CN110903690A - Cathode electrophoretic coating and preparation method thereof - Google Patents
Cathode electrophoretic coating and preparation method 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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- 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
- C09D5/4407—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 by polymerisation reactions involving only carbon-to-carbon unsaturated bonds
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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
- C09D5/443—Polyepoxides
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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
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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
- C09D5/4476—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes for electrophoretic applications comprising polymerisation in situ
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Abstract
The invention relates to a cathode electrophoretic coating and a preparation method thereof. The cathode electrophoretic coating comprises acrylic resin and modified epoxy resin, wherein the acrylic resin contains amino and hydroxyl, and the modified epoxy resin contains amino. The extinction effect of the cathode electrophoretic coating is uniform.
Description
Technical Field
The invention relates to the technical field of electrophoretic coatings, in particular to a cathode electrophoretic coating and a preparation method thereof.
Background
With the development of coating, the surface effect of the product after coating is diversified. In recent years, products exhibiting a low gloss effect on the surface after coating have been increasingly popular.
The primary means by which the coated product can exhibit a low gloss effect is paint matting. For example, a matting effect can be achieved by dispersing matting powder (e.g., ultrafine silica, paraffin, filler, etc.) into a paint in a spray coating process or a roll coating process. However, when the matting powder is added to an electrodeposition coating material in an electrodeposition coating process, matting tends to be uneven and the matting effect tends to be poor.
In addition, the synthesis of insoluble microgels using the host resin of the electrocoating is another method for producing products having matting effect, but this method has the same drawbacks as the addition of matting powder: the extinction is not uniform.
Disclosure of Invention
Based on this, it is necessary to provide a cathode electrophoretic coating material with uniform extinction.
A cathode electrophoretic coating, which comprises acrylic resin and modified epoxy resin; the monomer of the acrylic resin comprises an unsaturated monomer containing amino and an unsaturated monomer containing hydroxyl, or the monomer of the acrylic resin comprises an unsaturated monomer containing both amino and hydroxyl; the modified epoxy resin contains an amino group.
Through a great deal of research, the traditional electrophoretic material with the extinction effect mainly achieves the extinction effect by adding extinction powder, and because the viscosity of the bath solution of the electrophoretic paint is low during construction, the extinction powder in the electrophoretic paint is difficult to be uniformly distributed in the bath solution, and the particles do not have electrophoresis property, the extinction powder cannot be stably and uniformly coated on a workpiece along with other components of the electrophoretic paint under the condition of electrifying. The cathode electrophoretic coating contains amino and hydroxyl acrylic resin and amino-containing modified epoxy resin. The cathode electrophoretic paint has high electrophoresis performance and water solubility through the acrylic resin containing amino and hydroxyl, the modified epoxy resin containing amino and the acrylic epoxy resin polymer, and a uniform film layer with low glossiness can be formed after electrophoresis in use.
In one embodiment, the monomers of the acrylic resin include an amino group-containing unsaturated monomer and a hydroxyl group-containing unsaturated monomer, or the monomers of the acrylic resin include an amino group-and hydroxyl group-containing unsaturated monomer.
In one embodiment, the amino group-containing unsaturated monomer is selected from at least one of dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate; and/or
The unsaturated monomer containing hydroxyl is at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.
In one embodiment, the monomers of the acrylic resin further include monomers containing two or more ethylenically unsaturated groups; and/or
The monomers of the acrylic resin also include monomers containing one ethylenically unsaturated group.
In one embodiment, the monomer containing two or more ethylenically unsaturated groups is at least one selected from the group consisting of ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, hexylene glycol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate; and/or
The monomer containing one ethylenically unsaturated group is at least one selected from the group consisting of methyl methacrylate, butyl methacrylate, isobornyl methacrylate, ethyl acrylate, butyl acrylate and lauryl acrylate.
