CN115449289B - UV-cured cathode electrophoretic coating for metal and preparation method and application thereof - Google Patents
UV-cured cathode electrophoretic coating for metal and preparation method and application thereof Download PDFInfo
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- CN115449289B CN115449289B CN202210967894.6A CN202210967894A CN115449289B CN 115449289 B CN115449289 B CN 115449289B CN 202210967894 A CN202210967894 A CN 202210967894A CN 115449289 B CN115449289 B CN 115449289B
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- 238000001962 electrophoresis Methods 0.000 claims abstract description 18
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Classifications
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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
- C09D5/4473—Mixture of polymers
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
- C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
- C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
- C08G18/6225—Polymers of esters of acrylic or methacrylic acid
- C08G18/6229—Polymers of hydroxy groups containing esters of acrylic or methacrylic acid with aliphatic polyalcohols
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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
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C09D5/08—Anti-corrosive paints
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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
- C09D5/4465—Polyurethanes
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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
- C09D5/4488—Cathodic paints
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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
- C09D5/4488—Cathodic paints
- C09D5/4492—Cathodic paints containing special additives, e.g. grinding agents
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D13/00—Electrophoretic coating characterised by the process
- C25D13/22—Servicing or operating apparatus or multistep processes
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Materials Engineering (AREA)
- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Macromonomer-Based Addition Polymer (AREA)
- Paints Or Removers (AREA)
Abstract
The invention belongs to the technical field of electrophoretic coating, and in particular relates to a UV (ultraviolet) curing cathode electrophoretic coating for metal, a preparation method and application thereof, wherein the UV curing cathode electrophoretic coating for metal comprises the following components in parts by weight: 10-25 parts of active prepolymer, 0-5 parts of cross-linking agent, 0.1-2.4 parts of photoinitiator, 0.1-1.5 parts of auxiliary agent and 65-90 parts of water, wherein the active prepolymer is a mixture of polyacrylate resin and polyurethane acrylate with the weight ratio of 7:3-3:7. The invention solves the problems of poor shock resistance, poor solvent wiping resistance, poor alkali resistance, poor solvent wiping resistance, poor aging resistance and the like of the polyacrylate cathode electrophoresis coating film by a simple physical blending method, has the advantages of good adhesive force, high hardness, acid and alkali resistance, acetone resistance, impact resistance and the like, meets the requirements of the electrophoresis coating for metals, has simple preparation method, easily obtained raw materials, low cost and wide application prospect.
Description
Technical Field
The invention belongs to the technical field of electrophoretic coating, and particularly relates to a UV (ultraviolet) curing cathode electrophoretic coating for metal, and a preparation method and application thereof.
Background
The corrosion problem of metal affects the living aspects of people, so that the corrosion prevention of metal plays an important role in the economic development. The method for preventing corrosion of metal includes structure change (such as alloying), protection (such as painting on surface) and electrochemical method. The common and cheap method is to coat the metal surface with the anti-corrosion paint, the paint for metal anti-corrosion is generally oil-soluble, a large amount of organic solvent is needed to be added, and the metal surface is covered with a protective layer through the processes of spraying or roller coating, etc., but the method has the defects of enlarging the row of VOCs, being incapable of processing special-shaped pieces, etc.
The electrophoretic coating is a popular process for improving the corrosion resistance and the aesthetic properties of metal parts due to its excellent corrosion resistance and good covering ability. Compared with other processes, the electrophoresis process can not only meet the coating of the special-shaped metal piece, but also meet the environment-friendly requirement, water is used as a dispersion medium, and no VOCs are discharged, so that the electrophoresis process is greatly developed. The traditional electrophoretic coating adopts a heat curing mode, has high curing temperature exceeding 120 ℃ and high energy consumption, limits the use of the electrophoretic coating in heat-sensitive materials, and has long curing time and low production efficiency.
The UV curing refers to a process that after the curing material is irradiated by ultraviolet light, ultraviolet light with a certain wave band is absorbed to generate cross-linking polymerization reaction, and the curing material is instantaneously converted from liquid state to solid state. It has the advantages of high production efficiency, energy conservation, environmental protection and the like. The UV curing electrophoretic paint combines the advantages of the common electrophoretic paint and the photo-curing technology, thereby having wider application prospect.
The matrix resin of the UV curing electrophoretic coating mainly comprises polyurethane resin, epoxy resin and acrylate resin. The polyacrylate-based cathode electrophoretic coating is widely applied due to the excellent weather resistance and good color and gloss retention, but has poor flexibility, wear resistance and corrosion resistance; the polyurethane-based cathode electrophoretic coating has good scratch resistance, wear resistance and flexibility, but has poor weather resistance, alkali resistance and the like.
Disclosure of Invention
Aiming at the defects of the prior art, the invention combines the advantages of polyurethane resin and polyacrylic resin through a simple physical blending method, and adds a certain amount of cross-linking agent to improve the cross-linking density of the cured film, thereby improving the physical and mechanical properties of the UV curing electrophoretic coating and meeting the basic requirements of the electrophoretic coating for metals, such as the requirements of corrosion resistance, wear resistance, scratch resistance, impact resistance and the like.
The invention aims at providing the UV curing cathode electrophoretic coating for the metal, which has reasonable formula, good compatibility of all components and stable emulsion state.
