CN101560342B - Non-oriented electric steel semi-organic phosphate insulating paint with good corrosion resistance - Google Patents
Non-oriented electric steel semi-organic phosphate insulating paint with good corrosion resistance Download PDFInfo
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Abstract
The invention discloses a non-oriented electric steel semi-organic phosphate insulating paint with good corrosion resistance. The semi-organic phosphate insulating paint comprises the following main components: water-soluble phosphate, tungstate, organic resin, water, a titanate coupling agent, an organic solvent and the like; and contents of the components of the insulating paint (parts by weight) based on 100 parts of the water-soluble phosphate by weight are as follows: 1-15 parts of the tungstate, 20-200 parts of the organic resin, 500-2000 parts of the water, 0.1-3 parts of the titanate coupling agent, 10-50 parts of the organic solvent and 0.1-3 parts of other paint addictives. The semi-organic phosphate insulating paint contains no harmful ingredients restricted by an EU directive RoHS, which can meet the requirements for environmental protection; and compared with the common phosphate coating, the coating of the semi-organic phosphate insulating paint has better corrosion resistance, good insulating property, good adhesiveness, good blanking property, good welding property, good heat resistance and the like, which can meet the requirements of electric motor and transformer manufacturers for application to the electric steel coating.
Description
Technical field
The present invention relates to a kind of non-oriented electrical steel insulation compound, particularly a kind of cold rolling non-oriented electrical steel with environmental protection, have the semi-organic phosphate insulating paint of good corrosion resistance.
Background technology
Non-oriented electrical steel is widely used as the core material of motor and transformer.Increase eddy-current loss for preventing from being short-circuited between core lamination stack, need to be at cold-rolled non-oriented electrical steel surface-coated insulating coating.Because when making motor, transformer core, the electrical sheet punching need to be become the blank of core configuration, the applying working condition condition that also the lamination edge will be fixed and adapt to the different sorts iron core, therefore the non-oriented electrical steel insulating coating not only will have good insulativity, but also good punching, tack, weldability, thermotolerance, solidity to corrosion etc. need be arranged.The non-oriented electrical steel insulating coating includes organic coating, inorganic coating and half organic coating three major types.The maximum electric steel insulating coating of domestic application is half organic Chromium coating at present, such as Wuhan Iron and Steel Plant T4, Anshan iron and steel plant TM4, Baosteel A, Taiyuan Iron and Steel Co. G2 coating, the coating composition of these coatings is mainly the dichromate aqueous solution, organic resin emulsion, fusing assistant, reductive agent (such as ethylene glycol or glycerine), defoamer etc.Although half organic Chromium coating has been taken into account the desired various performances of non-oriented electrical steel coating, contains the Cr6+ of severe toxicity in its coating.Along with the increasingly stringent of environmental requirement, the especially enforcement of RoHS Directive, the environmental protection insulation compound becomes the focus of domestic and international non-oriented electrical steel insulation compound research and development.In addition, in the damp and hot area of weather, downstream user is also also had higher requirement to the solidity to corrosion of electrical steel.
For satisfying the environmental requirement of electric steel insulating paint, the equal Devoting Major Efforts To Developing semi-organic phosphate insulating paint of domestic and international electrical steel manufacturing enterprise.U.S. Amoca Corp in the patent 98125437.3 of China application, disclosed a kind of for non-oriented electrical steel inorganic/the organic insulation coating, the aluminum phosphate that wherein contains 20-60 part in per 100 parts of dry basises, at least a inorganic silicate particulate of 20-70 part, and a kind of acrylic resin of 10-25 part; This solidified coating is formed by a kind of sour water suspension, contains at the most a kind of water-miscible organic solvent of 1 part for per 1 part of acrylic resin; The pH value of this aqeous suspension is approximately 2.0-2.5, and the silicate median size is 0.3-60 μ m, resin particle diameter＜1 μ m, and proportion is approximately 1.0-1.3g/ml; This coating (aqeous suspension) toasts film forming under 220-350 ℃ of plate temperature, the single face coat-thickness is controlled at 0.5-8 μ m.
