CN114410178A - Low-temperature high-edge electrophoretic coating and preparation method thereof - Google Patents
Low-temperature high-edge electrophoretic coating and preparation method thereof Download PDFInfo
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- CN114410178A CN114410178A CN202011170833.4A CN202011170833A CN114410178A CN 114410178 A CN114410178 A CN 114410178A CN 202011170833 A CN202011170833 A CN 202011170833A CN 114410178 A CN114410178 A CN 114410178A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4419—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications with polymers obtained otherwise than by polymerisation reactions only involving carbon-to-carbon unsaturated bonds
- C09D5/443—Polyepoxides
- C09D5/4434—Polyepoxides characterised by the nature of the epoxy binder
- C09D5/4438—Binder based on epoxy/amine adducts, i.e. reaction products of polyepoxides with compounds containing amino groups only
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
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Abstract
The invention discloses a low-temperature high-edge electrophoretic coating which comprises the following raw materials in parts by weight: 500 parts of emulsion for electrophoretic paint, 90-100 parts of color paste and 800 parts of pure water; the emulsion for the electrophoretic paint comprises low-temperature amine modified epoxy resin and microgel; the low-temperature amine modified epoxy resin comprises the following components in percentage by mass: 50-70 wt% of organic acid modified epoxy resin, 2-10 wt% of amine compound, 1-8 wt% of cosolvent and 10-35 wt% of low-temperature blocked isocyanate curing agent. The electrophoretic coating does not contain heavy metal tin compounds, has low curing temperature, and has the advantages of environmental protection, good edge protection, excellent appearance and the like.
Description
Technical Field
The invention relates to the field of paint preparation. More particularly, relates to a low-temperature high-edge electrophoretic coating and a preparation method thereof.
Background
In order to realize cross-linking curing, a large amount of organic tin is added into the traditional electrophoretic paint, the baking temperature is high, energy is wasted while pollution is caused, the paint industry is led to develop towards the directions of green, environmental protection and low energy consumption for the sounding of a blue sky defense war of a corresponding country, and meanwhile, the problem of abnormal product performance caused by high-temperature baking can be solved aiming at certain enterprise requirements which are low in curing temperature requirement and have edge protection requirement.
In order to overcome the problems of the relevant customers in the using process, the field urgently needs to provide the heavy metal tin-free environment-friendly low-temperature type high-edge protection electrophoretic paint.
Disclosure of Invention
The invention aims to provide a low-temperature high-edge electrophoretic coating which does not contain heavy metal tin and is an environment-friendly low-temperature (130 ℃ x 20min) high-edge (blade 168H is less than 30 points) electrophoretic coating.
The invention also aims to provide a preparation method of the low-temperature high-edge electrophoretic coating.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a low-temperature high-edge electrophoretic coating, which comprises the following raw materials in parts by weight:
400 portions and 500 portions of the emulsion for electrophoretic paint,
90-100 parts of color paste,
400 portions of pure water and 800 portions;
the emulsion for the electrophoretic paint comprises low-temperature amine modified epoxy resin and microgel;
the low-temperature amine modified epoxy resin comprises the following components in percentage by mass:
optionally, the microgel is a polyether amine and epoxy addition modified cationic microgel.
Optionally, the amine equivalent of the low-temperature amine-modified epoxy resin is 1000-1200 g/mol.
Optionally, the preparation of the low-temperature amine-modified epoxy resin comprises the following steps: mixing the organic acid modified epoxy resin and the cosolvent, heating to the temperature of 110-140 ℃, adding the amine compound, preserving the heat for 1-3h at the temperature of 110-140 ℃, cooling to the temperature of 80-90 ℃, adding the low-temperature closed isocyanate curing agent, and preserving the heat for 0.5-3h to obtain the epoxy resin.
Optionally, the amine compound is at least one of diethanolamine, ketimine, methylethanolamine, diethylenetriamine, di-n-butylamine, and triethanolamine.
Optionally, the cosolvent is selected from at least one of methyl isobutyl ketone, ethylene glycol butyl ether, ethylene glycol hexyl ether, propylene glycol phenyl ether, methyl ethyl ketone oxime, and propylene glycol.
Optionally, the isocyanate group equivalent weight of the low-temperature blocked isocyanate curing agent is more than or equal to 42000g/mol, and the deblocking temperature is 100-130 ℃.
Optionally, the low-temperature blocked isocyanate curing agent comprises the following components in percentage by mass:
optionally, the low temperature blocking agent is selected from 1,2, 4-triazole, caprolactam, diethyl malonate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, isooctanol, methyl ethyl ketoxime, methyl amyl ketone oxime, phenol, dimethyl pyrazole, diethyl pyrazole, or ethyl acetate;
optionally, the 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.
In a second aspect, the invention provides a preparation method of a low-temperature high-edge electrophoretic coating, comprising the following steps:
s1: adding acid into pure water, adjusting the acid value of the solution to be 40-50mgKOH/g, sequentially adding low-temperature amine modified epoxy resin and microgel, uniformly stirring, adding pure water, emulsifying at 20-40 ℃ for 2-3 hours, and filtering to obtain the emulsion for the electrophoretic coating;
s2: and uniformly stirring the prepared electrophoretic coating with emulsion, color paste and pure water according to a proportion to obtain the low-temperature high-edge electrophoretic coating.