In order to achieve the above purpose, the present invention provides the following technical solutions:
the UV-cured cathode electrophoretic coating for the metal comprises the following components in parts by weight:
the reactive prepolymer is a mixture of polyacrylate resin and polyurethane acrylate, and the weight ratio of the polyacrylate resin to the polyurethane acrylate is 7:3-3:7.
As a preferable embodiment of the present invention, the polyacrylate resin comprises dimethylaminoethyl methacrylate (DMAEMA), hydroxyethyl methacrylate (HEMA) or hydroxyethyl acrylate (HEA), and other monomers selected from Methyl Methacrylate (MMA), methyl Acrylate (MA), butyl acrylate (n-BA) and isobutyl acrylate (i-BA), and the polyacrylate resin is a polyacrylate resin obtained by copolymerizing a mixture of multiple monomers, wherein the number average molecular weight Mn of the polyacrylate resin is 2000-32000.
As a preferred embodiment of the present invention, the crosslinking agent is a trifunctional acrylate, and the trifunctional acrylate may be one or more selected from trimethylolpropane triacrylate, ethoxylated trimethylolpropane triacrylate, and propoxylated trimethylolpropane triacrylate.
As a preferred embodiment of the present invention, the photoinitiator is a mixture of 2,4, 6-trimethylbenzoyl-diphenylphosphine oxide (TPO-L) and 2-hydroxy-2-methyl-1-phenylpropion (Doracur 1173) or 1-hydroxycyclohexylphenyl ketone (Iragcure 184).
As a preferable technical scheme of the invention, the auxiliary agent is at least one of an antifoaming agent, a leveling agent and a wetting agent, and the antifoaming agent is an organic modified polysiloxane antifoaming agent, such as: TEGO anti-foam 204, guangzhou, chemical AF-207, and the like; the leveling agent is organosilicon leveling agent, such as Digao TEGO 450, orthoco AKN-1126, pick byk348, etc.; the wetting agent is silicon-free wetting agent, such as TEGO Wet500, TEGO Wet 505, etc.
As a preferable technical scheme of the invention, the preparation method of the polyacrylate resin comprises the following steps:
s1, pretreatment of raw materials: the monomers (including DMAEMA, HEMA/HEA and a multi-component mixture composed of at least 1 of MMA, MA, n-BA and i-BA), propylene Glycol Methyl Ether Acetate (PGMEA), acetone and isophorone diisocyanate (IPDI) are respectively dehydrated by molecular sieves for later use;
s2, synthesizing an acrylic ester prepolymer: dropwise adding the mixture of the monomer, the Azodiisobutyronitrile (AIBN) and the mercaptoethanol in the step S1 into PGMEA heated to 80 ℃, controlling the speed to drop, and heating to 100 ℃ after the reaction at a constant temperature to stop the reaction;
s3, synthesis of IPDI-HEMA semi-grafted copolymer (PUA): dropwise adding HEMA, catalyst dibutyl tin dilaurate (DBTDL) and polymerization inhibitor p-hydroxyanisole (MEHQ) into IPDI, controlling the dropping speed, and stopping the reaction after the heat preservation reaction until the-NCO content reaches a theoretical value;
s4, preparing polyacrylate emulsion: and (3) adding a relative amount of acetone into the acrylate prepolymer obtained in the step (S2), reducing the viscosity, controlling Wen Di, adding the IPDI-HEMA semi-grafted copolymer obtained in the step (S3), controlling the speed to drop, and stopping the reaction when the-NCO content in the system reaches the calculated theoretical value again after the heat preservation reaction is finished, so that the polyacrylate resin with photosensitivity is prepared.
Preferably, the mass fraction of DMAEMA in the mixture in step S2 is 8% -20%; the mass fraction of HEMA/HEA is 15% -25%; the mass fraction of other monomers is 50-80%; the mass fraction of AIBN is 1-5%; the mass fraction of the mercaptoethanol is 0.1-3%.
More preferably, the mass fraction of DMAEMA in the mixture of step S2 is 12% to 16%; the mass fraction of HEMA/HEA is 18% -22%; the mass fraction of other monomers is 60% -70%; the mass fraction of AIBN is 1-3%; the mass fraction of the mercaptoethanol is 1-2%.
Preferably, the IPDI in step S3: the ratio of HEMA substances is 0.4:1-1:1.
More preferably, the IPDI in step S3: the ratio of HEMA substances is 0.6:1-0.8:1.
And adding glacial acetic acid into the prepared polyacrylate resin to form salt, and finally adding water to emulsify to obtain the polyacrylate emulsion with the solid content of 15%.
The polyurethane acrylic ester synthesis method refers to patent CN202111568121.2.
The invention also provides a preparation method of the UV curing cathode electrophoretic coating for metals, which comprises the following steps:
s1, pre-dispersing water, a photoinitiator and an auxiliary agent in parts by weight, and uniformly stirring;
s2, adding an active prepolymer and a cross-linking agent into the system in the step S1 according to parts by weight, mixing and stirring uniformly to obtain the photocuring cathode electrophoretic coating, wherein polyacrylate resin and polyurethane acrylate in the active prepolymer are respectively prepared into emulsion and then mixed.
