CN103555041A - Insulating paint with high punching performance for non-oriented electrical steel, and preparation method and application thereof - Google Patents
Insulating paint with high punching performance for non-oriented electrical steel, and preparation method and application thereof Download PDFInfo
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Abstract
An environment-friendly insulating paint with high punching performance for non-oriented electrical steel, and a preparation method and application thereof. The insulating paint comprises 20%-60% of aluminium dihydrogen phosphate, 2%-40% of an organic resin, 0.5%-5% of silica sol, 1%-10% of phosphate, 0.3-2% of nitrate, 1%-5% of magnesium oxide, 0.3%-5.5% of a rare earth salt mixed solution, 0.5%-5.5% of a silane coupling agent and the balance of solvent water. The insulating paint provided by the invention is a single component organic / inorganic waterborne environment-friendly paint, which has characteristics of good surface state, high adhesion, high insulation, high corrosion resistance and high temperature resistance and environment-friendly characteristics of no chrome or harmful ions, and can be widely used in surface coating treatment of cold-rolled non-oriented electrical steel plate. At the same time, the invention greatly improves and increase the smoothness and punching performance by improving the performance and the proportion of the organic resin, so that the insulating paint is comparable to a traditional chromate insulating coating; the insulating paint greatly prolongs the service life of the die and improves the product processing precision, and is in favor of improving production efficiency and reducing the cost.
Description
Technical field
The invention belongs to steel surface processing technology field, more specifically, the present invention relates to a kind of related manufacturing processes and application with the electrical steel environmental protection insulation compound of higher punching performance.
Background technology
Electrical steel (also claiming silicon steel) is the silicon-iron soft magnetic alloy that a kind of carbon content is extremely low, its purposes is very extensive, electrical sheet can be used for manufacturing electric motor, generator, transformer and ballast iron core, is important magneticsubstance indispensable in electric power, electronics and war industry.
Conventionally, the cold-rolled electric steel-board front surface that dispatches from the factory need apply the insulation film that a layer thickness is 0.5 μ m～5 μ m, to guarantee thering is higher interlamination resistance rate between the siliconized plate lamination of iron core in use procedure, reduce power loss between lamination layer, prevent from being short-circuited between core lamination stack and increase eddy-current loss, improving its electromagnetic performance.In addition, insulation film also can make electrical steel in storage, transportation and use procedure, slow down the erosion of various media, effectively prevents corrosion, to electrical sheet itself, provides suitable protection.
Make a general survey of development and the production practice of domestic and international cold rolling non-oriented electrical steel coating, coating system mainly includes organic coating, inorganic coating and half inorganic coating three major types.Because organic coating is large at coat-thickness, weldability is bad, coating and performance poor heat stability, hardness is low and the aspect such as environmental protection exists problems, current, the top coat of world Ge great steel mill cold-rolled electric steel-board is all to inorganic or half inorganic development, but owing to being subject to the especially not high restriction of punching of the attribute of inorganic coating own, apply at present more half inorganic coating that remains.
In existing invention and product, the insulating coating of cold rolling electric can be further divided into chromic salt system and the large classification of phosphate system two.Chromate coating appears at the 60-70 age in last century, and typical products has the L of Nippon Steel, L2, L3 coating, JFE AN, J coating, Korea S Pu item C6A, C6B coating, Wuhan Iron and Steel Plant T4, T5 coating, Taiyuan Iron and Steel Co. G2 coating, Baosteel A, H coating and Anshan iron and steel plant TM4 coating etc.Although can be rated as most widely used general and the most successful electric steel insulating coating in history containing chromium semi-inorganic insulation coating, product has also passed through SGS authentication, because this type coating contains sexavalent chrome (Cr
6+) etc. metallic element and the environmentally harmful composition of strong carinogenicity; in coating material production, on-the-spot use, operation and coat waste liquid treating processes, exist and impair one's health and the risk of welding; consideration for environment protection; European and American developed countries just propose to avoid using chromate coating as far as possible in the seventies, this, advocate the lower development and application that has started the environment-friendly coating of excellent performance.In fact, European Union stopped using containing Cr from 1 day July in 2006
6+the electrical steel of coating, domestic also from 1 day January in 2007 to domestic all containing Cr
6+household electrical appliance sell to implement restriction, stepped up thus the research and development of different performance electrical steel product chromium-free environmental-protection insulating paint and coating both at home and abroad.Up to the present, all there are some electrical steel chromium-free environment-friendly type insulation compound come out and drop into practical application both at home and abroad, typical products has phosphoric acid salt environmental protection half inorganic coating of U.S. Armco company exploitation, the more excellent EB53 series environment-friendly coating of performance of Austria Rembrandtin company exploitation, the G of Nippon Steel, XN coating, Korea S Pu item NS, NM, NT coating, Taiyuan Iron and Steel Co. Q3, X4, H5, Z6 series coating, Baosteel K is coated with room and horse steel M21 coating etc., and above-mentioned coating is mainly phosphate system.
Although current domestic steel mill manufactures still general a large amount of chromate coating that adopts of cold-rolled non-oriented electrical steel, in view of environmental protection and production development demand, aqueous, environmental protective insulating coating will become inevitable development trend.In existing invention and product, to compare with traditional chromate coating, environment friendly insulating coating has clear superiority at some aspect of performance.
If the patent No. is CN200910195533, " a kind of electric steel insulating paint, its preparation method and coating method " related to that a kind of to take phosphoric acid salt be main non-oriented electrical steel water-based insulating environment-friendly coating and related coatings preparation method, and this invention has adopted and SiO
2the compound prescription of colloidal sol, rare earths salt and silane coupling agent, make the coating of coating, the insulativity of coating, solidity to corrosion and thermotolerance etc. are better than chromate coating, coating can meet industrial motor Production requirement preferably, but because organic composition in this invention coating composition is not high, the smoothness of coatingsurface and punching still can not meet the requirement of compressor industry completely.
