is 20 wt%, and the ash content is 10 wt%;
the emulsion comprises 100 parts of amine modified epoxy resin, 20 parts of totally-enclosed curing agent, 3 parts of bismuth-zinc composite drier, 1.6 parts of neutralizer, 1.5 parts of assistant and 130 parts of deionized water by mass;
the totally-enclosed curing agent is prepared by the reaction of m-xylylene diisocyanate, methyl isobutyl ketone, methyl ethyl ketone oxime and ethylene glycol hexyl ether.
The color paste comprises, by mass, 20 parts of quaternary ammonium salt dispersion resin, 25 parts of deionized water, 15 parts of kaolin, 0.4 part of carbon black, 5 parts of an emulsifier, 20 parts of rutile titanium dioxide and 10 parts of titanium-based nano-slurry.
The formula of the titanium-based sodium rice pulp comprises, by mass, 80 parts of metal nano titanium particles, 10 parts of epoxy resin, 3 parts of silane coupling agent and 10 parts of butanone.
The neutralizer comprises formic acid, acetic acid, lactic acid and maleic acid.
The auxiliary agent comprises isopropanol, sec-butyl alcohol, dipropylene glycol methyl ether and propylene glycol methyl ether.
The preparation method of the emulsion comprises the following steps: 100 parts of amine modified epoxy resin, 20 parts of totally-enclosed curing agent and 2 parts of bismuth-zinc composite drier are mixed and stirred uniformly, then 1.6 parts of neutralizer, 1.5 parts of auxiliary agent and 130 parts of deionized water are sequentially added and stirred uniformly, and emulsion is obtained after emulsification.
The preparation method of the totally-enclosed curing agent comprises the following steps: 188.2 parts of m-xylylene diisocyanate and 85.0 parts of methyl isobutyl ketone are weighed in parts by mass and added into a reaction vessel, stirring is started, condensed water is turned on, and N is introduced2Heating to 70 ℃, weighing 87.5 parts of methyl ethyl ketone oxime, adding the methyl ethyl ketone oxime into a constant pressure titration funnel, beginning to dropwise add the methyl ethyl ketone oxime into a reaction container, keeping the temperature of the reaction container at (70 +/-2) DEG C, finishing dropwise adding the methyl ethyl ketone oxime within 2-3 h, then preserving heat for 1-2 h at the temperature of (70 +/-2) DEG C, weighing 146.5 parts of HCS, adding the HCS into the constant pressure titration funnel when the-NCO content reaches a theoretical value, beginning to dropwise add ethylene glycol hexyl ether at (70 +/-2) DEG C, finishing dropwise adding within 2-3 h, preserving heat for 2-3 h at (70 +/-2) DEG C, and preparing the totally-closed curing agent with the solid content of 80 wt% when the-NCO content reaches the theoretical value again.
Example 2
An energy-saving and environment-friendly cathode electrophoretic coating comprises water, color paste, an auxiliary agent and an emulsion; the solid content of the electrophoretic coating is 20 wt%, and the ash content is 10 wt%;
the emulsion comprises 100 parts of amine modified epoxy resin, 30 parts of totally-enclosed curing agent, 2 parts of bismuth-zinc composite drier, 1.8 parts of neutralizer, 1.5 parts of assistant and 120 parts of deionized water by mass;
the totally-enclosed curing agent is prepared by the reaction of m-xylylene diisocyanate, methyl isobutyl ketone, methyl ethyl ketone oxime and ethylene glycol hexyl ether.
The color paste comprises, by mass, 20 parts of quaternary ammonium salt dispersion resin, 25 parts of deionized water, 15 parts of kaolin, 0.2-part of carbon black, 5 parts of an emulsifier, 25 parts of rutile titanium dioxide and 10 parts of titanium-based nano-slurry.
The formula of the titanium-based sodium rice pulp comprises, by mass, 80 parts of metal nano titanium particles, 10 parts of epoxy resin, 3 parts of silane coupling agent and 10 parts of butanone.
The neutralizer comprises formic acid, acetic acid, lactic acid and maleic acid.
The auxiliary agent comprises isopropanol, sec-butyl alcohol, dipropylene glycol methyl ether and propylene glycol methyl ether.
The preparation method of the emulsion comprises the following steps: 100 parts of amine modified epoxy resin, 25 parts of totally-enclosed curing agent and 2.5 parts of bismuth-zinc composite drier are mixed and stirred uniformly, then 1.7 parts of neutralizer, 1.5 parts of auxiliary agent and 125 parts of deionized water are sequentially added and stirred uniformly, and emulsion is obtained after emulsification.