Preferably, the stirring speed in the step S1 is 2000-4000 r/min, and the stirring time is 5-6 min;
the stirring speed in the step S2 is 2000-4000 r/min, and the stirring time is 30-45 min.
Another object of the present invention is to provide the use of the above UV-curable cathodic electrocoat for metals in metal electrocoating.
Preferably, the process of the metal electrophoretic coating comprises the following steps: immersing the plated metal serving as a cathode and an anode plate into the prepared electrophoresis liquid containing the UV curing cathode electrophoresis paint, adjusting the parallel distance between the cathode and the anode plate, setting electrophoresis time and voltage, taking out the cathode plate after electrophoresis is finished, washing, drying and curing.
The paint film obtained by the electrophoresis is flat and smooth, high in hardness, resistant to impact, weather, acid and alkali, resistant to solvent and good in adhesion with metal.
Compared with the prior art, the invention has the beneficial effects that:
(1) The performances of the polyacrylate resin can be adjusted by adjusting the types and the amounts of the comonomers, and meanwhile, the polyurethane acrylate resin and the polyacrylate are compounded to be used as prepolymer, so that the defects of poor shock resistance and the like of a polyacrylate resin cathode electrophoresis paint film are effectively overcome; meanwhile, the prepolymer contains a double bond structure, can carry out photopolymerization, and effectively solves the problems of high polymerization temperature, high energy consumption, low production efficiency and the like of the traditional cathode electrophoretic coating.
(2) The photocuring speed can be increased by adding the trifunctional cross-linking agent, and the cross-linking density of the paint film is improved, so that the physical and mechanical properties of the paint film are improved, such as: solvent resistance, and the like.
(3) The photoinitiator is compounded by TPO-L and Doracur1173 or Iragcure184, so that the absorption wavelength range of the photoinitiator can be greatly widened, and the photoinitiator can be effectively absorbed within the range of 350-400 nm, thereby being beneficial to deep curing of a coating film. Proper auxiliary agents are selected, so that the wettability and leveling property of the paint can be effectively improved.
Drawings
FIG. 1 is a synthetic route diagram of a polyacrylate resin in an embodiment of the present invention.
FIG. 2 is a synthetic route diagram of an IPDI-HEMA semi-graft copolymer (PUA) in an embodiment of the invention.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in conjunction with examples of the present invention and comparative examples, and it is apparent that the described examples are only some of the examples of the present invention, but not all of the examples. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The test methods used in the following examples are conventional methods unless otherwise specified; the materials, reagents and the like used, unless otherwise specified, are those commercially available. The parts of the examples below are in grams.
Example 1
The UV curing cathode electrophoretic coating for the metal comprises the following raw materials in parts by weight:
wherein the reactive prepolymer is polyacrylate resin and polyurethane acrylate (the weight ratio of the reactive prepolymer to the polyurethane acrylate is 1:1), the crosslinking agent is trimethylolpropane triacrylate, the photoinitiator is a photoinitiator TPO-L, doracur1173 (the weight ratio of the reactive prepolymer to the polyurethane acrylate is 1:1), the auxiliary agent is a wetting agent TEGO Wet 505, a leveling agent Octono AKN-1126 and a defoaming agent Guangzhou side chemical AF-207 (the weight ratio of the reactive prepolymer to the polyurethane acrylate is 5:5:1)
In this example, the polyacrylate resin was synthesized as follows:
(1) Pretreatment of raw materials: methyl Methacrylate (MMA), butyl acrylate (n-BA), dimethylaminoethyl methacrylate (DMAEMA), hydroxyethyl methacrylate (HEMA), propylene Glycol Methyl Ether Acetate (PGMEA), acetone and isophorone diisocyanate (IPDI) are dehydrated by a 4A molecular sieve for more than one week for later use.
(2) Synthesis of acrylate prepolymer: a stirring paddle, a condenser tube, and a thermometer were fitted into a four-necked flask, and 30g of PGMEA was added thereto. The temperature was raised to 80℃and a mixture of monomers (comprising 21.1g MMA, 35.12. 35.12g n-BA, 13.72g DMAEMA, 16.41g HEMA quaternary mixture), 1g Azobisisobutyronitrile (AIBN) and 1.21g mercaptoethanol was added dropwise with a constant pressure funnel, the dropwise addition was completed over 2 hours, the reaction was continued at constant temperature for 3 hours, and then heated to 100℃for further 2 hours, and the reaction was stopped.
(3) Synthesis of IPDI-HEMA semi-graft copolymer: the stirring paddle, the condenser and the thermometer are assembled into a four-necked flask, 33.34g of IPDI is added into the four-necked flask, 17.41g of HEMA and 1 drop of catalyst dibutyl tin dilaurate (DBTDL) and polymerization inhibitor para-hydroxyanisole (MEHQ) are dropwise added by a constant pressure funnel, the dropping speed is controlled to ensure that the mixture is dropwise added within 0.5h, the reaction is kept at 20 ℃, the dropwise adding is controlled within 30min, and the reaction is stopped after the di-n-butylamine method is adopted for monitoring the-NCO content in real time until the theoretical value is reached.
