Classifications

• • 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
  • C23C22/73—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 characterised by the process
  • C23C22/74—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 characterised by the process for obtaining burned-in conversion coatings
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/34—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing cold phosphate binders
• • C—CHEMISTRY; METALLURGY
  • C21—METALLURGY OF IRON
  • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
  • C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
  • C21D8/12—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties
  • C21D8/1277—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of articles with special electromagnetic properties involving a particular surface treatment
• • 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
  • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
  • H01F41/005—Impregnating or encapsulating
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
  • H01F41/00—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties
  • H01F41/02—Apparatus or processes specially adapted for manufacturing or assembling magnets, inductances or transformers; Apparatus or processes specially adapted for manufacturing materials characterised by their magnetic properties for manufacturing cores, coils, or magnets
  • H01F41/0206—Manufacturing of magnetic cores by mechanical means
  • H01F41/0233—Manufacturing of magnetic circuits made from sheets
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/12—All metal or with adjacent metals
  • Y10T428/12229—Intermediate article [e.g., blank, etc.]

Definitions

• the present invention relates to a non-oriented electrical steel sheet having a small environmental load and a manufacturing method thereof.
• a non-oriented electrical steel sheet is used as an iron core material for motor, for example.
• a plurality of non-oriented electrical steel sheets are stacked on one another, so that they have to be insulated one from another.
• insulating films are formed on surfaces of the non-oriented electrical steel sheets.
• a material of the insulating film a compound containing chromate has been used.
• a technique regarding the environment-respective coating can be classified broadly into two types, based on a difference of inorganic component to be used.
• One is a technique in which colloidal silica is used as a main inorganic component, and the other is a technique in which phosphate is used as a main inorganic component.
• non-oriented electrical steel sheets having films containing phosphate if the non-oriented electrical steel sheets are stacked on one another over a long period at room temperature or temperature a little higher than the room temperature, the films may become sticky, or the films may adhere to one another.
• the non-oriented electrical steel sheets having the films formed thereon are sometimes transported by ships.
• the non-oriented electrical steel sheets are disposed, in a hold, in a state of “being rolled in a coil shape” and axial centers of coils become horizontal, namely, in a state where “the rolled sheets are aligned side by side”.
• a large surface pressure applies to the mutually contacted films, and this state is maintained over a long period.
• Patent Documents 1 to 29 Although there are various techniques regarding the environmental-responsive coating (Patent Documents 1 to 29), it is not possible to effectively suppress the adhesion in any of them.
• Patent Document 1 Japanese Laid-open Patent Publication No. 59-21927
• Patent Document 2 Japanese Laid-open Patent Publication No. H9-122582
• Patent Document 3 Japanese Laid-open Patent Publication No. H9-136061
• Patent Document 4 Japanese Laid-open Patent Publication No. H9-314733
• Patent Document 5 Japanese Laid-open Patent Publication No. H9-323066
• Patent Document 6 Japanese Laid-open Patent Publication No. H9-327886
• Patent Document 7 Japanese Laid-open Patent Publication No. H10-36976
• Patent Document 8 Japanese Laid-open Patent Publication No. H10-34812
• Patent Document 9 Japanese Laid-open Patent Publication No. H10-128903
• Patent Document 10 Japanese Laid-open Patent Publication No. H10-128904
• Patent Document 11 Japanese Laid-open Patent Publication No. H10-130858
• Patent Document 12 Japanese Laid-open Patent Publication No. H10-130859
• Patent Document 13 Japanese Laid-open Patent Publication No. 2001-240916
• Patent Document 14 Japanese Laid-open Patent Publication No. 2004-197202
• Patent Document 15 Japanese Laid-open Patent Publication No. H6-330338
• Patent Document 16 Japanese Laid-open Patent Publication No. H7-41913
• Patent Document 17 Japanese Laid-open Patent Publication No. H7-166365
• Patent Document 18 Japanese Laid-open Patent Publication No. H11-80971
• Patent Document 19 Japanese Laid-open Patent Publication No. H11-131250
• Patent Document 20 Japanese Laid-open Patent Publication No. H11-152579
• Patent Document 21 Japanese Laid-open Patent Publication No. 2000-129455
• Patent Document 22 Japanese Laid-open Patent Publication No. H10-15484
• Patent Document 23 Japanese Laid-open Patent Publication No. H10-15485
• Patent Document 24 Japanese Laid-open Patent Publication No. H10-46350
• Patent Document 25 Japanese Laid-open Patent Publication No. H10-130857
• Patent Document 26 Japanese Laid-open Patent Publication No. H9-316655
• Patent Document 27 Japanese Laid-open Patent Publication No. 2004-322079
• Patent Document 28 Japanese Laid-open Patent Publication No. 2000-26979
• Patent Document 29 Japanese Laid-open Patent Publication No. 2004-107796
• An object of the present invention is to provide a non-oriented electrical steel sheet capable of effectively suppressing adhesion even if a film thereof contains phosphate, and a manufacturing method thereof.
