CN101643625A - Insulating paint of semi-inorganic environmental non-oriented silicon steel insulating paint and application thereof - Google Patents
Insulating paint of semi-inorganic environmental non-oriented silicon steel insulating paint and application thereof Download PDFInfo
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- CN101643625A CN101643625A CN200910194759A CN200910194759A CN101643625A CN 101643625 A CN101643625 A CN 101643625A CN 200910194759 A CN200910194759 A CN 200910194759A CN 200910194759 A CN200910194759 A CN 200910194759A CN 101643625 A CN101643625 A CN 101643625A
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Abstract
The invention relates to an insulating paint of non-oriented silicon steel and discloses an insulating paint of semi-inorganic environmental non-oriented silicon steel insulating paint and an application thereof. The paint of the invention comprises the following components by weight percent: 5-20% of magnesium isopropylate, 5-25% of polyurethane-acrylate-ethylene oxide resin, 5-40% of aluminium dihydrogen phosphate, 5-10% of zinc acetate, 11-30% of colloidal silica, 1-5% of non-ionic surface active agent and the balance deionized water. The insulating paint of semi-inorganic environmental non-oriented silicon steel insulating paint of the invention can not only completely eliminate the environmental problem caused by chromium element, but also ensure that all the performances of the paintsuch as uniformity, corrosion resistance, heat resistance, weldability and the like are good.
Description
Technical field
The present invention relates to a kind of environment-friendly type organic and inorganic compo composition and application thereof that is used to form insulating coating, be used for the silicon steel insulating coating preparing technical field.
Background technology
Stacking factor that non orientating silicon steel is even because of its thickness, dimensional precision is high, smooth surface is smooth and higher and magnetism of material can be widely used as the core material of motor and transformer.For reducing the non orientating silicon steel eddy losses, guarantee that non orientating silicon steel has higher surface resistivity, make the interlayer power loss reduce to minimum, protect silicon steel to avoid the erosion and the corrosion of various corrosive mediums simultaneously, need carry out the insulation layer coating processing at surface of silicon steel.
The non-oriented silicon steel insulating coating is the insulating coating that one deck of being coated in the non orientating silicon steel surface is become to be grouped into by number of chemical.It can guarantee that non orientating silicon steel has higher surface resistivity, makes the interlayer power loss reduce to minimum; Protect non orientating silicon steel to avoid the erosion and the corrosion of various corrosive mediums simultaneously.Non orientating silicon steel surface insulation coating mainly includes organic coating, inorganic coating and half inorganic coating three major types, and total development trend is that organic coating is eliminated gradually, and inorganic coating will replace half inorganic coating gradually.But owing to be subjected to the restriction of each side condition and the attribute of inorganic coating itself, using more at present still is half inorganic coating.
Patent US 484753 has proposed a kind of method that forms one deck insulating coating on non-oriented silicon steel sheet.Mainly comprise acrylic resin, guanamine resin, chromic salt, emulsifying agent and dispersion agent in the prescription, form antiknock permeability good insulation coating.The formulation for coating material of insulating coating mainly comprises (methyl) Emulsion acrylic resin that contains unsaturated carboxylic acid on the non-oriented silicon steel sheet that patent US 483087 proposes, and adopts Powdered methyl methacrylate to improve the welding property of coating.Patent US 5624749 utilizes emulsion polymerisation process to prepare hud typed emulsion in addition, examines to be crosslinked hydrophobicity Resins, epoxy, and shell is the hydrophilic acrylic resin, and the insulating film that makes has the good comprehensive performance.
