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WO2003040432A1 - Pellicules de traitement de surface a base de nickel presentant une excellente adherence thermoresistante a une resine - Google Patents

Pellicules de traitement de surface a base de nickel presentant une excellente adherence thermoresistante a une resine Download PDF

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Publication number
WO2003040432A1
WO2003040432A1 PCT/JP2002/010825 JP0210825W WO03040432A1 WO 2003040432 A1 WO2003040432 A1 WO 2003040432A1 JP 0210825 W JP0210825 W JP 0210825W WO 03040432 A1 WO03040432 A1 WO 03040432A1
Authority
WO
WIPO (PCT)
Prior art keywords
nickel
surface treatment
based surface
treatment film
phosphorus
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2002/010825
Other languages
English (en)
Japanese (ja)
Inventor
Jun Kawaguchi
Hiroki Hayashi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nihon Parkerizing Co Ltd
Original Assignee
Nihon Parkerizing Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nihon Parkerizing Co Ltd filed Critical Nihon Parkerizing Co Ltd
Priority to KR10-2004-7005110A priority Critical patent/KR20040054703A/ko
Publication of WO2003040432A1 publication Critical patent/WO2003040432A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • 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
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating

Definitions

  • the present invention relates to a nickel-based surface treatment film formed on a surface of a metal substrate in order to provide a very strong adhesive force when bonding the substrate, particularly a metal substrate to a resin. . More specifically, the present invention relates to a nickel-based surface treatment film that can maintain excellent adhesive strength even when the metal-resin joined body is placed in a high temperature environment of 200 ° C. to 300 ° C. . Background art
  • thermosetting resins such as epoxy resin and polyimide resin or thermoplastic resin with high molding temperature used in such fields
  • the entire part is kept at 200 ° C to 300 ° C. Exposure to temperatures as high as 0 ° C is required.
  • soldering is used when mounting active components such as semiconductor devices and passive components such as LCRs.However, lead soldering cannot be used due to recent environmental issues, so the solder reflow temperature is becoming increasingly high. It is becoming.
  • a typical example is a copper oxide treatment called “black dyeing”.
  • the former involves contacting with a phosphoric acid aqueous solution in which a heavy metal having a very low solubility product with tertiary phosphoric acid, such as zinc, is dissolved.
  • a strong alkaline aqueous solution containing an appropriate oxidizing agent and boiled.
  • Japanese Patent Application Laid-Open No. 9-209916 and Japanese Patent Application Laid-Open No. 9-172125 the adhesion is improved by performing a chromate treatment on the surface of the metal substrate. I'm making it.
  • Japanese Patent Application Laid-Open No. 2000-183032 discloses a method of forming a special chromium compound layer having a large number of fine flake-like projections on the surface by using an electrolytic method. I have.
  • the present invention has been made to solve the above problems of the prior art, and an object of the present invention is to provide a method for manufacturing a metal substrate and a resin without using a substance causing environmental pollution such as hexavalent chromium.
  • An object of the present invention is to provide a surface-treated film having excellent adhesiveness with a coating, particularly at high temperatures.
  • the present inventors have conducted intensive studies to solve the above problems of the prior art, and as a result, have focused on nickel metal which is generally excellent in heat resistance and stability over time and nickel oxide formed on its surface.
  • the introduction of a third element into them has led to the discovery of a new nickel-based surface treatment film that is extremely excellent in adhesion to resins.
  • the present invention relates to a nickel-based surface treatment film having a two-layer structure formed on a target material, wherein nickel and phosphorus are provided in a lower layer in contact with the surface of the material, and nickel, oxygen and Provided is a nickel-based surface treatment film having excellent heat-resistant adhesion to a resin characterized by containing phosphorus.
  • boron can be used as an element instead of phosphorus contained in the nickel-based surface treatment film of the present invention.
  • phosphorus and boron may coexist.
  • the content ratio of phosphorus and / or boron to nickel in the nickel-based surface treatment film is more preferably such that the content ratio of the upper layer is larger than that of the lower layer, that is, the following relationship is satisfied.
  • the upper layer of the nickel-based surface treatment film preferably has a columnar structure, and more preferably has a fine gap between the columns of the columnar structure.
  • the nickel-based surface treatment film of the present invention is preferably formed on copper or a copper alloy.
  • the nickel-based surface treatment film of the present invention preferably has a gray, gray-black or black appearance.
  • the nickel-based surface treatment film of the present invention has a two-layer structure in which metal nickel and phosphorus, Z or boron are disposed on the lower layer in contact with the surface of the material, that is, an upper layer further includes a layer containing oxygen.
