Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J1/00—Adhesives based on inorganic constituents
  • C09J1/02—Adhesives based on inorganic constituents containing water-soluble alkali silicates
• • 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
  • C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J1/00—Adhesives based on inorganic constituents
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
  • C09J11/02—Non-macromolecular additives
  • C09J11/04—Non-macromolecular additives inorganic
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
  • C09J5/00—Adhesive processes in general; Adhesive processes not provided for elsewhere, e.g. relating to primers
• • 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
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
  • H01F3/00—Cores, Yokes, or armatures
  • H01F3/02—Cores, Yokes, or armatures made from sheets

Definitions

• the heat treatment is performed at room temperature or more and 300 or less, and thereafter annealing treatment such as strain relief annealing (this In the invention, unless otherwise specified, it means a heat treatment exceeding 300.)
• the present invention relates to a heat-resistant adhesive coating composition that can be produced and a surface-coated electrical steel sheet.
• Electrical steel sheets are mainly used as iron cores for motors and transformers.
• the surface of an electrical steel sheet is formed with an insulating coating, and after being continuously punched into a predetermined shape, it is laminated and integrated by a method such as welding or fitting of uneven parts called caulking. It is common to form an iron core.
• the integrated iron core can be used as it is incorporated in electrical equipment, or it can be used in electrical equipment after annealing at temperatures around 700 ⁇ to 800.
• the latter annealing is called strain relief annealing, and it removes or reduces the shear strain introduced into the steel sheet during punching / shearing, thermal strain generated by welding of the end face, and plastic deformation strain of the caulking portion.
• strain relief annealing removes or reduces the shear strain introduced into the steel sheet during punching / shearing, thermal strain generated by welding of the end face, and plastic deformation strain of the caulking portion.
• it is applied to iron cores used in electrical equipment applications that require high electrical efficiency.
• the edge of the iron core is short-circuited and insulation is lowered, and that magnetic properties are deteriorated due to processing strain.
• a method for producing a surface-coated electrical steel sheet for bonding characterized in that a liquid mixture mainly composed of acryl-modified epoxy resin emulsion containing a latent curing agent is applied and incompletely baked (patent no. No. 2613725) and electrical steel sheets with insulating coatings coated with an adhesive resin containing a foaming agent (Japanese Patent Laid-Open No. 2002-260910), and also Japanese Patent Publication No. 55-9815 and Japanese Patent Laid-Open No. 2-208034 The technology of the gazette is proposed.
• JP-B-42-24519, JP-A-58-128715, JP-B-47-47499 disclose so-called inorganic coatings that do not contain a resin component. . Since Japanese Patent Publication No. 42-24519 does not have a bonding function between steel plates, an integrated iron core cannot be obtained unless a fixing method other than bonding such as caulking or welding is performed. JP Japanese Laid-Open Patent Publication Nos. 58-128715 and 47-47499 have the problems that the film is hard because it is an inorganic film composed only of a low-melting-point glass component, and the punching die is adversely affected, and there is a lot of dust generation. It was. Disclosure of the invention
• the present invention improves the heat resistance of the adhesive insulating coating of the electrical steel sheet with the adhesive insulating coating, and the heat resistant adhesive insulating coating that can maintain the adhesive state and the insulating property even when strain relief is performed, and the same
• the present invention provides an electromagnetic steel sheet with a heat-resistant adhesive coating, an iron core using the electromagnetic steel sheet, and a method for manufacturing the same.
• the present invention uses the following means.
• a heat-resistant adhesive insulating coating comprising a resin having a softening point temperature of room temperature to 300 ° C and a low melting point inorganic component having a softening point temperature of 1000 or less.
• the heat-resistant adhesive insulating film according to (4) wherein the mixing ratio of the resin to the low-melting-point inorganic component is 20% or more and 500% or less by mass fraction.
