WO2004070080A1 - 接着用表面被覆電磁鋼板 - Google Patents
接着用表面被覆電磁鋼板 Download PDFInfo
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- WO2004070080A1 WO2004070080A1 PCT/JP2004/000802 JP2004000802W WO2004070080A1 WO 2004070080 A1 WO2004070080 A1 WO 2004070080A1 JP 2004000802 W JP2004000802 W JP 2004000802W WO 2004070080 A1 WO2004070080 A1 WO 2004070080A1
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- WIPO (PCT)
- Prior art keywords
- steel sheet
- epoxy resin
- bonding
- strip
- magnetic steel
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Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21C—MANUFACTURE OF METAL SHEETS, WIRE, RODS, TUBES OR PROFILES, OTHERWISE THAN BY ROLLING; AUXILIARY OPERATIONS USED IN CONNECTION WITH METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL
- B21C37/00—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape
- B21C37/02—Manufacture of metal sheets, bars, wire, tubes or like semi-manufactured products, not otherwise provided for; Manufacture of tubes of special shape of sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- 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
- C09D133/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides, or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D133/04—Homopolymers or copolymers of esters
- C09D133/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, the oxygen atom being present only as part of the carboxyl radical
- C09D133/08—Homopolymers or copolymers of acrylic acid esters
-
- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
- H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
- H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
- H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
- H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
- H01F1/14—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys
- H01F1/16—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets
- H01F1/18—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials metals or alloys in the form of sheets with insulating coating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/10—Metallic substrate based on Fe
- B05D2202/15—Stainless steel
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L33/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Compositions of derivatives of such polymers
- C08L33/04—Homopolymers or copolymers of esters
- C08L33/06—Homopolymers or copolymers of esters of esters containing only carbon, hydrogen and oxygen, which oxygen atoms are present only as part of the carboxyl radical
- C08L33/08—Homopolymers or copolymers of acrylic acid esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
Definitions
- the present invention relates to a surface-coated electrical steel sheet for bonding by heating and / or pressure after punching or shearing.
- the cores are unitized by shearing or punching and then laminated, then secured by port tightening, force crimping, welding or bonding, etc. I do. Then, it is sent to the next process such as the winding coil assembling process.
- an insulating film called a so-called adhered film that exerts adhesiveness by heating and Z or pressing is applied to the surface of the steel sheet.
- a laminated iron core having no rigidity and no mechanical distortion and excellent in rigidity can be obtained by punching and laminating a unit iron core, and then pressurizing and heating to form a fixed core.
- the adhesive film needs to function as an adhesive for fixing the core and as an insulating film formed on the surface of the magnetic steel sheet.
- the properties required for insulating coatings often conflict with each other, and advanced technology is required. For example, it is considered that the adhesive properties should be soft in order to easily achieve a uniform adhesive state.
- the surface should be It is better to have a hard coating so that scratches and the like do not occur.
- the adhesive should have a high wettability on the adhesive coating surface in order to firmly bond the iron cores to each other. In order to maintain corrosion resistance, the lower the wettability, the better.
- Japanese Patent Application Laid-Open No. Hei 6-18296 discloses a mixture mainly containing an acrylic-modified epoxy resin emulsion in which a latent hardener is previously blended on the surface of a steel sheet. Apply the liquid evenly
- the technology described in the above-mentioned Japanese Patent Application Laid-Open No. 6-182296 has a problem in that when the unitary iron cores are laminated and fixed by heating under pressure, it is difficult to adhere the entire surface of the unitary iron cores. .
- the latent curing agent that has been previously formulated chemically reacts with the epoxy resin by heating to cure and adhere the coating, but the adhesive coating applied to the surface of the unit iron core by heating becomes the same. Since the epoxy resin and the epoxy curing agent undergo a curing reaction at the same time as they mix and melt, the curing reaction partially precedes and the entire steel sheet may not adhere.
- the adhesion strength between the steel sheets fluctuates and a weak adhesive strength occurs, so the core may be disassembled during manufacturing, or it may rotate with a motor, etc. There is a problem that it causes abnormal vibration at the time.
