• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    1524997 Resin coated steel sheets KAWASAKI STEEL CORP 10 Oct 1975 [15 Oct 1974] 41705/75 Heading B2E Steel sheets are provided with an insulating coating by treating them with an aqueous resin emulsion in the presence of 3-40% chromic acid. The emulsion includes a separable and a non seperable resin (a separable resin is one forming two layers when shaken with chromic acid while a non separable resin remains mixed with chromic acid). The separable resin may be an acrylic copolymer or an ethylene vinyl acetate copolymer. The non separable resin may be an acrylic or an acrylic styrene resin.
    公开号:SU1050572A3
    申请号:SU752183060
    申请日:1975-10-14
    公开日:1983-10-23
    发明作者:Ирие Тосио；Танда Тосикуни；Ичи Томоюки；Садаери Тосио
    申请人:Кавасаки Стил Корпорейшн (Фирма)；
    IPC主号:
    专利说明:

    one . The invention relates to a method for producing clad electrical steel sheets having an excellent ability of stamping, weldability, electrical insulation and heat resistance. An insulating coating, such as silicon or low carbon steel, used as plate cores in generator and transformer motors, should have excellent heat resistance, corrosion resistance and cooling resistance, other than electrical insulation properties, on electrical steel sheets. In addition, improved punching capability is expected from clad steel sheets.8 In addition, clad sheets should not have gas bubbles in the weld when welding edges of an electrical sheet in an inert tungsten atmosphere, i.e. high punchability is required for a clad electrical sheet. These properties are mainly created by applying an insulating coating which, for an electrical sheet, is approximately CL and is classified into four classes: phosphate type, chromate type, organic resin type, and mixture of chromate-organic resin. The characteristics of clad steel sheets are summarized below. A known method for producing a clad steel sheet by depositing a composition on the surface of a steel sheet is a solution containing 0.5-20 hexavalent chromium ions of 0,., 0 copper ions, cadmium, calcium, magnesium barium, zinc, and a copolymer of polyvinyl methyl ether and maleic acid, followed by heat treatment of the sheet at 150-300 ° C for 10180 s JV. The closest in technical essence to the invention is a method for producing a clad steel sheet by treating it with a composition comprising 20.6-2b, an aqueous solution of a metal chromate or bichromate (calcium or magnesium or zinc) and an aqueous emulsion of a monovinyl aromatic polymer ™. hydrocarbons, for example styrene 72 .2 of acrylic or methacrylic acid ester, followed by heat treatment of the sheet at 150-280 ° C. 2. The sheet is coated evenly and brilliant by a known method. However, this method does not achieve the required comparability of sheet, ability to stamping and heat resistance. the invention is an increase in surface roughness, coating, improving the weldability and electrical insulation properties of steel; sheet. The goal is achieved in that according to the method of manufacturing a clad steel sheet by treating it with a composition comprising 20.6-2b, an aqueous solution of calcium or magnesium dichromate or zinc and an aqueous emulsion of the polymer, followed by heat treatment of the sheet, 12-83 ma.ch. on too. CrOZ TH, 3-21,0% aqueous emulsion of copolymer 8-10 wt.h. methacrylic acid and 90-92 wt. methyl methacrylate and butyl or ethyl acrylate, treated with 3 ma.h. diethanolamine or triethanolamine, or 6 may. m. “A 100 mac.h, GrO water emulsion of copolymer 80 mac.h. vinyl acetate and 29 wt. ethylene. An emulsion of acrylic resin (joint resin) on oenove 2 wt.h can be added to the initial treatment composition. methacrylic acid; s, 50 wt. methyl methacrylate and 48mae, h. butyl acrylate or acrylonitrilerol emoli on oenove 60 ma.ch. ; methyl methacrylate and YO ma.ch. an etheral monomer treated with OJ5 mac. h of diethanolamine or triethanolamine in an amount that provides the total amount of non-volatile substances in the aqueous emulsion of the polymer and emulsion of acrylic emole or acrylonitrilethyrene emole, equal to .h. i per 100 math. CrOo. 8 initial composition can be added 18 ma.h. on 100 ma.ch. SgO boron kieloty. At the same time, 11 wt.h. glycerol or; 16 ma.ch. diethylene glycol on 100mae. CrOj as a military reagent. In addition, heat treatment of coated steel is carried out at 300-700 ° C. The present invention is that the processing dispersion obtained by mixing a resin emulsion, which releases agglomerated particles having an average diameter of 3 - + 0 µm, when this resin on the emulsion is mixed with an aqueous solution containing chromic acid and resin. having compatibility with an aqueous solution containing chromic acid, such as MectBe, that the total amount of nonvolatile substances of both of the above resins is 26-5 May., 100 ma.h., CrO, is applied to electrical steel sheet, after What is subjected to heat treatment. The main purpose of the present invention is to obtain an electrical steel sheet having a coating with excellent punching ability. In order for these two components to be applied simultaneously and then