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WO2012041052A1 - 一种无取向硅钢用无铬绝缘涂层涂料 - Google Patents

一种无取向硅钢用无铬绝缘涂层涂料 Download PDF

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Publication number
WO2012041052A1
WO2012041052A1 PCT/CN2011/072727 CN2011072727W WO2012041052A1 WO 2012041052 A1 WO2012041052 A1 WO 2012041052A1 CN 2011072727 W CN2011072727 W CN 2011072727W WO 2012041052 A1 WO2012041052 A1 WO 2012041052A1
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Prior art keywords
silicon steel
parts
oriented silicon
insulating coating
coating
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PCT/CN2011/072727
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English (en)
French (fr)
Inventor
许云鹏
杨勇杰
李登峰
吉亚明
赵自鹏
陈凌云
陈晓
黄杰
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Publication date
Application filed by Baoshan Iron and Steel Co Ltd filed Critical Baoshan Iron and Steel Co Ltd
Priority to EP11827948.8A priority Critical patent/EP2623566B1/en
Priority to MX2013003263A priority patent/MX349911B/es
Priority to KR1020137004688A priority patent/KR101433276B1/ko
Priority to RU2013114863/05A priority patent/RU2556101C2/ru
Priority to US13/818,258 priority patent/US9334405B2/en
Priority to JP2013528499A priority patent/JP5648128B2/ja
Publication of WO2012041052A1 publication Critical patent/WO2012041052A1/zh
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
    • C09D7/40—Additives
    • C09D7/48—Stabilisers against degradation by oxygen, light or heat
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
    • C09D5/08—Anti-corrosive paints
    • C09D5/082—Anti-corrosive paints characterised by the anti-corrosive pigment
    • C09D5/084—Inorganic compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/40—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes epoxy resins