• the present inventors analyzed an adhesion as will be described later and started to set out a solution. As a result of this, the present inventors found out that the occurrence of adhesion is effectively suppressed by making a application liquid for forming film contain a specified inorganic powder so that the ceramics powder absorbs or immobilizes free phosphoric acid generated in accordance with a dehydration/condensation reaction. Further, the present inventors also found out that it is preferable to previously reduce phosphate groups in the application liquid within a range in which a desired property can be obtained, in order to reduce the amount of free phosphoric acid.
• the present invention has been made based on these findings, and the gist thereof is as follows.
• a manufacturing method of a non-oriented electrical steel sheet including:
• the application liquid contains phosphate as the inorganic component
• the application liquid further contains an inorganic powder having a BET specific surface area of 10 m 2 /g or more and exhibiting a particle size distribution with a 50% cumulative particle size of 5 ⁇ m or less and with a 90% cumulative particle size of 15 ⁇ m or less when measured by a laser diffraction particle size analyzer, the powder being contained at a ratio of no less than 1 mass %, nor more than 50 mass % with respect to a solid content of the phosphate.
• an inorganic powder having a BET specific surface area of 10 m 2 /g or more and exhibiting a particle size distribution with a 50% cumulative particle size of 5 ⁇ m or less and with a 90% cumulative particle size of 15 ⁇ m or less when measured by a laser diffraction particle size analyzer, the powder being contained at a ratio of no less than 1 mass %, nor more than 50 mass % with respect to a solid content of the phosphate.
• a non-oriented electrical steel sheet including an inorganic-organic composite film formed on a surface
• the inorganic-organic composite film contains:
• an inorganic powder having a BET specific surface area of 10 m 2 /g or more and exhibiting a particle size distribution with a 50% cumulative particle size of 5 ⁇ m or less and with a 90% cumulative particle size of 15 ⁇ m or less when measured by a laser diffraction particle size analyzer, and
• a content of the inorganic powder is no less than 1 mass %, nor more than 50 mass % with respect to a solid content of the phosphate.
• the inorganic-organic composite film contains, as the inorganic powder, at least one kind selected from a group consisting of alumina powder, silica powder, magnesia powder, titania powder and zirconia powder.
• An application liquid for a non-oriented electrical steel sheet containing:
• an inorganic powder having a BET specific surface area of 10 m 2 /g or more and exhibiting a particle size distribution with a 50% cumulative particle size of 5 ⁇ m or less and with a 90% cumulative particle size of 15 ⁇ m or less when measured by a laser diffraction particle size analyzer, the powder being contained at a ratio of no less than 1 mass %, nor more than 50 mass % with respect to a solid content of the phosphate.
• a application liquid contains a specified inorganic powder, even if a film contains phosphate, it is possible to effectively suppress adhesion.
