CN111793421B - Environment-friendly chromium-free insulating coating liquid for surface treatment of oriented silicon steel and preparation method and application thereof - Google Patents

Environment-friendly chromium-free insulating coating liquid for surface treatment of oriented silicon steel and preparation method and application thereof Download PDF

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CN111793421B
CN111793421B CN202010711828.3A CN202010711828A CN111793421B CN 111793421 B CN111793421 B CN 111793421B CN 202010711828 A CN202010711828 A CN 202010711828A CN 111793421 B CN111793421 B CN 111793421B
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parts
stirring
insulating coating
resin emulsion
coating liquid
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CN111793421A (en
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陆飚
万月
罗晓锋
郭文勇
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Wuhan Desytek Environmental Protection New Material Co ltd
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
    • B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
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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
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    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
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    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/60—Additives non-macromolecular
    • C09D7/61—Additives non-macromolecular inorganic
    • C09D7/62—Additives non-macromolecular inorganic modified by treatment with other compounds
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    • B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
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    • B05D2202/10—Metallic substrate based on Fe
    • B05D2202/15—Stainless steel
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    • C08K3/22—Oxides; Hydroxides of metals
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    • C08K2003/2241—Titanium dioxide
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Abstract

The invention belongs to the technical field of oriented silicon steel insulating paint, and particularly discloses an environment-friendly chromium-free insulating coating liquid for surface treatment of oriented silicon steel, and a preparation method and application thereof. The insulating coating liquid is an environment-friendly surface treatment liquid and is mainly prepared from modified aqueous resin emulsion, organic silicon modified nano-silica, organic acid treated composite salt solution, an auxiliary agent and other main raw materials. The insulating coating liquid forms an insulating coating on the surface of the oriented silicon steel in a roll coating mode, and shows excellent film forming property, moisture absorption resistance, corrosion resistance, adhesion, heat resistance, insulating property and humidity resistance. And the insulating coating liquid has simple production process, low cost, good stability and very high industrial application value.

Description

Environment-friendly chromium-free insulating coating liquid for surface treatment of oriented silicon steel and preparation method and application thereof
Technical Field
The invention belongs to the technical field of oriented silicon steel insulating coatings, and particularly relates to an environment-friendly chromium-free insulating coating liquid for surface treatment of oriented silicon steel, a preparation method thereof, and application of the environment-friendly chromium-free insulating coating liquid in improvement of film forming property, moisture absorption resistance, corrosion resistance, adhesiveness, heat resistance, insulativity and humidity resistance of the surface of the oriented silicon steel.
Background
Oriented silicon steel is also called cold-rolled transformer steel, and is an important ferrosilicon alloy used in the manufacturing industry of transformer iron cores. In the use process of the oriented silicon steel, in order to reduce the eddy current loss of the silicon steel and improve the electromagnetic performance and other performances, the surface of the silicon steel is protected by coating the insulating coating liquid on the surface of the silicon steel, so that the improvement of the practical performance of the oriented silicon steel is very important. At present, the surface insulating coating liquid of the oriented silicon steel mainly adopted by silicon steel manufacturers is a chromate system. In the chromate treatment process, hexavalent chromium is highly toxic and carcinogenic, causing serious harm to human body and environment. Therefore, the development of environment-friendly chromium-free silicon steel surface insulating coating liquid with excellent performance is an urgent requirement of domestic silicon steel manufacturers. In recent years, related chromium-free insulating coating liquid products are already available on the market, but most of the products have the problems of insufficient film forming property, moisture absorption resistance, corrosion resistance, adhesion, heat resistance, insulation and moist heat resistance after the surface of an insulating coating is cured, and the long-term use of silicon steel plates is directly influenced. Therefore, it is very urgent and important to develop an environment-friendly insulating coating solution with excellent comprehensive properties.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide the environment-friendly chromium-free insulating coating liquid for surface treatment of the oriented silicon steel, which can obviously improve various properties (film forming property, moisture absorption resistance, corrosion resistance, adhesion, heat resistance, insulativity and humidity resistance) of the surface coating of the oriented silicon steel and can be widely applied to silicon steel plants as an environment-friendly chromium-free insulating coating liquid product.
The second purpose of the invention is to provide a treatment mode of the composite salt in the chromium-free insulating coating liquid, which can provide reference for pertinently improving the practical performance of the silicon steel surface coating and has guiding significance for the development and performance optimization of related products.
The third purpose of the invention is to provide a preparation method of the environment-friendly chromium-free insulating coating liquid for surface treatment of the oriented silicon steel, the coating liquid has simple production process, low cost and good stability, is beneficial to expanding production and has very high industrial application prospect.
The technical scheme adopted by the invention is as follows: an environment-friendly chromium-free insulating coating liquid for surface treatment of oriented silicon steel is prepared from the following raw materials in parts by mass: 10-60 parts of modified water-based resin emulsion (A), 20-80 parts of organic silicon modified nano silicon dioxide (B), 10-80 parts of organic acid treated composite salt solution (C), 1-20 parts of auxiliary agent (D) and 10-100 parts of deionized water (E).
The preferable scheme is that the environment-friendly chromium-free insulating coating liquid for the surface treatment of the oriented silicon steel is prepared from the following raw materials in parts by mass: 20-55 parts of modified water-based resin emulsion (A), 30-75 parts of organic silicon modified nano silicon dioxide (B), 30-75 parts of organic acid treated composite salt solution (C), 1-8 parts of auxiliary agent (D) and 20-100 parts of deionized water (E).
