CN102079923B - Environmental friendly chromium-free insulating paint - Google Patents
Environmental friendly chromium-free insulating paint Download PDFInfo
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- CN102079923B CN102079923B CN 200910199396 CN200910199396A CN102079923B CN 102079923 B CN102079923 B CN 102079923B CN 200910199396 CN200910199396 CN 200910199396 CN 200910199396 A CN200910199396 A CN 200910199396A CN 102079923 B CN102079923 B CN 102079923B
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- zirconium
- coating
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- chromium
- parts
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- 239000003973 paint Substances 0.000 title abstract description 8
- 230000007613 environmental effect Effects 0.000 title abstract description 7
- 238000000576 coating method Methods 0.000 claims abstract description 75
- 239000011248 coating agent Substances 0.000 claims abstract description 74
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 claims abstract description 8
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 33
- 238000009413 insulation Methods 0.000 claims description 21
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 16
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 14
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- -1 Chloroalkyl Acrylates Chemical class 0.000 claims description 7
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 claims description 7
- 229920006026 co-polymeric resin Polymers 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 4
- 150000004706 metal oxides Chemical class 0.000 claims description 4
- 229910021518 metal oxyhydroxide Inorganic materials 0.000 claims description 4
- 239000011118 polyvinyl acetate Substances 0.000 claims description 4
- 229920003987 resole Polymers 0.000 claims description 4
- 229910000976 Electrical steel Inorganic materials 0.000 abstract description 15
- 230000007797 corrosion Effects 0.000 abstract description 11
- 238000005260 corrosion Methods 0.000 abstract description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 abstract description 3
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000004519 manufacturing process Methods 0.000 abstract description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 abstract 1
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 abstract 1
- DUFCMRCMPHIFTR-UHFFFAOYSA-N 5-(dimethylsulfamoyl)-2-methylfuran-3-carboxylic acid Chemical compound CN(C)S(=O)(=O)C1=CC(C(O)=O)=C(C)O1 DUFCMRCMPHIFTR-UHFFFAOYSA-N 0.000 abstract 1
- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 abstract 1
- 150000001845 chromium compounds Chemical class 0.000 abstract 1
- 229920001577 copolymer Polymers 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 abstract 1
- 239000005011 phenolic resin Substances 0.000 abstract 1
- 229920001568 phenolic resin Polymers 0.000 abstract 1
- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 abstract 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 19
- 238000012360 testing method Methods 0.000 description 13
- 229920005989 resin Polymers 0.000 description 12
- 239000011347 resin Substances 0.000 description 12
- 235000011007 phosphoric acid Nutrition 0.000 description 10
- 238000004080 punching Methods 0.000 description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 9
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 6
- RGPUVZXXZFNFBF-UHFFFAOYSA-K diphosphonooxyalumanyl dihydrogen phosphate Chemical class [Al+3].OP(O)([O-])=O.OP(O)([O-])=O.OP(O)([O-])=O RGPUVZXXZFNFBF-UHFFFAOYSA-K 0.000 description 6
- QQFLQYOOQVLGTQ-UHFFFAOYSA-L magnesium;dihydrogen phosphate Chemical compound [Mg+2].OP(O)([O-])=O.OP(O)([O-])=O QQFLQYOOQVLGTQ-UHFFFAOYSA-L 0.000 description 6
- 206010009866 Cold sweat Diseases 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 239000011701 zinc Substances 0.000 description 5
- 229910052804 chromium Inorganic materials 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 238000009472 formulation Methods 0.000 description 4
- 239000011777 magnesium Substances 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 238000012423 maintenance Methods 0.000 description 4
- 238000007761 roller coating Methods 0.000 description 4
- VAJVDSVGBWFCLW-UHFFFAOYSA-N 3-Phenyl-1-propanol Chemical compound OCCCC1=CC=CC=C1 VAJVDSVGBWFCLW-UHFFFAOYSA-N 0.000 description 3
- DYUQAZSOFZSPHD-UHFFFAOYSA-N Phenylpropyl alcohol Natural products CCC(O)C1=CC=CC=C1 DYUQAZSOFZSPHD-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 150000003016 phosphoric acids Chemical class 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical class [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 238000007334 copolymerization reaction Methods 0.000 description 2
- 238000006253 efflorescence Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- HXHCOXPZCUFAJI-UHFFFAOYSA-N prop-2-enoic acid;styrene Chemical compound OC(=O)C=C.C=CC1=CC=CC=C1 HXHCOXPZCUFAJI-UHFFFAOYSA-N 0.000 description 2
