WO2023088466A1 - 一种轻粘性硅钢环保绝缘涂料、硅钢板及其制造方法 - Google Patents

一种轻粘性硅钢环保绝缘涂料、硅钢板及其制造方法 Download PDF

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WO2023088466A1
WO2023088466A1 PCT/CN2022/133232 CN2022133232W WO2023088466A1 WO 2023088466 A1 WO2023088466 A1 WO 2023088466A1 CN 2022133232 W CN2022133232 W CN 2022133232W WO 2023088466 A1 WO2023088466 A1 WO 2023088466A1
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Prior art keywords
water
insulating coating
soluble
emulsion
insulating
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PCT/CN2022/133232
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English (en)
French (fr)
Inventor
李登峰
郝允卫
肖盼
王波
李国保
沈科金
王志成
姜全力
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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 KR1020247017671A priority Critical patent/KR20240095304A/ko
Priority to JP2024529718A priority patent/JP2024541430A/ja
Priority to US18/710,138 priority patent/US20250002730A1/en
Priority to EP22894995.4A priority patent/EP4435070A4/en
Publication of WO2023088466A1 publication Critical patent/WO2023088466A1/zh
Anticipated expiration legal-status Critical
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    • C08K2003/321—Phosphates
    • C08K2003/327—Aluminium phosphate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/32—Phosphorus-containing compounds
    • C08K2003/321—Phosphates
    • C08K2003/328—Phosphates of heavy metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/003—Additives being defined by their diameter
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/10—Metal compounds
    • C08K3/11—Compounds containing metals of Groups 4 to 10 or of Groups 14 to 16 of the Periodic Table
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/38—Boron-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Definitions

  • the disclosure relates to a paint, a silicon steel plate and a manufacturing method thereof, in particular to an insulating paint, a silicon steel plate and a manufacturing method thereof.
  • new energy vehicles In recent years, as China vigorously promotes the development of new energy vehicles, more and more automobile manufacturers and researchers have joined the research and development team in the field of new energy vehicles. In the research and development process of new energy vehicles, new energy vehicles usually have high performance requirements for the advanced motors used. Compared with the performance requirements of conventional motors, advanced motors represented by new energy vehicles generally require the motor core to have the characteristics of high fixing strength, high core efficiency and low magnetic vibration noise.
  • the thickness of a single film of the self-adhesive coating is generally ⁇ 3 ⁇ m. The thicker the film thickness or the thinner the substrate, the lower the lamination coefficient of the iron core and affect the efficiency of the motor;
  • the main component of the self-adhesive coating is organic resin, which is not resistant to stress relief annealing at ⁇ 750°C and bluing process above 400°C, and there are even few coating products that can withstand 210°C for a long time. Solderability poor;
  • the field expects to obtain a new light-adhesive silicon steel environmental protection insulating coating, which can be coated on the substrate surface of silicon steel plate and can form a coating on the substrate.
  • this coating also has the intersheet bonding effect similar to that of C-3 type self-adhesive coating (but it does not need to reach the level of C-3 type self-adhesive coating.
  • High bonding strength C-3 type self-adhesive coating generally requires bonding strength ⁇ 7N/mm 2 , ISO 4587 tensile shear method)), and can avoid the C-3 type self-adhesive coating that cannot withstand Disadvantages of thermal processing.
  • One of the purposes of the present disclosure is to provide an insulating coating, the coating formed by it not only has basic properties such as good insulation, adhesion, heat resistance, and weldability of conventional C-5 coatings, but also has similar It is better than the bonding effect between sheets of C-3 self-adhesive coating, and still has a certain bonding performance after the second heat/pressing process (bonding strength ⁇ 2N/mm 2 , ISO 4587 tensile shear method), which can generate a certain bonding force between the iron chips, so that the overall structure of the iron core can be strengthened, which can effectively improve the problems of low fixed strength of the iron core, low natural frequency and high vibration noise, so as to obtain higher efficiency and more Motor with low vibration and noise.
  • an insulating paint which comprises the following ingredients (preferably active ingredients):
  • Water-soluble metal inorganic salt A which includes water-soluble phosphate A1, and the water-soluble phosphate A1 includes at least one water-soluble phosphate of aluminum, zinc, magnesium, and manganese;
  • Water-dispersible organic emulsion B which comprises: at least one of epoxy emulsion and its curing agent, polyester, polyurethane, polyacrylate, ethylene-vinyl acetate copolymer;
  • Additive C which includes: at least one of structural enhancement additive C1 and heat resistance enhancement additive C2, wherein structure enhancement additive C1 contains inorganic nanoparticles, and heat resistance enhancement additive C2 is selected from boric acid and molybdenum, tungsten, vanadium, titanium water soluble at least one of sex salts;
  • the water-soluble metal inorganic salt A the water-dispersible organic emulsion B has a mass and fraction ratio of solid content of (35-85): (15-65).
  • the coating formed by the insulating coating of the present disclosure can be classified as C-5 or EC-5 type coating, which not only has good insulation, adhesion, Heat resistance, weldability and other basic properties, and also has an inter-sheet bonding effect similar to C-3 type self-adhesive coating (but it does not need to achieve the high bond strength of C-3 type self-adhesive coating ( It is generally required that the bond strength of C-3 type self-adhesive coating is ⁇ 7N/mm 2 , ISO 4587 tensile shear method), and can avoid the drawbacks of C-3 type self-adhesive coating that cannot withstand heat treatment .
  • the ratio of water-soluble metal inorganic salt A: water-dispersible organic emulsion B to a solid content by mass is: (40-75): (25-60).
  • the water-soluble metal inorganic salt A further includes the water-soluble silicate A2.
  • Adding an appropriate amount of water-soluble silicate A2 to the insulating coating of the present disclosure can improve the hardness of the coating formed by the insulating coating to a certain extent.
  • the water-soluble silicate A2 should not be added in excess, because when the water-soluble silicate A2 is excessive, it is easy to cause compatibility and stability problems of the coating system. Therefore, in the insulating coating of the present disclosure, the water-soluble silicate A2 accounts for 0-5% of the water-soluble metal inorganic salt A in terms of solid content mass percentage.
  • the modulus of the water-soluble silicate A2 is ⁇ 4.
  • the water-soluble silicate A2 includes sodium silicate and/or potassium silicate.
  • the water-soluble phosphate A1 accounts for 95% to 100% of the water-soluble metal inorganic salt A
  • the water-soluble silicate A2 accounts for 0-5% of A.
  • the water-soluble metal inorganic salt A contains at least a water-soluble phosphate of aluminum.
  • the water-soluble phosphate of aluminum accounts for 70-100% of the water-soluble phosphate A1 in terms of solid content by mass percentage.
  • the water-soluble phosphates of zinc, magnesium and manganese are respectively zinc dihydrogen phosphate, magnesium dihydrogen phosphate and manganese dihydrogen phosphate, and the total mass percentage thereof accounts for 0-30% of the water-soluble phosphate A1.
  • the particle size of the water-dispersible organic emulsion B satisfies: an average particle size D 50 ⁇ 2 ⁇ m, an average particle size D 90 ⁇ 5 ⁇ m, and a maximum particle size ⁇ 10 ⁇ m.
  • the particle size of the water-dispersible organic emulsion B satisfies: D 50 ⁇ 1 ⁇ m, D 90 ⁇ 3 ⁇ m.
  • the water-dispersible organic emulsion B includes an epoxy emulsion and a curing agent thereof.
  • the epoxy emulsion and its curing agent can play the main role of adhesion in the coating formed by the insulating coating of the present disclosure, and at the same time improve the mechanical protection, insulation and heat resistance of the final coating.
  • the curing agent of the epoxy emulsion is selected from at least one of dicyandiamide, amino resin, imidazole and polyisocyanate.
  • the curing agent of the epoxy emulsion is micronized dicyandiamide, and its average particle size satisfies: D 50 ⁇ 5 ⁇ m, D 90 ⁇ 10 ⁇ m.
  • the water-dispersible organic emulsion B comprises an epoxy emulsion and its curing agent, wherein the epoxy emulsion accounts for the total of the epoxy emulsion and its curing agent in terms of solid content mass percent 90-99%. More preferably, the epoxy emulsion accounts for 95-98% of the epoxy emulsion and its curing agent.
  • the epoxy equivalent of the epoxy emulsion is 100-2000g/eq, preferably 200-1000g/eq; the weight average molecular weight Mw is 200-4000, preferably 300-3000; the functionality 2 to 3.