(4) Synthesis of polyacrylate resin: and adding 30g of acetone into the acrylate prepolymer to reduce the viscosity, then dropwise adding 34.12g of the IPDI-HEMA semi-adduct mixed with DBTDL and MEHQ into acrylic resin under the condition of controlling the temperature to be 60 ℃, controlling the dropwise adding speed to finish dropwise adding within 0.5h, and keeping the temperature for reaction until the-NCO content in the system reaches the calculated theoretical value again, thereby obtaining the polyacrylate resin with photosensitivity.
5.24g glacial acetic acid is added at 50 ℃ to form salt, and finally 720g deionized water is added to emulsify, so that the solid content of the polyacrylate resin emulsion is about 15%.
In this example, the synthesis of urethane acrylate is referred to in patent CN202111568121.2, which is specifically as follows:
adding 52.38g of pretreated polytetrahydrofuran glycol (PTMG-1000) and 0.452g of catalyst dibutyltin dilaurate (DBTDL) into a constant pressure funnel, dripping 23.72g of Toluene Diisocyanate (TDI) into the mixture at the speed of 2-3 drops per second at the temperature of 60-70 ℃ and the speed of 300-500 r/min for full reaction for 1h, and titrating the NCO content by a di-n-butylamine method in the reaction process, wherein the NCO content reaches a theoretical value, and is a reaction end point A; after reaching the reaction end point A, adding 6.24g of a polyol chain extender 3-dimethylamino-1, 2-propanediol (DMAD) into the reaction product to react at the temperature of between 60 and 70 ℃ and at the speed of between 300 and 500r/min, and titrating the NCO content by a di-n-butylamine method in the reaction process, wherein the NCO content reaches the theoretical value again and is the reaction end point B; after reaching the reaction end point B, a mixture of 7.20g of end-capping agent hydroxyethyl acrylate (HEA) and 0.049g of polymerization inhibitor hydroxyanisole is dripped into the reaction product at the rate of 2-3 drops per second by using a constant pressure funnel, the reaction is carried out at the temperature of 60-70 ℃ under the condition of 300-500 r/min, the titration of NCO content is carried out by using a di-n-butylamine method in the reaction process, and the NCO content is the reaction end point C when the NCO content is reduced to 0. After reaching the reaction end point, adding a neutralizing agent glacial acetic acid with the mole ratio of 1:1 with the polyol chain extender into the reaction product, and maintaining the reaction product at the temperature of 60-70 ℃ for 5-10 min under the condition of 300-500 r/min to terminate the reaction; finally adding deionized water under high-speed stirring of 2000-3000 r/min, and stirring for 30min to finally obtain the polyurethane-based photosensitive resin emulsion with the solid content of 10-20%.
The preparation method of the UV curing cathode electrophoretic coating comprises the following steps:
(1) Adding deionized water, a photoinitiator and an auxiliary agent into a stirring pot according to parts by weight for pre-dispersing, stirring uniformly at a rotating speed of 3000r/min for 5min;
(2) Adding the active prepolymer and the cross-linking agent into a reaction bottle according to the weight parts, mixing and stirring uniformly, wherein the stirring speed is 4000r/min, and the stirring time is 30min, so as to prepare the UV curing cathode electrophoretic coating.
Example 2
The UV curing cathode electrophoretic coating for the metal comprises the following raw materials in parts by weight:
the reactive prepolymer is polyacrylate resin and polyurethane acrylate (the weight ratio of the reactive prepolymer to the polyurethane acrylate is 1:1), the crosslinking agent is trimethylolpropane triacrylate, the photoinitiator is a photoinitiator TPO-L, doracur1173 (the weight ratio of the reactive prepolymer to the polyurethane acrylate is 1:1), and the auxiliary agent is a wetting agent TEGO Wet 505, a leveling agent Octono AKN-1126 and a chemical AF-207 (the weight ratio of the reactive prepolymer to the polyurethane acrylate is 5:5:1) in Guangzhou side.
The method for synthesizing the polyacrylate resin is the same as in example 1.
In this example, the synthesis of urethane acrylate is referred to in patent CN202111568121.2, which is specifically as follows:
adding 52.38g of pretreated polytetrahydrofuran glycol (PTMG-1000) and 0.488g of catalyst dibutyltin dilaurate (DBTDL) into a constant pressure funnel, dripping 30.28g of isophorone diisocyanate (IPDI) into the constant pressure funnel at the temperature of 60-70 ℃ and the speed of 300-500 r/min at the rate of 2-3 drops per second for full reaction for 1h, titrating the NCO content by a di-n-butylamine method in the reaction process, and taking the NCO content as a reaction end point A when the NCO content reaches a theoretical value; after reaching the reaction end point A, adding 6.24g of a polyol chain extender 3-dimethylamino-1, 2-propanediol (DMAD) into the reaction product to react at the temperature of between 60 and 70 ℃ and at the speed of between 300 and 500r/min, and titrating the NCO content by a di-n-butylamine method in the reaction process, wherein the NCO content reaches the theoretical value again and is the reaction end point B; after reaching the reaction end point B, 7.20g of a mixture of a capping agent of hydroxyethyl acrylate (HEA) and 0.053g of polymerization inhibitor of hydroxyanisole is dripped into the reaction product at a rate of 2-3 drops per second by using a constant pressure funnel to react at 60-70 ℃ for 300-500 r/min, the titration of the NCO content is carried out by using a di-n-butylamine method in the reaction process, and the reaction end point C is the reaction end point C when the NCO content is reduced to 0. After reaching the reaction end point, adding a neutralizing agent glacial acetic acid with the molar ratio of the neutralizing agent glacial acetic acid to the polyol chain extender of 1:1 into the reaction product, and maintaining the temperature at 300-500 r/min for 5-10 min to terminate the reaction; finally adding deionized water under high-speed stirring of 2000-3000 r/min, and stirring for 30min to finally obtain the polyurethane-based photosensitive resin emulsion with the solid content of 10-20%.