In a more preferable scheme, the environment-friendly chromium-free insulating coating liquid for surface treatment of the oriented silicon steel is prepared from the following raw materials in parts by mass: 35 parts of modified water-based resin emulsion (A), 55 parts of organic silicon modified nano silicon dioxide (B), 60 parts of organic acid treated composite salt solution (C), 3 parts of auxiliary agent (D) and 80 parts of deionized water (E).
In a preferred embodiment, the preparation method of the modified aqueous resin emulsion (a) comprises: mixing 1 part by mass of cationic acrylic resin emulsion prepolymer and 2 parts by mass of cationic polyurethane resin emulsion prepolymer at 40 ℃, adjusting the pH value to 4.5 by using acetic acid, and stirring for 1 hour to obtain the acrylic resin emulsion prepolymer.
Preferably, the cationic acrylic resin emulsion prepolymer in the modified aqueous resin emulsion (A) is prepared by the following method: adding 50 parts of isophthalic acid (IPA), 6 parts of Acrylic Acid (AA), 18 parts of Butyl Acrylate (BA), 23 parts of Methyl Methacrylate (MMA), 2 parts of isobornyl methacrylate (IBOMA), 4 parts of hydroxyethyl acrylate (HEA) and 1 part of initiator Azobisisobutyronitrile (AIBN) into a reaction container, and uniformly mixing; adding the extracted 25% mixed solution into another reaction container, heating to 75 deg.C, stirring, dripping the remaining 75% mixed solution into the reaction container for 2 hr, reacting for 3 hr, and cooling to 40 deg.C.
Preferably, the cationic polyurethane resin emulsion prepolymer in the modified aqueous resin emulsion (a) is prepared by the following method: adding 100 parts of polyethylene glycol 400 and 59 parts of isophorone diisocyanate (IPDI) into a reaction container, and uniformly mixing and stirring; heating the reaction vessel to 82 ℃, reacting for 2 hours, and cooling to 55 ℃; adding 2 parts of Trimethylolpropane (TMP), 12 parts of N-methyldiethanolamine and 80 parts of acetone, reacting for 2 hours, cooling to 40 ℃, adding acetic acid to adjust the pH value to 5.0, and stirring for 0.5 hour to obtain the aqueous solution.
In a preferred embodiment, the organosilicon modified nano-silica (B) is prepared by the following method: adding 20 parts of water into a reaction kettle, adjusting the pH value to 4.5 by using acetic acid, heating to 50 ℃, then dripping 5 parts of a mixture of a silane coupling agent and ethanol (the silane coupling agent and the ethanol are mixed by mass, the concentration of the ethanol is more than 95 v/v%), preserving the temperature of a reaction solution at 50 ℃ for 1h after finishing dripping, cooling to room temperature, and adjusting the pH value to about 4.5 by using the acetic acid; and finally, adding 3 parts of nano-scale silicon dioxide under a high-speed stirring state, and stirring for 1 hour to obtain the nano-scale silicon dioxide.
Preferably, the silane coupling agent for preparing the organosilicon modified nano-silica (B) is amino-containing silane and/or epoxy-containing silane.
Further, the silane coupling agent is selected from one or more of 3- (2-aminoethylamino) propyltrimethoxysilane, 3-aminopropyltrimethoxysilane and gamma- (2, 3-epoxypropoxy) propyltrimethoxysilane.
In a preferred embodiment, the organic acid-treated complex salt solution (C) is prepared by the following method: adding 50 parts of deionized water into a reaction kettle, then sequentially adding 39 parts of dihydric phosphate and 32 parts of boric acid into the reaction kettle, uniformly mixing and stirring, then adding 18 parts of ammonium molybdate aqueous solution, uniformly stirring, finally sequentially adding 20 parts of titanium dioxide sol, 15 parts of organic acid and 20 parts of metal oxide, mixing, and stirring for 1 hour to obtain the catalyst.
In a preferred embodiment, the organic acid-treated complex salt solution (C) contains one or more salts selected from the group consisting of sodium dihydrogen phosphate, zinc dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, magnesium dihydrogen phosphate, aluminum dihydrogen phosphate, and ammonium dihydrogen phosphate; preferably, the dihydrogen phosphate is one or more of sodium dihydrogen phosphate, magnesium dihydrogen phosphate and zinc dihydrogen phosphate.
In a preferred embodiment, the aqueous solution of ammonium molybdate in the complex salt solution (C) is: preparing ammonium molybdate and water according to the concentration of 0.1g/mL-0.3g/mL to obtain the ammonium molybdate/water.
In a preferred embodiment, the preparation method of the titanium dioxide sol in the composite salt solution (C) comprises: mixing 12 parts of tetrabutyl titanate and 60 parts of absolute ethyl alcohol, stirring for 0.5h, adding into a mixed solution of 1.5 parts of acetic acid and 20 parts of water under a stirring state, and stirring for 2h to obtain the product.
In a preferred embodiment, the organic acid in the complex salt solution (C) is one or more of citric acid, tartaric acid, malic acid and ethylenediamine tetraacetic acid.
In a preferred embodiment, the metal oxide in the complex salt solution (C) is selected from one or more of zinc oxide, calcium oxide, magnesium oxide and aluminum oxide.
Preferably, the auxiliary agent (D) includes an antifoaming agent and a leveling agent, and may further include one or more of a dispersant, a thickener and a wetting agent, as required.
In the present specification, "parts" which are not described are all referred to as "parts by mass".
In a preferred scheme, the environment-friendly chromium-free insulating coating liquid for surface treatment of the oriented silicon steel comprises the following specific preparation steps: adding deionized water (E) into a reaction kettle, sequentially adding the modified water-based resin emulsion (A) and the organic silicon modified nano silicon dioxide (B), and mixing and stirring uniformly; and then dripping the organic acid treated composite salt solution (C) into a reaction kettle in a stirring state, stirring for 1h after finishing dripping, finally adding the auxiliary agent (D), and uniformly stirring to obtain the chromium-free insulating coating liquid.