- an epoxy resin curing agent is mixed with a resin composition obtained by esterifying an acrylic resin and an epoxy resin, and the peak temperature of the logarithmic decrement of the resin composition is determined.
- a technique for setting the temperature to 80 to 200 ° C is disclosed. With this technology, after the adhesive coatings on the surface of the steel sheet are melted and intermingled, the curing reaction of the resin composition proceeds, so that the entire surface can be adhered.
- the organic-inorganic mixed insulating coating applied to the non-oriented electrical steel sheet has a film thickness of about 1 to 2 ⁇ m, Usually, the film is thickly applied to a thickness of 3 to 8 ⁇ . The reason is that when the film thickness is small, even if the surface is fine, such as rolling flaws generated when rolling a steel sheet, some parts of the surface do not come into contact with each other, and some parts are bonded and some parts are not bonded. Because
- the difference (Rmax) between the highest point and the lowest point in the predetermined measurement range is about 1 to 5 ⁇ m, and This is because a coating thickness larger than this difference is required.
- a phenomenon that is particularly noticeable when the film thickness is small is that when the adhesive strength is measured using a single plate, the adhesive strength is relatively secured, but when the laminated iron core is used, the laminated surface is particularly pressed. There is a phenomenon that occurs when the strength in the opening direction decreases.
- Japanese Patent Laid-Open Publication No. Sho 62-50361 is characterized in that fine particles of a polymer whose glass transition temperature does not reach room temperature are present in the system.
- an epoxy resin composition Since the adhesive coating is used as an iron core for motors and transformers, it must have heat resistance to temperature rise due to the generation of Joule heat. According to the invention described in the above publication, it is possible to reduce internal stress while maintaining heat resistance.
- the present inventors have found from various experiments that the problem with reducing the film thickness is that the so-called internal stress generated by applying the adhesive coating is large, and that the It has been found that the problem can be solved by lowering the internal stress.
- the present inventors have found knowledge necessary to reduce the internal stress of the adhesive film, improved the adhesive strength in the direction of pushing the adhesive surface of the adhesive film in a thin film, and applied a normal insulating film.
- the present inventors have found an adhesive film capable of preventing a decrease in adhesive strength when an adhesive film is formed thereon, and completed the present invention.
- the gist of the present invention is as follows.
- an electromagnetic steel sheet having an insulation coating exhibits by Ri adhesion ability to heat and / or pressure
- the coating film is a glass transition temperature (T g) 80
- Adhesive surface coating characterized by a mixture of an epoxy resin or epoxy resin modified at a temperature of ° C to 150 ° C, an epoxy resin curing agent, and a particulate polymer having a particle size of 0.01 ⁇ m to 0.5 ⁇ m. Electrical steel sheet.
- FIG. 1 a sample plate punched into a shape of 2 cm ⁇ 3 cm was bonded by heating and pressing at 200 ° C. XlOkgf / cm 2 ⁇ 30 minutes, and then a crack test was performed at room temperature.
- 5 is a photograph of a surface state of a bonded surface where each sample was collected and broken and observed by a scanning electron microscope.
- FIG. 1A is a photograph of the conventional bonded surface in a broken state
- FIG. 1B is a photo of the bonded surface in a broken state according to the present invention.
- Figure 2 shows the peel strength that has been used as one of the methods for measuring adhesive strength.
- a conceptual diagram of a test method and a conceptual diagram of a push-in test method newly devised in practicing the present invention are shown.
- the peel strength is measured by peeling off the steel sheet bonded with an adhesive or an adhesive coating.However, the peel test method greatly affects the properties of the steel sheet because the steel sheet is greatly deformed.
- the push-in test method the effects of the steel sheets are minimized by laminating and bonding multiple steel sheets, and the properties of the adhesive member can be evaluated in detail.
- the epoxy resin curing agent and specific organic resin particles having a particle size in the range of 0.01 to 0.5 ⁇ m are dispersed in the epoxy resin or the modified epoxy resin. It is.
- the epoxy resin used in the present invention is a resin having a glass transition point (Tg) after curing in the range of 80 ° C to 150 ° C, and is a liquid, preferably a solid, at room temperature before the curing reaction.