• the present inventors focused attention on a chemical change at the time when phosphate is baked on a surface of a steel sheet (steel base material), and analyzed the chemical reaction. Note that the chemical reaction of phosphate is so complicated that it has not been clarified yet on a scientific study.
• the present inventors thought that an adhesion phenomenon occurred in stacked non-oriented electrical steel sheets is caused by the free phosphoric acid, and earnestly investigated a reaction mechanism of the adhesion phenomenon.
• the present inventors thought that if it is possible to inhibit sticking reaction with the moisture by inactivating or immobilizing the free phosphoric acid, an adhesion phenomenon occurred in an inorganic-organic composite film containing no chromate-based compound can be suppressed.
• the present inventors thought to previously make an application liquid used for forming the inorganic-organic composite film without chromate-based compound contain an inorganic powder such as ceramics so that free phosphoric acid generated in a dehydration/condensation reaction is absorbed and immobilized by the inorganic powder.
• the present inventors thought that even if free phosphoric acid is generated from phosphate through the dehydration/condensation reaction, the occurrence of stickiness and adhesion phenomenon may be prevented by making the free phosphoric acid to be absorbed on a surface of the inorganic powder to immobilize the free phosphoric acid.
• the present inventors thought that efficiency for capturing free phosphoric acid generated in a film using an inorganic powder is largely affected by a surface area of the inorganic powder. Therefore, alumina powders with various surface areas were prepared and used for the experiments.
• an alumina powder is relatively inexpensive. Further, products with variety of surface areas ranging from small to large are on the market, and it is easy to obtain alumina powders with various surface areas. Accordingly, the present inventors selected the alumina powder among various inorganic powders as a first evaluation target.
• the surface area of the alumina powder was evaluated using a BET (Brunauer, Emmett, Teller) method.
• a measurement method of a specific surface area using the BET method is commonly used as an evaluation method of a surface area of an inorganic powder.
• the BET method is a method of measuring, by making a powder absorb, for example, nitrogen gas of which absorption occupied area is known on a surface thereof, a surface area of the powder based on an absorption amount and a pressure change. Since the surface area is normally represented by a surface area (m 2 ) per unit weight (g) of a powder, it is called a specific surface area that has a unit of “m 2 /g”.
• the present inventors conducted experiments described as follows, in order to understand a suppress effect of the BET specific surface area of the alumina powder on the adhesion phenomenon.
• steel sheets were cold-rolled to a thickness of 0.5 mm and then annealed at 900° C., thereby producing a plurality of steel sheets on which films were not formed.
• alumina powders each formed by adding 5 g of alumina powder to a mixed solution of 100 g of an aqueous aluminum biphosphate solution having a concentration of 50 mass % and 40 g of an aqueous dispersion of acrylic organic resin having a concentration of 30 mass %.
• nine types of alumina powders each having a different BET specific surface area were used.
• the alumina powders ones having a 50% cumulative particle size of 0.15 ⁇ m and a 90% cumulative particle size of 0.73 ⁇ m regarding a particle size distribution measured by using a laser diffraction particle size analyzer were used, regardless of the BET specific surface area.
• the application liquids were coated on surfaces of the steel sheets and dried under a condition where an achieving temperature of the steel sheets became 300° C.
• a coating amount of the application liquid was set so that an amount of film after the drying (after the baking) became 2.5 g/m 2 per one side of the steel sheet.
• a measurement method of particle size distribution using a laser diffraction particle size analyzer is commonly used as an evaluation method of particle size distribution of an inorganic powder.
• a powder to be a measurement target is dispersed in a solvent such as water, and the solvent in which the powder is dispersed is placed in the laser diffraction particle size analyzer.
• the laser beam with specific wavelength was irradiated to the dispersion, analyzed scattered light and diffracted light from the dispersion, converted the analysis result into a particle size distribution and output it.
• the term particle size distribution indicates a particle size distribution (including 50% cumulative particle size and 90% cumulative particle size) measured by the laser diffraction particle size analyzer, unless otherwise stated.