In the chromium-free insulating coating of the present invention, the modified aqueous resin emulsion (a) mainly provides a film-forming skeleton for the insulating coating. The acrylic resin emulsion in the modified water-based resin emulsion can ensure that the coating does not yellow at high temperature and has better coating appearance. The polyurethane resin emulsion can provide higher strength for the coating film, thereby ensuring the coating performance. The modified water-based resin emulsion is prepared by adjusting the compounding mode of the two resins, can improve the performance of coating liquid in a targeted manner, can improve the moisture absorption resistance of the coating, has higher gloss, and improves the film forming property and the adhesiveness of the coating.
In the chromium-free insulating coating, the organosilicon modified nano silicon dioxide (B) mainly has the functions of improving the surface glossiness, moisture absorption resistance, corrosion resistance and insulating property of the coating.
In the chromium-free insulating coating of the present invention, the organic acid-treated complex salt solution (C) mainly functions as an insulating coating after complex salt treatment, and has excellent corrosion resistance, adhesion, heat resistance, insulation and wet heat resistance, thereby improving long-term service properties of the coating.
In the chromium-free insulating coating, the assistant (D) has the main functions of improving the production process of the chromium-free insulating coating liquid and improving the quality and the yield of products.
The invention also provides application of the coating liquid, and the coating liquid is applied to the treatment of the surface of an oriented silicon steel plate.
In a preferable scheme, the coating liquid has remarkable effects on improving the corrosion resistance, the surface resistance, the adhesive force, the humidity and heat resistance of the coating and the moisture absorption resistance of the coating.
Compared with the prior art, the technical scheme of the invention has the beneficial technical effects that:
the coating liquid prepared by the invention is environment-friendly chromium-free insulating coating liquid, and the chromium-free insulating coating liquid has good film forming property, can remarkably improve the film forming property, moisture absorption resistance, corrosion resistance, adhesion, heat resistance, insulativity and humidity resistance of a coating, has excellent comprehensive performance, is not lower than that of the traditional hexavalent chromium treatment liquid, and has very high industrial application value.
The chromium-free insulating coating liquid provided by the invention provides multiple treatment modes of the composite salt, can provide reference for pertinently improving the practical performance of the silicon steel surface coating, and has guiding significance for development and performance optimization of related products; the composite salt is applied to the coating liquid, and can obviously improve the heat resistance, the insulativity, the adhesiveness and the like of the coating liquid through the composite action with other components.
The chromium-free insulating coating liquid has the advantages of simple production process, low cost, good stability, simpler coating use and waste liquid treatment (the waste water generated by cleaning the tank after the coating liquid is used can be treated by simple alkali-adding precipitation), and is beneficial to industrial production.
Drawings
FIG. 1 is a view showing the surface of the oriented silicon steel treated with the coating solution of examples 1 to 5 after being subjected to a salt spray resistance test for 8 hours;
FIG. 2 is a surface treatment of the grain-oriented silicon steel with the coating solutions of examples 6 to 10, followed by a salt spray resistance test for 8 hours;
FIG. 3 is a schematic view of the surface of the oriented silicon steel treated with the coating solutions of examples 11 to 15 after being subjected to a salt spray resistance test for 8 hours;
FIG. 4 is a topographical view of the oriented silicon steel surface treated with the coating solutions of examples 16-19 after 8 hours of salt spray resistance testing.
Detailed Description
In order to better explain the technical solutions and advantages of the present invention, the following detailed description of the present invention is provided with reference to the embodiments. It should be noted that the following examples are given solely for the purpose of illustration and are not to be construed as limitations of the present invention, as many insubstantial modifications and variations of the present invention may be made by those skilled in the art in light of the above teachings.
In the following examples, "parts" means "parts by mass", and each "part" means 100 g.
In the following examples, the preparation method of the modified aqueous resin emulsion comprises the following steps:
(1) the cationic acrylic resin emulsion prepolymer is prepared by the following method: 50 parts of isophthalic acid, 6 parts of acrylic acid, 18 parts of butyl acrylate, 23 parts of methyl methacrylate, 2 parts of isobornyl methacrylate, 4 parts of hydroxyethyl acrylate and 1 part of initiator azobisisobutyronitrile are added into a reaction vessel and uniformly mixed. Extracting 25% of mixed solution, adding into another reaction container, heating to 75 deg.C, stirring, dripping the rest mixed solution into the reaction container for 2 hr, reacting for 3 hr, and cooling to 40 deg.C.
(2) The cationic polyurethane resin emulsion prepolymer is prepared by the following method: adding 100 parts of polyethylene glycol 400 and 59 parts of isophorone diisocyanate into a reaction container, and uniformly mixing and stirring; heating the reaction vessel to 82 ℃, reacting for 2 hours, and cooling to 55 ℃; adding 2 parts of trimethylolpropane, 12 parts of N-methyldiethanolamine and 80 parts of acetone, reacting for 2 hours, cooling to 40 ℃, adding acetic acid to adjust the pH value to 5.0, and stirring for 0.5 hour to obtain the aqueous solution.
(3) And (3) mixing the cationic acrylic resin emulsion prepolymer obtained in the step (1) and the cationic polyurethane resin emulsion prepolymer obtained in the step (2) according to the mass ratio of 1:2 at 40 ℃, adjusting the pH value to 4.5 by using acetic acid, and stirring for 1h to obtain the acrylic resin emulsion prepolymer.
