CN111234679B - Aqueous dispersion emulsion and process for producing the same - Google Patents
Aqueous dispersion emulsion and process for producing the same Download PDFInfo
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- CN111234679B CN111234679B CN201910475311.6A CN201910475311A CN111234679B CN 111234679 B CN111234679 B CN 111234679B CN 201910475311 A CN201910475311 A CN 201910475311A CN 111234679 B CN111234679 B CN 111234679B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/58—Epoxy resins
- C08G18/584—Epoxy resins having nitrogen
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/08—Anti-corrosive paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/4465—Polyurethanes
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Abstract
The invention belongs to the technical field of electrophoretic paint, and provides water dispersion emulsion for tin-free environment-friendly low-temperature electrophoretic paint. The invention also relates to a preparation method of the water dispersible emulsion. In the synthetic process of the electrophoretic paint based on the water dispersion emulsion, vegetable oleic acid with unsaturated double bonds is introduced into epoxy resin, so that the solubility is improved, low-temperature curing closed isocyanate and a film-forming drier cerium compound are added in the synthetic process for emulsification, a solvent is not required to be removed in the synthetic process, the defect of coating caused by precipitation in the emulsification process is prevented, the final product does not contain heavy metal tin compounds, the curing temperature is low, and the coating has the advantages of environmental protection, good flexibility, good leveling property, high gloss, good corrosion resistance and the like.
Description
The patent application is a divisional application; the original application date is 2018, 11 and 28, and the application number is 201811434210.6, and the invention is named as a tin-free environment-friendly low-temperature electrophoretic coating and a preparation method thereof.
Technical Field
The invention belongs to the technical field of cathode electrophoretic coatings, and relates to a water dispersion emulsion and a preparation method thereof.
Background
The cathodic electrophoretic paints frequently used at present often do not meet the requirements of corrosion resistance, edge protection, surface quality or other properties. The electrophoretic coating has high coating efficiency, small coating loss and good coating quality, can obtain even and smooth paint films at all parts of a workpiece, such as inner layers, depressions, welding seams and the like, can realize automatic continuous production during construction, and greatly improves the labor efficiency.
Most of electrophoretic coatings play a role in catalytic crosslinking by adding organic tin products in the processes of main resin synthesis and product curing, and the temperature of the products is generally required to be reduced in order to improve the crosslinking effect, so that most of electrophoretic coatings have the problems of baking temperature, coating performance and the like, and finally formed coating films and waste liquid contain organic tin, thereby having great harm to human bodies and environment.
In view of the above problems, there is a need for developing a low-temperature baking type electrophoretic paint without containing heavy metal tin.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a low-temperature ((140 ℃ x 20 min)) environment-friendly electrophoretic coating which does not contain heavy metal tin and a preparation method thereof.
In a first aspect of the present invention, there is provided a low temperature cathodic electrocoating composition comprising, based on the total weight of the composition:
and (2) component A:40-50 parts by weight of an aqueous dispersion emulsion; the water dispersion emulsion is prepared by uniformly mixing the vegetable oleic acid modified epoxy resin polymer and an emulsifier under the conditions of acid value of 50-60mg KOH/g and catalysis of a cerium catalyst, and emulsifying for 2-3 hours at 30-45 ℃;
and (B) component: 8-10 parts of color paste;
and (3) component C:40-80 parts by weight of pure water.
In another preferred example, in the component a, the vegetable oleic acid modified epoxy resin polymer is prepared by aminating a vegetable oleic acid modified epoxy resin with an amine compound and reacting with a blocked isocyanate curing agent, wherein the vegetable oleic acid modified epoxy resin, the amine compound and the blocked isocyanate curing agent are in the following weight parts: 50-70:2-10:10-35.
In another preferred embodiment, the emulsifier is selected from the group consisting of: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, diethylene glycol butyl ether, ethylene glycol isooctyl ether, propylene glycol methyl ether, propylene glycol phenyl ether, or combinations thereof. Preferably, the emulsifier is ethylene glycol butyl ether. The emulsifier belongs to alcohol ether solvents, can adjust the viscosity of the emulsion, increases the solubility and improves the emulsibility.
In another preferred example, the color paste is a color paste containing no heavy metal tin.
In another preferred embodiment, the color paste is selected from the following group: the set of instructions may include, for example, a set of instructions including, but not limited to, a set of top TOPCRON EXCEL 140TF F-1BLACK, a set of top powerics EXCEL 1600F-1BLACK, a set of top powerics EXCEL 0525F-1 BLACK, or a combination thereof.
In a second aspect of the present invention, there is provided a method of preparing the low temperature cathodic electrocoating composition of the first aspect of the present invention, comprising the steps of: based on the total weight of the composition, the following components are added by weight parts of 40-50: 8-10 parts by weight: 40-80 parts by weight of the following components in parts by weight to obtain the cathode electrophoretic coating composition:
component A: an aqueous dispersion emulsion;
and (B) component: color paste;
and (3) component C: pure water.