  • the target material is particularly limited as long as the metallic nickel can be formed with sufficient adhesion to the target material. Not determined. However, in the field of electronic and electrical components, in particular, heat resistance between copper or a copper alloy and a resin is often required, so copper will be mainly described as a target material.
  • FIG. 1 shows a cross-sectional scanning electron microscope (SEM) image of the nickel-based surface treatment film of the present invention
  • FIG. 2 shows a surface SEM image thereof.
  • Reference numeral 1 in FIG. 1 indicates an upper columnar structure (including nickel, oxygen, and phosphorus) of the nickel-based surface treatment film of the present invention
  • reference numeral 2 in FIG. indicates a copper substrate.
  • FIG. 2 shows a surface SEM image (X1000) of the nickel-based surface treatment film of the present invention.
  • the upper layer of the surface treatment film of the present invention has a columnar structure, and fine gaps are observed between the columns (comb structure). Therefore, when this is observed from the surface (Fig. 2), although it is irregular, it is observed as extremely fine irregularities on the order of several 10 O nm to several 10 O nm, and it is a huge, very effective when bonding with resin. A substantial surface area can be obtained.
  • the nickel in the upper layer is in an oxidized state and its thickness is about 50 O nm, but the oxide formed on the mere metallic nickel is thinner than this, and the present invention Is not formed.
  • Such a form can be obtained by introducing the third element introduced in the present invention, that is, phosphorus and / or boron. Empirically, it is preferred that these third elements range from 2% to 50% by weight. If the content is less than 2% by weight, such a form cannot be obtained, and if the content exceeds 50% by weight, formation of a nickel film having such a composition becomes gradually difficult as the content increases. That is, it is economically disadvantageous.
  • the height of the upper columnar structure of the nickel-based surface treatment film of the present invention is preferably in the range of 50 to 300 orchids. If it is less than 5 O nm, fine irregularities on the surface will not be sufficiently formed, and if it exceeds 300 O nm, the irregularities will be coarse.
  • the thickness of the lower metallic nickel layer is not particularly limited. However, in order to sufficiently cover the surface of the target material without exposing it, it is preferable that the length is 0.5 m or more. Good. Also, since unnecessary thick films are economically disadvantageous, an upper limit of 5 / m would be sufficient.
  • the appearance of the nickel-based surface treatment film of the present invention is gray, gray-black to black. This seems to be due to the columnar structure with gaps absorbing visible light as shown in FIGS. 1 and 2, which is particularly preferable in the field of electronic and electrical components.
  • the adhesive surface surface treated film surface of the present invention
  • the resin from the copper wiring pattern side, if it shows a black color, the contrast with the pattern becomes clear, and the inspection of the pattern becomes optical. This is advantageous when it is performed on a regular basis.
  • the nickel-based surface treatment film of the present invention can be formed by forming a metal nickel layer on a target material by various methods and then oxidizing the surface.
  • a physical method such as PVD can be used to form the nickel metal layer
  • a wet surface treatment method such as an electroplating method or an electroless plating method is superior in mass productivity.
  • a plating method for co-depositing the third element will be described.
  • hypophosphorous acid or phosphorous acid may be further added to a well-known pet bath.
  • electroless plating a commercially available type using hypophosphorous acid as a reducing agent may be used.
  • an electroless plating bath using a boron-containing reducing agent such as DMAB (dimethylamporane) may be used.
  • DMAB dimethylamporane
  • phosphorus and boron can be co-deposited at the same time.
  • carbon, nitrogen, sulfur and zinc can be co-deposited in addition to phosphorus and / or boron.
  • these methods work in a more favorable direction. For example, it becomes possible by introducing the additives described below.
  • a zinc compound such as zinc carbonate, zinc oxide, zinc chloride, and zinc sulfate may be added.
  • the copper surface may be cleaned and then directly electroplated.
  • a bath using an acid as a reducing agent copper cannot be applied as it is because it has no catalytic activity for hypophosphorous acid.
  • a small amount of palladium plating may be applied as a pretreatment by plating with palladium or the like, and electric nickel plating may be performed thinly (about submicron) as strike plating, followed by electroless nickel plating.
  • a columnar texture layer is formed on the surface.
  • an appropriate oxidizing agent such as nitric acid, permanganic acid, ferric ion or hydrogen peroxide may be added to a base of phosphoric acid, sulfuric acid, or hydrochloric acid.
  • the anode may be electrolyzed in the base aqueous acid solution.
  • the third element such as phosphorus introduced into the nickel-based surface treatment film of the present invention generally makes the crystal of metallic nickel finer, It is thought that this results in the formation of the characteristic columnar texture layer of the present invention as a result of miniaturizing the distribution state of the anode and the power source of the local battery formed by the oxidation treatment. It is.
  • the content ratio of the third element such as phosphorus to nickel is larger in the upper layer than in the lower layer. In other words, this suggests that nickel is more preferentially dissolved by the oxidation treatment, and that phosphorus and the like remain.