  • the water-dispersible organic emulsion B comprises ethylene-vinyl acetate copolymer, wherein the solid content is expressed in mass percent ,
  • the ethylene-vinyl acetate copolymer accounts for 0-20% of the water-dispersible organic emulsion B.
  • the mass percentage of vinyl acetate in the ethylene-vinyl acetate copolymer is 10-40%, more preferably 15-30%.
  • both the polyurethane and the polyacrylate are high molecular weight anionic water-dispersible emulsions.
  • the mass of the additive C relative to the total mass of the water-soluble metal inorganic salt A and the water-dispersible organic emulsion B is 0.1-10%.
  • the content of additive C is lower than the lower limit of the above-mentioned range, the performance characteristics of additive C cannot be obtained; when the content of additive C is higher than the upper limit of the above-mentioned range, it is easy to cause poor stability of the coating, which will reduce the interlaminarity of the coating. Bond strength.
  • the mass of the additive C is 0.5-5% relative to the total mass of the water-soluble metal inorganic salt A and the water-dispersible organic emulsion B.
  • the aggregates of inorganic nanoparticles have an average particle diameter of 50-800 nm, more preferably 80-500 nm.
  • the inorganic nanoparticles are metal oxides, and the metal oxides are selected from SiO 2 , Al 2 O 3 , TiO 2 , ZnO, ZrO 2 , Fe 3 O 4 and CaCO 3 at least one of .
  • the inorganic nanoparticles are SiO 2 , Al 2 O 3 , TiO 2 , ZnO or their composite oxides.
  • the heat resistance enhancing additive C2 is selected from at least one of boric acid, ammonium molybdate, and sodium tungstate.
  • the heat resistance enhancing additive C2 is a water-soluble salt of boric acid (H 3 BO 3 ) and a variable-valence metal (such as molybdenum, tungsten, vanadium, titanium).
  • H 3 BO 3 boric acid
  • a variable-valence metal such as molybdenum, tungsten, vanadium, titanium
  • the total mass of the additive D1 and the solvent D2 relative to the total mass of the water-soluble metal inorganic salt A and the water-dispersible organic emulsion B is 5-35%.
  • the auxiliary agent D1 is selected from defoamers, wetting agents, leveling agents, thickeners, anti-settling agents, At least one of the anti-flash rust agents.
  • the solvent D2 includes ethylene glycol, glycerol, n-butanol, isobutanol, isopropanol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, At least two of propylene glycol butyl ether and propylene glycol methyl ether acetate.
  • the solid content of the insulating coating of the present disclosure is 15-40%.
  • the insulating coating of the present disclosure is suitable for coating the substrate surface of silicon steel plates of various types of motors and generator iron cores, and can form a coating on the substrate, especially suitable for coating new energy vehicle motors, servo motors, micro-special motors, etc.
  • Non-oriented silicon steel sheet used in the field is suitable for coating the substrate surface of silicon steel plates of various types of motors and generator iron cores, and can form a coating on the substrate, especially suitable for coating new energy vehicle motors, servo motors, micro-special motors, etc.
  • the present disclosure provides a silicon steel sheet including a substrate, the surface of which has a coating layer formed of the insulating paint of the present disclosure.
  • the dry film thickness of the coating on one side is 0.3-2 ⁇ m, more preferably 0.5-1.5 ⁇ m.
  • the silicon steel plate of the present disclosure is coated with the insulating paint of the present disclosure, so that a coating is formed on the substrate of the silicon steel plate.
  • the silicon steel plate of the present disclosure can be used to prepare the iron core of the drive motor, and its coating still has certain bonding performance after the secondary heat/pressing process (bonding strength ⁇ 2N/mm 2 , ISO 4587 tensile shear method), which can effectively improve the problems of low iron core fixing strength, low natural frequency and high vibration noise, and can be widely used in new energy vehicle motors, servo motors and micro motors, and has good promotion prospects and application value.
  • the present disclosure provides a method for manufacturing a silicon steel plate, which includes the following steps: coating the substrate surface of the silicon steel plate with the insulating coating of the present disclosure; Insulating paint, forming a coating.
  • the insulating coating, silicon steel plate and manufacturing method thereof of the present disclosure have the following advantages and beneficial effects:
  • composition of the insulating coating of the present disclosure is rationally optimized and designed, based on water-soluble phosphate and film-forming emulsion, and a solvent with low toxicity and low hazard is selected, so that the obtained insulating coating is a non-hazardous chemical, VOC (volatile organic compounds , volatile organic compounds) low emissions, completely green and environmentally friendly.
  • VOC volatile organic compounds , volatile organic compounds
  • the insulating coating of the present disclosure can be coated on the substrate surface of the silicon steel plate of various motors and generator iron cores, and can form a coating on the substrate, and is especially suitable for use in fields such as new energy vehicle motors, servo motors, micro-special motors, etc.
  • the non-oriented silicon steel material has a large space for commercial application.
  • the coating formed by the insulating coating of the present disclosure not only has the characteristics of the conventional C-5 type coating, but also has the intersheet bonding effect similar to the C-3 type self-adhesive coating (but it is not necessary to achieve the C-3 type self-adhesive coating).
  • High bonding strength of the junction coating C-3 type self-adhesive coating generally requires bonding strength ⁇ 7N/mm 2 , ISO 4587 tensile shear method)), and completely avoids C-3 type self-adhesive Poor heat resistance of the coating, poor solderability, low lamination coefficient, hot-press overflow glue and other problems.
  • the silicon steel plate of the present disclosure can be used to prepare the iron core of the drive motor, and its coating still has certain bonding performance after the secondary heat/pressing process (bonding strength ⁇ 2N/mm 2 , ISO 4587 tensile shear method), which can generate a certain bonding force between the iron chips, so that the overall structure of the iron core can be strengthened, which can effectively improve the problems of low fixed strength of the iron core, low natural frequency and high vibration noise, so as to create higher efficiency, Motor with lower vibration and noise.
  • bonding strength ⁇ 2N/mm 2 ISO 4587 tensile shear method
  • the manufacturing method of the silicon steel plate of the present disclosure is environmentally friendly and efficient.
  • coated silicon steel plate of the present disclosure can be further processed by shearing and punching and stacked into an iron core, and then the magnetic steel is inserted into the slot hole of the iron core with an adhesive and heated for a second time, and the magnetic steel is fixed and fixed after curing. Iron core assembly, the overall strength of the obtained iron core is high, and the natural frequency is significantly improved.
  • the above-mentioned secondary curing process may be: 1-5 MPa pressure load, maintaining at an iron core temperature of 150-300°C for 1min-4h, preferably maintaining at an iron-core temperature of 150-250°C for 10min-2h.
  • a secondary heating process is also performed on the entire iron core. Therefore, this thermal process can be fully utilized to perform hot pressing on the silicon steel coating of the laminated iron core, thereby producing an inter-sheet bonding effect.
  • Fig. 1 schematically shows the changes of bonding strength and curing degree with coil baking temperature during silicon steel sheet manufacturing.
  • solid content refers to the mass percentage of the remaining part of the emulsion or coating after drying under specified conditions.
  • the measurement standard is EN ISO 3251, and the measurement condition is 1g/2h/130°C 1g of paint, kept at 130°C for 2 hours).
  • modulus refers to the ratio of moles.
  • the chemical formula is R2O ⁇ n SiO 2
  • n is the ratio of SiO 2 to the number of moles of R 2 O, which is called the modulus of R 2 O ⁇ n SiO 2 .
  • D 50 represents the particle diameter corresponding to when the cumulative particle size distribution percentage of the sample reaches 50%
  • D 90 represents the particle diameter corresponding to the cumulative particle size distribution percentage of the sample reaching 90%.
  • Particle size distribution refers to the use of specific instruments and methods to reflect the percentage of particles of different particle sizes in the powder sample to the total amount of particles.
  • Laser diffraction method can be used for measurement
  • the test standard can refer to ISO 13320 "Particle size analysis-Laser diffraction methods”
  • the measurement equipment that can be used is Mastersizer series laser diffraction particle size analyzer.
  • epoxy equivalent refers to the number of grams of epoxy resin containing one equivalent of epoxy group, and the unit is g/eq, that is, [gram/equivalent].
  • “Functionality” is defined as the number of epoxy groups contained in an epoxy resin molecule.
  • “functionality” refers to the average functionality of epoxy compounds, which is the average number of groups per molecule, that is, the total equivalents of epoxy functional groups that can undergo polycondensation reactions during epoxy curing. It can be determined by gel permeation chromatography (refer to standard ISO 13885-1) and nuclear magnetic resonance spectroscopy. Herein, “functionality” is calculated as the quotient of the weight average molecular weight Mw of the epoxy resin and the epoxy equivalent.