- 206010037844 rash Diseases 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical class O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 238000010998 test method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- ATYZRBBOXUWECY-UHFFFAOYSA-N zirconium;hydrate Chemical compound O.[Zr] ATYZRBBOXUWECY-UHFFFAOYSA-N 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- ZCILODAAHLISPY-UHFFFAOYSA-N biphenyl ether Natural products C1=C(CC=C)C(O)=CC(OC=2C(=CC(CC=C)=CC=2)O)=C1 ZCILODAAHLISPY-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 230000003628 erosive effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035807 sensation Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical compound [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 description 1
- 229910001866 strontium hydroxide Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- LRXTYHSAJDENHV-UHFFFAOYSA-H zinc phosphate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LRXTYHSAJDENHV-UHFFFAOYSA-H 0.000 description 1
- 229910000165 zinc phosphate Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 description 1
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- Chemical Treatment Of Metals (AREA)
Abstract
An environmental friendly chromium-free insulating paint contains the following components: 100 parts by weight of metal dihydrogen phosphate; 10-200 parts by weight of one or more than one of vinyl acetate, acrylic acid, styrene-acrylic acid copolymer or phenolic resin; 1-40 parts by weight of one or more than one of zirconium acetate, zirconium nitrate, zirconium chloride, zirconium oxychloride, zirconium n-propoxide, and zirconium n-butoxid; and 200-500 parts by weight of pure water. The insulating coating obtained by the paint of the present invention exhibits good corrosion resistance, adhesiveness, and heat resistance; the invention successfully realizes the replacement of chromium compounds and therefore realizes the environmental protection of the production process; and the chromium-free insulating paint is applicable to non-oriented silicon steel.
Description
Technical field
The present invention relates to a kind of insulation compound, relate in particular to a kind of environment-friendly chromium-free insulation compound that does not contain the chromium element that can be used for non orientating silicon steel.
Background technology
The non-oriented silicon steel sheet surface generally is coated with insulating coating, and this coating should be able to provide high-caliber interlamination resistance, so that siliconized plate is after the punching closed assembly becomes stator material, the eddy-current loss of stator is minimum.The manufacturability of siliconized plate requires insulating coating must have good tack, to guarantee not and can come off from the siliconized plate edge when the punching, simultaneously insulating coating in punching press, slot or cut off the excessive efflorescence of Shi Buying, in order to avoid be deposited on feeding roller or the miscellaneous equipment, wearing and tearing are used for punching press or shear the mould of lamination.
Traditional insulating coating often adopts chromic salt as component, and chromic salt is owing to having a carinogenicity, and in environmental requirement day by day harsh today, its use is subject to more and more stricter restriction.
In recent years, the chrome-free insulating coating is developed fast, usually uses at present phosphoric acid salt to replace chromic salt.Therefore easily phosphate coating can provide good insulating property and thermotolerance, but often contains excessive residual phosphoric acid in the phosphoric acid salt, produces the moisture absorption phenomenon (bonding die) that is clamminess, and needs to add the stablizer of residual phosphoric acid.For example European patent EP 1208166B1 adopts 100 parts of aluminium dihydrogen phosphates, 28～98 parts of vinylformic acid-styrene emulsions, 6～18 parts of zinc nitrates, the compound of 4～13 parts of silicon, 18～35g ethylene glycol, and the insulation compound of 3～11g nonionogenic tenside, owing to there not being the stablizer of residual phosphoric acid, therefore show suction and bonding die, owing to having adopted zinc nitrate, affect its solidity to corrosion simultaneously; United States Patent (USP) 5955201 adopts the inorganic silicic acid salt particle as the stablizer of residual phosphoric acid, though effectively avoided the problem of bonding die, inorganic silicic acid salt particle and solution system unmixing very easily produce precipitation, and its effect is difficult to embody when stirring inequality; PCT patent application WO2008/016220A1 adopts cobaltous hydroxide and strontium hydroxide as the stablizer of residual phosphoric acid, also can avoid the bonding die problem, but both is inorganic particle, is difficult to mix.On the whole, existing phosphoric acid salt insulating coating can't substitute the insulating coating that contains chromium fully.