subjected to drying in order to obtain a coating, the chromate and the resin must be compatible in an aqueous solution or in suspension form. The compatibility of these components is established as follows. To 100 ml of an aqueous solution of calcium dichromate at a concentration of 18% (CrOj), with stirring, add 10 ml of an aqueous solution or emulsion of a polymer having a concentration of non-volatile matter 15-25 i for 5-10 seconds. In this case, two cases are possible: the polymer does not substantially dissolve in the aqueous solution of the chromate, and the liquid medium is divided into two layers or macro-agglomerates are formed having a diameter of more than a few millimeters; the polymer is completely dissolved in an aqueous solution of calcium bichromate to form an opaque orange solution, and even if sedimentation of the said fatty medium occurs within a few hours, no change is observed; finely ground agglomerates and suspension are obtained. If this suspension is held for approximately 30 minutes, then the agglomerates are precipitated and a transparent, not containing resin is formed in the upper part of the tank. Any of the resins belonging to this class (the third case) is an emulsion type resin, and in the present invention these resins are referred to as resins that release particles. Resins of the above class (second case) are also emulsion type resin, which is called a compatible resin. According to the invention, electrical steel sheets having excellent electrical insulation and weldability are created by depositing a processing dispersion with suspended particles obtained by mixing: strictly defined amounts of a release agent resin and compatible resins with chromate on electrical steel sheets; followed by heat treatment of the steel sheet thus treated in order to obtain coatings. In addition, the resulting insulating coatings adhere tightly to electrical steel sheets, and even if annealing is performed to relieve internal stresses, the adhesion does not change and the insulation resistance remains high. As a rule, the sizes of emulsion particles are extremely small, on the order of less than 1 micron, but when using such an emulsion, adding a resin emulsion to an aqueous solution of the chromate produces agglomerates having a diameter from several microns to several tens of microns. Preferred is the particle size distribution of the agglomerates, measured using a specific gravimetric and photodeposition methods, in the order of 3 - + 0 microns in diameter (the particle size shows the highest particle size on the distribution curve) or the average diameter size (particle size corresponding to the central summation value (50) of the component curve). In the case when the average particle size is less than 3 µm, the surface roughness of the coating obtained is small and the weldability cannot be significantly improved, and when the particle size exceeds 40 µm, the dispersion is unsatisfactory and the particles are deposited on the bottom of the treatment tank and the number of inefficiently used particles is large.
    Stamping and electrical insulation characteristics can be achieved by selecting the total amount of nonvolatile substances of the particulate release resin and the compatible resin. Failure to ensure weldability and further improvement of electrical insulation and heat resistance can be achieved by mixing the emitting resin in an appropriate amount, i.e. among the mentioned number of 265 ma.ch. both resins are at least 1 ma.h. constitutes a particulate release resin.
    Even without using a compatible resin at all, it is possible to obtain coated steel sheets having a large surface roughness and sufficient ability to stamp and weld by mixing 2 to 5 mas.h. particle releasing resin
    However, if a treatment liquid containing a large amount of an evolving resin is applied to the electrical steel sheet on an industrial scale at a high speed, strips of a few millimeters wide will form on the sheet. These bands are observed when dispersing particles of the processing liquid are poured onto the surface of the steel sheet or when the steel sheet is immersed in the specified processing liquid, and then the steel sheet coated with the processing liquid is compressed with corrugated rollers in order to level the amount of coatings as a coating formation process specified the processing liquid, and when the alignment rate of the steel sheet is high, it is possible that streaks form on the surface of the steel sheet upon with the lower compression roller. The distance between the stripes ranges from several centimeters to several tens of centimeters, and the appearance of the finished product deteriorates.
    Steel sheet processing fluids, coating conditions and heat treatment and testing method are characterized as follows.
    Steel sheet:
    0, silicon steel sheet with surface roughness
     - motx, Processing medium, a mixture of calcium dichromate and diethylene glycol.
    The mixing ratio of the resins is based on 5 per weight ratio of non-volatile resin substances per 100 parts by weight. chromic acid (CrO. Resin excreting resin - emulsion acrylic resins.