In another preferred embodiment, the preparation method of the water dispersion emulsion comprises the steps of: under the condition of the acid value of 30-70mgKOH/g, preferably 40-60mgKOH/g, and catalysis of cerium catalyst, the vegetable oleic acid modified epoxy resin polymer and emulsifier are mixed uniformly and emulsified at 30-45 ℃ for 2-3 hours to prepare the water dispersible emulsion.
In another preferred embodiment, the preparation method of the water dispersion emulsion comprises the steps of:
(1) Mixing an epoxy resin polymer modified by acid, water and vegetable oil acid according to the weight ratio of 0.5-20:55-80:100 parts by weight of the mixture, and adjusting the acid value to be 30-70mgKOH/g (preferably 40-60 mgKOH/g) to prepare a first mixture;
(2) Adding an emulsifier and water to the first mixture, wherein the weight ratio of the emulsifier to the vegetable oleic acid modified epoxy resin polymer is 0.5-20:100, emulsifying for 2-3 hours at the temperature of 30-45 ℃ in the presence of a cerium catalyst, and filtering to obtain the water dispersion emulsion, wherein the solid content in the water dispersion emulsion is 25-45wt%;
wherein the acid is an organic acid and/or an inorganic acid,
the emulsifier is selected from the group consisting of: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, diethylene glycol butyl ether, ethylene glycol isooctyl ether, propylene glycol methyl ether, propylene glycol phenyl ether, or combinations thereof. Preferably, the emulsifier is ethylene glycol butyl ether. The emulsifier can adjust the viscosity of the emulsion and increase the solubility.
In another preferred embodiment, the organic acid is selected from the group consisting of: lactic acid, acetic acid, formic acid, citric acid, sulfamic acid, or combinations thereof.
In another preferred embodiment, the inorganic acid is nitric acid.
In another preferred embodiment, the cerium-based catalyst is selected from the group consisting of: cerium acetate, cerium carbonate, cerium octoate, or a combination thereof.
In another preferred example, in the component a, the vegetable oleic acid modified epoxy resin polymer is prepared by aminating a vegetable oleic acid modified epoxy resin with an amine compound and reacting with a blocked isocyanate curing agent, wherein the vegetable oleic acid modified epoxy resin, the amine compound and the blocked isocyanate curing agent are in the following weight parts: 15-70:2-10:10-35.
In another preferred embodiment, the preparation method of the vegetable oleic acid-modified epoxy resin polymer comprises the steps of:
(1) Uniformly mixing the vegetable oleic acid modified epoxy resin, the amine compound and the cosolvent at the temperature of 80-120 ℃,
(2) Heating to 110-140 ℃, preserving heat for 0.5-3 h, cooling to 80-90 ℃, adding a closed isocyanate curing agent and an organic silicon modified auxiliary agent, and preserving heat for 0.5-3 h to obtain the vegetable oleic acid modified epoxy resin polymer;
wherein the vegetable oleic acid modified epoxy resin, the amine compound, the cosolvent and the blocked isocyanate curing agent are mixed according to the weight ratio of 15-70:2-10:1-8:10-35.
In another preferred embodiment, the amine compound is selected from the group consisting of: diethylamine, dibutylamine, monoethanolamine, diethanolamine, methylethanolamine, ketimine, or combinations thereof.
In another preferred embodiment, the co-solvent is selected from the group consisting of: methyl isobutyl ketone, butyl glycol ether, hexyl glycol ether, propylene glycol phenyl ether, methyl ethyl ketone oxime, propylene glycol, or combinations thereof.
In another preferred embodiment, the preparation method of the vegetable oleic acid modified epoxy resin comprises the following steps:
(1) Mixing epoxy resin with the epoxy equivalent of 185-300 g/equivalent, bisphenol A and vegetable oil acid in an alcohol solvent and/or an alcohol ether solvent to prepare a mixture A;
(2) Reacting for 3-5h at 100-170 deg.C (preferably 110-160 deg.C) in the presence of alkaline catalyst to reach epoxy equivalent of 1100 + -10 g/equivalent, to obtain the vegetable oleic acid modified epoxy resin; wherein the weight ratio of the epoxy resin, the bisphenol A, the vegetable oleic acid, the alcohol solvent and/or the alcohol ether solvent and the alkaline catalyst is (15-70): 10-30:1-13:4-20:0.003-1.
In another preferred embodiment, the epoxy resin is selected from the group consisting of: a bisphenol a type epoxy resin, a bisphenol F type epoxy resin, a polyphenol type glycidyl ether epoxy resin, or a combination thereof, preferably, the epoxy resin is a bisphenol a type epoxy resin. It is understood that the epoxy resin may be a mixture of bisphenol a type epoxy resins, bisphenol F type epoxy resins, polyphenol type glycidyl ether epoxy resins having different molecular weights.
In another preferred embodiment, the vegetable oil acid is a fatty acid with one or more unsaturated double bonds.