Definitions

  • the present invention relates to the production of non-oriented silicon steel, and more particularly to a chromium-free insulating coating for non-oriented silicon steel. Background technique
  • Electrical steel is a ferrosilicon soft magnetic alloy with extremely low carbon content. It is mainly used in the manufacture of electrical equipment such as electric motors, generators, and transformer cores.
  • the iron loss of electrical steel is the main indicator to measure the performance of electrical steel products.
  • the iron loss mainly includes three parts: hysteresis loss, eddy current loss and abnormal loss.
  • Non-oriented Silicon steel is generally required to be stamped into a core-shaped blank during subsequent processing, and the laminate is fixed by riveting or splicing.
  • the surface of the non-oriented silicon steel sheet generally has an insulating coating to provide a high level of interlayer resistance, so that the eddy current loss of the stator is minimized after the silicon steel sheets are stacked into the stator material; the insulating coating is generally referred to as none.
  • Oriented coating should have good adhesion to ensure that the insulating coating does not fall off the edge of the silicon steel sheet when the silicon steel sheet is punched; the insulating coating should not be excessively powdered during stamping, grooving or shearing to prevent accumulation. On feed rolls or other equipment, wear the mold for stamping or shearing the lamination; at the same time, it should allow the core to be joined at a reasonable speed.
  • the insulating coating applied on the surface of non-oriented silicon steel can be divided into organic coating, inorganic coating and organic-inorganic composite coating, wherein the organic-inorganic composite coating combines the excellent punching property and pure inorganic coating of pure organic coating. It has excellent heat resistance and splicing properties, and it can meet the needs of users of the widest range, so it has been widely used.
  • U.S. Patent 4,844,753 discloses a solution for forming an insulating coating on electrical steel comprising an inorganic chromate film-forming component and a resin component, the resin component being a A mixture of acrylic acid or acrylic-styrene copolymer emulsion and melamine resin having a particle size of 0.2-1 ⁇ m.
  • U.S. Patent 4,618,377 discloses an inorganic/organic coating composition for forming an insulating coating on the surface of an electrical steel comprising an organic resin, a resin particle modified with a dispersing agent, and a resin containing at least one A solution of an inorganic phosphate or chromate component.
  • a method for producing a chromium-containing organic-inorganic insulating coating is disclosed in Korean Patent Nos. KR25106, No. 31,208, 31,219, U.S. Patent No. 4,316,751, U.S. Patent No. 4,498,936, and Japanese Patent Publication No. SHO-50-15013.
  • Korean Patent Nos. KR25106, No. 31,208, 31,219, U.S. Patent No. 4,316,751, U.S. Patent No. 4,498,936, and Japanese Patent Publication No. SHO-50-15013 due to the use of chromium oxides or chromates in these formulations, chromium Due to its carcinogenicity, acid salts are increasingly being restricted in their use today due to increasingly stringent environmental requirements.
  • chromium-free insulating coating formulations for non-oriented silicon steel have been rapidly developed.
  • a chromium-free semi-organic coating is typically introduced into the phosphate instead of the dichromate.
  • Phosphate coatings provide excellent insulation and heat resistance, but are prone to excessive wear on the mold when stamping the laminate, and the corrosion resistance and adhesion of the coating are degraded due to the absence of chromate.
  • U.S. Patent No. 2,743,203 discloses a good insulating film which can be obtained from a solution containing 7-50% of free phosphoric acid or phosphoric acid containing magnesium oxide.
  • U.S. Patent 4,496,399 is directed to an inorganic/organic phosphate insulating coating.
  • the inorganic portion of the composition is aluminum magnesium phosphate, colloidal silica and chromic anhydride, or an aluminum silicate microparticle, and the organic portion is an acrylic or vinyl acetate emulsion.
  • the disadvantage of this coating is that the inorganic portion contains free phosphoric acid, which reacts with the steel surface at high temperatures, and the magnesium phosphate compound must be cured at a high temperature to prevent the occurrence of the adhesive sheet, and the resin decomposes at a high temperature, resulting in a coating. It turns brown.
  • the use of chromic anhydride makes it not environmentally friendly.
  • Japanese Patent Publication No. 2004-322079 discloses that the corrosion resistance of the coating is improved by using a specific ratio of aluminum phosphate, magnesium phosphate, calcium phosphate complex phosphate. This coating is due to the use of phosphate, in which excess residual phosphoric acid is prone to sticking. Therefore, Japanese Inventions-JP-A-11-131250 and Korean Patent KR1999-26912 disclose the use of a silicon germanium coupling agent to prevent the occurrence of a sticking phenomenon caused by residual phosphoric acid.
  • a non-oriented silicon steel insulating coating excellent in corrosion resistance and adhesion is obtained by using a silica sol, an alumina sol, a zirconia fine particle or the like, as disclosed in Korean Patent No.
  • European Patent EP1208166B1 uses 100 parts of aluminum dihydrogen phosphate, 28-98 parts of acrylic acid-styrene emulsion, 6-18 parts of zinc nitrate, 4-13 parts of silicon compound, 18-35 g of ethylene glycol, and 3-l lg non-ion
  • the insulating coating liquid of the surfactant exhibits water absorption due to the absence of a stabilizer for residual phosphoric acid, and the presence of nitrate ions has a significant destructive effect on corrosion resistance due to the use of zinc nitrate.
  • 5,955,201 uses inorganic silicate particles as a stabilizer for residual phosphoric acid, effectively avoiding the problem of stickiness.
  • the inorganic silicate particles are not miscible with the solution system, so precipitation is likely to occur, and the effect is difficult to manifest when the mixing is uneven.
  • Patent WO 2008/016220 A1 discloses the use of cobalt hydroxide and barium hydroxide as residual phosphoric acid. Stabilizers can also avoid stickiness problems, but both are inorganic particles that are difficult to mix evenly.
  • the chromium-free coating used in domestic production has a small proportion of inorganic components.
  • the appearance of the coating is good and the punching performance is good, the high temperature resistance of the coating is poor, so that the interlayer resistance of the coating after high temperature treatment is lowered. Many, the insulation performance is greatly reduced, and it is easy to carburize, resulting in a decline in product performance.
  • Non-oriented silicon steel can be classified into white sheets and black sheets according to whether or not subjected to stress relief annealing.
  • Non-oriented silicon steel applications such as small and medium-sized motors and EI sheets require stress relief annealing of the coating to reduce the iron loss of the silicon steel sheet and improve its electrical properties.
  • Users in this field typically require a non-oriented silicon steel coating that exhibits a black-and-black appearance after being subjected to stress relief annealing. If the coating has no light after stress relief, it is generally considered that the annealing is not good and the insulation of the product is poor, which is likely to cause rejection by downstream users. After the stress-free annealing of the chrome-free coating, the coating has no gloss and does not meet the needs of the user.
  • an environmentally friendly semi-organic insulating coating for cold-rolled non-oriented electrical steel to provide good surface resistivity of non-oriented silicon steel sheets, reduce eddy current loss, good moisture absorption resistance, and silicon steel sheets.
  • the technical problem to be solved by the present invention is to provide a chromium-free insulating coating for non-oriented silicon steel, which uses cyclodecanoate and isooctanoate as a drier to effectively prevent the problem of stickiness of the chromium-free insulating coating.
  • the coated black sheet is black and has high gloss and is easily accepted by downstream users. It is a new type of non-oriented silicon steel chromium-free insulating coating with wide application prospects.
