WO2023109123A1 - Water-based ultraviolet curing cathode electrophoretic coating and preparation method therefor - Google Patents

Water-based ultraviolet curing cathode electrophoretic coating and preparation method therefor Download PDF

Info

Publication number
WO2023109123A1
WO2023109123A1 PCT/CN2022/106957 CN2022106957W WO2023109123A1 WO 2023109123 A1 WO2023109123 A1 WO 2023109123A1 CN 2022106957 W CN2022106957 W CN 2022106957W WO 2023109123 A1 WO2023109123 A1 WO 2023109123A1
Authority
WO
WIPO (PCT)
Prior art keywords
coating
reaction
polyurethane
chain extender
polyol
Prior art date
Application number
PCT/CN2022/106957
Other languages
French (fr)
Chinese (zh)
Inventor
吴淑芳
黄剑彬
刘晓暄
黄鸿宏
李治全
罗青宏
张婷
张永涛
黄洪填
Original Assignee
广东深展实业有限公司
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 广东深展实业有限公司 filed Critical 广东深展实业有限公司
Publication of WO2023109123A1 publication Critical patent/WO2023109123A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/14—Polyurethanes having carbon-to-carbon unsaturated bonds
    • C09D175/16—Polyurethanes having carbon-to-carbon unsaturated bonds having terminal carbon-to-carbon unsaturated bonds
    • 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
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0809—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups
    • C08G18/0814—Manufacture of polymers containing ionic or ionogenic groups containing cationic or cationogenic groups containing ammonium groups or groups forming them
    • 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
    • C08G18/08—Processes
    • C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/227—Catalysts containing metal compounds of antimony, bismuth or arsenic
    • 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
    • C08G18/08—Processes
    • C08G18/16—Catalysts
    • C08G18/22—Catalysts containing metal compounds
    • C08G18/24—Catalysts containing metal compounds of tin
    • C08G18/244—Catalysts containing metal compounds of tin tin salts of carboxylic acids
    • 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
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/73—Polyisocyanates or polyisothiocyanates acyclic
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/753—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group
    • C08G18/755—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate group and at least one isocyanate or isothiocyanate group linked to a secondary carbon atom of the cycloaliphatic ring, e.g. isophorone diisocyanate
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures
    • 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
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • 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