In one embodiment, the cathodic electrophoretic paint further comprises a curing agent, and the curing agent is selected from blocked isocyanate curing agents; and/or
The cathode electrophoretic paint also comprises an acrylic epoxy resin polymer, and the monomer of the acrylic epoxy resin polymer comprises the monomer of the acrylic resin and the modified epoxy resin.
A preparation method of a cathode electrophoretic coating comprises the following steps:
reacting a compound containing amino with epoxy resin to obtain modified epoxy resin;
mixing the modified epoxy resin, the monomer of the acrylic resin and an initiator, and then carrying out polymerization reaction to obtain a mixture, wherein the monomer of the acrylic resin comprises an unsaturated monomer containing amino and an unsaturated monomer containing hydroxyl, or the monomer of the acrylic resin comprises an unsaturated monomer containing both amino and hydroxyl, an unsaturated monomer containing amino and an unsaturated monomer containing hydroxyl; and
and mixing the mixture with a curing agent to obtain the cathode electrophoretic coating.
In one embodiment, the amino group-containing compound is selected from at least one of methylamine, N-methylethanolamine, and diethanolamine.
In one embodiment, the amino group-containing compound is 0.5 to 4 parts, the epoxy resin is 8 to 30 parts, the amino group-containing unsaturated monomer is 9.7 to 17.4 parts, and the hydroxyl group-containing unsaturated monomer is 12.4 to 30.2 parts by mass.
In one embodiment, the monomers of the acrylic resin further include monomers containing two or more ethylenically unsaturated groups; and/or
The monomer of the acrylic resin also comprises a monomer containing one ethylene unsaturated group, and a monomer containing one ethylene unsaturated group.
In one embodiment, the part of the monomer containing more than two ethylenically unsaturated groups is 0.5 to 2 parts by mass; the part of the monomer containing one ethylene unsaturated group is 60 to 75.4 parts.
A preparation method of a cathode electrophoretic coating comprises the following steps:
carrying out polymerization reaction on monomers of acrylic resin to obtain acrylic resin, wherein the monomers of the acrylic resin comprise unsaturated monomers containing amino and unsaturated monomers containing hydroxyl, or the monomers of the acrylic resin comprise unsaturated monomers containing both amino and hydroxyl, unsaturated monomers containing amino and unsaturated monomers containing hydroxyl;
reacting a compound containing amino with epoxy resin to obtain modified epoxy resin; and
and mixing the acrylic resin, the modified epoxy resin and a curing agent to obtain the cathode electrophoretic paint.
Detailed Description
In order that the invention may be more fully understood, reference will now be made to the following description. The present invention may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention.
The cathode electrophoretic paint of an embodiment includes an acrylic resin, a modified epoxy resin, and a curing agent. The acrylic resin contains amino and hydroxyl, and the modified epoxy resin contains amino.
Specifically, the monomers of the acrylic resin include amino group-containing unsaturated monomers and hydroxyl group-containing unsaturated monomers; or the monomer of the acrylic resin comprises an unsaturated monomer containing both amino and hydroxyl; or the monomers of the acrylic resin include unsaturated monomers containing both amino groups and hydroxyl groups, unsaturated monomers containing amino groups, and unsaturated monomers containing hydroxyl groups. The cathode electrophoretic coating enables the electrophoretic material to have electrophoresis performance through acrylic resin containing amino and hydroxyl and modified epoxy resin containing amino, and a uniform film layer can be formed after electrophoresis; and when a paint film is formed by electrophoresis, due to the compatibility of the acrylic resin and the modified epoxy resin and the shrinkage of the acrylic resin, tiny particles are formed on the surface of the formed paint film, so that the glossiness of the paint film is low, and the extinction effect is realized. In addition, the cathode electrophoretic coating has high water solubility, belongs to water-based coatings, and is environment-friendly.