In addition, patent CN201110137922 related to this has related to " a kind of anti-settling electrical steel aqueous, environmental protective insulation compound and preparation method thereof ", this invention has adopted and the essentially identical system of foregoing invention, by adding suitable anti-sedimentation agent, effectively improve the problem that coating is easy to delaminating deposition in storage process, significantly improved processing performance that coating applies and the homogeneity of coating performance.
Yet existing organic/inorganic system non-oriented electrical steel environment friendly insulating coating mainly contains following deficiency:
(1) punching of coating is bad, at the punching number of times of Compressor Manufacturing industry and traditional organic/inorganic chromic salt system coating, has larger gap, is difficult to meet the punching requirement of frequency-changeable compressor complicated shape chip.
(2) thermotolerance of coating is bad, is difficult to meet non-oriented electrical steel chip technology annealing requirement, after high temperature annealing coating carbonization serious, easy dry linting.
(3) coatingsurface state is bad, and coating is inhomogeneous, and coatingsurface easily produces longitudinal stripe, coating processes window narrows.
(4) resin and masking liquid compatibility are bad, and standing solution layering affects the homogeneity of coating processes and coating performance.
(5) resin high volatility, stimulates and not environmental protection.
Summary of the invention
Problem in view of above-mentioned existing invention and product existence, the present invention is on the basis of the existing invention of contriver, the multiple organic resin of having developed the existing phosphate system of coupling, by comprehensively composite, has obtained a kind of non-oriented electrical steel environmental protection insulation compound with high punching performance.
Coating of the present invention not only can meet production technique and the requirement of user to product general property of steel mill's cold rolling non-oriented electrical steel, and greatly improved the punching performance of electrical steel environment friendly insulating coating, it can be compared favourably with traditional chromate insulating coating, user's die life and processing precision of products have been increased substantially, the corresponding production efficiency that improved, has reduced production cost.
The object of the invention is to, a kind of high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound that has is provided, described coating can be used for manufacturing the non-oriented electromagnetic steel sheet surface insulation coating that various motors, transformer, ballast iron core and various electric elements are used, particularly, this coating has higher smoothness and punching, except meeting industrial motor production requirement, also can meet the requirement of Compressor Manufacturing industry.
Simultaneously, the object of the invention is to, a kind of high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound that has is provided, described have high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound when having higher smoothness and punching, also possess good stability and coating, the coating that obtains has the characteristics such as higher tack, insulativity, solidity to corrosion and high thermal resistance.
The present invention also aims to, a kind of high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound that has is provided, described have high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound when having higher smoothness and punching, also there is Chrome-free and not containing the environmental protection feature of any harmful element, be applicable to the surface-coated processing of the orientation-free cold-rolled electrical steel of Multiple Type.
The present invention also aims to, a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound is provided, prepared by described method has high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound when having higher smoothness and punching, also possess good stability and coating, the coating that obtains has higher tack, insulativity, the characteristic such as solidity to corrosion and high thermal resistance, and/or there is Chrome-free and not containing the environmental protection feature of any harmful element, the surface-coated that is applicable to the orientation-free cold-rolled electrical steel of Multiple Type is processed.
A kind of technical scheme with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention is as follows:
A high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, formulated by the component of following mass percent:
All the other are aqueous solvent.
The rare-earth salts mixing solutions adopting in described formulation for coating material is the solution of rare-earth salts, superoxide, buffer reagent and nitric acid, and while preparing described rare-earth salts mixing solutions, the proportioning of described conjugate solutions is:
All the other are aqueous solvent.
Rare-earth salts in described rare-earth salts mixing solutions be selected from Yttrium trinitrate, cerous nitrate, neodymium nitrate one or more/one or more and one or more the mixture that is selected from ammonium cerous sulfate, praseodymium chloride, cerous chlorate in Yttrium trinitrate, cerous nitrate, neodymium nitrate;
All the other are aqueous solvent.
Formulation for coating material of the present invention adopts aluminium dihydrogen phosphate, magnesium oxide, silicon dioxide gel and organic resin as the main ingredient of coating, there is excellent coating property, film-forming properties and corrosion resisting property, can effectively improve the ability of electrical steel surface and coating generation passivation reaction, be conducive to improve adhesion property and the insulating property of coating.
The Major Technology that improves the punching of non-oriented electrical steel insulating coating is to improve organic content in coating, mainly by adding appropriate organic resin, realize, wherein the consistency of resin and system, the dispersiveness of resin, the feature of environmental protection and thermotolerance etc. are extremely important, therefore the selection of resin kind and adding technology are crucial, resin kind and addition obvious difference in different formulas.
Organic resin can effectively improve coating oilness, improves steel plate stamping piece performance.Add silicon sol to be conducive to improve the electromagnetic performance of siliconized plate, the magnesium oxide adding and phosphoric acid can improve high thermal resistance and the insulating property of coating.The rare-earth salts mixing solutions adopting in anti-settling electrical steel aqueous, environmental protective insulation compound formula can replace chromic salts, improve the corrosion resisting property of coating, the silane coupling agent adding is for coupling mineral filler, strengthen adhesive property, improve solidity to corrosion, high thermal resistance, mechanical property, water resistance and the ageing resistance of coating, the anti-settling additive adding can reduce the settling velocity of macromolecular components in finished product coating greatly, improves dispersiveness and the levelling property of coating integral body.