Optionally, in S1, the low-temperature amine-modified epoxy resin and the microgel are added in a weight ratio of 100: 0.5-0.9.
The invention has the following beneficial effects:
the emulsion for the electrophoretic coating comprises low-temperature amine modified epoxy resin and microcapsules, wherein the microcapsules can prevent the electrophoretic coating from being exposed at the edge due to too low viscosity of the coating at the edge of a workpiece in the baking process; the low-temperature blocked isocyanate is fully coated by the branched-chain amine modified epoxy resin to ensure that the blocked isocyanate is not deblocked, and the emulsion for the electrophoretic coating formed by emulsification has good stability; meanwhile, the organic acid structure is introduced into the organic acid modified epoxy resin in the low-temperature amine modified epoxy resin, the defect that the low-temperature amine modified epoxy resin is easy to separate out in the emulsifying process can be improved, and the low-temperature deblocking type isocyanate curing agent which does not contain heavy metal tin ensures low-temperature deblocking of the electrophoretic paint in the baking process. Therefore, the electrophoretic coating does not contain heavy metal tin compounds, has low curing temperature, and the formed coating has the advantages of environmental protection, good edge protection, excellent appearance and the like.
Detailed Description
In order to make the technical solutions and advantages of the present invention clearer, the technical solutions of the present invention will be further described in detail with reference to specific embodiments. 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.
In the case where the objects of the present invention are illustrated and explained by the following examples, the components of the composition are all explained on the general standard of parts by weight. In the present invention, the term "part" is used in the same sense as part by weight for the sake of brevity without specific mention.
The invention provides a low-temperature high-edge electrophoretic coating which comprises the following raw materials in parts by weight:
400 portions and 500 portions of the emulsion for electrophoretic paint,
90-100 parts of color paste,
400 portions of pure water and 800 portions;
the emulsion for the electrophoretic coating comprises low-temperature amine modified epoxy resin and microcapsules;
the low-temperature amine modified epoxy resin comprises the following components in percentage by mass:
it should be noted that the microgel included in the low-temperature amine-modified epoxy resin is a polyether amine and epoxy addition modified cationic microgel, such as the microgel disclosed in patent CN 105331270B. The electrophoretic coating adopts low-temperature blocked isocyanate as a resin curing system, so that low-temperature deblocking is realized in the baking process; meanwhile, microgel with specific performance, such as cationic microgel disclosed in patent CN 105331270B, is introduced, so that the edge exposure phenomenon caused by too low viscosity of coating at the edge of a workpiece in the baking process is avoided, a good edge protection effect is realized, and a flat coating film is obtained.
One possible way of achieving this is that the amine equivalent weight of the low-temperature amine-modified epoxy resin is 1000-1200 g/mol. The preparation method of the low-temperature amine modified epoxy resin comprises the following steps: mixing the organic acid modified epoxy resin and the cosolvent, heating to the temperature of 110-140 ℃, adding the amine compound, preserving the heat for 1-3h at the temperature of 110-140 ℃, cooling to the temperature of 80-90 ℃, adding the low-temperature closed isocyanate curing agent, and preserving the heat for 0.5-3h to obtain the epoxy resin.
The low-temperature blocked isocyanate curing agent is added at a lower temperature in the process of preparing the low-temperature amine modified epoxy resin, so that the low-temperature blocked isocyanate is fully coated by the branched-chain amine modified epoxy resin to ensure that the blocked isocyanate is not deblocked, the emulsion for the electrophoretic coating formed by emulsification has good stability, and no abnormal phenomena such as precipitation, emulsion decomposition and the like are generated in the process of storing at 40 ℃ for 4 weeks.
The low-temperature amine modified epoxy resin is obtained by modifying organic acid modified epoxy resin with amine compounds, wherein the amine compounds used in the modification process include but are not limited to diethanolamine, methylethanolamine, diethylenetriamine, ketimine, di-n-butylamine or triethanolamine; co-solvents include, but are not limited to, methyl isobutyl ketone, butyl glycol ether, hexyl glycol ether, propylene glycol phenyl ether, methyl ethyl ketone oxime, or propylene glycol.
One possible way to realize this is that the isocyanate group equivalent of the low-temperature blocked isocyanate curing agent included in the low-temperature amine-modified epoxy resin is not less than 42000g/mol, and when the isocyanate group equivalent is less than 42000g/mol, the active hydrogen on the isocyanate is not completely blocked, and when the low-temperature blocked isocyanate curing agent is used for preparing an emulsion for an electrophoretic coating, the emulsion is caused to have an abnormal gelling process, resulting in non-uniform solid particle size in the emulsion and a rough coating film. The deblocking temperature of the low-temperature blocked isocyanate curing is 100-130 ℃; it can be deblocked at 100 deg.C, completely at 130 deg.C, and is stable during storage at room temperature.
