EP0558178B1 - Magnetisch permeabele Zusammensetzung und weichmagnetisches Teil - Google Patents

Magnetisch permeabele Zusammensetzung und weichmagnetisches Teil Download PDF

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Publication number
EP0558178B1
EP0558178B1 EP19930300361 EP93300361A EP0558178B1 EP 0558178 B1 EP0558178 B1 EP 0558178B1 EP 19930300361 EP19930300361 EP 19930300361 EP 93300361 A EP93300361 A EP 93300361A EP 0558178 B1 EP0558178 B1 EP 0558178B1
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Prior art keywords
composition
permeability
parts
based ferrite
polyarylene sulfide
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French (fr)
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EP0558178A2 (de
EP0558178A3 (en
Inventor
Masahito c/o Kureha Kagaku Kogyo K.K. Tada
Keiichiro c/o Kureha Kagaku Kogyo K.K. Suzuki
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Kureha Corp
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Kureha Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—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 non-metallic substances, e.g. ferrites
    • H01F1/36—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 non-metallic substances, e.g. ferrites in the form of particles
    • H01F1/37—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 non-metallic substances, e.g. ferrites in the form of particles in a bonding agent

Definitions

  • the present invention relates to a polyarylene sulfide resin composition excellent in permeability and a magnetic component shaped therefrom.
  • Polyarylene sulfide resin is an engineering plastic having excellent heat resistance, chemical resistance and electrical insulating property and, because of such properties, has been recently used in a wide scope of industries of, e.g., electrical, electronics and automobiles.
  • a permeable magnetic composition containing a powdery soft magnetic material dispersed in a binder of polyarylene sulfide resin is being considered for use as various magnetic components, such as coils, inductors and filters, by taking advantage of small mold shrinkage characteristics in addition to the heat resistance, chemical resistance and the electrical insulation properties of the polyarylene sulfide see US-A-4,268,430.
  • the soft magnetic material Ni-Zn-based ferrite is particularly suitable for use in circuit components for medium frequency or high frequency ranges.
  • An object of the present invention is to provide a composition comprising polyarylene sulfide resin and a Ni-Zn-based ferrite having a high permeability which has not been realized by this type of composition.
  • Ni-Zn-Cu-based ferrite of a specific composition provides a composition having a high permeability when combined with polyarylene sulfide resin.
  • a permeable magnetic composition comprising 5 - 30 wt. parts of polyarylene sulfide resin and 70 - 95 wt. parts of Ni-Zn-Cu-based ferrite powder providing a total of 100 wt. parts together with the polyarylene sulfide resin, said Ni-Zn-Cu-based ferrite having a composition represented by the following formula (1): Ni a Zn b Cu c Fe 2 O d , wherein a, b, c and d are numbers satisfying 0.10 ⁇ a ⁇ 0.70, 0.10 ⁇ b ⁇ 0.80, 0.10 ⁇ c ⁇ 0.35 and 3.97 ⁇ d ⁇ 4.20.
  • Figures 1 and 2 are a perspective view and a sectional view, respectively, of a coil and a core encapsulated in Examples 5 and 6.
  • Ni-Zn based ferrite it is well known that too much or too little Ni or Zn fails to provide a high permeability. This is also true in Ni-Zn-Cu based ferrite. More specifically, it is appropriate that the parameter a representing the nickel (Ni) content is in the range of 0.10 - 0.70, preferably 0.15 - 0.50, more preferably 0.17 - 0.30. It is appropriate that the parameter b representing the zinc (Zn) content is in the range of 0.10 - 0.80, preferably 0.40 - 0.75, more preferably 0.50 - 0.70.