• the heat-resistant adhesive insulation according to (4) characterized in that the low-melting point inorganic component is S i 0 2 -B 2 0 3 -R 2 0 series low-melting point glass (R is Al force re-metal) Coating.
• a magnetic steel sheet with a heat-resistant adhesive insulating coating having the coating according to (1) on at least one side of the steel plate.
• the composition of the insulating coating of the electrical steel sheet is combined to exert two types of adhesive performance.
• the measurement was performed by a resin that softens at room temperature to 300 and below and differential thermal analysis. It is a film containing a low melting point inorganic component having a softening point temperature of 1000 or less.
• the coating resin is softened during heat pressing and the iron core is bonded and integrated.
• the low melting point inorganic component fulfills the function of maintaining the core in a unified state when the core is strain-relieved.
• Figure 1 shows a typical differential thermal analysis curve for glass.
• Figure 2 shows a ladder-like siloxane polymer.
• an annealing temperature of about 700: to 800 ° C is usually required. At these annealing temperatures, organic matter decomposes and the structure cannot be maintained, so the adhesion cannot be maintained.
• a group of low-melting-point inorganic components called so-called low-melting-point glass frits and low-melting-point inorganic components such as water glass and colloidal sill force show good adhesion between steel plates in the vicinity of annealing temperature condition 750. I found.
• the low melting point inorganic component is the softening point temperature of the low-melting-point inorganic component that dominates the adhesiveness in the strain relief annealing temperature range.
• the mixing ratio of the resin to the glass frits was 100% in terms of solid content, that is, the same mass.
• the coating amount was 8 g / m 2 per side, and the film was dried at a plate temperature of 160. A test piece was cut out from the sample thus prepared. Next, 250 adhesive strength and 750 adhesive strength were measured.
• the softening point temperature is the fourth inflection point temperature observed after the start of measurement in the differential thermal analysis measurement curve shown in Fig. 1, or JI S-R3 103-1 “Glass The softening point test method ”(I SO 7884-6: 1987, ASTM C33 8), whichever is the lower temperature. If any of these methods are difficult to measure, replace with another softening point temperature. Also good.
• the 250 ° C adhesive strength refers to the addition of two specimens with a length of 10 cm in the rolling direction and a length of 3 cm perpendicular to the rolling direction, with the short side overlapped by l cm and the area of 3 cm 2. It is the value obtained by dividing the strength when it was pulled and peeled at room temperature after bonding, under the conditions of pressure 10kg / 3cm 2 , heating temperature 250 ⁇ , heating time 60 seconds, by area 3cm 2 .
• the applied pressure and the adhesive strength are values obtained by dividing the indicated value (kg) of the spring rod by the area and are expressed as kg / cm 2 , which corresponds to 9.8 ⁇ 10 4 Pa.
• the adhesive strength at 750 is the sample bonded under the above-mentioned low temperature bonding conditions, and further heated under the conditions of a heating temperature of 750 and a heating time of 2 hours without applying pressure, and then pulled in the rolling direction at room temperature.
• a heating temperature of 750 and a heating time of 2 hours without applying pressure, and then pulled in the rolling direction at room temperature.
• the inventors consider the following mechanism for the reason why the adhesive strength at 750 depends on the softening point temperature of the low melting point inorganic component. 250: During pressure and heat bonding near the resin, the resin softens and melts, and in the case of double-sided coating, the film interface disappears and adhesion between the films is achieved. However, at this stage, the low-melting-point inorganic component having high temperature stability hardly causes the reaction. Next, when heated at 750, the low melting point inorganic component softens and then melts depending on the low melting point inorganic component species, and the low melting point inorganic components coming into contact with each other are bonded together. As a result, the opposing coatings are integrated, and the adhesion between the steel plates is completed. Therefore, it is important that the low-melting-point inorganic component softens or melts in the heating stage near 750 ° C.