On February 13rd, 2003, EU Committee and European Parliament promulgated two stereotyped commands, that is: the instruction (ROHS) of some objectionable impurities of restriction use in the instruction of electronic and electrical equipment waste (WEEE) and the electronic and electrical equipment.Command request, the index of harmful element must be up to specification in the electric equipment products that on July 1st, 2006 rose to sell on the EU market, and the objectionable impurities that limit has: cadmium, lead, mercury, sexavalent chrome, Polybrominated biphenyl, polymerization bromination biphenyl ether etc.
Summary of the invention
The purpose of this invention is to provide a kind of environment-friendly chromium-free insulation compound, the insulating coating that obtains shows good solidity to corrosion, tack and thermotolerance, successfully realized the replacement of chromium cpd, thereby realized the environmental protection of production process, this Chrome-free insulation coating can be used for non orientating silicon steel.
For achieving the above object, technical scheme of the present invention is,
A kind of environment-friendly chromium-free insulation compound, its composition is:
Metal tripolyphosphate dihydric salt 100 mass parts;
One or more 10～200 mass parts in vinyl acetate, vinylformic acid, Styrene And Chloroalkyl Acrylates copolymerization or the resol;
One or more 1～40 mass parts in acetic acid zirconium, zirconium nitrate, zirconium chloride, basic zirconium chloride, zirconium-n-propylate, the zirconium-n-butylate;
Pure water 200～5000 mass parts.
Further, also comprise organic solvent, i.e. ethylene glycol or glycerol, with respect to the metal tripolyphosphate dihydric salt solution of 100 mass parts, the addition of organic solvent is no more than 50 mass parts.
Described metal tripolyphosphate dihydric salt is Al (H
2PO
4)
3, Mg (H
2PO
4)
2, Ca (H
2PO
4)
2And Zn (H
2PO
4)
2
Described Al (H
2PO
4)
3, its mol ratio that can pass through is 0.14～0.20 Al
2O
3And H
3PO
4Mixing obtaining, also can be 0.28～0.40 Al (OH) by mol ratio
3With H
3PO
4Mix and obtain.
Described for Mg (H
2PO
4)
2, Ca (H
2PO
4)
2And Zn (H
2PO
4)
2, it can be 0.40～0.6 metal oxide or oxyhydroxide and H by mol ratio
3PO
4Mix and obtain.
Chrome-free insulation coating coating method of the present invention, with the surface of above-mentioned Chrome-free insulation coating coating non orientating silicon steel, coating amount is controlled to be 0.6～6g/m
2, baking after applying, storing temperature is 200～550 ℃.
In Chrome-free insulation coating of the present invention,
The metal tripolyphosphate dihydric salt
The metal tripolyphosphate dihydric salt can improve thermotolerance and the solidity to corrosion of insulating coating, and preferred metal tripolyphosphate dihydric salt has Al (H
2PO
4)
3, Mg (H
2PO
4)
2, Ca (H
2PO
4)
2And Zn (H
2PO
4)
2Deng.In the process of preparation coating of the present invention, these metal tripolyphosphate dihydric salts can be commercial finished products, also can obtain by the mode that metal hydroxides or oxide compound mix with phosphoric acid, for example for Al (H
2PO
4)
3, its mol ratio that can pass through is 0.14～0.20 Al
2O
3And H
3PO
4Mixing obtaining, also can be 0.28～0.40 Al (OH) by mol ratio
3With H
3PO
4Mix obtaining, for Mg (H
2PO
4)
2, Ca (H
2PO
4)
2And Zn (H
2PO
4)
2Deng divalent metal, it can be 0.40～0.6 metal oxide or oxyhydroxide and H3PO4 mixing acquisition by mol ratio.The ratio of metal oxide or oxyhydroxide and phosphoric acid is lower than lower limit, and then residual phosphoric acid is too much in the coating, causes the deterioration of insulating coating bonding die and can not use; Being higher than the upper limit then causes coating unstable.The metal tripolyphosphate dihydric salt can be used alone, but also also mix together.
