JP4294428B2 - Magnetic base material and method for producing the same - Google Patents

Description

  The present invention relates to a magnetic base material in which a resin is coated on one side of a magnetic metal ribbon, and the magnetic base material has no resin substantially adhered to the back side of the resin coated surface, and a method for producing the same.

  In recent years, many electrical and electronic parts and products that use magnetic materials have been required to have higher magnetic performance (high magnetic permeability, smaller size), and even higher magnetic properties (low loss, Magnetic permeability, high magnetic flux density) and thinning are required.

  In response to such market demand, when a magnetic metal material having high magnetic properties such as an amorphous metal is used as a bulk body, a metal magnetic thin plate has been laminated. For example, when a magnetic metal ribbon is used as the magnetic metal material, since the thickness is about 20 to 50 μm, a specific adhesive is uniformly applied to the surface of the magnetic metal ribbon, Laminating these is generally performed.

  Japanese Patent Application Laid-Open No. 58-175654 (Patent Document 1) is characterized in that magnetic base materials coated with an adhesive mainly composed of a high heat-resistant polymer compound are stacked, pressure-bonded with a reduction roll, and heat-bonded. A method for manufacturing a laminate is proposed.

  Japanese Patent Application Laid-Open No. 11-31604 (Patent Document 2) uses an amorphous metal as a ribbon and uses an epoxy resin, a bisphenol A type epoxy resin, a partially saponified montanic acid ester wax, a modified polyester resin, or a phenol butyral as a resin. A method of manufacturing a laminate using a resin or the like has been proposed.

However, when resin is applied to the entire surface of one side of the magnetic metal ribbon, the resin is applied from the edge to the back side of the resin coating surface, and the resin is applied to the magnetic metal ribbon with minute pinholes. Then, there is a problem that the resin goes around from the pinhole to the back surface of the resin coating surface. In this way, the magnetic base material with the resin turned around and adhered to the back surface (uncoated surface of the resin) is not only out of specification, but also when winding a magnetic metal ribbon coated with resin, a winding roll, etc. Resin may adhere to the product and hinder the operation. A solution to such a problem has not been proposed so far, and a means for preventing the resin from adhering to an uncoated surface when a resin is applied to a magnetic metal ribbon is required. It was.
JP 58-175654 A Japanese Patent Laid-Open No. 11-312604

  An object of the present invention is to provide a magnetic base material in which a resin is coated on one side of a magnetic metal ribbon, and the resin is not substantially adhered to an uncoated surface, and a method for producing the same. It is in.

  The first magnetic base material of the present invention is a magnetic base material in which a resin is coated on one side of a magnetic metal ribbon, and the resin runs from the edge of the magnetic metal ribbon to the back surface of the resin coated surface. It is characterized by not.

The second magnetic base material of the present invention is a magnetic base material in which a resin is coated on one side of a magnetic metal ribbon having at least one pinhole, and the resin is applied from the pinhole to the back surface of the resin coated surface. It is characterized by not having a backside.

  The first method for producing a magnetic base material of the present invention is a method for producing a magnetic base material by applying a resin to one surface of a magnetic metal ribbon, and applying the resin at the end of the magnetic metal ribbon. By controlling the amount, it is characterized in that a magnetic base material is produced in which the resin is not backed from the end of the magnetic metal ribbon to the back surface of the resin coating surface.

  A second magnetic substrate manufacturing method of the present invention is a method of manufacturing a magnetic substrate by applying a resin to one surface of a magnetic metal ribbon, and the pinhole of the magnetic metal ribbon is detected by a pinhole detector. By measuring the position of the resin and controlling the resin application position so that the resin is not applied to the periphery of the pinhole based on the measurement results, the resin is not backed from the pinhole to the back of the resin coating surface. It is characterized by manufacturing a base material.

  According to the present invention, it is possible to manufacture a magnetic base material on which the resin is not substantially adhered to the back surface of the resin-uncoated surface, so that stable operation can be performed without the resin adhering to a winding roll or the like. Production efficiency can be improved.

  In addition, when the magnetic base material of the present invention is used, when the magnetic base material is laminated to produce a magnetic laminated body, it is difficult to cause a stacking deviation and the like, so that the production efficiency of the laminated body can be improved.

