JP2007531820A - Method for producing blackened surface-treated copper foil for electromagnetic wave shielding - Google Patents
Method for producing blackened surface-treated copper foil for electromagnetic wave shielding Download PDFInfo
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- JP2007531820A JP2007531820A JP2007506086A JP2007506086A JP2007531820A JP 2007531820 A JP2007531820 A JP 2007531820A JP 2007506086 A JP2007506086 A JP 2007506086A JP 2007506086 A JP2007506086 A JP 2007506086A JP 2007531820 A JP2007531820 A JP 2007531820A
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- copper foil
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000011889 copper foil Substances 0.000 title claims abstract description 73
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 22
- 238000007747 plating Methods 0.000 claims abstract description 68
- 239000010949 copper Substances 0.000 claims abstract description 21
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- 238000009713 electroplating Methods 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 9
- 239000011888 foil Substances 0.000 claims abstract description 3
- 239000002245 particle Substances 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 9
- 229910052751 metal Inorganic materials 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 238000010030 laminating Methods 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 3
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- 238000000151 deposition Methods 0.000 claims description 2
- 229910052725 zinc Inorganic materials 0.000 claims 1
- 230000002950 deficient Effects 0.000 abstract description 2
- 238000005868 electrolysis reaction Methods 0.000 abstract 1
- 238000002310 reflectometry Methods 0.000 abstract 1
- 239000003792 electrolyte Substances 0.000 description 12
- 230000002265 prevention Effects 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- 230000003746 surface roughness Effects 0.000 description 7
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 5
- 229940044175 cobalt sulfate Drugs 0.000 description 5
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000007853 buffer solution Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000004381 surface treatment Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000007788 roughening Methods 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 3
- 229910020599 Co 3 O 4 Inorganic materials 0.000 description 2
- 229910018916 CoOOH Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 239000011573 trace mineral Substances 0.000 description 2
- 235000013619 trace mineral Nutrition 0.000 description 2
- 206010040844 Skin exfoliation Diseases 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 235000019219 chocolate Nutrition 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000010410 dusting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 230000005670 electromagnetic radiation Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- -1 which is the cathode Substances 0.000 description 1
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/34—Anodisation of metals or alloys not provided for in groups C25D11/04 - C25D11/32
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/38—Chromatising
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
-
- 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
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0084—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising a single continuous metallic layer on an electrically insulating supporting structure, e.g. metal foil, film, plating coating, electro-deposition, vapour-deposition
-
- 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
- H05K1/00—Printed circuits
- H05K1/02—Details
- H05K1/0213—Electrical arrangements not otherwise provided for
- H05K1/0216—Reduction of cross-talk, noise or electromagnetic interference
- H05K1/0218—Reduction of cross-talk, noise or electromagnetic interference by printed shielding conductors, ground planes or power plane
-
- 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
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0355—Metal foils
-
- 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
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
- H05K2203/0703—Plating
- H05K2203/0723—Electroplating, e.g. finish plating
-
- 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
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0094—Shielding materials being light-transmitting, e.g. transparent, translucent
- H05K9/0096—Shielding materials being light-transmitting, e.g. transparent, translucent for television displays, e.g. plasma display panel
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Electromagnetism (AREA)
- Shielding Devices Or Components To Electric Or Magnetic Fields (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
本発明は、反射率が低く外観に斑が無く、残渣が殆ど無い均一な外観を有する電磁波遮蔽用黒化表面処理銅箔の製造方法及びその銅箔に関するものであって、電解メッキ浴に陰極として銅箔を配置し、前記銅薄箔の表面に黒化メッキ層を形成させることにより電磁波遮蔽用表面処理銅箔を製造する方法において、Co及び陰極における水素発生を抑制する酸化剤を含む電解メッキ浴を使用して前記銅箔表面に黒色のCo酸化物メッキ層を形成させることを特徴とする。
前記方法によって製造された表面処理銅箔は、反射率が低い黒色の外観を有するので、PDP表示画面の輝度を低下させないという長所がある。
さらに、本発明による表面処理銅箔は黒色の外観を有しながらも、外観に斑及び残渣が殆どない均一な外観を有するので、これを利用して製造された電磁波遮蔽用複合材料の不良率が顕著に低くなり、前記複合材料を使用して製造されたPDP表示画面の外観が優秀になる効果がある。
【選択図】 なしThe present invention relates to a method for producing a blackened surface-treated copper foil for electromagnetic wave shielding having a uniform appearance with low reflectivity, no appearance and almost no residue, and to the copper foil, which is used as a cathode in an electrolytic plating bath. In the method of manufacturing a surface-treated copper foil for shielding electromagnetic waves by forming a copper foil as a surface and forming a blackened plating layer on the surface of the copper thin foil, electrolysis containing an oxidizing agent that suppresses hydrogen generation at Co and the cathode A black Co oxide plating layer is formed on the surface of the copper foil using a plating bath.
Since the surface-treated copper foil manufactured by the above method has a black appearance with a low reflectance, there is an advantage that the brightness of the PDP display screen is not lowered.