  • a parameter c representing the copper (Cu) content fails to provide a high permeability and the required range therefor is rather narrower than a and b . More specifically, it is appropriate that the parameter c is in the range of 0.10 - 0.35, preferably 0.15 - 0.30, more preferably 0.17 - 0.25. Below 0.10 or in excess of 0.35, it is difficult to obtain the product obtained through, e.g., injection or compression molding with an increased permeability.
  • the parameter d representing the oxygen content is in the range of 3.97 - 4.20, preferably 3.98 - 4.15, more preferably 3.99 - 4.10.
  • the resultant product obtained through, e.g., injection or compression molding is caused to have a lower electrical insulating property, so that it becomes difficult to retain a high permeability in a high frequency region.
  • the Ni-Zn-Cu-based ferrite powder used in the present invention may preferably have an average particle size (diameter) according to the light scattering method (as measured by using Model "LA-500" available from Horiba Seisakusho K.K.) in the range of 3 - 200 ⁇ m, more preferably 5 - 200 ⁇ m. If the average particle size is below 3 ⁇ m, the composition is caused to have an excessively high melt viscosity, and it becomes difficult to form a molded product having a satisfactory appearance. Further, a smaller particle size tends to provide a smaller permeability. If the ferrite powder has an average particle size in excess of 200 ⁇ m, it becomes difficult to form a small size product and is liable to promote the wearing of a mold surface.
  • the Ni-Zn-Cu-based ferrite powder can be surface-treated with a known surface treating agent, such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, or a phosphorus-based coupling agent.
  • a known surface treating agent such as a silane coupling agent, a titanate coupling agent, an aluminum coupling agent, or a phosphorus-based coupling agent.
  • the polyarylene sulfide resin refers to a polymer comprising at least 50 wt. %, preferably at least 70 wt. %, more preferably at least 90 wt. %, of a recurring unit represented by ( ⁇ Ar-S) ⁇ , wherein -Ar- denotes an arylene group.
  • a polyarylene sulfide having a substantially linear structure formed from a monomer (or monomer mixture) comprising a bi-functional monomer-because of an excellent toughness It is however possible to use a polyarylene-sulfide having a partially crosslinked structure or subjected to curing for increasing the melt viscosity as far as the mechanical properties are not impaired thereby.
  • a preferred example of the recurring unit ( ⁇ Ar-S) ⁇ is a p-phenylene sulfite unit represented by
  • the polyarylene sulfide may be a homopolymer, a random copolymer or a block copolymer.
  • the copolymer may preferably comprise at least 50 wt. %, particularly at least 60 wt. %, of the p-phenylene sulfide having the structure shown above and at most 50 wt. %, particularly at most 40 wt.
  • % of at least one of m-phenylene sulfide unit, diphenylene sulfide unit, tri-functional phenyl sulfide unit, naphthalene sulfide unit, phenyl ketone phenyl sulfide unit, phenyl sulfone unit, phenyl ether phenyl sulfide unit, phenyl sulfone phenyl sulfide unit, and phenyl ketone phenyl ketone sulfide unit respectively represented by the following structural formulae: and
  • the polyarylene sulfide resin may preferably have a melt viscosity of 1 - 200 Pa.S (10 - 2000 poise), more preferably 2 - 120 Pa.S (20 - 1200 poise), further preferably 2.5 - 100 Pa.S (25 - 1000 poise), as measured at a temperature of 310 °C and a shear rate of 10 3 /sec.
  • the magnetic composition of the present invention comprises the above Ni-Zn-Cu-based ferrite in an amount of 70 - 95 wt. parts, preferably 75 - 93 wt. parts, and the polyarylene sulfide in an amount of 5 - 30 wt. parts, preferably 7 - 25 wt. parts, providing a total of 100 wt. parts together with the Ni-Zn-Cu-based ferrite. If the ferrite powder is less than 70 wt. parts, the permeability is lowered. In excess of 95 wt. parts, the composition becomes fragile.
