CN108504233B - Preparation method of low-gloss extinction electrophoretic coating - Google Patents
Preparation method of low-gloss extinction electrophoretic coating Download PDFInfo
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
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- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
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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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- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
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- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
- C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F220/10—Esters
- C08F220/12—Esters of monohydric alcohols or phenols
- C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Abstract
The invention relates to a preparation method of a low-gloss extinction electrophoretic coating, which comprises acrylic resin and amino resin, wherein the acrylic resin is prepared from the following raw materials in parts by mass: 3-4 parts of isooctyl methacrylate, 6-9 parts of n-butyl acrylate, 5-8 parts of methyl methacrylate, 1-3 parts of styrene, 0.5-1 part of acrylic acid, 1-2 parts of 2-hydroxyethyl methacrylate, 3-4 parts of 2-hydroxyethyl acrylate, 3-4 parts of 2-hydroxypropyl acrylate, 2-6 parts of polycarbonate, 0.05-0.3 part of dinonylnaphthalenesulfonic acid, 0.08-0.2 part of composite initiator, 1-2 parts of neutralizer, 0.01-0.02 part of defoaming agent, 8-15 parts of n-butanol, 8-15 parts of isopropanol and 10-50 parts of deionized water. The finally prepared electrophoretic paint has good extinction effect (the detection of a 60-degree gloss meter is less than 10 degrees), can be stored for more than one year, has no layering phenomenon and has good stability; and the paint film has good flatness and strong pollution resistance.
Description
Technical Field
The invention relates to a preparation method of a low-gloss extinction electrophoretic coating, belonging to the technical field of coatings.
Background
Electrophoresis is one of the most effective methods for coating metal workpieces. The electrophoretic coating is a novel coating with low pollution, energy conservation, resource conservation and good corrosion resistance, has the advantages of smooth coating and good water resistance and chemical resistance, is easy to realize mechanization and automation of the coating industry, is suitable for coating workpieces with edges, corners and holes, has complex shapes, and is widely applied to coating hardware such as automobiles, automatic vehicles, electromechanics, household appliances and the like.
One way to obtain a matting effect is to add matting agents, such as silica, organic microparticles, etc., to the coating. However, the matting agent ultrafine silica has a poor chemical resistance, particularly an alkali resistance, and a coating film having a good transparency cannot be obtained, and in a coated object having a complicated coating process, the ultrafine silica is deposited on the coated object, and therefore, there are disadvantages that a gloss difference occurs in a partial region of the coated object, particularly in a vertical plane or the like. The method of dispersing organic fine particles in a paint (Japanese patent publication No. 51-8975) is not suitable for an electrodeposition paint because the organic fine particles have poor electrophoretic properties and fall off when washed with water. In addition, coatings using cyclic amidine-containing matting agents tend to yellow and are poor in bake-hardenability.
Another method is to synthesize a matting resin, for example, similar techniques reported in JP-A59-67396, JP-A64-14281, JP-A05-263296, JP-A2-255871, JP-A11-315254 and JP-A2001-131494, but when the gloss is changed by changing the coating conditions, the matting resin is easily affected by the post-electrophoretic cleaning step and is a condition that restricts the coating workability.
In another method, a functional group reactive with a carboxyl group in a resin is added to the resin to form a microgel. Examples of such functional groups include epoxy groups (JP 59-138278A, JP 2-12511A and CN 1307270C) and oxazoline groups (JP 6-25568A). In such a method, in order to obtain a stable low gloss, it is necessary to form an intragranular gel by a heating reaction, and thus it is troublesome in production.
With the continuous development of the electrophoretic coating, the electrophoretic coating has more and more market applications, and has higher and higher requirements on the glossiness, the stability and the like of the electrophoretic coating. After the existing electrophoretic coating is added with the flatting agent, the glossiness of the electrophoretic coating can reach low light (the glossiness measured by a 60-degree gloss meter is less than or equal to 10 degrees), but the stability of the electrophoretic coating is poor, the electrophoretic coating can be layered after being stored for 3-5 months, and a paint film is uneven and not fine after being used. The development of novel high-stability low-gloss extinction electrophoretic coatings has become a research direction.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a high-stability low-gloss extinction electrophoretic coating aiming at the prior art.