Definitions

  • the invention belongs to the field of macromolecular materials, and in particular relates to a water-based ultraviolet light curing cathodic electrophoretic paint and a preparation method thereof.
  • metal coating provides an effective way to solve this problem.
  • the formation of metal coatings is mainly divided into two methods: the first is the chemical plating method, the principle is to use the chemical reduction method to prepare the film material into a solution, so that it can quickly participate in the reduction reaction, and after reduction, deposit on the surface of the processed part.
  • a processing method The problem with the electroless plating method is that the coating film is not easy to control, it is easy to cause unevenness, and the bonding strength with the substrate is poor.
  • the second method is the electrophoresis method, which uses colloidal particles Under the action of an electric field, the principle of electrophoresis can be generated, so that the matrix resin in the electrophoretic coating dissociates into charged ionic polymers in water, and under the action of an electric field, each moves to the electrode with the opposite polarity and deposits on the surface of the electrode to form paint film.
  • electrophoretic coatings have many advantages. For example, most of the solvents of coatings are water. From the perspective of safety and national environmental protection requirements, water-based coatings have a lot of room for growth.
  • Electrophoretic coatings include anodic electrophoretic coatings and cathodic electrophoretic coatings.
  • the problem of anodic electrophoretic coating is that it is easy to corrode the anode material and the electrolyte is not stable.
  • cathodic electrophoretic paint will not corrode electrodes and has excellent rust resistance. Therefore, there are many studies on cathodic electrophoretic paint.
  • a blocked isocyanate trimer is used as a crosslinking agent, and after it is mixed with a cationic hydroxyl-terminated polyurethane resin, a hydroxyl-terminated polyurethane is prepared.
  • Electrophoretic paint the post-treatment of the electrophoretic paint requires thermal curing and crosslinking, high drying temperature and high energy consumption.
  • Japanese Laid-open Patent No.sho63(1988)-69882 adopts the polyhydric alcohol containing hydroxy acid group or sulfonic acid group as hydrophilic chain extender to prepare self-emulsified anionic water-based polyurethane resin, and the hardness of the polyurethane coating prepared by it is lower , Comprehensive performance is still unsatisfactory.
  • Electrophoretic coatings as a kind of green and environment-friendly coatings, also need to be developed in the direction of low cost, no heavy metals, low curing temperature, and high storage stability.
  • the existing technology cannot meet the above shortcomings and meet the needs of the industry.
  • the curing temperature of UV curing technology is not high, which is especially suitable for heat-sensitive substrates; the curing rate is fast, which can significantly improve production efficiency; no solvent is required, less environmental pollution, and low energy consumption;
  • the properties of the coating film can be changed by changing the proportion of the volume diluent, which can just make up for the shortcomings of the electrophoretic paint.
  • the purpose of the present invention is to overcome the shortcomings of the prior art and provide a water-based ultraviolet light-curable cathodic electrophoretic coating and a preparation method thereof.
  • the invention realizes efficient ultraviolet light curing, and has the advantages of high efficiency, low energy consumption and extremely low VOC emission compared with thermal curing.
  • the prepared paint film has good flexibility and hardness drop.
  • the technical solution adopted by the present invention is: a water-based UV-curable cathodic electrophoretic coating, the coating includes a polyurethane-based photosensitive resin and a photoinitiator component; the raw materials for preparing the polyurethane-based photosensitive resin include the following components : Isocyanate monomer, polyether polyol, polyol chain extender, end-capping agent, neutralizing agent, polymerization inhibitor and catalyst.
  • This technical scheme uses isocyanate monomers, polyether polyols, polyol chain extenders, end-capping agents, neutralizing agents, polymerization inhibitors, catalysts and photoinitiators as raw materials, through the isocyanate groups on the isocyanate monomers and
  • the reaction between polyether polyol, polyol chain extender and the hydroxyl group in the end-capping agent grafts the carbon-carbon double bond of the photocuring active group and the hydrophilic group to the long chain of polyurethane to obtain a polyurethane-based photosensitive resin .
  • the paint mixed with polyurethane-based photosensitive resin and initiator has good conductivity and water solubility to meet the requirements of electrophoretic coating.
  • the coating of the present invention has fast polymerization speed, and is cured by UV, and the curing process is more energy-saving and environment-friendly.
  • the tertiary amine group in the polyurethane-based photosensitive resin is basic.
  • an acid neutralizer such as glacial acetic acid
  • the coating of the present invention has the advantages of both UV curing coatings and electrophoretic coatings. During construction, the coating is first coated by electrophoresis, and then quickly cured by UV light.
  • the prepared coating has high hardness, good adhesion and excellent water and solvent resistance. It has a good protective effect on metal substrates and shows a good application prospect in the field of metal coatings.
  • the isocyanate monomer is a 2-functional isocyanate monomer, including isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and hexamethylene diisocyanate. at least one of isocyanate and diphenylmethane diisocyanate.
  • the inventors have found through research that polyurethanes synthesized from different monomers have certain differences in performance, especially when they are used as electrophoretic coatings, they have a great influence on the flatness of the paint film.
  • the paint prepared by using the preferred monomer of the present invention has good flatness and smooth paint film, and the toluene diisocyanate paint film has the best performance.
  • the polyether polyol in the water-based UV-curable cathodic electrophoretic coating, includes polytetrahydrofuran diol and/or polyethylene glycol.
  • the polyether polyol in the water-based UV-curable cathodic electrophoretic coating, includes at least one of PTMG-1000, PTMG-2000, PEG-600, and PEG-1000.
  • the polyol chain extender in the water-based UV-curable cathodic electrophoretic coating, includes a polyester diol chain extender and/or N-methyldiethanolamine.
  • the polyol chain extender in the water-based UV-curable cathodic electrophoretic coating, includes 3-dimethylamino-1,2-propanediol.
  • the inventor has found through research that the polyol chain extender used in the present invention uses 3-dimethylamino-1,2-propanediol.
  • the amine-based chain extender has good water solubility of the coating, the emulsion particle size distribution is narrow and uniform, and the particle size is small, all less than 30nm, and has good dispersion uniformity and water solubility.
  • the end-capping agent is hydroxyethyl acrylate and/or hydroxyethyl methacrylate.
  • the inventors have discovered through research that using hydroxyethyl acrylate and/or hydroxyethyl methacrylate as a capping agent can introduce photopolymerizable vinyl groups into polyurethane prepolymers to prepare polyurethane-based photosensitive resins.
  • the polyurethane-based photosensitive resin is more environmentally friendly and energy-saving in curing, and has a fast polymerization speed. It can be completely cured under the light intensity of 30 mW/cm 2 for 25-60 s, which can greatly improve the construction efficiency.
  • the molar ratio of the isocyanate monomer to the blocking agent is (5.5-1.5):1.
  • impact strength, hardness, and corrosion resistance are related to the amount of end-capping agent added in the components.
  • the more the end-capping agent is added the greater the crosslinking density, and the impact resistance, hardness The greater the corrosion resistance strength.
  • the neutralizer is glacial acetic acid and/or acrylic acid.
  • the molar ratio of the neutralizer to the polyol chain extender is: 1:1.
  • the inventors have found through research that when the molar ratio of the neutralizer to the polyol chain extender is 1:1, the neutralization reaction between the tertiary amine group and the acid is complete, and the formed polyurethane prepolymer exhibits good water solubility.
  • the inventors have found through research that the conductivity and hydrophilicity are related to the content of the glycol chain extender in the paint. The more the glycol chain extender, the better the conductivity and hydrophilicity, and the worse the water resistance.
  • the inventor has found through research that the tertiary amine group on the polyol chain extender is alkaline, and the reaction of neutralizing and forming a salt with acid neutralizers such as glacial acetic acid can make the synthesized polyurethane prepolymer have good properties. water soluble.
  • the polymerization inhibitor is at least one of p-hydroxyanisole, hydroquinone, and tert-butylcatechol.
  • the catalyst is dibutyltin dilaurate or/and organic bismuth.
  • the photoinitiator is at least one of Darocur1173, TOPL, TPO, and photoinitiator 819.
  • the present invention also provides a method for preparing any one of the above-mentioned water-based UV-curable cathodic electrophoretic coatings, the method comprising the following steps: (1) vacuum distilling polyether polyol to obtain pretreated polyether polyol; (2) After mixing the pretreated polyether polyol and the catalyst, add it to the isocyanate monomer, and react until the NCO content reaches the theoretical value, which is the reaction end point A; (3) After reaching the reaction end point A, add polyhydric acid to the product of step (1) Alcohol chain extender, reacting until the NCO content reaches the theoretical value again is the reaction end point B; (4) After reaching the reaction end point B, add an end-capping agent and a polymerization inhibitor to the product in step (3), and react until the NCO content drops to 0 (5) After reaching the reaction end point C, add a neutralizing agent to the product in step (4) and stop the reaction; (6) add deionized water to the product in step (5) and stir to obtain a polyurethane-based
  • the conditions for the vacuum distillation are: vacuum distill the polyether polyol at 80-100°C and 300-500 r/min for 2-3 h.
  • the polyether polyol and the catalyst are added into a constant pressure funnel, and the mixture is heated at 2 ⁇ 100°C per second under the conditions of 50 ⁇ 100°C and 200 ⁇ 600 r/min. The rate of 3 drops was dropped into the isocyanate monomer to carry out the grafting reaction.
  • the organic bismuth is organic bismuth DY-20.
  • step (2) of the preparation method the mass of the catalyst accounts for 0.05-0.3% of the total mass of the system in step (2).
  • the reaction is carried out at 50-80° C. and 200-500 r/min.
  • step (4) of the preparation method the reaction product of step (3) is dripped with a mixture of end-capping agent and polymerization inhibitor at a rate of 2 to 3 drops per second using a constant pressure funnel and The reaction is carried out under the conditions of 60 ⁇ 70°C and 300 ⁇ 500 r/min.
  • the mass of the polymerization inhibitor accounts for 0.005-0.008% of the total mass of the system in step (4).
  • the titration of the NCO content is carried out by the di-n-butylamine method during the reaction.
  • step (5) of the preparation method after adding a neutralizing agent, react at 60-70°C, 300-500 r/min for 10 The reaction was terminated after min.
  • step (6) of the preparation method at 2000 ⁇ 3000 Under high-speed stirring at r/min, deionized water was added and stirred for 30 min.
  • step (6) of the preparation method a polyurethane-based photosensitive resin with a solid content of 10-20% is finally obtained.
  • the mass ratio of the photoinitiator to the polyurethane-based photosensitive resin is (1-5): (90-100).
  • the present invention also provides the application of any one of the above-mentioned water-based UV-curable cathodic electrophoretic coatings, the application comprising the following steps: (1) uniformly mixing the polyurethane-based photosensitive resin and the photoinitiator to obtain the water-based UV-curable cathodic electrophoretic coating; (2) ) Use the metal substrate to be plated as the cathode, and use the step (1) paint electrophoretic coating to obtain the coated metal substrate; (3) wash, dry and bake the coated metal substrate in step (2), and use UV light double-sided radiation curing.
  • step (2) of the application the coating of step (1) is placed in the electrophoresis tank, the tinplate is used as the anode, and the metal substrate to be plated is used as the cathode, and the process is carried out at a DC voltage of 100V. Electrophoretic coating, electrode distance is 10 cm, electrophoresis time is 3 ⁇ 5 min, to obtain a metal substrate coated with an insoluble paint film.
  • the metal substrate includes at least one of tinplate, copper, aluminum, zinc, and silver.
  • step (3) of the application the metal substrate coated with the insoluble paint film in step (2) is washed with water, dried, baked at 80-100°C for 3 minutes, and then cured by UV light In-machine double-sided radiation curing.
  • the coating of the present invention has excellent electrical conductivity, fully meets the requirements of electrophoresis, and can be used for electrophoretic coating.
  • the coating of the present invention can be completely cured under the light intensity of 30 mW/cm 2 for 25-60 s.
  • the curing process is more environmentally friendly and energy-saving, and the polymerization speed is fast, which greatly improves the construction efficiency.
  • the present invention combines the advantages of electrophoretic coating technology and ultraviolet light curing technology, and the prepared metal coating has high hardness, good adhesion and excellent water and solvent resistance, which can protect the metal substrate , so that the metal has obvious corrosion resistance and impact resistance, and has shown a good application prospect in the field of metal coatings.
  • the present invention utilizes the acid-base neutralization and salt-forming reaction of the tertiary amine group and the neutralizing agent to make the coating have good water solubility and conductivity. At the same time, the paint has good storage stability and can be stored stably for more than one month.
  • the coating of the invention is environmentally friendly and pollution-free, and is beneficial to sustainable development.
  • Figure 1 is a schematic diagram of the chemical reaction for preparing polyurethane-based water-based photosensitive resin according to the present invention.
  • Fig. 2 is the particle size distribution diagram of the emulsion of Examples 1-3.
  • Fig. 3 is a characterization diagram of the impact resistance performance of Effect Example 1.
  • Figure 4 is the characterization diagram of the corrosion resistance performance of Effect Example 2.
  • the raw material information used in the embodiment of the present invention is shown in Table 1.
  • polyurethane-based water-based UV-curable cathodic electrophoretic coating of the present invention Add 52.38g of pretreated polytetrahydrofuran diol (PTMG-1000) and 0.488g of catalyst dibutyltin dilaurate (DBTDL) into the constant pressure funnel, under the conditions of 60 ⁇ 70°C, 300 ⁇ 500 r/min Drop it into 30.28g isophorone diisocyanate (IPDI) at a rate of 2 ⁇ 3 drops per second to fully react for 1 h. During the reaction, use the di-n-butylamine method to titrate the NCO content.
  • PTMG-1000 pretreated polytetrahydrofuran diol
  • DBTDL catalyst dibutyltin dilaurate
  • IPDI isophorone diisocyanate
  • polyurethane-based water-based UV-curable cathodic electrophoretic coating of the present invention Add 52.38g of pretreated polytetrahydrofuran diol (PTMG-1000) and 0.452g of catalyst dibutyltin dilaurate (DBTDL) into the constant pressure funnel, under the conditions of 60 ⁇ 70°C, 300 ⁇ 500 r/min Drop it into 23.72g of toluene diisocyanate (TDI) at a rate of 2 ⁇ 3 drops per second and fully react for 1 h. During the reaction, use the di-n-butylamine method to titrate the NCO content. When the NCO content reaches the theoretical value, it is the reaction.
  • PTMG-1000 pretreated polytetrahydrofuran diol
  • DBTDL catalyst dibutyltin dilaurate
  • End point A after reaching the reaction end point A, add 6.24g polyol chain extender 3-dimethylamino-1,2-propanediol (DMAD) to the reaction product to react at 60 ⁇ 70°C, 300 ⁇ 500 r/min, During the reaction process, titrate the NCO content with the di-n-butylamine method. When the NCO content reaches the theoretical value again, it is the reaction end point B; Drop in a mixture of 7.20g end-capping agent hydroxyethyl acrylate (HEA) and 0.049g polymerization inhibitor hydroxyanisole at a high speed, and react at 60 ⁇ 70°C and 300 ⁇ 500 r/min.
  • HOA end-capping agent hydroxyethyl acrylate
  • polyurethane-based water-based UV-curable cathodic electrophoretic coating of the present invention Add 52.38g of pretreated polytetrahydrofuran glycol (PTMG-1000) and 0.487g of catalyst dibutyltin dilaurate (DBTDL) into the constant pressure funnel, under the conditions of 60 ⁇ 70°C, 300 ⁇ 500 r/min Drop into 30.28g isophorone diisocyanate (IPDI) at a rate of 2 ⁇ 3 drops per second and fully react for 1 hour. During the reaction, use the di-n-butylamine method to titrate the NCO content.
  • PTMG-1000 pretreated polytetrahydrofuran glycol
  • DBTDL catalyst dibutyltin dilaurate
  • IPDI isophorone diisocyanate
  • polyurethane-based water-based UV-curable cathodic electrophoretic coating of the present invention Add 52.38g of pretreated polytetrahydrofuran glycol (PTMG-1000) and 0.442g of catalyst dibutyltin dilaurate (DBTDL) into the constant pressure funnel, under the conditions of 60 ⁇ 70°C, 300 ⁇ 500 r/min Drop it into 36.05g of diphenylmethane diisocyanate (MDI) at a rate of 2-3 drops per second and fully react for 1 h. During the reaction, use the di-n-butylamine method to titrate the NCO content.
  • PTMG-1000 pretreated polytetrahydrofuran glycol
  • DBTDL catalyst dibutyltin dilaurate
  • MDI diphenylmethane diisocyanate
  • reaction endpoint A When the NCO content reaches the theoretical value, it is Reaction endpoint A; after reaching the reaction endpoint A, add 9.36g of polyol chain extender 3-dimethylamino-1,2-propanediol (DMAD) to the reaction product at 60 ⁇ 70°C, 300 ⁇ 500 r/min for reaction , titrate the NCO content with the di-n-butylamine method during the reaction, when the NCO content reaches the theoretical value again, it is the reaction end point B; Drop in a mixture of 2.43g end-capping agent hydroxyethyl acrylate (HEA) and 0.05g polymerization inhibitor hydroxyanisole at a rate of 60 ⁇ 70°C and 300 ⁇ 500 r/min for reaction, and di-n-butylamine is used during the reaction Titration of NCO content by method, when the NCO content drops to 0, it is the end point C of the reaction.
  • DMAD polyol chain extender 3-dimethylamino-1,2-propane
  • polyurethane-based water-based UV-curable cathodic electrophoretic coating of the present invention Add 52.38g of pretreated polytetrahydrofuran diol (PTMG-1000) and 0.256g of catalyst organic bismuth DY-20 into the constant pressure funnel, under the conditions of 60 ⁇ 70°C, 300 ⁇ 500 r/min Drop 2 ⁇ 3 drops into 33.03g of hexamethylene diisocyanate (HDI) and fully react for 1 hour. During the reaction, use the di-n-butylamine method to titrate the NCO content. When the NCO content reaches the theoretical value, it is the end of the reaction.
  • PTMG-1000 pretreated polytetrahydrofuran diol
  • HDI hexamethylene diisocyanate
  • reaction end point A When the NCO content reaches the theoretical value is the reaction end point A; after reaching the reaction end point A, add 6.24g of polyol chain extender N-methyldiethanolamine (MDEA) to the reaction product for reaction at 60 ⁇ 70°C and 300 ⁇ 500 r/min, during the reaction process Use the di-n-butylamine method to titrate the NCO content.
  • MDEA polyol chain extender N-methyldiethanolamine
  • the titration of the NCO content was carried out by the di-n-butylamine method.
  • the NCO content dropped to 0, it was the end point C of the reaction.
  • After reaching the end of the reaction add glacial acetic acid, a neutralizing agent with a molar ratio of 1:1 to the polyol chain extender, to the reaction product and keep at 300-500 r/min for 5-10 minutes at 60-70°C to terminate the reaction; finally Add deionized water and stir for 30 min under high-speed stirring at 2000-3000 r/min, and finally obtain a polyurethane-based photosensitive resin with a solid content of 10-20%.
  • FIG. 1 it is a schematic diagram of the chemical reaction for preparing polyurethane-based water-based photosensitive resin.
  • the inventor found through research that the polyether diol can increase the chain length and improve the flexibility of the resin.
  • the chain extender can increase the content of its hydrophilic groups, increase the hydrophilicity, and at the same time act as a hard segment to adjust the hardness. The more the content, the better the hydrophilicity and the higher the hardness.
  • the function of the end-capping agent is to increase the content of photocurable groups, the more the increase, the higher the degree of crosslinking and the higher the hardness.
  • the emulsion particle diameter of embodiment 1-3 is as shown in Figure 2, as can be seen from Figure 2, the emulsion particle diameter distribution of embodiment 1-3 is narrow and uniform, and particle diameter is smaller, all less than 30nm, proves that this technical route adopts the side chain containing The amine-based chain extender has better water solubility and uniform dispersion than the main chain-containing amine-based chain extender.
  • Example 1 The flatness of film has the greatest impact, and the paint film appearance of embodiment 1 is the best, smooth and smooth, and a small amount of accumulation is arranged on the paint film surface of embodiment 2, shrinkage cavity is arranged on the paint film surface of embodiment 3, and the flatness of paint film surface will be It affects its application in electrophoretic coatings, so Example 1 is a relatively better solution; the other properties of the paint film of Comparative Examples 1-3, the change is not obvious, and all have good mechanics, water resistance and solvent resistance.
  • the paint film of Comparative Example 1-2 is due to the use of a glycol chain extender with tertiary amine groups on the main chain and a formula with a neutralization degree of 50%, resulting in poor water solubility of the emulsion, instability of the emulsion, and delamination. And the mechanical properties, such as hardness, etc. are not up to the required requirements.
  • the corrosion test is carried out using the test methods and requirements specified in the national standard GB 10124-88 "Uniform Corrosion Full Immersion Test Method for Metal Materials Laboratory", and the interactive immersion test is used.
  • the same tinplate sample with half of the metal coating and the other half uncoated is alternately immersed in a liquid corrosive medium and exposed to air.
  • the test results are shown in Figure 4.
  • the uncoated metal substrate on the left has rust and corrosion, and the coated part on the right has protection for the metal substrate without corrosion.
  • the test results of Effect Example 1-2 show that the coating of the present invention has a good anti-corrosion effect on tinplate substrates and has strong impact resistance.

Abstract

The present invention relates to the field of high polymer materials, and disclosed are a water-based ultraviolet curing cathode electrophoretic coating and a preparation method therefor. The polyurethane-based electrophoretic coating of the present invention is prepared by using an isocyanate monomer, polyester polyol, a chain extender, an end-capping reagent, a neutralizer, a polymerization inhibitor, a catalyst, and a photoinitiator as raw materials, and grafting photocuring active groups (carbon-carbon double bonds) and a hydrophilic group onto a polyurethane long chain by means of the reaction between an isocyanate group on the isocyanate monomer and hydroxyl groups in the polyol, the chain extender, and the end-capping reagent. The coating of the present invention is good in emulsion stability, and a coating layer has relatively high hardness, good adhesive force, and excellent water resistance and solvent resistance. The preparation method of the present invention is simple, easy in raw material acquisition, environmentally friendly, and easy to industrialize and popularize and use on a large scale.