Further, in some preferred examples, the low-temperature blocked isocyanate curing agent comprises the following components in percentage by mass:
the low-temperature blocked isocyanate curing agent can be prepared by the following steps:
uniformly stirring and mixing polyisocyanate, a polymer of the polyisocyanate or a prepolymer of the polyisocyanate and a first part of inert solvent, heating and dropwise adding a low-temperature sealing agent, controlling the equivalent weight of NCO, heating and preserving heat after adding the solvent, controlling the equivalent weight of NCO, adding a second part of inert solvent, and controlling the solid content to obtain the low-temperature polyfunctional group-blocked isocyanate curing agent. The preparation process does not use a catalyst containing heavy metal tin, and the prepared low-temperature closed isocyanate curing agent does not contain heavy metal tin, so that the preparation method is more environment-friendly.
Wherein the polyisocyanate is at least one of aliphatic polyisocyanate, alicyclic polyisocyanate and aromatic polyisocyanate. The polymer of the polyisocyanate is selected from a trimer of toluene diisocyanate or a trimer of hexamethylene diisocyanate; the prepolymer of the polyisocyanate is selected from a toluene diisocyanate prepolymer of trimethylolpropane or a p-phenylene diisocyanate prepolymer of polyethylene glycol.
In some specific embodiments, for example, the aliphatic polyisocyanate includes, but is not limited to, 2, 4-xylene diisocyanate, 2, 6-xylene diisocyanate, butyl 1, 4-diisocyanate, or hexamethylene diisocyanate; the cycloaliphatic polyisocyanate includes, but is not limited to, 1, 3-cyclopentane diisocyanate, 1, 4-cyclohexane diisocyanate, isophorone diisocyanate, or diphenylmethane diisocyanate; the aromatic polyisocyanate is toluene diisocyanate, p-phenylene diisocyanate, p-phenylmethane diisocyanate or polymethylene polyphenyl polyisocyanate.
One possible implementation manner is that the inert solvent included in the low-temperature blocked isocyanate curing agent is selected from at least one of methyl isobutyl ketone, acetone, tetrahydrofuran; blocking agents include, but are not limited to, 1,2, 4-triazole, caprolactam, diethyl malonate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, isooctanol, methyl ethyl ketone oxime, methyl pentanone oxime, phenol, dimethylpyrazole, diethylpyrazole, or ethyl acetate; solvents include, but are 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.
The low-temperature amine modified epoxy resin is obtained by modifying organic acid modified epoxy resin with an amine compound. In one possible embodiment, the method for preparing the organic acid-modified epoxy resin comprises the steps of:
mixing epoxy resin, bisphenol A, organic acid A and an auxiliary solvent to serve as an initial reactant, heating the reactant to 110 ℃ under the protection of inert gas, adding an alkaline catalyst, then continuously heating to 170 ℃ for reaction for 3-5h, and detecting that the epoxy equivalent is qualified to obtain the organic acid modified epoxy resin.
Further preferably, in the process of preparing the organic acid modified epoxy resin, the weight ratio of the epoxy resin, the bisphenol A, the organic acid A, the auxiliary solvent and the alkaline catalyst is 50-70:10-30:1-13:4-20: 0.003-1.
Under the action of a catalyst, the epoxy resin reacts with bisphenol A and organic acid A to increase the chain extension. In a preferred example, the organic acid-modified epoxy resin has an epoxy equivalent of 1100. + -.10 g/equivalent.
Further, the epoxy equivalent of the epoxy resin as a raw material is 185-300 g/equivalent, and the epoxy resin includes, but is not limited to, bisphenol A type epoxy resin, bisphenol F type epoxy resin or polyphenol type glycidyl ether epoxy resin. More preferably, the epoxy resin is bisphenol a epoxy resin, which is more cost effective, and it should be understood by those skilled in the art that the selected epoxy resin may also be a mixture of bisphenol a epoxy resin, bisphenol F epoxy resin, and polyphenol glycidyl ether epoxy resin with different molecular weights.
The organic acid A used in the preparation of the organic acid-modified epoxy resin may be a monomer of an organic acid recognized by those skilled in the art as a raw material for a synthetic resin, and may be a fatty acid having one or more unsaturated double bonds. Organic acids a include, but are not limited to, soya oleic acid, benzoic acid, linolenic acid, coconut fatty acid, citric acid, acrylic acid, succinic acid, oxalic acid, palmitic acid, malonic acid, glutaric acid, stearic acid, isooctanoic acid, or glacial acetic acid, and the like.
In one possible embodiment, the auxiliary solvent is an alcohol solvent and/or an alcohol ether solvent. The alcoholic solvent includes, but is not limited to, isopropanol, n-butanol, isobutanol, n-hexanol, or isooctanol; the alcohol ether solvents include, but are 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 or propylene glycol phenyl ether, and the like.
In one possible embodiment, the basic catalyst used in the preparation of the organic acid-modified epoxy resin includes, but is not limited to, N-dimethylbenzylamine, triethylamine, dimethylaminopropylamine, dimethylaminobutylamine, diethylaminopropylamine, triethanolamine, tetramethylammonium chloride, triphenyl chloride, or the like.
The invention also provides a preparation method of the low-temperature high-edge electrophoretic coating, which comprises the following steps:
s1: adding acid into pure water, adjusting the acid value of the solution to be 40-50mgKOH/g, sequentially adding low-temperature amine modified epoxy resin and microgel, uniformly stirring, adding pure water, emulsifying at 20-40 ℃ for 2-3 hours, and filtering to obtain the emulsion for the electrophoretic coating;
s2: and uniformly stirring the prepared electrophoretic coating with emulsion, color paste and pure water according to a proportion to obtain the low-temperature high-edge electrophoretic coating.