Vinyl acetate, vinylformic acid, Styrene And Chloroalkyl Acrylates copolymerization or resol
Resin is tack and the toughness in order to improve insulating coating in coating, prevents the phenomenon of peeling off between coating and the substrate.This resinoid commonly used is one or more in polyvinyl acetate (PVA), polyacrylic ester, Styrene And Chloroalkyl Acrylates copolymer resins and the resol.With respect to the metal tripolyphosphate dihydric salt of 100 mass parts, the addition of resin is 10～200 mass parts.Resin content very little, then coatingsurface becomes too coarse and coating is easily peeled off and efflorescence, the tack of coating is difficult to be guaranteed, and content is too many, then can reduce thermotolerance and the weldability of insulating coating.In the process of preparation coating of the present invention, these resins also can commercial resin emulsion form provide.
Acetic acid zirconium, zirconium nitrate, basic zirconium chloride, zirconium-n-propylate, zirconium-n-butylate
The present invention is incorporated into acetic acid zirconium, zirconium nitrate, basic zirconium chloride, zirconium-n-propylate, zirconium-n-butylate in the insulation compound, make it in the coating sintering process, to react with phosphate radical, form the stable zirconium phosphate that is difficult for suction, thereby play the purpose of confining the residual phosphorus acid group, reach the problem that the coating moisture absorption is clamminess of eliminating.With respect to the metal tripolyphosphate dihydric salt solution of 100 mass parts, the addition of the compound of zirconium is 1～40 mass parts, if be lower than 1 part, then the problem that is clamminess of coating moisture absorption is not improved, but is higher than 40 parts, then can cause the coating tack significantly to descend.
Organic solvent
Organic solvent belongs to optional composition in the present invention, and it can improve the homogeneity of coating, to adapt to the nothing orientation coating production line of high speed coating.Preferred organic solvent is ethylene glycol, glycerol.With respect to the metal tripolyphosphate dihydric salt solution of 100 mass parts, the addition of organic solvent should be no more than 50 mass parts, otherwise easily causes the solidity to corrosion of coating, weldability to descend.
Pure water
Add a certain amount of pure water, could obtain the good masking liquid of stable coating.Also comprise the water of 200～5000 mass parts in the coating of the present invention, if the mass parts of water is lower than 200, then coating concentration is excessive, and poor stability easily forms precipitation, is difficult to coating, if surpass 5000, then coating concentration is excessively low, is difficult to form uniform coating.
Chrome-free insulation coating of the present invention can obtain by mixing mentioned component, and mixing can be carried out in the reactor of whipping appts.
Chrome-free insulation coating of the present invention adds the coating machine feeder system and just can apply, and coating amount is controlled to be 0.6～6g/m
2, be lower than 0.6g/m
2, the insulativity of coating, erosion resistance etc. are difficult to reach, and are higher than 6g/m
2Then the tack of coating is difficult to guarantee.Storing temperature after the coating is 200～550 ℃, and the too low then residual phosphoric acid of temperature is too much, and the too high resin that then causes of temperature decomposes the coating burning.
Beneficial effect of the present invention
By enforcement of the present invention, can obtain the chrome-free insulating coating non orientating silicon steel product of excellent performance, thereby be more prone to realize to the substituting of Chromium coating, satisfy the country such as European Union to the requirement of silicon steel product process environmental protection.
Embodiment
Embodiment 1
The non orientating silicon steel Chrome-free insulation coating prescription that is comprised of aluminium dihydrogen phosphate, ethylene glycol, vinylformic acid-styrene copolymerized resin, acetic acid zirconium, ethylene glycol and water sees Table 1.After this paint formulation at room temperature adopts magnetic stirring apparatus stirring at low speed 30min, adopt roller coating machine to be coated on the surface of thick 0.5mm orientation free silicon steel plate, the maintenance coating amount is 1.8g/m
2, adopt the naked light roaster, under 200～500 ℃ of plate temperature conditions, toast film forming.According to following condition test film properties, the coating performance result is as shown in table 2.