Specifically, the amine value of the acrylic resin is 40mgKOH/g to 100 mgKOH/g. When the amine value of the acrylic resin is too low, the water solubility of the acrylic resin is poor, so that the bath solution is white and turbid and precipitates are easy to generate; when the amine value of the acrylic resin is too high, the conductivity may be too high, so that the acrylic resin may have poor electrophoresis and decreased water resistance. The hydroxyl value of the acrylic resin is 50mgKOH/g to 140 mgKOH/g. When the hydroxyl value of the acrylic resin is lower than 50mgKOH/g, the resin is insufficiently cured, the crosslinking density is insufficient, and the mechanical physical property and the chemical resistance of a coating film are reduced; when the hydroxyl value of the acrylic resin is higher than 140mgKOH/g, the crosslinking density of the resin is too high, the coating film is brittle, and the comprehensive performance is reduced.
Specifically, the amino group-containing unsaturated monomer is an amino group-containing ethylenically unsaturated monomer. The acrylic resin has electrophoresis property and water solubility by introducing amino group into the acrylic resin. Further, the amino group-containing unsaturated monomer is an ethylenically unsaturated monomer containing a tertiary amine.
In one embodiment, the amino group-containing unsaturated monomer is at least one selected from dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate, and diethylaminoethyl methacrylate. Further, the unsaturated monomer containing an amino group is selected from one of dimethylamino methyl methacrylate and dimethylamino ethyl methacrylate.
Specifically, the hydroxyl group-containing unsaturated monomer is a hydroxyl group-containing ethylenically unsaturated monomer. By introducing hydroxyl groups into the acrylic resin, the water solubility of the acrylic resin is improved, and hydroxyl groups are provided for the reaction of the acrylic resin with the curing agent. Further, the hydroxyl group-containing unsaturated monomer is at least one selected from the group consisting of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate. Further, the unsaturated monomer containing hydroxyl group is selected from one of hydroxypropyl methacrylate and hydroxybutyl acrylate.
In one embodiment, the monomers of the acrylic resin are amino group-containing unsaturated monomers and hydroxyl group-containing unsaturated monomers.
In one embodiment, the monomers of the acrylic resin further include monomers containing two or more ethylenically unsaturated groups and/or monomers containing one ethylenically unsaturated group.
Specifically, the monomer containing more than two ethylenically unsaturated groups can enable the acrylic resin to have a large molecular weight, so that leveling shrinkage in the baking process of the cathode extinction electrophoretic paint is limited, a paint film is microscopically rough in surface, and the extinction effect is improved. Further, the monomer having two or more ethylenically unsaturated groups is at least one selected from the group consisting of ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate and pentaerythritol tetraacrylate. Further, the monomer having two or more ethylenically unsaturated groups is hexanediol diacrylate.
Specifically, a monomer having one ethylenically unsaturated group is used as a main monomer of the acrylic resin. The monomer having one ethylenically unsaturated group is at least one selected from the group consisting of methyl methacrylate, butyl methacrylate, isobornyl methacrylate, ethyl acrylate, butyl acrylate and lauryl acrylate. Further, the monomer having one ethylenically unsaturated group is one selected from the group consisting of methyl methacrylate, butyl acrylate and isobornyl methacrylate.
In one embodiment, the monomers of the acrylic resin are amino group-containing unsaturated monomers, hydroxyl group-containing unsaturated monomers, monomers containing two or more ethylenically unsaturated groups, and monomers containing one ethylenically unsaturated group.
The modified epoxy resin contains amino groups, and the modified resin has water solubility and electrophoresis property by introducing the amino groups into the epoxy resin.
In particular, the curing agent is selected from blocked isocyanate curing agents.
In one embodiment, the cathodic electrophoretic paint further includes an acrylic epoxy polymer. The monomer of the acrylic epoxy resin polymer comprises a monomer of acrylic resin and modified epoxy resin.