The technical scheme adopted by the invention for solving the problems is as follows: a low-gloss extinction electrophoretic coating comprises acrylic resin and amino resin; the mass ratio of the acrylic resin to the amino resin is 1: 0.2 to 1;
the acrylic resin is prepared from the following raw materials in parts by mass: 3-4 parts of isooctyl methacrylate, 6-9 parts of n-butyl acrylate, 5-8 parts of methyl methacrylate, 1-3 parts of styrene, 0.5-1 part of acrylic acid, 1-2 parts of 2-hydroxyethyl methacrylate, 3-4 parts of 2-hydroxyethyl acrylate, 3-4 parts of 2-hydroxypropyl acrylate, 2-6 parts of polycarbonate, 0.05-0.3 part of dinonylnaphthalenesulfonic acid, 0.08-0.2 part of composite initiator, 1-2 parts of neutralizer, 0.01-0.02 part of defoaming agent, 8-15 parts of n-butanol, 8-15 parts of isopropanol and 10-50 parts of deionized water.
The number average molecular weight of the polycarbonate is 2 to 10 ten thousand.
The composite initiator is prepared by compounding azodiisobutyronitrile and DCP (dicumyl peroxide) according to the mass ratio of 1: 2-5. DCP is adopted as an initiator, so that side chain reaction can be increased, the adhesive force and the corrosion resistance of the coating are increased, and particularly the anti-deformability is obviously enhanced; the adoption of the azodiisobutyronitrile can promote the conversion rate of the monomer, and the compatibility of the azodiisobutyronitrile and the monomer realizes low-temperature initiation and high-temperature continuous reaction. As heat energy is released in the reaction process, the temperature of the system rises and generates larger fluctuation, and in order to ensure that the reaction is not influenced by temperature change, the introduced DCP initiator mainly ensures stable reaction at high temperature and ensures high-low temperature uniform reaction.
The neutralizer is triethanolamine, methyldiethanolamine or triethylamine.
The preparation method of the acrylic resin comprises the following steps:
step one, preparing a mixed solution
Mixing isooctyl methacrylate, n-butyl acrylate, methyl methacrylate, styrene, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polycarbonate and dinonyl naphthalene sulfonic acid to form a mixed solution;
step two, forming water-soluble acrylic resin
Heating the reaction container to 95-105 ℃ by using n-butyl alcohol, isopropanol and deionized water accounting for 5-15% of the total amount of the deionized water as bottom materials, dropwise adding the mixed solution prepared in the first step into the reaction container, wherein the dropwise adding time is 150-200min, dropwise adding a composite initiator, dropwise adding the composite initiator for four times, and controlling the dropwise adding speed according to the intensity of the reaction; and then preserving the temperature of the reaction vessel for 150-280min, cooling the reaction vessel to below 60 ℃, adding a neutralizing agent into the reaction vessel, uniformly stirring, adding a defoaming agent into the reaction vessel, and finally adding the rest deionized water for dilution and molding.
The amino resin consists of the following raw materials: methylated melamine resin, butylated melamine resin, phosphate modified melamine resin, a coupling agent and modified nano aluminum oxide; the methylated melamine resin is resin obtained by condensing melamine and formaldehyde and etherifying the condensed melamine and formaldehyde with methanol; the butyl etherified melamine resin is obtained by condensing melamine and formaldehyde and etherifying the condensation product with butanol; the phosphate modified melamine resin is a resin obtained by condensing melamine, formaldehyde and modified phosphate; the mass ratio of the methylated melamine resin to the butylated melamine resin to the phosphate modified melamine resin is 30-40:30-40: 10-20.
Further, the molar ratio of the raw materials of melamine, formaldehyde and methanol in the methylated melamine resin is 1:4-6: 8-10.
