WO2005105937A1 - Aqueous self-adhesive coating for electrical steel and its uses - Google Patents

Aqueous self-adhesive coating for electrical steel and its uses Download PDF

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Publication number
WO2005105937A1
WO2005105937A1 PCT/CN2005/000578 CN2005000578W WO2005105937A1 WO 2005105937 A1 WO2005105937 A1 WO 2005105937A1 CN 2005000578 W CN2005000578 W CN 2005000578W WO 2005105937 A1 WO2005105937 A1 WO 2005105937A1
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WIPO (PCT)
Prior art keywords
coating
electrical steel
adhesive coating
water
self
Prior art date
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Ceased
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PCT/CN2005/000578
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English (en)
French (fr)
Inventor
Changguo Huang
Feng Yu
Xiao Chen
Zhigang Yu
Zhuolei Chen
Meiping Zou
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Baoshan Iron and Steel Co Ltd
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Baoshan Iron and Steel Co Ltd
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Priority to US11/587,733 priority Critical patent/US7655709B2/en
Priority to DE112005000992T priority patent/DE112005000992B4/de
Publication of WO2005105937A1 publication Critical patent/WO2005105937A1/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
    • C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/4007—Curing agents not provided for by the groups C08G59/42 - C08G59/66
    • C08G59/4014—Nitrogen containing compounds
    • C08G59/4021—Ureas; Thioureas; Guanidines; Dicyandiamides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
    • C08G59/686—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing nitrogen

Definitions

  • the invention relates to a coating for electrical steel and its use, in particular to a water-based self-adhesive coating for electrical steel and its use. Background technique
  • the welding fixing method causes short-circuits at the edges of the iron core, lowers the insulation properties, and has various problems such as deterioration of magnetic characteristics due to thermal deformation.
  • the coating film burns during welding to generate harmful gases, and the connection force is not very good.
  • the welding and riveting methods are not suitable for many micromotors. Therefore, the method of bonding electrical steel sheets together to form an iron core becomes an attractive fixing method. If an adhesive is applied to each of the cut electrical steel sheets, the production efficiency is very low, and the problems of difficult to control and uniform bonding conditions also exist. Therefore, directly applying the adhesive on the surface of the coil to form a self-adhesive coating can greatly improve the subsequent processing efficiency.
  • Such electrical steel sheets can be stored in sheet or rolled form for a long time before manufacturing the iron core.
  • the steel sheet will not rust during storage, and will not cause various problems such as cracking of the coating film.
  • the user can The coated surface of the substrate is heated and pressed to obtain an iron core with excellent performance with high interlayer adhesion strength.
  • Thyssen EBG has developed a steel plate with a self-adhesive coating, which at the same time has the functions of insulation, corrosion resistance, improved punchability and mutual bonding.
  • This product can be used for the long stator core of magnetic levitation train.
  • the self-adhesive coating used by EBG is a solvent-based product, and a large amount of solvent will be volatilized during the coating and baking process.
  • an incinerator needs to be added to burn off the solvent.
  • it is not suitable for open flame baking equipment.
  • Kawasaki Steel has proposed an aqueous thermal adhesive coating composition (Japanese Patent Publication Heisei 6—
  • This method uses a thermoplastic synthetic resin emulsion, an epoxy resin emulsion, a curing agent, and a film-forming aid, and can be coated on a steel plate to form a self-adhesive coating.
  • the composition is a mixture of a thermoplastic resin emulsion and an epoxy resin emulsion, the two are not completely compatible, and the resulting coating is non-uniform, opaque, and has poor peel strength and shear strength.
  • a large amount of film-forming aids must be added, which will cause peeling of the coating.
  • the water-based self-adhesive coating for electric steel of the present invention contains an aqueous epoxy resin emulsion and a curing agent.
  • the content of the water-based epoxy resin emulsion is 81 to 99.9 parts by weight, preferably 81 to 95 parts by weight, and more preferably 81 to 90 parts by weight; if the amount is higher than 99.9 parts by weight, it may be caused by the content of the curing agent in the system being too low. Insufficient curing of the coating; if the amount of epoxy resin emulsion is less than 81 parts by weight, excessive curing of the coating due to too much curing agent in the system will result in poor peel strength.
  • the solid content of the aqueous epoxy resin emulsion is 10-80%, based on the weight of the emulsion. The solid content is preferably 30-70% by weight, and more preferably 40-60% by weight.
  • Epoxy resin is a low-molecular-weight compound containing two (or more) active epoxy groups in one molecule, which is liquid or solid at room temperature.
  • Epoxy resins can be obtained by reacting polyhydric alcohols, polyhydric phenols and halogenated alcohols, including bisphenol A type, halogenated bisphenol A type, phenolic type, polyethylene glycol bisphenol A type, epoxidized oil, and the like.
  • all of the above epoxy resins having an epoxy equivalent range of 93 to 5500 can be used, and the epoxy equivalent is preferably 200 to 4000.
  • These epoxy resins can be used alone or in combination.
  • Representative epoxy resins are bisphenol A diglycidyl ether epoxy resins produced by Shell Chemicals, a joint venture between the United Kingdom and the Netherlands, such as Epikote # 828, # 1001, # 1002, # 1004, # 1007, their The molecular weight increases with the model.