  • the weight average molecular weight Mw is determined by gel chromatography.
  • the reference standard for gel chromatography is ISO 13885-1 "Binders for paints and varnishes-Gel permeation chromatography (GPC)-Part 1: Tetrahydrofuran (THF) as eluent".
  • the structure-enhancing additive C1 refers to reactive inorganic nanoparticles that can form physical/chemical cross-linking points with the functional groups of the film-forming resin, thereby introducing R-O-R and/or R-O-C bonds into the molecular chain (R represents Si/ Metal elements such as Al/Ti/Zr/Zn) form a network structure.
  • R represents Si/ Metal elements such as Al/Ti/Zr/Zn
  • Inorganic nanoparticles that meet the above characteristics can be prepared by a gas phase method, or by a gas phase deposition method or related hydrolysis and condensation methods, but they cannot be sol-type products.
  • the water-soluble metal inorganic salt A contains at least a water-soluble phosphate of aluminum.
  • the water-soluble phosphate of aluminum can be prepared by the following method: Phosphoric acid (H 3 PO 4 ) and aluminum hydroxide (Al(OH) 3 ) with a molar ratio of (2.3-3.5): 1 are put into the reaction kettle respectively, and the reaction is controlled. The temperature is 70-135°C, and after 30-120 minutes of heat preservation, the material is cooled and filtered.
  • the water-soluble phosphate of aluminum can be prepared by the following method: phosphoric acid (H 3 PO 4 ) and aluminum hydroxide (Al(OH) 3 ) in a molar ratio of (3.0-3.4):1 Put them into the reaction kettle respectively, control the reaction temperature at 70-135°C, keep the temperature for 60-90 minutes, then cool and filter to discharge.
  • phosphoric acid H 3 PO 4
  • aluminum hydroxide Al(OH) 3
  • the water-dispersible organic emulsion B is a water-dispersible organic emulsion, not a water-soluble resin solution.
  • Water-dispersible organic emulsion B can be further divided into the following two categories according to the type of film formation:
  • the main film-forming mechanism is cross-linking and curing film-forming, such as epoxy emulsion and its curing agent.
  • the main film-forming mechanism is particle aggregation film-forming, such as polyester, polyurethane, polyacrylate, ethylene-vinyl acetate copolymer emulsion, etc.
  • polyurethane and polyacrylate are preferably high-molecular-weight anionic water-dispersible emulsions.
  • the main film-forming method is particle aggregation, and the secondary film-forming method can also be self-crosslinking and curing by heating, which can affect the coating. Excellent structural properties, such as hardness, scratch resistance, heat resistance, chemical resistance, etc.
  • two or more composite organic components in epoxy emulsion and its curing agent, polyacrylate emulsion or polyester, polyurethane emulsion, and ethylene-vinyl acetate copolymer can improve the basic properties of the coating formed by the insulating paint.
  • the solvent D2 is mainly used to increase the solubility of the organic resin and the additive D1 in water, and at the same time reduce the surface tension of the solution to prevent defects such as shrinkage cavities and missing coatings in the coating during the baking process , and has a defoaming effect.
  • the solid content of the final insulating coating is 15 to 40%; the coating-4 cup viscosity is 10 to 40 seconds, thereby enabling better precise control of coating film thickness and High-speed roller coating workability.
  • the substrate composition of the silicon steel sheet there is no particular limitation on the substrate composition of the silicon steel sheet, and any prior art composition system that can achieve the technical effects of the present disclosure can be used.
  • the insulating coatings of Examples 1-6 include the following components: water-soluble metal inorganic salt A, water-dispersible organic emulsion B, additive C, auxiliary agent D1 and solvent D2. According to the components and proportions shown in the following Tables 1 to 8, after mixing and adding the above-mentioned water-soluble metal inorganic salt A, water-dispersible organic emulsion B, additive C, auxiliary agent D1 and solvent D2, add an appropriate amount of pure Mix with water and stir evenly to prepare the insulating coatings of Examples 1-6.
  • the water-soluble metal inorganic salt A that embodiment 1-6 adopts must comprise the water-soluble phosphate A1 of at least one in aluminum, zinc, magnesium, manganese;
  • the water dispersible organic emulsion B adopted in embodiment 1-6 comprises at least one in epoxy emulsion and curing agent thereof, polyester, polyurethane, polyacrylate, ethylene-vinyl acetate copolymer;
  • the additive C used in Examples 1-6 includes: a structure enhancing additive C1 and a heat resistance enhancing additive C2.
  • the structure-enhancing additive C1 may contain inorganic nanoparticles;
  • the heat-resistant enhancing additive C2 is selected from at least one of boric acid and water-soluble salts of molybdenum, tungsten, vanadium, and titanium;
  • the selected auxiliary agent D1 includes: at least one of defoaming agent, wetting agent, leveling agent, thickener, anti-settling agent, and anti-flash rust agent;
  • Selected solvent D2 includes: ethylene glycol, glycerol, n-butanol, isobutanol, isopropanol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol methyl ether, propylene glycol butyl ether, propylene glycol methyl ether acetic acid at least two of the esters.
  • the water-soluble metal inorganic salt A includes not only the water-soluble phosphate A1, but also the water-soluble silicate A2.
  • Water-soluble silicate A2 includes sodium silicate and/or potassium silicate. The modulus of the water-soluble silicate A2 is ⁇ 4.
  • Table 1 lists the specific components of the insulating coatings of Examples 1-6.
  • W 640ZX, A3017, 300, A3017, 380, CAB-O-SIL EH-5 are inorganic nanoparticles, which contain: at least one of SiO 2 , Al 2 O 3 , TiO 2 , ZnO, ZrO 2 , Fe 3 O 4 , CaCO 3 ; additives BYK-348 added in D1 can be used as wetting agent and defoamer, BYK-346 can be used as leveling agent and/or wetting agent, BYK-025 can be used as defoamer; Tego 245 can be used as wetting agent, Leveling agent and defoamer; ZT-709 is an anti-flash rust agent, Cellosize QP-100MH is an anti-settling agent or thickener.
  • Examples 1-6 of the above-mentioned Table 1 do not show an example of using a water-soluble salt of titanium or vanadium as the heat-resistant enhancing additive C2, it should be understood that in other embodiments of the present disclosure, a water-soluble salt of titanium or vanadium can be used. Water-soluble salt is used as heat resistance enhancing additive C2.
  • aluminum-containing water-soluble phosphates are all added to the water-soluble metal inorganic salts A used in Examples 1-6.
  • the aluminum-containing water-soluble phosphate is prepared by the following manufacturing method: Phosphoric acid (H 3 PO 4 ) and aluminum hydroxide (Al(OH) 3 ) are put into the reaction kettle with a molar ratio of (2.3-3.5): 1 , control the reaction temperature at 70-135°C, keep the temperature for 30-120min, then cool and filter to discharge.
  • the curing agent of the epoxy emulsion in the water-dispersible organic emulsion B used in Examples 1-6 is all micronized dicyandiamide.
  • the curing agent of the epoxy emulsion may also be amino resin, imidazole or polyisocyanate.
  • Table 2 has listed the content of each component of the insulating coating of embodiment 1-6 compared to the total mass of soluble metal inorganic salt A and water-dispersible organic emulsion B (combining water-soluble metal inorganic salt A and water-dispersible organic emulsion The total mass of organic emulsion B is calculated as 100%).
  • the average particle diameter D50 of the aggregates of inorganic nanoparticles of C1 used in Examples 1-6 is shown in Table 3 below.
  • the polyurethane and polyacrylate in the water-dispersible organic emulsion B are high-molecular-weight anionic water-dispersible emulsions.
  • the curing agent of the epoxy emulsion in the water-dispersible organic emulsion B used in Examples 1-6 is all micronized dicyandiamide.
  • D 50 represents the particle diameter corresponding to the cumulative particle size distribution percentage of the sample reaching 50%
  • D 90 represents the particle diameter corresponding to the cumulative particle size distribution percentage of the sample reaching 90%; wherein, each test The D 50 and D 90 in the particle size distribution are both a point value, but there are errors or variations in the test itself, so Table 3 is a range value rather than a single point value.
  • the solid content of the epoxy emulsion in the water-dispersible organic emulsion B of Examples 1-6 is compared with the proportion of the epoxy emulsion and its curing agent in the following Table 5.