Further, the mol ratio of the raw materials of melamine, formaldehyde and butanol in the butylated melamine resin is 1:2-4: 6-8.
Further, the modified phosphate is at least one of sodium hexametaphosphate and sodium tripolyphosphate.
Further, the addition amount of melamine, formaldehyde and modified phosphate in the preparation process of the phosphate modified melamine resin is 1:3-6:0.2-0.6 by mol ratio.
Further, the modified nano-alumina is hydrogen terminated silicone oil modified nano-alumina.
Further, the average particle size of the modified nano-alumina is 20 nm.
Further wherein the coupling agent is at least one of titanates and aluminic acid compounds.
Further, the molecular weight of the hydrogen-terminated silicone oil is 500-600.
A preparation method of the water-soluble bridging agent for the extinction electrophoresis paint comprises the following steps:
(1) evenly mixing hydrogen-terminated silicone oil and nano-alumina in a high-speed mixing machine at the speed of 1500-2000 rmp/min;
(2) regulating the pH value of a formaldehyde aqueous solution to 10.0-10.5 by using triethanolamine, then mixing melamine and the formaldehyde aqueous solution in proportion, heating to 75-85 ℃, adding methanol or butanol or modified phosphate to continue reacting for 3.5-4.5 hours after the color of the mixed solution is gradually changed from white to clear and transparent, and respectively obtaining methylated melamine resin, butylated melamine resin and phosphate modified melamine resin;
(3) the preparation method comprises the following steps of uniformly mixing methylated melamine resin, butylated melamine resin, phosphate modified melamine resin, a coupling agent and modified nano aluminum oxide in a mixer.
The composite water-soluble amino resin formed by compounding the methylated melamine resin, the butylated melamine resin and the phosphate modified melamine resin has good compatibility, and due to the addition of more free hydroxymethyl groups, a certain amount of imino groups and polyphosphate polar groups, molecular chains can be mutually crosslinked, so that the film forming firmness is improved. And through precondensation of melamine and formaldehyde in different proportions, and then addition of an unused amount of alcohols, the etherification degree and the free hydroxymethyl content of methylated melamine resin and butylated melamine resin can be effectively controlled, so that the solubility of amino resin and the bonding degree of the amino resin and different substrates are improved. In order to better realize the technical effect of the invention, the mass ratio of the methylated melamine resin, the butylated melamine resin and the phosphate modified melamine resin is 30-40:30-40:10-20, preferably 35:35: 15. In order to better realize the improvement of the solubility and the number of active ends, the molar ratio of raw materials of melamine, formaldehyde and methanol in the methylated melamine resin is 1:4-6:8-10, preferably 1:5: 9. In order to better realize the improvement of the solubility and the number of active ends, the mol ratio of raw materials of melamine, formaldehyde and butanol in the butylated melamine resin is 1:2-4:6-8, preferably 1:3: 7. The modified phosphate is at least one of sodium hexametaphosphate and sodium tripolyphosphate. In the preparation process of the phosphate modified melamine resin, the addition amount of melamine, formaldehyde and modified phosphate is 1:3-6:0.2-0.6 by mol ratio, preferably 1:4: 0.4.
The molecular weight of the hydrogen-terminated silicone oil is 500-600, the viscosity (25 ℃, mpa & s) of the hydrogen-terminated silicone oil under the molecular weight is 2-3, the hydrogen-terminated silicone oil under the viscosity has better binding property with the nano-alumina, and the modified nano-alumina has better dispersibility. The amount of hydrogen-terminated silicone oil added is preferably 5 to 10% by mass, and an excessive or insufficient amount does not achieve the optimum technical effect. By adding the hydrogen-terminated silicone oil, the active tail end of the hydrogen-terminated silicone oil can be utilized to effectively combine the imino in the resin component, so that the matching degree and the dispersity of the nano-alumina are improved, and the hydrogen-terminated silicone oil can be used as a cross-linking agent to promote the film forming property and the firmness. The particle size of the nano alumina is preferably 20nm, and the nano alumina has high extinction characteristic and can have high dispersity. The coupling agent is at least one of titanate and aluminate compounds, and is preferably a titanate coupling agent. The dispersion degree of the nano alumina is further promoted by adding the coupling agent.
