CN108531063B - Cathode electrophoretic coating and preparation method and application thereof - Google Patents
Cathode electrophoretic coating and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/44—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications
- C09D5/4488—Cathodic paints
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F283/00—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G
- C08F283/06—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals
- C08F283/065—Macromolecular compounds obtained by polymerising monomers on to polymers provided for in subclass C08G on to polyethers, polyoxymethylenes or polyacetals on to unsaturated polyethers, polyoxymethylenes or polyacetals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- 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
- C08G18/48—Polyethers
- C08G18/50—Polyethers having heteroatoms other than oxygen
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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
- C09D5/44—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
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Abstract
The invention discloses a cathode electrophoretic coating, a preparation method and an application thereof, wherein the cathode electrophoretic coating comprises cation perfluoropolyether modified resin and a closed polyisocyanate crosslinking agent, and the raw material of the cation perfluoropolyether modified resin comprises CF3CF2CF2O[CF(CF3)CF2O]nCF(CF3)‑Y‑C(R1)＝CH2、HC＝CRaCOORbThe copolymer, polyamine and organic acid are formed by copolymerizing with a monomer C, wherein the monomer C is one or more of structural monomers containing epoxy groups and double bonds; preparation: reacting the intermediate of the copolymer and the polyamine with organic acid to prepare cation perfluoropolyether modified resin, and mixing the modified resin and the blocked polyisocyanate crosslinking agent to prepare emulsion to obtain the cathode electrophoretic coating; it can be applied to hardware; the coating and the cured layer thereof have the advantages of excellent performance, easy degradation, low toxicity and the like.
Description
Technical Field
The invention relates to the field of coatings, in particular to a cathode electrophoretic coating and a preparation method and application thereof.
Background
The electrophoretic coating is a novel coating with low pollution, energy conservation, resource conservation, protection and corrosion resistance, has the characteristics of smooth coating, good water resistance and chemical resistance and the like, is easy to realize the mechanization and automation of the coating industry, is suitable for coating workpieces with edges, corners and holes, and is widely applied to coating hardware such as automobiles, automatic vehicles, electromechanics, household appliances and the like. The electrophoretic coating and the coating method are industrially applied after the 60 s in the 20 th century, a fully-closed circulating system can be operated by adopting the electrophoretic coating, and the utilization rate of the coating can reach about 95 percent.
However, as the demand for high-performance hardware is continuously increased and the electrophoretic coating technology is continuously developed and advanced, higher requirements are put on coating properties such as hydrophobicity, antifouling property, weather resistance and decorative property. The traditional electrophoretic paint has poor hydrophobicity, antifouling property and weather resistance, and cannot meet the new requirements of high-grade hardware products.
In recent years, some improvements have been made in the prior art gradually, for example, chinese invention CN 101993576, an acrylic acid fluorine monomer is introduced, and although an electrophoretic coating with better hydrophobicity and weather resistance is prepared to a certain extent, the applicant finds that in the actual use process, the coating is difficult to biodegrade in the later treatment process, and PFOA is formed by decomposition and/or metabolism (PFOA is classified in class 2B carcinogen list in carcinogen list published by international cancer research institute of world health organization 10 and 27 in 2017), and through the research of the applicant, the reason for such imagination is that the introduced acrylic acid fluorine monomer has great possibility that such long-chain fluoroalkyl group can not only decompose or metabolize to form PFOA, but also has the defects of difficult degradation, high biological cumulative toxicity and great environmental hazard, so the electrophoretic coating prepared according to the above method is not very consistent with the sustainable development of environment and is human-oriented And (5) a concept.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the cathode electrophoretic coating with excellent performances of hydrophobicity, oleophobicity, antifouling property, adhesive force, salt mist resistance and the like, and is more friendly to the environment and human bodies.
The invention also provides a preparation method of the cathode electrophoretic coating.
The invention also provides a hardware product.