In another preferred embodiment, the vegetable oil acid is selected from the group consisting of: ricinoleic acid, glyceolic acid, dehydrated ricinoleic acid, linoleic acid, linolenic acid, or a combination thereof.
In another preferred embodiment, the alcoholic solvent is selected from the group consisting of: isopropanol, n-butanol, isobutanol, n-hexanol, isooctanol, propylene glycol, or a combination thereof.
In another preferred embodiment, the alcohol ether solvent is selected from the group consisting of: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, diethylene glycol butyl ether, ethylene glycol isooctyl ether, propylene glycol methyl ether, propylene glycol phenyl ether, ethylene glycol hexyl ether, or combinations thereof.
In another preferred example, the ether alcohol solvent is at least one of ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, diethylene glycol butyl ether, ethylene glycol isooctyl ether, propylene glycol methyl ether, and propylene glycol phenyl ether.
In another preferred embodiment, the basic catalyst is selected from the group consisting of: triethylamine, N-dimethylbenzylamine, triethanolamine, tetramethylammonium chloride, triphenylphosphine, or a combination thereof.
In another preferred embodiment, the preparation method of the blocked isocyanate curing agent comprises the steps of:
in an inert solvent, mixing the component a: polyisocyanates, polymers of polyisocyanates and/or prepolymers of polyisocyanates; and
and (b) component b: oxime blocking agents are mixed, and NCO equivalent weight is controlled to be 250mg/g-270 mg/g;
adding an alcohol ether solvent, controlling the NCO equivalent to be more than or equal to 42000mg/g, and controlling the solid content to be 80 +/-2% to prepare the blocked isocyanate curing agent;
wherein the component a: and (b) component b: inert solvent: the alcohol ether solvent comprises the following components in parts by weight: 40-50:10-40:5-40:3-12.
In another preferred embodiment, the polyisocyanate is selected from the group consisting of: an aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, or a combination thereof; preferably, the aliphatic polyisocyanate is selected from the group consisting of: trimethylene diisocyanate, 1,4-butyl diisocyanate or Hexamethylene Diisocyanate (HDI), or combinations thereof; the cycloaliphatic polyisocyanate is selected from the group consisting of: 1,3-cyclopentane diisocyanate, 1,4-cyclohexane diisocyanate or isophorone diisocyanate, diphenylmethane diisocyanate, or combinations thereof; the aromatic polyisocyanate is Toluene Diisocyanate (TDI), p-phenylene diisocyanate, p-phenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate.
In another preferred embodiment, the polymer of the polyisocyanate is a trimer of toluene diisocyanate or a trimer of hexamethylene diisocyanate.
In another preferred example, the prepolymer of the polyisocyanate is a toluene diisocyanate prepolymer of trimethylolpropane or a p-phenylene diisocyanate prepolymer of polyethylene glycol.
In another preferred embodiment, the inert solvent is selected from the group consisting of: methyl isobutyl ketone, acetone, tetrahydrofuran, or combinations thereof.
In another preferred embodiment, the oxime blocking agent is selected from the group consisting of: methyl ethyl ketoxime, methyl amyl ketone oxime, phenol, dimethyl pyrazole, diethyl pyrazole, 1,2,4-triazole, caprolactam, diethyl malonate, or a combination thereof.
In another preferred embodiment, the alcohol ether solvent is selected from the group consisting of: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, diethylene glycol butyl ether, ethylene glycol isooctyl ether, propylene glycol methyl ether, propylene glycol phenyl ether, or combinations thereof.
In a third aspect of the present invention, a dry film of the coating film is provided, which is prepared from the cathodic electrophoretic coating composition provided in the first aspect of the present invention, and the dry film has a film thickness of 15-25 μm and a heavy metal tin content of < 2.0PPM (preferably < 0.2PPM, more preferably < 0.1 PPM).
Advantages and advantageous effects of the invention
Due to the adoption of the technical scheme, the invention has the following advantages and beneficial effects:
(1) According to the low-temperature cathode electrophoretic coating prepared by the invention, because the vegetable oil acid with unsaturated double bonds is introduced into the epoxy resin, the comprehensive performance of a paint film is improved, and the cost of the cathode electrophoretic coating prepared from the polymer emulsion can be reduced;
(2) In the synthesis process, the solubility is improved due to the addition of the vegetable oleic acid, the low-temperature curing enclosed isocyanate and the film-forming drier cerium compound are added in the synthesis process for emulsification, a solvent is not required to be removed in the synthesis process, the defect of film coating caused by precipitation in the emulsification process is prevented, and the product stability is good.
(3) The low-temperature cathode electrophoretic coating prepared by the invention does not contain heavy metal tin compounds, has low curing temperature, and has the advantages of environmental protection, good flexibility, good leveling property, high luster, good corrosion resistance and the like.
Detailed Description
After extensive and intensive studies, the inventors of the present invention have found that a coating film can be effectively prevented from being separated out during emulsification by adding a vegetable oil acid-modified epoxy resin polymer to an aqueous emulsion in a conventional cathodic electrodeposition coating composition. Based on the above findings, the present invention has been completed.