Compared with the prior art, the invention has the advantages that:
the invention adopts dinonyl naphthalenesulfonic acid for dewatering, adds polycarbonate as a flatting agent, adopts polycarbonate with the molecular weight of 2-10 ten thousand, improves the using amount of the polycarbonate, increases the using amount of the hydroxyl monomer, reduces the using amount of acrylic acid and an initiator, ensures that the finally prepared electrophoretic paint has good flatting effect (the using amount of a 60-degree gloss instrument is less than 10 degrees), has no layering phenomenon after being stored for more than one year and has good stability; by taking a ternary system consisting of methylated melamine resin, butylated melamine resin and phosphate modified melamine resin as a matrix and adding modified nano aluminum oxide, the extinction property and the adhesion can be effectively improved. And the paint film has good flatness and strong pollution resistance. In the reaction process, the compound initiator is dripped for four times, the reaction is complete, and the method is safe and controllable.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1, a low gloss matte electrophoretic coating, the mass ratio of acrylic resin and amino resin in the host material is 1: 0.5; wherein:
the acrylic resin is prepared from the following raw materials in percentage by mass: 3 parts of isooctyl methacrylate, 8 parts of n-butyl acrylate, 7 parts of methyl methacrylate, 2 parts of styrene, 0.5 part of acrylic acid, 2 parts of 2-hydroxyethyl methacrylate, 3 parts of 2-hydroxyethyl acrylate, 3 parts of 2-hydroxypropyl acrylate, 6 parts of polycarbonate (the number average molecular weight is 7 ten thousand), 0.1 part of dinonylnaphthalenesulfonic acid, 0.1 part of composite initiator (azodiisobutyronitrile and DCP (dicumyl peroxide) are in a ratio of 1: 3), 1 part of triethanolamine neutralizer, 0.01 part of defoaming agent, 10 parts of n-butanol, 10 parts of isopropanol and 30 parts of deionized water. The preparation method comprises the following steps:
step one, preparing a mixed solution
Mixing isooctyl methacrylate, n-butyl acrylate, methyl methacrylate, styrene, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polycarbonate and dinonyl naphthalene sulfonic acid to form a mixed solution;
step two, forming water-soluble acrylic resin
Heating the reaction container to 95-105 ℃ by using n-butyl alcohol, isopropanol and deionized water accounting for 5-15% of the total amount of the deionized water as bottom materials, dropwise adding the mixed solution prepared in the first step into the reaction container, wherein the dropwise adding time is 150-200min, dropwise adding a composite initiator, dropwise adding the composite initiator for four times, and controlling the dropwise adding speed according to the intensity of the reaction; and then preserving the temperature of the reaction vessel for 150-280min, cooling the reaction vessel to below 60 ℃, adding a neutralizing agent into the reaction vessel, uniformly stirring, adding a defoaming agent into the reaction vessel, and finally adding the rest deionized water for dilution and molding.
The amino resin consists of the following raw materials: methylated melamine resin, butylated melamine resin, phosphate modified melamine resin, a coupling agent and modified nano aluminum oxide; the mass ratio of the methylated melamine resin to the butylated melamine resin to the phosphate modified melamine resin is 35:35: 15.
The mol ratio of raw materials of melamine and formaldehyde in the methylated melamine resin is 1: 5.
the molar ratio of raw materials of melamine and formaldehyde in the butyl etherified melamine resin is 1: 3.
the modified phosphate is sodium hexametaphosphate. In the preparation process of the phosphate modified melamine resin, the addition amounts of melamine, formaldehyde and modified phosphate are 1:4:0.4 in a molar ratio. The modified nano-alumina is hydrogen terminated silicone oil modified nano-alumina. The average grain diameter of the modified nano-alumina is 20 nm. The coupling agent is titanate coupling agent. The molecular weight of the hydrogen-terminated silicone oil is 500-600, and the addition amount is 5 mass%.