    Compatible resin - emulsion acrylic resin.
    The value of the applied coating is 2-5 g / (on one side after heat treatment).
     Heat treatment at, for 1 min.
    The pattern on the steel sheet is formed when the coating is conducted at a speed of 60 m / min.
    The compressive pressure during welding is 100 kg / cm2, the current is too A, It does not form any grooves.
    The maximum welding speed is when gas bubbles do not form.
    For punching, a 15 mm piercer was used with a steel punch punched several times until the height of the grout reached 0 50.
    Aqueous solutions of chromates include aqueous solutions of divalent metal bichromates — magnesium, calcium, zinc, chromic acid.
    5; | (CrOz) added to the indicated solutions. -So, for example, when a solution of bichromate is obtained from a bivalent metal oxide and CrOj, then adding CrO in an amount
    0 greater or less than the stoichiometric amount, with the addition of resins, the stability of the processing liquid increases. In addition to the aqueous solution of bichromates
    5 boric acid compounds can be added
    The concentration of these aqueous solutions of chromates should be 20.6-26.6%, as is CrOj.
    0 In treating liquid media containing chromates, reducing agent CgO3 is added, and in treating liquid media to which organic resin is added,
    5 resin has the ability to reduce CrO3 so it is not always necessary to add a reducing agent. However, in the case when the coating after heat treatment absorbs moisture, it is preferable to add polyhydric alcohols, such as diethylene glycol, glycerin, as a reducing reagent. v Steel sheets, can be any sheet used as electrical steel sheet. As a pretreatment there is no need for any particular treatment until a large amount of oil or rust has been deposited. When preparing the processing liquid medium with stirring of an aqueous solution of bichromate, a certain amount of excreting part (resin resin, emulsion concentration; resin non-volatile matter is 1, k, 32, Q% is added to the treatment liquid medium, after which, if necessary, a compatible resin is added and its reducing agent t (polyhydric alcohol) .The mixing technique can be changed. The method of coating and processing the treatment liquid is common. The electrical steel sheet is immersed in the treatment liquid it is applied to or applied, after which the hedgehog coated steel sheet is coated with corrugated rollers to control the thickness of the coating, after which it is heat treated in a furnace at Ji30-70 & C for a certain time. In this processing liquid medium, the ground agglomerate is dispersed to pores until the concentration of the processing liquid reaches a low value, for example, a value of less than 3%, while significant precipitation is not observed and there is no need for a certain mixing effect. The following examples are provided to illustrate this invention. In these examples, all downloads are expressed in mph. or wt.%. PRI me R 1. As a release resin, an acryl resin obtained from 82 parts of methyl methacrylate, 10 parts of butacrylate, and 8 kg was used. methacrylic acid. In order to obtain a dilute emulsion resin, having a non-volatile substance concentration of 21%, to 100 liters of emulsion: VOO liters of water was added to this resin, n0 t 28 to the non-volatile substance concentration in the resin is 2%, To 100 liters 32% - Magnesium dichromate (a CgOz concentration is 26.6) is gradually added to 20 liters of the diluted resin emulsion (the amount of non-volatile matter is a resin emulsion to release particles is 12 parts per 100 hours CgO.) while stirring in order to release particles, after which 10 l-joint stimulated acrylic resin emulsion having a non-volatile concentration of 50% (trademark Woncote C001). (The amount of non-volatile compatible resin emulsion is 1 part per 100 parts CrOj), 5 kg of boric acid (15 parts per 100 hours CgOz), and 300 liters of water to produce the processing dispersion. Electrical steel sheet with a thickness of 0.5 mm and a width of mm, containing 0.32% silicon with a surface roughness of 0.9 / u.Hppj ,,: o speed of 60 m / min is immersed in the processing dispersion, compressed using corrugated rubber rollers j and heat treated in a hot air oven for 60 seconds to obtain a coating without any gloss pattern on the sheet. The characteristics of the coating obtained are shown in the table together with the characteristics of the coatings obtained. in the following examples and comparative examples. Example2. As a release resin of the resin in the form of an emulsion, the concentration of which is 55% of a non-volatile substance, vinyl acetate-ethylene copolymer, obtained at a ratio of vinyl acetate: ethylene to 80:20, is used. To 100 liters of a 30% aqueous solution of calcium dichromate (the concentration