• a large number of samples each having a size of 30 mm ⁇ 40 mm were cut out from a non-oriented electrical steel sheet. Subsequently, these samples were stacked so that a long side and a short side were alternately disposed, pressurized at a surface pressure of 40 kg/cm 2 , and fixed under a pressurized state. Specifically, surfaces of the non-oriented electrical steel sheets were contacted to one another in an area of 30 mm ⁇ 30 mm, namely, in an area of 9 cm 2 . The number of stacked non-oriented electrical steel sheets was set to ten under one condition.
• thermo-hygrostat in which the temperature was kept at 50° C. and the humidity was kept at 90%. This state simulated a situation where the non-oriented electrical steel sheets rolled in a coil shape are being transported.
• the non-oriented electrical steel sheets were taken out, at a time point at which one week has passed after the steel sheets were put into the thermo-hygrostat, and were cooled to room temperature. Thereafter, the pressurized state was released, and the non-oriented electrical steel sheets were peeled off one by one. Namely, the nine times of peeling were conducted for each stack of the ten pieces of non-oriented electrical steel sheets. At this time, a force required for the peeling was measured by using a spring scale, and an average value (peel force) of the nine times of peeling was calculated. Results thereof are shown in Table 1. Smaller peel force value indicates that the stickiness and adhesion phenomenon were unlikely to occur, and larger peel force value indicates that the stickiness and adhesion phenomenon were likely to occur.
• the BET specific surface area of the alumina powder is only required to be 10.0 m 2 /g or more in order to suppress the stickiness and adhesion phenomenon. Further, it was also confirmed that the effect of suppressing the stickiness and adhesion phenomenon is particularly excellent when the BET specific surface area of the alumina powder is 40 m 2 /g or more.
• the non-oriented electrical steel sheet according to the present invention is used, for example, as an iron core material for electric equipment, particularly, as an iron core material for rotating machine (motor).
• a plurality of non-oriented electrical steel sheets are sometimes stacked on one another.
• the iron core material for rotating machine is required to efficiently introduce a magnetic flux within the iron core when electric energy is converted into mechanical energy in accordance with the law of electrical induction. Specifically, the iron core material for rotating machine is required to have a high magnetic flux density.
• the non-oriented electrical steel sheet satisfies the requirement.
• a stack formed by stacking a plurality of non-oriented electrical steel sheets is also required to have a high magnetic flux density.
• a gap exists, to no small extent, between the non-oriented electrical steel sheets, and the magnetic flux density is lowered as the gap is larger. This is because the magnetic flux density in the air existing in the gap is significantly low. Therefore, in a film of a non-oriented electrical steel sheet, it is required that a convex portion is small and the number thereof is small in order not to generate the gap as described above.
• non-oriented electrical steel sheets which are stacked to be used to have coarse convex portions on surfaces of films thereof.
• the inorganic powders such as alumina powders
• a part of the inorganic powders is positioned on the surface of the film.
• convex portions ascribable to such coarse powders may be scattered on the surface of the film. In this case, a size of the gap between the non-oriented electrical steel sheets is varied by the convex portions.
• the present inventors defined the particle size distribution based on a 50% cumulative particle size and a 90% cumulative particle size measured by a laser diffraction particle size analyzer.
• the 50% cumulative particle size corresponds to a particle size, in a particle size distribution formed from a population of inorganic powder, when a mass is integrated in the order of smaller particle sizes and the integrated value reaches 50% of a total mass of the population.
• the 90% cumulative particle size corresponds to a particle size when the integrated value of the mass reaches 90% of the total mass of the population.
• the 50% cumulative particle size indicates a value close to an average particle size of the population
• the 90% cumulative particle size indicates a value close to an approximate particle size of a coarse particle fraction in the population.
• the present inventors conducted experiments regarding a relation between the particle size distribution of alumina powder and a surface roughness Ra (centerline average roughness) of a film.