  • a chromium-free insulating coating for non-oriented silicon steel in parts by mass, including the following components: 100 parts of metal dihydrogen phosphate;
  • the metal dihydrogen phosphate which is used in a chromium-free coating liquid to improve the heat resistance and corrosion resistance of the insulating coating, can be obtained by mixing a metal hydroxide or an oxide with phosphoric acid. Its chemical formula is MH 2 P0 4 i, where n is the valence of the metal ion M. Commonly used metal dihydrogen phosphates are A1(3 ⁇ 4P0 4 )3, Mg(3 ⁇ 4P04) 2 , Ca(H 2 P04) 2 or Zn(H 2 P04) 2 and the like.
  • the molar ratio of A1 2 0 3 to H 3 P0 4 is 0.14 ⁇ 0.20: 1 ; for Mg(3 ⁇ 4P04) 2 , Ca(H 2 P04) 2 or Zn(3 ⁇ 4P04
  • the molar ratio of MO (metal oxide) to H 3 P0 4 is from 0.40 to 0.6:1.
  • MO metal oxide
  • the ratio of the metal oxide to the phosphoric acid is lower than the lower limit, the residual phosphoric acid in the solution is excessive, resulting in deterioration of the adhesiveness of the insulating coating and cannot be used; above the upper limit, the solution is unstable.
  • Such metal dihydrogen phosphates may be used singly or in combination.
  • the epoxy resin may be an epoxy resin emulsion or a water-soluble epoxy resin solution, such as E51, E44, E20 epoxy resin emulsion of Shanxi Boao Chemical Co., Ltd., or 681, 682 of Yingkou Xinghuo Chemical Co., Ltd. 811 water soluble epoxy resin.
  • Epoxy resin is used as an organic component in the coating solution to improve the adhesion and toughness of the insulating coating and prevent peeling between the coating and the substrate.
  • Epoxy resin is divided into two types: water-soluble and water-insoluble. For water-insoluble epoxy resin, it can be configured to be added in the form of dairy, while other types of epoxy resin can be directly dissolved by certain modification means.
  • this type of epoxy resin can be used directly in chrome-free coatings. If the content of such a substance is too small, the surface of the coating becomes too rough, and the coating is easily peeled off and powdered, and the adhesion of the coating is difficult to be ensured; on the contrary, if the content of such a substance is too large, the insulating coating is lowered. Heat resistance and splicing.
  • the resin emulsion is added in an amount of 10 to 60 parts by weight, preferably 8 to 60 parts by weight based on 100 parts by weight of the metal dihydrogen phosphate.
  • the drier is a coating additive.
  • the German standard DIN55901 defines the drier as follows: "Drying agent, also known as dry material in solution state, is an organometallic compound that is soluble in organic solvents and resins. From a chemical point of view, it belongs to metal soaps (metal salts of higher fatty acids), which can be added to unsaturated oils and resins to greatly shorten the drying time, ie accelerate the curing speed. Driers are usually divided into the following categories: 1) Main driers: They are generally A metal soap containing a plurality of oxidized valence states can undergo a redox reaction. Such driers commonly used in the industry are cobalt, manganese, vanadium and bismuth metal soaps.
  • Auxiliary Drier A metal soap that exists only in an oxidized valence state. It usually does not dry out. It only has a drier when used in combination with a main drier, such as calcium, potassium, strontium and zinc. Metal soap.
  • Coupling drier The mechanism in accelerating the reaction is based on the reaction of the metal with a hydroxyl group or a carboxyl group in the resin. This drier is called a coupling drier, such as a zirconium metal soap.
  • the drier of the present invention may be a commonly used metal cyclic bismuth silicate such as cobalt citrate, manganese, iron, copper, bismuth, zinc, calcium, potassium, strontium or nickel salt; or a metal isooctanoic acid Salt, such as potassium isooctanoate, manganese, sodium, nickel, copper, bismuth, zinc, zirconium or calcium salts.
  • metal cyclic bismuth silicate such as cobalt citrate, manganese, iron, copper, bismuth, zinc, calcium, potassium, strontium or nickel salt
  • a metal isooctanoic acid Salt such as potassium isooctanoate, manganese, sodium, nickel, copper, bismuth, zinc, zirconium or calcium salts.
  • the organic solvent may be ethylene glycol or glycerin, and the materials can be mutually melted in water, and at the same time, the cyclopentate and the isooctanoate drier can be well dissolved to reduce the surface tension of the solution and prevent Defects such as shrinkage cavities, leak coating, etc. are formed during the baking process of the coating.
  • Such materials are added in an amount of from 0.001 to 100 parts by weight based on 100 parts by weight of the metal dihydrogen phosphate.
  • Water as a main solvent functions to adjust the specific gravity in the coating paint of the present invention to facilitate coating, and is added in an amount of 60 parts by weight based on 100 parts by weight of the metal dihydrogen phosphate.
  • the mixture is stirred to form a homogeneous phase solution, that is, a chromium-free coating solution, and the stirred solution can be directly applied to various types of coating machine systems.
  • the thickness specification of the non-oriented silicon steel sheet may be 0.20 mm, 0.35 mm, 0.50 mm,
  • the non-oriented steel sheet of the above specifications subjected to the cold rolling process needs to be subjected to surface cleaning, then annealed, and then post-cleaned, and then applied to a roll coater for coating without a chromium coating.
  • the roll coater can be either two-roller or three-roller, and the coating roll is not limited.
  • the temperature of the strip in the baking section is 200--350 ° C. If the temperature is too low, the coating coating is incomplete and sticky, and the strength cannot be achieved. If the temperature is too high, the epoxy resin is decomposed and the coating is over-fired. Yellowing.
  • the chromium-free insulating coating paint of the invention has high appearance and high transparency after being coated with non-oriented silicon steel, and has excellent insulation, corrosion resistance, adhesion, splicability and manufacturability, and eliminates
  • the chrome-free coating is sticky and non-abrasive, and can achieve environmental protection of non-oriented silicon steel coating.
  • the chromium-free insulating coating of the present invention can be applied to high-grade, high-efficiency non-oriented electrical steel products, and can also be applied to low-grade non-oriented electrical steel products.
  • the coating liquid can be applied to a cold-rolled silicon steel substrate by a roll coater for baking to form a film, and thus can be applied to manufacturers of oriented silicon steel at home and abroad.
  • Formulation in parts by mass: Includes aluminum dihydrogen phosphate, cyclodecanoate drier, water-soluble epoxy resin, ethylene glycol and pure water. See Table 1 for details.
  • Adhesive punching burrs weldability interlayer resistance number oxime view corrosion resistance
  • Example 1 Slightly shedding >1.5 million times ⁇ 40 Surface brightness 15% 30
  • Example 2 No detachment > 1.7 million times ⁇ 30 Surface brightness 25% 45
  • Example 3 No detachment > 1.6 million times ⁇ 50 Surface brightness 15% 25
  • Example 4 No detachment > 1.7 million times ⁇ 40 Surface brightness 10% 48
  • Example 5 No shedding > 1.8 million times ⁇ 60 Surface brightness 20% 36
  • Example 6 No shedding > 1.6 million times ⁇ 50 Surface brightness 10%
  • Comparative example 1 Slightly shedding > 1.4 million times ⁇ 10 Surface smoothness 40% 15 Among them
  • the test conditions are as follows (the same below):
  • the splicing test conditions (the same below): inert gas tungsten machine protection TI (TIG), current value 120A, electrode material Th-W, argon flow rate 6L / min, pressure 50kg / cm 2 .
  • the coatings prepared by using the chromium-free insulating coating paint of the present invention have excellent properties.
  • Dihydrogen phosphate dihydrogen phosphate, magnesium dihydrogen phosphate, calcium dihydrogen phosphate or zinc dihydrogen phosphate
  • epoxy resin emulsion in dry parts
  • iso-xin The acid salt is dried 1", glycerol and pure water. See Table 3 for details.
  • Example 9 Aluminum dihydrogen phosphate, 100 E20, 15 80 Calcium isooctanoate, 5 1500
  • Example 1 1 Magnesium dihydrogen phosphate, 100 E51, 50 40 Cobalt octoate, 8 300
  • Example 13 Aluminum dihydrogen phosphate, 100 E44, 30 2 Isooctanoate, 5 200 Comparative Example 2
  • P (phosphorus) dissolution test A fixed-area coating sample is placed in waste water and boiled for 10 mm, and then ICP is used to test the P dissolved in the wastewater and then converted.