of CrOj is 23,%) is gradually added + l of the resin emulsion (the amount of non-volatile substance of the separating resin particle is 6 parts per 100 hours of carbon dioxide) with mixing to separate the particles. Thereafter, in order to prepare the processing dispersion, 40 liters of a compatible acryl, styrene resin emulsion is added to this mass, having a concentration of a nonvolatile substance (trade mark Zoncout 9 4280) (the amount of a nonvolatile substance of a compatible resin emulsion is +8 hours at 100 hours SgOd) and 300 liters of water. Electrical steel sheet 0.5 mm thick and mm wide, containing 0.32% silicon, with a surface roughness of 1, groin. immersed in the processing dispersion at a speed of W m / min, compressed using corrugated rubber rollers and thermally treated in an oven at 500 ° C for 5 seconds to obtain a coating without any gloss and stripes. Example 3. using an acrylic resin obtained with a ratio of methyl methacrylate: ethylacrylate: methacrylic acid 70:20:10. In order to obtain a dilute resin emulsion having a non-volatile concentration of 14.31, 200 liters of water are added to 100 liters of this resin emulsion, the concentration of volatile matter of which is With the aim of separating particles with stirring, to 100 liters of a 291% aqueous solution zinc bichromate (concentration of CrOj 20.6) is gradually added 1 W O l of the aforementioned diluent {(1H emulsion (the amount of non-volatile substance is 85 parts per 100 parts of CrOj), after which, in order to obtain a processing dispersion, add to this mass are 2 liters of glycerin (11 parts per 100 hours CrOg), 5 kg bo acidic acids (18 parts per 100 hours and 250 liters of water Electrotechnical steel sheet 0.5 mm thick and 0 mm wide, containing 0.92% silicon with surface roughness l, H ,, and is coated at a speed of 30 m / min, and The prepared mentioned dispersion is sprayed onto a steel sheet, compressed by means of corrugated rubber rollers and heat-treated in a heating oven at 350 ° for 120 s in order to obtain a coating without gloss and pattern. Example (comparative) In order to prepare the treated liquid medium, to a 100 liter of a 30% aqueous solution of calcium dichromate, with stirring, add 20 l of the same compatible acrylic resin emulsion that was used in example 1 (the amount of non-volatile substance of this resin 2 of 10 tavl 28 hours per 100 parts of CrOg), l of ethylene glycol (17. hours based on 100 hours of CgOz) and 3QO of l iodine. The resulting processing liquid is applied to an electrical steel sheet (0.5 mm thick, 240 mm wide, with a silicon content of 0.30%, and surface roughness. (° 60 m / min at speed using corrugated rubber rollers, heat treated in a heating ovens at 400 ° C for 60 s in order to obtain a glistening coating having an equal appearance. Example 5 (comparative). To obtain a treatment liquid medium to 100 l of an 18% calcium bichromate solution. 5 liters of ethylene glycol and a very small amount are added. The quality of the surface active substance. The liquid processing medium is applied to the same electrical steel sheet as used in comparative example 4 and processed in the same way to obtain a uniform gloss coating. In order to obtain the processing liquid medium, 100 kg of a .35 aqueous solution of a primary acidic phosphorus are used to dissolve 6 kg of CrOj and 10 kg, A1 (MO3) 3 H20, after which 100 l of water are added to the solution. In order to obtain a glossy bass color transparent coating, the; The batting liquid medium is applied to the same electrical steel sheet as used in comparative Leveler 4 and processed at a speed of 60 m / min using corrugated rubber rollers in an electric furnace for 60 seconds. A conventional coating obtained by applying an aqueous solution of chromate mixed only with a solution of a compatible resin is very smooth, c) While the proposed coating is very coarse. The coating of comparative example 4 has a surface roughness of 1.3 max. As the coatings in examples 1, 2 and 3, respectively, have a surface roughness of 4.3; 3; and 6 ,. n 1 From the photographs of surface coatings it can be seen that the proposed coating contains a large number of precipitated particles. The table shows that the proposed coating has a very high electrical insulation, has excellent adhesion and heat resistance and does not stratify after annealing to relieve internal stresses. Clad sheet steel sheets should be welded at high speeds, and these sheets have excellent punching ability. The weight of the coating on one side should be 1.2-4.8 g / m. When the coating weight is less than 1.2 g / m, the stampability and electrical insulation characteristic of the clad steel sheet is poor. If the coating weight exceeds 8 g / m, the volume coefficient of the clad steel sheet is deteriorated.
    h
    .