The preparation method of the organic silicon modified nano silicon dioxide comprises the following steps: adding 20 parts of water into a reaction kettle, adjusting the pH value to 4.5 by using acetic acid, heating to 50 ℃, then dripping 5 parts of a mixture of 3-aminopropyltrimethoxysilane and ethanol (95 v/v%) in equal mass, keeping the temperature of a reaction solution at 50 ℃ for 1 hour after dripping is finished, cooling to room temperature, adjusting the pH value to 4.5 by using acetic acid, finally adding 3 parts of nanoscale silicon dioxide (the particle size is 11nm) in a high-speed stirring state (2000r/min), and stirring for 1 hour to obtain the nano silicon dioxide.
The concentration of the ammonium molybdate aqueous solution in the compound salt solution is 0.15 g/mL: mixing ammonium molybdate with deionized water to obtain the product.
The preparation method of the titanium dioxide sol in the composite salt solution comprises the following steps: mixing 12 parts of tetrabutyl titanate and 60 parts of absolute ethyl alcohol, stirring for 0.5h, adding into a mixed solution of 1.5 parts of acetic acid and 20 parts of water under a stirring state, and stirring for 2h to obtain the product.
The acetic acid is glacial acetic acid.
In each example, the antifoaming agent and the leveling agent are specifically BYK-024 antifoaming agent and BYK-354 leveling agent.
Example 1
The organic acid-treated complex salt solution (C) was prepared according to the following method: adding 50 parts of deionized water into a reaction kettle, then sequentially adding 39 parts of sodium dihydrogen phosphate and 32 parts of boric acid into the reaction kettle, mixing and stirring uniformly, then adding 18 parts of ammonium molybdate aqueous solution, and stirring uniformly; and finally, sequentially adding 20 parts of titanium dioxide sol, 15 parts of citric acid and 20 parts of zinc oxide, mixing, and stirring for 1 hour to obtain the zinc oxide sol.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; and then, dripping 60 parts of the organic acid-treated composite salt solution (C) into a reaction kettle in a stirring state, stirring for 1h after dripping is finished, finally adding 3 parts of an auxiliary agent (1.5 parts of a defoaming agent and 1.5 parts of a flatting agent are added respectively), and stirring the reaction solution at room temperature for 10min to obtain a coating solution 1.
Example 2 (in this example, the dihydrogen phosphate in the organic acid-treated complex salt solution (C) was magnesium dihydrogen phosphate, compared with example 1.)
The organic acid-treated complex salt solution (C) was prepared according to the following method: adding 50 parts of deionized water into a reaction kettle, then sequentially adding 39 parts of magnesium dihydrogen phosphate and 32 parts of boric acid into the reaction kettle, mixing and stirring uniformly, then adding 18 parts of ammonium molybdate aqueous solution, and stirring uniformly; and finally, sequentially adding 20 parts of titanium dioxide sol, 15 parts of citric acid and 20 parts of zinc oxide, mixing, and stirring for 1 hour to obtain the zinc oxide sol.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; and then, dripping 60 parts of the organic acid-treated composite salt solution (C) into a reaction kettle in a stirring state, stirring for 1 hour after finishing dripping, finally adding 3 parts of the auxiliary agent (1.5 parts of the defoaming agent and 1.5 parts of the flatting agent are respectively added), and stirring the reaction solution at room temperature for 10 minutes to obtain the coating solution 2.
Example 3 (in this example, the monobasic phosphate in the organic acid-treated complex salt solution (C) was zinc dihydrogen phosphate, compared to example 1.)
The organic acid-treated complex salt solution (C) was prepared according to the following method: adding 50 parts of deionized water into a reaction kettle, then sequentially adding 39 parts of zinc dihydrogen phosphate and 32 parts of boric acid into the reaction kettle, mixing and stirring uniformly, then adding 18 parts of ammonium molybdate aqueous solution, and stirring uniformly; and finally, sequentially adding 20 parts of titanium dioxide sol, 15 parts of citric acid and 20 parts of zinc oxide, mixing and stirring for 1 hour to obtain the zinc oxide sol.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; and then, dripping 60 parts of the organic acid-treated composite salt solution (C) into a reaction kettle in a stirring state, stirring for 1h after dripping is finished, finally adding 3 parts of an auxiliary agent (1.5 parts of a defoaming agent and 1.5 parts of a flatting agent are added respectively), and stirring the reaction solution at room temperature for 10min to obtain a coating solution 3.
Example 4 (in this example, the organic acid in the organic acid-treated complex salt solution (C) was ethylenediaminetetraacetic acid, compared to example 1.)
The organic acid-treated complex salt solution (C) was prepared according to the following method: adding 50 parts of deionized water into a reaction kettle, then sequentially adding 39 parts of sodium dihydrogen phosphate and 32 parts of boric acid into the reaction kettle, mixing and stirring uniformly, then adding 18 parts of ammonium molybdate water solution, and stirring uniformly; and finally, sequentially adding 20 parts of titanium dioxide sol, 15 parts of ethylene diamine tetraacetic acid and 20 parts of zinc oxide, mixing, and stirring for 1 hour.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; and then, dripping 60 parts of the organic acid-treated composite salt solution (C) into a reaction kettle in a stirring state, stirring for 1h after dripping is finished, finally adding 3 parts of an auxiliary agent (1.5 parts of a defoaming agent and 1.5 parts of a flatting agent are added respectively), and stirring the reaction solution at room temperature for 10min to obtain a coating solution 4.
Example 5 (in this example, the organic acid in the organic acid-treated complex salt solution (C) was malic acid, compared with example 1.)