  • the oxygen contained in the columnar structure in the upper layer is introduced along with such an oxidation treatment, and the content of the oxygen increases in the surface layer and decreases toward the lower layer.
  • the resin to be bonded to the nickel-based surface treatment film of the present invention is not particularly limited. However, in the field of electronic and electrical components, epoxy resins and polyimide resins are frequently used and are the main object of the present invention. From the viewpoint of adhesion, a resin having a lower glass transition temperature can be softened at a high temperature and can reduce the difference in coefficient of thermal expansion between a metal and a resin. However, such a resin has a lower glass transition temperature because the heat resistance of the resin itself is reduced. Empirically, the nickel-based surface treatment film of the present invention is particularly effective for such a resin having a high glass transition temperature.
  • FIG. 1 shows a cross-sectional SEM image (X3000) of the nickel-based surface treatment film of the present invention.
  • FIG. 2 shows a surface SEM image (X1000) of the nickel-based surface treatment film of the present invention.
  • the phosphorus content becomes 9% by weight. It was immersed in the electroless plating bath prepared as described above to form a 5 ⁇ m electroless Ni-P alloy layer. Furthermore, this was immersed in an oxidation treatment solution in which 75% phosphoric acid and 677.5% nitric acid were mixed at a volume ratio of 90:10 at 40 ° C for 3 minutes. A nickel layer in which phosphorus was concentrated was formed on the surface of the alloy layer. The surface after the oxidation treatment had a beautiful black appearance with no gloss.
  • FIG. 1 and FIG. 2 are for the first embodiment.
  • a polyimide adhesive (“Neoflex double-sided adhesive sheet” manufactured by Mitsui Chemicals, Inc.) was adhered to the copper plate having been subjected to the nickel-based surface treatment to a thickness of 50 m.
  • a copper foil of ⁇ m was arranged and press-bonded under the conditions of a pressing pressure of 50 kg / cm 2 , a heating temperature of 250 ° C, and a heating time of 2 hours.
  • This sample was cut into 5 mm squares, left in a heated and moist environment at 85 ° C and 85% RH for 24 hours to promote deterioration, and floated in a molten solder bath at 270 ° C. As a result, no longer than 300 seconds was observed.
  • the details of the plating bath and the processing conditions used in Example 1 are described below.
  • the strike nickel plating is performed in a hot water bath, that is, in a reagent bath (nickel sulfate: 330 gZL, nickel chloride: 45 gZL, boric acid: 38 g / L).
  • the test was performed at a bath temperature of 50 ° C. with a nickel plate as an anode and a cathode current density of 5 A / dm 2 .
  • Electroless plating bath Sodium hypophosphite: 0.15 mol ZL, ammonium sulfate: 0.5 mol / L, trisodium citrate: 0.2 mol / L, nickel sulfate: 0
  • Each of the reagents was dissolved in deionized water to a concentration of 0.1 m1 / L, and the pH was adjusted to 9 by adding caustic soda.
  • the electroless Ni-P alloy plating bath adjusted in this way was heated to 90 ° C to reduce the electroless plating. Then, the Ni-P alloy layer was formed.
  • Example 2 The same test as in Example 1 was performed using the following electroless Ni-B alloy plating bath instead of the electroless Ni-P alloy plating bath.
  • nickel chloride 0.126 mol ZL
  • DMA B 0.06 mol / L
  • malonic acid 0.378 mol / L
  • TIN ⁇ 3 The reagents were respectively dissolved in deionized water so as to have a concentration of 70 mg / L, and the pH was adjusted to 6 with aqueous ammonia.
  • the electroless Ni-B alloy plating bath thus adjusted was heated to 70 ° C and used.
  • the boron content in the obtained Ni_B alloy film was 2.8% by weight.
  • Example 2 This was subjected to an oxidation treatment in the same manner as in Example 1 to give a gray-black appearance. Similarly, after bonding to a copper foil via polyimide adhesive and placing it in a heated and humid environment, the heat resistance of the solder was examined, and blistering occurred in the copper foil in 240 seconds.
  • Example phosphorous acid 1 0 g / L was added to the Wa Tsu preparative bath for scan trike plated used in 1, temperature 4 0 ° C, current density: cathode electrolysis performed at 5 A / dm 2 conditions, A Ni-P alloy film having a phosphorus content of 10% by weight was formed at 5 ⁇ m.
  • a beautiful black appearance was exhibited.
  • a sample similar to that of Example 1 was prepared and evaluated, and no abnormality was found in the solder heat resistance after 300 seconds.
  • Example 1 Using the Ni strike plating bath used in Example 1 as it was, a 3 ⁇ m nickel plating was formed, and the same oxidation treatment as in Example 1 was performed. However, although the gloss was slightly lost, it had an almost white appearance.
  • the same sample as in Example 1 was prepared and evaluated. As a result, the adhesive layer was peeled off within 2 to 3 seconds, and the adhesive layer was peeled off.
  • the nickel-based surface treatment film of the present invention when bonding a metal substrate and a resin, it is possible to impart excellent wet resistance and high-temperature adhesion at high temperatures. High reliability can be provided. Further, as an incidental effect, the surface treatment film of the present invention has a dull black appearance, so that a good contrast can be obtained when optically inspecting electronic and electrical components. To improve the detection accuracy.