- Tg glass transition point
- the monomer has one or more epoxy groups on average in the monomer, but those having an epoxy equivalent of 100 to 5,000 are preferred.
- the coating of the present invention not only the epoxy resin but also a modified epoxy resin may be used.
- the method for converting the epoxy resin into a modified product is not particularly limited, but a specific substituent may be used in the main chain, or various compounds may be bonded to the epoxy group at the terminal of the epoxy resin or the hydroxyl group in the side chain. It was done. In particular, it is desirable that the curing reaction of the epoxy resin proceeds after the resin component melts as the adhesive coating.
- an acryl-modified epoxy resin obtained by subjecting an acryl-based resin to an esterification reaction with an epoxy resin is preferable.
- a polymer of a polymerizable monomer containing a carboxyl group-containing biel polymer is preferable.
- one monomer selected from the group consisting of ⁇ ,] 3-ethylenically unsaturated carboxylic acid anolequinole ester, hydroxyxanololekyl ester and ⁇ -hydroxyalkyl amide is used. It consists of an ⁇ ,] 3-ethylenically unsaturated monomer having a carboxyl group and a styrenic vinyl monomer, and the mixture thereof is copolymerized in an organic solvent using a usual radical polymerization initiator. Something that can be obtained
- alkyl ester of Q !,] 3-ethylenically unsaturated carboxylic acid used in the present invention include acrylate esters (methyl acrylate, methyl acrylate, isopropyl acrylate). Pills, isobutyl atalinoleate, ⁇ butyl acrylate, ⁇ amyl acrylate, ⁇ hexyl acrylate, isooctyl acrylate, ⁇ octyl acrylate, methoxyl acrylate, methacrylyl acrylate Toxityl, 2-ethylbutyl acrylate, 2-ethylhexyl acrylate, decyl acrylate, etc., methacrylates (methyl methacrylate, methyl methacrylate, methyl methacrylate) Propyl, isobutyl methacrylate, ⁇ -butyl methacrylate, ⁇ -amyl methacrylate, ⁇ -hexyl methacrylate,
- hydroxyalkyl ester of an ethylenically unsaturated carboxylic acid examples include 2-hydroxyxyl acrylate, hydroxypropyl acrylate, 3-hydroxybutyl acrylate, and atalinoleic acid. There are 2,2 bis (hydroxymethyl) ethyl, 2-hydroxymethyl methacrylate, 3-hydroxypropyl methacrylate, hydroxypropyl methacrylate, and 2,3-dihydroxypropyl methacrylate.
- ⁇ —Ethylene unsaturated carboxylic acid ⁇ —hydroxyalkyl amides include, for example, ⁇ —methylol acrylamide, ⁇ —methylol methacrylamide, ⁇ —butoxymethyl acrylamide, ⁇ —butoxymethyl methamide There are ⁇ -substituted acryl-based monomers such as tacrylamide.
- examples of the ⁇ , j8_ethylenically unsaturated monomer having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, maleic anhydride, fumaric acid, and croton. Acids, itaconic acid, citraconic acid, cinnamic acid and the like.
- styrene-based vinyl monomer examples include styrene, butyl toluene, t-butyl styrene, and the like.
- the ⁇ -ethylene unsaturated monomer having a carboxyl group is added in an amount of 10 to 60% by mass based on the total amount of the monomer. %, Particularly preferably 15 to 30% by mass, and a copolymerization temperature of 50 to 150 ° C, particularly preferably 60 to 90 ° C.
- the coating becomes too hard and the adhesive strength is reduced. This is because deterioration due to vibration during use as a transformer or a transformer progresses too much.
- it is in the range of 90 to 120 ° C, more preferably 110 to 120 ° C. Within this range, the internal stress is reduced by dispersing the particulate polymer in the epoxy resin.
- the fine particle polymer used in the present invention those having a particle size in the range of 0.01 m to 0.5 / xm and capable of being stably dispersed in the epoxy resin can be used.
- the type of the fine particle polymer that can be used in the present invention acryl resin, biel acetate, polyester, polyurethane, polyethylene, polypropylene, polycarbonate, and the like are preferable.