Description of the terms
As used in the present invention, component A is prepared by chain extension amination of vegetable oleic acid modified epoxy resin (preferably bisphenol A epoxy resin) by adding amine compounds, reaction with blocked isocyanate curing agent to form main resin, and acid neutralization. Amine compounds for reacting with vegetable oil acid-modified epoxy resins have at least one active hydrogen, including but not limited to: diethylamine, dibutylamine, monoethanolamine, diethanolamine, methylethanolamine, ketimine. The amount of each reaction component used in the above addition reaction is not particularly limited, and is suitably adjusted depending on the use of the coating composition.
As used herein, a blocked isocyanate curing agent is the product of the stoichiometric addition reaction of a polyisocyanate, a polymer of a polyisocyanate and/or a prepolymer of a polyisocyanate with an oxime type blocking agent. Polyisocyanates include, but are not limited to, aliphatic polyisocyanates, cycloaliphatic polyisocyanates, aromatic polyisocyanates, and the like. The oxime blocking agent is added to the polyisocyanate compound to block the isocyanate group, forming a stable blocked isocyanate compound.
As used herein, the vegetable oleic acid-modified epoxy resin polymer is dispersed in water using a sufficient amount of acid. The degree of acid neutralization depends on the reaction product and is generally at least 30 to 70mg KOH/g. Acids that may be used include, but are not limited to, lactic acid, acetic acid, formic acid, citric acid, sulfamic acid, nitric acid, and the like. The aqueous emulsifier may be an organic solvent miscible with water or immiscible with water, if necessary, and includes, but is not limited to, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, diethylene glycol butyl ether, ethylene glycol isooctyl ether, propylene glycol methyl ether, propylene glycol phenyl ether, and the like.
As used in the present invention, the component B is a color paste, preferably a color paste not containing heavy metal tin. More preferably, the color paste is tin-free color paste products of Nippon paint (China) Co., ltd, including but not limited to TOPCRON EXCEL 140TF F-1BLACK, POWERNICS EXCEL 1600F-1BLACK (SF), POWERNICS EXCEL 0525F-1 BLACK.
The present invention will be further described with reference to the following specific examples. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention. The test methods in the following examples, in which specific conditions are not specified, are generally carried out under conventional conditions or conditions recommended by the manufacturers. All percentages and parts are by weight unless otherwise indicated.
Example one
1. Preparing a low-temperature polyfunctional group-blocked isocyanate curing agent:
in a four-neck flask (manufactured by Shanghai Kanghua chemical company No. Ke Lingsi) with a condenser and nitrogen protection, 454.5g of diphenylmethane diisocyanate (Vanhua chemical group Co., ltd.) and 107.4g of methyl isobutyl ketone (Jinnan century Tongda chemical Co., ltd.) were charged, the temperature was raised to 40 ℃, 301.4g of methyl ethyl ketoxime (Baishun (Beijing) chemical technology Co., ltd.) was added dropwise, the temperature was controlled to 45 + -3 ℃, and the NCO equivalent was controlled to 250-270mg/g; adding 106.7g of ethylene glycol butyl ether (Jinda chemical company, ltd.) into the mixture, raising the temperature to 100 ℃ after the addition, keeping the temperature at 100 ℃ for 1 hour, actually measuring the NCO equivalent weight to 48120, adding 30.1g of methyl isobutyl ketone (Jinda chemical company, ltd.) into the mixture, controlling the solid content to be 80 +/-2 percent, and obtaining the low-temperature polyfunctional group blocked isocyanate curing agent.
2. Preparing vegetable oleic acid modified epoxy resin:
680.1g of bisphenol A type epoxy resin (initial epoxy equivalent of epoxy resin is 185-300 g/equivalent), 261.2g of bisphenol A (Shanghai purple reagent factory, brand: cramal product No.: 1227146698 pure for pharmaceutical analysis, >99.8% (HPLC)), 125.8g of soya oil acid (Kazakhstan Biotech Co., ltd., taian), 48g of ethylene glycol monobutyl ether (Berlin Tech Co., ltd., purity 99.5%) were added to a three-necked flask (Shanghai GaoXin Bo Co., ltd.; ke Lingsi) equipped with a stirrer, a condenser, and a thermometer, and the temperature was raised to 100 ℃ to 110 ℃ under nitrogen protection, 0.1g of N, N-dimethylbenzylamine (Kaita chemical Co., ltd., purity 98%) and the mixture was further raised to 160 ℃ to 170 ℃ for 3-5 hours, and the epoxy equivalent was 1100. + -. 10 g/equivalent as an end point of the reaction, to obtain a light yellow plant-modified epoxy resin.