In the preparation process, the acid added into the pure water is organic acid and/or inorganic acid. The low-temperature amine modified epoxy resin is emulsified in a dilute acid solution, the addition of the microgel is beneficial to improving the edge corrosion resistance of the electrophoretic paint, and the solid content of the finally prepared emulsion for the electrophoretic paint is 25-35 wt%. Preferably, the organic acid is at least one of lactic acid, acetic acid, formic acid and citric acid. The inorganic acid is nitric acid.
In a preferred example, in S1, the low-temperature amine-modified epoxy resin and the microgel are added in a weight ratio of 100: 0.5-0.9.
The technical solution of the present invention will be further described with reference to specific examples.
Examples
Example 1
The preparation method of the low-temperature blocked isocyanate curing agent comprises the following steps:
454.5g of isophorone diisocyanate (purchased from Wanhua chemical group Co., Ltd.) and 107.4g of methyl isobutyl ketone (purchased from Jinan century Tongda chemical Co., Ltd.) were put into a four-necked flask (manufactured by Kolings of Shanghai Kanghua glass Co., Ltd.) with a condenser and nitrogen protection, the temperature was raised to 40 ℃, 251.4g of an ethyl acetoacetate blocking agent (purchased from Baishui (Beijing) chemical technology Co., Ltd.) was added dropwise, the temperature was controlled to be 45 + -3 ℃, and the NCO equivalent was controlled to be 250-; adding 106.7g of butyl glycol ether (purchased from Tongda chemical company, Jinan century), raising the temperature to 100 ℃ after the addition, keeping the temperature at 100 ℃ for 1 hour, wherein the NCO equivalent is measured to be 48120, and the result is more than 42000, adding 30.1g of methyl isobutyl ketone (purchased from Tongda chemical company, Jinan century), and controlling the solid content to be 80 +/-2% to obtain the low-temperature polyfunctional group blocked isocyanate curing agent.
The preparation method of the organic acid modified epoxy resin comprises the following steps:
680.1g of bisphenol A type epoxy resin (initial epoxy equivalent of the epoxy resin is 185-, obtaining the faint yellow organic acid modified epoxy resin.
The preparation method of the low-temperature amine modified epoxy resin polymer comprises the following steps:
1165.2g of the organic acid modified epoxy resin, 95.12g of butyl cellosolve (purchased from Bailingwei science and technology Co., Ltd., purity 99.5%), heating to 110-120 ℃, adding 51g of diethanolamine (purchased from Tianjin Kaitai chemical Co., Ltd., purity 98%) and 62g of ketimine (purchased from Zidoku paint (China) Co., Ltd.), heating to 110-120 ℃, keeping the temperature for 1h, cooling to 90 ℃, adding 625g of the prepared low-temperature multifunctional blocked isocyanate curing agent, and keeping the temperature for 1h to obtain the modified epoxy resin polymer.
Preparation of an emulsion for electrophoretic coating, the preparation method comprising the steps of:
1139.2g of pure water, 30.05g of acetic acid (purchased from Shanghai purple reagent factory, analytical purity) and 6.1g of lactic acid (purchased from 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 be 40-50mgKOH/g, then 1935.6g of the modified epoxy resin polymer is slowly added, stirring is carried out for 1h, 15g of microgel in patent CN 105331270A is added, stirring is carried out for 30min, 412.5g of pure water and 1312.6g of pure water are added twice, emulsification is carried out for 2 h at the temperature of 25-45 ℃, and then filtration and packaging are carried out, thus obtaining the emulsion for the electrophoretic paint.
The technical indexes of the emulsion for the electrophoretic coating are as follows: the solid content is 36 plus or minus 2 percent, the grain diameter is less than or equal to 90nm, and the pH value is controlled to be 6.5 plus or minus 0.3. The electrophoretic paint prepared using the emulsion for electrophoretic paint has low-temperature high-edge characteristics, and in order to more easily illustrate the characteristics of the emulsion for electrophoretic paint, in the following examples, the emulsion for electrophoretic paint is also referred to as an emulsion for low-temperature high-edge electrophoretic paint. It should be understood by those skilled in the art that the definition of the emulsion for the low-temperature high-edge electrophoretic coating is merely to better illustrate the gist of the present invention by taking the following examples as examples, and should not be construed as any limitation or restriction on the emulsion for the electrophoretic coating.
The formulations for preparing the electrocoat are shown in table 1:
table 1 formulation of the electrocoat of example 1
| Name (R) | Specification of | Weight (parts) |
| Low temperature high edge electrophoresis emulsion | Self-contained articles | 421 |
| Color paste | Industrial product | 99 |
| Pure water | Industrial product | 670 |
The preparation method of the electrophoretic paint comprises the following steps:
uniformly stirring 421 parts of emulsion for low-temperature high-edge electrophoretic paint, 99 parts of color paste (ACECRON EXCEL 140TF BLACK of Nippon Industrial paint (Shanghai)) and 670 parts of pure water to obtain the electrophoretic paint; the electrophoretic coating is a cathode electrophoretic coating, the cathode electrophoretic coating is placed in an electrophoretic bath for curing for 16-24 hours, the blade construction voltage is controlled at 120 volts, the bath solution temperature is controlled at 28 ℃, electrophoresis is carried out for 3 minutes, the obtained coating is baked for 20 minutes (board surface) at 130 ℃, a black dry film is obtained, and the performance data are shown in table 6.