- acrylic resins include acrylates (methyl acrylate, ethyl acrylate, isopropyl acrylate, isobutyl acrylate, nbutyl acrylate, N-Amyl acrylate, n-hexyl acrylate, iso-octyl acrylate, n-octyl acrylate, methoxyl acrylate, ethoxyxyl acrylate, 2-ethyl butyl acrylate, 2 butyl acrylate Methyl hexyl, decyl acrylate, etc.), methacrylates (methyl methacrylate, methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, isobutyl methacrylate, methacrylic acid) n-butyl, n-amyl methacrylate, n-methyl methacrylate n-hexyl, laurine methacrylate, stearyl
- vinyl acetate examples include vinyl acetate, vinyl acetate-vapor copolymer, and vinylinoleate-ethylene copolymer.
- polyurethane those having a urethane bond in a monomer and mainly obtained by a chemical reaction between an isocyanate compound and a polyol or a polyether can be used.
- It is a compound of an isocyanate compound such as poly (ethylene glycol), polyols such as poly (ethylene glycol), polypropylene glycol, and polyether triol, and polyether.
- polyester a general ester obtained by reacting a dibasic acid with a dihydric alcohol can be used.
- dibasic acid anhydrous maleic acid, fumaric acid , Adipic acid, phthalic anhydride, isophthalic acid, and dihydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, 1,3 butylene glycol, dipropylene glycol, and neopentinoglycol
- bisphenol, bisphenol dioxetyl ether and the like can be used.
- the fine particle polymer used in the present invention needs to have a particle size in the range of ⁇ . ⁇ m to 0.5 ⁇ m. If the particle size is less than 0.01 / m, the film thickness of the present invention This is because even when the thickness of 0802 is thin, the effect of improving the adhesive strength cannot be obtained, and even when the thickness exceeds 0.5 ⁇ m, the melting of the epoxy resins is hindered and the adhesive strength is reduced.
- the particle size of the dispersed fine particle polymer has a more important function, and the particle size in the extremely narrow range from O. Ol / zm to 0.5 / xm is considered. It has been found that various properties required for an adhesive film can be satisfied by using a fine particle polymer.
- the adhesive coating has a very small thickness of several ⁇ and a thickness of more than ten / xm, so the fine particles must be naturally large in order to be uniformly dispersed in the epoxy resin. If, for example, fine particles having a particle size larger than the film thickness are added, a ⁇ island-in-sea structure '' cannot be formed due to the appearance of only the components of the fine particles during coating and drying. Therefore, it is estimated that the effects of the present invention cannot be obtained. Therefore, the particle size of the fine particle polymer in which the effect is obtained is limited to a very narrow range. According to the results of studies by the present inventors, it is preferably 0.05 / Xm or more, more preferably 0 / Xm or more. 1 ⁇ m or more, particularly preferably in the range of 0.2 ⁇ m to 0.4 m.
- the particulate polymer used in the present invention preferably has a glass transition point in the range of 10 ° C to 80 ° C. If the glass transition point is lower than 10 ° C, the coating tends to be scratched during slitting or punching, and if it exceeds 80 ° C, the coating may be whitened.
- a more preferable glass transition point has a lower limit of 25 ° C or higher, 35 ° C or higher, 45 ° C or higher, and further 55 ° C or higher, and an upper limit of 70 ° C or higher.
- the temperature should be below 65 ° C.
- the method for dispersing the fine particle polymer of the present invention in an epoxy resin is not particularly limited, and each resin may be mechanically mixed, or each may be mixed into an emulsion, or mixed.
- Atari The acryl resin may be used as a fine particle polymer by emulsion polymerization in a solution of a modified epoxy resin.
- the form of the fine particle polymer is desirably spherical, but it may be a modified form such as a hollow form or an oval form, or a so-called hybrid form having a different composition between the inner and outer peripheral sides.
- a clear appearance may not be obtained in some cases. Considering the possibility of applying excessive pressure partially during the processing of slits, etc., the higher the interfacial adhesion between the epoxy resin and the fine particle polymer, the better the workability, and the better the appearance. You don't have to.
- An appropriate amount of the particulate polymer is 1 to 30 parts by weight based on 100 parts by weight of the epoxy resin. If the amount is less than 1 part by weight, the effect of the present invention is not exhibited. If the amount is more than 30 parts by weight, aggregation and precipitation of the fine-particle polymers are liable to occur, which hinders handling.