The weldability test condition: rare gas element tungsten organizational security protects weldering (TIG), current value 120A, electrode materials Th-W, argon flow amount 6L/min, pressure 50kg/cm
2
Solidity to corrosion test: JIS Z2371 (salt-fog test method, Methods of Salt SprayTesting);
Interlamination resistance test: JIS C2550 (test method of magnet steel thin plate and steel band, Test Methodsfor Magnetic Steel and Strip);
Punching property testing: the punching number of times during burr height＞50 μ m;
Tack test: GB 2522-88 (electrical sheet (band) interlamination resistance, coating tack, pile pieces coefficient testing method).
Table 1 unit: mass parts
Table 2
| Numbering | Tack (Φ=20cm) | Punching (burr 50 μ m) | Weldability (cm/min) | Outward appearance | Solidity to corrosion | Interlamination resistance (Ω cm 2/ sheet) |
| 1 | Slightly have and come off | ＞130 ten thousand times | ≤60 | Surface irregularity | 5％ | 40 |
| 2 | Without coming off | ＞170 ten thousand times | ≤45 | Smooth surface | 5％ | 30 |
| 3 | Without coming off | ＞200 ten thousand times | ≤30 | Smooth surface | 5％ | 35 |
| 4 | Without coming off | ＞200 ten thousand times | ≤20 | Smooth surface | 5％ | 34 |
| 5 | Without coming off | ＞200 ten thousand times | ≤15 | Smooth surface | 30％ | 32 |
| 6 | Without coming off | ＞200 ten thousand times | ≤10 | Smooth surface | 70％ | 38 |
| 7 | Slightly have and come off | ＞170 ten thousand times | ≤10 | Smooth surface | Well | 10 |
Can be got by table 2 data, the addition of resin is during less than 10 parts, although weldability is more excellent, but coating is coarse, and tack is poor, and punching is also lower, and when resin content during more than 200 parts, solidity to corrosion, weldability descend obviously, therefore reasonably the resin content scope is 10～200 mass parts.
Embodiment 2:
The non orientating silicon steel Chrome-free insulation coating prescription that is comprised of aluminium dihydrogen phosphate, polyvinyl acetate (PVA), glycerol, zirconium nitrate and water sees Table 3.After this paint formulation at room temperature adopts magnetic stirring apparatus to stir 10min, adopt roller coating machine to be coated on the surface of thick 0.5mm orientation free silicon steel plate, the maintenance coating amount is 1.8g/m
2, adopt the naked light roaster, under 200～500 ℃ of plate temperature conditions, toast film forming.The coating performance result is as shown in table 4.Test condition is as follows:
P stripping test: place waste water to boil 10min on the coating sample of fixed-area, then adopt ICP that the P of stripping in the waste water is tested rear conversion and get.
Surfaces of tacky: use the hand touch-surface, judge whether the sensation that is clamminess.
All the other test conditions are identical with embodiment 1.
Table 3 unit: mass parts
Table 4
| Numbering | Tack (Φ=20cm) | Punching (burr 50 μ m) | Weldability (cm/min) | Outward appearance | Surfaces of tacky | P stripping (μ g/100cm 2) |
| 8 | Without coming off | ＞170 ten thousand times | ≤35 | Smooth surface | Be | 408 |
| 9 | Without coming off | ＞200 ten thousand times | ≤40 | Smooth surface | No | 250 |
| 10 | Without coming off | ＞190 ten thousand times | ≤40 | Smooth surface | No | 102 |
| 11 | Without coming off | ＞160 ten thousand times | ≤40 | Smooth surface | No | 60 |
| 12 | Without coming off | ＞200 ten thousand times | ≤40 | Smooth surface | No | 30 |
| 13 | Without coming off | ＞180 ten thousand times | ≤40 | Smooth surface | No | 30 |
| 14 | Come off | ＞150 ten thousand times | ≤40 | Smooth surface | No | 30 |
| 15 | Slightly have and come off | ＞170 ten thousand times | ≤10 | Smooth surface | Well | \ |
By as seen from Table 4, along with the increase of the compound addition of zirconium, the content of the residual phosphorus acid group in the insulating coating significantly descends, and has significantly improved the phenomenon of insulating coating surfaces of tacky, cause the coating tack to descend but add excessive meeting, reasonably interpolation scope is 1～40 mass parts.