• the low melting point inorganic component with a high softening point temperature does not progress in the temperature range of 750, even if the low melting point inorganic components are in contact with each other. A sufficient contact area cannot be obtained between inorganic components. Therefore, the bond between the low melting point inorganic components is not sufficiently formed. As a result, the adhesive strength cannot be obtained.
• Condition No. 1 to Condition No. 8 in Table 1 in the low melting point inorganic component having a low softening point temperature, if the low melting point inorganic components are in contact with each other, Since softening proceeds in the temperature range of 750, a constant contact area can be obtained between the low melting point inorganic components. Therefore, a bond between the low melting point inorganic components is formed. As a result, adhesive strength can be obtained.
• the adhesive strength of 10 kg / cm 2 or higher at 250 is defined as the adhesive strength that can be handled without peeling in the manufacturing process after temporary fixing by low-temperature bonding and until final fixing.
• the adhesive strength of 1 kg / cm 2 or higher at 750 stipulates the adhesive strength that does not peel after being installed in electrical equipment.
• a low melting point inorganic component of the present invention a low melting point glass frit, water glass or a mixture of these colloidal silicas can be used.
• the low-melting-point inorganic component to be used is an inorganic powder
• its particle size is also important. If the particle size is too large, coarse protrusions will be formed on the surface of the film, preventing contact between the films.
• the average particle size of the low-melting-point inorganic component to be used is 20 mm or less. In particular, it is desirable that the average particle size is 4 w m or less, and further 3 m or less.
• the present inventors examined the mixing ratio of the low melting point inorganic component and the resin.
• Condition No. 2 to Condition No. 6 that is, when the resin / glass frit mixing ratio is 20% or more and 500% or less, the adhesive strength is 250 and the adhesive strength is 10 kg / cm 2 or more, and the adhesive is 750. It can be seen that the strength is lkg / cni 2 and both values are good. On the other hand, when the resin / glass frit mixing ratio of Condition No. 1 is 10%, the adhesive strength is 250 kg and the adhesive strength is kg / cm 2 750, and the adhesive strength is 0.5 kg / cm 2 . Also, under condition No.
• the present inventors consider the following mechanism for the reason why the adhesive strength depends on the resin ratio to the low-melting-point inorganic component. Resins share the adhesive function when heated at 250 ° C, and the low melting point inorganic component is 750 ", and share the adhesive function when heated. Therefore, at each heating temperature, both are able to exert their functions. It is possible to infer the mechanism of the resin / low-melting-point inorganic component ratio dependence on the adhesive strength by examining whether there is an organic resin that performs an adhesive function when heated at 250, or at 750. The strength is 750, and the surface occupancy of each low melting point inorganic component that performs the adhesive function when heated can be considered.
• the inventors prepared a coated steel sheet and an iron core made of the steel sheet under the following conditions, and investigated the magnetic properties.
• a number of non-oriented electrical steel sheets having a plate thickness of 0.5 ⁇ and having no insulating coating on the surface were prepared.
• the coating amount was adjusted to 1 Og / ra 2 per side and dried at a plate temperature of 150.
• the inner diameter 10. 16cm (4 Lee inches), to produce a-ring-shaped sample having an outer diameter of 1 2. 7 cm (5 I inch), pressure 10 kg / cm 2 in a stacked state 20 sheets, the temperature Heated at 250 for 4 hours to produce a film-bonded iron core. Next, the iron core was annealed at 750 ° C. for 2 hours without pressing. Finally, the iron loss value was measured at a frequency of 50 ⁇ and a magnetic flux density of 1.5 Tesla. The results are shown in Table 3. Table 3
• the present inventors consider the following mechanism. Pressurization / heating adhesion at 250 ° C softens and melts the resin in the coating, and in the case of double-sided coating, the coating interface disappears and adhesion between coatings is realized. However, at this stage, the low-melting-point inorganic component with high temperature stability hardly reacts. Next, when heated at 750 ° C., the low-melting-point inorganic component softens this time, and depending on the low-melting-point inorganic component species, it melts and the low-melting-point inorganic components coming into contact with each other are bonded together.