The environment-friendly type coating that does not contain chromium has been invented in order to overcome the shortcoming that contains chromium half inorganic coating by company of Nippon Steel, Amoca Corp.That is: inorganic solution aluminum phosphate/100 part Al than solution
2O
3/ H
3PO
4Amount of substance than for 0.13-0.3.Less than 0.13, free phosphoric acid is many, and water absorbability was bad when baking was dry; Greater than 0.3 o'clock, aluminum phosphate itself was unstable, easily separates out from solution.Reach the organic resin of 6-50 part, organic resin is selected one or more for use in vinylformic acid, vinylbenzene, vinyl acetate between to for plastic, polyethylene, polypropylene, poly-phthalein amine, polycarbonate, trimeric cyanamide, Resins, epoxy, the polymer of these materials, crosslinked body all can use, also can add materials such as aluminium sesquioxide, titanium dioxide as required, vitrifying agent such as phosphorous acid, water glass and other inorganic additive are to guarantee high thermal resistance, insulativity.With half inorganic solution for preparing, on annealed wire, control coated weight to be coated with baking dry with the roller that is coated with of trough of belt.The insulating coating weight optimum range that forms on the surface of silicon steel is 0.5-4.0g/m
2Between, weight is less than 0.5g/m
2The time, punching can not get guaranteeing; Weight is greater than 4.0g/m
2The time, insulating coating has the danger of being stripped from during stress relieving.Best use range is at 1.0-2.5g/m
2Between, what can obtain in this scope that coating performance is good, outward appearance is bright and clean films.
Chinese patent 98125437.3 mentioned coatings have used commercial acid acrylic resin to be dispersed in this type of coating of preparation in the water by pure ethers organic solvent, have mainly improved the water absorbing properties of coating, make coating be difficult for being clamminess in the atmospheric environment of humidity.
By analysis, draw this class half inorganic mixing coating layer prescription and may have excellent comprehensive performances above-mentioned document.Though this type coating has been got rid of the influence to the harm of environment and human body of chromium element, volatile organic matter, it is undesirable on performances such as thermotolerance and weldability.
Summary of the invention
The object of the present invention is to provide a kind of semi-inorganic environmental non-oriented silicon steel insulation compound, not only eliminated the environmental issue that the chromium element brings fully, and can guarantee every excellent property such as thermotolerance, weldability of coating.
In order to develop the organic and inorganic compo composition that does not contain chromium cpd but can obtain every excellent property excellences such as thermotolerance, weldability, the present invention works out a kind of semi-inorganic environmental non-oriented silicon steel insulation compound that contains magnesium isopropoxide and zinc acetate, based on the total mass of coating, its chemical composition and corresponding mass percent are:
Magnesium isopropoxide, 5-20%, preferred 10-15%;
Polyurethane-acrylate-ethylene oxide resin, 5-25%, preferred 5-10%;
Aluminium dihydrogen phosphate, 5-40%, preferred 25-35%;
Zinc acetate, 5-10%
Colloid silica, 11-30%, preferred 12-14%;
Nonionogenic tenside, 1-5%;
Surplus is a deionized water.
The magnesium isopropoxide that the present invention uses plays important effect to thermotolerance, the weldability of improving coating.If its content is low excessively, thermotolerance and weldability are not strong; If too high, then the appearance property to coating is affected after the thermal treatment that discharges stress.The magnesium isopropoxide consumption that the present invention uses should account for the 5-20% of coating total mass.
Polyurethane-acrylate-ethylene oxide resin that the present invention uses, by the reacting ethylene oxide of the acrylate of the urethane of mass percent 20-50%, 25-50% and 10-30%, the molecular weight of gained polyurethane-acrylate-ethylene oxide resin is between 1000-20000, and their mean particle size should be between 0.2-2 μ m.And the pH value of coating is between 2-5.Polyurethane-acrylate used in the present invention-ethylene oxide resin consumption should account for the 5-25% of coating total mass.
In order to make the coating environmental protection and not contain the chromium element, aluminium dihydrogen phosphate has important effect to high temperature resistant, antidetonation, antistripping and the insulativity etc. that improve coating.The consumption of aluminium dihydrogen phosphate of the present invention accounts for the 5-40% of coating total mass.
The adding of zinc acetate can make the outward appearance of coating change, if the amount that adds is few, then the outward appearance of coating is undesirable; If add-on is too much, then this coated film may be peeled off after the thermal treatment that discharges stress.The add-on of zinc acetate accounts for the 5-10% of masking liquid total mass.
Colloid silica is that diameter is that nano level silicon-dioxide ultra-fine particles is dispersed in the oyster white colloidal solution in the water.Ion at the colloid silica particle surface is the hydration type, because of water molecules covers wetting ability is arranged.As the compounding ingredient of coating to improve associativity, wearability and stain resistance.