The organic acid-treated complex salt solution (C) was prepared according to the following method: adding 50 parts of deionized water into a reaction kettle, then sequentially adding 39 parts of sodium dihydrogen phosphate and 32 parts of boric acid into the reaction kettle, mixing and stirring uniformly, then adding 18 parts of ammonium molybdate water solution, and stirring uniformly; and finally, sequentially adding 20 parts of titanium dioxide sol, 15 parts of malic acid and 20 parts of zinc oxide, mixing, and stirring for 1h to obtain the zinc oxide.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; and then, dripping 60 parts of the organic acid-treated composite salt solution (C) into a reaction kettle in a stirring state, stirring for 1h after dripping is finished, finally adding 3 parts of an auxiliary agent (1.5 parts of a defoaming agent and 1.5 parts of a flatting agent are added respectively), and stirring the reaction solution at room temperature for 10min to obtain a coating solution 5.
Example 6 (this example compares to example 1, the organic acid in the organic acid-treated complex salt solution (C) was tartaric acid.)
The organic acid-treated complex salt solution (C) was prepared according to the following method: adding 50 parts of deionized water into a reaction kettle, then sequentially adding 39 parts of sodium dihydrogen phosphate and 32 parts of boric acid into the reaction kettle, mixing and stirring uniformly, then adding 18 parts of ammonium molybdate water solution, and stirring uniformly; and finally, sequentially adding 20 parts of titanium dioxide sol, 15 parts of tartaric acid and 20 parts of zinc oxide, mixing, and stirring for 1 hour to obtain the nano-silver zinc oxide.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; and then, dripping 60 parts of the organic acid-treated composite salt solution (C) into a reaction kettle in a stirring state, stirring for 1h after dripping is finished, finally adding 3 parts of an auxiliary agent (1.5 parts of a defoaming agent and 1.5 parts of a flatting agent are added respectively), and stirring the reaction solution at room temperature for 10min to obtain a coating solution 6.
Example 7 (in this example, the metal oxide in the organic acid-treated complex salt solution (C) was calcium oxide, compared to example 1.)
The organic acid-treated complex salt solution (C) was prepared according to the following method: adding 50 parts of deionized water into a reaction kettle, then sequentially adding 39 parts of sodium dihydrogen phosphate and 32 parts of boric acid into the reaction kettle, mixing and stirring uniformly, then adding 18 parts of ammonium molybdate water solution, and stirring uniformly; and finally, sequentially adding 20 parts of titanium dioxide sol, 15 parts of citric acid and 20 parts of calcium oxide, mixing, and stirring for 1 hour.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; and then, dripping 60 parts of the organic acid-treated composite salt solution (C) into a reaction kettle in a stirring state, stirring for 1h after dripping is finished, finally adding 3 parts of an auxiliary agent (1.5 parts of a defoaming agent and 1.5 parts of a flatting agent are added respectively), and stirring the reaction solution at room temperature for 10min to obtain a coating solution 7.
Example 8 (in this example, the metal oxide in the organic acid-treated complex salt solution (C) was magnesium oxide, compared to example 1.)
The organic acid-treated complex salt solution (C) was prepared according to the following method: adding 50 parts of deionized water into a reaction kettle, then sequentially adding 39 parts of sodium dihydrogen phosphate and 32 parts of boric acid into the reaction kettle, mixing and stirring uniformly, then adding 18 parts of ammonium molybdate water solution, and stirring uniformly; and finally, sequentially adding 20 parts of titanium dioxide sol, 15 parts of citric acid and 20 parts of magnesium oxide, mixing, and stirring for 1 hour.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; and then, dripping 60 parts of the organic acid-treated composite salt solution (C) into a reaction kettle in a stirring state, stirring for 1h after dripping is finished, finally adding 3 parts of an auxiliary agent (1.5 parts of a defoaming agent and 1.5 parts of a flatting agent are added respectively), and stirring the reaction solution at room temperature for 10min to obtain a coating solution 8.
Example 9 (in this example, the metal oxide in the organic acid-treated complex salt solution (C) was alumina, compared to example 1.)
The organic acid-treated complex salt solution (C) was prepared according to the following method: adding 50 parts of deionized water into a reaction kettle, then sequentially adding 39 parts of sodium dihydrogen phosphate and 32 parts of boric acid into the reaction kettle, mixing and stirring uniformly, then adding 18 parts of ammonium molybdate water solution, and stirring uniformly; and finally, sequentially adding 20 parts of titanium dioxide sol, 15 parts of citric acid and 20 parts of alumina, mixing, and stirring for 1 hour to obtain the titanium dioxide sol.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; then, 60 parts of the organic acid-treated composite salt solution (C) is dripped into the reaction kettle in a stirring state, the mixture is stirred for 1 hour after the dripping is finished, finally, 3 parts of the auxiliary agent (1.5 parts of the defoaming agent and 1.5 parts of the flatting agent are respectively added) are added, and the reaction solution is stirred for 10 minutes at room temperature to obtain the coating solution 9.
Example 10 (the modified aqueous resin emulsion of this example was different in parts by mass from example 1)
The organic acid-treated complex salt solution (C) was prepared in the same manner as in example 1.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 20 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; then, 60 parts of the organic acid-treated composite salt solution (C) is dripped into the reaction kettle in a stirring state, the mixture is stirred for 1 hour after the dripping is finished, finally, 3 parts of the auxiliary agent (1.5 parts of the defoaming agent and 1.5 parts of the flatting agent are respectively added) are added, and the reaction solution is stirred for 10 minutes at room temperature to obtain the coating solution 10.