In order to solve the above technical problems, the present invention adopts a technical scheme as follows:
a cathode electrophoretic coating, which comprises a cation perfluoropolyether modified resin and a blocked polyisocyanate crosslinking agent in a mass ratio of 1-5: 1;
the raw materials of the cation perfluoropolyether modified resin comprise a copolymer formed by copolymerizing a monomer A represented by a formula (I), a monomer B represented by a formula (II) and a monomer C, polyamine and an organic acid, wherein the cation perfluoropolyether modified resin is prepared by reacting an intermediate obtained by reacting the copolymer with the polyamine and the organic acid;
CF3CF2CF2O[CF(CF3)CF2O]nCF(CF3)-Y-C(R1)＝CH2(Ⅰ)
in the formula (I), n is an integer of 5-50, R1Is hydrogen or saturated alkane with 1-4 carbon atoms; y is C1-6 aliphatic group, C6-10 aromatic group, C6-10 cyclic aliphatic group, -CH2CH2N(R’)SO2-、-(CH2)a-O-CO-、-CO-O-(CH2)b-O-CO-、-CO-NH-(CH2) c-O-CO-or-CH2(CH2CH2O)m-, wherein R' is an alkyl group having 1 to 6 carbon atoms, and a, b, c and m are independently integers of 1 to 10;
H2C＝CRaCOORb(II)
in the formula (II), RaIs a hydrogen atom or a methyl group; rbIs a saturated hydrocarbon group having 1 to 20 carbon atoms;
the monomer C is one or more of structural monomers containing epoxy groups and double bonds.
According to some preferred aspects of the invention, in formula (I), n is an integer from 5 to 35.
According to some preferred aspects of the invention, a, b, c, m are independently 1, 2, 3, 4, 5 or 6.
According to some preferred aspects of the invention, R isbIs a saturated alkyl group.
According to some specific and preferred aspects of the present invention, the monomer B is a combination of one or more selected from the group consisting of methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, and octadecyl (meth) acrylate; and/or the presence of a gas in the gas,
the monomer C is one or more of glycidyl methacrylate, glycidyl acrylate and allyl glycidyl ether.
According to some preferred aspects of the present invention, the monomer A is 40 to 80%, the monomer B is 10 to 50%, and the monomer C is 1 to 10% by weight of the raw materials of the copolymer.
According to some preferred aspects of the present invention, in the raw material of the cationic perfluoropolyether-modified resin, the polyamine, the monomer C, and the organic acid are fed according to the following rules: the number of nitrogen atoms in the polyamine is equivalent or in excess with respect to the number of epoxy groups of the monomer C, and the number of hydrogen ions in the organic acid is equivalent or in excess with respect to the number of nitrogen atoms in the polyamine.
According to some specific and preferred aspects of the present invention, the polyamine is a combination of one or more selected from the group consisting of ethylenediamine, butanediamine, hexamethylenediamine, diethanolamine, and triethanolamine; and/or the presence of a gas in the gas,
the organic acid is one or more selected from formic acid, acetic acid and lactic acid.
The invention provides another technical scheme that: the preparation method of the cathode electrophoretic coating comprises the following steps:
(1) and preparing the cation perfluoropolyether modified resin: in the presence of an initiator, carrying out polymerization reaction on a monomer A represented by the formula (I), a monomer B represented by the formula (II) and a monomer C in a first organic solvent to obtain a copolymer, adding the polyamine into the copolymer for reaction, adding the organic acid for reaction, and obtaining the cationic perfluoropolyether modified resin;
(2) and preparing a cathode electrophoretic coating: and (2) respectively adding the cationic perfluoropolyether modified resin prepared in the step (1) and the blocked polyisocyanate crosslinking agent into a second organic solvent, acidifying, and adding medium water to obtain the cathode electrophoretic coating.
According to some preferred aspects of the present invention, in the step (1), the polymerization reaction and the reaction of the copolymer and the polyamine are respectively carried out at 60 to 90 ℃.
According to a particular aspect of the invention, in step (1), the polymerization reaction is carried out for a reaction time of 6 to 18 hours.