  Hereinafter, the present invention will be described in detail.

  The magnetic base material of the present invention is a magnetic base material in which a resin is coated on one surface of a magnetic metal ribbon, and the resin is not backed on the back surface of the resin coated surface.

(Magnetic metal ribbon)
The metal magnetic material used in the present invention is made of a high magnetic permeability material, and can be an amorphous magnetic material or a nanocrystalline magnetic material. Among these, as the amorphous metal magnetic material, Fe-based and Co-based amorphous metal ribbons are used. These amorphous metal ribbons are usually obtained by quenching molten metal using a quenching roll. Usually 10 ~
A ribbon having a thickness of 50 μm and preferably a thickness of 10 to 30 μm is used.

The amorphous metallic material, the general formula _{(Fe 1-x M x)} 100-abc Si a B b M 'c ( wherein, M represents Co and / or Ni, M' is Nb, Mo, Zr , W, Ta, Hf, Ti, V
Represents one or more elements selected from Cr, Mn, Y, Pd, Ru, Ga, Ge, C, and P. x represents an atomic ratio, a, b, and c represent atomic%, and satisfy 0 ≦ x <1, 0 ≦ a ≦ 24, 4 ≦ b ≦ 30, and 0 ≦ c ≦ 10, respectively. An amorphous metal material having a composition represented by In particular, in applications where high magnetic permeability is required, it is preferable to use an amorphous metal containing Co as a main component. In applications such as a magnetic shield that shield high-density magnetic flux, it is preferable to use an amorphous metal mainly composed of Fe having a high saturation magnetic flux density.

Fe-based amorphous metal materials include Fe-B-Si-based, Fe-B-based, and Fe-PC-based Fe-semi-metallic amorphous metal materials, Fe-Zr-based, Fe-Hf, and the like. Fe-transition metal amorphous metal materials such as Fe-Ti and Fe-Ti. For example, in the Fe—Si—B system, Fe ₇₈ Si ₉ B ₁₃ (at%), Fe ₇₈ Si ₁₀ B ₁₂ (at%), Fe ₈₁ Si _13.5 B _13.5 (at%), Fe ₈₁ Si _13.5 B _13.5 C ₂ (at%), Fe ₇₇ Si ₅ B ₁₆ Cr ₂ (at%), Fe ₆₆ Co ₁₈ Si ₁ B ₁₅ (at%), Fe ₇₄ Ni ₄ Si ₂ B ₁₇ Mo ₃ (at%), etc. be able to. Among them, Fe ₇₈ Si ₉ B ₁₃ (at%), Fe ₇₇ Si ₅ B ₁₆ Cr ₂ (at%)
Is preferably used, and Fe ₇₈ Si ₉ B ₁₃ (at%) is particularly preferably used.

Examples of the composition system of the Co-based amorphous metal material include a Co-Si-B system and a Co-B system. Among these, the composition of the amorphous metal ribbon has a general formula (Co _1-c Fe _c ) _100-ab X _a Y _b (wherein X is at least one selected from Si, B, C, Ge) Represents the above elements,
Y is at least one selected from Zr, Nb, Ti, Hf, Ta, W, Cr, Mo, V, Ni, P, Al, Pt, Ph, Ru, Sn, Sb, Cu, Mn, and rare earth elements. Expressed in elements. “a”, “b”, and “c” represent atomic% and satisfy 10 <a ≦ 35, 0 ≦ b ≦ 30, and 0 ≦ c ≦ 0.2, respectively. ) Is preferred.

  Co substitution of Fe in the amorphous metal ribbon tends to contribute to an increase in saturation magnetization of the amorphous alloy. For this reason, the substitution amount c is preferably 0 ≦ c ≦ 0.2. Furthermore, it is preferable that 0 ≦ c ≦ 0.1.

  The element X is an effective element for reducing the crystallization speed for making amorphous when producing the amorphous metal ribbon used in the present invention. If the amount of element X is less than 10 atomic%, amorphization is reduced and some crystalline is mixed. If it exceeds 35 atomic%, an amorphous structure is obtained, but the mechanical strength of the alloy ribbon is obtained. Decreases and a continuous ribbon cannot be obtained. Therefore, the amount a of the X element is preferably 10 <a ≦ 35, and more preferably 12 ≦ a ≦ 30.