Specifically, the acrylic epoxy resin polymer includes a polymer polymerized from a monomer of an acrylic resin and a modified epoxy resin and a polymer polymerized from a direct acrylic resin and a modified epoxy resin. That is, the number of repetitions of the acrylic resin monomer in the acrylic epoxy resin polymer is 1 or more. The monomer of the acrylic resin herein is a monomer of the acrylic resin of any of the above embodiments. The acrylic epoxy resin polymer can improve the water solubility of the cathodic electrophoretic coating, so that the extinction effect of the cathodic electrophoretic coating after electrophoresis is better and more stable.
In one embodiment, the cathodic electrophoretic paint is composed of acrylic resin, modified epoxy resin, acrylic epoxy resin polymer and a curing agent.
In one embodiment, the cathodic electrocoating further includes an acid. The acid can increase the water solubility of the cathodic electrophoretic paint, so that the cathodic electrophoretic paint is easier to mix when being mixed with water. The acid is acetic acid, diacetic acid, lactic acid, etc. The acid is 4 to 10 parts by mass. Further, the acid is 5.5 to 7.8 parts by mass. Further, the acid was added in an amount of 6.3 parts by mass.
In one embodiment, the cathodic electrophoretic paint is composed of acrylic resin, modified epoxy resin, acrylic epoxy resin polymer, a curing agent and acid.
The method for preparing a cathode electrophoretic coating according to an embodiment includes steps S110 to S130. Specifically, the method comprises the following steps:
and step S110, reacting the compound containing the amino with the epoxy resin to obtain the modified epoxy resin.
Specifically, a compound containing an amino group and an epoxy resin undergo a ring-opening reaction to obtain a modified epoxy resin. Further, the temperature of the ring-opening reaction is 80 ℃ to 100 ℃.
Specifically, the amino group-containing compound is at least one selected from methylamine, N-methylethanolamine and diethanolamine. Further, the amino group-containing compound is diethanolamine.
Specifically, the epoxy resin is a medium molecular weight epoxy resin such as E-12, E-14, E-20, and the like. When the molecular weight of the epoxy resin is too small, the compatibility with the acrylic resin is too good, so that the final paint film has higher gloss. When the molecular weight of the epoxy resin is too large and the compatibility with the acrylic resin is too poor, the paint formulation may be delaminated, which may affect the storage stability. Furthermore, the molecular weight of the epoxy resin is 800-2000. Such as E-12, E-20.
In one embodiment, the amino group-containing compound is 0.5 to 4 parts by mass, and the epoxy resin is 8 to 30 parts by mass. Furthermore, the parts of the compound containing amino are 1.2 to 2.5 parts by mass, and the parts of the epoxy resin are 11.2 to 15.9 parts by mass. Furthermore, the part of the compound containing amino is 1.8 to 3.7 parts by mass, and the part of the epoxy resin is 13 parts by mass.
And step S120, mixing the monomers of the modified epoxy resin and the acrylic resin with an initiator, and then carrying out polymerization reaction to obtain a mixture.
Specifically, the temperature of the polymerization reaction is 80 ℃ to 110 ℃. Further, the temperature of the polymerization reaction is 85 ℃ to 95 ℃. After polymerization, the mixture includes an acrylic resin, a modified epoxy resin, and an acrylic epoxy polymer.
Specifically, the monomer of the acrylic resin includes an amino group-containing unsaturated monomer and a hydroxyl group-containing unsaturated monomer, or the monomer of the acrylic resin includes an unsaturated monomer containing both an amino group and a hydroxyl group. The amino group-containing unsaturated monomer is the amino group-containing unsaturated monomer, the hydroxyl group-containing unsaturated monomer is the hydroxyl group-containing unsaturated monomer, and the amino group-and hydroxyl group-containing unsaturated monomer is the amino group-and hydroxyl group-containing unsaturated monomer, and the details thereof are omitted here.
In one embodiment, the part of the unsaturated monomer containing amino groups is 9.7 to 17.4 parts by mass. Further, the part of the amino group-containing unsaturated monomer is 10 to 14 parts by mass. Further, the part of the amino group-containing unsaturated monomer is 13.2 parts by mass.