Embodiment 3
The non orientating silicon steel Chrome-free insulation coating prescription that is comprised of primary magnesium phosphate, Styrene And Chloroalkyl Acrylates copolymer resins, zirconium chloride, ethylene glycol and water sees Table 5.After this paint formulation at room temperature adopts magnetic stirring apparatus to stir 10min, adopt roller coating machine to be coated on the surface of thick 0.5mm orientation free silicon steel plate, the maintenance coating amount is 1.8g/m
2, adopt the naked light roaster, under 200～500 ℃ of plate temperature conditions, toast film forming.The coating performance result is as shown in table 6.Test condition is identical with embodiment 1.
Table 5 unit: mass parts
| Numbering | Primary magnesium phosphate | The phenylpropyl alcohol copolymer resins | Ethylene glycol | Zirconium chloride | Water |
| 16 | 100 | 20 | 0 | 3 | 4000 |
| 17 | 100 | 10 | 10 | 2 | 3000 |
| 18 | 100 | 25 | 20 | 18 | 500 |
| 19 | 100 | 200 | 30 | 15 | 5000 |
| 20 | 100 | 150 | 40 | 25 | 1500 |
| 21 | 100 | 20 | 50 | 35 | 2900 |
| 22 | 100 | 60 | 55 | 30 | 300 |
Table 6
| Numbering | Tack (Φ=20cm) | Weldability (cm/min) | Outward appearance | Solidity to corrosion (μ g/100cm 2) |
| 16 | Without coming off | ≤40 | Smooth surface | 5％ |
| 17 | Without coming off | ≤40 | Smooth surface | 5％ |
| 18 | Without coming off | ≤40 | Smooth surface | 5％ |
| 19 | Without coming off | ≤40 | Smooth surface | 5％ |
| 20 | Without coming off | ≤35 | Smooth surface | 10％ |
| 21 | Without coming off | ≤20 | Smooth surface | 30％ |
| 22 | Without coming off | ≤10 | Smooth surface | 70％ |
By as seen from Table 6, the interpolation of a small amount of ethylene glycol can not impact the performance of coating, and after addition surpassed 50 mass parts, weldability, solidity to corrosion descended obviously.
Embodiment 4
Adopt the combination of compound, organic resin, organic solvent and water of other metal tripolyphosphate dihydric salt, zirconium, prescription sees Table 7.After each paint formulation at room temperature adopts magnetic stirring apparatus to stir 10min, adopt roller coating machine to be coated on the surface of thick 0.5mm orientation free silicon steel plate, the maintenance coating amount is 2.2g/m
2, adopt the naked light roaster, under 200～500 ℃ of plate temperature conditions, toast film forming.The coating performance result is as shown in table 8.Test condition is identical with embodiment 1.
Table 7 unit: mass parts
| Numbering | The metal tripolyphosphate dihydric salt | Resin | Organic solvent | The compound of zirconium | Water |
| 23 | Primary zinc phosphate/100 | Phenylpropyl alcohol copolymer resins/50 | Glycerol/10 | Acetic acid zirconium/15 | 200 |
| 24 | Primary magnesium phosphate/100 | Polyvinyl acetate (PVA)/80 | Ethylene glycol/20 | Zirconium nitrate/10 | 110 |
| 25 | Aluminium dihydrogen phosphate/100 | Polyacrylic ester/180 | Ethylene glycol/50 | Basic zirconium chloride/20 | 3000 |
| 26 | Aluminium dihydrogen phosphate/60+ primary magnesium phosphate/40 | Phenylpropyl alcohol copolymer resins/200 | Glycerol/40 | Zirconium-n-butylate/40 | 4000 |
| 27 | Aluminium dihydrogen phosphate/60+ primary magnesium phosphate/40 | Polyacrylic ester/130 | Ethylene glycol/30 | Zirconium-n-propylate/30 | 10000 |
Table 8
| Numbering | Tack (Φ=20cm) | Punching (burr 50 μ m) | Weldability (cm/min) | Solidity to corrosion | P stripping (g/9cm 2) | Interlamination resistance (Ω cm 2/ sheet) |
| 23 | Without coming off | ＞200 ten thousand times | ≤50 | Outstanding | 70 | 60 |
| 24 | Without coming off | ＞200 ten thousand times | ≤45 | Outstanding | 80 | 80 |
| 25 | Without coming off | ＞200 ten thousand times | ≤45 | Outstanding | 18 | 55 |
| 26 | Without coming off | ＞200 ten thousand times | ≤35 | Outstanding | 60 | 94 |
| 27 | Without coming off | ＞200 ten thousand times | ≤50 | Outstanding | 30 | 42 |
By as seen from Table 8, acetic acid zirconium, zirconium nitrate, basic zirconium chloride, zirconium-n-butylate, zirconium-n-propylate etc. can use as improving the auxiliary agent that the Chrome-free coatingsurface is clamminess, and simultaneously primary magnesium phosphate, calcium, zinc and aluminium and combination thereof can obtain good non orientating silicon steel without chromiumcoating.