Example 2
The preparation method of the low-temperature blocked isocyanate curing agent comprises the following steps:
in a four-neck flask (manufactured by Korlins of Shanghai Kangxin glass Co., Ltd.) with a condenser and nitrogen protection, 480.2g of diphenylmethane diisocyanate (purchased from Wanhua chemical group Co., Ltd.) and 123.2g of methyl isobutyl ketone (purchased from Jinda chemical Co., Ltd.) were charged, the temperature was raised to 40 ℃, 152.8g of diethylpyrazole (purchased from Baishun (Beijing) chemical technology Co., Ltd.) was added dropwise, the temperature was controlled to 45. + -. 3 ℃, and the NCO equivalent was controlled to 250-; 127.3g of butyl cellosolve (purchased from Tongda chemical company, Jinan century), heating to 100 ℃ after the addition, keeping the temperature at 100 ℃ for 1 hour, wherein the NCO equivalent is measured to be 48120 and the result is more than 42000, and 32.5g of methyl isobutyl ketone (purchased from Tongda chemical company, Jinan century) is added, the solid content is controlled to be 80 +/-2 percent, so that the low-temperature polyfunctional group blocked isocyanate curing agent is obtained.
The preparation method of the organic acid modified epoxy resin comprises the following steps:
705.6g of bisphenol A type epoxy resin (initial epoxy equivalent of the epoxy resin is 185-, obtaining the faint yellow organic acid modified epoxy resin.
The preparation method of the low-temperature amine modified epoxy resin comprises the following steps:
1183.5g of the organic acid-modified epoxy resin, 101.2g of butyl cellosolve (purchased from carbofuran technologies, Inc., purity 99.5%), heating to 120 ℃ of 110-.
Preparation of an emulsion for low temperature high edge electrophoretic coating, the preparation method comprising the steps of:
1148.3g of pure water, 32.15g of acetic acid (purchased from Shanghai purple reagent factory, analytical purity) and 5.54g of lactic acid (purchased from 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 be 40-50mgKOH/g, then 1948.3g of the modified epoxy resin polymer is slowly added, stirring is carried out for 1h, 21g of microgel in patent CN 105331270A is added, stirring is carried out for 30min, 423.1g of pure water and 1413.8g of pure water are added twice, emulsification is carried out for 2 h at the temperature of 25-45 ℃, and then filtration and packaging are carried out, thus obtaining the emulsion for the low-temperature high-edge electrophoretic paint.
The technical indexes of the emulsion for the low-temperature high-edge electrophoretic coating are as follows: the solid content is 36 plus or minus 2 percent, the grain diameter is less than or equal to 90nm, and the pH value is controlled to be 6.5 plus or minus 0.3.
The formulations for preparing the electrocoat are shown in Table 2:
table 2 formulation of the electrocoat in example 2
| Name (R) | Specification of | Weight (parts) |
| Low temperature high edge electrophoresis emulsion | Self-contained articles | 500 |
| Color paste | Industrial product | 90 |
| Pure water | Industrial product | 410 |
The preparation method of the electrophoretic paint comprises the following steps:
uniformly stirring 500 parts of emulsion for low-temperature high-edge electrophoretic paint, 90 parts of color paste (ACECRON EXCEL 140TF BLACK from Nippon Industrial paint (Shanghai)) and 410 parts of pure water to obtain the electrophoretic paint; the electrophoretic coating is a cathode electrophoretic coating, is cured in an electrophoresis tank for 16-24 hours, is subjected to electrophoresis for 3 minutes under the conditions that the construction voltage is controlled at 110 volts and the temperature of the tank liquor is controlled at 28 ℃, and a coating film is obtained and is baked for 20 minutes (board surface) at 130 ℃ to obtain a black dry film, and the performance data is shown in the following table 6.
Example 3
The preparation method of the low-temperature blocked isocyanate curing agent comprises the following steps:
in a four-neck flask (manufactured by Korlins of Shanghai Kangxin glass Co., Ltd.) with a condenser and nitrogen protection, 421.6g of diphenylmethane diisocyanate (purchased from Wanhua chemical group Co., Ltd.) and 108.2g of methyl isobutyl ketone (purchased from Jinda chemical Co., Ltd.) were put into the flask, the temperature was raised to 40 ℃, 264.5g of dimethylpyrazole (purchased from Baishun (Beijing) chemical technology Co., Ltd.) was added dropwise, the temperature was controlled to 45 + -3 ℃, and the NCO equivalent was controlled to 250-; adding 105.5g of ethylene glycol butyl ether (purchased from Tongda chemical company, Jinan century), raising the temperature to 100 ℃ after the addition, keeping the temperature at 100 ℃ for 1 hour, wherein the NCO equivalent is measured to be 48120, and the result is more than 42000, adding 42.7g of methyl isobutyl ketone (purchased from Tongda chemical company, Jinan century), and controlling the solid content to be 80 +/-2% to obtain the low-temperature polyfunctional group blocked isocyanate curing agent.