According to of the present invention, have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, described insulation compound comprises: anti-settling additive: 3%～20%.
According to of the present invention, have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, described insulation compound comprises: organic resin 2%～20%.
According to of the present invention, have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, described silicon sol adding proportion is 0.8%～3%.
According to of the present invention, have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the ratio of component of described magnesium oxide and phosphoric acid is respectively 1～3%-1～7%.
According to of the present invention, have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the organic resin in formulation for coating material is be selected from polymolecularity water-borne acrylic resin, aqueous epoxy resins or its two mixture a kind of.
Organic resin in this invention formulation for coating material is a kind of of polymolecularity water-borne acrylic resin, aqueous epoxy resins or its mixture, preferably water soluble acrylic acid-epoxy resin composite.
The rare-earth salts mixing solutions adopting in this invention formulation for coating material is the solution of rare-earth salts, superoxide, buffer reagent and nitric acid, and while preparing described rare-earth salts mixing solutions, the proportioning of described conjugate solutions is:
All the other are aqueous solvent.
Rare-earth salts in rare-earth salts mixing solutions is selected from one or more mixing in Yttrium trinitrate, ammonium cerous sulfate, cerous nitrate, praseodymium chloride, cerous chlorate, neodymium nitrate.Preferably, described rare-earth salts is ammonium cerous sulfate, cerous nitrate and praseodymium chloride, and its quality mixture ratio is in 1～5:3～7:1～4.Buffer reagent in rare-earth salts mixing solutions is selected from one or more mixing in boric acid, acetic acid, volatile salt.Preferably, described buffer reagent is boric acid and acetic acid, and its quality mixture ratio is in 1～5:1～4.Superoxide in rare-earth salts mixing solutions is selected from one or more mixing in hydrogen peroxide, sodium peroxide, Potassium peroxide, Magnesium peroxide, calcium peroxide, barium peroxide.Preferably, described superoxide is hydrogen peroxide, sodium peroxide, barium peroxide, and the quality mixture ratio of hydrogen peroxide, sodium peroxide, barium peroxide is in 1～8:1～6:1～4.
According to of the present invention, have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the polymolecularity of the organic resin in described formulation for coating material is characterized as molecular weight and is no more than 10000, and the kinetic viscosity of resin own is no more than 50mPa.s.
Thus, after adopting roller coating technology applying coating, coatingsurface does not produce obviously grow dim situation and striped.
According to of the present invention, there is high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, for can mix by arbitrary proportion with water, long-term standingly there is not simple organic resin and separate out the layering causing in the organic resin in described formulation for coating material with the compatible characteristics of system.
According to of the present invention, have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the organic resin in described formulation for coating material is not containing the organic resin of organic solvent.
Thus, do not have VOC to discharge, cycle annealing is after two hours in 750 ℃ of nitrogen for coating, and coating does not produce obvious destructive carbonization, and can meet the tack requirement of obviously peeling off does not occur after coating is burnt.
According to of the present invention, have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the ratio of the organic resin in described formulation for coating material is 10%～15%.
According to of the present invention, have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the ratio of the organic resin in described formulation for coating material is 15%～20%.
According to of the present invention, there is high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the anti-settling additive adopting in described formulation for coating material is the solution that mineral soil, glue class thickening material, cellulose thickener and water coordinate, and its proportioning is:
Mineral soil: 0.1%～5%
Glue class thickening material: 0.1%～5%
Cellulose thickener: 0.1%～5%
All the other are aqueous solvent.
According to of the present invention, there is high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the mineral soil in anti-settling additive is selected from one or more mixing in polygorskite, lithium magnesium silicate, natural mica powder, high clay, organobentonite, inorganic bentonite, active recessed soil.Preferably, described mineral soil is lithium magnesium silicate and inorganic bentonite, and the quality mixture ratio of lithium magnesium silicate and inorganic bentonite is in 1～2:5～10.
According to of the present invention, have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the glue class thickening material in anti-settling additive is selected from one or more mixing in guar gum, gelatin, gum arabic, xanthan gum.Preferably, described glue class thickening material is gum arabic and xanthan gum, and the quality mixture ratio of gum arabic and xanthan gum is in 1～2:5～10.
According to of the present invention, there is high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the cellulose thickener in anti-settling additive is selected from one or more mixing in Natvosol, Type 3U, methylhydroxypropylcellulose, 30000 fiber type elements, 100000 fiber type elements, 200000 fiber type elements.
According to of the present invention, there is high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, preferably, described cellulose thickener is Type 3U 30000 fiber type elements, and the quality mixture ratio of Type 3U and 30000 fiber type elements is in 1～2:5～10.
The silane coupling agent adopting in this invention formulation for coating material is selected from N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-(2,3-propylene oxide) propyl trimethoxy silicane), vinyltriethoxysilane, 1, the mixture of one or more in the hydrolyzate of 2-two (Trimethoxy silane ethane) and γ-aminopropyl triethoxysilanes, gamma-mercaptopropyltriethoxysilane.According to anti-settling electrical steel aqueous, environmental protective insulation compound of the present invention, preferably, described silane coupling agent is γ-(2,3-propylene oxide) propyl trimethoxy silicane and 1, the mixture of the hydrolyzate of 2-two (Trimethoxy silane ethane), the mass mixing ratio of the hydrolyzate of the two Trimethoxy silane ethane of described γ-(2,3-propylene oxide) propyl trimethoxy silicane and 1,2-is in 1～3:3～9.