The preparation method of the UV-cured cathode electrophoretic coating for metal is the same as that of example 1.
Example 3
The UV curing cathode electrophoretic coating for the metal comprises the following raw materials in parts by weight:
the reactive prepolymer is polyacrylate resin and polyurethane acrylate (the weight ratio of the reactive prepolymer to the polyurethane acrylate is 1:1), the crosslinking agent is trimethylolpropane triacrylate, the photoinitiator is a photoinitiator TPO-L, doracur1173 (the weight ratio of the reactive prepolymer to the polyurethane acrylate is 1:1), and the auxiliary agent is a wetting agent TEGO Wet 505, a leveling agent Octono AKN-1126 and a chemical AF-207 (the weight ratio of the reactive prepolymer to the polyurethane acrylate is 5:5:1) in Guangzhou side.
In this example, the synthesis of polyacrylate resin is mainly different from example 1 in that:
synthesis of acrylate prepolymer: a stirrer, a condenser, and a thermometer were fitted into a four-necked flask, and PGMEA was added thereto. The temperature was raised to 80℃and a mixture of monomer (comprising: 41.75g MA, 13.72g DMAEMA, 14.64g HEA ternary mixture), 1g Azobisisobutyronitrile (AIBN) and 1.21g mercaptoethanol was added dropwise with a constant pressure funnel, and the reaction was stopped after the dropwise addition was completed over 2 hours, reacted at constant temperature for 3 hours, and then heated to 100℃and continued for 2 hours.
Other preparation steps and conditions were the same as in example 1.
In this example, the urethane acrylate was synthesized in the same manner as in example 1.
The method for preparing the UV-cured cathode electrophoretic coating for metal of this example is the same as that of example 1.
Comparative example 1
The UV curing cathode electrophoretic coating for the metal comprises the following raw materials in parts by weight:
wherein the active prepolymer is polyurethane acrylate resin, the photoinitiator is photoinitiator TPO-L, doracur1173 (the weight ratio of the two is 1:1), and the auxiliary agent is wetting agent TEGO Wet 505, leveling agent Octono AKN-1126 and chemical AF-207 (the weight ratio of the two is 5:5:1) in Guangzhou prescription.
In this comparative example, the urethane acrylate resin was synthesized in the same manner as in example 1.
The comparative example metal UV-curable cathodic electrocoat was prepared in the same manner as in example 1.
Comparative example 2
The UV curing cathode electrophoretic coating for the metal comprises the following raw materials in parts by weight:
wherein the active prepolymer is polyacrylate resin, the photoinitiator is photoinitiator TPO-L, doracur1173 (the weight ratio of the two is 1:1), and the auxiliary agent is wetting agent TEGO Wet 505, leveling agent Octono AKN-1126 and chemical AF-207 (the weight ratio of the two is 5:5:1) in Guangzhou prescription.
In this comparative example, the polyacrylate resin was synthesized in the same manner as in example 1.
The preparation method of the UV-curable cathode electrophoretic coating for metals in this comparative example is the same as that of example 1.
Comparative example 3
The UV curing cathode electrophoretic coating for the metal comprises the following raw materials in parts by weight:
wherein the active prepolymer is polyacrylate resin, the cross-linking agent is trimethylolpropane triacrylate, the photoinitiator is photoinitiator TPO-L, doracur1173 (the weight ratio of the two is 1:1), and the auxiliary agent is wetting agent TEGO Wet 505, leveling agent Octono AKN-1126 and chemical AF-207 (the weight ratio of the two is 5:5:1) in Guangzhou prescription.
In this comparative example, the polyacrylate resin was synthesized as follows:
synthesis of acrylate prepolymer: a stirrer, a condenser, and a thermometer were fitted into a four-necked flask, and PGMEA was added thereto. The temperature was raised to 80℃and a mixture of monomer (comprising: 44.99g MA, 8.64g DMAEMA, 14.64g HEA ternary mixture), 1g Azobisisobutyronitrile (AIBN) and 1.21g mercaptoethanol was added dropwise with a constant pressure funnel, and the reaction was stopped after the dropwise addition was completed over 2 hours, reacted at constant temperature for 3 hours, and then heated to 100℃and continued for 2 hours.
Synthesis of IPDI-HEMA semi-graft copolymer: as in example 1.
Synthesis and preparation of acrylic emulsion: and adding 30g of acetone into the acrylate prepolymer to reduce the viscosity, then dropwise adding 34.12g of the IPDI-HEMA semi-adduct mixed with DBTDL and MEHQ into acrylic resin under the condition of controlling the temperature to be 60 ℃, controlling the dropwise adding speed to finish dropwise adding within 0.5h, and keeping the temperature for reaction until the-NCO content in the system reaches the calculated theoretical value again, thereby obtaining the polyacrylate resin with photosensitivity. Adding 3.3g of glacial acetic acid at 50 ℃ to form salt, and finally adding 720g of deionized water to emulsify, thus obtaining the polyacrylate resin emulsion with the solid content of about 15%.