According to the test-results among the embodiment as seen, by enforcement of the present invention, can obtain the chrome-free insulating coating of excellent performance, thereby realize the substituting of Chromium coating satisfied the requirement of environmental protection.
Claims (5)
1. environment-friendly chromium-free insulation compound, its composition is:
Metal tripolyphosphate dihydric salt 100 mass parts;
One or more 10～200 mass parts in polyvinyl acetate (PVA), polyacrylic ester, Styrene And Chloroalkyl Acrylates copolymer resins and the resol;
One or more 1～40 mass parts in acetic acid zirconium, zirconium nitrate, zirconium chloride, basic zirconium chloride, zirconium-n-propylate, the zirconium-n-butylate;
Pure water 200～5000 mass parts.
2. environment-friendly chromium-free insulation compound as claimed in claim 1 is characterized in that, also comprises organic solvent, i.e. ethylene glycol or glycerol, and with respect to the metal tripolyphosphate dihydric salt of 100 mass parts, the addition of organic solvent is no more than 50 mass parts.
3. Chrome-free insulation coating as claimed in claim 1 is characterized in that, described metal tripolyphosphate dihydric salt is Al (H
2PO
4)
3, Mg (H
2PO
4)
2, Ca (H
2PO
4)
2And Zn (H
2PO
4)
2
4. environment-friendly chromium-free insulation compound as claimed in claim 3 is characterized in that, described Al (H
2PO
4)
3, its mol ratio that can pass through is 0.14～0.20 Al
2O
3And H
3PO
4Mixing obtaining, also can be 0.28～0.40 Al (OH) by mol ratio
3With H
3PO
4Mix and obtain.
5. environment-friendly chromium-free insulation compound as claimed in claim 3 is characterized in that, and is described for Mg (H
2PO
4)
2, Ca (H
2PO
4)
2And Zn (H
2PO
4)
2, it can be 0.40～0.6 metal oxide or oxyhydroxide and H by mol ratio
3PO
4Mix and obtain.
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| CN 200910199396 CN102079923B (en) | 2009-11-26 | 2009-11-26 | Environmental friendly chromium-free insulating paint |
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| ES2693788T3 (en) * | 2014-01-30 | 2018-12-13 | Thyssenkrupp Electrical Steel Gmbh | Flat product of oriented grain electric steel comprising an insulating coating |
| CN107903693A (en) * | 2017-10-24 | 2018-04-13 | 李兴奇 | A kind of power equipment coatings and preparation method thereof |
| CN115651464B (en) * | 2022-11-03 | 2023-11-14 | 武汉科技大学 | Non-oriented silicon steel insulation coating liquid and preparation method thereof and non-oriented silicon steel plate |
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|---|---|---|---|---|
| CN1396226A (en) * | 2001-07-09 | 2003-02-12 | 关西涂料株式会社 | Metal surface processing composition |
| CN101135049A (en) * | 2006-08-31 | 2008-03-05 | 宝山钢铁股份有限公司 | Non-chromic environment protective oriented silicon steel insulating coating |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1396226A (en) * | 2001-07-09 | 2003-02-12 | 关西涂料株式会社 | Metal surface processing composition |
| CN101135049A (en) * | 2006-08-31 | 2008-03-05 | 宝山钢铁股份有限公司 | Non-chromic environment protective oriented silicon steel insulating coating |
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