• steel sheets were cold-rolled to a thickness of 0.15 mm and then annealed at 1050° C., thereby producing a plurality of steel sheets on which films were not formed.
• the application liquids were coated on surfaces of the steel sheets and dried under a condition where an achieving temperature of the steel sheets became 320° C.
• a coating amount of the application liquid was set so that an amount of film after the drying (after the baking) became 3.5 g/m 2 per one side of the steel sheet.
• the surface roughness Ra of each of the non-oriented electrical steel sheets was measured, and further, the peel force was measured in the same manner as that of the above-described experiments. Results thereof are shown in Table 2. Also in Table 2, an evaluation in which the peel force was less than 50 g was represented by ⁇ , an evaluation in which the peel force was not less than 50 g and less than 100 g was represented by ⁇ , and an evaluation in which the peel force was 100 g or more was represented by ⁇ . Further, regarding the surface roughness Ra, ⁇ represented an average roughness of 0.35 ⁇ m or less, ⁇ represented the average roughness which was more than 0.35 ⁇ m and was 0.8 ⁇ m or less, and ⁇ represented the average roughness which was more than 0.8 ⁇ m.
• the peel force was small to be less than 50 g under any of conditions of numbers B(1) to B(9). This is because the alumina powder having the BET specific surface area of 120 m 2 /g was used.
• the surface roughnesses Ra were small to be 0.21 ⁇ m to 0.63 ⁇ m. Specifically, no coarse convex portions were formed on the surfaces of the films, and thus a favorable state was provided.
• the surface roughnesses Ra were large to be 0.87 ⁇ m and 1.52 ⁇ m, respectively. Specifically, coarse convex portions were formed on the surfaces of the films.
• the 50% cumulative particle size is set to 5.0 ⁇ m or less
• the 90% cumulative particle size is set to 15.0 ⁇ m or less.
• the 90% cumulative particle size is preferably 5.0 ⁇ m or less, and more preferably 2.0 ⁇ m or less.
• the 90% cumulative particle size is preferably set to 0.5 ⁇ m or more.
• the present inventors examined an effect of the amount of addition of powder.
• steel sheets were cold-rolled to a thickness of 0.5 mm and then annealed at 900° C., thereby producing a plurality of steel sheets on which films were not formed.
• alumina powder there were prepared application liquids each formed by adding an alumina powder to a mixed solution of 100 g of an aqueous aluminum biphosphate solution having a concentration of 50 mass % and 40 g of an aqueous dispersion of acrylic organic resin having a concentration of 30 mass %.
• the amount of addition of the alumina powder was varied in nine ways. Further, as the alumina powder, one having a 50% cumulative particle size of 0.43 ⁇ m, a 90% cumulative particle size of 2.32 ⁇ m, and a BET specific surface area of 100 m 2 /g was used.
• the application liquids were coated on surfaces of the steel sheets and dried under a condition where an achieving temperature of the steel sheets became 310° C.
• a coating amount of the application liquid was set so that an amount of film after the drying (after the baking) became 3.0 g/m 2 per one side of the steel sheet.
• ratio with respect to aluminum phosphate indicates a ratio of a mass (g) of alumina powder with respect to a solid content (g) of aluminum biphosphate contained in an aqueous aluminum biphosphate solution having a concentration of 50 mass %.
• concentration of the aqueous aluminum biphosphate solution is 50 mass % and the mass thereof is 100 g, so that the solid content of aluminum biphosphate is 50 g.
• the conditions under which both the peel force and the appearance were favorable were the ones of the number C(3) to the number C(8). Specifically, it was confirmed that favorable peel force and appearance can be obtained when the ratio with respect to aluminum phosphate is 1.0 mass % to 50.0 mass %. Note that the ratio with respect to aluminum phosphate before and after the baking is the same. Namely, the ratio with respect to aluminum phosphate in the formed film is the same as that in the application liquid.
• a material of the inorganic powder is not limited to alumina.