In successive roller coating operating period, the pressure between the roller causes that temperature raises, thereby makes the water component evaporation that is coated with in the liquor.Therefore, inorganic salt and organic constituents rapid drying, and can be solid phase by liquid phase transition, the result produces tackiness, and its irreversible be water-soluble.In order to prevent this phenomenon, add nonionogenic tenside.But if non-ionic surfactant concentration is low excessively, then the performance of coating solution changes around roller, so that can cause producing tackiness, and solidified solution is adhered on the roller surface, forms thick-layer.If its content is excessive, then a large amount of foams that produce in treatment solution cause the aesthetic feeling of coated film to worsen.Therefore the content of nonionogenic tenside accounts for the 1-5% of masking liquid total mass among the present invention.The commercially available acquisition of nonionogenic tenside is as TRITONX-407.
Main preparation process is: polyurethane-acrylate-ethylene oxide resin and deionized water are joined in the reaction vessel, add aluminium dihydrogen phosphate, magnesium isopropoxide, zinc acetate, colloid silica and nonionogenic tenside more respectively, uniform mixing promptly.
Semi-inorganic environmental non-oriented silicon steel insulation compound of the present invention can be used as the non-oriented silicon steel insulating coating.
Semi-inorganic environmental non-oriented silicon steel insulation compound of the present invention, not only eliminated the environmental issue that the chromium element brings fully, and can provide surface of good resistivity, make the interlayer power loss reduce to minimum, good anti-water vapor receptivity is arranged, the tack good with surface of steel plate can be provided, make every excellent propertys such as homogeneity, rotproofness, thermotolerance, weldability of coating, reach the erosion resistance, punching and the anti-annealing that are equal to the coating that contains chromium.
Embodiment
The insulation compound that goes out by formulation as shown in table 1 is applied to not have and is orientated on the steel plate, carries out thermal treatment in 30 seconds under 650 ℃, can obtain the silicon steel sheet that thickness is the insulating coating film of 1.5 μ m.
Concrete preparation process is as follows: the formula rate of pressing table 1, polyurethane-acrylate-the ethylene oxide resin and the deionized water of respective amount are joined in the reaction vessel, the aluminium dihydrogen phosphate, magnesium isopropoxide, zinc acetate, colloid silica and the nonionogenic tenside that add respective amount more respectively successively, stirring makes coating.
The prescription (surplus is a deionized water) as shown in table 1 that each is formed:
The composition of table 1 coating composition
(annotate: A is a magnesium isopropoxide, and B polyurethane-acrylate-ethylene oxide resin, C are aluminium dihydrogen phosphate, and D is a zinc acetate, and E is a colloid silica, and F is a nonionogenic tenside, is the commodity TRITONX-407 type of U.S. combinating carbide company.)
Embodiment 1 and polyurethane-acrylate-ethylene oxide resin of 3 are for being obtained through polymerization by the urethane of mass percent 40%, 50% acrylate and 10% oxyethane, the molecular weight of gained polyurethane-acrylate-ethylene oxide resin is between 1000-20000, their mean particle size is at 0.2 μ m, and the pH value of coating solution is 3.Polyurethane-acrylate-ethylene oxide resin of embodiment 4-6 be by the reacting ethylene oxide of 20% urethane, 50% acrylate and 30%, the molecular weight of gained polyurethane-acrylate-ethylene oxide resin is between 1000-20000, their mean particle size is at 2 μ m, and the pH value of coating solution is 2.Polyurethane-acrylate-ethylene oxide resin of embodiment 7-10 be by the reacting ethylene oxide of 50% urethane, 27% acrylate and 23%, the molecular weight of gained polyurethane-acrylate-ethylene oxide resin is between 1000-20000, their mean particle size is at 1.2 μ m, and the pH value of coating solution is 4.Comparative Examples 1-4 is identical with polyurethane-acrylate-ethylene oxide resin of embodiment 1-3.
The various performances of table 2 coating that to be expressions obtain by the method for table 1.To being divided into of erosion resistance: on the insulating coating surface, represent with zero during rustless situation, represent with ◇ during situation that part is got rusty, represent with x during the situation of getting rusty on a large scale; For the weldability of coating, represent with zero when fine, represent with ◇ when general, represent with x when bad; The appearance of coat aesthetic feeling is represented with zero, generally uses ◇, and aesthetic feeling is not represented with x; Tack is well represented with zero, generally uses ◇, and difference is represented with x; Represent with zero during good heat resistance, generally use ◇, difference is represented with x.Insulativity is evaluated by measuring its interlamination resistance, represents with zero when good, generally represents with ◇, represents with x during difference.