A preparation method of the amino resin comprises the following steps:
(1) evenly mixing hydrogen-terminated silicone oil and nano-alumina in a high-speed mixing machine at the speed of 1500-2000 rmp/min;
(2) regulating the pH value of a formaldehyde aqueous solution to 10.0-10.5 by using triethanolamine, then mixing melamine and the formaldehyde aqueous solution in proportion, heating to 75-85 ℃, adding excessive methanol or excessive butanol or modified phosphate to continue reacting for 3.5-4.5 hours after the color of the mixed solution is gradually changed from white to clear and transparent, and respectively obtaining methylated melamine resin, butylated melamine resin and phosphate modified melamine resin;
(3) the preparation method comprises the following steps of uniformly mixing methylated melamine resin, butylated melamine resin, phosphate modified melamine resin, a coupling agent and modified nano aluminum oxide in a mixer.
The prepared acrylic resin and amino resin are mixed according to a proportion, and a neutralizing agent and proper deionized water are added to prepare the low-gloss extinction electrophoretic coating.
Example 2, a low gloss extinction electrophoretic coating, wherein the acrylic resin is prepared from the following raw materials in parts by mass: 4 parts of isooctyl methacrylate, 8 parts of n-butyl acrylate, 6 parts of methyl methacrylate, 3 parts of styrene, 1 part of acrylic acid, 1.5 parts of 2-hydroxyethyl methacrylate, 3.5 parts of 2-hydroxyethyl acrylate, 3.5 parts of 2-hydroxypropyl acrylate, 5 parts of polycarbonate (the number average molecular weight is 6 ten thousand), 0.15 part of dinonylnaphthalenesulfonic acid, 0.08 part of a composite initiator (azodiisobutyronitrile and DCP (dicumyl peroxide) are in a ratio of 1: 3), 1.2 parts of a triethanolamine neutralizer, 0.01 part of a defoaming agent, 10 parts of n-butanol, 10 parts of isopropanol and 30 parts of deionized water.
Otherwise, the procedure was as in example 1.
Example 3, a low gloss extinction electrophoretic coating, wherein the acrylic resin is prepared from the following raw materials in parts by mass: 3.5 parts of isooctyl methacrylate, 9 parts of n-butyl acrylate, 8 parts of methyl methacrylate, 2 parts of styrene, 0.8 part of acrylic acid, 1 part of 2-hydroxyethyl methacrylate, 4 parts of 2-hydroxyethyl acrylate, 3 parts of 2-hydroxypropyl acrylate, 4 parts of polycarbonate (the number average molecular weight is 8 ten thousand), 0.05 part of dinonylnaphthalenesulfonic acid, 0.1 part of composite initiator (azodiisobutyronitrile and DCP (dicumyl peroxide) are in a ratio of 1: 2), 1.5 parts of methyldiethanolamine neutralizer, 0.02 part of antifoaming agent, 15 parts of n-butanol, 15 parts of isopropanol and 40 parts of deionized water.
Otherwise, the procedure was as in example 1.
Example 4, a low gloss extinction electrophoretic coating, wherein the acrylic resin is prepared from the following raw materials in parts by mass: 4 parts of isooctyl methacrylate, 6 parts of n-butyl acrylate, 8 parts of methyl methacrylate, 3 parts of styrene, 1 part of acrylic acid, 2-hydroxyethyl methacrylate, 3 parts of 2-hydroxyethyl acrylate, 3 parts of 2-hydroxypropyl acrylate, 4 parts of polycarbonate (the number average molecular weight is 8 ten thousand), 0.2 part of dinonylnaphthalenesulfonic acid, 0.2 part of composite initiator (azodiisobutyronitrile and DCP (dicumyl peroxide) are in a ratio of 1: 5), 1.5 parts of methyldiethanolamine neutralizer, 0.02 part of defoaming agent, 10 parts of n-butanol, 8 parts of isopropanol and 20 parts of deionized water.