The preparation method of the totally-enclosed curing agent comprises the following steps: 188.2 parts of m-xylylene diisocyanate and 85.0 parts of methyl isobutyl ketone are weighed in parts by mass and added into a reaction vessel, stirring is started, condensed water is turned on, and N is introduced2Heating to 70 ℃, weighing 87.5 parts of methyl ethyl ketone oxime, adding the methyl ethyl ketone oxime into a constant pressure titration funnel, beginning to dropwise add the methyl ethyl ketone oxime into a reaction container, keeping the temperature of the reaction container at (70 +/-2) DEG C, finishing dropwise adding the methyl ethyl ketone oxime within 2-3 h, then preserving heat for 1-2 h at the temperature of (70 +/-2) DEG C, weighing 146.5 parts of HCS, adding the HCS into the constant pressure titration funnel when the-NCO content reaches a theoretical value, beginning to dropwise add ethylene glycol hexyl ether at (70 +/-2) DEG C, finishing dropwise adding within 2-3 h, preserving heat for 2-3 h at (70 +/-2) DEG C, and preparing the totally-closed curing agent with the solid content of 80 wt% when the-NCO content reaches the theoretical value again.
Example 3
An energy-saving and environment-friendly cathode electrophoretic coating comprises water, color paste, an auxiliary agent and an emulsion; the solid content of the electrophoretic coating is 20 wt%, and the ash content is 10 wt%;
the emulsion comprises 100 parts of amine modified epoxy resin, 30 parts of totally-enclosed curing agent, 2 parts of bismuth-zinc composite drier, 1.8 parts of neutralizer, 1.5 parts of assistant and 120 parts of deionized water by mass;
the totally-enclosed curing agent is prepared by the reaction of m-xylylene diisocyanate, methyl isobutyl ketone, methyl ethyl ketone oxime and ethylene glycol hexyl ether.
The color paste comprises, by mass, 20 parts of quaternary ammonium salt dispersion resin, 25 parts of deionized water, 15 parts of kaolin, 0.5 part of carbon black, 5 parts of an emulsifier, 23 parts of rutile titanium dioxide and 13 parts of titanium-based sodium rice paste.
The formula of the titanium-based sodium rice pulp comprises, by mass, 80 parts of metal nano titanium particles, 10 parts of epoxy resin, 3 parts of silane coupling agent and 10 parts of butanone.
The neutralizer comprises formic acid, acetic acid, lactic acid and maleic acid.
The auxiliary agent comprises isopropanol, sec-butyl alcohol, dipropylene glycol methyl ether and propylene glycol methyl ether.
The preparation method of the emulsion comprises the following steps: 100 parts of amine modified epoxy resin, 30 parts of totally-enclosed curing agent and 3 parts of bismuth-zinc composite drier are mixed and stirred uniformly, then 1.8 parts of neutralizer, 1.5 parts of auxiliary agent and 120 parts of deionized water are sequentially added and stirred uniformly, and emulsion is obtained after emulsification.
The preparation method of the totally-enclosed curing agent comprises the following steps: 188.2 parts of m-xylylene diisocyanate and 85.0 parts of methyl isobutyl ketone are weighed in parts by mass and added into a reaction vessel, stirring is started, condensed water is turned on, and N is introduced2Heating to 70 ℃, weighing 87.5 parts of methyl ethyl ketone oxime, adding the methyl ethyl ketone oxime into a constant pressure titration funnel, beginning to dropwise add the methyl ethyl ketone oxime into a reaction container, keeping the temperature of the reaction container at (70 +/-2) DEG C, finishing dropwise adding the methyl ethyl ketone oxime within 2-3 h, then preserving heat for 1-2 h at the temperature of (70 +/-2) DEG C, weighing 146.5 parts of HCS, adding the HCS into the constant pressure titration funnel when the-NCO content reaches a theoretical value, beginning to dropwise add ethylene glycol hexyl ether at (70 +/-2) DEG C, finishing dropwise adding within 2-3 h, preserving heat for 2-3 h at (70 +/-2) DEG C, and preparing the totally-closed curing agent with the solid content of 80 wt% when the-NCO content reaches the theoretical value again.
Comparative example 1
An energy-saving and environment-friendly cathode electrophoretic coating comprises water, color paste, an auxiliary agent and an emulsion; the solid content of the electrophoretic coating is 20 wt%, and the ash content is 10 wt%;
the emulsion comprises 100 parts of amine modified epoxy resin, 30 parts of totally-enclosed curing agent, 2 parts of bismuth-zinc composite drier, 1.8 parts of neutralizer, 1.5 parts of assistant and 120 parts of deionized water by mass;
the totally-enclosed curing agent is prepared by the reaction of m-xylylene diisocyanate, methyl isobutyl ketone, methyl ethyl ketone oxime and ethylene glycol hexyl ether.