  Y element is effective in the corrosion resistance of the amorphous metal ribbon used in the present invention. Among these, particularly effective elements are Zr, Nb, Mn, W, Mo, Cr, V, Ni, P, Al, Pt, Ph, and Ru. If the amount of Y element added is 30% or more, there is an effect of corrosion resistance, but the mechanical strength of the ribbon becomes weak, so 0 ≦ b ≦ 30 is preferable. A more preferable range is 0 ≦ b ≦ 20.

  Examples of the nanocrystalline magnetic metal material include materials having the following composition.

(1) General formula (Fe _1-x M _x ) _100-abcd Si _a Al _b B _c M ′ _d
(Wherein M represents Co and / or Ni, and M ′ represents Nb, Mo, Zr, W, Ta, H
It represents one or more elements selected from f, Ti, V, Cr, Mn, Pd, Ru, Ge, C, P, and rare earth elements. x represents an atomic ratio, a, b, c, and d represent atomic%, and 0 ≦ x ≦ 0.5, 0 ≦ a ≦ 24, 0.1 <b ≦ 20, 4 ≦ c ≦ 30, 0 ≦, respectively. It is assumed that d ≦ 20 is satisfied. ).

(2) General formula (Fe _1-x M _x ) _100-abcd Cu _a Si _b B _c M ′ _d
(Wherein M represents Co and / or Ni, and M ′ represents Nb, Mo, Zr, W, Ta, H
It represents one or more elements selected from f, Ti, V, Cr, Mn, Pd, Ru, Ge, C, P, and rare earth elements. x represents an atomic ratio, a, b, c, and d represent atomic%, and 0 ≦ x ≦ 0.4, 0.1 ≦ a ≦ 3, b ≦ 19, 5 ≦ c ≦ 25, and 0 <d ≦, respectively. 20, 15 ≦ b + C ≦ 30. ).

(3) General formula (Fe _1-x M _x ) _100-ab B _a M ′ _b
(Wherein M represents Co and / or Ni, and M ′ represents Nb, Mo, Zr, W, Ta, Hf, Ti, V, Cr, Mn, Pd, Ru, Ga, Ge, C, and rare earth elements. Represents one or more selected elements, where x is an atomic ratio, a and b are atomic%, and satisfy 0 ≦ x ≦ 0.5, 0 <a ≦ 20, and 2 ≦ b ≦ 20, respectively. )).

(4) General formula (Fe _1-x M _x ) _100-abc P _a M ′ _b Cu _c
(Wherein M represents Co and / or Ni, M ′ represents Nb, Mo, Zr, W, Ta, Hf, Ti, V, Cr, Mn, Pd, Ru, Ga, Ge, Al, C, rare earth Represents one or more elements selected from the elements, where x represents an atomic ratio, a, b, c, and d represent atomic%, and 0 ≦ x ≦ 0.50 <a ≦ 20, 2 ≦ b ≦ 20, 0 ≦ c ≦ 3)).

(5) General formula (Fe _1-x M _x ) _100-ab M _a M ′ _b
(Wherein M represents Co and / or Ni, and M ′ represents Ta, Zr, Hf, Ti, Nb, Mo, W, V, Cr, Mn, Pd, Ru, Ga, Ge, Si, Al, P , Cu, and one or more elements selected from rare earth elements, M ′ represents one or more elements selected from C, N, and O. x represents an atomic ratio, a and b represent atomic%, Each satisfying 0 ≦ x ≦ 0.52 <a ≦ 304 ≦ b ≦ 30).

  These magnetic materials can be made into a nanocrystalline material by a known method, for example, heat treatment.

(resin)
As the resin to be applied to the magnetic metal ribbon of the present invention, a known so-called resin can be used, but when heat treatment at 200 ° C. or higher is required for improving the magnetic properties of the metal magnetic material, Compounding a heat-resistant resin having a low elastic modulus is effective in achieving excellent performance. The heat treatment temperature for expressing good magnetic properties of the magnetic metal ribbon used in the present invention is usually in the range of 200 to 700 ° C, more preferably in the range of 300 to 600 ° C.