• the opposing coatings are integrated, and the adhesion between the steel plates is completed. And after cooling to room temperature, the iron loss value is measured. What should be considered here is the problem of stress generated in the formed iron core when the steel sheet surface is fully bonded in the high temperature state of 750 and cooled to room temperature.
• the magnetic properties deteriorate when stress acts on the iron core.
• the relationship between the thermal expansion coefficient and stress of the substance will be described.
• a substance with a large coefficient of thermal expansion and a substance with a small coefficient of thermal expansion are bonded at a high temperature and cooled to room temperature
• a substance with a large coefficient of thermal expansion has a tensile stress.
• compressive stress acts on materials with small thermal expansion coefficients.
• Linear thermal expansion coefficient of the electromagnetic steel sheet is also non-oriented electrical steel sheet oriented electrical steel sheet is a contact about 100x 10- 7 (tr 1).
• the low-melting-point inorganic component of the present invention contributes to the development of adhesiveness after strain relief annealing, and is preferably a low melting point glass having a softening point of 750 or less, which is a normal strain relief annealing temperature.
• the low-melting glass can be softened and melted during strain relief annealing and solidified by cooling, and the two plates can be bonded after strain relief annealing.
• the composition of low melting glass is Si0 2 -B 2 0 3 -R 2 0 (R is alkali metal), P 2 0 5 -R 2 0 (R is alkali metal), Si0 2 -Pb0- B 2 0 3 series, B 2 0 3 -B i 2 0 3 series, S i 0 2 -B 2 0 3 -ZnO series, SnO- P 2 0 5 series, S i 0 2 -B 2 0 3 -Z r 0 2 And the like.
• the Si 0 2 -B 2 0 3 -R 2 0 (R is alkali metal) system is preferable because it is lead-free and has high adhesion after strain relief annealing.
• the low melting point inorganic component may be added as a liquid like water glass.
• the water glass is particularly preferably soda silicate.
• the advantage of using water glass is that it does not contain powder particles, so there is no unevenness due to particles on the coated surface, and it is easy to obtain a smooth surface.
• silicate soda Adhesive strength after strain relief annealing 1. High strength over OMPa
• the low-melting-point inorganic component of the present invention it is possible to use a material obtained by further mixing the above-mentioned inorganic component with colloidal silica.
• colloidal U force, etc. By mixing colloidal U force, etc., the viscosity when machine components are softened during strain relief annealing can be adjusted. ⁇ Silicier force also remains in the membrane even if it remains unsoftened during strain relief annealing. It functions as an aggregate and can increase the bond strength after strain relief annealing.
• thermosetting resin that causes a curing reaction when the steel sheets are bonded together by pressing and heating, such as phenol resin or epoxy resin, can be applied.
• the resin of the present invention softens at room temperature or more and 300 or less, but considering blocking properties, it is preferably 50 or more, 80 or more, 100 or more, especially 120 to 300 ° C or less. It is preferable to soften to such an extent that fluidity is exhibited. The softening to such an extent that fluidity is exhibited is that the viscosity is 1 xl 0 8 dPa s or less. Baking on steel plate surface As a mechanism of softening by the following heating with a resin strength of 300 cured by heating, there is a case where the cured resin is a thermoplastic resin and the temperature force at which the thermoplastic develops is 300 or more and the following. .
• the resin As a softening mechanism when the resin is thermosetting, there is a case where it is softened to a rubber state or a fluid state by heating to a temperature higher than the glass transition temperature.
• the resin undergoes a glass transition while softening once through a cross-linking reaction that forms a three-dimensional skeleton by heating.
• the cross-linking reaction may proceed again to be cured.
• the acrylic modified epoxy resin emulsion previously incorporated with a latent curing agent used as the resin of the present invention is an epoxy resin obtained by compounding a latent curing agent with an epoxy resin and then chemically reacting the acrylic resin. And a mixture of latent hardeners and emulsions.