3. Preparation of vegetable oleic acid modified epoxy resin polymer:
1165.2g of the above-mentioned vegetable oil acid-modified epoxy resin, 95.12g of butyl cellosolve (99.5% purity, bailingwei science and technology Co., ltd.) were added to a three-necked flask (Shanghai GaoXin glass Co., ltd.; ke Lingsi) equipped with a stirrer, a condenser tube, and a thermometer, and heated to 90-100 ℃ and 51g of diethanolamine (98% purity, manufactured by Tay chemical Co., ltd., mich., in Tianjin) and 62g of ketimine (manufactured by Libang coating Co., ltd., china) were added thereto, heated to 110-120 ℃ and kept warm for 1 hour, cooled to 90 ℃ and 625g of the above-mentioned low-temperature polyfunctional group-blocked isocyanate curing agent was added thereto, and kept warm for 1 hour, thereby obtaining a vegetable oil acid-modified epoxy resin polymer.
4. Preparation of aqueous dispersion emulsion for electrophoretic coating:
1139.2g pure water, 30.05g acetic acid (analytical pure, shanghai Ziyi reagent factory) and 6.1g lactic acid (L-lactic acid, purity 98%) were added into a clean emulsification tank, stirred at high speed to adjust the acid value to 40-50mgKOH/g, then 1935.6g of the vegetable oil acid modified epoxy resin polymer was slowly added, stirred for 1 hour, 15g of ethylene glycol monobutyl ether was added, stirred for 30min, pure water 412.5g and 1312.6g were added twice, emulsified for 2 hours at 25 ℃ -45 ℃, added with 7.5g cerium acetate (Chengdubeister reagent limited, purity 99.9%), stirred for 30min, and then filtered and packaged with a filter bag to obtain a water dispersion emulsion.
The technical indexes of the water dispersible emulsion are as follows: the solid content is 36 +/-2%, the grain diameter is less than or equal to 90nm, and the PH is controlled to be 6.5 +/-0.3.
5. The formulations for preparing the cathodic electrocoat compositions are shown in Table 1:
TABLE 1 formulation of cathodic electrocoating composition of example one
| Name (R) | Specification of | Weight (parts) |
| Aqueous dispersion emulsion | Self-contained articles | 421 |
| Color paste | Industrial product | 99 |
| Pure water | Industrial product | 670 |
Preparing a cathode electrophoretic coating composition:
uniformly stirring 421 parts by weight of water-dispersed emulsion, 99 parts by weight of color paste (TOPCRON EXCEL 140TF F-1BLACK of Nippon paint (China) Co., ltd.) and 670 parts by weight of pure water to obtain the cathode electrophoretic paint composition, placing the cathode electrophoretic paint composition in an electrophoresis tank for curing for 16-24 hours, controlling the construction voltage at 120 volts and the tank liquor temperature at 28 ℃, carrying out electrophoresis for 3 minutes, baking the obtained coating film at 140 ℃ for 20 minutes (plate surface), obtaining a BLACK dry film, wherein the film thickness is 20 mu m, the content of heavy metal tin is less than 2PPM, the appearance is smooth and flat, SST (5 percent NaCL 35 ℃) 800H, the unilateral extension corrosion is less than 3mm, and all indexes of the coating film meet the product standard.
Example two
1. Preparing a low-temperature polyfunctional group-blocked isocyanate curing agent:
in a four-neck flask (manufactured by Shanghai Kanghua glass company No. Ke Lingsi) with a condenser and nitrogen protection, 480.2g of diphenylmethane diisocyanate (Wanhua chemical group Co., ltd.) and 123.2g of methyl isobutyl ketone (Jinnan century Tongda chemical company Co., ltd.) are put into the flask, the temperature is raised to 40 ℃, 315.3g of methyl ethyl ketoxime (Baishui (Beijing) chemical technology Co., ltd.) is dripped, the temperature is controlled to be 45 +/-3 ℃, and the NCO equivalent weight is controlled to be 250-270mg/g; adding 127.3g of ethylene glycol butyl ether (Jinda chemical company, ltd.) into the mixture, raising the temperature to 100 ℃ after the addition, keeping the temperature at 100 ℃ for 1 hour, actually measuring the NCO equivalent weight of 48120, adding 32.5g of methyl isobutyl ketone (Jinda chemical company, ltd.) into the mixture, controlling the solid content to be 80 +/-2 percent, and obtaining the low-temperature polyfunctional group blocked isocyanate curing agent.
2. Preparing vegetable oleic acid modified epoxy resin:
705.6g bisphenol A epoxy resin (initial epoxy equivalent of epoxy resin is 185-300 g/equivalent), 312.2g bisphenol A (Shanghai purple reagent factory, brand: clarmay | product number: 1227146698 purity: analytical standard for pharmaceutical analysis, >99.8% (HPLC)), 131.4g soya oil acid (Kazakhstan Biotech Co., ltd.), 53g ethylene glycol monobutyl ether (Bailingwei Tech Co., ltd., purity 99.5%) were added to a three-necked flask (Shanghai Kagaku Co., ltd.; ke Lingsi) equipped with a stirrer, a condenser, and a thermometer, and the temperature was raised to 100 ℃ -110 ℃ under nitrogen protection, 0.1gN, N-dimethylbenzylamine (Kazaita chemical Co., ltd., tianjin) was added, and the mixture was further raised to 160-170 ℃ to react for 3-5 hours, and 1100 g/10 g of epoxy equivalent was detected to obtain a qualified epoxy resin modified by pale yellow plant oleic acid.