Example 11 (this example differs in the parts by mass of the silicone-modified nanosilica compared with example 1)
The organic acid-treated complex salt solution (C) was prepared in the same manner as in example 1.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 30 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; then, 60 parts of the organic acid-treated composite salt solution (C) is dripped into the reaction kettle in a stirring state, the mixture is stirred for 1 hour after the dripping is finished, finally, 3 parts of the auxiliary agent (1.5 parts of the defoaming agent and 1.5 parts of the flatting agent are respectively added) are added, and the reaction solution is stirred for 10 minutes at room temperature to obtain the coating solution 11.
Example 12 (different parts by mass of the organic acid-treated complex salt solution in this example compared with example 1)
The organic acid-treated complex salt solution (C) was prepared in the same manner as in example 1.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; then, 30 parts of the organic acid-treated composite salt solution (C) is dripped into the reaction kettle under the stirring state, the mixture is stirred for 1 hour after the dripping is finished, finally, 3 parts of the auxiliary agent (1.5 parts of the antifoaming agent and 1.5 parts of the leveling agent are respectively added) are added, and the reaction solution is stirred for 10 minutes at room temperature, so that the coating solution 12 is obtained.
Example 13 (the modified aqueous resin emulsion of this example was different in parts by mass from example 1)
The organic acid-treated complex salt solution (C) was prepared in the same manner as in example 1.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 55 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; then, 60 parts of the organic acid-treated composite salt solution (C) is dropped into the reaction kettle while stirring, and after the dropping is completed, the mixture is stirred for 1 hour, finally, 3 parts of the auxiliary agent (1.5 parts of the antifoaming agent and 1.5 parts of the leveling agent are added respectively) are added, and the reaction solution is stirred for 10 minutes at room temperature, so that the coating solution 13 is obtained.
Example 14 (this example differs in the parts by mass of the silicone-modified nanosilica compared with example 1)
The organic acid-treated complex salt solution (C) was prepared in the same manner as in example 1.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 75 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; then, 60 parts of the organic acid-treated composite salt solution (C) is dripped into the reaction kettle under the stirring state, the mixture is stirred for 1 hour after the dripping is finished, finally, 3 parts of the auxiliary agent (1.5 parts of the antifoaming agent and 1.5 parts of the leveling agent are respectively added) are added, and the reaction solution is stirred for 10 minutes at room temperature, so that the coating solution 14 is obtained.
Example 15 (different parts by mass of the organic acid-treated complex salt solution in this example compared with example 1)
The organic acid-treated complex salt solution (C) was prepared in the same manner as in example 1.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; and then, dropwise adding 75 parts of the organic acid-treated composite salt solution (C) into the reaction kettle while stirring, stirring for 1h after dropwise adding is completed, finally adding 3 parts of an auxiliary agent (1.5 parts of a defoaming agent and 1.5 parts of a leveling agent are respectively added), and stirring the reaction solution at room temperature for 10min to obtain a coating solution 15.
Example 16 (the modified aqueous resin emulsion of this example was different in parts by mass from example 1)
The organic acid-treated complex salt solution (C) was prepared in the same manner as in example 1.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 8 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; then, 60 parts of the organic acid-treated composite salt solution (C) is dripped into the reaction kettle under the stirring state, the mixture is stirred for 1 hour after the dripping is finished, finally, 3 parts of the auxiliary agent (1.5 parts of the antifoaming agent and 1.5 parts of the flatting agent are respectively added) are added, and the reaction solution is stirred for 10 minutes at room temperature, so that the coating solution 16 is obtained.
The chromium-free insulating coating liquid prepared by the embodiment can obviously improve the appearance, corrosion resistance and adhesive force of a coating film within a certain using range because the modified water-based resin emulsion is used as a main film forming framework in the film forming process; and vice versa, worse. In addition, the modified resin emulsion is organic resin, and can obviously improve the moisture absorption resistance of the coating film after being compounded with inorganic salt within a certain range; conversely, the resistance to moisture absorption is poor.
Example 17 (this example differs in the parts by mass of the silicone-modified nanosilica compared with example 1)
The organic acid-treated complex salt solution (C) was prepared in the same manner as in example 1.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 16 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; then, 60 parts of the organic acid-treated composite salt solution (C) is dripped into the reaction kettle under the stirring state, the mixture is stirred for 1 hour after the dripping is finished, finally, 3 parts of the auxiliary agent (1.5 parts of the antifoaming agent and 1.5 parts of the leveling agent are respectively added) are added, and the reaction solution is stirred for 10 minutes at room temperature, so that the coating solution 17 is obtained.
The chromium-free insulating coating liquid prepared by the embodiment mainly plays a role in connecting organic and inorganic bridges due to the structural characteristics of the organosilicon modified nano silicon dioxide, and can obviously improve the appearance of a coating in a certain application range; conversely, the coating appearance was poor. In addition, due to the characteristics of the organosilicon modified nano-silica material, the coating has obvious benefits on corrosion resistance, moisture absorption resistance and insulation property of the coating in a certain use range; and vice versa, worse.
Example 18 (different parts by mass of the organic acid-treated complex salt solution in this example compared with example 1)
The organic acid-treated complex salt solution (C) was prepared in the same manner as in example 1.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; then 8 parts of the organic acid-treated composite salt solution (C) is dripped into the reaction kettle under the stirring state, the mixture is stirred for 1 hour after the dripping is finished, finally 3 parts of the auxiliary agent (1.5 parts of the antifoaming agent and 1.5 parts of the flatting agent are respectively added), and the reaction solution is stirred for 10min at room temperature, thus obtaining the coating solution 18.
In the chromium-free insulating coating solution prepared in this example, the organic acid-treated composite salt solution (C) is mainly prepared by compounding an organic acid and a plurality of inorganic salts, and mainly meets the requirements of the coating on corrosion resistance, adhesion, heat resistance, insulation and wet and heat resistance during the use process. These properties essentially all require the presence of a certain amount of complex inorganic salts to be able to meet the requirements; the reduction of the amount of complex inorganic salt leads to a significant deterioration of the properties of the film.