  • YD-011, 001, 001Z, 012, 014, ST-5080, 5100; YDCN-701, 702, 703, 704; YDPN-638, etc. produced by Toto Kasei Corporation of Japan can be used in the present invention.
  • rubber-modified epoxy resins can also be used, such as EPI-REZ3519 from Resolution Corporation in the United States. Such epoxy resins will increase the toughness of the coating, thereby improving the bonding strength of the coating.
  • the preparation of the aqueous epoxy resin emulsion of the present invention is: pulverizing the epoxy resin, for example, using a Raymond machine, or a jet mill, or a pendulum mill; then, in the presence of an emulsifier, the Formed by forced emulsification.
  • an emulsifier In addition to the emulsifier, a polyoxyethylene alkylphenol ether system can also be used.
  • co-emulsifiers are: polyoxyethylene, polyoxypropylene, block polyethers, or adducts of these and diisocyanate compounds, which can be used alone or in combination.
  • the present invention can also directly use water-based epoxy resin emulsion products, such as the emulsion GEM03 of Shanghai Lujia Water-based Coatings Co., Ltd., which is a bisphenol A epoxy resin emulsion; Type; for example, EPI-REZ3540 from the US Resolution Corporation.
  • aqueous epoxy resin emulsion can also be prepared in a synthetic manner and used in the present invention.
  • a polyhydric alcohol, a polyhydric phenol, and a halogenated alcohol are polymerized in water to obtain an aqueous epoxy resin emulsion.
  • the amount of the curing agent is 0.07 to 17 parts by weight, preferably
  • the curing agent of the present invention is selected from one of dicyandiamide series, boron trifluoride complex, imidazole derivative, organic hydrazide, diaminomaleonitrile and its derivative, melamine and its derivative, or the like Multiple.
  • dicyandiamide adipic acid dihydrazide, amide ethylpiperazine, piperidine heterocyclic amides (eg, EPOMET, a trade name of Ajinomoto, Japan), cyclohexamethylenetetramine, Triaminoacetamidine, triethanolamine, 4, 4'-methylene vicinal triethylenediamine, isopyrazoles, and imidazoline derivatives, only Bronsted acid salts developed by Solectron Corporation of Japan * cp66, cp77 and the like; dicyandiamide is preferred.
  • the curing agent After the curing agent is mixed with the epoxy resin emulsion, it is coated on the surface of the steel plate. After the coating film is formed, it is left at room temperature for a long time, such as one year, and it will not cause a substantial reaction with the epoxy resin component. It only needs to be exposed to heat, light, moisture and other conditions, and the curing reaction will begin, and it is better to perform the curing reaction under exposure to heat. When heated to about 100 ⁇ 300 ° C and pressurized, it can react with epoxy resin components to cure.
  • the water-based self-adhesive coating of the present invention optionally further contains an accelerator in an amount of 0 to 3 parts by weight, preferably 0 to 2 parts by weight, and more preferably 0 to 1 part by weight; the use of the accelerator can further improve the peeling strength of the coating, etc. Performance; If the amount is higher than 3 parts by weight, the curing reaction proceeds very fast, resulting in excessive curing of the coating on the surface of the steel product, and also causing the peeling strength of the coating to be greatly deteriorated.
  • an accelerator in an amount of 0 to 3 parts by weight, preferably 0 to 2 parts by weight, and more preferably 0 to 1 part by weight; the use of the accelerator can further improve the peeling strength of the coating, etc. Performance; If the amount is higher than 3 parts by weight, the curing reaction proceeds very fast, resulting in excessive curing of the coating on the surface of the steel product, and also causing the peeling strength of the coating to be greatly deteriorated.
  • the accelerators that can be used in the present invention include urea derivatives, imidazole derivatives, and organic guanidine derivatives. They can be used individually or in combination.
  • Representative examples of urea derivatives include N-p-chlorophenyl N ', N, -dimethyl urea, and the like;
  • imidazole derivatives include 2-methylimidazole (2-MI), 2-ethylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole and the like;
  • organic guanidine derivatives include tetramethylguanidine, acyl-substituted guanidine, alkyl-substituted guanidine and the like.
  • the composition of the present invention optionally further comprises a diluent, a filler, a toughener, a colorant, a flame retardant, a rust inhibitor, an anti-settling agent, a thixotropic agent or a defoamer, a tackifier, and a pigment dispersion.
  • a diluent e.g., a filler, a toughener, a colorant, a flame retardant, a rust inhibitor, an anti-settling agent, a thixotropic agent or a defoamer, a tackifier, and a pigment dispersion.
  • Diluents used such as ethylene glycol monoethyl ether), fillers (such as silica fume), tougheners (such as polypropylene glycol diglycidyl ether), colorants (such as titanium dioxide or carbon black), flame retardants (such as hydrogen Alumina), rust inhibitors (such as water-emulsifying rust inhibitors from Nopcochex RD, Corning, Germany), anti-settling agents (such as organic bentonite), thixotropic agents (such as fumed silica), or defoamers (Such as Nopco 8034 defoamer from Corning, Germany), tackifier (such as SO-Thick 30 water-based tackifier from Taiwan Sanhua Industrial Co., Ltd.), pigment dispersant (such as Degussa's Dispers 715w pigment dispersant), preservatives (such as CANGUARD 327 germicidal preservatives, Angus Chemical Company, USA). They are all used in the industry.