Otherwise, the procedure was as in example 1.
Example 5, a low gloss extinction electrophoretic coating, wherein the acrylic resin is prepared from the following raw materials in parts by mass: 3.5 parts of isooctyl methacrylate, 9 parts of n-butyl acrylate, 5 parts of methyl methacrylate, 1 part of styrene, 0.5 part of acrylic acid, 1 part of 2-hydroxyethyl methacrylate, 4 parts of 2-hydroxyethyl acrylate, 4 parts of 2-hydroxypropyl acrylate, 3 parts of polycarbonate (the number average molecular weight is 8 ten thousand), 0.2 part of dinonylnaphthalenesulfonic acid, 0.2 part of composite initiator (azodiisobutyronitrile and DCP (dicumyl peroxide) are in a ratio of 1: 4), 1.5 parts of methyldiethanolamine neutralizer, 0.02 part of antifoaming agent, 10 parts of n-butanol, 8 parts of isopropanol and 20 parts of deionized water.
Otherwise, the procedure was as in example 1.
The comparative examples of the water-soluble acrylic resin comprise the following raw material components:
comparative example 1, an acrylic resin for an electrodeposition coating, prepared from the following raw materials in parts by mass: 3 parts of isooctyl methacrylate, 8 parts of n-butyl acrylate, 7 parts of methyl methacrylate, 2 parts of styrene, 0.5 part of acrylic acid, 2 parts of 2-hydroxyethyl methacrylate, 3 parts of 2-hydroxyethyl acrylate, 3 parts of 2-hydroxypropyl acrylate, 6 parts of polycarbonate (the number average molecular weight is 7 ten thousand), 0.1 part of composite initiator (azodiisobutyronitrile and DCP (dicumyl peroxide) are in a ratio of 1: 3), 1 part of triethanolamine neutralizer, 0.01 part of defoaming agent, 10 parts of n-butanol, 10 parts of isopropanol and 30 parts of deionized water.
Namely, it is different from example 1 only in that comparative example 1 does not use dinonylnaphthalenesulfonic acid for the preparation of the acrylic resin.
Comparative example 2, an acrylic resin for an electrodeposition coating, which was prepared from the following raw materials in mass fraction: 3 parts of isooctyl methacrylate, 8 parts of n-butyl acrylate, 7 parts of methyl methacrylate, 2 parts of styrene, 0.5 part of acrylic acid, 3 parts of 2-hydroxyethyl methacrylate, 6 parts of polycarbonate (the number average molecular weight is 7 ten thousand), 0.1 part of dinonyl naphthalene sulfonic acid, 0.1 part of a composite initiator (azodiisobutyronitrile and DCP (dicumyl peroxide) are in a ratio of 1: 3), 1 part of triethanolamine neutralizer, 0.01 part of defoaming agent, 10 parts of n-butanol, 10 parts of isopropanol and 30 parts of deionized water.
Namely, the only difference from example 1 is that the methylated melamine resin is absent from the starting materials for preparing the amino resin not only from 2-hydroxyethyl methacrylate but also from 2-hydroxyethyl acrylate and 2-hydroxypropyl acrylate (i.e., only 2-hydroxyethyl methacrylate alone provides the hydroxyl functionality).
Comparative example 3
It differs from example 1 only in that silica is used as matting agent for the preparation of acrylic resins and the methylated melamine resin is absent from the starting materials for the preparation of amino resins.
Comparative example 4
It differs from example 1 only in that the number average molecular weight of the polycarbonate, which was an acrylic resin, was 5000, and the methylated melamine resin was absent from the raw materials for preparing the amino resin.