- the epoxy resin curing agent used in the present invention is capable of curing an epoxy resin, and usually initiates a curing reaction by heating to a predetermined temperature.
- acid anhydride curing agents phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, pyromellitic anhydride, pyromellitic anhydride, etc.
- aliphatic Pyridine diethylene triamine, triethylene tetramin, polyamide, 2ethyl 4-methylimidazole, etc.
- the weight ratio of the epoxy resin curing agent is preferably 1 to 30 parts by weight based on 100 parts by weight of the esterification reaction product with the epoxy resin.
- the epoxy resin curing agent is less than 1 part by weight, the heat resistance of the film after bonding tends to be inferior, and when it exceeds 30 parts by weight, the curing agent tends to concentrate near the film surface and become cloudy after coating and drying. .
- the coating amount is: ⁇ 6 g Z m 2 is good, especially; ⁇ 3 g Z m 2 is preferred. If it is less than 1 g / m 2 , the adhesive strength tends to decrease, and if it exceeds 6 g Z m 2 , the space factor tends to be inferior.
- the setting conditions for baking when forming a coating on the electrical steel sheet are not particularly limited, but the baking temperature set in a drying furnace set at 150 to 800 ° C, which is commonly used, is used to quickly set the sheet temperature. It is good to be 100-300 ° C.
- the mechanism of the present invention is presumed to be due to the reduction in internal stress, the details are not clear, and the technology disclosed in the above-mentioned Japanese Patent Application Laid-Open No. 62-50361 has a glass transition point below room temperature.
- the glass transition point of the particulate polymer is rather good in the range of 10 ° C to 80 ° C, and the reason why the particle size of the particulate polymer greatly affects the adhesive strength is detailed. Is not clear.
- the coefficient of thermal expansion is very small compared to that of an organic resin, and the epoxy resin layer is used on a highly rigid steel plate with a very thin epoxy resin layer. It is presumed that different factors act on the internal stress reduction mechanism of the organic resin.
- Fig. 1 shows a sample (N0.2) in which a coated steel sheet coated with a resin composition according to the present invention was applied and baked under the conditions of 200 ° C X 10 kgfZ cm 2 X 30 minutes, and a sample based on the conventional example.
- Fig. 1A which is a sample based on the conventional example, the broken part has a smooth surface, indicating that crack propagation occurred quickly.
- the shear bond strength and the bond strength of the push test performed in the present invention behave differently.
- the shear strength test no force acts in the direction perpendicular to the bonded surface of the steel sheet
- the push test there is a component acting in the direction perpendicular to the bonded surface, which naturally changes the peeling behavior of the adhesive film.
- the push-in test is the strength required for the actual laminated iron core.
- a peel strength measurement method is generally used as a method for measuring the strength in the cracking direction.
- the peel strength was measured using an electrical steel sheet, the samples were broken and it was difficult to peel the adhered samples smoothly. Very large and difficult to measure.
- the present inventors have found that, as a method of measuring the adhesive strength in the pressing direction, the pressing strength in the pressing direction can be measured by pressing a wedge into the iron core sample laminated and bonded.
- a peel test method (ASTM D1876) is used as a method of measuring the adhesive strength.
- Fig. 2 shows the conventional peel test method and the split test method measured in the present invention.
- an epoxy resin emulsion shown in Table 1 and an epoxy resin curing agent, and a fine particle polymer shown in Table 2 were sequentially mixed to prepare a treatment liquid shown in Table 3.
- baking treatment was performed at a plate temperature of 160 ° C. so that the coating amount of the coating became the amount shown in the table.