Example 19 (compare example 1, no adjuvant added)
The organic acid-treated complex salt solution (C) was prepared in the same manner as in example 1.
The preparation method of the chromium-free insulating coating liquid comprises the following steps: adding 80 parts of deionized water into a reaction kettle, sequentially adding 35 parts of modified water-based resin emulsion and 55 parts of organic silicon modified nano silicon dioxide, and uniformly mixing and stirring; then, 60 parts of the organic acid-treated composite salt solution (C) is dripped into the reaction kettle in a stirring state, and the mixture is stirred for 1 hour after the dripping is finished, so that the coating solution 19 is obtained.
In the chromium-free insulating coating liquid prepared by the embodiment, as no auxiliary agent is added, the corresponding auxiliary agent mainly plays a role in promoting production and application in the coating liquid. Especially the defoaming agent and the leveling agent, and the proper amount of the defoaming agent plays a great role in the production of the coating liquid, and a great amount of bubbles cannot be generated in the reaction kettle to influence the production efficiency. The leveling agent can promote the film formation of the coating liquid, so that the coating has better appearance.
The performance of the chromium-free insulating coating solutions prepared in examples 1 to 19 was evaluated by the following specific method:
test substrates: and (4) orientation silicon steel bare plates (not coated with the insulating coating liquid).
Preparing an insulating coating:
(1) cutting an oriented silicon steel bare plate into 7.5cm by 15cm, soaking the oriented silicon steel bare plate in a 2% degreasing agent for a period of time, cleaning grease on the surface, activating and derusting with dilute hydrochloric acid, determining activation time (ensuring complete derusting) according to derusting degree, taking out a sample plate, washing with running water, washing with deionized water, and immediately drying with an air cooler for later use;
(2) coating the chromium-free insulating coating liquid on a silicon steel plate by a roller coating method, wherein the coating is controlled to be 1.0-2.0 um;
(3) and (3) placing the coated silicon steel plate at 400 ℃, curing for 20s, and taking out. The appearance was observed at room temperature and then performance tests were performed.
The evaluation method comprises the following steps:
(1) film forming property: visually, evaluation was carried out according to the following criteria.
V: the insulating coating is glossy and compact;
o: the insulating coating is matt and compact;
x: the insulating coating is uneven, loose and hazy.
(2) Moisture absorption resistance: evaluation was performed according to the following criteria.
V: the insulating coating has excellent moisture absorption resistance;
o: the insulating coating has general moisture absorption resistance effect;
x: the insulating coating has poor moisture absorption resistance.
(3) Corrosion resistance: performing a neutral salt spray accelerated corrosion test by using a JH-60 type salt spray corrosion test box according to GB/T10125-2012 salt spray test for artificial atmosphere corrosion test; test medium: chemically pure NaCl deionized water solution with medium concentration of 50g/L and pH value of 6.5; test temperature: 35 +/-2 ℃; the settling amount of the salt spray: 1-2 mL/h 80cm2(ii) a Placing a sample: the experimental surface and the vertical direction form an angle of 30 degrees; spraying continuously in each period with 1h as a period, opening the box to check the sample once before each period is finished, wherein the checking time is not more than 10min, and evaluating according to the following standard.
V: the salt spray time is 8h, and the corrosion area is 0%;
o: the salt spray time is 8h, and the corrosion area is 1-10%;
x: the salt spray time is 8h, and the corrosion area is more than 10%;
(4) adhesion: the cracking and peeling of the surface coating was examined according to the method specified in GB2522-2007 test method for the adhesion of insulation resistance coating on the surface of electrical steel sheet (strip), and evaluated according to the following criteria.
V: the insulating coating does not crack or peel;
o: the insulating coating cracked very slightly but did not peel off;
x: the insulating coating cracks or peels seriously;
(4) heat resistance: test in high temperature chamberIn an electric resistance furnace. Conditions for heat resistance: introducing N at 850 DEG C2The heating was continued for 2 hours, and the surface of the sample was observed after taking out and evaluated according to the following criteria.
V: the insulating coating is glossy and dark gray;
o: the insulating coating is matt and grey;
x: the surface of the insulating coating is whitish or pulverized.
(5) Insulating property: the interlayer resistance was measured by an insulation resistance tester according to a method prescribed in GB2522-2007 test method for the adhesion of insulation resistance coatings on the surfaces of electrical steel sheets (strips), and evaluated according to the following criteria.
V: the interlayer resistance was 30 Ω · cm2Sheet)-1The above;
o: the interlayer resistance is 5-30 omega (cm)2Sheet)-1；
X: the interlayer resistance is 5 omega (cm)2Sheet)-1The following.
(6) Moisture and heat resistance: the passivated panel was placed in a constant temperature and humidity chamber at 50 ℃ and 80% RH, taken out after 15 days, observed for the corrosion area of the sample panel, and evaluated according to the following criteria.
V: the corrosion area of the insulating coating is 0-10%;
o: the corrosion area of the insulating coating is 10-40%;
x: the corrosion area of the insulating coating is more than 40%;
TABLE 1 evaluation results of Properties
Figure BDA0002596838220000141
Figure BDA0002596838220000151
As can be seen from the above table, after the surface treatment of the oriented silicon steel plate, the film forming property, the moisture absorption resistance, the corrosion resistance, the adhesion, the heat resistance, the insulation property and the humidity resistance are obviously enhanced. The appearance patterns of the oriented silicon steel surface treated by the coating liquid in the examples 1 to 19 after 8 hours of salt spray resistance test are shown in the figures 1 to 4. The insulating coating liquid has good stability, does not cause the problems of product deterioration and the like after being placed for a long time in the industrial use process, and can be popularized and used in the oriented silicon steel plant.