  • the method for preparing the water-based self-adhesive coating material of the present invention is: by mixing the above components, that is, the water-based epoxy resin emulsion, curing agent, accelerator, and optional auxiliary components, the water-based self-adhesive material of the present invention can be directly obtained. Then paint.
  • the water-based self-adhesive paint of the present invention is coated on the surface of electrical steel, baked, cooled, and then coiled to obtain a self-adhesive-coated electrical steel sheet with excellent properties.
  • the water-based self-adhesive coating of the present invention can be applied to electrical steel, including non-oriented electrical steel and oriented electrical steel, to produce electrical steel with a self-adhesive coating.
  • the water-based self-adhesive paints of the present invention have surprisingly good effects.
  • Most of the existing self-adhesive coated electrical steel products in foreign countries are made of solvent-based coatings; and the non-solvent-based water-based self-adhesive coatings developed by the present invention do not contain toxic organic solvents, which are green and environmentally friendly, and have high safety; Eliminates equipment that burns organic solvents and reduces investment costs.
  • the self-adhesive coating has a longer storage time and is convenient for construction.
  • the electrical steel with a self-adhesive coating made from the coating of the present invention is excellent in performance, the coating is uniform, transparent, and the peel strength and shear strength are high.
  • the Japanese patented method of manufacturing self-adhesive coated electrical steels with water-based self-adhesive coatings has uneven coatings, opacity, poor peel strength and shear strength, and must be prepared and stored before coating. Short time, causing numbness to construction Annoying question.
  • the epoxy resin adhesive used in the present invention as the main agent does not use the thermoplastic resin emulsion, which is the main component in the Japanese patent, and obtains a good self-adhesive coating.
  • the self-adhesive coated electrical steel manufactured has excellent properties and solves the problem. The above problem.
  • the self-adhesive-coated electrical steels can be manufactured by means of open flame heating; and no toxic organic solvents are volatilized throughout the manufacturing process.
  • the water-based self-adhesive paint of the present invention is applied to the surface of electrical steel by a roller coating method to form a coating layer having a thickness of 1 to 20 microns.
  • T-peel strength (I) refers to the T-peel strength measured by hot-pressing the self-adhesive coating sample directly. It is on a tensile testing machine, such as the zwick zlOO electronic tensile testing machine, according to the Chinese national standard GB / 2791. -1981 test; T-peel strength (II) refers to the T-peel strength of the self-adhesive coating sample after the aging test, followed by hot pressing. It is used to characterize the adhesive properties of the coating after a storage period of several months. It is tested on a tensile tester, such as the zwick zlOO electronic tensile tester, according to the Chinese national standard GB / 2791-1981.
  • the hot pressing process is as follows:
  • the laminated sheet group is placed on a press with a hot stage for hot pressing, the pressure is 0.8 ⁇ 3Mpa, the temperature is 160 ⁇ 250 ° C, the heating time is 30 ⁇ 300min, and it is cooled to room temperature;
  • the aging test is described as follows-the electrical steel sheet with a self-adhesive coating with a thickness of 5 micrometers is heated at 60 ⁇ 120 ° C for 48 ⁇ 96 hours, taken out, and cooled. A 5 micron thick coating of the present invention was roller coated on electrical steel. Then, it was baked at 300 F for 30 seconds, and then cooled.
  • the brine was sprayed on the electrical steel coating using a brine spray at a concentration of 5%. Observation with the naked eye is "good" if the surface of the coating is not rusted, or if the rusted area is ⁇ 10%.
  • a 5 micron thick coating of the present invention was roller coated on electrical steel. Next, bake at 300 ° C for 30 seconds, and then cool.
  • the solid bisphenol A diglycidyl ether epoxy resin Epikote # 1007 purchased from the joint venture company Shell Chemical Company in the United Kingdom and the Netherlands was pulverized with a jet mill or a pendulum mill to an average particle size of 10 kg. About 20 microns, put into the reactor. The epoxy equivalent of the epoxy resin is 2000 (see Table 1). Then, 10 kg of water and 200 g of fluorene glycol ethoxylate (RHODASURF BEH-25 purchased from Rhodia, France) non-ionic emulsifier were added to the reaction kettle, and vigorously stirred at 500 rpm or higher. Stir to obtain an aqueous epoxy resin emulsion. The solids content of this emulsion was 50% by weight.
  • the prepared emulsion is mixed with a curing agent dicyandiamide and an accelerator 2-methylimidazole to obtain an aqueous self-adhesive coating material of the present invention.
  • the amount of emulsion, curing agent and accelerator is shown in Table 2.
  • the coating was applied to electrical steel by a roller coating method and baked in a baking oven at a baking temperature of 150 ° C and a baking time of 100 seconds to obtain a self-adhesive coating with a thickness of 3 microns. Then, use the test method described above to test. The measured properties of the coating are shown in Table 2.
  • Table 1 shows the types of epoxy resins used in the present invention
  • Table 2 shows the performances of the examples, comparative examples, and both of the present invention.
  • the epoxy equivalent of the emulsion is 205, and the amount and the amount of the curing agent and the accelerator are shown in Table 2.