Description

一种水性紫外光固化阴极电泳涂料及其制备方法A kind of water-based ultraviolet light curing cathodic electrophoretic coating and preparation method thereof 技术领域technical field
本发明属于高分子材料领域，具体涉及一种水性紫外光固化阴极电泳涂料及其制备方法。The invention belongs to the field of macromolecular materials, and in particular relates to a water-based ultraviolet light curing cathodic electrophoretic paint and a preparation method thereof.
背景技术Background technique
金属的腐蚀氧化会给实际生活中的很多方面带来困扰，而金属镀膜为解决这个问题提供了有效的方法。金属镀膜形成主要分为两种方法：第一种为化学镀法，其原理是利用化学还原法，将膜材配制成溶液，使其迅速参加还原反应，还原后沉积在被加工零件表面的一种加工方法。化学镀法存在的问题是镀膜不易控制，容易导致不均匀，且与基材结合强度差，同时还会产生大量的废液，造成严重的环境污染；第二种方法为电泳法，利用胶体粒子在电场作用下能产生电泳现象的原理，使电泳涂料中的基体树脂在水中离解成带电荷的离子聚合物，在电场作用下各自向与其极性相反的电极移动，并沉积在电极表面，形成漆膜。相比之下，电泳涂料具有很多优点，如涂料的大部分溶剂为水，从安全性和国家对环保的要求来看，涂料水性化具有很大的成长空间。另外，由于是电沉积成膜，因此可以在复杂形状的元器件上涂装，成膜均匀，附着力强。电泳涂料包括阳极电泳涂料和阴极电泳涂料。阳极电泳涂料存在的问题是容易腐蚀阳极材料，且电解液不稳定。与阳极电泳漆相比，阴极电泳涂料不会腐蚀电极，且具有优良的防锈能力。因此，对于阴极电泳漆的研究较多，如在专利CN104945590A中，利用以封端型异氰酸酯三聚体为交联剂，将其与阳离子型端羟基聚氨酯树脂混合后，制备出端羟基改性聚氨酯电泳漆。但该电泳漆后处理需要热固化交联，烘干温度高，能耗较高。日本公开专利No.sho63(1988)-69882采用含有羟酸基或磺酸基的多元醇作为亲水性扩链剂制备出自乳化的阴离子水基聚氨酯树脂，由其制备的聚氨酯涂料的硬度较低、综合性能仍然不尽人意。在专利US6232364 中，通过使用合成主链结构上含有叔胺二元醇为成盐基团的聚氨酯型阳离子电沉积的紫外线固化型涂料，但此类聚氨酯电泳涂料的预聚体在分散时，由于聚氨酯分子的缠绕，容易将部分亲水基包裹在聚氨酯颗粒内部，影响水分散效果，需要使用较多含叔胺的单体，不仅味道大，其漆膜性能也较差。电泳涂料作为一种绿色环保型涂料，同样需要向低成本、无重金属、低固化温度、高存储稳定性等方向发展，而现有技术并不能满足克服上述缺点，满足产业的需要。此外，紫外光固化技术固化温度不高，特别适用于热敏基材；固化速率快，能显著提高了生产效率；无需溶剂，对环境污染小，能耗低；并且可通过调节树脂与活性单体稀释剂的比例来改变涂膜的性质，正好可以弥补电泳漆的缺点。Corrosion and oxidation of metal will cause problems in many aspects of real life, and metal coating provides an effective way to solve this problem. The formation of metal coatings is mainly divided into two methods: the first is the chemical plating method, the principle is to use the chemical reduction method to prepare the film material into a solution, so that it can quickly participate in the reduction reaction, and after reduction, deposit on the surface of the processed part. A processing method. The problem with the electroless plating method is that the coating film is not easy to control, it is easy to cause unevenness, and the bonding strength with the substrate is poor. At the same time, a large amount of waste liquid will be generated, causing serious environmental pollution; the second method is the electrophoresis method, which uses colloidal particles Under the action of an electric field, the principle of electrophoresis can be generated, so that the matrix resin in the electrophoretic coating dissociates into charged ionic polymers in water, and under the action of an electric field, each moves to the electrode with the opposite polarity and deposits on the surface of the electrode to form paint film. In contrast, electrophoretic coatings have many advantages. For example, most of the solvents of coatings are water. From the perspective of safety and national environmental protection requirements, water-based coatings have a lot of room for growth. In addition, due to the electrodeposition film formation, it can be coated on components with complex shapes, and the film formation is uniform and the adhesion is strong. Electrophoretic coatings include anodic electrophoretic coatings and cathodic electrophoretic coatings. The problem of anodic electrophoretic coating is that it is easy to corrode the anode material and the electrolyte is not stable. Compared with anodic electrophoretic paint, cathodic electrophoretic paint will not corrode electrodes and has excellent rust resistance. Therefore, there are many studies on cathodic electrophoretic paint. For example, in the patent CN104945590A, a blocked isocyanate trimer is used as a crosslinking agent, and after it is mixed with a cationic hydroxyl-terminated polyurethane resin, a hydroxyl-terminated polyurethane is prepared. Electrophoretic paint. However, the post-treatment of the electrophoretic paint requires thermal curing and crosslinking, high drying temperature and high energy consumption. Japanese Laid-open Patent No.sho63(1988)-69882 adopts the polyhydric alcohol containing hydroxy acid group or sulfonic acid group as hydrophilic chain extender to prepare self-emulsified anionic water-based polyurethane resin, and the hardness of the polyurethane coating prepared by it is lower , Comprehensive performance is still unsatisfactory. In patent US6232364 Among them, by using the ultraviolet curable coating of polyurethane type cationic electrodeposition containing tertiary amine diol as salt-forming group on the synthetic main chain structure, but when the prepolymer of this type of polyurethane electrophoretic coating is dispersed, due to the polyurethane molecule Winding, it is easy to wrap part of the hydrophilic group inside the polyurethane particles, which affects the water dispersion effect, and needs to use more monomers containing tertiary amines, which not only tastes bad, but also has poor paint film performance. Electrophoretic coatings, as a kind of green and environment-friendly coatings, also need to be developed in the direction of low cost, no heavy metals, low curing temperature, and high storage stability. However, the existing technology cannot meet the above shortcomings and meet the needs of the industry. In addition, the curing temperature of UV curing technology is not high, which is especially suitable for heat-sensitive substrates; the curing rate is fast, which can significantly improve production efficiency; no solvent is required, less environmental pollution, and low energy consumption; The properties of the coating film can be changed by changing the proportion of the volume diluent, which can just make up for the shortcomings of the electrophoretic paint.
因此，开发一种兼具阴极电泳漆和紫外光固化涂料二者优点的光固化阴极电泳漆，不仅能进一步拓宽电泳漆的应用范围，而且可以顺应环境友好的发展趋势，已成为电泳漆发展的新方向。Therefore, the development of a light-curing cathodic electrophoretic paint that has the advantages of both cathodic electrophoretic paint and UV-curable paint can not only further broaden the application range of electrophoretic paint, but also conform to the development trend of environmental friendliness, and has become the development trend of electrophoretic paint. New Direction.
技术问题technical problem
本发明的目的在于克服现有技术存在的不足之处而提供一种水性紫外光固化阴极电泳涂料及其制备方法。本发明实现了高效的紫外光固化，与热固化相比，具有高效、低能耗和极低VOC排放的优势。同时，制得的漆膜具有良好的柔顺性和硬度落。The purpose of the present invention is to overcome the shortcomings of the prior art and provide a water-based ultraviolet light-curable cathodic electrophoretic coating and a preparation method thereof. The invention realizes efficient ultraviolet light curing, and has the advantages of high efficiency, low energy consumption and extremely low VOC emission compared with thermal curing. At the same time, the prepared paint film has good flexibility and hardness drop.
技术解决方案technical solution
为实现上述目的，本发明采取的技术方案为：一种水性紫外光固化阴极电泳涂料，所述涂料包括聚氨酯基光敏树脂和光引发剂组分；所述制备聚氨酯基光敏树脂的原料包括以下组分：异氰酸酯单体、聚醚多元醇、多元醇扩链剂、封端剂、中和剂、阻聚剂和催化剂。In order to achieve the above object, the technical solution adopted by the present invention is: a water-based UV-curable cathodic electrophoretic coating, the coating includes a polyurethane-based photosensitive resin and a photoinitiator component; the raw materials for preparing the polyurethane-based photosensitive resin include the following components : Isocyanate monomer, polyether polyol, polyol chain extender, end-capping agent, neutralizing agent, polymerization inhibitor and catalyst.
本技术方案用异氰酸酯单体、聚醚多元醇、多元醇扩链剂、封端剂、中和剂、阻聚剂、催化剂和光引发剂为原料，通过异氰酸酯单体上的异氰酸根基团和聚醚多元醇、多元醇扩链剂与封端剂中的羟基之间的反应，将光固化活性基团碳碳双键，亲水基团接枝到聚氨酯长链上，得到聚氨酯基光敏树脂。聚氨酯基光敏树脂与引发剂混和后的涂料，具有良好的导电性和水溶性满足电泳涂装的要求。同时，本发明涂料与普通水性涂料相比，聚合速度快，通过UV固化，固化过程更加节能环保。聚氨酯基光敏树脂中的叔胺基团呈碱性，当将冰醋酸等酸类中和剂加入体系后，进行中和成盐的反应，使所合成的聚氨酯预聚物具有良好的水溶性和稳定性。本发明涂料兼具UV固化涂料和电泳涂料的优点，施工时先通过电泳方式镀膜，后通过UV光迅速固化，制备出的涂层具有较高的硬度、良好附着力和优良耐水耐溶剂性能，对金属基材起到良好的保护作用，在金属用涂料领域展现了良好的应用前景。This technical scheme uses isocyanate monomers, polyether polyols, polyol chain extenders, end-capping agents, neutralizing agents, polymerization inhibitors, catalysts and photoinitiators as raw materials, through the isocyanate groups on the isocyanate monomers and The reaction between polyether polyol, polyol chain extender and the hydroxyl group in the end-capping agent grafts the carbon-carbon double bond of the photocuring active group and the hydrophilic group to the long chain of polyurethane to obtain a polyurethane-based photosensitive resin . The paint mixed with polyurethane-based photosensitive resin and initiator has good conductivity and water solubility to meet the requirements of electrophoretic coating. At the same time, compared with ordinary water-based paints, the coating of the present invention has fast polymerization speed, and is cured by UV, and the curing process is more energy-saving and environment-friendly. The tertiary amine group in the polyurethane-based photosensitive resin is basic. When an acid neutralizer such as glacial acetic acid is added to the system, the reaction of neutralization and salt formation is carried out, so that the synthesized polyurethane prepolymer has good water solubility and stability. The coating of the present invention has the advantages of both UV curing coatings and electrophoretic coatings. During construction, the coating is first coated by electrophoresis, and then quickly cured by UV light. The prepared coating has high hardness, good adhesion and excellent water and solvent resistance. It has a good protective effect on metal substrates and shows a good application prospect in the field of metal coatings.
作为本发明的优选实施方式，这种水性紫外光固化阴极电泳涂料中，所述异氰酸酯单体为2 官能度的异氰酸酯单体，包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯和二苯甲烷二异氰酸酯中的至少一种。As a preferred embodiment of the present invention, in this water-based UV-curable cathodic electrophoretic coating, the isocyanate monomer is a 2-functional isocyanate monomer, including isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate, and hexamethylene diisocyanate. at least one of isocyanate and diphenylmethane diisocyanate.
发明人经过研究发现，用不同单体合成出来的聚氨酯性能上有一定差异，特别是作为电泳涂料进行应用时，对漆膜的平整度影响大。使用本发明优选单体制备出的涂料平整度良好，漆膜平整，其中甲苯二异氰酸酯漆膜表现最好。The inventors have found through research that polyurethanes synthesized from different monomers have certain differences in performance, especially when they are used as electrophoretic coatings, they have a great influence on the flatness of the paint film. The paint prepared by using the preferred monomer of the present invention has good flatness and smooth paint film, and the toluene diisocyanate paint film has the best performance.
作为本发明的优选实施方式，这种水性紫外光固化阴极电泳涂料中，所述聚醚多元醇包括聚四氢呋喃二醇和/或聚乙二醇。As a preferred embodiment of the present invention, in the water-based UV-curable cathodic electrophoretic coating, the polyether polyol includes polytetrahydrofuran diol and/or polyethylene glycol.
作为本发明的更加优选的实施方式，这种水性紫外光固化阴极电泳涂料中，所述聚醚多元醇包括PTMG-1000、PTMG-2000、PEG-600、PEG-1000中的至少一种。As a more preferred embodiment of the present invention, in the water-based UV-curable cathodic electrophoretic coating, the polyether polyol includes at least one of PTMG-1000, PTMG-2000, PEG-600, and PEG-1000.
作为本发明的优选实施方式，这种水性紫外光固化阴极电泳涂料中，所述多元醇扩链剂包括聚酯型二元醇扩链剂和/或N-甲基二乙醇胺。As a preferred embodiment of the present invention, in the water-based UV-curable cathodic electrophoretic coating, the polyol chain extender includes a polyester diol chain extender and/or N-methyldiethanolamine.
作为本发明的优选实施方式，这种水性紫外光固化阴极电泳涂料中，所述多元醇扩链剂包括3-二甲胺基-1,2-丙二醇。As a preferred embodiment of the present invention, in the water-based UV-curable cathodic electrophoretic coating, the polyol chain extender includes 3-dimethylamino-1,2-propanediol.
发明人经过研究发现，本发明使用的多元醇扩链剂使用3-二甲胺基-1,2-丙二醇，与常用的侧链含胺基的扩链剂相比，本发明采用主链含胺基扩链剂得到涂料的水溶性良好，乳液粒径分布窄且均一，粒径较小，均小于30nm，具有良好的分散均一性和水溶性。The inventor has found through research that the polyol chain extender used in the present invention uses 3-dimethylamino-1,2-propanediol. The amine-based chain extender has good water solubility of the coating, the emulsion particle size distribution is narrow and uniform, and the particle size is small, all less than 30nm, and has good dispersion uniformity and water solubility.
作为本发明的优选实施方式，这种水性紫外光固化阴极电泳涂料中，所述封端剂为丙烯酸羟乙酯和/或甲基丙烯酸羟乙酯。As a preferred embodiment of the present invention, in the water-based UV-curable cathodic electrophoretic coating, the end-capping agent is hydroxyethyl acrylate and/or hydroxyethyl methacrylate.
发明人经过研究发现，使用丙烯酸羟乙酯和/或甲基丙烯酸羟乙酯为封端剂可在聚氨酯预聚体中引入可光聚合的乙烯基基团，制备出聚氨酯基光敏树脂。该聚氨酯基光敏树脂与普通水性聚氨酯相比，固化更环保节能，聚合速度快，在30 mW/cm 2的光强下辐照25~60 s即可实现完全固化，能大大提高施工效率。 The inventors have discovered through research that using hydroxyethyl acrylate and/or hydroxyethyl methacrylate as a capping agent can introduce photopolymerizable vinyl groups into polyurethane prepolymers to prepare polyurethane-based photosensitive resins. Compared with ordinary water-based polyurethane, the polyurethane-based photosensitive resin is more environmentally friendly and energy-saving in curing, and has a fast polymerization speed. It can be completely cured under the light intensity of 30 mW/cm 2 for 25-60 s, which can greatly improve the construction efficiency.