  • the magnetic composition of the present invention can further contain 0 - 25 wt. % of a thermoplastic resin other than the polyarylene sulfide resin, such as polyamide resin, polyphenylene ether resin, polyether ether ketone, polyether ketone, polycarbonate or polystyrene, or a thermosetting resin, such as epoxy resin or a cured product thereof.
  • a thermoplastic resin other than the polyarylene sulfide resin such as polyamide resin, polyphenylene ether resin, polyether ether ketone, polyether ketone, polycarbonate or polystyrene, or a thermosetting resin, such as epoxy resin or a cured product thereof.
  • the magnetic composition according to the present invention can further contain an inorganic filler or fibrous reinforcing material, such as glass fiber, potassium titanate, silicon carbide, ceramic fiber, silicon nitride or asbestos, or an organic fibrous reinforcing material, such as aramide fiber.
  • an inorganic filler or fibrous reinforcing material such as glass fiber, potassium titanate, silicon carbide, ceramic fiber, silicon nitride or asbestos, or an organic fibrous reinforcing material, such as aramide fiber.
  • epoxidized silicone oil into the composition of the present invention so as to improve the adhesiveness to a coil or a terminal electrode.
  • the epoxidized silicone oil may preferably be added in an amount of 0.1 - 5 wt. %, more preferably 0.2 - 2 wt. %.
  • the total amount of the Ni-Zn-Cu ferrite powder and the polyarylene sulfide resin occupies at least 85 wt. %, more preferably at least 95 wt. %, further preferably at least 97 wt. % of the composition.
  • the molding or shaping method applicable to the composition is not particularly limited but may preferably be one of applying a high pressure, such as injection molding or compression molding.
  • the injection molding may preferably be performed while applying a pressure of 400 - 3000 kgf/cm 2 , more preferably 500 - 2000 kgf/cm 2 at a temperature which may be 15 - 100 °C higher than the melting point of the polyarylene sulfide resin.
  • the permeable magnetic composition according to the present invention may suitably be used for production of, e.g., magnetic components, suitable for use as or use in coil and core, inductor, rotary transformer, EMI filter, and balun requiring a high permeability and electrical insulation.
  • a pellet-form composition in each Example was supplied to an injection molding machine ("PS-10E", available from Nissei Jushi K.K.) to form a toroidal core having an outer diameter of 36 mm, an inner diameter of 24 mm and a thickness of 10 mm by injection molding under the conditions of a cylinder temperature of 340 °C, a nozzle temperature of 340 °C, an injection pressure of 1500 kgf/cm 2 and a mold temperature of 160 °C.
  • PS-10E injection molding machine
  • Ni-Zn-Cu-based ferrite powder (average particle size: 11 ⁇ m) having a composition represented by the chemical formula Ni 0.19 Zn 0.63 Cu 0.18 Fe 2 O 4.00 and 1.5 kg of linear phenyl sulfide homopolymer (melt viscosity: about 20 Pa.s (200 poise), melting point: 290 °C) were blended in a 20 liter-Henschel mixer and melt-kneaded through a twin-screw kneading extruder to prepare a composition in the form of pellets. A toroidal core was molded from the composition and the permeability thereof was measured in the above-described manner, whereby a value of 14.8 was obtained.
  • a composition was prepared from 13.5 kg of Ni-Zn-Cu-based ferrite powder represented by the formula Ni 0.20 Zn 0.58 Cu 0.22 Fe 2 O 4.01 and 1.5 kg of the linear phenylene sulfide homopolymer and formed into a toroidal core in the same manner as in Example 1.
  • the core provided a permeability shown in Table 1.