Comparative example 5
The acrylic resin for the electrophoretic coating is prepared from the following raw materials in percentage by mass: 3 parts of isooctyl methacrylate, 8 parts of n-butyl acrylate, 7 parts of methyl methacrylate, 2 parts of styrene, 3 parts of acrylic acid, 6 parts of 2-hydroxyethyl methacrylate, 6 parts of polycarbonate (the number average molecular weight is 7 ten thousand), 0.1 part of dinonyl naphthalene sulfonic acid, 1 part of a composite initiator (azodiisobutyronitrile and DCP (dicumyl peroxide) in a ratio of 1: 3), 1 part of triethanolamine neutralizer, 0.01 part of defoaming agent, 10 parts of n-butyl alcohol, 10 parts of isopropanol and 30 parts of deionized water.
It differs from example 1 only in that: the dosage of the acrylic acid and the composite initiator for preparing the acrylic resin is obviously increased, and methylated melamine resin is lacked in the raw materials for preparing the amino resin.
The gloss and stability measurements of examples 1-5 and comparative examples 1-5 are shown in Table 1.
And (3) gloss detection: after the coating prepared by the same method is formed into a film, the film is detected by a 60-degree gloss meter.
Stability: storing at normal temperature.
TABLE 1
| Degree of gloss | Appearance of film formation | Washing and brushing resistance/1 ten thousand times | Resin stability | |
| Example 1 | 6 degree | The paint film is smooth and fine | Not less than 1 ten thousand | Can be stored at normal temperature for one year without layering |
| Example 2 | 7 degree | The paint film is smooth and fine | Not less than 1 ten thousand | Can be stored at normal temperature for one year without layering |
| Example 3 | 9 degree | The paint film is smooth and fine | Not less than 1 ten thousand | Can be stored at normal temperature for one year without layering |
| Example 4 | 8 degree | The paint film is smooth and fine | Not less than 1 ten thousand | Can be stored at normal temperature for one year without layering |
| Example 5 | 9 degree | The paint film is smooth and fine | Not less than 1 ten thousand | Can be stored at normal temperature for one year without layering |
| Comparative example 1 | 35 degree | Uneven and rough paint film | 6-8 thousand | Storing at room temperature for 6 months, and demixing |
| Comparative example 2 | 28 degree | To generate spots | 6-8 thousand | Storing at room temperature for 3 months, and demixing |
| Comparative example 3 | 8 degree | The paint film is uneven and rough | 6-8 thousand | Storing at room temperature for 3 months, and demixing |
| Comparative example 4 | 35 degree | Film leveling | 6-8 thousand | Can be stored at normal temperature for one year without layering |
| Comparative example 5 | 19 degree | Film leveling | 6-8 thousand | Can be stored at normal temperature for one year without layering |
In addition to the above embodiments, the present invention also includes other embodiments, and any technical solutions formed by equivalent transformation or equivalent replacement should fall within the scope of the claims of the present invention.
Claims (6)
1. A low-gloss extinction electrophoretic coating is characterized in that: it comprises acrylic resin and amino resin; the mass ratio of the acrylic resin to the amino resin is 1: 0.2 to 1;
the acrylic resin is prepared from the following raw materials in parts by mass: 3-4 parts of isooctyl methacrylate, 6-9 parts of n-butyl acrylate, 5-8 parts of methyl methacrylate, 1-3 parts of styrene, 0.5-1 part of acrylic acid, 1-2 parts of 2-hydroxyethyl methacrylate, 3-4 parts of 2-hydroxyethyl acrylate, 3-4 parts of 2-hydroxypropyl acrylate, 2-6 parts of polycarbonate, 0.05-0.3 part of dinonylnaphthalenesulfonic acid, 0.08-0.2 part of composite initiator, 1-2 parts of neutralizer, 0.01-0.02 part of defoaming agent, 8-15 parts of n-butanol, 8-15 parts of isopropanol and 10-50 parts of deionized water; the composite initiator is compounded by azodiisobutyronitrile and DCP according to the mass ratio of 1: 2-5;
the number average molecular weight of the polycarbonate is 2-10 ten thousand;
the amino resin consists of the following raw materials: methylated melamine resin, butylated melamine resin, phosphate modified melamine resin, a coupling agent and modified nano aluminum oxide; the methylated melamine resin is highly methylated melamine resin obtained by condensing melamine and formaldehyde and etherifying the condensed melamine and formaldehyde with excessive methanol; the butyl etherified melamine resin is high-degree butyl etherified melamine resin obtained by condensing melamine and formaldehyde and etherifying the condensation product with excessive butanol; the phosphate modified melamine resin is a resin obtained by condensing melamine, formaldehyde and modified phosphate; the mass ratio of the methylated melamine resin to the butylated melamine resin to the phosphate modified melamine resin is 30-40:30-40: 10-20; the modified nano-alumina is hydrogen terminated silicone oil modified nano-alumina.