  • the coating was applied to electrical steel by a roller coating method and baked in a baking oven at a baking temperature of 180 ° C and a baking time of 90 seconds to obtain a self-adhesive coating with a thickness of 5 microns. Then, the test is performed by the above-mentioned test method. The measured properties of the coating are shown in Table 2.
  • the bisphenol A type GEM03 epoxy resin emulsion purchased from Shanghai Lvjia Waterborne Coatings Co., Ltd. was mixed with the curing agent dicyandiamide and the accelerator 2-methylimidazole to form an aqueous self-adhesive coating.
  • the epoxy equivalent of the emulsion is 450, and the amount and the amount of the curing agent and the accelerator are shown in Table 2.
  • the coating was applied to electrical steel by a roller coating method, and baked in a baking oven at a baking temperature of 250 ° C and a baking time of 60 seconds to obtain a self-adhesive coating with a thickness of 9 microns. Then, test using the test method described above. The measured properties of the coating are shown in Table 2.
  • Example 4 The measured properties of the coating are shown in Table 2.
  • the prepared emulsion is mixed with a curing agent dicyandiamide to obtain the aqueous self-adhesive coating material of the present invention. See Table 2 for the amount of emulsion and curing agent.
  • the coating was applied to electrical steel by a roller coating method, and was baked in a baking oven at a baking temperature of 350 ° C and a baking time of 30 seconds to obtain a self-adhesive coating with a thickness of 6 microns. Then, the test is performed by the above-mentioned test method. The measured properties of the coating are shown in Table 2.
  • Example 5 The bisphenol A epoxy resin EPONOL Resin 55-BH-30 purchased from the Shell Chemical Company, a joint venture between the United Kingdom and the Netherlands, was removed from the solvent, and 10 kg was taken and pulverized by using a Raymond machine or a jet mill. The average particle size is 20 micrometers, and the epoxy equivalent of the epoxy resin is 5500 (see Table 1) when added to the reaction kettle.
  • the prepared emulsion is mixed with a curing agent dicyandiamide and an accelerator 2-methylimidazole to obtain an aqueous self-adhesive coating material of the present invention. See Table 2 for the amount of emulsion, curing agent and accelerator.