The present invention provides again a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound:
It is characterized in that, comprise following operation:
(1) silicon sol is fully mixed with phosphate dihydrogen aluminum solution;
(2) add successively phosphoric acid and magnesium oxide, fully stir and add a small amount of aqueous solvent to reacting completely, magnesium oxide all dissolves;
(3) mix the solution that above-mentioned steps obtains, be stirred well to few 1h;
(4) slowly add rare-earth salts mixing solutions, limit edged stirs, until be dissolved as homogeneous phase completely;
(5) slowly add silane coupling agent, limit edged stirs, until be dissolved as homogeneous phase completely;
(6) slowly add organic resin, limit edged stirs, until be dissolved as homogeneous phase completely;
(7) slowly add anti-settling additive, limit edged stirs, until be dissolved as homogeneous phase completely;
(8) water is fixed molten, and fully stirs 1h, even to Solution Dispersion, adopts 200 mesh filter screens to filter, the coating that gets product, wherein,
All the other are aqueous solvent,
The rare-earth salts mixing solutions adopting in described formulation for coating material is the solution of rare-earth salts, superoxide, buffer reagent and nitric acid, and while preparing described rare-earth salts mixing solutions, the quality mixture ratio of described conjugate solutions is:
All the other are aqueous solvent;
Rare-earth salts in described rare-earth salts mixing solutions be selected from Yttrium trinitrate, cerous nitrate, neodymium nitrate one or more/one or more and one or more the mixture that is selected from ammonium cerous sulfate, praseodymium chloride, cerous chlorate in Yttrium trinitrate, cerous nitrate, neodymium nitrate.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention:
It is characterized in that, in step (6), slowly add organic resin, limit edged stirs, until after being dissolved as homogeneous phase completely,
(7) slowly add anti-settling additive, limit edged stirs, until be dissolved as homogeneous phase completely,
Described anti-settling additive 3%～20%, described anti-settling additive is the solution that mineral soil, glue class thickening material, cellulose thickener and water coordinate, its quality mixture ratio is:
Mineral soil: 0.1%～5%
Glue class thickening material: 0.1%～5%
Cellulose thickener: 0.1%～5%.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention:
Described insulation compound comprises: organic resin 2%～20%.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, described silicon sol adding proportion is 0.8%～3%.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, the ratio of component of described magnesium oxide and phosphoric acid is respectively 1～3%-1～7%.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, the organic resin in formulation for coating material is be selected from polymolecularity water-borne acrylic resin, aqueous epoxy resins or polymolecularity water-borne acrylic resin and aqueous epoxy resins mixture a kind of.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, the organic resin in described formulation for coating material is water soluble acrylic acid-epoxy resin composite.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, the polymolecularity of the organic resin in described formulation for coating material is characterized as molecular weight and is no more than 10000, and the kinetic viscosity of resin own is no more than 50mPa.s
Like this, after adopting roller coating technology applying coating, coatingsurface does not produce obviously grow dim situation and striped.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, for can mix by arbitrary proportion with water, long-term standingly there is not simple organic resin and separate out the layering causing in the organic resin in described formulation for coating material with the compatible characteristics of system.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, the organic resin in described formulation for coating material is not contain the organic resin of organic solvent.
Like this, do not have VOC to discharge, cycle annealing is after two hours in 750 ℃ of nitrogen for coating, and coating does not produce obvious destructive carbonization, and can meet the tack requirement of obviously peeling off does not occur after coating is burnt.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, the ratio of the organic resin in described formulation for coating material is 10%～15%.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, the ratio of the organic resin in described formulation for coating material is 15%～20%.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, described rare-earth salts is the mixture of ammonium cerous sulfate, cerous nitrate and praseodymium chloride, its quality mixture ratio is in 1～5:3～7:1～4.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, described rare-earth salts is one or more mixing that are selected from Yttrium trinitrate, cerous nitrate and neodymium nitrate.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, the buffer reagent in described rare-earth salts mixing solutions is selected from one or more mixing in boric acid, acetic acid, volatile salt.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, described buffer reagent is the mixture of boric acid and acetic acid, its quality mixture ratio is in 1～5:1～4.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, the superoxide in rare-earth salts mixing solutions is selected from one or more mixing in hydrogen peroxide, sodium peroxide, Potassium peroxide, Magnesium peroxide, calcium peroxide, barium peroxide.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, described superoxide is hydrogen peroxide, sodium peroxide, barium peroxide, and the quality mixture ratio of described hydrogen peroxide, sodium peroxide, barium peroxide is in 1～8:1～6:1～4.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, the mineral soil in anti-settling additive is selected from one or more mixing in polygorskite, lithium magnesium silicate, natural mica powder, high clay, organobentonite, inorganic bentonite, active recessed soil.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, described mineral soil is lithium magnesium silicate and inorganic bentonite, and the quality mixture ratio of lithium magnesium silicate and inorganic bentonite is in 1～2:5～10.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, the glue class thickening material in described anti-settling additive is selected from one or more mixing in guar gum, gelatin, gum arabic, xanthan gum.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, described glue class thickening material is gum arabic and xanthan gum, the quality mixture ratio of gum arabic and xanthan gum is in 1～2:5～10.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, cellulose thickener in described anti-settling additive is selected from one or more mixing in Natvosol, Type 3U, methylhydroxypropylcellulose, and described Natvosol is selected from 30000 fiber types elements, 100000 fiber types elements or 200000 fiber types element.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, described cellulose thickener is Type 3U and 30000 fiber types element, and the quality mixture ratio of Type 3U and 30000 fiber type elements is in 1～2:5～10.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, the silane coupling agent adopting in anti-settling electrical steel aqueous, environmental protective insulation compound is selected from N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane, γ-(2,3-propylene oxide) propyl trimethoxy silicane, vinyltriethoxysilane, 1, the mixture of one or more in the hydrolyzate of the two Trimethoxy silane ethane of 2-and γ-aminopropyl triethoxysilane, gamma-mercaptopropyltriethoxysilane.