作为本发明更加优选的实施方式，这种水性紫外光固化阴极电泳涂料中，所述异氰酸酯单体与封端剂的摩尔比为（5.5~1.5）:1。As a more preferred embodiment of the present invention, in the water-based UV-curable cathodic electrophoretic coating, the molar ratio of the isocyanate monomer to the blocking agent is (5.5-1.5):1.
发明人经过研究发现，抗冲击强度、硬度、耐腐蚀性能与组分中封端剂添加量有关，在本发明优选的范围内封端剂加入越多，交联密度越大，抗冲击、硬度与耐腐蚀强度越大。The inventor found through research that impact strength, hardness, and corrosion resistance are related to the amount of end-capping agent added in the components. In the preferred range of the present invention, the more the end-capping agent is added, the greater the crosslinking density, and the impact resistance, hardness The greater the corrosion resistance strength.
作为本发明的优选实施方式，这种水性紫外光固化阴极电泳涂料中，所述中和剂为冰乙酸和/或丙烯酸。As a preferred embodiment of the present invention, in the water-based UV-curable cathodic electrophoretic coating, the neutralizer is glacial acetic acid and/or acrylic acid.
发明人经过研究发现，利用与冰乙酸、丙烯酸的中和反应，使该光敏树脂聚氨酯具有良好的水溶性和存储稳定性，可稳定储存一个月以上。The inventor found through research that the photosensitive resin polyurethane has good water solubility and storage stability through the neutralization reaction with glacial acetic acid and acrylic acid, and can be stored stably for more than one month.
作为本发明的优选实施方式，这种水性紫外光固化阴极电泳涂料中，所述中和剂和多元醇扩链剂的摩尔比为：1:1。As a preferred embodiment of the present invention, in the water-based UV-curable cathodic electrophoretic coating, the molar ratio of the neutralizer to the polyol chain extender is: 1:1.
发明人经过研究发现，当中和剂和多元醇扩链剂的摩尔比为：1:1时，叔胺基团与酸中和反应完全，形成的聚氨酯预聚物表现出良好的水溶性。The inventors have found through research that when the molar ratio of the neutralizer to the polyol chain extender is 1:1, the neutralization reaction between the tertiary amine group and the acid is complete, and the formed polyurethane prepolymer exhibits good water solubility.
作为本发明的优选实施方式，这种水性紫外光固化阴极电泳涂料中，所述异氰酸酯单体的摩尔量与聚醚多元醇和多元醇扩链剂摩尔量之和的比为：异氰酸酯单体：（聚醚多元醇+多元醇扩链剂）=（1.1~1.6）:1。 As a preferred embodiment of the present invention, in this water-based UV-curable cathodic electrophoretic coating, the ratio of the molar weight of the isocyanate monomer to the sum of the molar weight of polyether polyol and polyol chain extender is: isocyanate monomer: ( Polyether polyol + polyol chain extender) = (1.1~1.6):1.
作为本发明的优选实施方式，这种水性紫外光固化阴极电泳涂料中，所述聚醚多元醇和多元醇扩链剂摩尔比为：聚醚多元醇：多元醇扩链剂= （0.8~1.5）:1。As a preferred embodiment of the present invention, in this water-based UV-curable cathodic electrophoretic coating, the molar ratio of the polyether polyol to the polyol chain extender is: polyether polyol: polyol chain extender = (0.8~1.5) :1.
发明人经过研究发现，导电性能和亲水性与涂料中二元醇扩链剂的含量相关，二元醇扩链剂越多，导电性能与亲水性能越好，相反耐水性能就越差。发明人经过研究发现，多元醇扩链剂上的叔胺基团呈碱性，与冰醋酸等酸类中和剂进行中和成盐的反应，可以使所合成的聚氨酯预聚物具有良好的水溶性。The inventors have found through research that the conductivity and hydrophilicity are related to the content of the glycol chain extender in the paint. The more the glycol chain extender, the better the conductivity and hydrophilicity, and the worse the water resistance. The inventor has found through research that the tertiary amine group on the polyol chain extender is alkaline, and the reaction of neutralizing and forming a salt with acid neutralizers such as glacial acetic acid can make the synthesized polyurethane prepolymer have good properties. water soluble.
作为本发明的优选实施方式，所述阻聚剂为对羟基苯甲醚、对苯二酚、叔丁基邻苯二酚中的至少一种。As a preferred embodiment of the present invention, the polymerization inhibitor is at least one of p-hydroxyanisole, hydroquinone, and tert-butylcatechol.
作为本发明的优选实施方式，所述催化剂为二月桂酸二丁基锡或/和有机铋。As a preferred embodiment of the present invention, the catalyst is dibutyltin dilaurate or/and organic bismuth.
作为本发明的优选实施方式，所述光引发剂为Darocur1173、TOPL、TPO、光引发剂819中的至少一种。As a preferred embodiment of the present invention, the photoinitiator is at least one of Darocur1173, TOPL, TPO, and photoinitiator 819.
本发明还提供了上述任一项水性紫外光固化阴极电泳涂料的制备方法，所述方法包括以下步骤：（1）将聚醚多元醇真空蒸馏，得到预处理的聚醚多元醇；（2）将预处理的聚醚多元醇和催化剂混合后，加入到异氰酸酯单体中，反应至NCO含量达到理论值时为反应终点A；（3）到达反应终点A后，在步骤（1）产物中加入多元醇扩链剂，反应至NCO含量再次达到理论值时为反应终点B；（4）到达反应终点B后，在步骤（3）产物加入封端剂与阻聚剂，反应至NCO含量降至0时为反应终点C；（5）到达反应终点C后，在步骤（4）产物中加入中和剂反应后终止反应；（6）在步骤（5）产物中加入去离子水搅拌得到聚氨酯基光敏树脂；（7）将步骤（6）中的聚氨酯基水性光敏树脂和光引发剂混合均匀得到水性紫外光固化阴极电泳涂料。The present invention also provides a method for preparing any one of the above-mentioned water-based UV-curable cathodic electrophoretic coatings, the method comprising the following steps: (1) vacuum distilling polyether polyol to obtain pretreated polyether polyol; (2) After mixing the pretreated polyether polyol and the catalyst, add it to the isocyanate monomer, and react until the NCO content reaches the theoretical value, which is the reaction end point A; (3) After reaching the reaction end point A, add polyhydric acid to the product of step (1) Alcohol chain extender, reacting until the NCO content reaches the theoretical value again is the reaction end point B; (4) After reaching the reaction end point B, add an end-capping agent and a polymerization inhibitor to the product in step (3), and react until the NCO content drops to 0 (5) After reaching the reaction end point C, add a neutralizing agent to the product in step (4) and stop the reaction; (6) add deionized water to the product in step (5) and stir to obtain a polyurethane-based photosensitive Resin; (7) uniformly mixing the polyurethane-based water-based photosensitive resin and the photoinitiator in step (6) to obtain a water-based UV-curable cathodic electrophoretic coating.
作为本发明的优选实施方式，制备方法的步骤（1）中，所述真空蒸馏的条件为：将聚醚多元醇在80~100℃、300~500 r/min的条件下真空蒸馏2~3 h。As a preferred embodiment of the present invention, in the step (1) of the preparation method, the conditions for the vacuum distillation are: vacuum distill the polyether polyol at 80-100°C and 300-500 r/min for 2-3 h.
作为本发明的优选实施方式，制备方法的步骤（2）中，所述聚醚多元醇和催化剂加入恒压漏斗中，在50~100℃、200~600 r/min的条件下以每秒 2~3滴的速率滴入异氰酸酯单体中进行接枝反应。As a preferred embodiment of the present invention, in the step (2) of the preparation method, the polyether polyol and the catalyst are added into a constant pressure funnel, and the mixture is heated at 2~100°C per second under the conditions of 50~100°C and 200~600 r/min. The rate of 3 drops was dropped into the isocyanate monomer to carry out the grafting reaction.
作为本发明的优选实施方式，制备方法的步骤（2）中，所述有机铋为有机铋DY-20。As a preferred embodiment of the present invention, in the step (2) of the preparation method, the organic bismuth is organic bismuth DY-20.
作为本发明的优选实施方式，制备方法的步骤（2）中，所述催化剂的质量占步骤（2）体系总质量的0.05~0.3%。As a preferred embodiment of the present invention, in step (2) of the preparation method, the mass of the catalyst accounts for 0.05-0.3% of the total mass of the system in step (2).
作为本发明的优选实施方式，制备方法的步骤（3）中，反应在50~80℃、200~500 r/min下进行。As a preferred embodiment of the present invention, in the step (3) of the preparation method, the reaction is carried out at 50-80° C. and 200-500 r/min.
作为本发明的优选实施方式，制备方法的步骤（4）中，步骤（3）的反应产物中利用恒压漏斗以每秒 2~3滴的速率滴入封端剂与阻聚剂的混合物并在60~70℃、300~500 r/min的条件下进行反应。As a preferred embodiment of the present invention, in step (4) of the preparation method, the reaction product of step (3) is dripped with a mixture of end-capping agent and polymerization inhibitor at a rate of 2 to 3 drops per second using a constant pressure funnel and The reaction is carried out under the conditions of 60~70°C and 300~500 r/min.
作为本发明的优选实施方式，制备方法的步骤（4）中，所述阻聚剂的质量占步骤（4）体系总质量的0.005~0.008%。As a preferred embodiment of the present invention, in step (4) of the preparation method, the mass of the polymerization inhibitor accounts for 0.005-0.008% of the total mass of the system in step (4).
作为本发明的优选实施方式，制备方法的步骤（2-4）中，反应过程中用二正丁胺法进行NCO含量的滴定。As a preferred embodiment of the present invention, in the step (2-4) of the preparation method, the titration of the NCO content is carried out by the di-n-butylamine method during the reaction.
作为本发明的优选实施方式，制备方法的步骤（5）中，加入中和剂后在60~70℃、300~500 r/min下反应10 min后终止反应。As a preferred embodiment of the present invention, in step (5) of the preparation method, after adding a neutralizing agent, react at 60-70°C, 300-500 r/min for 10 The reaction was terminated after min.
作为本发明的优选实施方式，制备方法的步骤（6）中，在2000~3000 r/min的高速搅拌下加入去离子水搅拌30 min。As a preferred embodiment of the present invention, in the step (6) of the preparation method, at 2000~3000 Under high-speed stirring at r/min, deionized water was added and stirred for 30 min.
作为本发明的优选实施方式，制备方法的步骤（6）中，最终得到固含量为10~20%的聚氨酯基光敏树脂。As a preferred embodiment of the present invention, in step (6) of the preparation method, a polyurethane-based photosensitive resin with a solid content of 10-20% is finally obtained.
作为本发明的优选实施方式，这种水性紫外光固化阴极电泳涂料中，所述光引发剂和聚氨酯基光敏树脂的质量比为（1~5）：（90~100）。As a preferred embodiment of the present invention, in the water-based UV-curable cathodic electrophoretic coating, the mass ratio of the photoinitiator to the polyurethane-based photosensitive resin is (1-5): (90-100).
发明人经过研究发现，光引发剂和聚氨酯基光敏树脂的质量比为（1~5）：（90~100）时形成的涂料UV固化速度快，涂料施工效率高。The inventor found through research that when the mass ratio of photoinitiator and polyurethane-based photosensitive resin is (1-5): (90-100), the UV curing speed of the coating formed is fast, and the coating construction efficiency is high.
本发明还提供了上述任一项水性紫外光固化阴极电泳涂料的应用，所述应用包括以下步骤：（1）将聚氨酯基光敏树脂和光引发剂混合均匀得到水性紫外光固化阴极电泳涂料；（2）将被镀金属基材作为阴极，使用步骤（1）涂料电泳涂装，得到镀膜的金属基材；（3）将步骤（2）中镀膜的金属基材水洗、干燥、烘烤后，使用UV光双面辐照固化。The present invention also provides the application of any one of the above-mentioned water-based UV-curable cathodic electrophoretic coatings, the application comprising the following steps: (1) uniformly mixing the polyurethane-based photosensitive resin and the photoinitiator to obtain the water-based UV-curable cathodic electrophoretic coating; (2) ) Use the metal substrate to be plated as the cathode, and use the step (1) paint electrophoretic coating to obtain the coated metal substrate; (3) wash, dry and bake the coated metal substrate in step (2), and use UV light double-sided radiation curing.
作为本发明的优选实施方式，应用的步骤（2）中，将步骤（1）涂料置于电泳槽中，以马口铁作为阳极，以需要被镀金属基材作为阴极，在100V的直流电压下进行电泳涂装，电极极距为10 cm、电泳时间为3~5 min，得到镀有不溶性漆膜的金属基材。As a preferred embodiment of the present invention, in step (2) of the application, the coating of step (1) is placed in the electrophoresis tank, the tinplate is used as the anode, and the metal substrate to be plated is used as the cathode, and the process is carried out at a DC voltage of 100V. Electrophoretic coating, electrode distance is 10 cm, electrophoresis time is 3~5 min, to obtain a metal substrate coated with an insoluble paint film.
作为本发明的优选实施方式，应用的步骤（2）中，所述金属基材包括马口铁、铜、铝、锌、银中的至少一种。As a preferred embodiment of the present invention, in the application step (2), the metal substrate includes at least one of tinplate, copper, aluminum, zinc, and silver.
作为本发明的优选实施方式，应用的步骤（3）中，将步骤（2）中镀有不溶性漆膜的金属基材水洗、干燥、80~100℃下烘烤3 min后，在UV光固化机中双面辐照固化。As a preferred embodiment of the present invention, in step (3) of the application, the metal substrate coated with the insoluble paint film in step (2) is washed with water, dried, baked at 80-100°C for 3 minutes, and then cured by UV light In-machine double-sided radiation curing.
有益效果Beneficial effect
与现有技术相比，本发明的有益效果在于：Compared with prior art, the beneficial effect of the present invention is:
（1）本发明涂料电导率优良，完全满足电泳要求，可用于电泳涂装。(1) The coating of the present invention has excellent electrical conductivity, fully meets the requirements of electrophoresis, and can be used for electrophoretic coating.
（2）本发明涂料在30 mW/cm 2的光强下辐照25~60 s即可实现完全固化，固化过程更加环保节能，聚合速度快，大大提高了施工效率。 (2) The coating of the present invention can be completely cured under the light intensity of 30 mW/cm 2 for 25-60 s. The curing process is more environmentally friendly and energy-saving, and the polymerization speed is fast, which greatly improves the construction efficiency.
（3）本发明兼具电泳涂装技术和紫外光固化技术的优点，制备出的金属用涂层具有较高的硬度、良好附着力和优良耐水耐溶剂性能，对金属基材起到保护作用，使金属具有明显的耐腐蚀性和抗冲击性能，在金属用涂层领域展现了良好的应用前景。(3) The present invention combines the advantages of electrophoretic coating technology and ultraviolet light curing technology, and the prepared metal coating has high hardness, good adhesion and excellent water and solvent resistance, which can protect the metal substrate , so that the metal has obvious corrosion resistance and impact resistance, and has shown a good application prospect in the field of metal coatings.