  • the coating was applied to electrical steel by a roller coating method, and baked in a baking oven at a baking temperature of 350 ° C and a baking time of 40 seconds to obtain a self-adhesive coating with a thickness of 15 microns. Then, use the test method described above to test. The measured properties of the coating are shown in Table 2.
  • Table 1 Epoxy resin emulsion
  • the amount of the curing agent dicyandiamide in Comparative Example 1 exceeds 17 parts by weight and reaches 18.71 parts by weight.
  • the T peel strength was 1.1 and 1.3, which decreased significantly.
  • the amount of dicyandiamide in Comparative Example 2 was less than 0.07 parts by weight and was 0.05 parts by weight, and T peel strength was not measured.
  • the amount of the accelerator exceeded 3 parts by weight, reaching 4.12 parts by weight, and the T peel strength was 0.5 and 0.7, which decreased.
  • the amount of the epoxy resin in Comparative Example 4 was less than 81 parts by weight, was 70 parts by weight, and the T peel strength was 0.4 and 0.3, which was the worst.
  • Table 3 shows the comparison of the peel strength of the two coatings formed by the coating of the present invention and the existing coatings (coatings formed under the same conditions, N / mm). The results in Table 3 show that the performance of the aqueous self-adhesive coating of the present invention is better than that of the existing solvent-based self-adhesive coating.
  • Examples 1 to 6 of the water-based coatings in Table 3 are Examples 1 to 6 in Table 2 and correspond one-to-one.

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Description

电工钢用水性自粘接涂料及其用途 技术领域
本发明涉及一种电工钢用涂料及其用途， 尤其涉及一种电工钢用水性自粘 接涂料及其用途。 背景技术
多数电工钢片通过焊接或铆接组装成产品。 然而， 焊接固定法会造成铁芯 边部短路， 绝缘性下降， 而且存在由于热变形造成磁特性变差之类的各种问题。 此外， 焊接时涂膜燃烧会生成有害气体， 连接力也不太好， 焊接、 铆接的方式 对许多微型电机不适用。 因此， 将电工钢片粘接在一起形成铁芯的方法成为一 种很有吸引力的固定方式。 如果在每一片剪切好的电工钢片上涂粘接剂， 生产 效率非常低， 还存在着粘接状况难以控制和均一的问题。 因此， 直接将粘接剂 涂覆在卷钢表面形成自粘接涂层能大大提高后续的加工效率。
这样的电工钢板可以片状或卷状形式长期保存后再制造铁芯， 保存期间钢 板不会生锈， 不会产生涂膜断裂之类的各种问题， 之后根据需要， 用户可在任 何时间， 让基材被涂面经加热压紧， 获得层间粘接强度很高的性能优良之铁芯。
德国蒂森 EBG公司已经开发出了带有自粘接涂层的钢板，该涂层同时具有 绝缘、 耐蚀、 提高冲片性以及相互粘接的功能。 这样， 利用钢板组装铁芯产品 时就不需要用悍接或铆接的方式， 避免了焊接时产生的有害气体， 而且片间连 接力也很大。 该产品可用于磁悬浮列车长定子铁芯。
然而 EBG公司采用的自粘接涂料是溶剂型产品， 在涂覆烘烤过程中会挥发 大量溶剂， 为了避免污染环境， 需要增加焚烧炉将溶剂烧掉。 另外它不适合于 明火烘烤的设备。
川崎制铁提出了一种水性热粘接涂覆组合物 （日本专利公告平成 6—
21274)， 该方法使用热塑性合成树脂乳液、环氧树脂乳液、 固化剂和成膜助剂， 可以涂覆于钢板上形成自粘接涂层。
但是， 由于该组合物由热塑性树脂乳液和环氧树脂乳液混合而成， 二者并 非完全相容性， 得到的涂层不均匀， 不透明， 剥离强度和剪切强度较差。 而且 为了形成连续而没有龟裂的涂膜， 必须加入大量的成膜助剂， 这会使涂层的剥