According to a kind of preparation method with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound of the present invention, it is characterized in that, described silane coupling agent is γ-(2,3-propylene oxide) propyl trimethoxy silicane and 1, the mixture of the hydrolyzate of the two Trimethoxy silane ethane of 2-, the mass mixing ratio of the hydrolyzate of the two Trimethoxy silane ethane of described γ-(2,3-propylene oxide) propyl trimethoxy silicane and 1,2-is in 1～3:3～9.
The present invention also provides a kind of application method with high punching performance non-oriented electrical steel environmental protection insulation compound: it is characterized in that, comprise the steps:
(1) before coating, first siliconized plate is passed through to oil removing, alkali cleaning, acid etching, washing successively;
(2) on electrical steel, apply the described electric steel insulating paint that aforesaid method makes;
(3) described coating processes is roller coat;
(4) solidification value is 300～400 ℃, and the residence time is 60s～240s;
(5) forming thickness is the electric steel insulating paint of 0.3～8 μ m.
Beneficial effect
(1) of the present invention a kind of to have high punching performance non-oriented electrical steel environmental protection insulation compound be single component water soluble paint, possesses good stability and coating, can fully meet roller coating technology requirement, facilitates situ production and management; Adopt the non-oriented electrical steel insulating coating of this coating preparation to there is the characteristics such as higher tack, insulativity, solidity to corrosion and high thermal resistance.
(2) a kind of shortcoming that high punching performance non-oriented electrical steel environment friendly insulating coating has overcome existing environment friendly insulating coating poor heat resistance, coatingsurface state and performance inequality that has of the present invention, greatly improved the punching performance of electrical steel environment friendly insulating coating, it can be compared favourably with traditional chromate insulating coating, user's die life and processing precision of products have been increased substantially, the corresponding production efficiency that improved, has reduced production cost.
It is (3) of the present invention that a kind of to have high punching performance non-oriented electrical steel environmental protection insulation compound be environmentally friendly green coating product, it is not containing chromium or other harmful element composition, production and the use of coating meets the requirement of " cleaner production ", production process can be accomplished zero release, harmless to the person, environmentally safe.
Embodiment
For showing actual effect of the present invention, take component of the present invention and composition useful range proportioning as basis, stress to adjust organic resin content, prepare several coating finished product; Adopt steel mill's coating production unit, with same process preparation, there is the same code non-oriented electrical steel insulating coating product of conventional thickness, the relevant sample of preparation; According to concerned countries standard and common test method (table 1), the fundamental propertys such as state, insulativity, solidity to corrosion and tack of comprehensively carrying out related coatings in laboratory detect, and it is qualified to determine; Adopt test punching equipment to carry out high-speed and continuous punching, with the comparison of contrast sample, the punching improvement effect of relative evaluation coating.
Embodiment 1: numbering No.1
In following ratio, prepare the high punching performance non-oriented electrical steel environmental protection insulation compound that has of the present invention:
All the other are aqueous solvent.
In the present embodiment, organic resin is a kind of of polymolecularity water-borne acrylic resin, aqueous epoxy resins or its mixture, preferably water soluble acrylic acid-aqueous epoxy resins mixture.
In the present embodiment, rare-earth salts mixing solutions is the solution that rare-earth salts, superoxide, buffer reagent and nitric acid coordinate, and its proportioning is:
All the other are aqueous solvent.
In the present embodiment, the rare-earth salts in rare-earth salts mixing solutions is selected from cerous nitrate and praseodymium chloride, and its quality mixture ratio is at 3:1.Superoxide in rare-earth salts mixing solutions is hydrogen peroxide and sodium peroxide, and the quality mixture ratio of hydrogen peroxide and sodium peroxide is at 5:2.Buffer reagent in rare-earth salts mixing solutions is boric acid and acetic acid, and the quality mixture ratio of boric acid and acetic acid is at 5:2.
In the present embodiment, anti-settling additive is the solution of mineral soil, glue class thickening material, cellulose thickener cooperation, and its proportioning is:
Mineral soil: 0.5%
Glue class thickening material: 0.5%
Cellulose thickener: 0.3%
All the other are aqueous solvent.
In the present embodiment, the mineral soil in anti-settling additive is selected from lithium magnesium silicate and inorganic bentonite, and its quality mixture ratio is at 2:3.Glue class thickening material in anti-settling additive is gelatin and xanthan gum, and the quality mixture ratio of gelatin and xanthan gum is at 2:5.Cellulose thickener in anti-settling additive is 30000 fiber type elements and 200000 fiber types element, and the quality mixture ratio of 30000 fiber type elements and 200000 fiber type elements is at 5:3.
In the present embodiment, silane coupling agent is the two Trimethoxy silane ethane of 1,2-.
Process for preparation is as follows:
(1) silicon sol is fully mixed with phosphate dihydrogen aluminum solution;
(2) add successively phosphoric acid and magnesium oxide, fully stir and add a small amount of aqueous solvent to reacting completely, magnesium oxide all dissolves;
(3) mix the solution that above-mentioned steps obtains, be stirred well to few 1h;
(4) slowly add rare-earth salts mixing solutions, limit edged stirs, until be dissolved as homogeneous phase completely;
(5) slowly add silane coupling agent, limit edged stirs, until be dissolved as homogeneous phase completely;
(6) slowly add organic resin, limit edged stirs, until be dissolved as homogeneous phase completely;
(7) slowly add anti-settling additive, limit edged stirs, until be dissolved as homogeneous phase completely;
(8) water is fixed molten, and fully stirs 1h, even to Solution Dispersion, can obtain the anti-settling electrical steel water-borne coatings of above-mentioned height.