• silica, magnesia, titania and zirconia also exhibit the same behavior as that of alumina.
• the present inventors conducted experiments described below with respect to these inorganics.
• steel sheets were cold-rolled to a thickness of 0.35 mm and then annealed at 920° C., thereby producing a plurality of steel sheets on which films were not formed.
• the application liquids were coated on surfaces of the steel sheets and dried under a condition where an achieving temperature of the steel sheets became 285° C.
• a coating amount of the application liquid was set so that an amount of film after the drying (after the baking) became 2.3 g/m 2 per one side of the steel sheet.
• any of silica, magnesia, titania and zirconia was confirmed to show the same tendency as that of alumina. Specifically, an excellent result was obtained when the BET specific surface area was 10 m 2 /g or more, the 50% cumulative particle size and the 90% cumulative particle size were 5 ⁇ m or less and 15 ⁇ m or less, respectively, regarding the particle size distribution measured by the laser diffraction particle size analyzer, and the ratio with respect to aluminum phosphate was 1.0 mass % to 50.0 mass %. Therefore, these inorganic powders can also be used in the same manner as the alumina powder. Further, these powders can also be combined to be used.
• silica, magnesia, titania and zirconia can be used as an inorganic powder, similar to alumina.
• an alumina powder is most suitable.
• the organic resin contained in the mixed solution used for forming the film is not particularly limited.
• a polyacrylic resin, a polystyrene resin, a polyethylene resin, a polyester resin, a polyolefin resin, a polyvinyl alcohol resin, a polypropylene resin, a polyamide resin, a polyurethane resin, a phenol resin, an epoxy resin and a vinyl acetate resin can be used. Further, it is also possible that two kinds or more of these resins are combined to be used.
• Phosphate is also not particularly limited.
• magnesium phosphate, calcium phosphate, zinc phosphate, potassium phosphate, sodium phosphate, nickel phosphate and the like, other than aluminum biphosphate can be used. Further, it is also possible that two kinds or more of these phosphates are combined to be used. It is only required to use an aqueous solution of these phosphates at the time of forming the film.
• the present inventors also examined a range of baking temperature of the film.
• steel sheets were cold-rolled to a thickness of 0.35 mm and then annealed at 1020° C., thereby producing a plurality of steel sheets on which films were not formed.
• an application liquid formed by adding 5 g of alumina powder having an average particle size of 100 nm and a BET specific surface area of 120 m 2 /g to a mixed solution of 100 g of an aqueous aluminum biphosphate solution having a concentration of 50 mass % and 40 g of an aqueous dispersion of acrylic organic resin having a concentration of 30 mass %.
• the application liquid was coated on surfaces of the steel sheets and dried under various achieving temperatures of the steel sheets.
• a coating amount of the application liquid was set so that an amount of film after the drying (after the baking) became 3.0 g/m 2 per one side of the steel sheet.
• the baking temperature of the film is preferably 270° C. or higher, and more preferably 285° C. or higher.
• an upper limit of the baking temperature of the film is not particularly limited.
• the present inventors also examined a baking atmosphere of the film.
• the examined atmosphere includes a nitrogen atmosphere and an air atmosphere. Further, a dew point being an index that indicates a concentration of water vapor in the atmosphere was also evaluated by setting various conditions. As a result of this, a dependence of the stickiness and adhesion phenomenon on the atmosphere was not particularly observed. Therefore, the baking atmosphere is not particularly limited.
• the present inventors also examined an amount of film.
• steel sheets were cold-rolled to a thickness of 0.5 mm and then annealed at 850° C., thereby producing a plurality of steel sheets on which films were not formed.
• an application liquid formed by adding 5 g of alumina powder having a 50% cumulative particle size of 0.55 ⁇ m, a 90% cumulative particle size of 2.32 ⁇ m, and a BET specific surface area of 190 m 2 /g to a mixed solution of 100 g of an aqueous aluminum biphosphate solution having a concentration of 50 mass % and 40 g of an aqueous dispersion of acrylic organic resin having a concentration of 30 mass %. Further, there was also prepared an application liquid to which no alumina powder was added.