（4）本发明利用叔胺基团和中和剂的酸碱中和成盐反应，使涂料具有良好的水溶性和导电性。同时，涂料的存储稳定性良好，可稳定储存一个月以上。本发明涂料环保无污染，有利于可持续发展。(4) The present invention utilizes the acid-base neutralization and salt-forming reaction of the tertiary amine group and the neutralizing agent to make the coating have good water solubility and conductivity. At the same time, the paint has good storage stability and can be stored stably for more than one month. The coating of the invention is environmentally friendly and pollution-free, and is beneficial to sustainable development.
附图说明Description of drawings
图1 为本发明制备聚氨酯基水性光敏树脂的化学反应示意图。Figure 1 is a schematic diagram of the chemical reaction for preparing polyurethane-based water-based photosensitive resin according to the present invention.
图2 为实施例1-3乳液粒径分布图。Fig. 2 is the particle size distribution diagram of the emulsion of Examples 1-3.
图3 为效果例1抗冲击性能表征图。Fig. 3 is a characterization diagram of the impact resistance performance of Effect Example 1.
图4 为效果例2耐腐蚀性能表征图。Figure 4 is the characterization diagram of the corrosion resistance performance of Effect Example 2.
本发明的最佳实施方式BEST MODE FOR CARRYING OUT THE INVENTION
为更好的说明本发明的目的、技术方案和优点，下面将结合具体实施例和对比例对本发明作进一步说明。本发明实施例中所述实验方法如无特殊说明，均为常规方法；如无特殊说明，所述试剂和材料，均可从商业途径获得。In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific examples and comparative examples. Unless otherwise specified, the experimental methods described in the examples of the present invention are conventional methods; unless otherwise specified, the reagents and materials can be obtained from commercial sources.
本发明实施例中采用的原材料信息如表1所示。The raw material information used in the embodiment of the present invention is shown in Table 1.
Figure 144079dest_path_image001
Figure 144079dest_path_image001
实施例1Example 1
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种实施例。将52.38g的预处理后的聚四氢呋喃二醇（PTMG-1000）与0.488g的催化剂二月桂酸二丁基锡（DBTDL）加入恒压漏斗中，在60~70℃、300~500 r/min的条件下以每秒 2~3滴的速率滴入30.28g异佛尔酮二异氰酸酯（IPDI）中充分反应1 h，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量达到理论值时为反应终点A；到达反应终点A后，在反应产物中加入6.24g多元醇扩链剂3-二甲胺基-1,2-丙二醇（DMAD）60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量再次达到理论值时为反应终点B；到达反应终点B后，在反应产物中利用恒压漏斗以每秒 2~3滴的速率滴入7.20g封端剂丙烯酸羟乙酯（HEA）与0.053g阻聚剂羟基苯甲醚的混合物60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量降至0时为反应终点C。到达反应终点后，在反应产物中加入与多元醇扩链剂摩尔比1:1的中和剂冰醋酸60~70℃、在300~500 r/min条件下保持5~10 min终止反应；最后在2000~3000 r/min的高速搅拌下加入去离子水搅拌30 min，最终得到固含量为10~20%的聚氨酯基光敏树脂。As an embodiment of the polyurethane-based water-based UV-curable cathodic electrophoretic coating of the present invention. Add 52.38g of pretreated polytetrahydrofuran diol (PTMG-1000) and 0.488g of catalyst dibutyltin dilaurate (DBTDL) into the constant pressure funnel, under the conditions of 60~70℃, 300~500 r/min Drop it into 30.28g isophorone diisocyanate (IPDI) at a rate of 2~3 drops per second to fully react for 1 h. During the reaction, use the di-n-butylamine method to titrate the NCO content. When the NCO content reaches the theoretical value The time is the reaction end point A; after reaching the reaction end point A, add 6.24g of polyol chain extender 3-dimethylamino-1,2-propanediol (DMAD) to the reaction product at 60~70°C, 300~500 r/min Carry out reaction, carry out the titration of NCO content with di-n-butylamine method in the reaction process, when NCO content reaches theoretical value again, be reaction end point B; 3 drops of the mixture of 7.20g end-capping agent hydroxyethyl acrylate (HEA) and 0.053g polymerization inhibitor hydroxyanisole were dropped into the reaction at 60~70℃, 300~500 r/min. During the reaction, two normal The NCO content was titrated by the butylamine method, and when the NCO content dropped to 0, it was the end point C of the reaction. After reaching the end of the reaction, add glacial acetic acid, a neutralizing agent with a molar ratio of 1:1 to the polyol chain extender, to the reaction product and keep at 300-500 r/min for 5-10 minutes at 60-70°C to terminate the reaction; finally Add deionized water and stir for 30 min under high-speed stirring at 2000-3000 r/min, and finally obtain a polyurethane-based photosensitive resin with a solid content of 10-20%.
实施例2Example 2
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种实施例。将52.38g的预处理后的聚四氢呋喃二醇（PTMG-1000）与0.452g的催化剂二月桂酸二丁基锡（DBTDL）加入恒压漏斗中，在60~70℃、300~500 r/min的条件下以每秒 2~3滴的速率滴入23.72g甲苯二异氰酸酯（TDI）中充分反应1 h，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量达到理论值时为反应终点A；到达反应终点A后，在反应产物中加入6.24g多元醇扩链剂3-二甲胺基-1,2-丙二醇（DMAD）60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量再次达到理论值时为反应终点B；到达反应终点B后，在反应产物中利用恒压漏斗以每秒 2~3滴的速率滴入7.20g封端剂丙烯酸羟乙酯（HEA）与0.049g阻聚剂羟基苯甲醚的混合物，在60~70℃、300~500 r/min条件下反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量降至0时为反应终点C。到达反应终点后，在反应产物中加入与多元醇扩链剂摩尔比1:1的中和剂冰醋酸，在60~70℃、300~500 r/min条件下保持5~10 min终止反应；最后在2000~3000 r/min的高速搅拌下加入去离子水搅拌30 min，最终得到固含量为10~20%的聚氨酯基光敏树脂。As an embodiment of the polyurethane-based water-based UV-curable cathodic electrophoretic coating of the present invention. Add 52.38g of pretreated polytetrahydrofuran diol (PTMG-1000) and 0.452g of catalyst dibutyltin dilaurate (DBTDL) into the constant pressure funnel, under the conditions of 60~70℃, 300~500 r/min Drop it into 23.72g of toluene diisocyanate (TDI) at a rate of 2~3 drops per second and fully react for 1 h. During the reaction, use the di-n-butylamine method to titrate the NCO content. When the NCO content reaches the theoretical value, it is the reaction. End point A; after reaching the reaction end point A, add 6.24g polyol chain extender 3-dimethylamino-1,2-propanediol (DMAD) to the reaction product to react at 60~70℃, 300~500 r/min, During the reaction process, titrate the NCO content with the di-n-butylamine method. When the NCO content reaches the theoretical value again, it is the reaction end point B; Drop in a mixture of 7.20g end-capping agent hydroxyethyl acrylate (HEA) and 0.049g polymerization inhibitor hydroxyanisole at a high speed, and react at 60~70°C and 300~500 r/min. During the reaction, use two normal The NCO content was titrated by the butylamine method, and when the NCO content dropped to 0, it was the end point C of the reaction. After reaching the end of the reaction, add neutralizing agent glacial acetic acid with a molar ratio of 1:1 to the polyol chain extender to the reaction product, and keep it at 60~70°C and 300~500 r/min for 5~10 minutes to terminate the reaction; Finally, deionized water was added and stirred for 30 min under high-speed stirring at 2000-3000 r/min, and finally a polyurethane-based photosensitive resin with a solid content of 10-20% was obtained.
实施例3Example 3
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种实施例。将52.38g预处理后的聚四氢呋喃二醇（PTMG-1000）与0.487g的催化剂二月桂酸二丁基锡（DBTDL）加入恒压漏斗中，在60~70℃、300~500 r/min的条件下以每秒 2~3滴的速率滴入30.28g异佛尔酮二异氰酸酯（IPDI）中充分反应1 h，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量达到理论值时为反应终点A；到达反应终点A后，在反应产物中加入6.24g多元醇扩链剂3-二甲胺基-1,2-丙二醇（DMAD）60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量再次达到理论值时为反应终点B；到达反应终点B后，在反应产物中利用恒压漏斗以每秒 2~3滴的速率滴入8.14g封端剂甲基丙烯酸羟乙酯（HEMA）与0.058g阻聚剂羟基苯甲醚的混合物60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量降至0时为反应终点C。到达反应终点后，在反应产物中加入与多元醇扩链剂摩尔比1:1的中和剂冰醋酸，在60~70℃、300~500 r/min条件下保持5~10 min终止反应；最后在2000~3000r/min的高速搅拌下加入去离子水搅拌30min，最终得到固含量为10~20%的聚氨酯基光敏树脂。As an embodiment of the polyurethane-based water-based UV-curable cathodic electrophoretic coating of the present invention. Add 52.38g of pretreated polytetrahydrofuran glycol (PTMG-1000) and 0.487g of catalyst dibutyltin dilaurate (DBTDL) into the constant pressure funnel, under the conditions of 60~70℃, 300~500 r/min Drop into 30.28g isophorone diisocyanate (IPDI) at a rate of 2~3 drops per second and fully react for 1 hour. During the reaction, use the di-n-butylamine method to titrate the NCO content. When the NCO content reaches the theoretical value is the reaction end point A; after reaching the reaction end point A, add 6.24g of polyol chain extender 3-dimethylamino-1,2-propanediol (DMAD) to the reaction product at 60~70°C, 300~500 r/min Reaction, during the reaction, use the di-n-butylamine method to titrate the NCO content. When the NCO content reaches the theoretical value again, it is the reaction end point B; The rate of drop drops into the mixture of 8.14g end-capping agent hydroxyethyl methacrylate (HEMA) and 0.058g polymerization inhibitor hydroxyanisole to react at 60~70°C and 300~500 r/min. During the reaction, use two The n-butylamine method is used to titrate the NCO content, and when the NCO content drops to 0, it is the reaction end point C. After reaching the end of the reaction, add neutralizing agent glacial acetic acid with a molar ratio of 1:1 to the polyol chain extender to the reaction product, and keep it at 60~70°C and 300~500 r/min for 5~10 minutes to terminate the reaction; Finally, add deionized water and stir for 30 minutes under high-speed stirring at 2000-3000 r/min, and finally obtain a polyurethane-based photosensitive resin with a solid content of 10-20%.
实施例4Example 4
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种实施例。将52.38g预处理后的聚四氢呋喃二醇（PTMG-1000）与0.442g的催化剂二月桂酸二丁基锡（DBTDL）加入恒压漏斗中，在60~70℃、300~500 r/min的条件下以每秒 2~3滴的速率滴入36.05g二苯甲烷二异氰酸酯（MDI）中充分反应1 h，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量达到理论值时为反应终点A；到达反应终点A后，在反应产物中加入9.36g多元醇扩链剂3-二甲胺基-1,2-丙二醇（DMAD）60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量再次达到理论值时为反应终点B；到达反应终点B后，在反应产物中利用恒压漏斗以每秒 2~3滴的速率滴入2.43g封端剂丙烯酸羟乙酯（HEA）与0.05g阻聚剂羟基苯甲醚的混合物60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量降至0时为反应终点C。到达反应终点后，在反应产物中加入与多元醇扩链剂摩尔比1:1的中和剂丙烯酸，在60~70℃、300~500 r/min条件下保持5~10 min终止反应；最后在2000~3000r/min的高速搅拌下加入去离子水搅拌30min，最终得到固含量为10~20%的聚氨酯基光敏树脂。As an embodiment of the polyurethane-based water-based UV-curable cathodic electrophoretic coating of the present invention. Add 52.38g of pretreated polytetrahydrofuran glycol (PTMG-1000) and 0.442g of catalyst dibutyltin dilaurate (DBTDL) into the constant pressure funnel, under the conditions of 60~70℃, 300~500 r/min Drop it into 36.05g of diphenylmethane diisocyanate (MDI) at a rate of 2-3 drops per second and fully react for 1 h. During the reaction, use the di-n-butylamine method to titrate the NCO content. When the NCO content reaches the theoretical value, it is Reaction endpoint A; after reaching the reaction endpoint A, add 9.36g of polyol chain extender 3-dimethylamino-1,2-propanediol (DMAD) to the reaction product at 60~70℃, 300~500 r/min for reaction , titrate the NCO content with the di-n-butylamine method during the reaction, when the NCO content reaches the theoretical value again, it is the reaction end point B; Drop in a mixture of 2.43g end-capping agent hydroxyethyl acrylate (HEA) and 0.05g polymerization inhibitor hydroxyanisole at a rate of 60~70°C and 300~500 r/min for reaction, and di-n-butylamine is used during the reaction Titration of NCO content by method, when the NCO content drops to 0, it is the end point C of the reaction. After reaching the end of the reaction, add acrylic acid, a neutralizing agent with a molar ratio of 1:1 to the polyol chain extender, to the reaction product, and keep it at 60~70°C and 300~500 r/min for 5~10 minutes to terminate the reaction; finally Add deionized water and stir for 30 minutes under high-speed stirring at 2000~3000r/min, and finally obtain a polyurethane-based photosensitive resin with a solid content of 10~20%.
实施例5Example 5
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种实施例。将52.38g预处理后的聚四氢呋喃二醇（PTMG-1000）与0.256g的催化剂有机铋DY-20加入恒压漏斗中，在60~70℃、300~500 r/min的条件下以每秒 2~3滴的速率滴入33.03g六亚甲基二异氰酸酯(HDI)中充分反应1 h，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量达到理论值时为反应终点A；到达反应终点A后，在反应产物中加入9.36g多元醇扩链剂3-二甲胺基-1,2-丙二醇（DMAD）60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量再次达到理论值时为反应终点B；到达反应终点B后，在反应产物中利用恒压漏斗以每秒 2~3滴的速率滴入15.21g封端剂丙烯酸羟乙酯（HEA）与0.092g阻聚剂叔丁基邻苯二酚的混合物60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量降至0时为反应终点C。到达反应终点后，在反应产物中加入与多元醇扩链剂摩尔比1:1的中和剂冰醋酸，在60~70℃、300~500 r/min条件下保持5~10 min终止反应；最后在2000~3000r/min的高速搅拌下加入去离子水搅拌30min，最终得到固含量为10~20%的聚氨酯基光敏树脂。As an embodiment of the polyurethane-based water-based UV-curable cathodic electrophoretic coating of the present invention. Add 52.38g of pretreated polytetrahydrofuran diol (PTMG-1000) and 0.256g of catalyst organic bismuth DY-20 into the constant pressure funnel, under the conditions of 60~70℃, 300~500 r/min Drop 2~3 drops into 33.03g of hexamethylene diisocyanate (HDI) and fully react for 1 hour. During the reaction, use the di-n-butylamine method to titrate the NCO content. When the NCO content reaches the theoretical value, it is the end of the reaction. A; After reaching the reaction end point A, add 9.36g of polyol chain extender 3-dimethylamino-1,2-propanediol (DMAD) to the reaction product to react at 60~70℃, 300~500 r/min, the reaction During the titration of the NCO content with the di-n-butylamine method, when the NCO content reaches the theoretical value again, it is the reaction end point B; after reaching the reaction end point B, use a constant pressure funnel in the reaction product at a rate of 2 to 3 drops per second Drop in a mixture of 15.21g end-capping agent hydroxyethyl acrylate (HEA) and 0.092g polymerization inhibitor tert-butylcatechol to react at 60~70℃, 300~500 r/min, and use di-n-butylamine method during the reaction Carry out the titration of NCO content, when NCO content drops to 0, it is reaction end point C. After reaching the end of the reaction, add neutralizing agent glacial acetic acid with a molar ratio of 1:1 to the polyol chain extender to the reaction product, and keep it at 60~70°C and 300~500 r/min for 5~10 minutes to terminate the reaction; Finally, add deionized water and stir for 30 minutes under high-speed stirring at 2000-3000 r/min, and finally obtain a polyurethane-based photosensitive resin with a solid content of 10-20%.