According to a further specific aspect of the present invention, in step (1), the duration of the reaction of the copolymer with the polyamine is 1 to 3 hours.
According to another specific aspect of the present invention, in the step (1), after the organic acid is added, stirring is performed for 10 to 60 minutes, so as to obtain the cationic perfluoropolyether modified resin.
In some embodiments of the present invention, the first organic solvent and the second organic solvent are one or more of alcohol solvents and alcohol ether solvents, respectively. Wherein, the alcohol solvent comprises: methanol, ethanol, isopropanol, diethylene glycol, tripropylene glycol, and the like; the alcohol ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, etc.
In some embodiments of the invention, the initiator may be azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, cumyl hydroperoxide, t-butyl peroxypivalate, diisopropyl peroxydicarbonate, or the like.
In some preferred embodiments of the present invention, the cationic perfluoropolyether modified resin accounts for 5-30 wt% of the cathodic electrophoretic paint, the blocked polyisocyanate crosslinking agent accounts for 1-20 wt% of the cathodic electrophoretic paint, the second organic solvent accounts for 1-20 wt% of the cathodic electrophoretic paint, and the medium water accounts for 30-80 wt% of the cathodic electrophoretic paint.
In some preferred embodiments of the present invention, in the step (2), the acidification is to add the organic acid (which may be other suitable acids) into the mixture, and the addition amount of the organic acid may be specifically added according to actual conditions, only to ensure that the whole mixed solution is in an acidic condition.
In the present invention, preferably, the blocked polyisocyanate crosslinking agent is prepared by the following method: and (2) reacting the polyisocyanate with the blocking agent in a solvent at the temperature of between 60 and 80 ℃ to obtain the blocked polyisocyanate crosslinking agent.
More preferably, the blocking agent is firstly dissolved in the solvent, then the polyisocyanate is dripped into the solvent, and the heat preservation reaction is carried out for 1-2 hours. When the completion of the-NCO reaction is confirmed by IR, the solvent is distilled off under reduced pressure, and the blocked polyisocyanate crosslinking agent can be obtained.
According to a specific aspect of the invention, a blocking agent is dissolved in a first solvent, the solution is added into a reaction bottle provided with a calcium chloride tube, the temperature is controlled to be 60-80 ℃, polyisocyanate is dissolved into a second solvent, a polyisocyanate solution is dripped into the reaction bottle, the dripping is controlled to be completed within 1-3 hours, after the dripping is completed, the reaction is kept for 1-2 hours, when the IR confirms that the-NCO reaction is complete, the first solvent and the second solvent are distilled off under the reduced pressure condition, and the blocked polyisocyanate crosslinking agent is obtained.
Preferably, the polyisocyanate is one or a combination of more selected from aliphatic polyisocyanates and aromatic polyisocyanates.
Preferably, the blocking agent is a combination of one or more selected from 3, 5-dimethylpyrazole, methyl ethyl ketone oxime and malonic acid.
The first solvent and the second solvent are respectively one or more of methyl isobutyl ketone, ethyl acetate and butyl acetate.
In the present invention, the blocked polyisocyanate crosslinking agent is also commercially available.
The invention provides another technical scheme that: the hardware comprises a hardware body and a coating formed on the hardware body, wherein the coating at least comprises a cured layer obtained by curing the cathodic electrophoretic coating.
Due to the implementation of the technical scheme, compared with the prior art, the invention has the following advantages:
the cathode electrophoretic coating provided by the invention not only meets the high standard requirements on hydrophobicity, oleophobicity, corrosion resistance, adhesive force and the like of the electrophoretic coating at present, but also meets the requirements on bottom surface integration of the electrophoretic coating at present, and more importantly, the cathode electrophoretic coating provided by the invention is easy to degrade and low in toxicity in the post-treatment process, and is more friendly to the environment and human bodies.