In one embodiment, the part of the unsaturated monomer containing hydroxyl is 12.4 to 30.2 parts by mass. Further, the part of the unsaturated monomer containing hydroxyl is 14 to 22 parts by mass. Further, the part of the hydroxyl group-containing unsaturated monomer was 18.6 parts by mass.
In one embodiment, the monomers of the acrylic resin further include monomers containing two or more ethylenically unsaturated groups and monomers containing one ethylenically unsaturated group. Specifically, the monomer having two or more ethylenically unsaturated groups is the monomer having two or more ethylenically unsaturated groups according to any of the above embodiments; the monomer containing one ethylenically unsaturated group is the monomer containing one ethylenically unsaturated group according to any of the above embodiments, and is not described herein again.
In one embodiment, the part of the monomer containing two or more ethylenically unsaturated groups is 0.5 to 4 parts by mass. Further, the part of the monomer containing two or more ethylenically unsaturated groups is 0.8 to 2.1 parts by mass. Further, the part of the monomer containing two or more ethylenically unsaturated groups is 1.2 parts by mass
In one embodiment, the part of the monomer containing one ethylenically unsaturated group is 60 to 75.4 parts by mass. Furthermore, the part of the monomer containing one ethylene unsaturated group is 66.4 to 72 parts by mass fraction.
The initiator is an initiator commonly used in the art, such as dibenzoyl peroxide, azobisisobutyronitrile, azobisisoheptonitrile, and the like. The initiator is 0.6-3.0 parts by mass. Furthermore, the part of the initiator is 0.7 to 1.6 parts by mass. Further, the part of the initiator is 0.9 part by mass.
In one embodiment, the monomers of the acrylic resin include an amino group-containing unsaturated monomer, a hydroxyl group-containing unsaturated monomer, a monomer containing two or more ethylenically unsaturated groups, and a monomer containing one ethylenically unsaturated group. The weight portion of the unsaturated monomer containing amino is 9.7 to 17.4, the weight portion of the unsaturated monomer containing hydroxyl is 12.4 to 30.2, the weight portion of the monomer containing more than two ethylene unsaturated groups is 0.5 to 2, and the weight portion of the monomer containing one ethylene unsaturated group is 50 to 75.4. Furthermore, the weight portion of the unsaturated monomer containing amino is 10 to 14, the weight portion of the unsaturated monomer containing hydroxyl is 14 to 22, the weight portion of the monomer containing more than two ethylene unsaturated groups is 0.8 to 2.1, and the weight portion of the monomer containing one ethylene unsaturated group is 52.7 to 62.9.
Specifically, the solvent for the polymerization reaction is a water-soluble solvent, for example, an alcohol solvent or an alcohol ether solvent. The solvent of the polymerization reaction is used to dissolve the monomers of the reaction. Further, the solvent for the polymerization reaction is at least one selected from the group consisting of ethanol, n-propanol, isopropanol, butanol, ethylene glycol ethyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol ethyl ether and propylene glycol butyl ether. The parts of the solvent for the polymerization reaction are 75.3 to 194.7 parts by mass, so that the mass percentage of the solid of the synthetic resin is 35 to 55 percent. Further, the part of the solvent for the polymerization reaction is 139.4 to 174 parts by mass. Further, the part of the solvent for polymerization was 156.4 parts by mass.
And step S130, mixing the mixture with a curing agent to obtain the cathode electrophoretic paint.
Specifically, after the mixture is mixed with a curing agent, an acid is added to obtain the cathodic electrophoretic paint. The purpose of the acid is to neutralize the base in the mixture, increasing the water solubility of the mixture. Specifically, the curing agent is a blocked isocyanate curing agent. The blocked isocyanate curing agent consists of polyisocyanate, a blocking agent and a solvent, and the blocked isocyanate curing agent comprises 25 to 72.2 parts by mass of the curing agent. And further 51.2 to 72.2 parts by mass of a curing agent.