3. Preparation of vegetable oleic acid modified epoxy resin polymer:
1183.5g of the plant oleic acid modified epoxy resin and 101.2g of butyl cellosolve (99.5% purity) were added to a three-necked flask (Ke Lingsi, shanghai GaoXin chemical Co., ltd.) equipped with a stirrer, a condenser and a thermometer, heated to 90-100 ℃ and 57.21g of diethanolamine (98% purity, manufactured by Tianjin Cekaita chemical Co., ltd.) and 68.14g of ketimine (manufactured by Nippon paint Co., ltd.) were added, heated to 110-120 ℃ and heat-preserved for 1 hour, cooled to 90 ℃ and 693.2g of the low-temperature multifunctional group-blocked isocyanate curing agent was added and heat-preserved for 1 hour to obtain a plant oleic acid modified epoxy resin polymer.
4. Preparation of aqueous dispersion emulsion for electrophoretic coating:
1148.3g pure water, 32.15g acetic acid (analytical pure, shanghai Ziyi reagent factory) and 5.54g lactic acid (L-lactic acid, purity 98%) were added to a clean emulsification tank, high speed stirring was started to adjust the acid value to 40-50mgKOH/g, then 1948.3g of the above modified epoxy resin polymer was slowly added, stirring was carried out for 1 hour, 21g butyl cellosolve was added, stirring was carried out for 30 minutes, 423.1g and 1413.8g of pure water were added twice, emulsification was carried out at 25 ℃ -45 ℃ for 2 hours, 5.5g cerium carbonate (purity 99.9% by Chengdout Bester reagent limited) was added, stirring was carried out for 30 minutes, and filtration packaging was carried out with a filter bag to obtain a water dispersion emulsion.
The technical indexes of the water dispersible emulsion are as follows: the solid content is 36 +/-2%, the grain diameter is less than or equal to 90nm, and the PH is controlled to be 6.5 +/-0.3.
5. The formulations for preparing the cathodic electrocoat compositions are shown in Table 2:
TABLE 2 formulation of cathodic electrocoating composition of example two
| Name (R) | Specification of | Weight (parts) |
| Aqueous dispersion emulsion | Self-contained articles | 500 |
| Color paste | Industrial product | 90 |
| Pure water | Industrial product | 410 |
Preparing a cathode electrophoretic coating composition:
uniformly stirring 500 parts by weight of the emulsion for the electrophoretic paint, 90 parts by weight of color paste (POWERNICS EXCEL 3500F-1BLACK (SF) of Nippon paint (China)) and 410 parts by weight of pure water, curing the mixture in an electrophoresis tank for 16 to 24 hours, controlling the construction voltage at 110 volts and the tank liquor temperature at 28 ℃, performing electrophoresis for 3 minutes, baking the obtained coating film at 140 ℃ for 20 minutes (plate surface) to obtain a BLACK dry film, wherein the film thickness is 20 mu m, the content of heavy metal tin is less than 2PPM, the appearance is smooth and flat, SST (5 NaCL 35 ℃) 800H, the unilateral corrosion is less than 3mm, and all indexes of the coating film meet the product standard.
EXAMPLE III
1. Preparing a low-temperature polyfunctional group-blocked isocyanate curing agent:
in a four-neck flask (Ke Lingsi manufactured by Shanghai Kangxin glass Co., ltd.) with condenser and nitrogen protection, 421.6g of diphenylmethane diisocyanate (Wanhua chemical group Co., ltd.) and 108.2g of methyl isobutyl ketone (Jinnan century Tongda chemical Co., ltd.) were put into the flask, the temperature was raised to 40 ℃ and 304.5g of methyl ethyl ketoxime (Baishui (Beijing) chemical technology Co., ltd.) was added dropwise while controlling the NCO equivalent at 45. + -. 3 ℃ and 250-270mg/g; adding 103.5g of ethylene glycol butyl ether (Jinan century Tongda chemical Co., ltd.), heating to 100 ℃ after the addition, keeping the temperature at 100 ℃ for 1 hour, actually measuring the NCO equivalent of 48120 to obtain a result of more than 42000, adding 42.7g of methyl isobutyl ketone (Jinan century Tongda chemical Co., ltd.), controlling the solid content to be 80 +/-2%, and obtaining the low-temperature multifunctional group-blocked isocyanate curing agent.