The color paste comprises, by mass, 20 parts of quaternary ammonium salt dispersion resin, 25 parts of deionized water, 15 parts of kaolin, 0.2-part of carbon black, 5 parts of an emulsifier, 25 parts of rutile titanium dioxide and 10 parts of titanium-based nano-slurry.
The formula of the titanium-based sodium rice pulp comprises, by mass, 80 parts of metal nano titanium particles, 10 parts of epoxy resin, 3 parts of silane coupling agent and 10 parts of butanone.
The neutralizer comprises formic acid, acetic acid, lactic acid and maleic acid.
The auxiliary agent comprises isopropanol, sec-butyl alcohol, dipropylene glycol methyl ether and propylene glycol methyl ether.
The preparation method of the emulsion comprises the following steps: 100 parts of amine modified epoxy resin, 10 parts of totally-enclosed curing agent and 0 part of bismuth-zinc composite drier are mixed and stirred uniformly, then 1.7 parts of neutralizer, 1.5 parts of auxiliary agent and 125 parts of deionized water are sequentially added and stirred uniformly, and emulsion is obtained after emulsification.
The preparation method of the totally-enclosed curing agent comprises the following steps: 188.2 parts of m-xylylene diisocyanate and 85.0 parts of methyl isobutyl ketone are weighed in parts by mass and added into a reaction vessel, stirring is started, condensed water is turned on, and N is introduced2Heating to 70 ℃, weighing 87.5 parts of methyl ethyl ketone oxime, adding the methyl ethyl ketone oxime into a constant pressure titration funnel, beginning to dropwise add the methyl ethyl ketone oxime into a reaction container, keeping the temperature of the reaction container at (70 +/-2) DEG C, finishing dropwise adding the methyl ethyl ketone oxime within 2-3 h, then preserving heat for 1-2 h at the temperature of (70 +/-2) DEG C, weighing 146.5 parts of HCS, adding the HCS into the constant pressure titration funnel when the-NCO content reaches a theoretical value, beginning to dropwise add ethylene glycol hexyl ether at (70 +/-2) DEG C, finishing dropwise adding within 2-3 h, preserving heat for 2-3 h at (70 +/-2) DEG C, and preparing the totally-closed curing agent with the solid content of 80 wt% when the-NCO content reaches the theoretical value again.
Comparative example 2
An energy-saving and environment-friendly cathode electrophoretic coating comprises water, color paste, an auxiliary agent and an emulsion; the solid content of the electrophoretic coating is 20 wt%, and the ash content is 10 wt%;
the emulsion comprises 100 parts of amine modified epoxy resin, 40 parts of totally-enclosed curing agent, 2 parts of bismuth-zinc composite drier, 1.8 parts of neutralizer, 1.5 parts of assistant and 120 parts of deionized water by mass;
the totally-enclosed curing agent is prepared by the reaction of m-xylylene diisocyanate, methyl isobutyl ketone, methyl ethyl ketone oxime and ethylene glycol hexyl ether.
The color paste comprises, by mass, 20 parts of quaternary ammonium salt dispersion resin, 25 parts of deionized water, 15 parts of kaolin, 0.2-part of carbon black, 5 parts of an emulsifier, 25 parts of rutile titanium dioxide and 10 parts of titanium-based nano-slurry.
The formula of the titanium-based sodium rice pulp comprises, by mass, 80 parts of metal nano titanium particles, 10 parts of epoxy resin, 3 parts of silane coupling agent and 10 parts of butanone.
The neutralizer comprises formic acid, acetic acid, lactic acid and maleic acid.
The auxiliary agent comprises isopropanol, sec-butyl alcohol, dipropylene glycol methyl ether and propylene glycol methyl ether.
The preparation method of the emulsion comprises the following steps: 100 parts of amine modified epoxy resin, 10 parts of totally-enclosed curing agent and 2.5 parts of bismuth-zinc composite drier are mixed and stirred uniformly, then 1.7 parts of neutralizer, 1.5 parts of auxiliary agent and 125 parts of deionized water are sequentially added and stirred uniformly, and emulsion is obtained after emulsification.