In one embodiment, the mass of the curing agent is 20% to 60% of the mass of the mixture. Further, the mass of the curing agent is 32-48% of the mass of the mixture. The solid content of the closed isocyanate curing agent is 60-75%.
In one embodiment, the method further comprises a preparation step of the blocked isocyanate curing agent. Specifically, polyisocyanate and a solvent are mixed, then the temperature is raised to 45-50 ℃, a sealant is dripped for 3-3.5 h, and the temperature is kept for 4h after dripping is finished, so that the blocked isocyanate curing agent is obtained. Further, the polyisocyanate is selected from at least one of HDI biuret, HDI trimer and IPDI trimer. The blocking agent is selected from at least one of phenol, caprolactam, methyl ethyl ketoxime and pyrazole. The solvent corresponding to the polyisocyanate is a lipid or an alcohol ether ester. Of course, in some embodiments, blocked isocyanate curing agents are commercially available.
The preparation method of the cathode electrophoretic coating has simple steps and is easy for industrial production. In addition, the cathode electrophoretic coating prepared by the preparation method of the cathode electrophoretic coating has better extinction effect and more stable extinction effect.
The method for using the cathode electrophoretic paint comprises the following steps S210 to S220. Specifically, the method comprises the following steps:
and step S210, carrying out electrophoresis on the workpiece by using the cathode electrophoretic paint to obtain a paint film.
Specifically, the cathodic electrophoretic paint is the cathodic electrophoretic paint of any one of the above embodiments. The voltage of electrophoresis is 20V-150V, and the time is 10 s-180 s. Further, the voltage of electrophoresis is 30V-80V, and the time is 20 s-60 s.
Specifically, the cathodic electrophoretic coating is mixed with water and then subjected to electrophoresis to obtain a paint film.
And S220, baking the paint film.
Specifically, the baking temperature is 140-170 ℃, and the baking time is 20-50 min. The baking temperature is 140-170 ℃, and the phenomenon that the extinction effect is unstable due to overhigh baking temperature can be avoided.
The application method of the cathode electrophoretic paint is simple and convenient, and the film layer prepared by the application method of the cathode electrophoretic paint has good extinction effect, low glossiness and good stability.
The preparation method of the cathode electrophoretic coating of another embodiment includes steps S210 to S230, specifically:
and step S210, carrying out polymerization reaction on monomers of the acrylic resin to obtain the acrylic resin.
Specifically, the monomer of the acrylic resin is the monomer of the acrylic resin of any one of the above embodiments, and is not described herein again.
And S220, reacting the compound containing the amino with the epoxy resin to obtain the modified epoxy resin.
The amino-containing compound and the epoxy resin are both monomers of the acrylic resin of any of the above embodiments, and are not described herein again.
And step S230, mixing the acrylic resin, the modified epoxy resin and the curing agent to obtain the cathode electrophoretic coating.
The curing agent is a monomer of the acrylic resin of any one of the above embodiments, and is not described herein again.
The application method of the cathode electrophoretic paint is simple and convenient, and the film layer prepared by the application method of the cathode electrophoretic paint has good extinction effect and low glossiness.
The following detailed description is given with reference to specific examples. The examples, which are not specifically illustrated, employ drugs and equipment, all of which are conventional in the art. The experimental procedures, in which specific conditions are not indicated in the examples, were carried out according to conventional conditions, such as those described in the literature, in books, or as recommended by the manufacturer. The reagents in the examples are not particularly limited and are commercially available.
Examples 1 to 3
(1) The components of each example were weighed out as in table 1.
TABLE 1
(2) Respectively mixing the polyisocyanates of each embodiment with the corresponding first solvent, heating to 45-50 ℃, dropwise adding the corresponding sealant of each embodiment for 3-3.5 h, and preserving heat for 4h after dropwise adding to obtain the blocked isocyanate curing agent of each embodiment.