Detailed Description
The application aims to provide the cathode electrophoretic coating which is easy to degrade, low in toxicity, environment-friendly and human-friendly and can meet the requirements of excellent performances such as hydrophobicity, oleophobicity, antifouling property, adhesive force and salt mist resistance in the using process. The electrophoretic coating based on the prior art realizes good hydrophobicity, weather resistance or corrosion resistance to a certain extent, but is difficult to decompose and absorb by the environment and has great potential threat to human body, and the electrophoretic coating is not in accordance with sustainable development and people-oriented concept.
In the invention, the applicant innovatively provides a perfluoropolyether derivative monomer, the perfluoropolyether derivative monomer is copolymerized with a monomer B and a monomer C, then ring opening and salt forming are carried out, so as to obtain the cationic perfluoropolyether modified resin, the obtained cationic perfluoropolyether modified resin is mixed with a closed polyisocyanate crosslinking agent in a second organic solvent, medium water is added after acidification, so as to obtain the cathode electrophoretic coating, and the prepared cathode electrophoretic coating has better performances in all aspects, so that the prepared coating or the coating after curing and forming has the advantages of easy degradation, lower surface energy, high stability, low toxicity and the like, and the prepared cathode electrophoretic coating has excellent advantages of easy degradation, low surface energy, high stability, low toxicity and the like, and the strategy of sustainable development and the people-oriented concept at present are well agreed.
The above-described scheme is further illustrated below with reference to specific examples; it is to be understood that these embodiments are provided to illustrate the general principles, essential features and advantages of the present invention, and the present invention is not limited in scope by the following embodiments; the implementation conditions used in the examples can be further adjusted according to specific requirements, and the implementation conditions not indicated are generally the conditions in routine experiments.
All starting materials are either commercially available or prepared by methods conventional in the art, unless otherwise specified in the following.
In the following, for convenience of description, a1, a2, A3, a4, a5 appearing in examples are monomers of the following structures, respectively, Ph is benzene:
CF3CF2CF2O[CF(CF3)CF2O]25.5CF(CF3)CON(H)CH2CH2OC(O)C(CH3)＝CH2A1；
CF3CF2CF2O[CF(CF3)CF2O]15.6CF(CF3)CON(H)CH2CH2OC(O)CH＝CH2A2；
CF3CF2CF2O[CF(CF3)CF2O]11.2CF(CF3)CH2CH2OC(O)CH＝CH2A3；
CF3CF2CF2O[CF(CF3)CF2O]18CF(CF3)CH2CH2-Ph-CH＝CH2A4；
CF3CF2CF2O[CF(CF3)CF2O]20.1CF(CF3)CH2CH2N(CH2CH3)SO2-CH＝CH2A5。
example 1 preparation of cationic perfluoropolyether modified resin
Adding 70.00g of A1, 20.00g of tert-butyl (meth) acrylate, 10.00g of glycidyl methacrylate, 100.00g of ethylene glycol monomethyl ether and 0.50g of azobisisobutyronitrile into a reaction vessel provided with a thermometer, a reflux condenser, a stirrer and nitrogen protection, heating to control the reaction temperature to 65 ℃, reacting for 12 hours, then adding 8.00g of ethylenediamine, keeping the temperature and reacting for 3 hours, finally adding 16.50g of acetic acid, and stirring for 60 minutes to obtain the cationic perfluoropolyether modified resin B1.
Example 2 preparation of cationic perfluoropolyether modified resin
In a reaction vessel equipped with a thermometer, reflux condenser, stirrer, and nitrogen blanket, 50.00g of A2, 45.00g of octadecyl (meth) acrylate, 5.00g of glycidyl methacrylate, 100.00g of ethylene glycol monoethyl ether, and 0.50g of azobisisobutyronitrile were charged. Heating to control the reaction temperature to 65 ℃, reacting for 12 hours, then adding 4.00g of ethylenediamine, reacting for 3 hours under heat preservation, finally adding 8.50g of acetic acid, and stirring for 60 minutes to obtain the cation perfluoropolyether modified resin B2.