Tack is measured with reference to GB2522-88, and corrosion resistance measurement is with reference to GB3826-1999, GB5944-86, and the mensuration of insulativity is to adopt the Frankin tester, the evaluation of appearance of coat performance is judged by SEM.
The comparison of table 2 coating performance
Can learn that from table 2 under the condition of embodiment 1-10, the characteristic of coating such as aesthetic feeling, insulation strength, erosion resistance, coating stripping and weldability are all excellent.This is owing to filled resin and inorganic additives between phosphate crystal, thereby makes the compact structure of coating.
Comparative Examples 2 is compared with embodiment 2, the magnesium isopropoxide too high levels, and it is relatively poor that every performance of coating is compared embodiment 2.In the Comparative Examples 1, magnesium isopropoxide content is on the low side, and insulativity, thermotolerance and weldability all can not be satisfactory.And in other Comparative Examples, the performance of film is affected because of other content is undesirable.
Claims (9)
1. semi-inorganic environmental non-oriented silicon steel insulation compound, based on the total mass of coating, its component and corresponding mass percent are:
Magnesium isopropoxide, 5-20%;
Polyurethane-acrylate-ethylene oxide resin, 5-25%;
Aluminium dihydrogen phosphate, 5-40%;
Zinc acetate, 5-10%
Colloid silica, 11-30%;
Nonionogenic tenside, 1-5%;
Surplus is a deionized water.
2. semi-inorganic environmental non-oriented silicon steel insulation compound according to claim 1 is characterized in that based on the total mass of coating, the mass percent of described magnesium isopropoxide is 10-15%.
3. semi-inorganic environmental non-oriented silicon steel insulation compound according to claim 1 is characterized in that based on the total mass of coating, the mass percent of described polyurethane-acrylate-ethylene oxide resin is 5-10%.
4. semi-inorganic environmental non-oriented silicon steel insulation compound according to claim 1 is characterized in that based on the total mass of coating, the mass percent of described aluminium dihydrogen phosphate is 25-35%.
5. semi-inorganic environmental non-oriented silicon steel insulation compound according to claim 1 is characterized in that based on the total mass of coating, the mass percent of described colloid silica is 12-14%.
6. as semi-inorganic environmental non-oriented silicon steel insulation compound as described in arbitrary claim among the claim 1-5, it is characterized in that, described polyurethane-acrylate-ethylene oxide resin be by the reacting ethylene oxide of the acrylate of the urethane of mass percent 20-50%, 25-50% and 10-30%.
7. as semi-inorganic environmental non-oriented silicon steel insulation compound as described in arbitrary claim among the claim 1-5, it is characterized in that the molecular-weight average of described polyurethane-acrylate-ethylene oxide resin is between 1000-20000.
8. as semi-inorganic environmental non-oriented silicon steel insulation compound as described in arbitrary claim among the claim 1-5, it is characterized in that the mean particle size of described polyurethane-acrylate-ethylene oxide resin is between 0.2-2 μ m.
As semi-inorganic environmental non-oriented silicon steel insulation compound as described in arbitrary claim among the claim 1-8 as the non-oriented silicon steel insulating coating.