(3) The amino group-containing compound, the corresponding epoxy resin, and the second solvent of each example were mixed, and then heated to 90 ℃ to react for 3 hours, respectively, to obtain the modified epoxy resin of each example.
(4) And (3) at 90 ℃, mixing the monomers of the acrylic resin and the initiator of each embodiment, dropwise adding the mixture into the modified epoxy resin prepared in the step (3) and corresponding to each embodiment, keeping the temperature for 2h after dropwise adding for 3h, supplementing the initiator, and continuing to keep the temperature for reaction for 4h to obtain the transparent and viscous mixture of each embodiment.
(5) The blocked isocyanate curing agent prepared in the step (2) in each example is correspondingly added into the transparent viscous mixture obtained in the step (4), and is uniformly mixed, and then 8 parts of lactic acid is added and is uniformly stirred, so that the cathode electrophoretic paint in each example is obtained.
(6) The cathodic electrodeposition coating materials of the respective examples were mixed with water corresponding to the respective examples to obtain electrolyte solutions of the respective examples. And (3) taking the workpiece as a cathode and a stainless steel sheet as an anode, and performing electrophoresis for 30S under the voltage of 40V to obtain a paint film. Then, the workpiece was baked at 160 ℃ for 30 minutes to obtain the workpiece after the electrodeposition coating of each example.
(7) Adhesion, hardness, gloss, flexibility and impact resistance of the work pieces after electrophoretic coating of each example were measured by GB/T9286-1998 test for marking test of paint films of colored paints and varnishes, GB/T6739 1996 pencil determination for hardness of coating film, GB/T9754-1998 test for determination of 20 DEG, 60 DEG and 85 DEG specular gloss of paint films of colored paints and varnishes not containing metallic pigments, GB/T1731-93 determination for flexibility of paint films, and GB1732-79 determination for impact resistance of paint films, and the results are shown in Table 2.
TABLE 2
As can be seen from Table 2, the cathodic electrophoretic paints according to examples 1 to 3 have good extinction effect, stability and good paint film comprehensive performance.
Comparative examples 1 to 3
The preparation steps of the cathodic electrodeposition coatings of comparative examples 1 to 3 are substantially the same as those of example 1, except that the raw materials of comparative examples 1 to 3 are different from those of example 1, and the raw materials of comparative examples 1 to 3 are shown in Table 3.
TABLE 3
Comparative example 1: because of the small amount of dimethylaminoethyl acrylate which is a water-soluble monomer, the final synthesized electrophoretic paint has poor water solubility, white bath solution and insoluble flocs.
Comparative example 2: the use level of the bifunctional monomer 1,6 hexanediol diacrylate is large, and the bifunctional monomer gels at the later reaction stage of the synthetic resin, so that the reaction cannot be continued.
Comparative example 3: the epoxy resin accounts for a little bit of the whole electrophoretic paint component, the glossiness of an electrophoretic paint film is not enough, and the glossiness is 89.
The technical features of the embodiments described above may be arbitrarily combined, and for the sake of brevity, all possible combinations of the technical features in the embodiments described above are not described, but should be considered as being within the scope of the present specification as long as there is no contradiction between the combinations of the technical features.
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (12)
1. The cathode electrophoretic coating is characterized by comprising acrylic resin and modified epoxy resin, wherein the acrylic resin contains amino and hydroxyl, and the modified epoxy resin contains amino.
2. The cathodic electrocoating of claim 1 wherein the acrylic resin monomers comprise amino group-containing unsaturated monomers and hydroxyl group-containing unsaturated monomers, or the acrylic resin monomers comprise both amino group-and hydroxyl group-containing unsaturated monomers.