• surfaces of the steel sheets were coated with various amounts of the application liquid, and the drying was performed under a condition where an achieving temperature of the steel sheets became 375° C.
• the peel force was rather small to be 51 g. Accordingly, it cannot be clearly said that the adhesion phenomenon occurred.
• the peel force under the condition of the number F(11) was twice or more as large as that under the condition of the number F(3) with the same amount of film.
• the peel forces were large to be 100 g or more. Specifically, the peel forces of the number F(12) to the number F(16) were remarkably larger than those of the number F(4) to the number F(8) with the same amount of film. This indicates that the adhesion phenomenon occurred.
• the amount of film is at least within a range of 1.0 g/m 2 to 6.5 g/m 2 , the peel force becomes small in accordance with the addition of the alumina powder.
• the amount of film is 2.0 g/m 2 or more, the decrease in the peel force in accordance with the addition of the alumina powder is significant, so that it was confirmed that the amount of film is preferably 2.0 g/m 2 or more.
• an upper limit of the amount of film is not particularly limited.
• the present inventors examined in which level of a temperature range in the vicinity of room temperature the adhesion phenomenon is effectively suppressed.
• steel sheets were cold-rolled to a thickness of 0.5 mm and then annealed at 900° C., thereby producing a plurality of steel sheets on which films were not formed.
• an application liquid formed by adding 5 g of alumina powder having a 50% cumulative particle size of 1.55 ⁇ m, a 90% cumulative particle size of 3.57 ⁇ m, and a BET specific surface area of 130 m 2 /g to a mixed solution of 100 g of an aqueous aluminum biphosphate solution having a concentration of 50 mass % and 40 g of an aqueous dispersion of acrylic organic resin having a concentration of 30 mass %.
• the application liquid was coated on surfaces of the steel sheets and dried under a condition where an achieving temperature of the steel sheets became 375° C.
• a coating amount of the application liquid was set so that an amount of film after the drying (after the baking) became 4.1 g/m 2 per one side of the steel sheet.
• thermo-hygrostat in which the temperature was kept at ⁇ 30° C. to +70° C. and the humidity was kept at 90%. This state simulated a situation where the non-oriented electrical steel sheets rolled in a coil shape are being transported.
• the adhesion phenomenon is suppressed when the temperature is at least within a range of ⁇ 30° C. to +60° C.
• the temperature after the stacking is preferably +60° C. or lower.
• a lower limit of the temperature after the stacking is not particularly limited.
• the steel sheet namely, the base material on which the inorganic-organic composite film is formed functions as a non-oriented electrical steel sheet
• a composition thereof is not particularly limited.
• an effect of the present invention regarding an alumina powder was verified.
• steel sheets were cold-rolled to a thickness of 0.5 mm and then annealed at 880° C., thereby producing a plurality of steel sheets on which films were not formed.
• an application liquid formed by adding 10 g of alumina powder having a 50% cumulative particle size of 0.35 ⁇ m, a 90% cumulative particle size of 1.25 ⁇ m, and a BET specific surface area of 220 m 2 /g to a mixed solution of 100 g of an aqueous aluminum biphosphate solution having a concentration of 50 mass % and 40 g of an aqueous dispersion of acrylic organic resin having a concentration of 30 mass %. Further, there was also prepared an application liquid containing no alumina powder.
• the application liquids were coated on surfaces of the steel sheets and dried under a condition where an achieving temperature of the steel sheets became 315° C.
• a coating amount of the application liquid was set so that an amount of film after the drying (after the baking) became 3.1 g/m 2 per one side of the steel sheet.
• an effect of the present invention regarding a silica powder was verified.
• steel sheets were cold-rolled to a thickness of 0.25 mm and then annealed at 1050° C., thereby producing a plurality of steel sheets on which films were not formed.