1
确 认 本 离强度和粘接强度大大下降， 涂液必须在实施涂覆之前配制， 保存时间较短， 给施工造成麻烦。 发明内容
本发明的目的是提供一种电工钢用的非溶剂型的水性自粘接涂料， 它应用 于制造电工钢涂层时， 能够用明火加热的方式制造自粘接涂层电工钢。 . 本发明的另一个目的是提供该水性自粘接涂料的用途。
本发明的电工钢用水性自粘接涂料包含水性环氧树脂乳液、 固化剂。
其中水性环氧树脂乳液的含量为 81〜99.9重量份， 优选 81〜95重量份， 更优选 81〜90重量份； 如果其用量高于 99.9重量份， 则因为体系中固化剂含量 过低而导致涂料固化不足； 如果环氧树脂乳液用量低于 81重量份， 则会因为体 系中固化剂过多而导致涂料的固化过度， 都会造成剥离强度很差。 该水性环氧 树脂乳液中的固体含量为 10-80 %， 以该乳液的重量为基准。 所述固体含量优选 为 30-70重量％， 更优选 40-60重量％。
环氧树脂是一个分子中含有两个 （或以上） 活性环氧基的低分子质量化合 物， 在室温下呈液态或固态。 环氧树脂可通过多元醇、 多元酚与卤代醇反应获 得， 有双酚 A型、 卤化双酚 A型、 酚醛型、 聚乙二醇双酚 A型、 环氧化油等。 本发明可以使用环氧当量范围在 93〜5500的所有上述环氧树脂， 环氧当量优选 200〜4000。这些环氧树脂可以单独或组合使用。考虑到防止涂料在管道中阻塞， 更优选使用常温下呈固态的环氧树脂， 环氧当量更优选 500〜3000。
具有代表性的环氧树脂， 有英国、 荷兰合资的壳牌化学公司生产的双酚 A 二缩水甘油醚型环氧树脂，例如 Epikote# 828、 # 1001、 # 1002、 # 1004、 # 1007, 它们的分子量随型号增大而增大。 美国道化学公司生产的脂肪族环氧树脂， 例 如 D.E.R 511-A80、 732， 它们的环氧当量为 310〜330。 还有日本东都化成社生 产的 YD— 011、 001、 001Z、 012、 014、 ST— 5080、 5100； YDCN—701、 702、 703、 704； YDPN—638等都可以用于本发明。 另外， 还可以使用橡胶改性型的 环氧树脂， 例如美国 Resolution公司的 EPI— REZ3519, 这样的环氧树脂会增加 涂层的韧性， 进而提高涂层的粘接强度。
本发明的水性环氧树脂乳液的制备是： 将环氧树脂经过粉碎， 比如用雷蒙 机、 或气流粉碎机、 或摆锤式粉碎机进行粉碎； 然后在乳化剂的存在下， 由通 常的强制乳化方式形成。 另外， 除了乳化剂， 还可以使用聚氧乙烯烷基酚醚系 非离子型界面活性剂和助乳化剂， 助乳化剂的例子有： 聚氧乙烯、 聚氧丙烯、 嵌段聚醚类或它们和二异氰酸酯化合物的加成物， 它们可以单独使用或组合使 用。
本发明也可直接采用水性环氧树脂乳液成品， 如中国上海绿嘉水性涂料有 限公司的乳液 GEM03 , 它为双酚 A 型环氧树脂乳液； 日本东都化成社的 ACUATORT 5003， 它为酚醛树脂型； 再比如美国 Resolution 公司的 EPI— REZ3540 等产品。 当然也可以以合成的方式制成水性环氧树脂乳液， 用于本发 明， 例如用多元醇、 多元酚与卤代醇在水中聚合获得水性环氧树脂乳液。
由于使用了环氧树脂乳液， 涂膜对基材的附着力及防锈力均得到提高。 在本发明的水性环氧树脂乳液中， 固化剂的用量是 0.07〜17重量份， 优选
0.1〜10重量份， 更优选 0.5〜5重量； 如果用量低于 0.07%， 则因为体系中较大 量的环氧树脂未能被固化， 所得涂层的剥离强度会很差； 如果用量高于 17重量 份， 则固化反应进行非常快， 致使钢板产品表面的涂层固化过度， 同样造成涂 层的剥离强度大大恶化。
本发明的固化剂选自双氰胺系列、 三氟化硼络合物、 咪唑衍生物、 有机酰 肼类、 二氨基马来腈及其衍生物、 三聚氰胺及其衍生物等中的一种或多种。 其 代表性的例子有双氰胺、 己二酸二酰肼、 酰胺乙基哌嗪， 哌啶杂环形酰胺 （例 如 EPOMET, 日本味之素公司生产商品名） 、 环六亚甲基四胺、 三氨基乙垸、 三乙醇胺、 4， 4' 一亚甲基邻联三乙二胺、 异吡唑类、 咪唑啉衍生物， 日本旭 电公司开发的布朗斯台德酸盐才 *卜 cp66、 cp77等； 优选双氰胺。
固化剂与环氧树脂乳液混合后， 涂覆在钢板表面， 涂膜形成后， 在常温下 长时间放置， 例如 1 年， 也不会和环氧树脂成份产生实质性的反应。 而只需暴 露在热、 光、 湿气等条件下， 即开始固化反应， 以暴露在热条件下进行固化反 应为好。 在加热到大约 100〜300°C进行加压时， 能和环氧树脂成份进行固化反 应。
本发明的水性自粘接涂料还任选含有促进剂，用量为 0〜3重量份，优选 0〜 2重量份， 更优选 0〜1重量份； 使用促进剂可以进一步提高涂层的剥离强度等 性能； 如果用量高于 3 重量份， 则固化反应进行非常快， 致使钢板产品表面的 涂层固化过度， 同样造成涂层的剥离强度大大恶化。
可以用于本发明的促进剂有脲类衍生物、 咪唑类衍生物、有机胍类衍生物。 它们可以单独使用或组合使用。 脲类衍生物的代表性例子有 N-对氯代苯基 N'、 N，-二甲基脲等； 咪唑类衍生物有 2-甲基咪唑 （2-MI) 、 2-乙基咪唑、 2-苯基咪 唑、 2-十一垸基咪唑、 2-十七烷基咪唑等； 有机胍类衍生物有四甲基胍、 酰基取 代胍、 烷基取代胍等。
根据实际需要， 本发明组合物还任选包含稀释剂、 填料、 增韧剂、 着色剂、 阻燃剂、 防锈剂、 防沉剂、 触变剂或消泡剂、 增粘剂、 颜料分散剂、 防腐剂等 各种外加添加剂。