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Description

一种无取向硅钢用无铬绝缘涂层涂料 发明领域
本发明涉及无取向硅钢生产，具体涉及一种无取向硅钢的无铬绝缘涂 层涂料。 背景技术
电工钢是一种含碳量极低的硅铁软磁合金， 其主要用于制造电动机、 发电机、变压器铁心等电器设备。 电工钢的铁损是衡量电工钢产品性能的 主要指标， 铁损主要包括磁滞损耗、 涡流损耗和反常损耗三部分。 无取向 硅钢在后续加工时一般需要冲压成铁芯形状的坯料，叠片后通过铆接或悍 接的方式固定。
无取向硅钢片表面一般要有一层绝缘涂层，以提供一个高水平的层间 电阻， 使得硅钢片在冲片叠装成定子材料后， 定子的涡流损耗最小； 该绝 缘涂层一般称为无取向涂层。无取向涂层应该具有良好的附着性， 以保证 硅钢片在冲片时， 绝缘涂层不会从硅钢片边缘脱落； 绝缘涂层在冲压、 开 槽或剪断时不应过度粉化， 防止堆积在进料辊或其它设备上， 磨损用于冲 压或剪切叠片的模具； 同时应该允许以合理的速度进行铁心悍接。
涂敷在无取向硅钢表面的绝缘涂层可分为有机涂层、无机涂层和有机 无机复合涂层，其中有机无机复合涂层综合了纯有机涂层的优良冲片性和 纯无机涂层的优良耐热性和悍接性， 能够满足最大范围的用户的需要， 故 得到了广泛的应用。
例如， 美国专利 US4,844,753披露了一种用于在电工钢上形成绝缘涂 层的溶液， 它包括一种无机铬酸盐成膜组分和一种树脂组分， 所述树脂组 分为一种丙烯酸或丙烯酸 -苯乙烯共聚乳液和粒度为 0.2-1 μπι 的三聚氰胺 树脂的混合物。 美国专利 US4,618,377披露了一种用在电工钢表面形成绝 缘涂层的无机 /有机涂料组合物， 它包含一种有机树脂、 一种用助分散剂 改进了的树脂颗粒和一种含有至少一种无机磷酸盐或铬酸盐组分的溶液。 韩国专利 KR25106,31208,31219、 美国专利 US4,316,751、 US4,498,936以 及日本发明特公 -JP昭 50-15013 都分别披露了含铬有机-无机绝缘涂层的 制造方法。 然而， 由于这些配方中均使用到了铬的氧化物或铬酸盐， 而铬 酸盐由于其致癌性， 在环保要求日益苛刻的今天， 其使用也正在受到越来 越严格的限制。
由于上述原因， 无取向硅钢用无铬绝缘涂层配方得以快速的发展。一 般无铬半有机涂层引入磷酸盐代替重铬酸盐。磷酸盐涂层可以提供优良的 绝缘性能和耐热性， 但是容易在冲压叠片时对模具造成过分磨损， 而且由 于铬酸盐的缺失，使涂层耐蚀性和附着性下降。例如美国专利 US2,743,203 披露了可从含有 7-50%游离磷酸的溶液或溶有氧化镁的磷酸组成的溶液 获得良好的绝缘膜。美国专利 US4,496,399涉及到一种无机 /有机磷酸盐绝 缘涂层。 其成分的无机部分为磷酸铝镁、 胶体二氧化硅和铬酐， 或一种硅 酸铝微粒， 有机部分为丙烯酸或醋酸乙烯酯乳液。这种涂层的缺点是其无 机部分含有游离磷酸， 在高温下会与钢表面发生反应， 并且磷酸镁化合物 必须在高温下固化， 以预防粘片的发生， 而高温下树脂分解， 导致涂层变 成褐色。 同时铬酐的使用使其不具备环保的属性。
日本发明特公 -JP昭 2004-322079披露了通过采用特定比例的磷酸铝、 磷酸镁、磷酸钙复合磷酸盐的方法提高了涂层的耐蚀性。这种涂层由于采 用了磷酸盐， 其中过量的残余磷酸很容易产生粘片的现象。故日本发明特 公 -JP昭 11-131250和韩国专利 KR1999-26912披露了采用硅垸偶联剂防止 残余磷酸导致的粘片的现象发生。 韩国专利 KR1999-26911和日本发明特 公 -JP昭 3370235披露了采用氧化硅溶胶、 氧化铝溶胶、 氧化锆微粒等来 获得耐蚀性、 附着性优良的无取向硅钢绝缘涂层。这类以磷酸盐和无机溶 胶作为主剂的配方， 由于磷酸盐的存在使粘片性问题仍然突出， 而胶体氧 化硅的存在则导致了耐蚀性的降低。
对于采用磷酸盐作为主剂的无铬半有机涂层而言，由于残余磷酸的原 因， 极易出现粘片性差的问题。 欧洲专利 EP1208166B1采用 100份磷酸 二氢铝、 28-98份丙烯酸-苯乙烯乳液、 6-18份硝酸锌、 4-13份硅的化合物、 18-35g乙二醇， 以及 3-l lg非离子表面活性剂的绝缘涂液， 由于没有残余 磷酸的稳定剂， 故表现出吸水性， 同时由于采用了硝酸锌， 硝酸根离子的 存在对耐蚀性具有显著的破坏作用。 美国专利 US5,955,201采用无机硅酸 盐颗粒作为残余磷酸的稳定剂， 有效避免了粘片性的问题。但无机硅酸盐 颗粒与溶液体系不混溶，故极易产生沉淀，在搅拌不均时其效果难以体现。 专利 WO2008/016220A1公开了采用氢氧化钴和氢氧化锶作为残余磷酸的 稳定剂， 也可以避免粘片性问题， 但两者均为无机颗粒， 难以混合均匀。 目前国内生产使用的无铬涂层中， 无机成分比例较少， 虽然涂层的外 观好， 冲片性能好， 但是涂层的耐高温性能差， 使高温处理后涂层的层间 电阻值降低很多， 绝缘性能大为降低， 而且容易渗碳， 导致产品性能的下 降。