• an application liquid formed by adding 25 g of silica powder having a 50% cumulative particle size of 0.55 ⁇ m, a 90% cumulative particle size of 1.05 ⁇ m, and a BET specific surface area of 380 m 2 /g to a mixed solution of 100 g of an aqueous aluminum biphosphate solution having a concentration of 50 mass % and 40 g of an aqueous dispersion of acrylic organic resin having a concentration of 30 mass %. Further, there was also prepared an application liquid containing no silica powder.
• the application liquids were coated on surfaces of the steel sheets and dried under a condition where an achieving temperature of the steel sheets became 355° C.
• a coating amount of the application liquid was set so that an amount of film after the drying (after the baking) became 3.9 g/m 2 per one side of the steel sheet.
• an effect of the present invention regarding a magnesia powder was verified.
• steel sheets were cold-rolled to a thickness of 0.55 mm and then annealed at 850° C., thereby producing a plurality of steel sheets on which films were not formed.
• an application liquid formed by adding 2.5 g of magnesia powder having a 50% cumulative particle size of 0.34 ⁇ m, a 90% cumulative particle size of 2.12 ⁇ m, and a BET specific surface area of 150 m 2 /g to a mixed solution of 100 g of an aqueous aluminum biphosphate solution having a concentration of 50 mass % and 40 g of an aqueous dispersion of acrylic organic resin having a concentration of 30 mass %. Further, there was also prepared an application liquid containing no magnesia powder.
• the application liquids were coated on surfaces of the steel sheets and dried under a condition where an achieving temperature of the steel sheets became 285° C.
• a coating amount of the application liquid was set so that an amount of film after the drying (after the baking) became 2.0 g/m 2 per one side of the steel sheet.
• an application liquid formed by adding 3.0 g of titania powder having a 50% cumulative particle size of 2.56 ⁇ m, a 90% cumulative particle size of 8.92 ⁇ m, and a BET specific surface area of 220 m 2 /g to a mixed solution of 100 g of an aqueous aluminum biphosphate solution having a concentration of 50 mass % and 40 g of an aqueous dispersion of acrylic organic resin having a concentration of 30 mass %. Further, there was also prepared an application liquid containing no titania powder.
• the application liquids were coated on surfaces of the steel sheets and dried under a condition where an achieving temperature of the steel sheets became 315° C.
• a coating amount of the application liquid was set so that an amount of film after the drying (after the baking) became 2.5 g/m 2 per one side of the steel sheet.
• an application liquid formed by adding 1.0 g of zirconia powder having a 50% cumulative particle size of 4.33 ⁇ m, a 90% cumulative particle size of 10.12 ⁇ m, and a BET specific surface area of 90 m 2 /g to a mixed solution of 100 g of an aqueous aluminum biphosphate solution having a concentration of 50 mass % and 40 g of an aqueous dispersion of acrylic organic resin having a concentration of 30 mass %. Further, there was also prepared an application liquid containing no zirconia powder.
• the application liquids were coated on surfaces of the steel sheets and dried under a condition where an achieving temperature of the steel sheets became 315° C.
• a coating amount of the application liquid was set so that an amount of film after the drying (after the baking) became 2.5 g/m 2 per one side of the steel sheet.
• examples 6 to 11 and comparative examples 12 to 17 various organic resins were used, and further, various ceramics powders were used as inorganic powders.
• steel sheets were cold-rolled to a thickness of 0.5 mm and then annealed at 950° C., thereby producing a plurality of steel sheets on which films were not formed.
• the application liquids were coated on surfaces of the steel sheets and dried under a condition where an achieving temperature of the steel sheets became 320° C.
• a coating amount of the application liquid was set so that an amount of film after the drying (after the baking) became 3.5 g/m 2 per one side of the steel sheet.
• the present invention can be utilized in, for example, an electrical steel sheet manufacturing industry and an industry using electrical steel sheets.

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