所采用的稀释剂 （如乙二醇单乙醚) 、 填料 （如硅微粉） 、 增韧剂 （如聚 丙二醇二缩水甘油醚）、着色剂（如二氧化钛或炭黑）、 阻燃剂（如氢氧化铝）、 防锈剂（如购自德国科宁公司的 Nopcochex RD的水乳化性防锈剂）、防沉剂（如 有机膨润土） 、 触变剂 （如气相二氧化硅） 或消泡剂 （如购自德国科宁公司的 Nopco 8034消泡剂） 、 增粘剂 （如中国台湾三化实业有限公司的 SO-Thick 30 水性增粘剂）、颜料分散剂（如德国德固萨公司的 Dispers 715w的颜料分散剂）、 防腐剂 （如美国安格斯化学公司的 CANGUARD 327杀菌防腐剂） 。 它们的用 量均为本行业内的常规用量。
本发明的水性自粘接涂料的制备方法是： 将以上各成分， 即水性环氧树脂 乳液、 固化剂、 促进剂和任选的辅助组分进行混合， 就能够直接得到本发明的 水性自粘接涂料。
将本发明的水性自粘接涂料涂覆在电工钢表面上， 烘烤、 并冷却后进行卷 取， 就获得了性能优良的自粘接涂层电工钢板。
本发明的水性自粘接涂料可以应用于电工钢， 包括无取向电工钢和取向电 工钢， 制造具有自粘接涂层的电工钢。
本发明的水性自粘接涂料与已有的涂料相比， 具有意外好的效果。 国外已 有的自粘接涂层电工钢产品大都是采用溶剂型涂料制造的； 而本发明开发的非 溶剂型水性自粘接涂料不含有毒的有机溶剂， 属绿色环保， 安全性高； 也免除 了焚烧有机溶剂的设备， 降低了投资成本。 该自粘接涂料保存时间较长， 给施 工也带来方便。 另外， 由本发明的涂料制成的具有自粘接涂层的电工钢性能优 异， 涂层均匀， 透明， 剥离强度和剪切强度很高。 相比之下， 日本专利用水性 自粘接涂料制造自粘接涂层电工钢的方法存在涂层不均勾， 不透明， 剥离强度 和剪切强度较差以及必须在实施涂覆之前配制， 保存时间较短， 给施工造成麻 烦的问题。 此外， 本发明釆用环氧树脂胶粘剂为主剂， 不用日本专利中最主要 成分热塑性树脂乳液， 获得了很好的自粘接涂料， 所制造的自粘接涂层电工钢 性能优异， 解决了上述问题。
本发明的水性自粘接涂料， 应用于制造电工钢涂层时， 能够以明火加热的 方式制造自粘接涂层电工钢； 而且整个制造过程都没有有毒的有机溶剂挥发。 测试方法
1.测试样品的制备：
将本发明的水性自粘接涂料采用辊涂方式， 涂到电工钢表面上， 形成厚度 为 1〜20微米的涂层。
2.电工钢涂层的 T剥离强度
T剥离强度（I)指将自粘接涂层样板直接热压测得的 T型剥离强度,它是在 拉伸试验机上， 例如 zwick zlOO 型电子拉伸试验机， 按中国国家标准 GB/2791-1981测试； T剥离强度（II)指自粘接涂层样板经老化试验后，再热压， 然后测得的 T型剥离强度。 它用于表征经过数月的储存期后涂层的粘接性能， 它是在拉伸试验机上， 例如 zwick zlOO 型电子拉伸试验机， 按中国国家标准 GB/2791-1981测试。
所述热压过程如下所述：
( i ) 将带有厚度为 5微米自粘接涂层的电工钢板裁剪成尺寸为 25mmX 120mm的样板， 每一种电工钢板裁剪成 3〜5对；
( i i )将样板的涂层面相对叠合， 每一种电工钢板叠合成 3〜5对， 叠合 成一个叠片组；
( i i i ) 将叠片组放在具有热台的压机上进行热压， 压力 0.8〜3Mpa， 温度 160〜250°C， 加热时间 30〜300min， 冷却到室温；
( i V ) 取出一对对的试样， 他们已相互粘接在一起， 即可进行 T剥离强 度测试。
所述的老化实验如下所述- 将带有厚 5微米的自粘接涂层的电工钢板在 60〜 120°C下加热 48〜96小时， 取出， 并冷却。 在电工钢上辊涂厚 5微米的本发明涂料。 接着， 在 300Ό烘烤 30秒钟， 然 后冷却。
采用浓度为 5 %的盐水， 用盐水喷雾机， 向电工钢涂层上喷洒盐水。 裸眼 观察， 如果涂层表面没有锈蚀， 或锈蚀面积 < 10 %， 就为 "良好" 。
4. 电工钢涂层的外观性能
在电工钢上辊涂厚 5微米的本发明涂料。 接着， 在 300°C烘烤 30秒钟， 然 后冷却。
用裸眼观察涂层。 如果表面没有涂层缺损、 斑点、 裂纹等， 涂层外观为良 好， 否则为不良。 实施例
实施例 1
将购自英国、荷兰的合资公司一壳牌化学公司的固态的双酚 A二縮水甘油醚 型环氧树脂 Epikote # 1007 10公斤用气流粉碎机或摆锤式粉碎机， 进行粉碎， 至平均粒度为 20微米左右， 放入反应釜内。 该环氧树脂的环氧当量为 2000 (见 表 1 )。然后，向该反应釜中加入水 10公斤和廿二醇乙氧基化物（购自法国 Rhodia 公司的 RH0DASURF BEH- 25 )非离子型乳化剂 200克， 在 500rpm或更高搅拌速度 下， 进行剧烈搅拌， 获得水性环氧树脂乳液。 该乳液的固含量为 50重量％。
将制成的上述乳液与固化剂双氰胺、促进剂 2-甲基咪唑进行混合， 得到本发 明的水性自粘接涂料。 乳液、 固化剂与促进剂的用量见表 2。
将该涂料采用辊涂方式， 涂到电工钢上， 并在烘烤炉内进行烘烤， 烘烤温度 150°C， 烘烤时间 100秒钟， 获得自粘接涂层， 厚度为 3微米。 然后， 以上述测 试方法进行测试。 测得的涂层的性能如表 2所示。
表 1为本发明所采用的环氧树脂类型； 表 2为本发明的实施例、 比较例及 两者性能的比较。 实施例 2
釆用购自日本东都化成社的 ACUATORT 5003酚醛树脂型环氧树脂乳液， 与固化剂双氰胺、 促进剂 2-甲基咪唑混合， 形成水性自粘接涂料。 所述乳液的 环氧当量为 205， 其用量和固化剂与促进剂的用量如表 2所示。 将该涂料采用辊涂方式， 涂到电工钢上， 并在烘烤炉内进行烘烤， 烘烤温 度 180°C， 烘烤时间 90秒钟， 获得自粘接涂层， 厚度为 5微米。 然后， 以上述 测试方法进行测试。 测得的涂层的性能如表 2所示。 实施例 3