Claims (5)

1. The environment-friendly chromium-free insulating coating liquid for surface treatment of oriented silicon steel is characterized by being prepared from the following raw materials in parts by mass: 10-60 parts of modified water-based resin emulsion, 20-80 parts of organic silicon modified nano silicon dioxide, 10-80 parts of organic acid treated composite salt solution, 1-20 parts of auxiliary agent and 10-100 parts of deionized water;
the preparation method of the modified water-based resin emulsion comprises the following steps: mixing the acrylic resin emulsion prepolymer and the cationic polyurethane resin emulsion prepolymer according to the mass ratio of 1:2 at 40 ℃, adjusting the pH value to 4.5 by using acetic acid, and stirring for 1h to obtain the acrylic resin emulsion prepolymer and the cationic polyurethane resin emulsion prepolymer;
the acrylic resin emulsion prepolymer in the modified water-based resin emulsion is prepared by the following method: adding 50 parts of isophthalic acid, 6 parts of acrylic acid, 18 parts of butyl acrylate, 23 parts of methyl methacrylate, 2 parts of isobornyl methacrylate, 4 parts of hydroxyethyl acrylate and 1 part of initiator azobisisobutyronitrile into a reaction container, and uniformly mixing; adding the extracted 25% mixed solution into another reaction container, heating to 75 ℃, stirring, dripping the remaining 75% mixed solution into the reaction container for 2 hours, continuing to react for 3 hours, and cooling the reaction solution to 40 ℃ to obtain the product;
the cationic polyurethane resin emulsion prepolymer in the modified water-based resin emulsion is prepared by the following method: adding 100 parts of polyethylene glycol 400 and 59 parts of isophorone diisocyanate into a reaction container, and uniformly mixing and stirring; heating the reaction vessel to 82 ℃, reacting for 2 hours, and cooling to 55 ℃; adding 2 parts of trimethylolpropane, 12 parts of N-methyldiethanolamine and 80 parts of acetone, reacting for 2 hours, cooling to 40 ℃, adding acetic acid to adjust the pH value to 5.0, and stirring for 0.5 hour to obtain the aqueous solution;
the organic silicon modified nano silicon dioxide is prepared by the following method: adding 20 parts of water into a reaction kettle, adjusting the pH value to 4.5 by using acetic acid, heating to 50 ℃, then dripping 5 parts of silane coupling agent, ethanol and the like for mixing by mass, preserving the temperature of a reaction solution at 50 ℃ for 1h after dripping is finished, cooling to room temperature, and adjusting the pH value to 4.5 by using acetic acid; finally, adding 3 parts of nano-scale silicon dioxide under a high-speed stirring state, and stirring for 1 hour to obtain the nano-scale silicon dioxide;
the silane coupling agent is selected from one or more of 3- (2-aminoethylamino) propyl trimethoxy silane, 3-aminopropyl trimethoxy silane and gamma- (2, 3-epoxypropoxy) propyl trimethoxy silane;
the organic acid treated composite salt solution is prepared by the following method, wherein the raw materials in parts by mass are as follows: adding 50 parts of deionized water into a reaction kettle, then sequentially adding 39 parts of dihydric phosphate and 32 parts of boric acid into the reaction kettle, uniformly mixing and stirring, then adding 18 parts of ammonium molybdate aqueous solution, uniformly stirring, finally sequentially adding 20 parts of titanium dioxide sol, 15 parts of organic acid and 20 parts of metal oxide, mixing, and stirring for 1 hour to obtain the catalyst;
the preparation method of the titanium dioxide sol comprises the following steps: mixing 12 parts of tetrabutyl titanate and 60 parts of absolute ethyl alcohol, stirring for 0.5 hour, adding the mixture into a mixed solution of 1.5 parts of acetic acid and 20 parts of water under a stirring state, and stirring for 2 hours to obtain the product;
the dihydric phosphate is selected from one or more of sodium dihydrogen phosphate, zinc dihydrogen phosphate, potassium dihydrogen phosphate, calcium dihydrogen phosphate, magnesium dihydrogen phosphate, aluminum dihydrogen phosphate and ammonium dihydrogen phosphate;
the organic acid is one or more of citric acid, tartaric acid, malic acid and ethylenediamine tetraacetic acid;
the metal oxide is selected from one or more of zinc oxide, calcium oxide, magnesium oxide and aluminum oxide.
2. The environment-friendly chromium-free insulating coating liquid for the surface treatment of oriented silicon steel according to claim 1, which is prepared from the following raw materials in parts by mass: 20-55 parts of modified water-based resin emulsion, 30-75 parts of organic silicon modified nano silicon dioxide, 30-75 parts of organic acid treated composite salt solution, 1-8 parts of auxiliary agent and 20-100 parts of deionized water.
3. The environment-friendly chromium-free insulating coating solution for surface treatment of oriented silicon steel according to claim 1 or 2, wherein the concentration of the aqueous solution of ammonium molybdate is 0.1g/mL to 0.3 g/mL.
4. The environment-friendly chromium-free insulating coating solution for surface treatment of oriented silicon steel according to claim 1 or 2, wherein the auxiliary agent comprises an antifoaming agent and a leveling agent.
5. The environment-friendly chromium-free insulating coating solution for surface treatment of oriented silicon steel as claimed in claim 4, wherein the auxiliary agent further comprises one or more of a dispersant, a thickener and a wetting agent.
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