The preparation method of the totally-enclosed curing agent comprises the following steps: 188.2 parts of m-xylylene diisocyanate and 85.0 parts of methyl isobutyl ketone are weighed in parts by mass and added into a reaction vessel, stirring is started, condensed water is turned on, and N is introduced2Heating to 70 ℃, weighing 87.5 parts of methyl ethyl ketone oxime, adding the methyl ethyl ketone oxime into a constant pressure titration funnel, beginning to dropwise add the methyl ethyl ketone oxime into a reaction container, keeping the temperature of the reaction container at (70 +/-2) DEG C, finishing dropwise adding the methyl ethyl ketone oxime within 2-3 h, then preserving heat for 1-2 h at the temperature of (70 +/-2) DEG C, weighing 146.5 parts of HCS, adding the HCS into the constant pressure titration funnel when the-NCO content reaches a theoretical value, beginning to dropwise add ethylene glycol hexyl ether at (70 +/-2) DEG C, finishing dropwise adding within 2-3 h, preserving heat for 2-3 h at (70 +/-2) DEG C, and preparing the totally-closed curing agent with the solid content of 80 wt% when the-NCO content reaches the theoretical value again.
Curing the electrophoretic paint of the examples and the comparative examples for 24h, then preparing a plate, carrying out electrophoretic coating on the self-made phosphated plate by using the bath solution at the temperature of 28 +/-1 ℃ for 180s (soft start for 30s) and the voltage of 100-250V, and baking the plate for 20min (plate surface temperature) at the temperature of 120-140 ℃. Gel fraction determination, salt spray resistance, and electrophoretic paint film sample preparation were then performed as per Q/SZSJ 2101133-2003. The Gel fraction determination method is that the Gel fraction of the electrophoretic paint is called as the ratio of the mass of the electrophoretic paint film after being cured is soaked in a specified mixed solvent for a certain time to the mass of the electrophoretic paint film before the solvent is soaked. Gel fraction is a test method for determining the degree of curing of an electrophoretic paint film.
The results of Gel fraction (%) at different drying temperatures in different examples and comparative examples are shown in table 1, and it is generally considered that when the Gel fraction of the cathode electrophoretic coating film after drying is more than 90%, the coating film is considered to be completely cured, and it can be seen from table 1 that when the amount of the totally-sealing agent is 20-30% of the resin amount, the cathode electrophoretic coating film under the action of the composite drier is completely dried at 130 ℃ for 20 min. Comparative example 1 the electrophoretic coating film without the composite drier added needs to reach 86.14 percent at 140 ℃ for 20 min. The totally enclosed curing agent of comparative example 2 accounts for 10% of the resin amount, and the curing temperature thereof needs to be 140 ℃ or higher. Therefore, the curing temperature can be reduced by 10-20 ℃ by selecting a proper cathode electrophoretic paint drier. Because of cathodic electrocoating such as epoxy systems, the curing catalyst can be a metal such as zinc, bismuth, etc.; a small amount of zinc and bismuth cations are deposited on the coating film along with the coating resin, and the catalytic action is generated during heating and curing.
The Gel fraction crosslinking density result shows that the complete deblocking temperature of the m-xylylene diisocyanate and the methyl ethyl ketoxime serving as the totally-closed curing agent can reach 130 ℃ under the action of the organic metal composite drier.
The corrosion resistance of the electrophoretic coating is an important index of the performance of the electrophoretic coating, and a neutral salt spray test is widely adopted when the accelerated corrosion test method is used for judging and evaluating the corrosion resistance of the organic coating, particularly when the coatings of a steel plate and a galvanized plate are examined. The neutral salt spray test is used to simulate the atmospheric environmental conditions in coastal areas and is considered to be the most traditional, most useful, and most widespread accelerated corrosion test. The neutral salt spray test is adopted to carry out experiments on the electrophoretic paint of different examples and comparative examples, and the results show that the board surface of the example 2 is not obviously changed, the anticorrosion performance is the best as the performance of the example 2, the anticorrosion performance is related to the amount of the curing agent and the crosslinking density, compared with the electrophoretic paint without the addition of the drier, the consumption of the curing agent is 20%, and the anticorrosion performance is the best under the addition of the drier.
TABLE 1 Gel fraction at different stoving temperatures for different examples and comparative examples
| 120℃ | 130℃ | 140℃ | |
| Example 1 | 85.21 | 90.37 | 92.91 |
| Example 2 | 85.11 | 90.91 | 93.23 |
| Example 3 | 85.32 | 91.69 | 94.31 |
| Comparative example 1 | 80.32 | 83.21 | 86.14 |
| Comparative example 2 | 85.31 | 86.92 | 88.92 |
Compared with the traditional lead and tin containing cathode electrophoretic coating on the market, the color paste does not contain lead and tin, is more green and environment-friendly, can be completely crosslinked and cured under the condition of 130 ℃ multiplied by 20min at the ultralow temperature and has excellent stability. According to the preparation method, three problems of application of the epoxy cathode electrophoretic coating are solved through selection of a sealant of an isocyanate curing agent and selection of a curing catalyst and the using amount: controlling the low-temperature dissociation property of the blocked isocyanate in the bath solution; the low-temperature curing property and the coating stability are both provided; low-temperature curability and coating film surface smoothness. The requirements of low-temperature drying, energy conservation and environmental protection of the cathode electrophoretic coating are realized, and the technical level of the cathode electrophoretic coating product is greatly improved.