The preparation method of the organic acid modified epoxy resin comprises the following steps:
712.8g of bisphenol A type epoxy resin (initial epoxy equivalent of 185-), 305.6g of bisphenol A (product number 1227146698| Purity: analytical standard for pharmaceutical analysis > 99.8% (HPLC)), 125.8g of soya-oil acid (product number tai-jiaye biotechnology, tai-gaku, inc.), 52g of butyl glycol (product number bacilyn, Purity 99.5%) were added to a three-necked flask (shanghai gao hua glass co., ltd.; colling) equipped with a stirrer, a condenser, a thermometer, a Coprinus, a reaction end point detection epoxy equivalent of 1100 + -10 g/equivalent, obtaining the faint yellow organic acid modified epoxy resin.
The preparation method of the low-temperature amine modified epoxy resin comprises the following steps:
1184.2g of the organic acid-modified epoxy resin, 141.3g of butyl cellosolve (purchased from carbony technologies, Inc., having a purity of 99.5%), heating to 120 ℃ of 110-.
The preparation method of the emulsion for the low-temperature high-edge electrophoretic coating comprises the following steps of:
1146.3g of pure water, 31.2g of acetic acid (Shanghai purple reagent factory, analytical purity) and 6.3g of lactic acid (L-type lactic acid with purity of 98% from Henan Jindan lactic acid science and technology Co., Ltd.) are added into a clean emulsification tank, high-speed stirring is started to stir the materials evenly, the acid value is adjusted to be 40-50mgKOH/g, then 1983.2g of the modified epoxy resin polymer is slowly added, stirring is carried out for 1h, 17g of microgel in patent CN 105331270A is added, stirring is carried out for 30min, 416.3g of pure water and 1423.9g of pure water are added twice, emulsification is carried out for 2 h at 25-45 ℃, and then filtration and packaging are carried out to obtain the emulsion for the low-temperature high-edge electrophoretic paint.
The technical indexes of the emulsion for the low-temperature high-edge electrophoretic coating are as follows: the solid content is 36 plus or minus 2 percent, the grain diameter is less than or equal to 90nm, and the pH value is controlled to be 6.5 plus or minus 0.3.
The formulations for preparing the electrocoat are shown in Table 3:
table 3 formulation of the electrocoat in example 3
| Name (R) | Specification of | Weight (parts) |
| Low temperature high edge electrocoat emulsion | Self-contained articles | 450 |
| Color paste | Industrial product | 100 |
| Pure water | Industrial product | 450 |
The preparation method of the electrophoretic paint comprises the following steps:
uniformly stirring 450 parts of emulsion for electrophoretic paint, 100 parts of color paste (ACECRON EXCEL 140TF BLACK from Nippon industrial paint (Shanghai) Co., Ltd.) and 450 parts of pure water to obtain the electrophoretic paint; the electrophoretic coating is a cathode electrophoretic coating, is cured in an electrophoresis tank for 16-24 hours, is subjected to electrophoresis for 3 minutes under the conditions that the construction voltage is controlled at 120 volts and the temperature of the tank liquor is controlled at 28 ℃, and is baked for 20 minutes (board surface) at 130 ℃ to obtain a black dry film with the film thickness of 20 microns, and the performance data are shown in table 6.
Comparative example 1
The low-temperature polyfunctional group blocked isocyanate curing agent adopts a traditional high-temperature blocked isocyanate product, namely blocked isocyanate FND-4252 for Nippon electrophoresis:
preparation of organic acid-modified epoxy resin the organic acid-modified epoxy resin of example 3 was used.
The preparation method of the low-temperature amine modified epoxy resin comprises the following steps:
1184.2g of the organic acid-modified epoxy resin and 141.3g of butyl cellosolve (purchased from carbony technologies, Inc., having a purity of 99.5%) were added to a three-necked flask (Korlington, Ltd.) equipped with a stirrer, a condenser and a thermometer, heated to 120 ℃ at 110-.
The preparation method of the emulsion for the electrophoretic coating comprises the following steps:
1146.3g of pure water, 31.2g of acetic acid (Shanghai purple reagent factory, analytical purity) and 6.3g of lactic acid (L-type lactic acid with purity of 98% from Henan Jindan lactic acid science and technology Co., Ltd.) are added into a clean emulsification tank, high-speed stirring is started to stir the materials uniformly, the acid value is adjusted to be 40-50mgKOH/g, then 1983.2g of the modified epoxy resin polymer is slowly added, 17g of the microgel in the patent CN 105331270A is added, stirring is carried out for 1h, stirring is carried out for 30min, 416.3g of the pure water and 1423.9g of the pure water are added twice, emulsification is carried out for 2 hours at the temperature of 25-45 ℃, and then filtration and packaging are carried out to obtain the emulsion for the electrophoretic paint.
The technical indexes of the emulsion for the electrophoretic coating are as follows: the solid content is 36 plus or minus 2 percent, the grain diameter is less than or equal to 90nm, and the pH value is controlled to be 6.5 plus or minus 0.3.