• the epoxy resin here refers to a resin having two or more epoxy groups in the monomer, and includes bisphenol A type, bisphenol F type, bisphenol AD type, naphthenic type, phenol novolac type, There are orthocresol novolac type, glycidyl ester type, alicyclic type, etc.
• latent curing agents dicyandiamide, melamine, organic acid dihydrazide, amine amide, keramin, tertiary amine salt, imidazole salt, boron trifluoride amine salt, microcapsule type curing agent And molecular sieve type curing agents.
• the acrylic resin is transformed into a mixed system of the above epoxy resin and epoxy resin curing agent.
• modification means that the acrylic resin is chemically bonded to the surface of the epoxy resin and epoxy resin curing agent mixture.
• acrylic resins used for such modification include maleic acid, methacrylic acid esters, acrylic acid, acrylate esters, styrene, and acetic acid. It is a polymerized or copolymerized one or more of vinyl.
• the mixing ratio of epoxy resin and latent epoxy resin curing agent varies greatly depending on the type of epoxy resin and the type of curing agent, but usually 0.05 to 2 parts by mass is appropriate for 1 part by mass of epoxy resin. It is.
• a liquid mixture mainly composed of acrylic-modified epoxy resin emulsion pre-blended with a latent curing agent is baked in an incomplete state after being applied to the surface of the steel sheet. There is no sticking or blocking, and it is in a state where it is bonded by pressing and heating after shearing and laminating. Usually, it can be baked in an incomplete state by drying at a furnace temperature of 100 to 300 for 10 to 90 seconds.
• siloxane polymer can be used as a resin that is softened by heating.
• Siloxane polymers are polymers whose main skeleton is composed of inorganic Si-0-Si bonds. Si, like C, like Si-CH 3 , Si-C 6 H 5 , Si-H, Si can be directly chemically bonded to organic groups and H, so organic groups and H A siloxane polymer having a modified skeleton can be obtained.
• Si nuclides can be examined by ⁇ R.
• Si nuclei that form siloxane polymers include D nuclei and Q nuclei in addition to T nuclei.
• the D nucleus is one in which four of Si's four bonds form Si-R (R is an organic group or H) bond, and the remaining two are Si-0 bonds.
• Q nucleus is a Si-0 bond in four of Si's four bonds.
• a ladder molecule as shown in Fig. 2 is formed.
• a polymer composed of ladder-like molecules causes entanglement of ladder-like molecule chains by coating and baking, and a hardened surface state with no stickiness or blocking is obtained.
• Molecular chains that have been entangled at 100 ° C or higher will break and become fluid.
• Si nuclei to which epoxy groups are bonded may be included in addition to Si nuclei to which methyl groups are bonded.
• the siloxane polymer of the present invention is obtained by hydrolysis in the presence of one or both of organotrialkoxysilane and organotrichlorosilane in the presence of a hydrochloric acid catalyst.
• Organotrioxyxyfun can be selected from the group consisting of ⁇ ⁇ ⁇ xylan, ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇
• organotrialkoxysilane or organotrimethyl ⁇ D silane may be hydrolyzed after being dispersed in an organic solvent.
• Solvents include methanol, ethanol, ethanol, and bueno.
• the mass ratio of the organic solvent to the organoalkoxysilano at the time of hydrolysis is preferably 1: 0.5 to 1: 2.
• Hydrolysis is performed by adding 0.1 to 1 times as much water as the number of moles of all alkoxy groups in the starting material. Add hydrochloric acid as catalyst for hydrolysis
• organotrichlorosilane is used as a raw material
• hydrochloric acid is produced as a by-product when water is added, and hydrolysis is carried out under a hydrochloric acid catalyst without any special treatment. Sometimes it is not necessary.