2. Preparing vegetable oleic acid modified epoxy resin:
712.8g of bisphenol A epoxy resin (initial epoxy equivalent of epoxy resin is 185-300 g/equivalent), 305.6g of bisphenol A (Shanghai purple reagent factory, brand: clarmay | product No.: 1227146698 purity: analytical standard for pharmaceutical analysis, >99.8% (HPLC)), 125.8g of soya oil acid (Kazakhstan Biotech Co., ltd.), 52g of butyl cellosolve (Berlingwei Co., ltd., purity 99.5%) were added to a three-necked flask (Shanghai Kagaku, ke Lingsi) equipped with a stirrer, a condenser tube, and a thermometer, and the mixture was heated to 110 ℃ under nitrogen protection, 0.1gN, N-dimethylbenzylamine (Kazata chemical Co., ltd., purity 98%) and reacted for 3-5 hours, and 1100 + -10 g/equivalent of epoxy acid was detected as acceptable, thereby obtaining a pale yellow plant oil acid-modified epoxy resin.
3. Preparation of vegetable oleic acid modified epoxy resin polymer:
1184.2g of the above-mentioned vegetable oil acid-modified epoxy resin and 141.3g of butyl cellosolve (Prodweiser technologies Co., ltd., purity 99.5%) were added to a three-necked flask (Shanghai Kanghua glass Co., ltd.; ke Lingsi) equipped with a stirrer, a condenser tube and a thermometer, and heated to 90-100 ℃ and 53g of diethanolamine (Navy, mikana Tai chemical Co., ltd., purity 98%) and 60g of ketimine (manufactured by Libang paint Co., ltd.), heated to 110-120 ℃ and kept warm for 1 hour, cooled to 90 ℃ and then 613g of the above-mentioned low-temperature polyfunctional group-blocked isocyanate curing agent and kept warm for 1 hour were added to obtain a vegetable oil acid-modified epoxy resin polymer.
4. Preparation of aqueous dispersion emulsion for electrophoretic coating:
1146.3g pure water, 31.2g acetic acid (Shanghai Ziyi reagent factory, analytical purity) and 6.3g lactic acid (Henan Jindan lactic acid science and technology Co., ltd., L-type lactic acid, purity 98%) are added into a clean emulsification tank, high-speed stirring is started to stir the materials evenly, the acid value is adjusted to 40-50mgKOH/g, then 1983.2g of the modified epoxy resin polymer is slowly added, stirring is carried out for 1h, 17g ethylene glycol butyl ether is added, stirring is carried out for 30min, 416.3g pure water and 1423.9g pure water are added twice, emulsification is carried out for 2 h at the temperature of 25-45 ℃, 8.1g cerium octoate (Chengdebaster reagent Co., ltd., purity 99.9%) is added, stirring is carried out for 30min, and then filtration and packaging are carried out by using filter bags, thus obtaining the water dispersible emulsion.
The technical indexes of the water dispersible emulsion are as follows: the solid content is 36 +/-2%, the grain diameter is less than or equal to 90nm, and the PH is controlled to be 6.5 +/-0.3.
5. The formulations for preparing the cathodic electrocoat compositions are shown in Table 3:
TABLE 3 formulation of cathodic electrocoating composition of example III
| Name (R) | Specification of | Weight (parts) |
| Aqueous dispersion emulsion | Self-contained articles | 450 |
| Color paste | Industrial product | 100 |
| Pure water | Industrial product | 450 |
Preparing a cathode electrophoretic coating composition:
uniformly stirring 450 parts of water-dispersed emulsion, 100 parts of color paste (POWERNICS EXCEL 1600F-1BLACK (SF) of Nippon paint (China) Co., ltd.) and 450 parts of pure water to obtain the cathode electrophoretic paint composition, curing the cathode electrophoretic paint composition in an electrophoresis tank for 16-24 hours, controlling the construction voltage at 120 volts and the tank liquor temperature at 28 ℃, performing electrophoresis for 3 minutes, baking the obtained coating film at 140 ℃ for 20 minutes (plate surface), and obtaining a BLACK dry film with the film thickness of 20 mu m, the heavy metal tin content of less than 2.0PPM, smooth and flat appearance, SST (5 NaCL 35 ℃) 800H, the unilateral corrosion of less than 3mm, and all indexes of the coating film accord with product standards.