The preparation method of the UV-curable cathode electrophoretic coating for metals in this comparative example is the same as that of example 1.
Comparative example 4
The UV curing cathode electrophoretic coating for the metal comprises the following raw materials in parts by weight:
wherein the active prepolymer is polyacrylate resin, the cross-linking agent is trimethylolpropane triacrylate, the photoinitiator is photoinitiator TPO-L, doracur1173 (the weight ratio of the two is 1:1), and the auxiliary agent is wetting agent TEGO Wet 505, leveling agent Octono AKN-1126 and chemical AF-207 (the weight ratio of the two is 5:5:1) in Guangzhou prescription.
In this comparative example, the polyacrylate resin was synthesized as follows:
synthesis of acrylate prepolymer: a stirrer, a condenser, and a thermometer were fitted into a four-necked flask, and PGMEA was added thereto. The temperature was raised to 80℃and a mixture of monomer (comprising: 41.75g MA, 13.72g DMAEMA, 14.64g HEA ternary mixture), 1g Azobisisobutyronitrile (AIBN) and 1.21g mercaptoethanol was added dropwise with a constant pressure funnel, and the reaction was stopped after the dropwise addition was completed over 2 hours, reacted at constant temperature for 3 hours, and then heated to 100℃and continued for 2 hours.
Synthesis of IPDI-HEMA semi-graft copolymer: as in example 1.
Synthesis and preparation of acrylic emulsion: 30g of acetone is added into the acrylate prepolymer to reduce the viscosity, 21.32g of the IPDI-HEMA semi-adduct mixed with DBTDL and MEHQ is added into acrylic resin dropwise under the condition of controlling the temperature to be 60 ℃, the dropwise addition is completed within 0.5h, the reaction is stopped when the-NCO content in the system reaches the calculated theoretical value again after the dropwise addition is completed, and the polyacrylate resin with photosensitivity is prepared. 5.24g glacial acetic acid is added at 50 ℃ to form salt, and finally 720g deionized water is added to emulsify, so that the solid content of the polyacrylate resin emulsion is about 15%.
The preparation method of the UV-curable cathode electrophoretic coating for metals in this comparative example is the same as that of example 1.
Comparative example 5
The UV curing cathode electrophoretic coating for the metal comprises the following raw materials in parts by weight:
the reactive prepolymer is polyacrylate resin and polyurethane acrylate (the weight ratio of the reactive prepolymer to the polyurethane acrylate is 1:1), the crosslinking agent is trimethylolpropane triacrylate, the photoinitiator is a photoinitiator TPO-L, doracur1173 (the weight ratio of the reactive prepolymer to the polyurethane acrylate is 1:1), and the auxiliary agent is a wetting agent TEGO Wet 505, a leveling agent Octono AKN-1126 and a chemical AF-207 (the weight ratio of the reactive prepolymer to the polyurethane acrylate is 5:5:1) in Guangzhou side.
In this comparative example, the synthesis of polyacrylate resin is mainly different from that of example 1 in that:
synthesis of acrylate prepolymer: a stirring paddle, a condenser tube, and a thermometer were fitted into a four-necked flask, and 30g of PGMEA was added thereto. The temperature was raised to 80℃and a mixture of monomers (comprising 21.1g MMA, 13.72g DMAEMA, 16.41g HEMA, 28.54g styrene quaternary mixture), 1g Azobisisobutyronitrile (AIBN) and 1.21g mercaptoethanol was added dropwise with a constant pressure funnel, the reaction was stopped after the dropwise addition was completed over 2 hours under controlled dropping speed, and then heated to 100℃for 2 hours.
Other preparation steps and conditions were the same as in example 1.
In this comparative example, urethane acrylate was synthesized in the same manner as in example 1.
The comparative example metal UV-curable cathodic electrocoat was prepared in the same manner as in example 1.
Comparative example 6
The UV curing cathode electrophoretic coating for the metal comprises the following raw materials in parts by weight:
wherein the reactive prepolymer is polyacrylate resin and epoxy acrylate resin (the weight ratio of the reactive prepolymer to the epoxy acrylate resin is 1:1), the crosslinking agent is trimethylolpropane triacrylate, the photoinitiator is a photoinitiator TPO-L, doracur1173 (the weight ratio of the reactive prepolymer to the epoxy acrylate resin is 1:1), the auxiliary agent is a wetting agent TEGO Wet 505, a leveling agent Octono AKN-1126 and a chemical AF-207 (the weight ratio of the reactive prepolymer to the epoxy acrylate resin is 5:5:1).
In this comparative example, the polyacrylate resin was synthesized in the same manner as in example 1.
In this comparative example, the epoxy acrylic resin was SD-108 of Sanben chemical technology Co., ltd.
The comparative example metal UV-curable cathodic electrocoat was prepared in the same manner as in example 1.
Experimental example UV-cured cathode electrophoretic paint prepared in the inventive example and comparative example and paint film performance test thereof
The test method is as follows:
appearance of emulsion: visual observation (observation of emulsion color, uniformity, and delamination) was performed.