  • Table 6 has listed the solid content ratio of water-soluble phosphate A1 compared to water-soluble metal inorganic salt A in the insulating coating of embodiment 1-6, the mass percentage of aluminum salt is compared to the solid content of water-soluble phosphate A1 Content ratio, the ratio of water-soluble metal inorganic salt A: the solid content of water-dispersible organic emulsion B, the ratio of additive C to the total solid content of water-soluble metal inorganic salt A and water-dispersible organic emulsion B , Auxiliary D1, solvent D2 are compared to the content of the total mass of both water-soluble metal inorganic salt A and water-dispersible organic emulsion B.
  • the contrast paint of comparative example 1 selects commercially available Remisol EB 5350S type paint for use, and Remisol EB 5350S is the typical paint model of commercially available non-oriented silicon steel C-5 class coating;
  • the comparative paint of Comparative Example 2 is selected from commercially available Remisol EB 549 paint, and Remisol EB 549 paint is a typical paint model of commercially available non-oriented silicon steel C-3 type self-adhesive coating.
  • the insulating coatings of Examples 1-6 and the comparative coatings of Comparative Examples 1-2 are coated on both surfaces of the substrate of the silicon steel plate, and dried and cured at a coil temperature of 150-250° C. to obtain coatings with different coatings.
  • the dry film thickness of one side of the coating is between 0.3-2 ⁇ m.
  • Table 7 lists the process parameters of the finished silicon steel plate obtained by coating B30A250 brand non-oriented silicon steel with the insulating paint of Examples 1-6 and the comparative paint of Comparative Examples 1-2.
  • Table 8 lists the relevant performance test results of the finished silicon steel sheets of Examples 1-6 and Comparative Examples 1-2.
  • Example 3-5 can better take into account the performance of non-oriented silicon steel C-5 coatings, and has the unique bonding performance of C-3 self-adhesive coatings, which is the best implementation example.
  • Comparative example 1 is a typical coating model of commercially available non-oriented silicon steel C-5 type coating. The general properties of this coating are generally good, but it does not have the characteristics of adhesion performance at all.
  • Comparative example 2 is a typical coating model of commercially available non-oriented silicon steel C-3 type self-adhesive coating. The self-adhesive coating has excellent related properties, but it cannot withstand heat treatment above 250°C at all, and requires high The thickness of the coating film is high, and the product cost is high.
  • the finished silicon steel sheets of Examples 1-6 were formed by coil slitting and stacking of punched sheets to obtain iron cores.
  • insert different types of magnetic steel into the reserved iron core slot and fill the surface of the magnetic steel and the side wall of the iron core with adhesive, and carry out secondary curing heating. After curing, the magnetic steel is fixed and the iron core is completed. assembly.
  • the secondary curing process is controlled as follows: a pressure load of 1-5 MPa is maintained at an iron core temperature of 150-300° C. for 1 min-4 hours.
  • the effect is the same as that of self-adhesive coated steel, the higher the bonding strength of the coating of the prepared silicon steel plate, the stronger the overall bonding force of the iron core prepared corresponding to the silicon steel plate, and the more conducive to the fixed strength of the iron core, the overall Vibration frequency and core efficiency are improved and noise is effectively reduced.