Nippon in the patent 200310124259.9 of China application, disclosed a kind of with metal phosphate (aluminum phosphate, calcium phosphate, zinc phosphate and trimagnesium phosphate) and organic resin as main ingredient, the treatment solution that also comprises water-soluble organic compounds, the boiling point of this organic compound or sublimation point temperature are 100 ℃ at least, and its addition is that the metal phosphate of 100 weight parts is than 5-50 weight part organic compound; Organic resin is that the organic resin composition of 5 to 300 weight parts is than the phosphoric acid salt of 100 weight parts with phosphatic preferred mixed ratio; This coating has high percent break, good die-cutting performance, film adhesive property and sliding capability after stress relief annealing.
Japan JFE (former Kawasaki Steel Corp and NKK merge) has disclosed a kind for the treatment of solution that is used to form the electrical sheet insulating coating in the patent 95103838.9 of China's application, it is characterized in that containing in the treatment solution resin microparticle emulsion, reductive agent and promotor, and resin is in derivative thermogravimetric analysis(DTG) during with certain heat-up rate heating sample, changes in weight is that great peak temperature is more than 400 ℃, and has tolerate P-levels acidity; Reductive agent is the aqueous phosphatic of at least a sodium, potassium, magnesium, calcium, manganese, molybdenum, zinc, aluminium; Promotor is then contained at least a in sodium alkyl benzene sulfonate, polyoxyethylene, polyoxypropylene block polymer, polyoxyethylene phenolic ether, aluminum nitrate, nitric acid, assorted molybdic acid, the potassium permanganate.
Korea S's Pu item has disclosed the coating composition of the formation insulating coating that a kind of non-oriented electromagnetic steel sheet uses in the patent 00807715.0 of China application, this coating composition is to per 100 gram phosphoric acid in the phosphate dihydrogen aluminum solution, comprise 28-98 gram (solid weight) solubility in acid emulsion acrylate-styrene copolymer resin, 6-18 restrains zinc nitrate, 4-13 restrains silicon additive, 18-35 gram ethylene glycol and 3-11 gram nonionogenic tenside; This coating composition is doing well aspect the roller coat processibility and aspect the coating performance, in addition, and coating environmental protection and very attractive in appearance.
Although the half organic insulation coating that above-mentioned these non-oriented electrical steels are used does not contain poisonous chromic salt, all be to select phosphoric acid salt as anti-rust agent for treatment, it is still waiting to improve aspect solidity to corrosion.
Summary of the invention
Technical problem to be solved by this invention provides a kind of non-oriented electric steel semi-organic phosphate insulating paint with good corrosion resistance, do not contain the toxic substance that the RoHS instruction limits the use of in the described coating, its coating has good insulativity, tack, punching, weldability simultaneously, thermotolerance, particularly solidity to corrosion has obtained large increase.
For solving the problems of the technologies described above, the non-oriented electric steel semi-organic phosphate insulating paint with good corrosion resistance provided by the invention comprises water-soluble phosphate, tungstate, organic resin, water, organic solvent, titanate coupling agent.
The content of each component of coating of the present invention (parts by weight) is: take 100 weight part water-soluble phosphates as benchmark, and tungstate 1-15 part, organic resin 20-200 part, water 500-2000 part, organic solvent 10-50 part, titanate coupling agent 0.1-3 part.
The content of each component of coating of the present invention (parts by weight) is preferably: take 100 weight part water-soluble phosphates as benchmark, and tungstate 2-8 part, organic resin 30-100 part, water 800-1500 part, organic solvent 20-40 part, titanate coupling agent 0.5-1 part.
In the such scheme, described phosphoric acid salt is one or several the mixture in water-soluble phosphoric acid aluminum dihydrogen, monocalcium phosphate, primary zinc phosphate, biphosphate nickel, primary magnesium phosphate, the phosphate dihydrogen manganese.
Described tungstate is one or several the mixture in sodium wolframate, potassium wolframate, the ammonium tungstate.
Described organic resin is one or several the mixture in acrylic resin, Styrene And Chloroalkyl Acrylates copolymer resins, vinyl acetate between to for plastic-acrylic copolymeric resin, vibrin, urethane resin, styrene resin, resol, Synolac, Resins, epoxy, silicone resin, the fluorocarbon resin.
Described organic solvent is one or several mixture of ethylene glycol, glycerol, propylene oxide, ethylene glycol monobutyl ether.