Conclusion
The low-temperature cathode electrophoretic coating prepared by the invention has the advantages that the vegetable oleic acid structure with unsaturated double bonds is introduced into the epoxy resin, the desolvation link is avoided, meanwhile, the low-temperature curing enclosed isocyanate is added in the synthesis process as a curing agent, the cerium catalyst is added in the emulsification process, the coating defect caused by the precipitation of the modified epoxy resin polymer in the emulsification process is improved, the coating has the characteristics of no heavy metal tin and low-temperature baking, and the electrophoretic coating has the advantages of good wet coating appearance, high gloss, strong covering power, high hardness, excellent scratch resistance, good salt mist resistance and the like. The dry coating prepared by the low-temperature cathode electrophoretic coating has the advantages of no heavy metal tin, low-temperature baking and the like.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (2)
1. A method of preparing an aqueous dispersion emulsion comprising the steps of:
mixing an epoxy resin polymer modified by acid, water and vegetable oil acid according to the weight ratio of 0.5-20:55-80: mixing 100 weight parts, and adjusting the acid value to 30-70mgKOH/g to obtain a first mixture;
adding an emulsifier and water to the first mixture, wherein the weight ratio of the emulsifier to the vegetable oleic acid modified epoxy resin polymer is 0.5-20:100, emulsifying for 2-3 hours at the temperature of 30-45 ℃ in the presence of a cerium catalyst, and filtering to obtain the water dispersion emulsion, wherein the solid content in the water dispersion emulsion is 25-45wt%;
wherein the acid is an organic acid and/or an inorganic acid,
the emulsifier is selected from the group consisting of: ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, diethylene glycol butyl ether, ethylene glycol isooctyl ether, propylene glycol methyl ether, propylene glycol phenyl ether, or combinations thereof;
the preparation method of the vegetable oleic acid modified epoxy resin polymer comprises the following steps:
uniformly mixing the vegetable oleic acid modified epoxy resin, the amine compound and the cosolvent at the temperature of 80-120 ℃, heating to 110-140 ℃, preserving heat for 0.5-3 h, cooling to 80-90 ℃, adding a closed isocyanate curing agent and an organic silicon modified additive, and preserving heat for 0.5-3 h to obtain the vegetable oleic acid modified epoxy resin polymer;
wherein the vegetable oleic acid modified epoxy resin, the amine compound, the cosolvent and the blocked isocyanate curing agent are mixed according to the weight ratio of 15-70:2-10:1-8:10-35;
the preparation method of the vegetable oleic acid modified epoxy resin comprises the following steps:
mixing epoxy resin with the epoxy equivalent of 185-300 g/equivalent, bisphenol A and vegetable oil acid in an alcohol solvent and/or an alcohol ether solvent to prepare a mixture A;
reacting for 3-5h at the temperature of 100-170 ℃ in the presence of an alkaline catalyst to obtain 1100 +/-10 g/equivalent of epoxy equivalent, and preparing the vegetable oleic acid modified epoxy resin;
wherein the weight ratio of the epoxy resin, the bisphenol A, the vegetable oleic acid, the alcohol solvent and/or the alcohol ether solvent and the alkaline catalyst is (15-70): 10-30:1-13:4-20:0.003 to 1;
wherein the preparation method of the blocked isocyanate curing agent comprises the following steps: in an inert solvent, mixing the component a: polyisocyanates, polymers of polyisocyanates and/or prepolymers of polyisocyanates; and a component b: oxime blocking agents are mixed, and NCO equivalent weight is controlled to be 250mg/g-270 mg/g; adding an alcohol ether solvent, controlling the NCO equivalent to be more than or equal to 42000mg/g, and controlling the solid content to be 80 +/-2% to prepare the blocked isocyanate curing agent;
wherein the component a: and (b) component b: inert solvent: the alcohol ether solvent comprises the following components in parts by weight: 40-50:10-40:5-40:3-12.
2. An aqueous dispersion emulsion prepared by the method of claim 1.
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| CN112457721B (en) * | 2020-12-03 | 2023-02-03 | 上海瑞君电泳涂料有限公司 | Color paste for epoxy electrophoretic coating, electrophoretic coating and preparation process thereof |
| CN112430420B (en) * | 2020-12-03 | 2022-06-28 | 上海瑞君电泳涂料有限公司 | Scratch-resistant tin-free cathode electrophoretic coating and preparation method thereof |
| JP6912683B1 (en) * | 2021-03-09 | 2021-08-04 | 日本ペイント・インダストリアルコ−ティングス株式会社 | Method for Producing Aqueous Clear Paint Composition Containing Aqueous Silicone Resin Emulsion |
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| US5135994A (en) * | 1989-09-08 | 1992-08-04 | Rhone-Poulenc Inc. | Rare earth containing catalyst for epoxy resin systems |
| EP0692000B1 (en) * | 1993-03-30 | 1997-06-25 | Shell Internationale Researchmaatschappij B.V. | Epoxidized vegetable oil modification of epoxy esters |
| KR20020077131A (en) * | 2001-03-28 | 2002-10-11 | 닛본 페인트 가부시끼가이샤 | Lead-free cationic electrodeposition coating composition, and electrodeposition coating process |
| CN1235987C (en) * | 2003-08-04 | 2006-01-11 | 江苏鸿业涂料科技产业有限公司 | Low temp. solidifeed resin emulion used for cathode electrolytic coating |
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| CN104513343A (en) * | 2014-12-04 | 2015-04-15 | 北京金汇利应用化工制品有限公司 | Preparation method for low acid value and low VOC waterborne acrylic acid and fatty acid modified epoxy resin |
| JP2018070663A (en) * | 2015-03-06 | 2018-05-10 | 日本ペイント・オートモーティブコーティングス株式会社 | Cationic electrodeposition coating composition |
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| CN107880628A (en) * | 2017-12-18 | 2018-04-06 | 枣阳市旺前电泳涂料有限公司 | A kind of anodic electrophoresis paint and its manufacture method containing efficient drier |
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