    2, $
    2.7
    Elektroizol ITSIA, CM / LAYER
    before annealing
    18
    23 Properties of strain OBKt, number. . 240 .. 10 200x10 23,000 increments
    130 100 120 20 50 10 -10 10 10 10 15 15 15 15 15
    6.8
    1.6
    1,3
    B5
    2.6
    2,
    2.5
    2.9
    310
    five ,
    1.8
    0.5
    0.7
    100
    15
    140 220-10 30-10 6-10
    13
    Corrosion resistance
     ASTM measurement -3.
    1, the stampability characteristic is shown by means of several punctures until the height of the bur reaches 30 microns and when the plated steel sheet is punched by means of a steel stamp. # The maximum welding speed at which ha / does not form at all. . cry bubbles
    The "" ("is the maximum bending diameter at which delamination is observed | rustiness after 10 hours when tested by salt spray.
    105057211+
    Table continuation
    权利要求:
    Claims (5)
    [1]
    1. METHOD FOR MANUFACTURING A CLADED STEEL SHEET by treating it with a composition comprising a 20.6-26.6 ^ -d aqueous solution of calcium or magnesium dichromate, or zinc and an aqueous polymer emulsion followed by heat treatment of the sheet, which is characterized in that, for the purpose increase the surface roughness of the coating, improve weldability and electrical insulation properties of the steel sheet, 12-83 parts by weight are used as the polymer emulsion. on .11) 0 parts by weight CrO ^ 14.3-21.0 ^ -th aqueous emulsion of the copolymer 8-10 wt.h. methacrylic acid and 90-92 parts by weight methyl methacrylate and butyl or ethyl acrylate treated with 3 parts by weight di-g 'ethanolamine or triethanolamine, or 6 parts by weight per 100 parts by weight CgO e 55% aqueous emulsion of copolymer 80, parts by weight vinyl acetate and 20, by weight. ethylene.
    [2]
    2. The method according to π. 1, characterized in that in the initial composition add an emulsion of acrylic resin based on 2 parts by weight of methacrylic acid, 50 parts by weight methyl methacrylate and 48 parts by weight butyl acrylate or acrylonitrile styrene resin based on 60 parts by weight methyl methacrylate and 40 parts by weight of styrene monomer treated with 0.5 parts by weight of diethanolamine or triethyl nolamine, in an “amount providing the total amount of non-volatiles in the aqueous polymer emulsion and“ acrylic resin or acrylonitrile styrene resin emulsion, equal to 26-54 parts by weight. per 100 parts by weight CrOj.
    [3]
    3. The method according to π. 1, t l and the fact that in the initial composition add 18 wt.h. per 100 parts by weight CrOj boric acid.
    [4]
    4. The method according to π. 1, characterized in that in the original 1 composition add 11 parts by weight glycerol or 16 parts by weight diethylene glycol per 100 parts by weight CrOj.
    [5]
    ! 5. The method according to π. 1, it is distinguished by the fact that the heat treatment is carried out at ZOO “7OO ° C.
    >
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    同族专利:
    公开号 | 公开日
    GB1524997A|1978-09-13|
    DE2546190A1|1976-04-22|
    DE2546190C3|1981-02-19|
    DE2546190B2|1980-06-12|
    JPS553429B2|1980-01-25|
    JPS51128650A|1976-11-09|
    BE840739A|1976-08-02|
    US4032675A|1977-06-28|
    SE7511469L|1976-04-20|
    AU8571275A|1976-11-04|
    SE415785B|1980-10-27|
    IT1043377B|1980-02-20|
    引用文献:
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    US3053692A|1958-01-29|1962-09-11|Allied Res Products Inc|Protective coating|
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    US3632362A|1969-06-27|1972-01-04|Nippon Steel Corp|Insulation coating for electrical steel sheet and method of application|US4138276A|1976-03-01|1979-02-06|J. M. Eltzroth & Associates, Inc.|Coating compositions|
    JPS5521111B2|1975-09-11|1980-06-07|
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    JPH0144387B2|1984-01-17|1989-09-27|Kawasaki Steel Co|
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    DE3520090C2|1985-06-05|1988-10-13|Stahlwerke Bochum Ag, 4630 Bochum, De|
    JPH0469664B2|1985-10-28|1992-11-06|Nisshin Steel Co Ltd|
    JPS6333578A|1986-07-25|1988-02-13|Nisshin Steel Co Ltd|Electrical steel sheet insulating film composition and method for forming insulating film|
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    JP2728836B2|1993-02-08|1998-03-18|川崎製鉄株式会社|Electrical steel sheet with electrical insulation coating with excellent weldability|
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    法律状态:
    优先权:
    申请号 | 申请日 | 专利标题
    JP11764674A|JPS553429B2|1974-10-15|1974-10-15|
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