CN102079922B - Chromium-free environmental-protection insulating paint - Google Patents

Chromium-free environmental-protection insulating paint Download PDF

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CN102079922B
CN102079922B CN 200910199394 CN200910199394A CN102079922B CN 102079922 B CN102079922 B CN 102079922B CN 200910199394 CN200910199394 CN 200910199394 CN 200910199394 A CN200910199394 A CN 200910199394A CN 102079922 B CN102079922 B CN 102079922B
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chromium
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metal
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CN102079922A (en
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许云鹏
黄杰
肖盼
陈凌云
陈卓雷
刘宝军
陈晓
韩鹏钧
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Baoshan Iron and Steel Co Ltd
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Abstract

The invention relates to a chromium-free environmental-protection insulating paint which comprises the following components in parts by mass: 100 parts of metallic dihydric phosphate, 10-100 parts of one or more of vinyl acetate, polyvinyl acetate and styrene-acrylic acid copolymer and epoxy resin, 1-40 parts of soluble metallic salt of organic acid, 12-30 parts of boron compound and 200-5000 parts of pure water. The semi-organic chromium-free coating formed by the chromium-free environmental-protection insulating paint has excellent appearance, corrosion resistance and adhesiveness, and appears jet-black and lustrous after being subjected to stress relief annealing.

Description

A kind of chromium-free environmental-protection insulating paint
Technical field
The present invention relates to a kind of insulation compound, relate in particular to a kind of nothing that can be used for non orientating silicon steel and contain chromium environmental protection insulation compound.
Background technology
The used non-oriented silicon steel sheet of electric motor and transformer will have one deck insulating coating, so that siliconized plate after the punching closed assembly becomes stator material, reduces the eddy-current loss of stator.This siliconized plate also needs to 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.Insulating coating must tolerate stress relieving, and the coating after the annealing should possess as black as jet outward appearance.
Traditional insulating coating often adopts chromic salt as component, and chromic salt is owing to have 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 is not the stablizer of residual phosphoric acid, so show suction and bonding die, owing to 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.Simultaneously, above patented technology does not all possess as black as jet outward appearance without the chromiumcoating black-film.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.The companies such as Nippon Steel, Pu item are are all researching and developing for Chrome-free half organic coating simultaneously, and actively attempt substituting containing chromium half organic coating.In case the market share without chromiumcoating significantly promotes, the Baosteel non orientating silicon steel is then in the face of quite passive situation.
Summary of the invention
The purpose of this invention is to provide a kind of chromium-free environmental-protection insulating paint, non orientating silicon steel applies should be partly organic without chromiumcoating, has good outward appearance, erosion resistance, tack, and coating has as black as jet outward appearance after the stress relieving.
For achieving the above object, technical scheme of the present invention is,
A kind of chromium-free environmental-protection insulating paint, its composition is:
Metal tripolyphosphate dihydric salt 100 mass parts;
In polyvinyl acetate (PVA), polyacrylic ester, Styrene And Chloroalkyl Acrylates copolymer resins and the Resins, epoxy one or more, 10~100 mass parts;
Metal organic acid salt 1~40 mass parts of solubility;
12~30 parts of the compounds of boron;
Pure water 200~5000 mass parts.
Further, also comprise organic solvent, its addition is no more than 50 mass parts with respect to the metal tripolyphosphate dihydric salt solution of 100 mass parts, comprises ethylene glycol or glycerol.
Again, described metal tripolyphosphate dihydric salt is Al (H 2PO 4) 3, Mg (H 2PO 4) 2, Ca (H 2PO 4) 2Or Zn (H 2PO 4) 2
Described Al (H 2PO 4) 3, it is 0.14~0.20 Al by mol ratio 2O 3And H 3PO 4Mixing obtaining, also can be 0.28~0.40 Al (OH) by mol ratio 3With H 3PO 4Mix and obtain; Mg (H 2PO 4) 2, Ca (H 2PO 4) 2And Zn (H 2PO4) 2, be 0.40~0.6 metal oxide or oxyhydroxide and H by mol ratio 3PO 4Mix and obtain.
The metal organic acid salt of described solubility is the organic acid salt of divalence and trivalent metal, comprises lactic acid salt, acetate, gluconate and the Citrate trianion of Mg, Al, Ca, Zn, Co, Ni and Sr etc.
The compound of described boron comprises boric acid, sodium tetraborate, lithium tetraborate or potassium tetraborate.
The coating method of chromium-free environmental-protection insulating paint of the present invention, in the non orientating silicon steel surface-coated, the coating quality of unit surface coating is 0.6g/m with above-mentioned chromium-free environmental-protection insulating paint 2~4g/m 2, baking after applying, storing temperature is 200~550 ℃.
In the present invention,
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 2PO4) 2Deng divalent metal, it can be 0.40~0.6 metal oxide or oxyhydroxide and H by mol ratio 3PO 4Mix and obtain.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 Resins, epoxy
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 Resins, epoxy.With respect to the metal tripolyphosphate dihydric salt of 100 mass parts, the addition of resin is 10~100 mass parts.Resin content very little, then coatingsurface becomes too coarse and coating is peeled off and efflorescence easily, 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.
The metal organic acid salt of solubility
The metal organic acid salt that the present invention will be selected from lactic acid salt, acetate, gluconate and Citrate trianion is incorporated in the insulation compound, these metal organic acid salts have certain solubleness in water, can realize metal is introduced in the solution system with the form of ion, and do not cause that solution produces precipitation, guarantee the homogeneity of coating.The applicant finds in the coating sintering process, this class material decomposition, and metallic cation just can react with the phosphate radical of remnants, thereby plays the purpose of confining the residual phosphorus acid group.This metal organic acid salt can be the organic acid salt of divalence and trivalent metal, comprises the lactic acid salt of Mg, Al, Ca, Zn, Co, Ni and Sr etc., acetate, gluconate and Citrate trianion etc.With respect to the metal tripolyphosphate dihydric salt solution of 100 mass parts, the addition of this metal organic acid salt 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 be higher than 40 parts, then can significantly reduce the stability of coating system, even cause separating out of large quantity of material.
The compound of boron
The compound of boron is the key substance that has pitch-black gloss after the coating annealing.Optional boron compound has boric acid, sodium tetraborate and lithium tetraborate, potassium tetraborate etc.The compound of these boron can effectively improve the transparency of coating and the appearance of coat after the annealing, makes it to show glossiness appearance of black.With respect to the metal tripolyphosphate dihydric salt solution of 100 mass parts, the amount of filling of this class material is 12~30 parts, if be lower than 12 parts, then the outward appearance after the coating annealing presents brown color, and lackluster; If be higher than 30 parts, then coating tack variation is easy to come off.
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 causes easily 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 forms precipitation easily, 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 the coating quality of unit surface coating is 0.6g/m 2~4g/m 2Between, then the erosion resistance of coating and insulativity are defective very little in coating, coating too thick then coating tack and weldability variation; 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 close chrome-free insulating coating non orientating silicon steel product of excellent performance and outward appearance and Chromium coating, 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
The present invention will be further described below in conjunction with 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, metal organic acid salt, boric acid 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 Spray Testing);
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
Figure GDA00002706359900061
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 100 parts, solidity to corrosion, weldability descend obviously, so reasonably the resin content scope is 10~100 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, nickel acetate 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
Figure GDA00002706359900071
Table 4
Figure GDA00002706359900072
By as seen from Table 4, along with the increase of metal organic acid salt addition, 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 coating unstable 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, metal organic acid salt, sodium tetraborate, 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
Figure GDA00002706359900081
Table 6
Figure GDA00002706359900082
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
The non orientating silicon steel Chrome-free insulation coating prescription that is comprised of aluminium dihydrogen phosphate, Styrene And Chloroalkyl Acrylates copolymer resins, zinc acetate, boric acid, ethylene glycol and water sees Table 7.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 8.Test condition is identical with embodiment 1.
Table 7 unit: mass parts
Figure GDA00002706359900091
Table 8
Figure GDA00002706359900092
By as seen from Table 8, when boric acid adds when being lower than 12 mass parts, the black-film of coating presents brown color, tarnish, and addition is during more than 30 mass parts, the masking liquid Precipitation.Reasonably the interpolation scope is 12~30 parts.The sodium tetraborate that adds simultaneously 12~30 parts can reach same effect.
Embodiment 5
Adopt the combination of other metal tripolyphosphate dihydric salt, metal organic acid salt, resin, organic solvent and water, prescription sees Table 9.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 10.Test condition is identical with embodiment 1.
Table 9v unit: mass parts
Figure GDA00002706359900101
Table 10
By as seen from Table 10, the solubility salts such as metal acetate salt, lactic acid salt, citrate and dextrose hydrochlorate 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 (2)