The formulations for preparing the electrocoat are shown in Table 4:
table 4 formulation of the electrodeposition paint of comparative example 1
| Name (R) | Specification of | Weight (parts) |
| Electrophoretic paint emulsion | Self-contained articles | 450 |
| Color paste | Industrial product | 100 |
| Pure water | Industrial product | 450 |
The preparation method of the electrophoretic paint comprises the following steps:
uniformly stirring 450 parts of emulsion for electrophoretic paint, 100 parts of color paste (ACECRON EXCEL 140TF BLACK from Nippon industrial paint (Shanghai) Co., Ltd.) and 450 parts of pure water to obtain the electrophoretic paint; the electrophoretic coating is a cathode electrophoretic coating, the cathode electrophoretic coating is placed in an electrophoretic bath for curing for 16-24 hours, the construction voltage is controlled at 120 volts, the bath solution temperature is controlled at 28 ℃, electrophoresis is carried out for 3 minutes, the obtained coating is baked for 20 minutes (plate surface) at 130 ℃, a black dry film is obtained, the film thickness is 20 micrometers, and the comparison result is shown in table 6.
Comparative example 2
Preparation of Low temperature blocked isocyanate curing agent the low temperature polyfunctional blocked isocyanate curing agent prepared in example 3 was used.
Preparation of organic acid-modified epoxy resin the organic acid-modified epoxy resin prepared in example 3 was used.
Preparation of a Low temperature amine-modified epoxy Polymer the modified epoxy polymer prepared in example 3 was used.
The preparation method of the emulsion for the electrophoretic coating comprises the following steps:
1146.3g of pure water, 31.2g of acetic acid (Shanghai purple reagent factory, analytical purity) and 6.3g of lactic acid (L-type lactic acid with purity of 98% from Henan Jindan lactic acid science and technology Co., Ltd.) are added into a clean emulsification tank, high-speed stirring is started to stir the materials evenly, the acid value is adjusted to be 40-50mgKOH/g, 1983.2g of the modified epoxy resin polymer is slowly added, stirring is carried out for 1h, 416.3g and 1423.9g of pure water are added twice, emulsification is carried out for 2 hours at the temperature of 25-45 ℃, and then the emulsion for the low-temperature high-edge electrophoretic paint is prepared by filtering and packaging with a filter bag.
The technical indexes of the emulsion for the low-temperature high-edge electrophoretic coating are as follows: the solid content is 36 plus or minus 2 percent, the grain diameter is less than or equal to 90nm, and the pH value is controlled to be 6.5 plus or minus 0.3.
The formulations for preparing the electrocoat are shown in Table 5:
TABLE 5 formulation of the electrocoat of comparative example 2
| Name (R) | Specification of | Weight (parts) |
| Electrophoretic paint emulsion | Self-contained articles | 450 |
| Color paste | Industrial product | 100 |
| Pure water | Industrial product | 450 |
The preparation method of the electrophoretic paint comprises the following steps:
uniformly stirring 450 parts of emulsion for electrophoretic paint, 100 parts of color paste (ACECRON EXCEL 140TF BLACK from Nippon industrial paint (Shanghai) Co., Ltd.) and 450 parts of pure water to obtain the electrophoretic paint; the electrophoretic coating is a cathode electrophoretic coating, is cured in an electrophoresis tank for 16-24 hours, is subjected to electrophoresis for 3 minutes under the conditions that the construction voltage is controlled at 120 volts and the temperature of the tank liquor is controlled at 28 ℃, and is baked for 20 minutes (board surface) at 130 ℃ to obtain a black dry film with the film thickness of 20 microns, and the performance data are shown in table 6.
The test results of examples 1-3 and comparative examples 1-2 are shown in Table 6:
TABLE 6 test results of examples 1-3 and comparative examples 1-2
The results in table 6 show that the electrophoretic coating provided by the invention has excellent curing performance, no problems of light loss and fading, smooth coating film, satisfactory hardness, and excellent water resistance, salt spray resistance, impact resistance, acid resistance and alkali resistance. In a comparative example 1, a traditional high-temperature blocked isocyanate product is used to replace the low-temperature polyfunctional blocked isocyanate curing agent in example 3, and the prepared electrophoretic paint has the results of light loss, fading, large blade rust point, roughness and low hardness, and the electrophoretic paint has water resistance, salt spray resistance, impact resistance, acid resistance and alkali resistance which do not reach the standard; the electrocoat of comparative example 2 does not include microcapsules and has much higher blade rust points than the electrocoats of examples 1-3.
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 (10)
1. The low-temperature high-edge electrophoretic coating is characterized by comprising the following raw materials in parts by weight:
400 portions and 500 portions of the emulsion for electrophoretic paint,
90-100 parts of color paste,
400 portions of pure water and 800 portions;
the emulsion for the electrophoretic paint comprises low-temperature amine modified epoxy resin and microgel;
the low-temperature amine modified epoxy resin comprises the following components in percentage by mass:
2. the electrodeposition coating according to claim 1, wherein the microgel is a polyetheramine and epoxy addition-modified cationic microgel.
3. The electrodeposition coating composition according to claim 1, wherein the amine equivalent of the low-temperature amine-modified epoxy resin is 1000-1200 g/mol.