- BPA bisphenol A type epoxy
- NR novolak type epoxy
- PR phenol resole type hardener
- AR amino resin hardener
- EA ethyl acrylate
- MMA methyl methacrylate
- St styrene
- BA Butyl acrylate
- PVA Bull acetate
- PA Polyethylene
- PU Polyurethane
- HPMA Hydroxypropyl methacrylate
- MA Acrylic acid
- EHMA 2-Ethyl methacrylate Kisil
- Processing solution 1 Epoxy 2 fine particles 1 10 parts by weight of the present invention Processing solution 2 Epoxy 2 fine particles 15 parts by weight of the present invention Processing solution 3 Epoxy 2 fine particles 2 20 parts by weight of the present invention Processing solution 4 Epoxy 1 fine particles 18 parts by weight of the present invention 5 Epoxy 1 fine particles 2 10 parts by weight Treatment liquid 6 Epoxy 1 Fine particles 3 10 parts by weight Treatment liquid 7 Epoxy 2 Fine particles 3 5 parts by weight Treatment liquid 8 Epoxy 4 Fine particles 4 5 parts by weight Treatment liquid 9 Epoxy 4 Fine particles 1 7 parts by weight Treatment liquid of the present invention 10 Epoxy 3 Fine particles 3 5 parts by weight Treatment liquid of the present invention 11 Epoxy 2 Fine particles 6 30 parts by weight Fine particle small particle size treatment liquid 12 Epoxy 1 Fine particles 3 0.5 parts by weight Fine particle addition amount Processing solution 13 Epoxy 1 Fine particle 1 50 parts by weight Fine particle added Processing solution 14 Epoxy 3 Fine particle 7 15 parts by weight Fine particle large particle size Processing liquid 15 Epoxy 2 Fine particle 8 8 parts by weight Fine Tg point off Processing liquid 16 Epoxy 3 Fine particle 9 20 parts by weight Fine particles Out
- Example 1 Treatment solution 1 2.0 160 75 866 ⁇ Example 2 Treatment solution 2 2.2 155 50 671 ⁇ Example 3 Treatment solution 3 2.8 154 82 755 ⁇ Example 4 Treatment solution 4 1.9 142 55 748 ⁇ Example 5 Treatment solution 5 2.3 134 80 841 ⁇ Example & Treatment 6 2.1 147 49 D33 ⁇ Example 7 Treatment 7 2.7 144 57 533 ⁇ Example 8 Treatment 8 2.4 152 63 583 ⁇ Example 9 Treatment 9 1.6 154 69 775 ⁇ Execution Example 10 Treatment liquid 10 1.5 108 52 480 ⁇ Comparative example 1 Treatment liquid 11 2.1 136 49 124 ⁇ Comparative example 2 Treatment liquid 12 2.9 141 41 231 ⁇ Comparative example 3 Treatment liquid 13 3.4 131 38 614 X Comparative example 4 Treatment liquid 14 1.9 87 23 364 ⁇ Comparative example 5 Treatment liquid 15 3.1 143 10 450 ⁇ Comparative example 6 Treatment liquid 16 1.9 128 52 264 ⁇ Comparative example 7 Treatment liquid 17 3.1 163 16 735 X Compar
- Example 1 Treatment liquid 1 1.4 113 36 461 ⁇ Example 2 Treatment liquid 2 1.3 102 44 270 ⁇ Example 3 Treatment liquid 3 1.5 104 31 344 ⁇ Example 4 Treatment liquid 4 1.6 127 33 416 ⁇ Example 5 Treatment liquid 5 1.4 98 41 462 ⁇ Example 6 Treatment solution 6 1.3 119 40 311 ⁇ Example 7 Treatment solution 7 1.3 112 38 217 ⁇ Example 8 Treatment solution 8 1.6 102 31 238 ⁇ Example 9 Treatment solution 9 1.1 137 43 357 ⁇ Execution Example 10 Treatment liquid 10 1.3 121 38 360 ⁇ Comparative example 1 Treatment liquid 11 1.7 81 43 98 ⁇ Comparative example 2 Treatment liquid 12 1.6 73 38 125 ⁇ Comparative example 3 Treatment liquid 13 1.5 67 29 166 ⁇ Comparative example 4 Treatment liquid 14 1.4 88 31 155 ⁇ Comparative example 5 Treatment liquid 15 1.2 104 13 162 ⁇ Comparative example 6 Treatment liquid 16 1.1 101 34 132 ⁇ Comparative example 7 Treatment liquid 17 1.3 105 10 241 ⁇ Comparative example
- a modified epoxy resin or epoxy resin having a glass transition point (Tg) of 80 ° C. to 150 ° C., an epoxy resin curing agent, and a particulate polymer having a particle size of 0.01 to 0.5 m are provided.