  • Fig. 1 schematically shows the changes of bonding strength and curing degree with coil baking temperature during silicon steel sheet manufacturing.
  • the suitable baking plate temperature ranges from 150 to 250°C; the higher the temperature, the shorter the baking time required.
  • the temperature of the baking and curing process has a significant impact on the performance of the coated steel sheet.

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Abstract

本公开涉及一种绝缘涂料，其包含以下成分：水溶性金属无机盐A，其包含水溶性磷酸盐A1，所述水溶性磷酸盐A1包括铝、锌、镁、锰中至少一种的水溶性磷酸盐；水可分散性有机乳液B，其包含：环氧乳液及其固化剂、聚酯、聚氨酯、聚丙烯酸酯、乙烯-醋酸乙烯共聚物中的至少一种；添加剂C，其包含：结构增强添加剂C1和耐热增强添加剂C2中的至少一种，其中结构增强添加剂C1包含无机纳米颗粒物，耐热增强添加剂C2选自硼酸和钼、钨、钒、钛的水溶性盐中的至少一种；助剂D1和溶剂D2；其中水溶性金属无机盐A：水可分散性有机乳液B的固含量质量份数比为(35～85)∶(15～65)。此外，本公开还涉及一种硅钢板，其基板表面具有由本公开的绝缘涂料形成的涂层。

Description

一种轻粘性硅钢环保绝缘涂料、硅钢板及其制造方法 技术领域
本公开涉及一种涂料、硅钢板及其制造方法，尤其涉及一种绝缘涂料、硅钢板及其制造方法。
背景技术
近年来，随着中国大力推进发展新能源汽车，越来越多的汽车生产厂商和研究人员加入了新能源汽车领域的研发队伍。在新能源汽车的研发过程中，新能源汽车对于所采用的先进电机的性能要求通常较高。与常规电机的性能要求相比，以新能源汽车为代表的先进电机普遍要求电机铁芯具有高固定强度、高铁芯效率和磁振噪音小的特点。
在现有技术中，通常选用如自粘结这种特殊C-3类涂层硅钢来制作满足以上性能要求的铁芯。例如：CN201810275197.8、CN201810885096.2、CN202010591227.3、CN200580037004.6、CN 200410017997.8、US 2007/0087201、WO 2004/070080、特开平6-21274等诸多中外专利申请，均披露了这种C-3类自粘结涂层产品的成份及其应用。
但是，由于下列原因，当前这种C-3类自粘结涂层产品只能被用于部分用户或部分机型，并不能被广泛应用：
(1)自粘结涂层产品的价格昂贵，使用成本较高；
(2)自粘结涂层的单面膜厚一般≥3μm，膜厚越厚或基材越薄，会致使铁芯叠片系数降低而影响电机效率；
(3)自粘结涂层主要成份为有机树脂，不耐受≥750℃的去应力退火和400℃以上的发蓝工艺，甚至少有能长期耐受210℃的涂层产品，可焊性较差；
(4)自粘结涂层铁芯边部经终态固化时可能存在热压溢胶的问题。
因此，上述C-3类自粘结涂层产品的实际应用效果并不佳。
就现阶段而言，以新能源汽车为代表的先进电机的主流涂层品种仍然广泛使用的是C-5类属磷酸盐基环保薄涂层(膜厚范围0.5～1.5μm)产品，其应用最广，发展最为成熟且生产成本相对较低。
在现有技术中，常规C-5类属磷酸盐基环保薄涂层的硅钢板具有十分良好的性能，其绝缘性(≥5Ω.cm 2/片，ASTM A717，1μm膜厚)、附着性(A级，GB/T 2522)、耐热性(耐受≥750℃去应力退火，IEC 60404-12)、可焊性(≥40cm/min，SEP 1210)等基本性能均十分优异。
然而，部分用户为了追求更高的电机效能，会利用专用设备将胶粘剂对硅钢片表面进行阵列式点胶，以此将相邻两片硅钢进行胶粘成型。这种处理方式不仅对硅钢板表面的涂层材料和胶粘剂的相容性提出高粘结强度要求，还对点胶设备和工艺的适应性和规模化量产稳定性提出了挑战，且其制造成本高昂。
可见，在现有技术中，常用的涂覆C-5型涂层或C-3型自粘结涂层的硅钢板均存在一定的缺陷与不足，它们已经难以满足行业内对于电机铁芯的进一步需求。
因此，对铁芯固定强度、磁振噪音、铁芯效率有较高要求的驱动电机铁芯行业急需一种成本较低、可制造性较强且具有环保功能性涂层的硅钢产品。
基于此，本领域期望获得一种新的轻粘性硅钢环保绝缘涂料，其可以涂覆于硅钢板的基板表面，并可以在基板上形成涂层。该涂层在具备常规C-5型涂层特性的基础上，还具有类似于C-3型自粘结涂层的片间粘结效果(但无需达到C-3型自粘结涂层的高粘结强度(C-3型自粘结涂层一般要求粘结强度≥7N/mm 2，ISO 4587拉伸剪切法))，且可规避C-3型自粘结涂层不能耐受热工艺处理的弊端。
发明内容
本公开的目的之一在于提供一种绝缘涂料，其形成的涂层不仅具有常规C-5型涂层的良好绝缘性、附着性、耐热性、可焊性性等基本性能，还具有类似于C-3型自粘结涂层的片间粘结效果，且经二次热/压工艺处理后仍然具有一定的粘结性能(粘结强度≥2N/mm 2，ISO 4587拉伸剪切法)，由此能够在铁芯片间产生一定的粘结力，使得铁芯结构得到整体增强，可以有效改善铁芯固定强度低、固有频率低且振动噪音高等问题，从而获得更高效率、更低振动噪音的电机。
为了实现上述目的，在第一方面，本公开提供了一种绝缘涂料，其包含以下成分(优选有效成分)：
水溶性金属无机盐A，其包含水溶性磷酸盐A1，所述水溶性磷酸盐A1包括铝、锌、镁、锰中至少一种的水溶性磷酸盐；
水可分散性有机乳液B，其包含：环氧乳液及其固化剂、聚酯、聚氨酯、聚丙烯酸酯、乙烯-醋酸乙烯共聚物中的至少一种；
添加剂C，其包含：结构增强添加剂C1和耐热增强添加剂C2中的至少一种，其中结构增强添加剂C1包含无机纳米颗粒物，耐热增强添加剂C2选自硼酸和钼、钨、钒、钛的水溶性盐中的至少一种；
助剂D1和溶剂D2；
其中水溶性金属无机盐A∶水可分散性有机乳液B的固含量质量份数比为(35～85)∶(15～65)。
由本公开的绝缘涂料形成的涂层按ASTM A976或DIN EN 10342标准可以分类为C-5或EC-5类属涂层，其不仅具有常规C-5型涂层的良好绝缘性、附着性、耐热性、可焊性性等基本性能，还具有类似于C-3型自粘结涂层的片间粘结效果(但无需达到C-3型自粘结涂层的高粘结强度(一般要求C-3型自粘结涂层的粘结强度≥7N/mm 2，ISO 4587拉伸剪切法)，且可规避C-3型自粘结涂层不耐受热工艺处理的弊端。
优选地，在本公开的绝缘涂料中，水溶性金属无机盐A∶水可分散性有机乳液B的固含量质量份数比为∶(40～75)∶(25～60)。
优选地，在本公开的绝缘涂料中，水溶性金属无机盐A还包含水溶性硅酸盐A2。在本公开的绝缘涂料中添加适量的水溶性硅酸盐A2可以在一定程度上提高由绝缘涂料形成的涂层的强硬度。但水溶性硅酸盐A2不宜过量添加，因为当水溶性硅酸盐A2过量时，容易引发涂料体系的相容稳定性问题。因此，在本公开的绝缘涂料中，以固含量质量百分含量计，水溶性硅酸盐A2占水溶性金属无机盐A的0～5％。
优选地，在本公开的绝缘涂料中，水溶性硅酸盐A2的模数＜4。
优选地，在本公开的绝缘涂料中，水溶性硅酸盐A2包括硅酸钠和/或硅酸钾。
优选地，在本公开的绝缘涂料中，以固含量质量百分含量计，水溶性磷酸盐A1占水溶性金属无机盐A的95～100％，水溶性硅酸盐A2占水溶性金属无机盐A的0～5％。
优选地，在本公开的绝缘涂料中，水溶性金属无机盐A至少包含铝的水溶性磷酸盐。
优选地，在本公开的绝缘涂料中，以固含量质量百分含量计，铝的水溶性磷酸盐占水溶性磷酸盐A1的70～100％。
优选地，锌、镁、锰的水溶性磷酸盐分别为磷酸二氢锌、磷酸二氢镁、磷酸二氢锰，且其总质量百分含量占水溶性磷酸盐A1的0～30％。
优选地，在本公开的绝缘涂料中，水可分散性有机乳液B的粒径满足：平均粒径D 50≤2μm，平均粒径D 90≤5μm，最大粒径≤10μm。
优选地，在本公开的绝缘涂料中，水可分散性有机乳液B的粒径满足：D 50≤1μm，D 90≤3μm。
优选地，在本公开的绝缘涂料中，水可分散性有机乳液B包括环氧乳液及其固化剂。环氧乳液及其固化剂能够在由本公开的绝缘涂料形成的涂层中发挥主要粘结性的作用，同时提高最终涂层的机械防护性、绝缘性和耐热性等。
优选地，在本公开的绝缘涂料中，环氧乳液的固化剂选自双氰胺、氨基树脂、咪唑和聚异氰酸酯中的至少一种。