无取向硅钢按照是否经历消除应力退火可以分为白片和黑片。中小电 机、 EI 片等无取向硅钢应用领域需要对涂层进行消除应力退火， 以降低 硅钢片的铁损值， 改善其电性能。这一领域的用户一般要求无取向硅钢涂 层在经受消除应力退火后， 呈现乌黑发亮的外观。若涂层消除应力后无光 泽， 则一般认为退火不佳， 产品绝缘性差， 容易引起下游用户的拒绝。 以 上无铬涂层在消除应力退火后， 涂层均没有光泽， 未满足用户的需要。
因此，特别需要研制一种用于冷轧无取向电工钢的环保型半有机绝缘 涂层， 以提供无取向硅钢片良好的表面电阻率， 降低涡流损耗， 良好的抗 吸湿性能， 以及与硅钢片具有良好的附着性， 使得在分条、 冲压过程中不 粉化以保护模具； 在悍接过程中不产生过量气孔， 且能与压缩机中采用的 各种冷冻剂以及冷冻机油不反应；并且在生产过程中以及用户使用过程中 不产生六价铬等有害物质。
2003年 2月 13日欧盟委员会和欧洲议会颁布了两项标准指令， g卩： 电子电器设备废弃物的指令 （WEEE) 和电子电器设备中限制使用某些有 害物质的指令 （ROHS ) 。 该指令要求， 2006年 7月 1 日起欧盟市场上销 售的电子电器产品中有害元素的指标必须符合规定， 要限制的有害物质 有： 镉、 铅、 水银、 六价铬、 多溴联苯、 聚合溴化联苯乙醚等。 发明概述
本发明所要解决的技术问题在于提供一种无取向硅钢用无铬绝缘涂 层涂料， 采用环垸酸盐和异辛酸盐类为催干剂， 有效的防止了无铬绝缘涂 层发粘的问题， 同时涂层黑片乌黑且光泽度高， 易于被下游用户接受， 是 一种具有广泛应用前景的新型无取向硅钢无铬绝缘涂层涂料。
为了达到上述目的， 本发明采用以下技术方案来实现。
一种无取向硅钢用无铬绝缘涂层涂料，以质量份数计，包括以下组分: 金属磷酸二氢盐 100份；
环氧树脂 10~60份；
环垸酸盐或金属异辛酸盐催干剂 0.001 10份；
有机溶剂 0.001~100份；
纯水 60 2000份。
所述金属磷酸二氢盐，其在无铬涂液中用以提高绝缘涂层的耐热性和 耐蚀性， 可以通过金属氢氧化物或氧化物与磷酸混合的方式获得。其化学 通式为 M H2P04 i， 其中 n为金属离子 M的化合价。 常用的金属磷酸二 氢盐有 A1(¾P04)3、 Mg(¾P04)2、 Ca(H2P04)2或 Zn(H2P04)2等。 对于 A1(H2P04)3而言， 其 A1203与 H3P04 的摩尔比为 0.14〜 0.20: 1 ; 对于 Mg(¾P04)2、 Ca(H2P04)2或 Zn(¾P04)2类二价金属磷酸盐而言， 其 MO (金属氧化物）与 H3P04的摩尔比为 0.40〜0.6: 1。一般来说， 当金属氧化 物与磷酸的比值低于下限， 则溶液中残余磷酸过多， 导致绝缘涂层粘片性 恶化而不能使用； 高于上限则造成溶液不稳定。这类金属磷酸二氢盐可以 单独使用， 也可以混合使用。
所述环氧树脂， 可以是环氧树脂乳液或水溶性环氧树脂溶液， 例如山 西博奥化工有限公司的 E51、 E44、 E20环氧树脂乳液， 或营口市星火化 工有限公司的 681、 682、 811水溶性环氧树脂。 环氧树脂作为有机组分在 涂层溶液中用以提高绝缘涂层的附着性和韧性，防止涂层与基板之间发生 剥离的现象。环氧树脂分为水溶性和水不溶两大品种， 对于不溶于水的环 氧树脂， 可以配置成乳业形式加入， 而其他种类的环氧树脂， 可以通过一 定的改性手段， 使之直接溶解到水中， 这类环氧树脂可以直接应用于无铬 涂液中。 若此类物质含量太少， 则涂层表面变得过于粗糙、 且涂层容易剥 落和粉化， 涂层的附着性难以得到保证； 反之， 此类物质含量太多， 则会 降低绝缘涂层的耐热性和悍接性。 该树脂乳液的添加量为 10~60重量份， 优选 8~60重量份 （以 100重量份金属磷酸二氢盐计） 。
所述催干剂是一种涂料添加剂， 德国标准 DIN55901对催干剂有如下 定义： "催干剂， 在溶液状态也称为干料， 是一种有机金属化合物， 可以 溶于有机溶剂和树脂中。 从化学角度讲， 它属于金属皂类（即高级脂肪酸 的金属盐类） ， 加入到不饱和油类和树脂中， 可以大大缩短干燥时间， 即 加快固化速度" 。 催干剂通常分为以下几类： 1 ) 主催干剂： 它们一般是 含有多个氧化价态的金属皂， 能发生氧化还原反应。工业上常用的这类催 干剂有钴、 锰、 钒和铈类金属皂。 2 ) 辅助催干剂： 只以一种氧化价态存 在的金属皂， 本身通常不起催干作用， 只有和主催干剂配合使用时才具有 催干作用， 如钙、 钾、 钡和锌类金属皂。 3 ) 偶联催干剂： 在加速反应过 程中的机理是基于金属与树脂中羟基基团或羧基基团的反应，这种催干剂 称为偶联催干剂， 如锆类金属皂。
本发明所述的催干剂可以是常用的金属环垸酸盐， 如环垸酸钴、 锰、 铁、 铜、 铈、 锌、 钙、 钾、 钡或镍盐等； 或者是金属异辛酸盐， 如异辛酸 钾、 锰、 钠、 镍、 铜、 铈、 锌、 锆或钙盐等。 此类物质可以单独使用， 也 可以多种复合使用，在无铬涂液中，催化树脂的交联反应，使之更快成膜， 同时提高涂层的硬度和耐磨性。该催干剂的添加量为 0.001 10重量份（以 100重量份金属磷酸二氢盐计） 。
所述有机溶剂可以是乙二醇或丙三醇， 此类物质在水中可以互融， 同 时可以很好的溶解如环垸酸盐和异辛酸盐类催干剂， 降低溶液的表面张 力， 防止在涂层烘烤过程中形成缩孔、 漏涂等缺陷。 此类物质的添加量为 0.001~100重量份 （以 100重量份金属磷酸二氢盐计） 。