In the present invention, the heat-resistant resin is one having a weight reduction rate of 5% by weight or less due to thermal decomposition at 300 ° C. for 2 hours in a nitrogen atmosphere, and further has one or more of the following characteristics. It is preferable.
(1) The tensile strength after passing through a thermal history at 350 ° C. for 2 hours in a nitrogen atmosphere is 30 MPa or more,
(2) The glass transition temperature is 120 ° C to 250 ° C,
(3) The temperature at which the melt viscosity is 1000 Pa · s is 250 ° C. or higher and 400 ° C. or lower. (4) After the temperature is lowered from 400 ° C. to 120 ° C. at a constant rate of 0.5 ° C./min, The heat of fusion due to the crystal is 10 J / g or less.

  The heat-resistant resin that can be used in the present invention is a weight loss measured using DTA-TG when dried at 120 ° C. for 4 hours as a pretreatment and then kept at 300 ° C. for 2 hours in a nitrogen atmosphere. The amount is usually 1% or less, preferably 0.3% or less. Specific resins include polyimide resins, silicon-containing resins, ketone resins, polyamide resins, liquid crystal polymers, nitrile resins, thioether resins, polyester resins, arylate resins, sulfone resins, Examples thereof include imide resins and amide imide resins. Of these, it is preferable to use polyimide resins, sulfone resins, and amideimide resins.

Further, in the present invention, when heat resistance of 200 ° C. or higher is not required, the present invention is not limited to this. Specific thermoplastic resins that can be used in the present invention include polyethersulfone, polyetherimide, polyetherketone. , Polyethylene terephthalate, nylon, polybutylene terephthalate, polycarbonate, polyphenylene ether, polyphenylene sulfide, polysulfone, polyamide, polyamideimide, polylactic acid, polyethylene, polypropylene, epoxy resin, silicone resin, rubber resin (chloroprene rubber, silicone rubber), etc. Can be mentioned.

  The thickness of the resin layer of the present invention is preferably in the range of 0.1 μm to 1 mm, more preferably 0.5 μm to 10 μm, and further preferably 1 μm to 6 μm.

(Coating method)
In the present invention, the magnetic substrate refers to one obtained by coating a resin on one side of a magnetic metal ribbon. As a method of applying a resin to a magnetic metal ribbon, it is common to apply a resin varnish obtained by dissolving a resin in an organic solvent using a roll coater or the like.

  The viscosity of the resin is usually in a concentration range of 0.005 to 200 Pa · s, preferably 0.01 to 50 Pa · s, and more preferably 0.05 to 5 Pa · s. When the viscosity is less than 0.005 Pa · s, the viscosity becomes too low, so that it flows from the amorphous metal ribbon, and a sufficient coating amount cannot be obtained on the thin plate, resulting in an extremely thin coating film. is there. When the viscosity exceeds 200 Pa · s, it is extremely difficult to control the film thickness for forming a thin coating film on the amorphous metal ribbon due to the high viscosity.

  As a method of applying the liquid resin as described above, a method using a coater, for example, a roll coater method, a (micro) gravure coater method, an air doctor coater method, a blade coater method, a knife coater method, a rod coater method, Kiss coater method, bead coater method, cast coater method, rotary screen method, or ink jet method, dip coating method of coating while immersing amorphous metal ribbon in liquid resin, dropping liquid resin to magnetic metal ribbon from orifice Physical coating such as slot orifice coater method, bar code method, spray coating method, spray coating method, spray coating method, electrodeposition coating method, sputtering method in which liquid resin is sprayed onto magnetic metal ribbon on mist using the principle of spraying Like vapor deposition, CVD Such as the phase, and the like.

  The first magnetic base material according to the present invention is characterized in that the resin does not surround the back of the resin coating surface from the end by reducing the amount of resin applied at the end of the magnetic metal ribbon. To do. For example, as shown in FIG. 1, a method of applying the resin a plurality of times by narrowing the resin application range step by step so that the thickness of the resin 2 on the end surface of the magnetic metal ribbon 1 decreases stepwise, or FIG. As shown in FIG. 2, it is possible to prevent the resin from going around from the end portion to the back surface of the resin coating surface by controlling so that the resin 2 is not applied to the end portion of the magnetic metal ribbon 1.