采用购自上海绿嘉水性涂料有限公司的双酚 A型 GEM03环氧树脂乳液， 与固化剂双氰胺、 促进剂 2-甲基咪唑混合， 形成水性自粘接涂料。 所述乳液的 环氧当量为 450， 其用量和固化剂与促进剂的用量如表 2所示。
将该涂料采用辊涂方式， 涂到电工钢上， 并在烘烤炉内进行烘烤， 烘烤温 度 250°C， 烘烤时间 60秒钟， 获得自粘接涂层， 厚度为 9微米。 然后， 以上述 测试方法进行测试。 测得的涂层的性能如表 2所示。 实施例 4
将购自日本三菱瓦斯化学公司的液态的缩水甘油胺型环氧树脂 Tetm-GXDA 10公斤加入反应釜， 该环氧树脂的环氧当量为 93 (见表 1 ) 。 然后， 向该反应 釜中加入水 23公斤和廿二醇乙氧基化物 （购自法国 Rhodia公司的 RHODASURF BEH-25 )非离子型乳化剂 200克，在 800rpm或更高搅拌速度下，进行剧烈搅拌， 获得水性环氧树脂乳液。 该乳液的固含量为 30重量％。
将制成的上述乳液与固化剂双氰胺进行混合， 得到本发明的水性自粘接涂 料。 乳液、 固化剂的用量见表 2。
将该涂料采用辊涂方式， 涂到电工钢上， 并在烘烤炉内进行烘烤， 烘烤温度 350Ό , 烘烤时间 30秒钟， 获得自粘接涂层， 厚度为 6微米。 然后， 以上述测 试方法进行测试。 测得的涂层的性能如表 2所示。 实施例 5 将购自英国、荷兰合资的壳牌化学公司的双酚 A型环氧树脂 EPONOL Resin 55-BH-30脱除溶剂后， 取 10公斤， 采用雷蒙机或气流粉碎机进行粉碎， 至平 均粒度为 20微米， 加入反应釜， 该环氧树脂的环氧当量为 5500 (见表 1 ) 。 然 后， 向该反应釜中加入水 4. 3公斤和廿二醇乙氧基化物（购自法国 Rhodia公司 的 RHODASURF BEH-25 ) 非离子型乳化剂 200克， 在 800rpm或更高搅拌速度下， 进行剧烈搅拌， 获得水性环氧树脂乳液。 该乳液的固含量为 70重量％。
将制成的上述乳液与固化剂双氰胺、 促进剂 2-甲基咪唑进行混合， 得到本 发明的水性自粘接涂料。 乳液、 固化剂、 促进剂的用量见表 2。
将该涂料采用辊涂方式， 涂到电工钢上， 并在烘烤炉内进行烘烤， 烘烤温度 350°C , 烘烤时间 40秒钟， 获得自粘接涂层， 厚度为 15微米。 然后， 以上述测 试方法进行测试。 测得的涂层的性能如表 2所示。 表 1 环氧树脂乳液
实施例 商品名 生产厂名 环氧当量
类型
No 1 双酚 A型 Epikote # 1007 壳牌化学公司 2000
ACUATORT
No 2 酚醛树脂型 东都化成社 205
5003
上海绿嘉水性涂
No 3 双酚 A型 乳液 GEM03 450
料有限公司
Teerady-y (三菱
No 4 缩水甘油胺型 Tetra-GXDA 93
瓦斯化学）
EPONOL Resin
No 5 双酚 A型 壳牌化学公司 5500
55-BH-30
表 2
Figure imgf000010_0001
可看出， 比较例 1中固化剂双氰胺用量超过 17重量份，达到 18.71重量份， T剥离强度为 1.1和 1.3， 显著下降。 比较例 2中双氰胺用量不足 0.07重量份， 为 0.05重量份， Τ剥离强度测不出。 比较例 3中促进剂用量超过了 3重量份， 达到 4.12重量份， Τ剥离强度为 0.5和 0.7， 下降了。 比较例 4中环氧树脂用量 不足 81重量份， 为 70重量份， Τ剥离强度为 0.4和 0.3， 最差。
表 3为本发明涂料与已有涂料所形成的两种涂层的剥离强度的对比 （在同 样条件下形成涂层， N/mm) 。 表 3的结果表明： 本发明的水性自粘接涂层的性 能优于已有的溶剂型自粘接涂层的性能。 表 3
Figure imgf000011_0001
注- 表 3中水性涂层的试样 1〜6就是表 2中的实施例 1〜6， 一一对应。

Claims

权 利 要 求
1. 电工钢用水性自粘接涂料， 其包含：
水性环氧树脂乳液 81〜99.9重量份；
固化剂 0.07〜17重量份；
其中， 环氧树脂的环氧当量范围在 93〜5500。
2. 如权利要求 1所述的电工钢用水性自粘接涂料， 其特征是， 它还包含促进剂， 含量为 0〜3重量份。
3. 如权利要求 1所述的电工钢用水性自粘接涂料， 其特征是， 所述的环氧树脂 的环氧当量范围为 200〜4000。
4. 如权利要求 1所述的电工钢用水性自粘接涂料， 其特征是， 所述的环氧树脂 的环氧当量范围为 500〜3000。
5. 如权利要求 1所述的电工钢用水性自粘接涂料， 其特征是， 所述的固化剂为 双氰胺系列、 三氟化硼络合物、 咪唑衍生物、 有机酰肼类、 二氨基马来腈及 其衍生物或三聚氰胺及其衍生物等中的一种或多种。
6. 如权利要求 1或 5所述的电工钢用水性自粘接涂料， 其特征是， 所述的固化剂 为双氰胺。
7. 如权利要求 2所述的电工钢用水性自粘接涂料， 其特征是， 所述的促进剂为 脲类衍生物、 咪唑类衍生物、 或有机胍类衍生物中的一种或多种。
8. 如权利要求 7所述的电工钢用水性自粘接涂料， 其特征是， 所述促进剂中的 脲类衍生物为 N-对氯代苯基 Ν，、 Ν'-二甲基脲；所述咪唑类衍生物为 2-甲基咪 唑、 2-乙基咪唑、 2-苯基咪唑、 2- ^—烷基咪唑或 2-十七烷基咪唑； 所述有机 胍类衍生物为四甲基胍、 酰基取代胍或垸基取代胍。
9.一种如权利要求 1或 2所述的电工钢用水性自粘接涂料的用途，它用于制造电工 钢涂层。
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