水作为主要溶剂， 在本发明的涂层涂料中起到调节比重的功能， 以更 利于涂敷，其添加量为 60 2000重量份（以 100重量份金属磷酸二氢盐计）。
将上述五种成分，按照所述比例混合后，搅拌使之成为均一相的溶液， 即为无铬涂层涂料溶液，搅拌好的溶液可以直接应用于各种类型的涂层机 系统。
所述的无取向硅钢板的厚度规格可以是 0.20mm、 0.35mm, 0.50mm,
0.65mm等各种规格， 经过冷轧工序的上述规格的无取向钢板需要再经历 表面清洗后， 进行退火， 然后进行后清洗， 即可进入辊涂机进行无铬涂层 的涂敷。 辊涂机可以是两辊式， 也可以是三辊式， 涂层辊刻槽与否不受限 制。 烘烤段的带钢温度为 200--350°C， 温度太低则涂层涂料反应不完全而 发粘， 无法达到应有的强度； 温度太高则导致环氧树脂分解， 涂层过烧发 黄。
有益效果
本发明的无铬绝缘涂层涂料， 经向无取向硅钢涂层后， 其外观高度透 明， 具有优异的绝缘性、 耐腐蚀性、 附着性、 悍接性、 可制造性， 消除了 无铬涂层发粘、 不耐磨的缺陷， 可以实现无取向硅钢涂层的环保。
本发明的无铬绝缘涂层涂料可以应用于高牌号、高效无取向电工钢产 品， 也可以应用在中低牌号无取向电工钢产品中。仅通过辊涂机将涂层涂 料液涂覆到冷轧硅钢基板上进行烘烤成膜即可，因此可以向国内外取向硅 钢的生产厂家推广应用。 发明的详细说明
以下结合具体实施例进一歩阐述本发明的技术方案，但实施例并不限制本 发明技术方案的保护范围。
实施例 1~6
1 ) 配方 （以质量份数计） ： 包括磷酸二氢铝、 环垸酸盐催干剂、 水 溶性环氧树脂、 乙二醇和纯水， 具体参见表 1。
2 ) 制备及应用： 常温下将上述各组分混合后采用搅拌装置低速搅拌 使之成为均一相的溶液， 采用辊涂机涂敷于厚 0.5mm 的无取向硅钢板的 表面， 保持涂敷量为 1.8g/m2， 采用明火烘烤炉， 在 200-500°C板温条件下 烘烤成膜， 各涂层的性能结果参见表 2。 表 1
Figure imgf000007_0001
表 2
附着性 冲片性毛剌 焊接性 层间电阻 编 号 夕卜 观 耐蚀性
O=20cm 50μηι cm/min Ω ιη2/片 实施例 1 稍有脱落 >150万次 <40 表面光亮 15% 30 实施例 2 无脱落 >170万次 <30 表面光亮 25% 45 实施例 3 无脱落 >160万次 <50 表面光亮 15% 25 实施例 4 无脱落 >170万次 <40 表面光亮 10% 48 实施例 5 无脱落 >180万次 <60 表面光亮 20% 36 实施例 6 无脱落 >160万次 <50 表面光亮 10% 42 比较例 1 稍有脱落 >140万次 <10 表面光滑 40% 15 其中各性能测试条件分别如下 （下同） ：
附着性测试： GB 2522-88。
冲片性测试： 毛剌高度>5(^111时的冲片次数。
悍接性测试条件（下同）：惰性气体钨机保护悍（TIG) ,电流值 120A, 电极材料 Th-W， 氩气流量 6L/min， 压力 50kg/cm2。
耐蚀性测试： JIS Z2371。
层间电阻测试： JIS C2550 o
由表 2数据可可以看出：使用本发明的无铬绝缘涂层涂料制得的涂层 各项性能均较优秀。
实施例 8~14
1 ) 配方 （以质量份数计） ： 磷酸二氢盐 （磷酸二氢铝、 磷酸二氢镁、 磷酸二氢钙或磷酸二氢锌） 、 环氧树脂乳液 （以干份计） 、 异辛酸盐催干 齐 1」、 丙三醇和纯水， 具体参见表 3。
2 ) 制备及应用： 室温下将上述各组分混合后采用磁力搅拌装置搅拌 lOmin后，采用辊涂机涂敷于厚 0.5mm无取向硅钢板的表面，保持涂敷量 为 1.8g/m2， 采用明火烘烤炉， 在 200-500°C板温条件下烘烤成膜， 各涂层 性能结果参见表 4。 表 3
配 方
编 号
磷酸二氢盐 环氧树脂乳液 丙三醇 异辛酸盐催干剂 纯水 实施例 7 磷酸二氢镁， 100 E51 , 10 0.01 异辛酸锰， 1 700 实施例 8 磷酸二氢钙， 100 E44, 35 100 异辛酸锆， 0.5 900 实施例 9 磷酸二氢铝， 100 E20, 15 80 异辛酸钙， 5 1500 实施例 10 磷酸二氢锌， 100 E44, 60 50 异辛酸铈， 2 1900 实施例 1 1 磷酸二氢镁， 100 E51 , 50 40 异辛酸钴， 8 300 实施例 12 磷酸二氢锌， 100 E20, 45 10 异辛酸锌， 10 400 实施例 13 磷酸二氢铝， 100 E44, 30 2 异辛酸铈， 5 200 比较例 2 含铬绝缘涂层， 配方： 铬酸盐 +苯丙共聚乳液 +硼酸 +丙三醇 表 4
Figure imgf000009_0001
其中：
P (磷） 溶出测试： 将固定面积的涂层试样置于废水中煮沸 lOmm, 然后采用 ICP对废水中溶出的 P进行测试后换算而得。
外观： 表面是否发粘， 用手触摸表面， 判断是否有发粘的感觉。 从表 4可以看出： 实施例 7--13的无铬涂层各项性能均较为优秀， 且 P溶出数据均较低， 有效避免了涂层发粘的问题。
从以上实施例 1~13可以看出： 通过本发明的实施， 可以获得性能优 异的无铬绝缘涂层无取向硅钢产品， 从而实现了对含铬涂层的替代， 满足 欧盟等国家对硅钢产品过程环保的要求。