(9) adopt 200 mesh filter screens to filter resulting solution, coating gets product.
Adopt following technique preparation to there is high punching performance non-oriented electrical steel environment friendly insulating coating.
(1) before coating, first siliconized plate is passed through to oil removing, alkali cleaning, acid etching, washing successively;
(2) on electrical steel, apply the described electric steel insulating paint that aforesaid method makes;
(3) described coating processes is roller coat;
(4) solidification value is 300～400 ℃, and the residence time is 60s～240s;
(5) forming thickness is the electric steel insulating paint of 0.3～8 μ m.
Detected result is in Table 2.
Embodiment 2: numbering No.2
Except following difference, other are as embodiment 1:
All the other are aqueous solvent.
In the present embodiment, rare-earth salts mixing solutions is the solution that rare-earth salts, superoxide, buffer reagent and nitric acid coordinate, and its proportioning is:
All the other are aqueous solvent.
In the present embodiment, the rare-earth salts in rare-earth salts mixing solutions is selected from neodymium nitrate and praseodymium chloride, and its quality mixture ratio is at 2:1.Superoxide in rare-earth salts mixing solutions is hydrogen peroxide and Potassium peroxide, and the quality mixture ratio of hydrogen peroxide and Potassium peroxide is at 3:2.Buffer reagent in rare-earth salts mixing solutions is boric acid and acetic acid, and the quality mixture ratio of boric acid and acetic acid is at 5:2.
In the present embodiment, anti-settling additive is the solution of mineral soil, xanthan gum, cellulose thickener cooperation, and its proportioning is:
Mineral soil: 1%
Xanthan gum: 1%
Cellulose thickener: 0.5%
All the other are aqueous solvent.
In the present embodiment, the mineral soil in anti-settling additive is selected from organobentonite and natural mica powder, and its quality mixture ratio is at 2:5.Cellulose thickener in anti-settling additive is Type 3U and 200000 fiber types element, and the quality mixture ratio of Type 3U and 200000 fiber type elements is at 5:1.
In the present embodiment, silane coupling agent is the mixture of the hydrolyzate of γ-aminopropyl triethoxysilane, gamma-mercaptopropyltriethoxysilane and 1,2-two (Trimethoxy silane ethane), and its mass mixing ratio is at 1:3:1.
Detected result is in Table 2.
Embodiment 3: numbering No.3
Except following difference, other are as embodiment 1:
All the other are aqueous solvent.
In the present embodiment, rare-earth salts mixing solutions is the solution that cerous nitrate and cerous chlorate, praseodymium chloride mixture, sodium peroxide, boric acid and nitric acid coordinate, and its proportioning is:
All the other are aqueous solvent.
In the present embodiment, anti-settling additive is the solution of natural mica powder, glue class thickening material, cellulose thickener cooperation, and its proportioning is:
Natural mica powder: 3%,
Glue class thickening material: 4%,
Cellulose thickener: 5%,
All the other are aqueous solvent.
In the present embodiment, the glue class thickening material in anti-settling additive is guar gum and gum arabic, and the quality mixture ratio of guar gum and gum arabic is at 2:1.Cellulose thickener in anti-settling additive is 30000 fiber type elements and 100000 fiber types element, and the quality mixture ratio of 30000 fiber type elements and 100000 fiber type elements is at 3:1.
In the present embodiment, silane coupling agent is the mixture of the hydrolyzate of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and vinyltriethoxysilane, and its mass mixing ratio is at 1:2.
Detected result is in Table 2.
Embodiment 4: numbering No.4
Except following difference, other are as embodiment 1:
All the other are aqueous solvent.
In the present embodiment, anti-settling additive is the solution of mineral soil, glue class thickening material, cellulose thickener cooperation, and its proportioning is:
Mineral soil: 5%
Glue class thickening material: 1%
Cellulose thickener: 2%
All the other are aqueous solvent.
In the present embodiment, the mineral soil in anti-settling additive is selected from inorganic bentonite and high clay, and its quality mixture ratio is at 2:1.Glue class thickening material in anti-settling additive is gum arabic and xanthan gum, and the quality mixture ratio of gum arabic and xanthan gum is at 1:3.Cellulose thickener in anti-settling additive is 30000 fiber type elements, 100000 fiber type elements and 200000 fiber types element, and the quality mixture ratio of 30000 fiber type elements, 100000 fiber type elements and 200000 fiber type elements is at 3:1:1.
In the present embodiment, silane coupling agent is gamma-mercaptopropyltriethoxysilane.
Detected result is in Table 2.
Embodiment 5: numbering No.5
Except following difference, other are as embodiment 1:
All the other are aqueous solvent.
In the present embodiment, rare-earth salts mixing solutions is the solution that Yttrium trinitrate, hydrogen peroxide, acetic acid and nitric acid coordinate, and its proportioning is:
All the other are aqueous solvent.
In the present embodiment, anti-settling additive is the solution of mineral soil, glue class thickening material, cellulose thickener cooperation, and its proportioning is:
Mineral soil: 4.5%
Glue class thickening material: 1.1%
Cellulose thickener: 2.3%
All the other are aqueous solvent.