Titanate coupling agent can improve coating property and the appearance of coat of coating, the mixture of one or several in the wetting agent that can also add 0.1-3 weight part (with respect to the water-soluble phosphate of 100 weight parts) for the coating property of further improving coating and appearance of coat, flow agent, the defoamer, wherein defoamer must add.
Added tungstate in the coating of the present invention, because PO
4 3-With WO
4 2-Can form the strong oxidizing property phosphorus heteropoly tungstic acid at acidic conditions, thereby form comparatively fine and close insulating coating, and improve the solidity to corrosion of coating.Add coating property and the appearance of coat that titanate coupling agent can improve coating in the coating.With the thick non-oriented electromagnetic steel sheet of 0.5mm as substrate, apply semi-organic phosphate coating of the present invention with special cutting rubber rollers coating machine, then under 300 ℃ of steel billet temperatures, toast 30s, coating is silvery white, coating is complete, and all have good insulativity, interlamination resistance is all at 150 Ω mm
2Above, the corrosion area behind the 5hr neutral salt spray test illustrates that below 20% coating of the present invention has fabulous corrosion resisting property.
Embodiment
Below in conjunction with embodiment the present invention is described in detail.The detection of interlayer resistance is carried out according to GB/T 2522-2007 " electrical sheet (band) surface insulation resistance, coating tack testing method " in the embodiment of the invention; Solidity to corrosion then is to characterize by 5 hours neutral salt spray tests, and test condition is: room temperature, the NaCl aqueous solution, spraying, 5hr, then judge according to the corrosion area of sample.
The content of coating composition is as shown in table 1 among the semi-organic phosphate insulating paint embodiment 1-10 of the present invention.
The content of coating composition among table 1 embodiment
Among above-described embodiment 1-10:
Phosphoric acid salt described in the embodiment 1 is the mixture of aluminium dihydrogen phosphate, primary magnesium phosphate; Tungstate is sodium wolframate; Organic resin is the Styrene And Chloroalkyl Acrylates copolymer resins, and organic solvent is ethylene glycol; Described other auxiliary agents are wetting agent, defoamer.
Phosphoric acid salt described in the embodiment 2 is the mixture of aluminium dihydrogen phosphate, biphosphate nickel; Tungstate is potassium wolframate; Organic resin is acrylic resin, urethane resin, and organic solvent is ethylene glycol; Described other auxiliary agents are flow agent, defoamer.
Phosphoric acid salt described in the embodiment 3 is primary magnesium phosphate, phosphate dihydrogen manganese; Tungstate is the mixture of sodium wolframate, potassium wolframate; Organic resin is silicone resin, styrene resin, and organic solvent is glycerol; Described other auxiliary agents are defoamer.
Phosphoric acid salt described in the embodiment 4 is the mixture of primary magnesium phosphate, monocalcium phosphate, primary zinc phosphate; Tungstate is the mixture of ammonium tungstate, potassium wolframate; Organic resin is fluorocarbon resin, and organic solvent is propylene oxide; Described other auxiliary agents are the mixture of wetting agent, flow agent, defoamer.
Phosphoric acid salt described in the embodiment 5 is primary zinc phosphate; Tungstate is the mixture of ammonium tungstate, sodium wolframate; Organic resin is the mixture of Resins, epoxy and silicone resin, and organic solvent is the mixture of ethylene glycol and glycerol; Described other auxiliary agents are the mixture of wetting agent, defoamer.
Phosphoric acid salt described in the embodiment 6 is aluminium dihydrogen phosphate; Tungstate is the mixture of ammonium tungstate, sodium wolframate, potassium wolframate; Organic resin is the mixture of vinyl acetate between to for plastic-acrylic copolymeric resin and Synolac; Organic solvent is ethylene glycol monobutyl ether; Described other auxiliary agents are the mixture of flow agent, defoamer.
Phosphoric acid salt described in the embodiment 7 is the mixture of primary zinc phosphate, aluminium dihydrogen phosphate, primary magnesium phosphate; Tungstate is ammonium tungstate; Organic resin is the mixture of acrylic resin, styrene-propene acid resin, resol, and organic solvent is the mixture of ethylene glycol monobutyl ether and glycerol; Described other auxiliary agents are the mixture of wetting agent, flow agent, defoamer.