Claims

权 利 要 求 书
1. 一种无取向硅钢用无铬绝缘涂层涂料，以质量份数计， 包括以下组 分：
金属磷酸二氢盐 100份；
环氧树脂 10~60份；
环垸酸盐或金属异辛酸盐催干剂 0.001 10份；
有机溶剂 0.001~100份；
纯水 60 2000份。
2. 根据权利要求 1所述的无取向硅钢用无铬绝缘涂层涂料，其特征在 于， 所述金属磷酸二氢盐为 A1(H2P04)3、 Mg(¾P04)2、 Ca(H2P04)2或 Zn(H2P04)2 o
3. 根据权利要求 2所述的无取向硅钢用无铬绝缘涂层涂料，其特征在 于， 所述 A1(H2P04)3中， A1203与 ¾P04的摩尔比为 0.14〜0.20: 1。
4. 根据权利要求 2所述的无取向硅钢用无铬绝缘涂层涂料，其特征在 于， 所述 Mg(H2P04)2、 Ca(H2P04)2或 Zn(¾P04)2中， MgO、 CaO或 ZnO 与 H3P04的摩尔比为 0.40〜0.6: 1。
5. 根据权利要求 1所述的无取向硅钢用无铬绝缘涂层涂料，其特征在 于， 所述环氧树脂为水溶性环氧树脂或环氧树脂乳液。
6. 根据权利要求 1所述的无取向硅钢用无铬绝缘涂层涂料，其特征在 于， 所述环垸酸盐催干剂为环垸酸钴、 锰、 铁、 铜、 铈、 锌、 钙、 钾、 钡 或镍盐。
7. 根据权利要求 1所述的无取向硅钢用无铬绝缘涂层涂料，其特征在 于， 所述金属异辛酸盐催干剂为异辛酸钾、 锰、 钠、 镍、 铜、 铈、 锌、 锆 或钙盐。
8. 根据权利要求 1所述的无取向硅钢用无铬绝缘涂层涂料，其特征在 于， 所述有机溶剂为乙二醇或丙三醇。
9. 根据权利要求 1所述的无取向硅钢用无铬绝缘涂层涂料，其特征在 于， 所述环垸酸盐或金属异辛酸盐催干剂优选 5~8份。
PCT/CN2011/072727 2010-09-29 2011-04-13 一种无取向硅钢用无铬绝缘涂层涂料 Ceased WO2012041052A1 (zh)

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KR1020137004688A KR101433276B1 (ko) 2010-09-29 2011-04-13 무방향성 실리콘 강을 위한 크롬-비함유 절연 코팅 물질
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US13/818,258 US9334405B2 (en) 2010-09-29 2011-04-13 Chromium-free insulation coating material for non-oriented silicon steel
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109251603A (zh) * 2018-08-14 2019-01-22 常州工程职业技术学院 一种电工钢用耐高温环保型绝缘涂料及其制备方法
CN116144240A (zh) * 2021-11-22 2023-05-23 宝山钢铁股份有限公司 一种轻粘性硅钢环保绝缘涂料、硅钢板及其制造方法

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* Cited by examiner, † Cited by third party
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Citations (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB252288A (en) 1925-05-06 1926-05-27 Edward Charles Wasdell Improved attachment of bracket or the like to the blade of a cycle mudguard
US2743203A (en) 1951-08-29 1956-04-24 Westinghouse Electric Corp Phosphate coating for electrical steel
JPS5015013A (zh) 1973-04-30 1975-02-17
US4316751A (en) 1980-04-14 1982-02-23 Hooker Chemicals & Plastics Corp. Electrical resistance coating for steel
US4496399A (en) 1984-05-21 1985-01-29 Armco Inc. Method and aqueous coating compositions for forming anti-stick and insulative coatings on semi-processed and fully-processed electrical steels
US4498936A (en) 1984-05-21 1985-02-12 Armco Inc. Insulative coating composition for electrical steels
US4618377A (en) 1985-02-09 1986-10-21 Nippon Steel Corporation Method for surface treatment of electrical steel sheet
US4844753A (en) 1986-07-25 1989-07-04 Nisshin Steel Co. Ltd. Method for forming insulating films on electromagnetic steel plates
JPH11131250A (ja) 1997-10-28 1999-05-18 Nippon Steel Corp 被膜特性の優れる無方向性電磁鋼板用表面処理剤とそれを用いた被膜形成方法
US5955201A (en) 1997-12-19 1999-09-21 Armco Inc. Inorganic/organic insulating coating for nonoriented electrical steel
WO2001068778A1 (en) * 2000-03-16 2001-09-20 Pohang Iron & Steel Co., Ltd. Coating composition for forming insulating films, non-oriented electrical steel sheet with the coating composition coated thereon, and method for forming the insulating films on the steel sheet
JP3370235B2 (ja) 1996-07-30 2003-01-27 川崎製鉄株式会社 耐食性に優れた歪取り焼鈍が可能なクロム化合物を含まない絶縁被膜を電磁鋼板の表面に形成する方法
JP2004322079A (ja) 2003-04-10 2004-11-18 Nippon Steel Corp 被膜性能の優れる無方向性電磁鋼板と絶縁被膜処理剤および絶縁被膜処理方法
WO2008016220A1 (en) 2006-08-02 2008-02-07 Posco Coating solution for forming insulating film with excellent corrosion resistance property and film close adhesion property and film intensity without chrome and a method for making the insulation film on non-oriented electrical steel sheet by using it
CN101486866A (zh) * 2009-02-20 2009-07-22 南京大学 耐高温退火处理的单组分无铬水基硅钢片绝缘涂液
CN101560342A (zh) * 2008-12-17 2009-10-21 马鞍山钢铁股份有限公司 具有优良耐蚀性能的无取向电工钢半有机磷酸盐绝缘涂料
CN101659799A (zh) * 2009-09-11 2010-03-03 艾宝魁 一种电工钢绝缘涂料,其制备方法及涂覆方法