4. The electrodeposition paint according to claim 1, wherein the preparation of the low-temperature amine-modified epoxy resin comprises the steps of: mixing the organic acid modified epoxy resin and the cosolvent, heating to the temperature of 110-140 ℃, adding the amine compound, preserving the heat for 1-3h at the temperature of 110-140 ℃, cooling to the temperature of 80-90 ℃, adding the low-temperature closed isocyanate curing agent, and preserving the heat for 0.5-3h to obtain the epoxy resin.
5. The electrophoretic paint according to claim 1, wherein the amine compound is at least one of diethanolamine, ketimine, methylethanolamine, diethylenetriamine, di-n-butylamine, and triethanolamine; preferably, the cosolvent is selected from at least one of methyl isobutyl ketone, ethylene glycol butyl ether, ethylene glycol hexyl ether, propylene glycol phenyl ether, methyl ethyl ketone oxime and propylene glycol.
6. The electrodeposition coating according to claim 1, wherein the low-temperature blocked isocyanate curing agent has an isocyanate group equivalent weight of 42000g/mol or more and a deblocking temperature of 100 ℃ and 130 ℃.
7. The electrophoretic paint according to claim 1, wherein the low-temperature blocked isocyanate curing agent comprises the following components in percentage by mass:
8. the electrodeposition paint according to claim 7, wherein the low-temperature blocking agent is selected from 1,2, 4-triazole, caprolactam, diethyl malonate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol butyl ether, ethylene glycol hexyl ether, diethylene glycol butyl ether, propylene glycol methyl ether, isooctanol, methyl ethyl ketoxime, methyl pentanone oxime, phenol, dimethylpyrazole, diethylpyrazole, or ethyl acetate; preferably, the 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.
9. A method for preparing a low temperature type high edge electrocoating paint as claimed in any one of claims 1-8, comprising the steps of:
s1: adding acid into pure water, adjusting the acid value of the solution to be 40-50mgKOH/g, sequentially adding low-temperature amine modified epoxy resin and microgel, uniformly stirring, adding pure water, emulsifying at 20-40 ℃ for 2-3 hours, and filtering to obtain the emulsion for the electrophoretic coating;
s2: and uniformly stirring the prepared electrophoretic coating with emulsion, color paste and pure water according to a proportion to obtain the low-temperature high-edge electrophoretic coating.
10. The method as set forth in claim 9, wherein the low-temperature amine-modified epoxy resin and the microgel are added in a weight ratio of 100: 0.5-0.9.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115101891A (en) * | 2022-07-19 | 2022-09-23 | 中材锂膜有限公司 | Preparation method of lithium ion battery diaphragm |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105255240A (en) * | 2015-11-05 | 2016-01-20 | 浩力森涂料（上海）有限公司 | Corrosion prevention additive and electrophoretic coating for highly preventing corrosion of edges |
| CN105331270A (en) * | 2015-12-02 | 2016-02-17 | 立邦涂料（中国）有限公司 | Cationic microgel and preparation method and application thereof |
| CN106905664A (en) * | 2017-04-10 | 2017-06-30 | 立邦涂料（中国）有限公司 | A kind of function polyamine modified microgel, preparation method and its usage |
| US20170226653A1 (en) * | 2014-10-31 | 2017-08-10 | Valspar Sourcing, Inc. | High Edge Cathodic Epoxy Electrocoat Composition |
| CN108976884A (en) * | 2018-07-29 | 2018-12-11 | 立邦工业涂料(上海)有限公司 | A kind of electrophoretic coating and preparation method thereof |
| CN111234678A (en) * | 2018-11-28 | 2020-06-05 | 立邦涂料（中国）有限公司 | Tin-free environment-friendly low-temperature electrophoretic coating and preparation method thereof |
-
2020
- 2020-10-28 CN CN202011170833.4A patent/CN114410178A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170226653A1 (en) * | 2014-10-31 | 2017-08-10 | Valspar Sourcing, Inc. | High Edge Cathodic Epoxy Electrocoat Composition |
| CN105255240A (en) * | 2015-11-05 | 2016-01-20 | 浩力森涂料（上海）有限公司 | Corrosion prevention additive and electrophoretic coating for highly preventing corrosion of edges |
| CN105331270A (en) * | 2015-12-02 | 2016-02-17 | 立邦涂料（中国）有限公司 | Cationic microgel and preparation method and application thereof |
| CN105331270B (en) * | 2015-12-02 | 2018-04-06 | 立邦涂料（中国）有限公司 | A kind of cationic microgel, preparation method and its usage |
| CN106905664A (en) * | 2017-04-10 | 2017-06-30 | 立邦涂料（中国）有限公司 | A kind of function polyamine modified microgel, preparation method and its usage |
| CN108976884A (en) * | 2018-07-29 | 2018-12-11 | 立邦工业涂料(上海)有限公司 | A kind of electrophoretic coating and preparation method thereof |
| CN111234678A (en) * | 2018-11-28 | 2020-06-05 | 立邦涂料（中国）有限公司 | Tin-free environment-friendly low-temperature electrophoretic coating and preparation method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115101891A (en) * | 2022-07-19 | 2022-09-23 | 中材锂膜有限公司 | Preparation method of lithium ion battery diaphragm |
| CN115101891B (en) * | 2022-07-19 | 2024-03-05 | 中材锂膜有限公司 | Preparation method of lithium ion battery diaphragm |
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