Although the invention has been described and illustrated in some detail, it should be understood that various modifications may be made to the described embodiments or equivalents may be substituted, as will be apparent to those skilled in the art, without departing from the spirit of the invention.
Claims (7)
1. An energy-saving and environment-friendly cathode electrophoretic coating is characterized by comprising water, color paste, an auxiliary agent and an emulsion; the solid content of the electrophoretic coating is 20 wt%, and the ash content is 10 wt%;
the emulsion comprises 100 parts by mass of amine modified epoxy resin, 20-30 parts by mass of a totally-enclosed curing agent, 2-3 parts by mass of a bismuth-zinc composite drier, 1.6-1.8 parts by mass of a neutralizer, 1.5 parts by mass of an auxiliary agent and 130 parts by mass of deionized water;
the totally-enclosed curing agent is prepared by the reaction of m-xylylene diisocyanate, methyl isobutyl ketone, methyl ethyl ketone oxime and ethylene glycol hexyl ether.
2. The energy-saving and environment-friendly cathode electrophoretic paint as claimed in claim 1, characterized in that: the color paste comprises, by mass, 20 parts of quaternary ammonium salt dispersion resin, 25 parts of deionized water, 15 parts of kaolin, 0.2-0.5 part of carbon black, 5 parts of an emulsifier, 20-25 parts of rutile titanium dioxide and 10-15 parts of titanium-based sodium rice paste.
3. The energy-saving and environment-friendly cathode electrophoretic paint as claimed in claim 2, characterized in that: the formula of the titanium-based sodium rice pulp comprises, by mass, 80 parts of metal nano titanium particles, 10 parts of epoxy resin, 3 parts of silane coupling agent and 10 parts of butanone.
4. The energy-saving and environment-friendly cathode electrophoretic paint as claimed in claim 1, characterized in that: the neutralizer comprises formic acid, acetic acid, lactic acid and maleic acid.
5. The energy-saving and environment-friendly cathode electrophoretic paint as claimed in claim 1, characterized in that: the auxiliary agent comprises isopropanol, sec-butyl alcohol, dipropylene glycol methyl ether and propylene glycol methyl ether.
6. The energy-saving and environment-friendly cathode electrophoretic paint as claimed in claim 1, wherein the preparation method of the emulsion comprises the following steps: 100 parts of amine modified epoxy resin, 20-30 parts of totally-enclosed curing agent and 2-3 parts of bismuth-zinc composite drier are mixed and stirred uniformly, then 1.6-1.8 parts of neutralizer, 1.5 parts of auxiliary agent and 120-130 parts of deionized water are sequentially added and stirred uniformly, and emulsion is obtained after emulsification.
7. The energy-saving environment-friendly cathode electrophoretic paint as claimed in claim 1, wherein the preparation method of the totally-enclosed curing agent comprises the following steps: 188.2 parts of m-xylylene diisocyanate and 85.0 parts of methyl isobutyl ketone are weighed in parts by mass and added into a reaction vessel, stirring is started, condensed water is turned on, and N is introduced2Heating to 70 deg.CWeighing 87.5 parts of methyl ethyl ketone oxime, adding the methyl ethyl ketone oxime into a constant pressure titration funnel, beginning to dropwise add the methyl ethyl ketone oxime into a reaction container, keeping the temperature of the reaction container at (70 +/-2) DEG C, finishing dropwise adding the methyl ethyl ketone oxime within 2-3 h, then preserving heat for 1-2 h at the temperature of (70 +/-2) DEG C, weighing 146.5 parts of HCS, adding the HCS into the constant pressure titration funnel when the-NCO content reaches a theoretical value, beginning to dropwise add ethylene glycol hexyl ether at (70 +/-2) DEG C, finishing dropwise adding within 2-3 h, preserving heat for 2-3 h at (70 +/-2) DEG C, and preparing a fully-closed curing agent when the-NCO content reaches the theoretical value again, wherein the solid content of the fully-closed curing agent is 80 wt%.
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