Paint film appearance: visual observation (observation of the state of the paint film, uniformity, and presence or absence of orange peel) was adopted.
Emulsion storage stability: using a TG1650-WS bench centrifuge (test conditions: test temperature: 25 ℃ C., rotational speed: 3000r/min, centrifugation time: 30 min) from Shanghai Lu Xiangyi centrifuge instruments Co., ltd. After the test, observing whether layering and precipitation occur; if no delamination or precipitation occurs, the emulsion is considered to be stable for more than 180 days.
The electrophoretic coating process comprises the following steps:
immersing the plated metal (serving as a cathode) and the anode plate into the prepared electrophoresis liquid, adjusting the parallel distance between the cathode and the anode plate to be 15cm, and setting the electrophoresis time to be 5min and the voltage to be 100V. And after the electrophoresis is finished, taking out the cathode plate, washing the cathode plate with a large amount of deionized water to clean the surface foam, flash evaporating the cathode plate in an oven at 80 ℃ for 3min, and then placing the cathode plate into an ultraviolet crawler-type photo-curing machine to be cured for 3-5 times at a crawler speed of 0.5 m/s.
Hardness: the cured paint films were measured with 3M pencils of different hardness according to GB/T6739-2006 test standard.
Gloss level: the test was performed according to GB 1743-1979 (1989) test standard using a triangular gloss meter (60 ℃) model YG268, sanhen technology Co., ltd.
Adhesion force: the film thickness of the paint film applied to the tin plate was made to be 22 μm according to the GB/T9286-1998 test standard, and the adhesion of the electrophoretic paint film was measured by the hundred-cell method.
Salt spray resistance: the measurement was carried out using a salt spray box 60 from the company of Lepidium-free technology, inc. according to the GB/T1771-2007 test standard.
Impact resistance: the measurement was carried out by using a DWTT-H drop weight tear tester from Jinan Mei Tex Co., according to GB/T1732-1993 test standard.
Acid and alkali resistance: the test was carried out according to GB/T9274-1988.
Aging resistance: the measurement was carried out by using a QUV/SPRAY type ultraviolet accelerated aging tester of Q.PANEL company in the U.S.A., according to GB/T1865-1997 test standard.
Acetone-resistant wiping: testing was performed according to GB/T23989-2009.
The test results are shown in Table 1.
TABLE 1
As can be seen from Table 1, the UV-cured cathode electrophoretic coating (examples 1-3) prepared by the invention has the advantages of good compatibility of each component of emulsion, good storage stability, no precipitation and layering, high hardness of a paint film, good adhesion to metal, good ageing resistance, acid and alkali resistance and salt spray resistance of the paint film, meeting the requirements, and good impact resistance and acetone wiping resistance of the paint film. As can be seen from comparative example 1, when urethane acrylic resin is used alone instead of the mixed prepolymer of the present invention, the resulting paint film has lower hardness and is inferior in aging resistance, alkali resistance and acetone wiping resistance. As can be seen from comparative example 2, when the polyacrylic resin was used alone instead of the mixed prepolymer of the present invention, the resulting paint film was inferior in both impact resistance and acetone rub resistance. As can be seen from comparative example 3, when the amount of the monomer component DMAEMA is small, the acrylic resin is poor in water solubility and the flatness of the paint film is poor, resulting in unsatisfactory salt spray resistance, acid and alkali resistance, solvent resistance and impact resistance of the paint film. As can be seen from comparative example 4, when the grafting ratio of the IPDI-HEMA semi-adduct to the acrylic resin is reduced, that is, the double bond density is lowered, the hardness, acid-base resistance and solvent-wiping resistance of the paint film are deteriorated. As can be seen from comparative example 5, when the comonomer is DMAEMA, HEMA, MMA and styrene, and double bonds are introduced by grafting with IPDI-HEMA semi-adducts, the adhesion, aging resistance, acid-base resistance, solvent wiping resistance and the like of the paint film are all deteriorated. As can be seen from comparative example 6, when the polyacrylic resin is mixed with the industrially produced epoxy acrylate resin, the acid-base resistance, solvent wiping resistance, impact resistance and the like of the paint film are deteriorated. Therefore, the invention adopts a scientific formula, provides the UV curing cathode electrophoretic coating for metals, which has good compatibility of various components and stable emulsion state, solves the problems of poor shock resistance, poor solvent wiping resistance, poor alkali resistance, poor solvent wiping resistance, poor aging resistance and the like of the polyacrylate cathode electrophoretic coating, has the advantages of good adhesive force, high hardness, acid and alkali resistance, acetone resistance, impact resistance and the like, and has the advantages of simple preparation method, easily obtained raw materials, low cost and wide application prospect.
It is apparent that the above examples of the present invention are only for clearly illustrating the technical solution of the present invention, and are not limited to the specific embodiments of the present invention. Any modification, equivalent replacement, improvement, etc. that comes within the spirit and principle of the claims of the present invention should be included in the protection scope of the claims of the present invention.