In the present embodiment, the mineral soil in anti-settling additive is selected from polygorskite and natural mica powder, and its quality mixture ratio is at 2:3.Glue class thickening material in anti-settling additive is gum arabic and gelatin, and the quality mixture ratio of gum arabic and gelatin is at 1:3.Cellulose thickener in anti-settling additive is 30000 fiber type elements, 100000 fiber type elements and 200000 fiber types element, and the quality mixture ratio of 30000 fiber type elements, 100000 fiber type elements and 200000 fiber type elements is at 3:1:2.
In the present embodiment, silane coupling agent is the mixture of the hydrolyzate of N-(β-aminoethyl)-γ-aminopropyltrimethoxysilane and gamma-mercaptopropyltriethoxysilane, and its mass mixing ratio is at 2:3.
Detected result is in Table 2.
Embodiment 6: numbering No.6
Except following difference, other are as embodiment 1:
All the other are aqueous solvent.
In the present embodiment, rare-earth salts mixing solutions is the solution that rare-earth salts, superoxide, buffer reagent and nitric acid coordinate, and its proportioning is:
All the other are aqueous solvent.
In the present embodiment, the rare-earth salts in rare-earth salts mixing solutions is the mixture of Yttrium trinitrate and cerous nitrate, and its quality mixture ratio is at 2:1.Superoxide in rare-earth salts mixing solutions is sodium peroxide and barium peroxide, and the quality mixture ratio of sodium peroxide and barium peroxide is at 3:2.Buffer reagent in rare-earth salts mixing solutions is boric acid and acetic acid, and the quality mixture ratio of boric acid and acetic acid is in 1～5:2～4.
In the present embodiment, anti-settling additive is the solution of mineral soil, xanthan gum, cellulose thickener cooperation, and its proportioning is:
Mineral soil: 1.5%
Xanthan gum: 3%
Cellulose thickener: 4.5%
All the other are aqueous solvent.
In the present embodiment, the mineral soil in anti-settling additive is selected from organobentonite and natural mica powder, and its quality mixture ratio is at 2:5.Cellulose thickener in anti-settling additive is Type 3U and 200000 fiber types element, and the quality mixture ratio of Type 3U and 200000 fiber type elements is at 5:1.
In the present embodiment, silane coupling agent is vinyltriethoxysilane, 1, the mixture of the hydrolyzate of 2-two (Trimethoxy silane ethane) and γ-aminopropyl triethoxysilane, and its mass mixing ratio is at 1:3:1.
Detected result is in Table 2.
Embodiment 7: numbering No.7
Except following difference, other are as embodiment 6:
Organic resin: 30%
In the present embodiment, rare-earth salts mixing solutions is the solution that rare-earth salts, superoxide, buffer reagent and nitric acid coordinate, and its proportioning is:
All the other are aqueous solvent.
In the present embodiment, the rare-earth salts in rare-earth salts mixing solutions is Yttrium trinitrate, cerous nitrate, praseodymium chloride, neodymium nitrate mixture, and its quality mixture ratio is at 2:1:1:1.Superoxide in rare-earth salts mixing solutions is hydrogen peroxide and sodium peroxide, calcium peroxide, and the quality mixture ratio of hydrogen peroxide and sodium peroxide, calcium peroxide is at 2:1:1.Buffer reagent in rare-earth salts mixing solutions is boric acid and acetic acid, and the quality mixture ratio of boric acid and acetic acid is at 5:2.
In the present embodiment, anti-settling additive is the solution of mineral soil, xanthan gum, cellulose thickener cooperation, and its proportioning is:
Mineral soil: 1.5%
Xanthan gum: 3%
Cellulose thickener: 4.5%
All the other are aqueous solvent.
In the present embodiment, the mineral soil in anti-settling additive is selected from organobentonite and natural mica powder, and its quality mixture ratio is at 2:5.Cellulose thickener in anti-settling additive is Type 3U and 200000 fiber types element, and the quality mixture ratio of Type 3U and 200000 fiber type elements is at 5:1.
In the present embodiment, silane coupling agent is the mixture of the hydrolyzate of γ-aminopropyl triethoxysilane, gamma-mercaptopropyltriethoxysilane and 1,2-two (Trimethoxy silane ethane), and its mass mixing ratio is at 1:3:1.
Detected result is in Table 2.
Embodiment 8: numbering No.8
Except following difference, other are as embodiment 7:
Organic resin: 40%
Detected result is in Table 2.
Table 1 the present invention has high punching performance non-oriented electrical steel environment friendly insulating coating salient features detection method
Table 2 the present invention has high punching performance non-oriented electrical steel environment friendly insulating coating salient features detected result
A kind of organic/inorganic Environmental Protective Water-paint that high punching performance non-oriented electrical steel environmental protection insulation compound is one-component that has of the present invention, be applicable to various roller coating technologies in cold-rolled non-oriented electrical steel surface-coated, through suitable hot setting, process and form insulating coating, the characteristics such as the insulating coating that obtains has good condition of surface, high tack, high-insulativity, height is anti-corrosion and high temperature resistant, there is Chrome-free and not containing the environmental protection feature of harmful ion, can be widely used in cold-rolled non-oriented electrical steel surface-coated and process.Simultaneously, the present invention is a kind of to be had high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound and possesses good stability and coating, the coating that obtains has the characteristics such as higher tack, insulativity, solidity to corrosion and high thermal resistance, there is Chrome-free simultaneously and not containing the environmental protection feature of any harmful element, be applicable to the surface-coated processing of the orientation-free cold-rolled electrical steel of Multiple Type.The more important thing is, the present invention is by improving organic resin performance and proportioning, overcome the shortcoming of existing environment friendly insulating coating poor heat resistance, coatingsurface state and performance inequality, smoothness and the punching of electrical steel environment friendly insulating coating have greatly been improved, it can be compared favourably with traditional chromate insulating coating, increased substantially user's die life and processing precision of products, be conducive to enhance productivity, reduced costs.