优选地，在本公开的绝缘涂料中，环氧乳液的固化剂为微粉化的双氰胺，其平均粒径满足：D 50≤5μm，D 90≤10μm。
优选地，在本公开的绝缘涂料中，水可分散性有机乳液B包含环氧乳液及其固化剂，其中以固含量质量百分含量计，环氧乳液占环氧乳液及其固化剂总体的90～99％。更优选地，环氧乳液占环氧乳液及其固化剂总体的95～98％。
优选地，在本公开的绝缘涂料中，环氧乳液的环氧当量为100～2000g/eq，优选为200～1000g/eq；重均分子量Mw为200～4000，优选为300～3000；官能度为2～3。
为了获得涂层粘结性和耐热性的良好平衡，优选地，在本公开的绝缘涂料中，水可分散性有机乳液B包含乙烯-醋酸乙烯共聚物，其中以固含量质量百分含量计，乙烯-醋酸乙烯共聚物占水可分散性有机乳液B的0～20％。
优选地，在本公开的绝缘涂料中，乙烯-醋酸乙烯共聚物中醋酸乙烯的质量百分含量为10～40％，更优选15～30％。
优选地，在本公开的绝缘涂料中，聚氨酯和聚丙烯酸酯均为高分子量的阴离子型水可分散性乳液。
优选地，在本公开的绝缘涂料中，添加剂C的质量相对于水溶性金属无机盐A和水可分散性有机乳液B的总质量为0.1～10％。当添加剂C的含量低于上述范围的下限时，无法获得添加剂C的性能特点；当添加剂C的含量高于上述范围的上限时，容易导致涂料的稳定性不良，反而会降低涂层的片间粘结强度。为了获得更优的效果，更优选添加剂C的质量相对于水溶性金属无机盐A和水可分散性有机乳液B的总质量为0.5～5％。
优选地，在本公开的绝缘涂料中，无机纳米颗粒物的聚集体的平均粒径为50-800nm， 更优选80-500nm。
优选地，在本公开的绝缘涂料中，无机纳米颗粒物为金属氧化物，所述金属氧化物选自SiO 2、Al 2O 3、TiO 2、ZnO、ZrO 2、Fe 3O 4和CaCO 3中的至少一种。
优选地，在本公开的绝缘涂料中，无机纳米颗粒物为SiO 2、Al 2O 3、TiO 2、ZnO或它们的复合氧化物。
优选地，在本公开的绝缘涂料中，耐热增强添加剂C2选自硼酸、钼酸铵、钨酸钠中的至少一种。
优选地，耐热增强添加剂C2为硼酸(H 3BO 3)和变价金属(如钼、钨、钒、钛)的水溶性盐。
优选地，在本公开的绝缘涂料中，助剂D1和溶剂D2的总质量相对于水溶性金属无机盐A和水可分散性有机乳液B的总质量为5～35％。
优选地，为了保证涂料对高速辊涂的涂层缺陷控制能力，在本公开的绝缘涂料中，助剂D1选自消泡剂、润湿剂、流平剂、增稠剂、防沉剂、防闪锈剂中的至少一种。
优选地，在本公开的绝缘涂料中，溶剂D2包括乙二醇、丙三醇、正丁醇、异丁醇、异丙醇、乙二醇甲醚、乙二醇丁醚、丙二醇甲醚、丙二醇丁醚、丙二醇甲醚醋酸酯中的至少两种。
优选地，本公开的绝缘涂料的固含量为15～40％。
本公开的绝缘涂料适用于涂覆各类电动机、发电机铁芯的硅钢板的基板表面，并可以在基板上形成涂层，尤其适用于涂覆新能源汽车电机、伺服电机、微特电机等领域使用的无取向硅钢板。
在第二方面，本公开提供了一种硅钢板，其包括基板，所述基板的表面具有由本公开的绝缘涂料形成的涂层。
优选地，在本公开的硅钢板中，涂层的单面干膜厚度为0.3-2μm，更优选0.5-1.5μm。
本公开的硅钢板上涂覆有本公开的绝缘涂料，从而使得硅钢板的基板上形成涂层。本公开的硅钢板可以用于制备驱动电机的铁芯，其涂层经二次热/压工艺处理后仍然具有一定的粘结性能(粘结强度≥2N/mm 2，ISO 4587拉伸剪切法)，可以有效改善铁芯固定强度低、固有频率低且振动噪音高等问题，可以广泛应用于新能源汽车电机、伺服电机和微特电机中，具有良好的推广前景和应用价值。
在第三方面，本公开提供了一种硅钢板的制造方法，其包括以下步骤：在硅钢板的基板 表面涂覆本公开的绝缘涂料；在150-250℃的板卷温度下烘干所述绝缘涂料，形成涂层。
与现有技术相比，本公开的绝缘涂料、硅钢板及其制造方法具有如下所述的优点以及有益效果：
本公开的绝缘涂料的成分经合理的优化设计，以水溶性磷酸盐和成膜乳液为基础，选用低毒低危害的溶剂，使得所获的绝缘涂料为非危险化学品，VOC(volatile organic compounds，挥发性有机化合物)排放低，完全绿色环保。
本公开的绝缘涂料可以涂覆于各类电动机、发电机铁芯的硅钢板的基板表面，并可以在基板上形成涂层，尤其适用于新能源汽车电机、伺服电机、微特电机等领域使用的无取向硅钢材料，商业化应用的空间较大。
由本公开的绝缘涂料形成的涂层不仅具有常规C-5型涂层的特性，还具有类似于C-3型自粘结涂层的片间粘结效果(但无需达到C-3型自粘结涂层的高粘结强度(C-3型自粘结涂层一般要求粘结强度≥7N/mm 2，ISO 4587拉伸剪切法))，且完全避免了C-3型自粘结涂层的耐热性差、可焊性差、叠片系数低、热压溢胶等问题。
本公开的硅钢板可以用于制备驱动电机的铁芯，其涂层经二次热/压工艺处理后仍然具有一定的粘结性能(粘结强度≥2N/mm 2，ISO 4587拉伸剪切法)，由此能够在铁芯片间产生一定的粘结力，使得铁芯结构得到整体增强，可以有效改善铁芯固定强度低、固有频率低且振动噪音高等问题，从而制造出更高效率、更低振动噪音的电机。
本公开的硅钢板的制造方法绿色环保高效。
另外，本公开的具有涂层的硅钢板可以进一步经过剪冲加工后叠装成铁芯，再用胶粘剂将磁钢插入铁芯槽孔中并进行二次加热，固化后即完成磁钢固定和铁芯装配，所得铁芯整体强度高、固有频率提升明显。
上述二次固化工艺可以为：1～5MPa压力负载，在150～300℃的铁芯温度下维持1min～4h，优选在150～250℃的铁芯温度下维持10min～2h。该二次固化工艺的目的虽然是使胶粘剂固化，但实际也对铁芯整体进行了二次加热工艺处理。因此，可充分利用这种热工艺，对叠层铁芯的硅钢涂层进行热压加工，从而产生片间粘结效果。
附图说明
图1示意性地显示了粘结强度和固化程度随硅钢板制造期间的板卷烘烤温度的变化图。
具体实施方式
除非另有定义，否则本文使用的所有技术和科学术语具有与本公开所属领域的普通技术人员的通常理解相同的含义。
如本文所用，术语“和/或”涉及并涵盖一个以上所列项目的任何和所有可能组合。
在本文中，“固含量”是指乳液或涂料在规定条件下烘干后剩余部分占总量的质量百分数，其测定标准为EN ISO 3251，测定条件为1g/2h/130℃(意即取1g涂料，经130℃保温2小时)。
在本文中，“模数”是指摩尔数的比值。例如：化学式为R2O·n SiO 2，n为SiO 2与R 2O摩尔数的比值，称为R 2O·n SiO 2的模数。
在本文中，D 50表示样品的累计粒度分布百分数达到50％时所对应的粒径，D 90表示样品的累计粒度分布数达到90％时所对应的粒径。“粒度分布”是指用特定的仪器和方法反映出粉体样品中不同粒径颗粒占颗粒总量的百分数。可使用激光衍射法进行测量，测试标准可参考ISO 13320《Particle size analysis-Laser diffraction methods》，可使用的测量设备例如Mastersizer系列激光衍射粒度仪。
在本文中，环氧当量是指含有一当量环氧基的环氧树脂克数，单位为g/eq，即[克/当量]。
“官能度”定义为环氧树脂分子中含有环氧基团的数目。在本文中，“官能度”指环氧化合物的平均官能度，为每一分子平均带有的基团数，即能在环氧固化过程中起缩聚反应的环氧官能团总当量数。可以通过凝胶渗透色谱法(参照标准ISO 13885-1)和核磁共振波谱法来测定。在本文中，“官能度”计算为环氧树脂的重均分子量Mw与环氧当量的商。
在本文中，重均分子量Mw通过凝胶色谱法测定。凝胶色谱法的参考标准为ISO 13885-1《Binders for paints and varnishes-Gel permeation chromatography(GPC)-Part 1：Tetrahydrofuran(THF)as eluent》。
在本文中，结构增强添加剂C1是指具备反应活性的无机纳米颗粒物，可与成膜树脂官能团间形成物理/化学交联点，从而在分子链中引入R-O-R和/或R-O-C键(R代表Si/Al/Ti/Zr/Zn等金属元素)而成为网状结构。符合上述特征的无机纳米颗粒物可以采用气相法制备，也可通过气相沉积法或相关水解与缩合法来制备，但不能为溶胶型产品。
在本公开的绝缘涂料的一个优选实施方案中，水溶性金属无机盐A至少包含铝的水溶性磷酸盐。
铝的水溶性磷酸盐可以采用如下方法制备：将摩尔比为(2.3～3.5)∶1的磷酸(H 3PO 4) 和氢氧化铝(Al(OH) 3)分别投入反应釜中，控制反应温度为70～135℃，保温30～120min后，冷却过滤出料。在一些优选的实施方式中，铝的水溶性磷酸盐可以采用如下方法制备：将摩尔比为(3.0～3.4)∶1的磷酸(H 3PO 4)和氢氧化铝(Al(OH) 3)分别投入反应釜中，控制反应温度为70～135℃，保温60～90min后，冷却过滤出料。