Example 3 preparation of cationic perfluoropolyether modified resin
60.00g of A3, 35.00g of hexadecyl (methyl) acrylate, 5.00g of glycidyl acrylate, 100.00g of ethylene glycol monoethyl ether and 0.50g of azobisisobutyronitrile are added into a reaction vessel provided with a thermometer, a reflux condenser, a stirrer and nitrogen protection, the reaction temperature is controlled to be 65 ℃ by heating, the reaction is carried out for 12 hours, then 4.00g of ethylenediamine is added, the temperature is kept for 3 hours, and finally 10.00g of formic acid is added, and the stirring is carried out for 60 minutes, so that the cation perfluoropolyether modified resin B3 is prepared.
Example 4 preparation of cationic perfluoropolyether modified resin
Adding 55.00g of A4, 40.00g of octyl (meth) acrylate, 5.00g of allyl glycidyl ether, 100.00g of ethylene glycol monoethyl ether and 0.50g of benzoyl peroxide into a reaction vessel provided with a thermometer, a reflux condenser tube, a stirrer and nitrogen protection, heating to control the reaction temperature to 65 ℃, reacting for 12 hours, adding 5.00g of butanediamine, preserving the temperature for 3 hours, adding 8.00g of formic acid, and stirring for 60 minutes to obtain the cationic perfluoropolyether modified resin B4.
Example 5 preparation of cationic perfluoropolyether modified resin
Adding 57.00g of A5, 35.00g of octyl (meth) acrylate, 8.00g of allyl glycidyl ether, 100.00g of ethylene glycol monoethyl ether and 0.50g of benzoyl peroxide into a reaction vessel provided with a thermometer, a reflux condenser tube, a stirrer and nitrogen protection, heating to control the reaction temperature to 65 ℃, reacting for 12 hours, adding 7.00g of hexamethylenediamine, preserving the temperature for 3 hours, adding 10.00g of formic acid, and stirring for 60 minutes to obtain the cationic perfluoropolyether modified resin B5.
EXAMPLE 6 preparation of blocked polyisocyanate crosslinking agent
4.00g of 3, 5-dimethylpyrazole was dissolved in 40.00g of methyl isobutyl ketone, the solution was added to a reaction flask equipped with a calcium chloride tube, the temperature was controlled by heating to 80 ℃, 8.00g of HDI trimer was dissolved in 10.00g of methyl isobutyl ketone, the HDI trimer solution was dropwise added to the reaction flask, the dropwise addition was controlled to be completed within 2 hours, and after the completion of the dropwise addition, the reaction was allowed to proceed with incubation for 2 hours. And (3) confirming that NCO is reacted completely by IR, and distilling off methyl isobutyl ketone under the reduced pressure condition to obtain the blocked polyisocyanate crosslinking agent C.
EXAMPLE 7 preparation of cathodic electrodeposition coating
20g of prepared cation perfluoropolyether modified resin B1 and 10g of blocked polyisocyanate crosslinking agent C are added into a reaction vessel provided with a stirrer and a reflux condenser pipe, 10g of ethylene glycol monomethyl ether is added, and 0.5g of organic acid is added for acidification. Under the condition of stirring, 80g of deionized water is added, and after stirring for 0.5h, the cathode electrophoretic coating D1 is prepared.
EXAMPLE 8 preparation of cathodic electrodeposition coating
30g of prepared cation perfluoropolyether modified resin B2 and 10g of blocked polyisocyanate crosslinking agent C are added into a reaction vessel provided with a stirrer and a reflux condenser pipe, 10g of ethylene glycol monomethyl ether is added, and 1g of organic acid is added for acidification. Under the condition of stirring, 80g of deionized water is added, and after stirring for 0.5h, the cathode electrophoretic coating D2 is prepared.
EXAMPLE 9 preparation of cathodic electrodeposition coating
15g of prepared cation perfluoropolyether modified resin B3 and 10g of blocked polyisocyanate crosslinking agent C are added into a reaction vessel provided with a stirrer and a reflux condenser pipe, 15g of ethylene glycol monomethyl ether is added, and 1g of organic acid is added for acidification. Under the condition of stirring, 80g of deionized water is added, and after stirring for 0.5h, the cathode electrophoretic coating D3 is prepared.