Family Cites Families (19)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
SU380680A1 (ru) * 1970-03-06 1973-05-15 Электроизоляционный лак
JPS589522B2 (ja) * 1973-04-23 1983-02-21 リケンデンセン カブシキガイシヤ ナンネンセイゼツエンデンセン
SU655712A1 (ru) * 1977-03-15 1979-04-05 Хабаровский институт инженеров железнодорожного транспорта Электроизол ционный состав
KR900004225B1 (ko) * 1987-02-04 1990-06-18 금성전선 주식회사 자기 융착 절연 바니쉬 조성물
US5364899A (en) * 1992-01-24 1994-11-15 Denki Kagaku Koguo Kabushiki Kaisha Flame-retardant resin composition
JP3117846B2 (ja) * 1993-07-26 2000-12-18 新日本製鐵株式会社 皮膜特性の優れる無方向性電磁鋼板及びその鋼板用表面処理剤
JP2944849B2 (ja) * 1993-05-21 1999-09-06 新日本製鐵株式会社 被膜特性の極めて良好な無方向性電磁鋼板の製造方法
JP3397291B2 (ja) * 1997-09-01 2003-04-14 新日本製鐵株式会社 被膜特性に優れた絶縁被膜を有する無方向性電磁鋼板及びその製造方法並びにその製造に用いる絶縁被膜形成剤
JP3408410B2 (ja) * 1997-11-19 2003-05-19 新日本製鐵株式会社 無方向性電磁鋼板用表面処理剤とそれを用いた皮膜形成方法
KR100388025B1 (ko) 1998-11-09 2003-12-31 주식회사 포스코 외관 및 슬리팅 가공특성이 우수한 절연피막형성용 피복조성물및 이를 이용한 무방향성 전기강판의 절연피막 형성방법
CN1306051A (zh) * 2000-11-16 2001-08-01 于清文 钢釉王涂漆及其生产方法
JP2004111884A (ja) 2002-07-24 2004-04-08 Nippon Steel Corp 絶縁性と耐食性の極めて優れる変圧器鉄心およびその製造方法
DE10202545A1 (de) * 2002-01-24 2003-08-07 Basf Coatings Ag Korrosionshemmende Mischung und Beschichtungsstoffe, enthaltend die korrosionshemmende Mischung
JP4500113B2 (ja) * 2003-06-16 2010-07-14 Ｊｆｅスチール株式会社 高耐食性表面処理鋼板及びその製造方法
KR100762465B1 (ko) * 2006-08-02 2007-10-04 주식회사 포스코 크롬이 배제된 내식성과 응력제거소둔후 피막밀착성이우수한 절연피막 형성용 피복조성물 및 이를 이용한무방향성 전기강판의 절연피막 형성방법
CN101358096B (zh) * 2008-09-05 2011-12-07 首钢总公司 一种无取向电工钢用的绝缘环保涂料
EP3483195A1 (en) * 2009-09-18 2019-05-15 Swimc, LLC Polyurethane coating composition
US9279051B2 (en) * 2011-09-22 2016-03-08 Elite Material Co., Ltd. Halogen-free resin composition, and copper clad laminate and printed circuit board using same
WO2014115778A1 (ja) * 2013-01-25 2014-07-31 カネカ ノース アメリカ エルエルシー ポリマー微粒子含有硬化性樹脂組成物

Patent Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB252288A (en) 1925-05-06 1926-05-27 Edward Charles Wasdell Improved attachment of bracket or the like to the blade of a cycle mudguard
US2743203A (en) 1951-08-29 1956-04-24 Westinghouse Electric Corp Phosphate coating for electrical steel
JPS5015013A (zh) 1973-04-30 1975-02-17
US4316751A (en) 1980-04-14 1982-02-23 Hooker Chemicals & Plastics Corp. Electrical resistance coating for steel
US4496399A (en) 1984-05-21 1985-01-29 Armco Inc. Method and aqueous coating compositions for forming anti-stick and insulative coatings on semi-processed and fully-processed electrical steels
US4498936A (en) 1984-05-21 1985-02-12 Armco Inc. Insulative coating composition for electrical steels
US4618377A (en) 1985-02-09 1986-10-21 Nippon Steel Corporation Method for surface treatment of electrical steel sheet
US4844753A (en) 1986-07-25 1989-07-04 Nisshin Steel Co. Ltd. Method for forming insulating films on electromagnetic steel plates
JP3370235B2 (ja) 1996-07-30 2003-01-27 川崎製鉄株式会社 耐食性に優れた歪取り焼鈍が可能なクロム化合物を含まない絶縁被膜を電磁鋼板の表面に形成する方法
JPH11131250A (ja) 1997-10-28 1999-05-18 Nippon Steel Corp 被膜特性の優れる無方向性電磁鋼板用表面処理剤とそれを用いた被膜形成方法
US5955201A (en) 1997-12-19 1999-09-21 Armco Inc. Inorganic/organic insulating coating for nonoriented electrical steel
WO2001068778A1 (en) * 2000-03-16 2001-09-20 Pohang Iron & Steel Co., Ltd. Coating composition for forming insulating films, non-oriented electrical steel sheet with the coating composition coated thereon, and method for forming the insulating films on the steel sheet
EP1208166B1 (en) 2000-03-16 2004-07-14 POHANG IRON &amp; STEEL CO., LTD. Coating composition for forming insulating films, non-oriented electrical steel sheet with the coating composition coated thereon, and method for forming the insulating films on the steel sheet
JP2004322079A (ja) 2003-04-10 2004-11-18 Nippon Steel Corp 被膜性能の優れる無方向性電磁鋼板と絶縁被膜処理剤および絶縁被膜処理方法
WO2008016220A1 (en) 2006-08-02 2008-02-07 Posco Coating solution for forming insulating film with excellent corrosion resistance property and film close adhesion property and film intensity without chrome and a method for making the insulation film on non-oriented electrical steel sheet by using it
CN101560342A (zh) * 2008-12-17 2009-10-21 马鞍山钢铁股份有限公司 具有优良耐蚀性能的无取向电工钢半有机磷酸盐绝缘涂料
CN101486866A (zh) * 2009-02-20 2009-07-22 南京大学 耐高温退火处理的单组分无铬水基硅钢片绝缘涂液
CN101659799A (zh) * 2009-09-11 2010-03-03 艾宝魁 一种电工钢绝缘涂料,其制备方法及涂覆方法

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
EU COMMISSION AND EUROPEAN PARLIAMENT, 13 February 2003 (2003-02-13)
See also references of EP2623566A4

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109251603A (zh) * 2018-08-14 2019-01-22 常州工程职业技术学院 一种电工钢用耐高温环保型绝缘涂料及其制备方法
CN116144240A (zh) * 2021-11-22 2023-05-23 宝山钢铁股份有限公司 一种轻粘性硅钢环保绝缘涂料、硅钢板及其制造方法
CN116144240B (zh) * 2021-11-22 2024-04-05 宝山钢铁股份有限公司 一种轻粘性硅钢环保绝缘涂料、硅钢板及其制造方法

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