  • a composition was prepared from 13.5 kg of Ni-Zn-Cu-based ferrite powder represented by the formula Ni 0.63 Zn 0.31 Cu 0.15 Fe 2 O 4.09 and 1.5 kg of the linear phenylene sulfide homopolymer and formed into a toroidal core in the same manner as in Example 1.
  • the core provided a permeability shown in Table 1.
  • a composition was prepared from 13.5 kg of Ni-Zn-Cu-based ferrite powder represented by the formula Ni 0.27 Zn 0.67 Cu 0.16 Fe 2 O 4.10 and 1.5 kg of the linear phenylene sulfide homopolymer and formed into a toroidal core in the same manner as in Example 1.
  • the core provided a permeability shown in Table 1.
  • a chip-form ferrite core for an inductor having a shape as shown in Figure 1 (perspective view) and Figure 2 (sectional view) was provided.
  • the core had two end disks 1 each having a diameter of 3 mm and a thickness of 1 mm and a through hole 2 to pass a lead wire therethrough.
  • the disks 1 were connected with a cylindrical bar 3 having a length of 3 mm and a diameter of 1.8 mm.
  • a copper wire was wound in the form of a coil 4 about the bar 3 and the two ends thereof were passed through the disks 1 to form leads 4a and 4b.
  • the coil and core were placed in a mold as an insert and encapsulated except for the leads 4a and 4b with the composition of the above Example 1 to form a molded product in the form of a rectangular parallelepiped measuring 7 mm x 4 mm x 4 mm by using an injection molding machine ("JT-40", available from Nippon Seiko-sho K.K.).
  • JT-40 injection molding machine
  • the molded product was immersed for 10 seconds in a solder bath at 260 °C and then taken out for inspection of the appearance. As a result, no crack was observed at the parts contacting the leads of the molded product, and no surface abnormality was observed either. Further, no change in inductance was observed before and after the immersion in the solder bath.
  • Ni-Zn-Cu-based ferrite represented by the chemical formula Ni 0.20 Zn 0.58 Cu 0.22 Fe 2 O 4.01 and 2.25 kg of the polyphenylene sulfide resin were blended in a 20 liter-Henschel mixer, and 112.5 g of epoxidized silicone oil was added and mixed therewith. The resultant mixture was melt-kneaded through a twin-screw kneading extruder to prepare a composition in the form of pellets, which was then molded into a toroidal core in the above-described manner. The core provided a permeability shown in Table 1 above.
  • Example 5 A coil and a core identical to those used in Example 5 were encapsulated with the composition of this Example in a similar manner as in Example 5 to form a similar molded product.
  • the molded product was immersed for 10 seconds in a solder bath at 260 °C and then taken out for inspection of the appearance. As a result, no crack was observed at the parts contacting the leads of the molded product, and no surface abnormality was observed either. Further, no change in inductance was observed before and after the immersion in the solder bath.
  • a composition was prepared from 13.5 kg of Ni-Zn-based ferrite powder represented by the formula Ni 0.36 Zn 0.62 Fe 2 O 3.98 and 1.5 kg of the linear phenylene sulfide homopolymer and formed into a toroidal core in the same manner as in Example 1.
  • the core provided a permeability shown in Table 1.
  • a composition was prepared from 13.5 kg of Ni-Zn-based ferrite powder represented by the formula Ni 0.60 Zn 0.37 Fe 2 O 3.97 and 1.5 kg of the linear phenylene sulfide homopolymer and formed into a toroidal core in the same manner as in Example 1.
  • the core provided a permeability shown in Table 1.
  • a composition was prepared from 13.5 kg of Ni-Zn-Cu-based ferrite powder represented by the formula Ni 0.30 Zn 0.3 Cu 0.41 Fe 2 O 4.01 and 1.5 kg of the linear phenylene sulfide homopolymer and formed into a toroidal core in the same manner as in Example 1.
  • the core provided a permeability shown in Table 1.
  • a polyarylene sulfide resin composition showing a high permeability.