EXAMPLE 10 preparation of cathodic electrodeposition coating
25g of prepared cation perfluoropolyether modified resin B4 and 10g of blocked polyisocyanate crosslinking agent C are added into a reaction vessel provided with a stirrer and a reflux condenser, 15g of ethylene glycol monomethyl ether is added, and 1.5g of organic acid is added for acidification. And adding 100g of deionized water under the stirring condition, and stirring for 0.5h to obtain the cathode electrophoretic paint D4.
EXAMPLE 11 preparation of cathodic electrodeposition coating
20g of prepared cation perfluoropolyether modified resin B5 and 10g of blocked polyisocyanate crosslinking agent C are added into a reaction vessel provided with a stirrer and a reflux condenser pipe, 10g of ethylene glycol monomethyl ether is added, and 0.5g of organic acid is added for acidification. Under the condition of stirring, 80g of deionized water is added, and after stirring for 0.5h, the cathode electrophoretic coating D5 is prepared.
Performance testing
The specific test items, and test methods and/or standards are as follows:
contact angle test: the contact angle test is to use a contact measuring instrument (OCA-20) of Germany Datophysics company to represent the quality of the hydrophobic performance by the contact angle of the formed water drop, the larger the contact angle is, the better the hydrophobic performance is, and the test result is the average value of three parallel tests.
Adhesion of base material: according to GB/T9286-1998
Salt water resistance: according to GB/T1763-1979
Pencil hardness: according to GB/T6739-
Stain resistance: according to GB/T9780-88
The prepared cathode electrophoretic coating C1-C5 is directly subjected to electrophoretic coating, the electrophoretic voltage is 250V, the conductivity is 1500 +/-200 mu s-cm, the electrophoretic temperature is 25 ℃, and the electrophoretic time is 3 minutes. After completion of the electrophoresis, the resulting coating film was cured at 150 ℃ for 20 min. Thus obtaining the transparent film with smooth appearance. The test results are given in the following table:
the present invention is described in detail in order to make those skilled in the art understand the content and practice the invention, and the invention is not limited to the above embodiments, and all equivalent changes or modifications made according to the spirit of the invention should be covered by the scope of the invention.
Claims (7)
1. The cathode electrophoretic coating is characterized by comprising cationic perfluoropolyether modified resin and a closed polyisocyanate crosslinking agent in a mass ratio of 1-5: 1;
the raw materials of the cation perfluoropolyether modified resin comprise a copolymer formed by copolymerizing a monomer A represented by a formula (I), a monomer B represented by a formula (II) and a monomer C, polyamine and an organic acid, wherein the cation perfluoropolyether modified resin is prepared by reacting an intermediate obtained by reacting the copolymer with the polyamine and the organic acid; in the raw materials of the copolymer, the monomer A accounts for 40-80%, the monomer B accounts for 10-50%, and the monomer C accounts for 1-10% by weight percentage;
CF3CF2CF2O[CF(CF3)CF2O]nCF(CF3)-Y-C(R1)=CH2（Ⅰ）
in the formula (I), n is an integer of 5-35, R1Is hydrogen or saturated alkane with 1-4 carbon atoms; y is C1-6 aliphatic group, C6-10 aromatic group, C6-10 cyclic aliphatic group, -CH2CH2N(R’)SO2-、-(CH2)a-O-CO-、-CO-O-(CH2)b-O-CO-、-CO-NH-(CH2) c-O-CO-or-CH2(CH2CH2O)m-, wherein R' is an alkyl group having 1 to 6 carbon atoms, a, b, c, m are independently 1, 2, 3, 4, 5 or 6;
H2C=CRaCOORb（Ⅱ）
in the formula (II), RaIs a hydrogen atom or a methyl group; rbIs saturated alkyl with 1-20 carbon atoms;
the monomer C is one or more of structural monomers containing epoxy groups and double bonds.