  For example, if the width of the magnetic metal ribbon is constant, the position of the end and the position of the nozzle for applying the resin can be controlled using a control device or the like. As the resin application method, a resin application method using a micro gravure coater is preferable because the application thickness of the resin can be controlled to a minute amount of several μm level.

  The second magnetic base material according to the present invention controls the resin application surface from the pinhole by controlling the resin application position so that the resin is not applied to the pinhole and its peripheral part existing in the magnetic metal ribbon. The back surface of the resin is characterized in that the resin does not surround the back. For example, as shown in FIG. 3, the resin is placed in the peripheral portion 4 ′ of the pinhole 4 existing in the magnetic metal ribbon 1, specifically, within a range of 0.5 mm, preferably 0.1 mm from the position of the pinhole. By not coating, it is possible to prevent the resin from turning around from the pinhole to the back surface of the resin coating surface.

The pinhole refers to a hole having a longest diameter of 5 mm or less generated during the production of a magnetic metal ribbon. Such a pinhole can be detected by, for example, a commercially available pinhole detector or a surface roughness measuring instrument. Moreover, you may use the pinhole detection apparatus currently disclosed by Unexamined-Japanese-Patent No. 6-18445, Unexamined-Japanese-Patent No. 6-222016, etc.

For example, as shown in FIG. 4, the second magnetic base material of the present invention has a pinhole detection device 7, a coating device 8, a feed roll unit 5 and a take-up roll unit 6 electrically connected to the control unit 9. In the resin coating system connected to
(I) The position of the pinhole 4 of the magnetic metal ribbon 1 is detected by the pinhole detection device 7, and a signal of this detection result is output to the control device 9,
(Ii) Based on the output result, the length between the pinhole detection device 7 and the coating device 8, the feeding speed (winding speed) of the magnetic metal ribbon 1, etc., the resin 2 A signal that does not apply is output from the control device 9 to the coating device 8,
(Iii) On the basis of this signal, the coating device 8 applies resin 2 to the surface other than the pinhole peripheral portion 4.
It can manufacture by coating.

  As the resin application method, for example, a spray nozzle method or an ink jet method is preferable in that it is easy to precisely control the resin application position.

  Moreover, the manufacturing method of the 1st magnetic base material which concerns on this invention, and the manufacturing method of the 2nd magnetic base material can also be combined. Thereby, the back periphery of the resin from both the end of the magnetic metal ribbon and the pinhole can be prevented.

It is sectional drawing which shows the example of the 1st magnetic base material of this invention. It is sectional drawing which shows the example of the 1st magnetic base material of this invention. It is sectional drawing which shows the example of the 2nd magnetic base material of this invention. It is a figure which shows the example of the manufacturing method of the 2nd magnetic base material of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Magnetic metal ribbon 2 ... Resin layer 3 ... Magnetic base material 4 ... Pinhole 4 '... Pinhole peripheral part 5 ... Delivery roll part 6 ... Winding roll Part 7: Pinhole detection device 8 ... Coating device 9 ... Control device

Claims (5)

  A method of manufacturing a magnetic base material in which a resin is coated on one side of a magnetic metal ribbon, and the resin is not backed from the end of the magnetic metal ribbon to the back surface of the resin coated surface. A method for producing a magnetic base material, comprising a step of applying a resin a plurality of times with a step of narrowing a resin application range so that the thickness of the resin on the end face of the band is reduced stepwise.   A method of manufacturing a magnetic base material by coating a resin on one side of a magnetic metal ribbon, measuring the pinhole position of the magnetic metal ribbon with a pinhole detection device, and pinholes based on the measurement results By controlling the resin application position so that the resin is not applied to the peripheral part, a magnetic base material in which the resin does not back from the back surface of the resin coated surface from the pinhole is manufactured. Production method. The method for producing a magnetic substrate according to claim 2 , wherein the resin is applied by a spray nozzle method. The method for producing a magnetic substrate according to claim 2 , wherein the resin is applied by an inkjet method. Magnetic substrate, characterized in that it is manufactured by the manufacturing method of the magnetic substrate according to any one of claims 1-4.

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