2. The low gloss matte electrophoretic paint according to claim 1, wherein: the neutralizing agent is triethanolamine, methyldiethanolamine or triethylamine.
3. The low gloss matte electrophoretic paint according to claim 1, wherein: the modified phosphate is at least one of sodium hexametaphosphate and sodium tripolyphosphate.
4. The low gloss matte electrophoretic paint according to claim 1, wherein: wherein the addition amount of the melamine, the formaldehyde and the modified phosphate in the preparation process of the phosphate modified melamine resin is 1:3-6:0.2-0.6 by mol ratio.
5. The low gloss matte electrophoretic paint according to claim 1, wherein: wherein the average particle size of the modified nano-alumina is 20 nm.
6. Process for the preparation of a low gloss matte electrophoretic paint according to any one of claims 1 to 5, characterized in that it comprises the following steps:
firstly, preparing acrylic resin:
step one, preparing a mixed solution
Mixing isooctyl methacrylate, n-butyl acrylate, methyl methacrylate, styrene, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, 2-hydroxypropyl acrylate, polycarbonate and dinonyl naphthalene sulfonic acid to form a mixed solution;
step two, forming water-soluble acrylic resin
Heating the reaction container to 95-105 ℃ by using n-butyl alcohol, isopropanol and deionized water accounting for 5-15% of the total amount of the deionized water as bottom materials, dropwise adding the mixed solution prepared in the first step into the reaction container, wherein the dropwise adding time is 150-200min, dropwise adding a composite initiator, dropwise adding the composite initiator for four times, and controlling the dropwise adding speed according to the intensity of the reaction; then keeping the temperature of the reaction container for 150-;
secondly, preparing amino resin:
(1) evenly mixing hydrogen-terminated silicone oil and nano-alumina in a high-speed mixing machine at the speed of 1500-2000 rmp/min;
(2) regulating the pH value of a formaldehyde aqueous solution to 10.0-10.5 by using triethanolamine, then mixing melamine and the formaldehyde aqueous solution in proportion, heating to 75-85 ℃, adding excessive methanol or excessive butanol or modified phosphate to continue reacting for 3.5-4.5 hours after the color of the mixed solution is gradually changed from white to clear and transparent, and respectively obtaining methylated melamine resin, butylated melamine resin and phosphate modified melamine resin;
(3) uniformly mixing methylated melamine resin, butylated melamine resin, phosphate modified melamine resin, a coupling agent and modified nano aluminum oxide in a mixer;
preparation of electrophoretic paint
Mixing the acrylic resin and the amino resin prepared in the above way according to a mass ratio of 1: 0.2 to 1, adding a neutralizer and proper deionized water, and uniformly stirring.
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| CN112175468A (en) * | 2020-10-26 | 2021-01-05 | 厦门市金宝源实业有限公司 | Electrophoretic paint, preparation method and coating process thereof |
| CN112430414B (en) * | 2020-11-11 | 2021-12-14 | 江阴恒兴涂料有限公司 | Weather-resistant colored electrophoretic paint and preparation method thereof |
| CN115895376A (en) * | 2022-12-16 | 2023-04-04 | 广州优达涂料有限公司 | Extinction electrophoretic paint and preparation method thereof |
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| CN104558374A (en) * | 2013-10-29 | 2015-04-29 | 谭克凰 | Method for preparing acrylic resin |
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