对比例1Comparative example 1
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种对比例。将52.38g的预处理后的聚四氢呋喃二醇（PTMG-1000）与0.488g的催化剂二月桂酸二丁基锡（DBTDL）加入恒压漏斗中，在60~70℃、300~500 r/min的条件下以每秒 2~3滴的速率滴入30.28g异佛尔酮二异氰酸酯（IPDI）中充分反应1 h，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量达到理论值时为反应终点A；到达反应终点A后，在反应产物中加入6.24g多元醇扩链剂N-甲基二乙醇胺（MDEA）60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量再次达到理论值时为反应终点B；到达反应终点B后，在反应产物中利用恒压漏斗以每秒 2~3滴的速率滴入7.20g封端剂丙烯酸羟乙酯（HEA）与0.053g阻聚剂羟基苯甲醚的混合物60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量降至0时为反应终点C。到达反应终点后，在反应产物中加入与多元醇扩链剂摩尔比1:1的中和剂冰醋酸60~70℃、在300~500 r/min条件下保持5~10 min终止反应；最后在2000~3000 r/min的高速搅拌下加入去离子水搅拌30 min，最终得到固含量为10~20%的聚氨酯基光敏树脂。As a comparative example of the polyurethane-based water-based UV-curable cathodic electrophoretic coating of the present invention. Add 52.38g of pretreated polytetrahydrofuran diol (PTMG-1000) and 0.488g of catalyst dibutyltin dilaurate (DBTDL) into the constant pressure funnel, under the conditions of 60~70℃, 300~500 r/min Drop it into 30.28g isophorone diisocyanate (IPDI) at a rate of 2~3 drops per second to fully react for 1 h. During the reaction, use the di-n-butylamine method to titrate the NCO content. When the NCO content reaches the theoretical value is the reaction end point A; after reaching the reaction end point A, add 6.24g of polyol chain extender N-methyldiethanolamine (MDEA) to the reaction product for reaction at 60~70°C and 300~500 r/min, during the reaction process Use the di-n-butylamine method to titrate the NCO content. When the NCO content reaches the theoretical value again, it is the reaction end point B; Mixture of 7.20g end-capping agent hydroxyethyl acrylate (HEA) and 0.053g polymerization inhibitor hydroxyanisole 60~70℃, 300~500 The reaction was carried out at r/min. During the reaction, the titration of the NCO content was carried out by the di-n-butylamine method. When the NCO content dropped to 0, it was the end point C of the reaction. After reaching the end of the reaction, add glacial acetic acid, a neutralizing agent with a molar ratio of 1:1 to the polyol chain extender, to the reaction product and keep at 300-500 r/min for 5-10 minutes at 60-70°C to terminate the reaction; finally Add deionized water and stir for 30 min under high-speed stirring at 2000-3000 r/min, and finally obtain a polyurethane-based photosensitive resin with a solid content of 10-20%.
对比例2Comparative example 2
作为本发明聚氨酯基水性紫外光固化阴极电泳涂料的一种对比例。将52.38g的预处理后的聚四氢呋喃二醇（PTMG-1000）与0.488g的催化剂二月桂酸二丁基锡（DBTDL）加入恒压漏斗中，在60~70℃、300~500 r/min的条件下以每秒 2~3滴的速率滴入30.28g异佛尔酮二异氰酸酯（IPDI）中充分反应1 h，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量达到理论值时为反应终点A；到达反应终点A后，在反应产物中加入6.24g多元醇扩链剂3-二甲胺基-1,2-丙二醇（DMAD）60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量再次达到理论值时为反应终点B；到达反应终点B后，在反应产物中利用恒压漏斗以每秒 2~3滴的速率滴入7.20g封端剂丙烯酸羟乙酯（HEA）与0.053g阻聚剂羟基苯甲醚的混合物60~70℃、300~500 r/min进行反应，反应过程中用二正丁胺法进行NCO含量的滴定，当NCO含量降至0时为反应终点C。到达反应终点后，在反应产物中加入与多元醇扩链剂摩尔比1:0.5的中和剂冰醋酸60~70℃、在300~500 r/min条件下保持5~10 min终止反应；最后在2000~3000 r/min的高速搅拌下加入去离子水搅拌30 min，最终得到固含量为10~20%的聚氨酯基光敏树脂。As a comparative example of the polyurethane-based water-based UV-curable cathodic electrophoretic coating of the present invention. Add 52.38g of pretreated polytetrahydrofuran diol (PTMG-1000) and 0.488g of catalyst dibutyltin dilaurate (DBTDL) into the constant pressure funnel, under the conditions of 60~70℃, 300~500 r/min Drop it into 30.28g isophorone diisocyanate (IPDI) at a rate of 2~3 drops per second to fully react for 1 h. During the reaction, use the di-n-butylamine method to titrate the NCO content. When the NCO content reaches the theoretical value The time is the reaction end point A; after reaching the reaction end point A, add 6.24g of polyol chain extender 3-dimethylamino-1,2-propanediol (DMAD) to the reaction product at 60~70°C, 300~500 r/min Carry out reaction, carry out the titration of NCO content with di-n-butylamine method in the reaction process, when NCO content reaches theoretical value again, be reaction end point B; 3 drops of the mixture of 7.20g end-capping agent hydroxyethyl acrylate (HEA) and 0.053g polymerization inhibitor hydroxyanisole were dropped into the reaction at 60~70℃, 300~500 r/min. During the reaction, two normal The NCO content was titrated by the butylamine method, and when the NCO content dropped to 0, it was the end point C of the reaction. After reaching the end of the reaction, add glacial acetic acid, a neutralizing agent with a molar ratio of 1:0.5 to the polyol chain extender, to the reaction product and keep it at 300~500 r/min for 5~10 minutes at 60~70°C to terminate the reaction; Add deionized water and stir for 30 min under high-speed stirring at 2000-3000 r/min, and finally obtain a polyurethane-based photosensitive resin with a solid content of 10-20%.
如图1所示为制备聚氨酯基水性光敏树脂的化学反应示意图。发明人经过研究发现，聚醚二元醇起到增加链长，提高树脂柔韧性的作用。扩链剂可以增加其亲水基团含量，增加亲水性，同时作为硬段调节硬度，含量越多，亲水性越好，硬度越高。封端剂的作用为增加光固化基团含量，增加越多，交联度越高，硬度越高。中和剂加入量越高中和度越高，成盐越多，水溶性越好。As shown in Figure 1, it is a schematic diagram of the chemical reaction for preparing polyurethane-based water-based photosensitive resin. The inventor found through research that the polyether diol can increase the chain length and improve the flexibility of the resin. The chain extender can increase the content of its hydrophilic groups, increase the hydrophilicity, and at the same time act as a hard segment to adjust the hardness. The more the content, the better the hydrophilicity and the higher the hardness. The function of the end-capping agent is to increase the content of photocurable groups, the more the increase, the higher the degree of crosslinking and the higher the hardness. The higher the amount of neutralizing agent added, the higher the degree of neutralization, the more salt is formed, and the better the water solubility.
实施例1-3的乳液粒径如图2所示，由图2可知，实施例1-3乳液粒径分布窄且均一，粒径较小，均小于30nm，证明本技术路线采用侧链含胺基的扩链剂较主链含胺基扩链剂水溶性良好，且分散均一。The emulsion particle diameter of embodiment 1-3 is as shown in Figure 2, as can be seen from Figure 2, the emulsion particle diameter distribution of embodiment 1-3 is narrow and uniform, and particle diameter is smaller, all less than 30nm, proves that this technical route adopts the side chain containing The amine-based chain extender has better water solubility and uniform dispersion than the main chain-containing amine-based chain extender.
实施例1-5和对比例1-2漆膜的基本性能表征结果如表2所示。由表2可知，实施例1-3乳液的电导率均大于0.003，满足电泳的需求；同时，采用不同单体合成出来的聚氨酯性能上有一定差异，特别是作为电泳涂料进行应用时，对漆膜的平整度影响最大，实施例1的漆膜外观最好，平整而光滑，实施例2漆膜表面有少量堆积，实施例3的漆膜表面有缩孔，而漆膜表面的平整度将影响其在电泳涂料中的应用，所以实施例1是相对较优的方案；对比实施例1-3漆膜的其他性能，变化并不明显，都有较好的力学、耐水耐溶剂性能。对比例1-2漆膜由于分别采用了叔胺基团在主链上的二元醇扩链剂和50%的中和度的配方，导致乳液水溶性差，出现乳液不稳定，分层现象，且力学性能，如硬度等均达不到所需要求。The basic performance characterization results of the paint films of Examples 1-5 and Comparative Examples 1-2 are shown in Table 2. It can be seen from Table 2 that the conductivity of the emulsions of Examples 1-3 are all greater than 0.003, which meets the needs of electrophoresis; at the same time, there are certain differences in the properties of polyurethanes synthesized by using different monomers, especially when they are used as electrophoretic coatings. The flatness of film has the greatest impact, and the paint film appearance of embodiment 1 is the best, smooth and smooth, and a small amount of accumulation is arranged on the paint film surface of embodiment 2, shrinkage cavity is arranged on the paint film surface of embodiment 3, and the flatness of paint film surface will be It affects its application in electrophoretic coatings, so Example 1 is a relatively better solution; the other properties of the paint film of Comparative Examples 1-3, the change is not obvious, and all have good mechanics, water resistance and solvent resistance. The paint film of Comparative Example 1-2 is due to the use of a glycol chain extender with tertiary amine groups on the main chain and a formula with a neutralization degree of 50%, resulting in poor water solubility of the emulsion, instability of the emulsion, and delamination. And the mechanical properties, such as hardness, etc. are not up to the required requirements.
Figure 676692dest_path_image002
Figure 676692dest_path_image002
效果例1Effect Example 1
发明人将一块马口铁将表面处理后，一半置于实施例1所述聚氨酯基光敏树脂和3 wt.%光引发剂（Darocur1173）均匀混合的电泳槽中，在100 V的直流电压下进行电泳涂装，电极极距为10 cm、电泳时间为3~5 min，得到不溶性漆膜，后经水洗、干燥、在80~100℃下烘烤3 min，在UV光固化机中双面辐照固化，即得金属用阴极电泳涂层。另一半未经涂装漆膜的马口铁作为空白对照。将一半带有金属涂层而另一半未涂装的同一块马口铁，利用国家标准GB/T 1732-1993薄膜冲击检测方法测试抗冲击性。试验结果如图3所示，结果显示落锤在50cm出下落，左侧漆膜无裂痕，皱纹及剥落现象产生，而右侧未经涂装的空白对照出现明显凹坑。After the inventor treated the surface of a piece of tinplate, half of it was placed in the polyurethane-based photosensitive resin described in Example 1 and 3 In the electrophoresis tank uniformly mixed with wt.% photoinitiator (Darocur1173), the electrophoretic coating was carried out at a DC voltage of 100 V, the electrode distance was 10 cm, and the electrophoresis time was 3-5 min to obtain an insoluble paint film. Wash with water, dry, bake at 80-100°C for 3 minutes, and cure with radiation on both sides in a UV light curing machine to obtain a cathodic electrophoretic coating for metals. The other half of the tinplate without paint film was used as a blank control. Use the same piece of tinplate with half of the metal coating and the other half uncoated, using the national standard GB/T 1732-1993 Thin film impact test method for testing impact resistance. The test results are shown in Figure 3. The results showed that the drop hammer dropped at 50cm, and the paint film on the left had no cracks, wrinkles and peeling, while the unpainted blank control on the right had obvious pits.
效果例2Effect example 2
发明人将一块马口铁将表面处理后，一半置于实施例1所述聚氨酯基光敏树脂和3 wt.%光引发剂（Darocur1173）均匀混合的电泳槽中，在100 V的直流电压下进行电泳涂装，电极极距为10 cm、电泳时间为3~5 min，得到不溶性漆膜，后经水洗、干燥、在80~100℃下烘烤3 min，在UV光固化机中双面辐照固化，即得金属用阴极电泳涂层。另一半未经涂装漆膜的马口铁作为空白对照。利用国家标准GB 10124-88《金属材料实验室均匀腐蚀全浸试验方法》中详细规定的试验方法和要求进行腐蚀试验，利用交互浸渍试验。将一半带有金属涂层另一半未涂装的同一块马口铁试样交替地浸入液态腐蚀介质和暴露在空气中。试验结果如图4所示，左侧未涂膜的金属基材出现生锈腐蚀现象，右侧涂有涂层的部分，对金属基材具有保护现象，未有腐蚀现象产生。After the inventor treated the surface of a piece of tinplate, half of it was placed in the polyurethane-based photosensitive resin described in Example 1 and 3 In the electrophoresis tank uniformly mixed with wt.% photoinitiator (Darocur1173), the electrophoretic coating was carried out at a DC voltage of 100 V, the electrode distance was 10 cm, and the electrophoresis time was 3-5 min to obtain an insoluble paint film. Wash with water, dry, bake at 80-100°C for 3 minutes, and cure with radiation on both sides in a UV light curing machine to obtain a cathodic electrophoretic coating for metals. The other half of the tinplate without paint film was used as a blank control. The corrosion test is carried out using the test methods and requirements specified in the national standard GB 10124-88 "Uniform Corrosion Full Immersion Test Method for Metal Materials Laboratory", and the interactive immersion test is used. The same tinplate sample with half of the metal coating and the other half uncoated is alternately immersed in a liquid corrosive medium and exposed to air. The test results are shown in Figure 4. The uncoated metal substrate on the left has rust and corrosion, and the coated part on the right has protection for the metal substrate without corrosion.
效果例1-2的测试结果表明本发明涂层对马口铁基材防腐蚀效果良好，且抗冲击性强。The test results of Effect Example 1-2 show that the coating of the present invention has a good anti-corrosion effect on tinplate substrates and has strong impact resistance.
最后所应当说明的是，以上实施例仅用以说明本发明的技术方案而非对本发明保护范围的限制，尽管参照较佳实施例对本发明作了详细说明，本领域的普通技术人员应当理解，可以对本发明的技术方案进行修改或者等同替换，而不脱离本发明技术方案的实质和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than limit the protection scope of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those of ordinary skill in the art should understand that The technical solution of the present invention can be modified or equivalently replaced without departing from the spirit and scope of the technical solution of the present invention.