• the hydrolyzed sol is usually converted into a siloxane polymer by promoting the polycondensation reaction by a process such as concentration. Concentration is performed by removing the organic solvent and by-product alcohol, etc. using a rotary evaporator, etc., and the mass of the concentrate is about 15 to 60 of the solution mass before concentration. It is preferable from the viewpoint of expression.
• an alkoxide such as K0H can be added and refluxed in a nitrogen atmosphere or the like to accelerate the polycondensation reaction and obtain a siloxane polymer.
• the obtained siloxane polymer is diluted 1.5 to 10 times with an organic solvent or water to make a coating solution. Usually, by baking at 100 to 200 for 15 to 120 seconds, a state of adhesion by pressure heating can be obtained.
• the resin and low-melting-point inorganic component in the present invention do not show at least apparent melting in the film of the present invention depending on conditions such as heating and annealing atmosphere, and the grains remain as they are. However, there is no problem in the present invention as long as the bonding function is exhibited by the heating and annealing.
• the present invention can be applied to any type of magnetic steel sheet produced by ordinary rolling and annealing, such as a directional magnetic steel sheet and a non-oriented electrical steel sheet, but is particularly applicable to a non-oriented electrical steel sheet for motor cores. If this is the case, the effect can be demonstrated most.
• a surface coating is formed on the steel sheet surface by finish annealing for both steel sheets.
• a phosphate-based film containing a silica component is formed in the case of grain-oriented electrical steel.
• a chromate-based film is formed in the case of non-oriented electrical steel.
• a manufacturing method that forms a film mainly composed of forsterite silicate during finish annealing, a manufacturing method that does not intentionally form the film, and a forsterite film that has been formed are pickled. There is a manufacturing method that removes by means.
• the present invention can be applied with or without these various surface coatings.
• the magnetic steel sheet with a heat-resistant adhesive insulating coating of the present invention is prepared by applying a coating solution containing a heat-resistant adhesive insulating film composition by a method such as rollco, overnight, burco, dipco, or spray. Apply to steel plate.
• the coating amount is preferably lg / m 2 or more and 30 g / m 2 or less, particularly preferably 2 g / m 2 or more and 10 g / m 2 or less.
• the heat-resistant adhesive insulating coating composition is preferably a mixture of a resin and a low-melting-point inorganic component, but it may be a mixture in which both are dispersed in a lump or two layers are separately applied. good.
• Low-melting-point inorganic components may be dispersed in the form of dots or stripes in the matrix due to organic components, or the organic components may be dotted in the inorganic matrix due to siloxane bonds, etc. It may be dispersed in stripes.
• the film thickness is desirably 0.5 m or more and 20 m or less per side. If the film thickness is less than 0.5, it is difficult to sufficiently cover the entire surface of the steel sheet, so that sufficient adhesive strength cannot be obtained. On the other hand, if it exceeds 20 ⁇ m, the space factor greatly decreases when pressed and heated. End up. Therefore, the film thickness should be 0.5 m or more and 20 m or less.
• the coating composition of the present invention is first baked and cured after application to the surface of the magnetic steel sheet so as not to cause stickiness or blocking.
• the steel sheet with a heat-resistant adhesive insulating coating can be produced by baking at 50 to 200. This process involves punching the iron core May be immediately before the lamination of the iron cores, but it is particularly preferable to apply a so-called pre-coated electromagnetic steel sheet at the time of producing the steel sheets in terms of simplifying the iron core production process.
• the resin is softened by heating to a temperature higher than the baking temperature.
• the resin component softened by heating spreads uniformly on the surface of the electromagnetic steel sheet pieces without the coating layer of the present invention. Can be glued during cooling. Since high temperature hot pressing results in high costs, the hot pressing temperature is preferably 300 ° C or lower.
• the pressure of the hot press is preferably 0. IMPa or more and 50MPa or less, and particularly preferably IMPa or more and 20MPa or less. If the pressure of the hot press is low, sufficient adhesion cannot be obtained, making it difficult to integrate as an iron core. When the pressure of hot press is high, the adhesive layer may flow and protrude from the interlayer.