3. The cathodic electrodeposition coating according to claim 2, wherein the amino group-containing unsaturated monomer is at least one selected from the group consisting of dimethylaminoethyl acrylate, diethylaminoethyl acrylate, dimethylaminoethyl methacrylate and diethylaminoethyl methacrylate; and/or
The unsaturated monomer containing hydroxyl is at least one of hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxybutyl acrylate and hydroxybutyl methacrylate.
4. The cathodic electrophoretic paint according to any one of claims 1 to 3, wherein the monomers of the acrylic resin further comprise monomers containing two or more ethylenically unsaturated groups; and/or
The monomers of the acrylic resin also include monomers containing one ethylenically unsaturated group.
5. The cathodic electrophoretic paint according to claim 4, wherein the monomer containing two or more ethylenically unsaturated groups is at least one selected from the group consisting of ethylene glycol diacrylate, propylene glycol diacrylate, butylene glycol diacrylate, hexanediol diacrylate, trimethylolpropane triacrylate, and pentaerythritol tetraacrylate; and/or
The monomer containing one ethylenically unsaturated group is at least one selected from the group consisting of methyl methacrylate, butyl methacrylate, isobornyl methacrylate, ethyl acrylate, butyl acrylate and lauryl acrylate.
6. The cathode electrophoretic paint according to any one of claims 1 to 3, further comprising a curing agent, wherein the curing agent is selected from blocked isocyanate curing agents; and/or
The cathode electrophoretic paint also comprises an acrylic epoxy resin polymer, and the monomer of the acrylic epoxy resin polymer comprises the monomer of the acrylic resin and the modified epoxy resin.
7. The preparation method of the cathode electrophoretic coating is characterized by comprising the following steps:
reacting a compound containing amino with epoxy resin to obtain modified epoxy resin;
mixing the modified epoxy resin, the monomer of the acrylic resin and an initiator, and then carrying out polymerization reaction to obtain a mixture, wherein the monomer of the acrylic resin comprises an unsaturated monomer containing amino and an unsaturated monomer containing hydroxyl, or the monomer of the acrylic resin comprises an unsaturated monomer containing both amino and hydroxyl, an unsaturated monomer containing amino and an unsaturated monomer containing hydroxyl; and
and mixing the mixture with a curing agent to obtain the cathode electrophoretic coating.
8. The method of claim 7, wherein the amino group-containing compound is at least one selected from the group consisting of methylamine, N-methylethanolamine, and diethanolamine.
9. The method for preparing the cathodic electrophoretic paint according to claim 7, wherein the amino group-containing compound is 0.5 to 4 parts, the epoxy resin is 8 to 30 parts, the amino group-containing unsaturated monomer is 9.7 to 17.4 parts, and the hydroxyl group-containing unsaturated monomer is 12.4 to 30.2 parts by mass.
10. The method for preparing the cathode electrophoretic coating according to any one of claims 7 to 9, wherein the monomers of the acrylic resin further include monomers containing two or more ethylenically unsaturated groups; and/or
The monomer of the acrylic resin also comprises a monomer containing one ethylene unsaturated group, and a monomer containing one ethylene unsaturated group.
11. The preparation method of the cathode electrophoretic coating according to claim 10, wherein the monomer containing two or more ethylenically unsaturated groups is present in an amount of 0.5 to 2 parts by mass; the part of the monomer containing one ethylene unsaturated group is 60 to 75.4 parts.
12. The preparation method of the cathode electrophoretic coating is characterized by comprising the following steps:
carrying out polymerization reaction on monomers of acrylic resin to obtain acrylic resin, wherein the monomers of the acrylic resin comprise unsaturated monomers containing amino and unsaturated monomers containing hydroxyl, or the monomers of the acrylic resin comprise unsaturated monomers containing both amino and hydroxyl, unsaturated monomers containing amino and unsaturated monomers containing hydroxyl;
reacting a compound containing amino with epoxy resin to obtain modified epoxy resin; and
and mixing the acrylic resin, the modified epoxy resin and a curing agent to obtain the cathode electrophoretic paint.
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