在本公开的绝缘涂料中，水可分散性有机乳液B为水可分散性的有机乳液，而不是水可溶解性的树脂溶液。水可分散性有机乳液B按成膜类型可以进一步分为以下两类：
I.主要成膜机理为交联固化型成膜，如环氧乳液及其固化剂。
II.主要成膜机理为颗粒聚集型成膜，如聚酯、聚氨酯、聚丙烯酸酯、乙烯-醋酸乙烯共聚物乳液等。其中，聚氨酯和聚丙烯酸酯优选为高分子量的阴离子型水可分散性乳液，其主要成膜方式为颗粒聚集型，次要成膜方式也可为受热自交联固化型，其可以影响涂层的结构性能，如强硬度、抗划伤性、耐热性、耐化学品性等。
在本公开的绝缘涂料的一个优选实施方案中，将环氧乳液及其固化剂、聚丙烯酸酯乳液或聚酯、聚氨酯乳液、乙烯-醋酸乙烯共聚物中的两种以上的复配型有机成膜乳液作为水可分散性有机乳液B的成份，可以使绝缘涂料形成的涂层的基本性能更佳。
在本公开的绝缘涂料中，溶剂D2主要用来增加有机树脂和助剂D1在水中的溶解性，同时可以降低溶液的表面张力，防止在烘烤过程中涂层出现缩孔、漏涂等缺陷，并兼具消泡作用。
对于本公开的绝缘涂料的制备，可以在添加水溶性金属无机盐A、水可分散性有机乳液B、添加剂C、助剂D1和溶剂D2并混合后，加入适量的纯水混合搅拌均匀。
在本公开的绝缘涂料的一个优选实施方案中，最终绝缘涂料的固含量为15～40％；涂-4杯粘度为10～40秒，由此可以实现较好的涂层膜厚精确控制和高速辊涂作业性。
在本公开中，对硅钢板的基板成分组成没有特别限制，可以采用能够实现本公开的技术效果的任意现有技术的成分体系。
下面将结合附图和实施例对本公开的绝缘涂料、硅钢板及其制造方法做进一步的解释和说明，然而该解释和说明并不对本公开的技术方案构成不当限定。
实施例1-6及对比例1-2
实施例1-6的绝缘涂料包含以下成分：水溶性金属无机盐A、水可分散性有机乳液B、添加剂C、助剂D1和溶剂D2。按照下述表1至表8所示的组分和配比，混合添加上述水溶性金属无机盐A、水可分散性有机乳液B、添加剂C、助剂D1和溶剂D2后，加入 适量的纯水混合搅拌均匀，制得的实施例1-6的绝缘涂料。
需要说明的是，在具体设计时，针对水溶性金属无机盐A、水可分散性有机乳液B、添加剂C、助剂D1和溶剂D2的具体要求如下述(1)-(4)所示：
(1)实施例1-6所采用的水溶性金属无机盐A必须包含铝、锌、镁、锰中至少一种的水溶性磷酸盐A1；
(2)实施例1-6所采用的水可分散性有机乳液B包含环氧乳液及其固化剂、聚酯、聚氨酯、聚丙烯酸酯、乙烯-醋酸乙烯共聚物中的至少一种；
(3)实施例1-6所采用的添加剂C包含：结构增强添加剂C1和耐热增强添加剂C2。其中，结构增强添加剂C1可以包含无机纳米颗粒物；耐热增强添加剂C2选自硼酸和钼、钨、钒、钛的水溶性盐中的至少一种；
(4)在实施例1-6的部分中，选用的助剂D1包括：消泡剂、润湿剂、流平剂、增稠剂、防沉剂、防闪锈剂中的至少一种；选用的溶剂D2包括：乙二醇、丙三醇、正丁醇、异丁醇、异丙醇、乙二醇甲醚、乙二醇丁醚、丙二醇甲醚、丙二醇丁醚、丙二醇甲醚醋酸酯中的至少两种。
需要说明的是，在实施例1-6的部分中，水溶性金属无机盐A除包含水溶性磷酸盐A1外，还包含有水溶性硅酸盐A2。水溶性硅酸盐A2包括硅酸钠和/或硅酸钾。水溶性硅酸盐A2的模数＜4。
表1列出了实施例1-6的绝缘涂料的具体成分。
Figure PCTCN2022133232-appb-000001
注：上述表1中，
Figure PCTCN2022133232-appb-000002
W 640ZX、
Figure PCTCN2022133232-appb-000003
A3017、
Figure PCTCN2022133232-appb-000004
300、
Figure PCTCN2022133232-appb-000005
A3017、
Figure PCTCN2022133232-appb-000006
380、CAB-O-SIL EH-5均为无机纳米颗粒物，其含有：SiO 2、Al 2O 3、TiO 2、ZnO、ZrO 2、Fe 3O 4、CaCO 3中的至少一种；助剂D1中添加的BYK-348可作为润湿剂和消泡剂使用、BYK-346可作为流平剂和/或润湿剂使用、BYK-025为消泡剂；Tego 245可作为润湿剂、流平剂和消泡剂使用；ZT-709为防闪锈剂，Cellosize QP-100MH是一种防沉剂或增稠剂。
虽然上述表1的实施例1-6并未示出采用钛、钒的水溶性盐作为耐热增强添加剂C2的例子，但是应理解，在本公开的其他实施方式中，可以采用钛、钒的水溶性盐作为耐热增强添加剂C2。
如上述表1所示，实施例1-6所采用的水溶性金属无机盐A中均添加有含铝的水溶性磷酸盐。其中，含铝的水溶性磷酸盐采用如下制造方法制备：将摩尔比为(2.3～3.5)∶1的磷酸(H 3PO 4)和氢氧化铝(Al(OH) 3)分别投入反应釜中，控制反应温度为70～135℃，保温30～120min后，冷却过滤出料。
此外，根据上述表1可以看出，实施例1-6所采用的水可分散性有机乳液B中的环氧乳液的固化剂均为微粉化的双氰胺。
应理解，在本公开的其他实施方式中，环氧乳液的固化剂也可以为氨基树脂、咪唑或聚异氰酸酯。
表2列出了实施例1-6的绝缘涂料的各成分相较于溶性金属无机盐A和水可分散性有机乳液B的总质量的含量(将水溶性金属无机盐A和水可分散性有机乳液B的总质量计为100％)。
Figure PCTCN2022133232-appb-000007
实施例1-6所采用的C1的无机纳米颗粒物的聚集体的平均粒径D 50如下述表3所示。
实施例1-6所采用的水可分散性有机乳液B的平均粒径D 50和D 90的具体数值列于下述表3之中。
此外，如表1中所示，在实施例1-6中，水可分散性有机乳液B中的聚氨酯、聚丙烯酸酯为高分子量的阴离子型水可分散性乳液。实施例1-6所采用的水可分散性有机乳液B中的环氧乳液的固化剂均为微粉化的双氰胺。
实施例1-6所添加的微粉化的双氰胺的具体粒径数据列于下述表3之中。
表3
Figure PCTCN2022133232-appb-000008
注：上述表3中，D 50表示样品的累计粒度分布百分数达到50％时所对应的粒径，D 90表示样品的累计粒度分布数达到90％时所对应的粒径；其中，每次测试粒径分布时的D 50、D 90都是一个点值，但测试本身存在误差或变差，因此表3中均为范围值而非一个单一的点值。
实施例1-6的水可分散性有机乳液B中的环氧乳液的环氧当量、重均分子量Mw以及官能度列于下述表4之中。
表4
Figure PCTCN2022133232-appb-000009
实施例1-6的水可分散性有机乳液B中的环氧乳液的固含量质量百分含量相较于环氧乳液及其固化剂的占比列于下述表5之中。
实施例1-6的水可分散性有机乳液B中的乙烯-醋酸乙烯共聚物相较于水可分散性有机乳液B的占比，以及乙烯-醋酸乙烯共聚物中醋酸乙烯的质量百分含量列于下述表5之中。
表5
Figure PCTCN2022133232-appb-000010
需要说明的是，虽然实施例1-6中仅实施例4的水可分散性有机乳液B中添加了乙烯-醋酸乙烯共聚物，但仍然存在众多添加了乙烯-醋酸乙烯共聚物的实施例未在本公开中示出。
表6列出了实施例1-6的绝缘涂料中水溶性磷酸盐A1相较于水溶性金属无机盐A的固含量比，铝盐的质量百分含量相较于水溶性磷酸盐A1的固含量比，水溶性金属无机盐A∶水可分散性有机乳液B的固含量质量份数比，添加剂C相对于水溶性金属无机盐A和水可分散性有机乳液B二者总固含量的比例，助剂D1、溶剂D2相较于水溶性金属无机盐A和水可分散性有机乳液B二者总质量的含量。
表6
Figure PCTCN2022133232-appb-000011
Figure PCTCN2022133232-appb-000012
不同于上述实施例1-6的绝缘涂料，对比例1-2选用的均是常用的市售涂料：
对比例1的对比涂料选用市售的Remisol EB 5350S型涂料，Remisol EB 5350S是市售无取向硅钢C-5类属涂层的典型涂料型号；
对比例2的对比涂料选用市售的Remisol EB 549型涂料，Remisol EB 549型涂料是市售无取向硅钢C-3类属自粘结涂层的典型涂料型号。
将实施例1-6的绝缘涂料和对比例1-2的对比涂料涂覆在硅钢板的基板的两个表面上，采用150-250℃的板卷温度进行烘干固化，得到具有不同涂层的成品硅钢板。涂层的单面干膜厚度在0.3-2μm之间。
需要说明的是，实施例1-6以及对比例1-2的硅钢板基板所采用的各化学元素的质量百分比均相同，统一为市售的B30A250牌号无取向硅钢。