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- Health & Medical Sciences (AREA)
- Polymers & Plastics (AREA)
- General Chemical & Material Sciences (AREA)
- Metallurgy (AREA)
- Laminated Bodies (AREA)
- Adhesives Or Adhesive Processes (AREA)
- Application Of Or Painting With Fluid Materials (AREA)
- Soft Magnetic Materials (AREA)
- Adhesive Tapes (AREA)
Abstract
Description
Claims
Priority Applications (1)
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JP2005504797A JP4143090B2 (ja) | 2003-02-03 | 2004-01-29 | 接着用表面被覆電磁鋼板 |
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JP2003-025742 | 2003-02-03 | ||
JP2003025742 | 2003-02-03 |
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WO2004070080A1 true WO2004070080A1 (ja) | 2004-08-19 |
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PCT/JP2004/000802 WO2004070080A1 (ja) | 2003-02-03 | 2004-01-29 | 接着用表面被覆電磁鋼板 |
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JP (1) | JP4143090B2 (ja) |
KR (1) | KR100698431B1 (ja) |
CN (1) | CN100476030C (ja) |
MY (1) | MY153191A (ja) |
TW (1) | TWI231775B (ja) |
WO (1) | WO2004070080A1 (ja) |
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CN112368144A (zh) * | 2018-05-18 | 2021-02-12 | 奥钢联钢铁公司 | 电工钢带材或电工钢板材、用于生产这种电工钢带材或电工钢板材的方法以及由其制成的叠片组 |
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RU2814180C1 (ru) * | 2020-06-17 | 2024-02-26 | Ниппон Стил Корпорейшн | Покрывающая композиция для листа электротехнической стали, лист электротехнической стали с покрытой адгезивом поверхностью и шихтованный сердечник |
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WO2007116670A1 (ja) * | 2006-03-27 | 2007-10-18 | Kabushiki Kaisha Kobe Seiko Sho | プレコート金属板 |
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JP5675418B2 (ja) * | 2011-02-17 | 2015-02-25 | Jfeスチール株式会社 | 絶縁被膜付き電磁鋼板およびその製造方法ならびに積層鉄心 |
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JP7311791B2 (ja) | 2018-12-17 | 2023-07-20 | 日本製鉄株式会社 | 積層コアおよび回転電機 |
US20220025228A1 (en) * | 2018-12-17 | 2022-01-27 | Nippon Steel Corporation | Laminated core, laminated core manufacturing method, and electric motor |
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- 2004-01-29 KR KR1020057014201A patent/KR100698431B1/ko active IP Right Grant
- 2004-01-29 WO PCT/JP2004/000802 patent/WO2004070080A1/ja active Application Filing
- 2004-01-29 CN CNB2004800034464A patent/CN100476030C/zh not_active Expired - Lifetime
- 2004-01-29 JP JP2005504797A patent/JP4143090B2/ja not_active Expired - Fee Related
- 2004-01-31 MY MYPI20040301A patent/MY153191A/en unknown
- 2004-02-02 TW TW093102303A patent/TWI231775B/zh not_active IP Right Cessation