2. The cathodic electrocoating of claim 1 wherein the monomer B is a combination of one or more selected from methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, n-hexyl (meth) acrylate, octyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) acrylate, dodecyl (meth) acrylate, hexadecyl (meth) acrylate, and octadecyl (meth) acrylate; and/or the presence of a gas in the gas,
the monomer C is one or more of glycidyl methacrylate, glycidyl acrylate and allyl glycidyl ether.
3. The cathodic electrophoretic paint according to claim 1, wherein the polyamine, the monomer C and the organic acid are fed into the raw materials of the cationic perfluoropolyether modified resin according to the following rule: the number of nitrogen atoms in the polyamine is equivalent or in excess with respect to the number of epoxy groups of the monomer C, and the number of hydrogen ions in the organic acid is equivalent or in excess with respect to the number of nitrogen atoms in the polyamine.
4. The cathodic electrocoating material of claim 1 or 3 wherein the polyamine is one or a combination of more selected from the group consisting of ethylenediamine, butanediamine, and hexanediamine; and/or the presence of a gas in the gas,
the organic acid is one or more selected from formic acid, acetic acid and lactic acid.
5. A method for preparing the cathodic electrocoating material of any one of claims 1-4, comprising:
(1) and preparing the cation perfluoropolyether modified resin: in the presence of an initiator, carrying out polymerization reaction on a monomer A represented by the formula (I), a monomer B represented by the formula (II) and a monomer C in a first organic solvent to obtain a copolymer, adding the polyamine into the copolymer for reaction, adding the organic acid for reaction, and obtaining the cationic perfluoropolyether modified resin;
(2) and preparing a cathode electrophoretic coating: and (2) respectively adding the cationic perfluoropolyether modified resin prepared in the step (1) and the blocked polyisocyanate crosslinking agent into a second organic solvent, acidifying, and adding medium water to obtain the cathode electrophoretic coating.
6. The method for preparing a cathodic electrocoating as defined in claim 5 wherein in step (1), the polymerization and the reaction of the copolymer with the polyamine are carried out at 60-90 ℃.
7. An article of hardware comprising an article of hardware body and a coating formed on the article of hardware body, the coating comprising at least a cured layer obtained by curing the cathodic electrocoating material of any one of claims 1 to 4.
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| CN101679548A (en) * | 2007-06-06 | 2010-03-24 | 3M创新有限公司 | Fluorinated composition and surface treatment agent prepared therefrom |
| WO2014100580A1 (en) * | 2012-12-20 | 2014-06-26 | 3M Innovative Properties Company | Fluoropolymer composition including an oligomer having an ultraviolet absorbing group |
| CN104884486A (en) * | 2012-12-20 | 2015-09-02 | 3M创新有限公司 | Copolymers including ultraviolet absorbing groups and fluoropolymer compositions including them |
| CN106634384A (en) * | 2016-10-01 | 2017-05-10 | 浙江科技学院 | Preparation method of cation acrylate resin of cathode electrophoresis coating |
| CN107586365A (en) * | 2016-07-08 | 2018-01-16 | 浙江省化工研究院有限公司 | It is a kind of can room temperature film-forming water-based fluororesin/acrylate core-shell latex |
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| JP2543670B2 (en) * | 1986-06-17 | 1996-10-16 | エヌティエヌ株式会社 | Manufacturing method of cleaning blade |
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| CN101679548A (en) * | 2007-06-06 | 2010-03-24 | 3M创新有限公司 | Fluorinated composition and surface treatment agent prepared therefrom |
| WO2014100580A1 (en) * | 2012-12-20 | 2014-06-26 | 3M Innovative Properties Company | Fluoropolymer composition including an oligomer having an ultraviolet absorbing group |
| CN104884486A (en) * | 2012-12-20 | 2015-09-02 | 3M创新有限公司 | Copolymers including ultraviolet absorbing groups and fluoropolymer compositions including them |
| CN107586365A (en) * | 2016-07-08 | 2018-01-16 | 浙江省化工研究院有限公司 | It is a kind of can room temperature film-forming water-based fluororesin/acrylate core-shell latex |
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