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  • Chemical & Material Sciences (AREA)
  • Dispersion Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Power Engineering (AREA)
  • Soft Magnetic Materials (AREA)

Claims (5)

  1. Eine magnetische Zusammensetzung mit Permeabilität, umfassend 5 - 30 Gewichtsteile eines Polyarylensulfidharzes und 70 - 95 Gewichtsteile eines Ferritpulvers auf der Grundlage von Ni-Zn-Cu, wobei dieser Anteil zusammen mit dem Anteil an Polyarylensulfidharz 100 Gewichtsteile ausmacht und der besagte Ferrit auf der Grundlage von Ni-Zn-Cu eine Zusammensetzung aufweist, welche der nachstehenden Formel (1) entspricht:

            NiaZnbCucFe2Od,

    in welcher a,b,c und d Zahlenwerte darstellen, welche die nachstehenden Beziehungen befriedigen: 0.10 ≤ a ≤0.70, 0.10 ≤ b ≤ 0.80, 0.10 ≤ c ≤ 0.35 und 3.97 ≤ d ≤ 4.20.
  2. Eine Zusammensetzung gemäß Anspruch 1, in welcher die Zahlenwerte für a bis d die nachstehenden Beziehungen befriedigen: 0.15 ≤ a ≤ 0.50, 0.40 ≤ b ≤ 0.75, 0.15 ≤ c ≤ 0.30 und 3.98 ≤ d ≤ 4.15.
  3. Eine Zusammensetzung gemäß Anspruch 1 oder 2, umfassend 7 - 25 Gewichtsteile des Polyarylensulfidharzes und 75 - 93 Gewichtsteile des Ni-Zn-Cu-Ferrits.
  4. Eine Zusammensetzung gemäß irgendeinem der Ansprüche 1 bis 3, welche außerdem 0.1 - 5 Gew% epoxidiertes Silikonöl enthält.
  5. Eine magnetische Komponente, welche ein geformtes Produkt aus einer magnetischen Zusammensetzung mit Permeabilität nach irgendeinem der vorstehenden Ansprüche umfaßt.
EP19930300361 1992-02-28 1993-01-20 Magnetisch permeabele Zusammensetzung und weichmagnetisches Teil Expired - Lifetime EP0558178B1 (de)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP78679/92 1992-02-28
JP7867992 1992-02-28
JP234267/92 1992-08-10
JP23426792A JP3283918B2 (ja) 1992-02-28 1992-08-10 高透磁性組成物

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EP0558178A2 EP0558178A2 (de) 1993-09-01
EP0558178A3 EP0558178A3 (en) 1993-12-08
EP0558178B1 true EP0558178B1 (de) 1997-03-26

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19908374B4 (de) * 1999-02-26 2004-11-18 Magnequench Gmbh Teilchenverbundwerkstoff aus einer thermoplastischen Kunststoffmatrix mit eingelagertem weichmagnetischen Material, Verfahren zur Herstellung eines solchen Verbundkörpers, sowie dessen Verwendung
CN100424505C (zh) * 2005-12-21 2008-10-08 宋京伟 塑料制品裂纹的涡流探伤方法

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10000523A1 (de) * 2000-01-08 2001-07-26 Inst Maschinen Antriebe Und El Ferrit-Compound-Material mit hoher elektromagnetischer Absorption im Frequenzbereich von 20 MHz bis 40 GHz
EP1502930A1 (de) * 2003-07-26 2005-02-02 ABC Taiwan Electronics Corp. Elektromagnetische Interferenzen unterdrückendes Epoxid Harz, dessen Herstellungsverfahren und Induktor mit EMI Unterdrückung
DE10356094A1 (de) * 2003-12-01 2005-07-14 Siemens Audiologische Technik Gmbh Induktionsspule mit Querempfindlichkeit für Hörgeräte
KR100803297B1 (ko) * 2006-08-09 2008-02-14 현대자동차주식회사 크래쉬 패드 장착용 그리핑 브래킷
CN109559865B (zh) * 2018-12-04 2020-10-30 安徽迪维乐普非晶器材有限公司 一种新型非晶磁芯粘结剂的制备方法
CN113972046A (zh) * 2021-10-26 2022-01-25 安徽华林磁电科技有限公司 一种用于制造汽车车载天线的磁芯及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS55103705A (en) * 1979-01-31 1980-08-08 Kanegafuchi Chem Ind Co Ltd Ferrite composition with high initial permeability and method of manufacturing its compact

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19908374B4 (de) * 1999-02-26 2004-11-18 Magnequench Gmbh Teilchenverbundwerkstoff aus einer thermoplastischen Kunststoffmatrix mit eingelagertem weichmagnetischen Material, Verfahren zur Herstellung eines solchen Verbundkörpers, sowie dessen Verwendung
CN100424505C (zh) * 2005-12-21 2008-10-08 宋京伟 塑料制品裂纹的涡流探伤方法

Also Published As

Publication number Publication date
EP0558178A2 (de) 1993-09-01
DE69309135D1 (de) 1997-04-30
DE69309135T2 (de) 1997-07-31
JP3283918B2 (ja) 2002-05-20
JPH0669023A (ja) 1994-03-11
EP0558178A3 (en) 1993-12-08

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