• the electromagnetic steel sheet of the present invention can be integrated as an iron core by punching into a desired shape, laminating, pressurizing and heating. After that, even if stress relief annealing is performed as necessary, the adhesion between the laminated steel sheets is maintained.
• the temperature of strain relief annealing is usually 650 or more and 850 ° C or less, and is often 700 or more and 800 or less.
• the coating film of the present invention has an adhesive ability without performing annealing such as strain relief annealing, it can be used for an iron core that does not perform strain relief annealing. In other words, it can be used as an adhesive film for both strain relief annealing and non-strain relief annealing. Further, in the case of strain relief annealing, it is possible to use caulking or fixing with a jig together when fixing by pressurization or heating. This
• a solution containing the tutu was prepared.
• the resin / glass frits mixing ratio in the liquid containing glass frits was set to 200%.
• This coating solution has a thickness of 0.5mm and has a coating amount of 6g / m per side using a mouthpiece for a non-oriented electrical steel sheet that has been annealed without an insulating coating on the steel sheet surface. Painted to be 2 . Then, it was dried at a drying temperature of 150 and cooled.
• the film thickness per side was 10 m.
• a specimen having a length of 3 cm in the direction perpendicular to the rolling direction was cut out from the sample thus prepared. Then, two test pieces with a length of 1 cm at the short side and an overlap area of 3 cm 2 were heated to 250 with pressure of 10 kg / cm 2 , held for 60 seconds, cooled, and bonded at 250 A test piece for strength measurement was prepared. Further, a part of the test piece for measuring 250 ° C adhesion strength was heated to 750 under no load, held for 2 hours, cooled, and a test piece for measuring 750 adhesive strength was prepared. The test piece thus prepared was measured for adhesive strength using a tensile tester. The results are shown in Table 4.
• the bond strength is 250 and the bond strength is 10 kg / cm 2 or more, and 750 bond strength is also lkg. / cDi 2 or better, but with a glass frit of Condition No. 6 with an average particle size of 25 ⁇ m, the adhesive strength was measured at 750 ° C with a 250 bond strength of 5 kg / cm 2 The value was so small that it was not possible.
• the example in which the average particle size of the glass frit is 20 im or less is superior to the comparative example in which the average particle size is 25 m.
• the coating amount is 8 g / m per side using a roll coater. 2 was applied. Then, it was dried at a drying temperature of 140 and cooled. The film thickness per side was 6 jm. From this to the samples prepared, the inner diameter 10. 16cm (4 inches), to produce a-ring-shaped sample having an outer diameter of 12.7 cm (5 Lee inches), pressure 10 kg m 2 stacked state 20 sheets, the temperature 250 And heated for 4 hours to produce a coated adhesive core. Next, the iron core was annealed at a temperature of 750 for 2 hours without being pressurized. Finally, the iron loss value was measured at a frequency of 50 Hz and a magnetic flux density of 1.5 Tesla. The results are shown in Table 5.
• the glass transition temperature of the resin obtained by applying and baking this coating solution was 104 and softened at 120 or more.
• aqueous solution prepared by mixing 35.3 g of water and 1.04 g of 35% hydrochloric acid was dropped into a liquid for mixing 178 g of methyltrioxysilane and 138 g of ethanol to perform hydrolysis.
• the hydrolyzed solution was concentrated by using a mouth evaporator until the solvent disappeared at 58.
• the mass of the concentrate was 30% of the solution mass before concentration.
• the mass average molecular weight of this concentrate was 10,000. Since this concentrate showed a pliability, it is thought that methyltriethoxysilane was polymerized in the form of a chain polymer. When this concentrate was heat-treated at 70 for 15 minutes, it solidified but at 180 it softened from around. 200 parts by mass of ethanol was blended with 100 parts by mass of the concentrate.
• a coating solution was prepared by hydrolyzing 36 g of water using 4.8 g of acetic acid as a catalyst. This siloxane polymer was not softened by heating.