Claims (10)
1. there is high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, formulated by the component of following mass percent:
All the other are aqueous solvent.
The rare-earth salts mixing solutions adopting in described formulation for coating material is the solution of rare-earth salts, superoxide, buffer reagent and nitric acid, and while preparing described rare-earth salts mixing solutions, the proportioning of described conjugate solutions is:
All the other are aqueous solvent.
Rare-earth salts in described rare-earth salts mixing solutions be selected from Yttrium trinitrate, cerous nitrate, neodymium nitrate one or more/one or more and one or more the mixture that is selected from ammonium cerous sulfate, praseodymium chloride, cerous chlorate in Yttrium trinitrate, cerous nitrate, neodymium nitrate;
All the other are aqueous solvent.
2. as claimed in claim 1 have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, described silicon sol adding proportion is 0.8%～3%.
3. as claimed in claim 1 have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the ratio of component of described magnesium oxide and phosphoric acid is respectively 1～3%-1～7%.
4. as claimed in claim 1 have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the organic resin in formulation for coating material is be selected from polymolecularity water-borne acrylic resin, aqueous epoxy resins or its two mixture a kind of.
5. as claimed in claim 1 have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, the polymolecularity of the organic resin in described formulation for coating material is characterized as molecular weight and is no more than 10000, and the kinetic viscosity of resin own is less than 50mPa.s.
6. as claimed in claim 1 have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, for can mix by arbitrary proportion with water, long-term standingly there is not simple organic resin and separate out the layering causing in the organic resin in described formulation for coating material with the compatible characteristics of system.
7. as claimed in claim 1 have a high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, described insulation compound comprises anti-settling additive: 3%～20%, described anti-settling additive is the solution that mineral soil, glue class thickening material, cellulose thickener and water coordinate, and its quality mixture ratio is:
Mineral soil: 0.1%～5%
Glue class thickening material: 0.1%～5%
Cellulose thickener: 0.1%～5%.
8. the preparation method described in claim 1 with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound:
It is characterized in that, comprise following operation:
(1) silicon sol is fully mixed with phosphate dihydrogen aluminum solution;
(2) add successively phosphoric acid and magnesium oxide, fully stir and add a small amount of aqueous solvent to reacting completely, magnesium oxide all dissolves;
(3) mix the solution that above-mentioned steps obtains, be stirred well to few 1h;
(4) slowly add rare-earth salts mixing solutions, limit edged stirs, until be dissolved as homogeneous phase completely;
(5) slowly add silane coupling agent, limit edged stirs, until be dissolved as homogeneous phase completely;
(6) slowly add organic resin, limit edged stirs, until be dissolved as homogeneous phase completely;
(7) slowly add anti-settling additive, limit edged stirs, until be dissolved as homogeneous phase completely;
(8) water is fixed molten, and fully stirs 1h, even to Solution Dispersion, adopts 200 mesh filter screens to filter, the coating that gets product, wherein,
All the other are aqueous solvent,
The rare-earth salts mixing solutions adopting in described formulation for coating material is the solution of rare-earth salts, superoxide, buffer reagent and nitric acid, and while preparing described rare-earth salts mixing solutions, the quality mixture ratio of described conjugate solutions is:
All the other are aqueous solvent;
Rare-earth salts in described rare-earth salts mixing solutions be selected from Yttrium trinitrate, cerous nitrate, neodymium nitrate one or more/one or more and one or more the mixture that is selected from ammonium cerous sulfate, praseodymium chloride, cerous chlorate in Yttrium trinitrate, cerous nitrate, neodymium nitrate.
9. the preparation method described in claim 8 with high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound:
It is characterized in that, in step (6), slowly add organic resin, limit edged stirs, until after being dissolved as homogeneous phase completely,
(7) slowly add anti-settling additive, limit edged stirs, until be dissolved as homogeneous phase completely,
Described anti-settling additive 3%～20%, described anti-settling additive is the solution that mineral soil, glue class thickening material, cellulose thickener and water coordinate, its quality mixture ratio is:
Mineral soil: 0.1%～5%
Glue class thickening material: 0.1%～5%
Cellulose thickener: 0.1%～5%.
10. there is as claimed in claim 1 the application of high punching performance non-oriented electrical steel aqueous, environmental protective insulation compound, it is characterized in that, it is characterized in that, comprise the steps:
(1) before coating, first siliconized plate is passed through to oil removing, alkali cleaning, acid etching, washing successively;
(2) on electrical steel, apply the described electric steel insulating paint that aforesaid method makes;
(3) described coating processes is roller coat;
(4) solidification value is 300～400 ℃, and the residence time is 60s～240s;
(5) forming thickness is the electric steel insulating coating of 0.3～8 μ m.
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| CN111748248A (en) * | 2020-06-15 | 2020-10-09 | 武汉钢铁有限公司 | Chromium-free semi-organic insulating paint suitable for Bi-containing ultrahigh magnetic induction oriented silicon steel without bottom layer |
| WO2022088134A1 (en) * | 2020-10-31 | 2022-05-05 | 河北比尔尼克新材料科技股份有限公司 | Waterborne environment-friendly insulating coating, preparation method therefor and application thereof |
| CN113337146A (en) * | 2021-05-28 | 2021-09-03 | 武汉慧晶新材料科技股份有限公司 | Auxiliary agent for silicon steel water-based inorganic insulating coating and preparation method thereof |
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