Phosphoric acid salt described in the embodiment 8 is the mixture of the mixture of aluminium dihydrogen phosphate, monocalcium phosphate; Tungstate is the mixture of ammonium tungstate, sodium wolframate; Organic resin is vibrin; Organic solvent is the mixture of propylene oxide, ethylene glycol; Described other auxiliary agents are wetting agent, defoamer.
Phosphoric acid salt described in the embodiment 9 is the mixture of monocalcium phosphate, primary zinc phosphate; Tungstate is the mixture of sodium wolframate, potassium wolframate; Organic resin is urethane resin; Organic solvent is the mixture of ethylene glycol, glycerol, propylene oxide; Described other auxiliary agents are the mixture of flow agent, defoamer.
Phosphoric acid salt described in the embodiment 10 is the mixture of the mixture of hydrogen nickel, primary magnesium phosphate; Organic resin is the mixture of urethane resin, vibrin; Do not add tungstate; Organic solvent is the mixture of ethylene glycol monobutyl ether, glycerol, propylene oxide; Described other auxiliary agents are wetting agent, defoamer.
As substrate, apply the semi-organic phosphate coating of composition shown in the embodiment 1-10 with the thick non-oriented electromagnetic steel sheet of 0.5mm with special cutting rubber rollers coating machine, then under 300 ℃ of steel billet temperatures, toast 30s; Clip interlamination resistance and neutral salt spray test test sample plate detect, and test result is as shown in table 2.
Interlamination resistance and the solidity to corrosion of coating described in the table 2 embodiment 1-10
Embodiment 1-10 explanation: the coating described in the embodiment 1-10 is silvery white, and coating is complete, and all has good insulativity, and interlamination resistance is all more than 150 Ω mm2; Corrosion resistance coating described in the embodiment 1-9 is better, and the corrosion area behind the 5hr neutral salt spray test is below 20%, and it is relatively relatively poor not add the solidity to corrosion of embodiment 10 of tungstate, and the corrosion area of coating model has reached 90%.
Claims (6)
1. have the non-oriented electric steel semi-organic phosphate insulating paint of good corrosion resistance, it is characterized in that, described coating composition comprises water-soluble phosphate, tungstate, organic resin, water, organic solvent, titanate coupling agent; The content of described each component of coating (parts by weight) is: take 100 weight part water-soluble phosphates as benchmark, and tungstate 1-15, organic resin 20-200, water 500-2000, organic solvent 10-50, titanate coupling agent 0.1-3 part; Described organic resin is one or several the mixture in acrylic resin, Styrene And Chloroalkyl Acrylates copolymer resins, vinyl acetate between to for plastic-acrylic copolymeric resin, vibrin, urethane resin, styrene resin, resol, Synolac, Resins, epoxy, silicone resin, the fluorocarbon resin.
2. non-oriented electric steel semi-organic phosphate insulating paint according to claim 1, it is characterized in that, the content of described each component of coating (parts by weight) is: take 100 weight part water-soluble phosphates as benchmark, tungstate 2-8, organic resin 30-100, water 800-1500, organic solvent 20-40, titanate coupling agent 0.5-1 part.
3. non-oriented electric steel semi-organic phosphate insulating paint according to claim 1 and 2, it is characterized in that, described phosphoric acid salt is one or several the mixture in water-soluble phosphoric acid aluminum dihydrogen, monocalcium phosphate, primary zinc phosphate, biphosphate nickel, primary magnesium phosphate, the phosphate dihydrogen manganese.
4. non-oriented electric steel semi-organic phosphate insulating paint according to claim 1 and 2 is characterized in that, described tungstate is one or several the mixture in sodium wolframate, potassium wolframate, the ammonium tungstate.
5. non-oriented electric steel semi-organic phosphate insulating paint according to claim 1 and 2 is characterized in that, described organic solvent is one or several the mixture in ethylene glycol, glycerol, propylene oxide, the ethylene glycol monobutyl ether.
6. non-oriented electric steel semi-organic phosphate insulating paint according to claim 1 and 2, it is characterized in that, take 100 weight part water-soluble phosphates as benchmark, also contain one or several the mixture in 0.1-3 weight part wetting agent, flow agent, the defoamer, wherein defoamer must add.
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