表7列出了采用实施例1-6的绝缘涂料和对比例1-2的对比涂料涂覆B30A250牌号无取向硅钢获得的成品硅钢板的工艺参数。
表7
编号 涂层的单面干膜厚度(μm) 板卷烘烤温度(℃)
实施例1 0.7 180
实施例2 0.5 170
实施例3 1.0 190
实施例4 1.2 200
实施例5 1.4 210
实施例6 1.6 240
对比例1 1.0 250
对比例2 2.0 160
对于得到的各实施例和对比例的带涂层的成品硅钢板，对各成品硅钢板分别进行取样，获得样品钢板，并针对各样品钢板进行各项测试。测试结果列于下述表8中。
表8列出了实施例1-6和对比例1-2的成品硅钢板的相关性能测试结果。
表8
Figure PCTCN2022133232-appb-000013
Figure PCTCN2022133232-appb-000014
注：评价符号代表的含义为：◎表示优秀；⊙表示良好；○表示一般；△表示偏差；×表示不可接受。
如表8所示，相较于对比例1和对比例2，实施例1-6的成品硅钢板性能明显更优。参阅表8，并结合表1-表7可以看出，在实施例1-6中，涂料中有机成份含量越高，则所形成的硅钢板的涂层的粘结强度、耐蚀性、绝缘性就越好，但耐退火、焊接等耐热性就越差；同时涂料中含有交联固化型成膜乳液和颗粒聚集型成膜乳液两种及以上的复配型有机成膜乳液，有利于冷粘结缺陷控制和抗划伤性能，可使整个涂层性能更优。
如表8所示，实施例3-5能更好地兼顾无取向硅钢C-5类涂层的性能，同时具有C-3类自粘结涂层所特有的粘结性能，是最佳实施例。
对比例1是市售无取向硅钢C-5类属涂层的典型涂料型号，该涂层的常规特性整体优良，但完全不具备粘结性能特征。对比例2是市售无取向硅钢C-3类属自粘结涂层的典型涂料型号，该自粘结涂层的相关特性优良，但完全不能耐受250℃以上的热处理，且需要较高的涂层膜厚，产品成本高昂。
此外，将实施例1-6的成品硅钢板通过卷材分条、冲片叠装成型，获得铁芯。在装配时，将不同类型的磁钢插入预留的铁芯槽孔中，并用胶粘剂填充到磁钢和铁芯侧壁表面，并进行二次固化加热，固化后即完成磁钢固定和铁芯装配。
该二次固化工艺控制为：1～5MPa压力负载，在150～300℃的铁芯温度下维持1min～4h。
与自粘结涂层钢材的效果一样，制得的硅钢板的涂层的粘结强度越高，硅钢板对应制备的铁芯整体结合力越强，进而越有利于铁芯的固定强度、整体振动频率及铁芯效率的提高且有效降噪。
图1示意性地显示了粘结强度和固化程度随硅钢板制造期间的板卷烘烤温度的变化图。
如图1所示，合适的烘烤板温(金属峰值温度PMT)范围为150～250℃；温度越高所需 的烘烤时间可越短。
参阅图1可以看出，烘烤固化工艺温度对涂层钢板的性能影响明显。烘烤板温越低，涂层固化程度就越低，涂层钢片经叠压成型并再经热压固化后的粘结强度就越好，但涂层的抗划伤性(防护性)、焊接性、耐蚀性、附着性和冷粘结控制性越差，甚至造成涂层钢卷的连续生产稳定性问题。
需要说明的是，本公开中各技术特征的组合方式并不限本公开权利要求中所记载的组合方式或具体实施例所记载的组合方式。本公开记载的所有技术特征可以以任何方式进行自由组合或结合，除非相互之间产生矛盾。
还需要注意的是，以上所列举的实施例仅为本公开的具体示例。本公开不局限于以上实施例。若随之做出的类似变化或变形是本领域技术人员能从本公开公开的内容直接得出或者很容易便联想到的，则均属于本公开的保护范围。

Claims (29)

  1. 一种绝缘涂料，其特征在于，所述绝缘涂料包含以下成分：
    水溶性金属无机盐A，其包含水溶性磷酸盐A1，所述水溶性磷酸盐A1包括铝、锌、镁、锰中至少一种的水溶性磷酸盐；
    水可分散性有机乳液B，其包含：环氧乳液及其固化剂、聚酯、聚氨酯、聚丙烯酸酯、乙烯-醋酸乙烯a聚物中的至少一种；
    添加剂C，其包含：结构增强添加剂C1和耐热增强添加剂C2中的至少一种，结构增强添加剂C1包含无机纳米颗粒物，耐热增强添加剂C2选自硼酸和钼、钨、钒、钛的水溶性盐中的至少一种；
    助剂D1和溶剂D2；
    其中水溶性金属无机盐A：水可分散性有机乳液B的固含量质量份数比为(35～85)∶(15～65)。
  2. 如权利要求1所述的绝缘涂料，其特征在于，水溶性金属无机盐A：水可分散性有机乳液B的固含量质量份数为：(40～75)∶(25～60)。
  3. 如权利要求1所述的绝缘涂料，其特征在于，水溶性金属无机盐A还包含水溶性硅酸盐A2。
  4. 如权利要求3所述的绝缘涂料，其特征在于，水溶性硅酸盐A2的模数＜4。
  5. 如权利要求4所述的绝缘涂料，其特征在于，水溶性硅酸盐A2包括硅酸钠和/或硅酸钾。
  6. 如权利要求1所述的绝缘涂料，其特征在于，以固含量质量百分含量计，水溶性磷酸盐A1占水溶性金属无机盐A的95～100％。
  7. 如权利要求1所述的绝缘涂料，其特征在于，水溶性金属无机盐A至少包含铝的水溶性磷酸盐。
  8. 如权利要求7所述的绝缘涂料，其特征在于，以固含量质量百分含量计，铝的水溶性磷酸盐占水溶性磷酸盐A1的70～100％。
  9. 如权利要求1所述的绝缘涂料，其特征在于，水可分散性有机乳液B的粒径满足：平均粒径D 50≤2μm，平均粒径D 90≤5μm，最大粒径≤10μm。
  10. 如权利要求9所述的绝缘涂料，其特征在于，水可分散性有机乳液B的粒径满足：D 50≤1μm，D 90≤3μm。
  11. 如权利要求1所述的绝缘涂料，其特征在于，环氧乳液的固化剂选自双氰胺、氨基树脂、咪唑、聚异氰酸酯中的至少一种。
  12. 如权利要求11所述的绝缘涂料，其特征在于，环氧乳液的固化剂为微粉化的双氰胺，其平均粒径满足：D 50≤5μm，D 90≤10μm。
  13. 如权利要求1所述的绝缘涂料，其特征在于，水可分散性有机乳液B包含环氧乳液及其固化剂，其中以固含量质量百分含量计，环氧乳液占环氧乳液及其固化剂总体的90～99％，优选95～98％。
  14. 如权利要求1所述的绝缘涂料，其特征在于，环氧乳液的环氧当量为100～2000g/eq，优选为200～1000g/eq；重均分子量Mw为200～4000，优选为300～3000；官能度为2～3。
  15. 如权利要求1所述的绝缘涂料，其特征在于，水可分散性有机乳液B包含乙烯-醋酸乙烯共聚物，其中以固含量质量百分含量计，乙烯-醋酸乙烯共聚物占水可分散性有机乳液B的0～20％。
  16. 如权利要求15所述的绝缘涂料，其特征在于，乙烯-醋酸乙烯共聚物中醋酸乙烯的质量百分含量为10～40％，优选15～30％。
  17. 如权利要求1所述的绝缘涂料，其特征在于，聚氨酯和聚丙烯酸酯均为高分子量的阴离子型水可分散性乳液。
  18. 如权利要求1所述的绝缘涂料，其特征在于，添加剂C的质量相对于水溶性金属无机盐A和水可分散性有机乳液B的总质量为0.1～10％，优选0.5～5％。
  19. 如权利要求1所述的绝缘涂料，其特征在于，无机纳米颗粒物的聚集体的平均粒径为50-800nm22.，优选80-500nm。
  20. 如权利要求1所述的绝缘涂料，其特征在于，无机纳米颗粒物为金属氧化物，所述金属氧化物选自SiO 2、Al 2O 3、TiO 2、ZnO、ZrO 2、Fe 3O 4和CaCO 3中的至少一种。
  21. 如权利要求1所述的绝缘涂料，其特征在于，无机纳米颗粒物为SiO 2、Al 2O 3、TiO 2、ZnO或它们的复合氧化物。
  22. 如权利要求1所述的绝缘涂料，其特征在于，耐热增强添加剂C2选自硼酸、钼酸铵和钨酸钠中的至少一种。
  23. 如权利要求1所述的绝缘涂料，其特征在于，助剂D1和溶剂D2的总质量相对于水溶性金属无机盐A和水可分散性有机乳液B的总质量为5～35％。
  24. 如权利要求1所述的绝缘涂料，其特征在于，助剂D1选自消泡剂、润湿剂、流平剂、增稠剂、防沉剂和防闪锈剂中的至少一种。
  25. 如权利要求1所述的绝缘涂料，其特征在于，溶剂D2包括乙二醇、丙三醇、正丁醇、异丁醇、异丙醇、乙二醇甲醚、乙二醇丁醚、丙二醇甲醚、丙二醇丁醚、丙二醇甲醚醋酸酯中的至少两种。
  26. 如权利要求1所述的绝缘涂料，其特征在于，绝缘涂料的固含量为15～40％。
  27. 一种硅钢板，其包括基板，其特征在于，所述基板表面具有由权利要求1-26中任一项所述的绝缘涂料形成的涂层。
  28. 如权利要求27所述的硅钢板，其特征在于，涂层的单面干膜厚度为0.3-2μm，优选0.5-1.5μm。
  29. 权利要求27或28所述的硅钢板的制造方法，其包括以下步骤：在硅钢板的基板表面涂覆权利要求1-26中任一项所述的绝缘涂料；以及，在150-250℃的板卷温度下烘干所述绝缘涂料，形成涂层。
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