1. chromium-free environmental-protection insulating paint, its composition is:
Metal tripolyphosphate dihydric salt 100 mass parts;
In polyvinyl acetate (PVA), polyacrylic ester, Styrene And Chloroalkyl Acrylates copolymer resins and the Resins, epoxy one or more, 10~100 mass parts;
Metal organic acid salt 1~40 mass parts of solubility;
Compound 12~30 mass parts of boron;
Pure water 200~5000 mass parts;
Wherein, described metal tripolyphosphate dihydric salt is Al (H 2PO 4) 3, Mg (H 2PO 4) 2, Ca (H 2PO 4) 2Or Zn (H 2PO 4) 2
Described Al (H 2PO 4) 3, it is 0.14~0.20 Al by mol ratio 2O 3And H 3PO 4Mix obtaining, or be 0.28~0.40 Al (OH) by mol ratio 3With H 3PO 4Mix and obtain; Mg (H 2PO 4) 2, Ca (H 2PO 4) 2And Zn (H 2PO 4) 2, be 0.40~0.6 metal oxide or oxyhydroxide and H by mol ratio 3PO 4Mix and obtain;
The metal organic acid salt of described solubility is the organic acid salt of divalence and trivalent metal, comprises lactic acid salt, acetate, gluconate and the Citrate trianion of Mg, Al, Ca, Zn, Co, Ni and Sr;
The compound of described boron comprises boric acid, sodium tetraborate, lithium tetraborate or potassium tetraborate.
2. chromium-free environmental-protection insulating paint as claimed in claim 1 is characterized in that, also comprises organic solvent, and its addition is no more than 50 mass parts with respect to the metal tripolyphosphate dihydric salt of 100 mass parts, comprises ethylene glycol or glycerol.
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