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  • Chemical & Material Sciences (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Organic Chemistry (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemically Coating (AREA)
  • Chemical Treatment Of Metals (AREA)
  • ing And Chemical Polishing (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une pellicule de traitement de surface à base de nickel présentant une excellente adhérence à une résine et pourvue d'une structure bicouche formée sur un matériau cible. La pellicule décrite dans la présente invention présente la caractéristique de contenir du nickel et du phosphore dans la couche inférieure en contact avec le matériau et du nickel, de l'oxygène et du phosphore dans la couche supérieure la recouvrant; ou encore, du nickel et du bore dans la couche inférieure, et du nickel, de l'oxygène et du bore dans la couche supérieure la recouvrant; ou encore, du nickel, du phosphore et du bore dans la couche inférieure et du nickel, de l'oxygène, du phosphore et du bore dans la couche supérieure la recouvrant.
PCT/JP2002/010825 2001-11-08 2002-10-18 Pellicules de traitement de surface a base de nickel presentant une excellente adherence thermoresistante a une resine Ceased WO2003040432A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR10-2004-7005110A KR20040054703A (ko) 2001-11-08 2002-10-18 수지와의 내열 접착성이 우수한 니켈계 표면 처리 피막

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2001-342880 2001-11-08
JP2001342880A JP4027642B2 (ja) 2001-11-08 2001-11-08 樹脂との耐熱接着性に優れたニッケル系表面処理皮膜

Publications (1)

Publication Number Publication Date
WO2003040432A1 true WO2003040432A1 (fr) 2003-05-15

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PCT/JP2002/010825 Ceased WO2003040432A1 (fr) 2001-11-08 2002-10-18 Pellicules de traitement de surface a base de nickel presentant une excellente adherence thermoresistante a une resine

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Country Link
JP (1) JP4027642B2 (fr)
KR (1) KR20040054703A (fr)
CN (1) CN1568380A (fr)
TW (1) TW574420B (fr)
WO (1) WO2003040432A1 (fr)

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005320905A (ja) * 2004-05-10 2005-11-17 Boc Edwards Kk 真空ポンプ
JP4705776B2 (ja) * 2004-12-17 2011-06-22 日本カニゼン株式会社 リン酸塩被膜を有する無電解ニッケルめっき膜の形成方法およびその形成膜
JP4809037B2 (ja) * 2005-10-27 2011-11-02 日本カニゼン株式会社 黒色めっき膜およびその形成方法、めっき膜を有する物品
JP4539869B2 (ja) * 2006-03-10 2010-09-08 セイコーエプソン株式会社 配線基板の製造方法
JP4975344B2 (ja) * 2006-03-15 2012-07-11 大和電機工業株式会社 めっき方法
WO2008152974A1 (fr) * 2007-06-15 2008-12-18 Nippon Mining & Metals Co., Ltd. Procédé de fabrication d'un substrat de résine polyimide revêtu de métal ayant une excellente propriété de résistance au vieillissement thermique
JP5385625B2 (ja) * 2008-12-08 2014-01-08 株式会社Ｊｃｕ ２層フレキシブル銅張積層基材及びその製造方法
JP5846655B2 (ja) * 2014-02-05 2016-01-20 Ｓｈマテリアル株式会社 半導体装置の製造方法
US9708693B2 (en) 2014-06-03 2017-07-18 Macdermid Acumen, Inc. High phosphorus electroless nickel
US20170181292A1 (en) 2015-12-16 2017-06-22 Rohm And Haas Electronic Materials Llc Method for forming organic coating on nickel surface

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62222419A (ja) * 1986-03-24 1987-09-30 Seiko Epson Corp 磁気記憶体

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS62222419A (ja) * 1986-03-24 1987-09-30 Seiko Epson Corp 磁気記憶体

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KR20040054703A (ko) 2004-06-25
JP2003147549A (ja) 2003-05-21
JP4027642B2 (ja) 2007-12-26
CN1568380A (zh) 2005-01-19
TW574420B (en) 2004-02-01

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