Claims (10)

  1. 一种水性紫外光固化阴极电泳涂料，其特征在于，所述涂料包括聚氨酯基光敏树脂和光引发剂组分；所述聚氨酯基光敏树脂的制备原料包括以下组分：异氰酸酯单体、聚醚多元醇、多元醇扩链剂、封端剂、中和剂、阻聚剂和催化剂。A water-based UV-curable cathodic electrophoretic coating is characterized in that the coating includes a polyurethane-based photosensitive resin and a photoinitiator component; the raw materials for the preparation of the polyurethane-based photosensitive resin include the following components: isocyanate monomers, polyether polyols , polyol chain extender, end-capping agent, neutralizing agent, polymerization inhibitor and catalyst.
  2. 根据权利要求1所述涂料，其特征在于，所述异氰酸酯单体的摩尔量与聚醚多元醇和多元醇扩链剂摩尔量之和的比为：异氰酸酯单体：（聚醚多元醇+多元醇扩链剂）=（1.1~1.6）:1。The coating according to claim 1, wherein the ratio of the molar weight of the isocyanate monomer to the sum of the molar weight of polyether polyol and polyol chain extender is: isocyanate monomer: (polyether polyol+polyol chain extender)=(1.1~1.6):1.
  3. 根据权利要求1所述涂料，其特征在于，所述聚醚多元醇和多元醇扩链剂的摩尔比为：聚醚多元醇：多元醇扩链剂= （0.8~1.5）:1。The coating according to claim 1, wherein the molar ratio of the polyether polyol to the polyol chain extender is: polyether polyol:polyol chain extender=(0.8~1.5):1.
  4. 根据权利要求1所述涂料，其特征在于，所述中和剂和多元醇扩链剂的摩尔比为：1:1。According to the described coating of claim 1, it is characterized in that, the molar ratio of described neutralizing agent and polyol chain extender is: 1:1.
  5. 根据权利要求1所述涂料，其特征在于，所述异氰酸酯单体为2 官能度的异氰酸酯单体，包括异佛尔酮二异氰酸酯、甲苯二异氰酸酯、六亚甲基二异氰酸酯和二苯甲烷二异氰酸酯中的至少一种。According to the described coating of claim 1, it is characterized in that, described isocyanate monomer is the isocyanate monomer of 2 functionalities, comprises isophorone diisocyanate, toluene diisocyanate, hexamethylene diisocyanate and diphenylmethane diisocyanate at least one of the
  6. 根据权利要求1所述涂料，其特征在于，所述聚醚多元醇包括聚四氢呋喃二醇和/或聚乙二醇。The coating according to claim 1, wherein the polyether polyol comprises polytetrahydrofuran diol and/or polyethylene glycol.
  7. 根据权利要求1所述涂料，其特征在于，所述多元醇扩链剂包括聚酯型二元醇扩链剂和/或N-甲基二乙醇胺。The coating according to claim 1, wherein the polyol chain extender comprises a polyester diol chain extender and/or N-methyldiethanolamine.
  8. 根据权利要求1所述涂料，其特征在于，所述封端剂为丙烯酸羟乙酯和/或甲基丙烯酸羟乙酯。The coating according to claim 1, wherein the end-capping agent is hydroxyethyl acrylate and/or hydroxyethyl methacrylate.
  9. 一种水性紫外光固化阴极电泳涂料的制备方法，其特征在于，所述方法包括以下步骤：（1）将聚醚多元醇真空蒸馏，得到预处理的聚醚多元醇；（2）将经过预处理的聚醚多元醇和催化剂混合后，加入到异氰酸酯单体中反应至NCO含量达到理论值时为反应终点A；（3）到达反应终点A后，在步骤（1）产物中加入多元醇扩链剂，反应至NCO含量再次达到理论值时为反应终点B；（4）到达反应终点B后，在步骤（3）产物加入封端剂与阻聚剂，反应至NCO含量降至0时为反应终点C；（5）到达反应终点C后，在步骤（4）产物中加入中和剂反应；（6）在步骤（5）产物中加入去离子水搅拌得到聚氨酯基光敏树脂；（7）将步骤（6）中的聚氨酯基光敏树脂和光引发剂混合均匀得到聚氨酯基水性紫外光固化阴极电泳涂料。A method for preparing a water-based UV-curable cathodic electrophoretic coating, characterized in that the method comprises the following steps: (1) vacuum distilling polyether polyol to obtain pretreated polyether polyol; (2) pretreated polyether polyol; After the treated polyether polyol is mixed with the catalyst, it is added to the isocyanate monomer to react until the NCO content reaches the theoretical value, which is the reaction end point A; (3) After reaching the reaction end point A, add polyol to the product of step (1) to extend the chain (4) After reaching the reaction end point B, add end-capping agent and polymerization inhibitor to the product in step (3), and react until the NCO content drops to 0. End point C; (5) After reaching the reaction end point C, add a neutralizing agent to the product in step (4) for reaction; (6) Add deionized water to the product in step (5) and stir to obtain a polyurethane-based photosensitive resin; (7) The polyurethane-based photosensitive resin and the photoinitiator in step (6) are uniformly mixed to obtain the polyurethane-based water-based UV-curable cathodic electrophoretic coating.
  10. 一种水性紫外光固化阴极电泳涂料的应用，其特征在于，所述应用包括以下步骤：（1）将聚氨酯基光敏树脂和光引发剂混合均匀得到水性紫外光固化阴极电泳涂料；（2）将被镀金属基材作为阴极，使用步骤（1）涂料电泳涂装，得到镀膜的金属基材；（3）将步骤（2）中镀膜的金属基材水洗、干燥、烘烤后，使用UV光双面辐照固化。An application of a water-based UV-curable cathodic electrophoretic coating, characterized in that the application comprises the following steps: (1) uniformly mixing a polyurethane-based photosensitive resin and a photoinitiator to obtain a water-based UV-curable cathodic electrophoretic coating; The metal-plated substrate is used as the cathode, and the coated metal substrate is obtained by electrophoretic coating in step (1); (3) After washing, drying, and baking the metal substrate coated in step (2), use UV light to double surface radiation curing.
PCT/CN2022/106957 2021-12-17 2022-07-21 Water-based ultraviolet curing cathode electrophoretic coating and preparation method therefor WO2023109123A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111568121.2A CN114316660A (en) 2021-12-17 2021-12-17 Water-based ultraviolet-curing cathode electrophoretic coating and preparation method thereof
CN202111568121.2 2021-12-17