• each coating solution is applied to both sides of a non-oriented electrical steel sheet having a thickness of 0.5 ⁇ . It was applied in the evening and baked in a furnace set at 70 for 15 minutes. The coating amount was 7 g / m 2 . In any case, there was no stickiness of the film surface after baking. Using two test pieces having a width of 3 cm and a length of 10 cm, a part of the test pieces was overlapped so that the area of the bonded portion was 6 cm 2 and hot pressing was performed.
• Example 4 An inorganic / organic mixed treatment liquid mainly composed of magnesium chromate and acrylic resin was applied and baked to provide an insulating film on the surface.
• Example 4 An inorganic / organic mixed treatment liquid mainly composed of magnesium chromate and acrylic resin was applied and baked to provide an insulating film on the surface.
• Hydrolysis was performed by adding dropwise an aqueous solution containing 35.3 g of water and 1.04 g of 35% hydrochloric acid to a mixture of 178 g of methyltriethoxysilane and 138 g of ethanol.
• the hydrolyzed solution was concentrated using a rotary evaporator until the solvent disappeared at 58.
• the mass of the concentrate was 30% of the solution mass before concentration.
• the concentrate had a mass average molecular weight of 10 000. Since this concentrate showed stubbornness, it is thought that methyltrioxysilane was polymerized in the form of a chain polymer.
• this concentrate was heat-treated at 70 for 15 minutes, it solidified, but softened from around 180 ° C. 200 parts by mass of ethanol was added to 100 parts by mass of this concentrate.
• the coating solutions A to were diluted with water, and various water glasses were added to prepare coating solutions.
• the examples and comparative examples are both surfaces of non-oriented electrical steel sheets with a thickness of 0.5 mm.
• Each coating solution was applied on a rollco overnight and baked for 15 minutes in an oven set at 70 ° C.
• the coating amount was 10 g / m 2 . In any case, there was no stickiness of the film surface after baking.
• test pieces each having a width of 3 cm and a length of 10 cm
• a part of the test piece was overlapped so that the area of the bonded portion was 6 cm 2 and hot pressing was performed. Prior to hot pressing, the applied film was scraped off other than the bonded area.
• two test pieces were bonded by hot press of 1 OMPa for 1 minute.
• the strain relief annealing was performed in nitrogen at 750 for 2 hours.
• the adhesive strength before and after strain relief annealing was evaluated using the shear tensile strength, which is the horizontal strength of the bonded surface.
• Example 5 An inorganic-organic mixed processing liquid mainly composed of magnesium chromate and acrylic resin was applied and baked to provide an insulating film on the surface.
• Example 5 An inorganic-organic mixed processing liquid mainly composed of magnesium chromate and acrylic resin was applied and baked to provide an insulating film on the surface.
• the coating liquid D described in Example 3 was prepared. To 100 parts by mass of coating solution D, 10 parts by mass of spherical particles of polyester having an average particle diameter of 4 m and a softening temperature force of S 200 were mixed and dispersed. It was applied to a non-oriented electrical steel sheet with a surface coating with an inorganic / organic mixed treatment liquid in a rollco and then baked in a furnace set at 100 for 2 minutes. The coating amount was 10 g / m 2 . Two pieces of a test piece having a width of 3 cm and a length of 10 cm were used, and a part of the test piece was overlapped so that the area of the bonded portion was 6 cm 2 and hot pressing was performed.
• the present invention after punching or shearing, it is bonded by pressurization and heating, and can be integrated as an iron core. Thereafter, the adhesive ability can be maintained even after further strain relief annealing. It is possible to provide an attached magnetic steel sheet.
• the iron core can be integrated without welding or caulking, and iron loss deterioration due to welding or caulking can be avoided, and the adhesion and insulation properties are maintained even after stress relief annealing, resulting in excellent magnetic properties.
• An iron core can be produced.

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