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Cited By (21)
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JP6037055B2 (ja) * | 2014-07-29 | 2016-11-30 | Jfeスチール株式会社 | 積層用電磁鋼板、積層型電磁鋼板、積層型電磁鋼板の製造方法、および自動車モーター用鉄心 |
CN112368144A (zh) * | 2018-05-18 | 2021-02-12 | 奥钢联钢铁公司 | 电工钢带材或电工钢板材、用于生产这种电工钢带材或电工钢板材的方法以及由其制成的叠片组 |
CN112368144B (zh) * | 2018-05-18 | 2023-11-14 | 奥钢联钢铁公司 | 电工钢带材或电工钢板材、用于生产电工钢带材或电工钢板材的方法以及由其制成的叠片组 |
KR20220140636A (ko) * | 2020-06-17 | 2022-10-18 | 닛폰세이테츠 가부시키가이샤 | 전자 강판, 적층 코어 및 회전 전기 기기 |
KR20230008811A (ko) | 2020-06-17 | 2023-01-16 | 닛폰세이테츠 가부시키가이샤 | 전자 강판용 코팅 조성물, 전자 강판, 적층 코어 및 회전 전기 기기 |
WO2021256538A1 (ja) | 2020-06-17 | 2021-12-23 | 日本製鉄株式会社 | 電磁鋼板用コーティング組成物、電磁鋼板、積層コア及び回転電機 |
JPWO2021256532A1 (ja) * | 2020-06-17 | 2021-12-23 | ||
WO2021256532A1 (ja) * | 2020-06-17 | 2021-12-23 | 日本製鉄株式会社 | 電磁鋼板、積層コア及び回転電機 |
WO2021256533A1 (ja) | 2020-06-17 | 2021-12-23 | 日本製鉄株式会社 | 電磁鋼板用コーティング組成物、電磁鋼板、積層コア及び回転電機 |
JP7095819B2 (ja) | 2020-06-17 | 2022-07-05 | 日本製鉄株式会社 | 電磁鋼板、積層コア及び回転電機 |
WO2021256529A1 (ja) | 2020-06-17 | 2021-12-23 | 日本製鉄株式会社 | 電磁鋼板用コーティング組成物、接着用表面被覆電磁鋼板及び積層鉄心 |
KR20230008192A (ko) | 2020-06-17 | 2023-01-13 | 닛폰세이테츠 가부시키가이샤 | 전자 강판용 코팅 조성물, 전자 강판, 적층 코어 및 회전 전기 기기 |
WO2021256536A1 (ja) | 2020-06-17 | 2021-12-23 | 日本製鉄株式会社 | 電磁鋼板用コーティング組成物、電磁鋼板、積層コア及び回転電機 |
KR20230008865A (ko) | 2020-06-17 | 2023-01-16 | 닛폰세이테츠 가부시키가이샤 | 전자 강판용 코팅 조성물, 전자 강판, 적층 코어 및 회전 전기 기기 |
KR20230008879A (ko) | 2020-06-17 | 2023-01-16 | 닛폰세이테츠 가부시키가이샤 | 전자 강판용 코팅 조성물, 전자 강판, 적층 코어 및 회전 전기 기기 |
KR20230010702A (ko) | 2020-06-17 | 2023-01-19 | 닛폰세이테츠 가부시키가이샤 | 전자 강판용 코팅 조성물, 접착용 표면 피복 전자 강판 및 적층 철심 |
KR102493101B1 (ko) | 2020-06-17 | 2023-01-31 | 닛폰세이테츠 가부시키가이샤 | 전자 강판, 적층 코어 및 회전 전기 기기 |
JP7343823B2 (ja) | 2020-06-17 | 2023-09-13 | 日本製鉄株式会社 | 電磁鋼板用コーティング組成物、電磁鋼板、積層コア及び回転電機 |
WO2021256531A1 (ja) | 2020-06-17 | 2021-12-23 | 日本製鉄株式会社 | 電磁鋼板用コーティング組成物、電磁鋼板、積層コア及び回転電機 |
EP4170690A4 (en) * | 2020-06-17 | 2023-11-29 | Nippon Steel Corporation | ELECTROMAGNETIC STEEL SHEET, LAMINATED CORE AND ROTARY ELECTRIC MACHINE |
RU2814180C1 (ru) * | 2020-06-17 | 2024-02-26 | Ниппон Стил Корпорейшн | Покрывающая композиция для листа электротехнической стали, лист электротехнической стали с покрытой адгезивом поверхностью и шихтованный сердечник |
Also Published As
Publication number | Publication date |
---|---|
KR20050097967A (ko) | 2005-10-10 |
KR100698431B1 (ko) | 2007-03-22 |
TWI231775B (en) | 2005-05-01 |
CN1748045A (zh) | 2006-03-15 |
MY153191A (en) | 2015-01-29 |
JPWO2004070080A1 (ja) | 2006-05-25 |
TW200418581A (en) | 2004-10-01 |
JP4143090B2 (ja) | 2008-09-03 |
CN100476030C (zh) | 2009-04-08 |
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