Publications (1)

Publication Number Publication Date
WO2023109123A1 true WO2023109123A1 (en) 2023-06-22

Family

ID=81054528

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/106957 WO2023109123A1 (en) 2021-12-17 2022-07-21 Water-based ultraviolet curing cathode electrophoretic coating and preparation method therefor

Country Status (3)

Country Link
CN (1) CN114316660A (en)
DE (1) DE202022104348U1 (en)
WO (1) WO2023109123A1 (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114316660A (en) * 2021-12-17 2022-04-12 广东工业大学 Water-based ultraviolet-curing cathode electrophoretic coating and preparation method thereof
CN117143511B (en) * 2023-10-30 2024-02-13 福建兴宇树脂有限公司 Polyurethane coating material for high weather-resistant automotive interior leather and preparation method thereof

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357221A (en) * 1980-02-11 1982-11-02 Basf Aktiengesellschaft Process for coating electrically conductive objects with polyurethane
US20120070647A1 (en) * 2010-09-16 2012-03-22 O'Neill LLC Thin-wall polymer coated articles and gloves and a method therefor
CN105176155A (en) * 2015-07-29 2015-12-23 华南理工大学 UV cured cathode electrophoresis paint with side chain containing ammonium salt positive ions and preparation method therefor
CN106634525A (en) * 2016-10-19 2017-05-10 东莞市霖辉金属表面处理材料有限公司 Polyurethane-acrylate cathodic electrophoretic coating material, preparation method therefor and application of polyurethane-acrylate cathodic electrophoretic coating material
CN107987716A (en) * 2017-11-17 2018-05-04 华南理工大学 A kind of phenyl compound and UV type cathode electrophoresis dope and its preparation and application
CN114316660A (en) * 2021-12-17 2022-04-12 广东工业大学 Water-based ultraviolet-curing cathode electrophoretic coating and preparation method thereof

Family Cites Families (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL282471A (en) 1961-08-25
JPH09188736A (en) * 1996-01-08 1997-07-22 Nippon Paint Co Ltd Cationic electrodeposition coating excellent in surface smoothness
US6232364B1 (en) 1999-02-18 2001-05-15 Shimizu Co., Ltd. Ultraviolet curable coating compositions for cationic electrodeposition applicable to metallic materials and electrically conductive plastic materials
CN104945590B (en) 2015-05-15 2018-11-16 武汉科利尔新材料有限公司 Terminal hydroxy group modified polyurethane resin and its cataphoresis paint composition and preparation method
CN107163664A (en) * 2017-06-14 2017-09-15 深圳市天泽科技实业有限公司 Ultraviolet light solidifies the preparation method of cathode electrodip painting
CN107974191B (en) * 2017-11-17 2020-05-22 华南理工大学 Naphthyl modified compound, UV type cathode electrophoretic coating, preparation and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4357221A (en) * 1980-02-11 1982-11-02 Basf Aktiengesellschaft Process for coating electrically conductive objects with polyurethane
US20120070647A1 (en) * 2010-09-16 2012-03-22 O'Neill LLC Thin-wall polymer coated articles and gloves and a method therefor
CN105176155A (en) * 2015-07-29 2015-12-23 华南理工大学 UV cured cathode electrophoresis paint with side chain containing ammonium salt positive ions and preparation method therefor
CN106634525A (en) * 2016-10-19 2017-05-10 东莞市霖辉金属表面处理材料有限公司 Polyurethane-acrylate cathodic electrophoretic coating material, preparation method therefor and application of polyurethane-acrylate cathodic electrophoretic coating material
CN107987716A (en) * 2017-11-17 2018-05-04 华南理工大学 A kind of phenyl compound and UV type cathode electrophoresis dope and its preparation and application
CN114316660A (en) * 2021-12-17 2022-04-12 广东工业大学 Water-based ultraviolet-curing cathode electrophoretic coating and preparation method thereof

Also Published As

Publication number Publication date
CN114316660A (en) 2022-04-12
DE202022104348U1 (en) 2022-08-09
DE202022104348U9 (en) 2022-12-22

Similar Documents

Publication Publication Date Title
WO2023109123A1 (en) Water-based ultraviolet curing cathode electrophoretic coating and preparation method therefor
EP1245590B1 (en) Curable coating composition and coating film forming method
US4865704A (en) Non-autocrosslinking binder combination for water-dilutable lacquers
CN106634525A (en) Polyurethane-acrylate cathodic electrophoretic coating material, preparation method therefor and application of polyurethane-acrylate cathodic electrophoretic coating material
CN111154383A (en) Radiation curing coating for household appliance metal plate and application thereof
CN105176155A (en) UV cured cathode electrophoresis paint with side chain containing ammonium salt positive ions and preparation method therefor
CN113801565B (en) UV-cured water-based cathode electrophoretic coating and preparation method and application thereof
CN111073459A (en) Energy-saving and environment-friendly cathode electrophoretic coating
JP4440590B2 (en) Cationic coating composition and coating film forming method
CN105440894B (en) For Metal surface anti-corrosion light solidifying paint composition
CN103554429A (en) Light-curable polyurethane-poly(methyl) acrylate pressure-sensitive polymer and preparation method thereof
CN109942772A (en) A kind of preparation method of the UV-Curing Waterborne Resin of adjustable degree of functionality
Chen et al. Effects of different molecular chain lengths and side groups on structure and property of UV-curable waterborne cathodic electrophoretic deposition coatings
US6447931B1 (en) Plural layer coating film-forming method
CN110903690B (en) Cathode electrophoretic coating and preparation method thereof
CN111073431B (en) Ultraviolet light curing cathode electrophoretic coating for multi-material metal collinear coating and preparation method thereof
CN107987716B (en) Phenyl compound and UV type cathode electrophoretic coating as well as preparation and application thereof
CN1307268C (en) Ultraviolet light curing cathodic electrophoretic coating and preparation thereof
CN113402966A (en) Electrostatic spraying UV-LED curing vacuum coating primer and preparation method thereof
JP4420302B2 (en) Electrodeposition coating repair method
JP2002356646A (en) Lead-less cationic-electrodeposition paint composition containing crosslinked resin particle
JP2009235351A (en) Cationic electrodeposition coating composition
CN110016144A (en) A kind of water solubility polyfunctional group resin and preparation method thereof
CN115449289B (en) UV-cured cathode electrophoretic coating for metal and preparation method and application thereof
CN109957299A (en) A kind of light-curved aqueous crylic acid cathode electrophoresis dope

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 22905885

Country of ref document: EP

Kind code of ref document: A1