Claims (6)
1. The UV-curable cathode electrophoretic coating for the metal is characterized by comprising the following components in parts by weight:
10-25 parts of active prepolymer
0-5 parts of cross-linking agent
0.1-2.4 parts of photoinitiator
0.1-1.5 parts of auxiliary agent
65-90 parts of water
The reactive prepolymer is a mixture of polyacrylate resin and polyurethane acrylate, and the weight ratio of the polyacrylate resin to the polyurethane acrylate is 7:3-3:7;
the number average molecular weight Mn of the polyacrylate resin is 2000-32000;
the polyacrylate resin is prepared by the following method:
s1, pretreatment of raw materials: dehydrating the monomer, propylene glycol methyl ether acetate, acetone and isophorone diisocyanate;
s2, synthesizing an acrylic ester prepolymer: heating to 80 ℃, dropwise adding the mixture of the monomer, the azodiisobutyronitrile and the mercaptoethanol treated in the step S1 into propylene glycol methyl ether acetate at a controlled speed, reacting at a constant temperature, and then heating to 100 ℃ for reacting;
s3, synthesizing the IPDI-HEMA semi-grafted copolymer: dripping the mixture of hydroxyethyl methacrylate, dibutyl tin dilaurate and para-hydroxyanisole in the same amount of substances such as isophorone diisocyanate at a controlled speed, and stopping the reaction after the temperature is kept for reaction until the-NCO content reaches a theoretical value;
s4, synthesizing polyacrylate resin: adding acetone into the acrylic ester prepolymer obtained in the step S2 to reduce the viscosity, dropwise adding the IPDI-HEMA semi-grafted copolymer obtained in the step S3 at a controlled temperature and a controlled speed, and carrying out heat preservation reaction until the-NCO content in the system reaches a theoretical value again to stop the reaction;
the acrylic ester prepolymer is obtained by copolymerizing tetramonomers of dimethylaminoethyl methacrylate, hydroxyethyl methacrylate, methyl methacrylate and butyl acrylate, or by copolymerizing ternary monomers of dimethylaminoethyl methacrylate, hydroxyethyl acrylate and methyl acrylate;
the cross-linking agent is trifunctional acrylate, and the trifunctional acrylate is trimethylolpropane triacrylate;
the photoinitiator is a mixture of 2,4, 6-trimethylbenzoyl phenyl ethyl phosphonate and 2-hydroxy-2-methyl-1-phenyl-1-acetone.
2. The UV-curable cathode electrophoretic coating for metals according to claim 1, wherein the auxiliary agent is at least one of an antifoaming agent, a leveling agent and a wetting agent, the antifoaming agent is an organic modified polysiloxane-based antifoaming agent, the leveling agent is an organosilicon-based leveling agent, and the wetting agent is a silicon-free wetting agent.
3. A method for preparing a UV-curable cathodic electrocoat for metals according to any one of claims 1-2, comprising the steps of:
s1, pre-dispersing water, a photoinitiator and an auxiliary agent in parts by weight, and uniformly stirring;
s2, adding the active prepolymer and the cross-linking agent into the system in the step S1 according to parts by weight, and uniformly mixing and stirring;
the reactive prepolymer in the step S2 is a mixture obtained by respectively preparing the contained resins into emulsion and then mixing the emulsion.
4. The method for preparing the UV-curable cathode electrophoretic coating for metals according to claim 3, wherein the stirring speed in the step S1 is 2000-4000 r/min, and the stirring time is 5-6 min; and the stirring speed in the step S2 is 2000-4000 r/min, and the stirring time is 30-45 min.
5. Use of a UV-curable cathodic electrocoat for metals according to any one of claims 1-4 in metal electrocoating.
6. The use according to claim 5, wherein the process of metal electrophoretic coating comprises: immersing the plated metal serving as a cathode and an anode plate into prepared electrophoresis liquid comprising the UV curing cathode electrophoresis paint for metal, adjusting the parallel distance between the cathode and the anode plate, setting electrophoresis time and voltage for electrophoresis, taking out the cathode plate after electrophoresis is finished, flushing, drying and curing.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629050A (en) * | 2009-06-30 | 2010-01-20 | 广东华润涂料有限公司 | Urethane acrylate waterborne UV coating and preparation method thereof |
| CN104151890A (en) * | 2014-07-30 | 2014-11-19 | 中国海洋石油总公司 | Ultraviolet-curable cathode electrophoresis coating composition |
| CN104987761A (en) * | 2015-07-29 | 2015-10-21 | 湖南省霖辉高新材料科技有限公司 | UV cathode electrophoresis paint and coating process of same |
| CN106497372A (en) * | 2016-10-19 | 2017-03-15 | 东莞市霖辉金属表面处理材料有限公司 | A kind of production composite coating acrylic CED paint and its application |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101629050A (en) * | 2009-06-30 | 2010-01-20 | 广东华润涂料有限公司 | Urethane acrylate waterborne UV coating and preparation method thereof |
| CN104151890A (en) * | 2014-07-30 | 2014-11-19 | 中国海洋石油总公司 | Ultraviolet-curable cathode electrophoresis coating composition |
| CN104987761A (en) * | 2015-07-29 | 2015-10-21 | 湖南省霖辉高新材料科技有限公司 | UV cathode electrophoresis paint and coating process of same |
| CN106497372A (en) * | 2016-10-19 | 2017-03-15 | 东莞市霖辉金属表面处理材料有限公司 | A kind of production composite coating acrylic CED paint and its application |
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