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| CN2009101947597A CN101643625B (en) | 2009-08-28 | 2009-08-28 | Insulating paint of semi-inorganic environmental non-oriented silicon steel insulating paint and application thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101857761A (en) * | 2010-06-01 | 2010-10-13 | 上海迪升防腐新材料科技有限公司 | Environment-friendly non-oriented silicon steel insulating coating and application thereof |
| CN101974279A (en) * | 2010-11-23 | 2011-02-16 | 上海迪升防腐新材料科技有限公司 | Environment-friendly semi-inorganic non-oriented silicon steel insulating coating |
| CN102101961A (en) * | 2010-12-30 | 2011-06-22 | 上海迪升防腐新材料科技有限公司 | Organic-inorganic environment-friendly insulating coating solution and application thereof |
| CN102344701A (en) * | 2010-07-30 | 2012-02-08 | 上海迪升防腐新材料科技有限公司 | Surface coating for non-oriented silicon steel and application of surface coating |
| CN103468034A (en) * | 2013-09-09 | 2013-12-25 | 华东理工大学 | Method for preparing semi-inorganic styrene-acrylic silicon steel insulating coating through in-situ compatibilization polymerization |
| CN105153930A (en) * | 2015-09-16 | 2015-12-16 | 上海迪升防腐新材料科技有限公司 | Non-oriented silicon steel coating and application thereof |
| CN110099980A (en) * | 2016-12-23 | 2019-08-06 | Posco公司 | The manufacturing method of non-oriented electromagnetic steel sheet adhesive coating composition and non-oriented electromagnetic steel sheet product |
| CN110819879A (en) * | 2019-11-22 | 2020-02-21 | 马鞍山钢铁股份有限公司 | Non-oriented silicon steel with excellent magnetic property and manufacturing method thereof |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101857761A (en) * | 2010-06-01 | 2010-10-13 | 上海迪升防腐新材料科技有限公司 | Environment-friendly non-oriented silicon steel insulating coating and application thereof |
| CN102344701A (en) * | 2010-07-30 | 2012-02-08 | 上海迪升防腐新材料科技有限公司 | Surface coating for non-oriented silicon steel and application of surface coating |
| CN102344701B (en) * | 2010-07-30 | 2013-08-07 | 上海迪升防腐新材料科技有限公司 | Surface coating for non-oriented silicon steel and application of surface coating |
| CN101974279A (en) * | 2010-11-23 | 2011-02-16 | 上海迪升防腐新材料科技有限公司 | Environment-friendly semi-inorganic non-oriented silicon steel insulating coating |
| CN102101961A (en) * | 2010-12-30 | 2011-06-22 | 上海迪升防腐新材料科技有限公司 | Organic-inorganic environment-friendly insulating coating solution and application thereof |
| CN102101961B (en) * | 2010-12-30 | 2012-12-19 | 上海迪升防腐新材料科技有限公司 | Organic-inorganic environment-friendly insulating coating solution and application thereof |
| CN103468034A (en) * | 2013-09-09 | 2013-12-25 | 华东理工大学 | Method for preparing semi-inorganic styrene-acrylic silicon steel insulating coating through in-situ compatibilization polymerization |
| CN103468034B (en) * | 2013-09-09 | 2015-10-28 | 华东理工大学 | A kind of In Situ Compatibilization is polymerized the preparation method of half inorganic styrene-acrylic silicon steel insulating coating |
| CN105153930A (en) * | 2015-09-16 | 2015-12-16 | 上海迪升防腐新材料科技有限公司 | Non-oriented silicon steel coating and application thereof |
| CN105153930B (en) * | 2015-09-16 | 2017-08-25 | 上海迪升防腐新材料科技有限公司 | A kind of non-orientation silicon steel coating and its application |
| CN110099980A (en) * | 2016-12-23 | 2019-08-06 | Posco公司 | The manufacturing method of non-oriented electromagnetic steel sheet adhesive coating composition and non-oriented electromagnetic steel sheet product |
| CN110099980B (en) * | 2016-12-23 | 2021-11-19 | Posco公司 | Non-oriented electrical steel plate adhesive coating composition and method for manufacturing non-oriented electrical steel plate product |
| US11505723B2 (en) | 2016-12-23 | 2022-11-22 | Posco | Adhesive coating composition for non-oriented electrical steel sheet, and method for manufacturing non-oriented electrical steel sheet |
| CN110819879A (en) * | 2019-11-22 | 2020-02-21 | 马鞍山钢铁股份有限公司 | Non-oriented silicon steel with excellent magnetic property and manufacturing method thereof |
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Denomination of invention: Semi environment friendly non oriented silicon steel insulating coating and its application Effective date of registration: 20210909 Granted publication date: 20110824 Pledgee: The Bank of Shanghai branch Caohejing Limited by Share Ltd. Pledgor: SHANGHAI DISHENG ANTICORROSION NEW MATERIAL TECHNOLOGY Co.,Ltd. Registration number: Y2021310000063 |
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