Furthermore, since the surface-treated copper foil according to the present invention has a black appearance but has a uniform appearance with few spots and residues on the appearance, the defective rate of the electromagnetic shielding composite material produced using this Is significantly reduced, and the appearance of the PDP display screen manufactured using the composite material is excellent.
[Selection figure] None
Description
この発明は、反射率が低く、外観に斑が無く、残渣が殆どない均一な外観を有する電磁波遮蔽用黒化表面処理銅箔の製造方法とその表面処理銅箔に関する。 The present invention relates to a method for producing a blackened surface-treated copper foil for shielding electromagnetic waves and having a uniform appearance with low reflectance, no appearance and no residue, and the surface-treated copper foil.
プラズマデイスプレーパネル(PDP)は画像表示面から人体に有害な強力な電磁波を放射するため電磁波遮蔽体を設置して電磁波の放射を防止する必要がある。電磁波遮蔽体としては、銅回路を、例えば、PET等のような絶縁性透明基材に積層させて製造した複合材料が使用されているが、前記複合材料は電磁波放射防止能力と光線透過性が優れた長所がある。具体的に、前記複合材料は、所定の表面粗度を有する銅箔(copper foil)を前記透明基材に積層し、エッチングによって不必要な銅箔を除去して望む銅回路を形成することにより製造される。
銅回路の線幅とパターンは必要とする電磁波放射能力と光線の透過性を根拠に選択される。
ところが、前記銅回路が外観を反射すると表示画面の輝度(brightness)を低下させる問題がある。従って、電磁波遮蔽用銅箔としては、黒色に近いように表面処理され低い反射率を有する銅箔が選好されている。
しかしながら、表面処理された銅箔の表面が黒色に近いほど、その外観に斑が発生しやすくなるか、表面から粉末が付いて出る等残渣が発生しやすくなる傾向がある。銅箔表面の斑はPDPの画質を劣らせ、残渣はエッチングされ透明基材が表れるべき部分に落ちて光線の透過性を劣らせるので、PDP解像度が全般的に低下される短所がある。
このため、従来では銅箔の表面を完全に黒色にしないで、黒色に近いチョコレート色や暗い金属色を有するように表面処理する方向に主に研究が行われている。しかし、前記のような方法で製造された銅箔の表面は完全な黒色でないので、電磁波遮蔽用銅箔としての反射率の改善には限界があった。
Since a plasma display panel (PDP) emits a strong electromagnetic wave harmful to the human body from an image display surface, it is necessary to install an electromagnetic wave shield to prevent the emission of the electromagnetic wave. As the electromagnetic wave shielding body, a composite material produced by laminating a copper circuit on an insulating transparent base material such as PET is used. However, the composite material has an electromagnetic radiation prevention ability and light transmittance. There are excellent advantages. Specifically, the composite material is formed by laminating a copper foil having a predetermined surface roughness on the transparent substrate and removing unnecessary copper foil by etching to form a desired copper circuit. Manufactured.
The line width and pattern of the copper circuit are selected based on the required electromagnetic wave radiation ability and light transmittance.
However, when the copper circuit reflects the appearance, there is a problem that the brightness of the display screen is lowered. Therefore, as an electromagnetic shielding copper foil, a copper foil that is surface-treated so as to be close to black and has a low reflectance is preferred.
However, the closer the surface of the surface-treated copper foil is to black, the easier it is for spots to appear on its appearance or for residues to be generated, such as powder coming out of the surface. The spots on the surface of the copper foil deteriorate the image quality of the PDP, and the residue is etched and falls on the portion where the transparent substrate should appear, resulting in inferior light transmittance. Therefore, the PDP resolution is generally lowered.
For this reason, research has been mainly conducted in the direction of surface treatment so that the surface of the copper foil is not completely black but has a chocolate color or dark metal color close to black. However, since the surface of the copper foil manufactured by the method as described above is not completely black, there is a limit in improving the reflectance as an electromagnetic shielding copper foil.
本発明は、黒色の外観を有するので反射率が低い電磁波遮蔽用黒化表面処理銅箔及びその製造方法を提供することを目的とする。
また、本発明は、黒色の外観を有しながらも、斑及び残渣が殆ど無い均一な外観を有する電磁波遮蔽用黒化表面処理銅箔及びその製造方法を提供することを目的とする。
また、本発明の更に他の目的は、剥離強度(peel strength)が優秀な電磁波遮蔽用黒化表面処理銅箔及びその製造方法を提供することにある。
An object of the present invention is to provide a blackened surface-treated copper foil for electromagnetic wave shielding and a method for producing the same, which has a black appearance and has a low reflectance.
Another object of the present invention is to provide a blackened surface-treated copper foil for electromagnetic wave shielding and a method for producing the same having a uniform appearance with almost no spots and residues while having a black appearance.
Still another object of the present invention is to provide an electromagnetic shielding blackened surface-treated copper foil having excellent peel strength and a method for producing the same.
前記目的を達成するための、本発明の電磁波遮蔽用黒化表面処理銅箔の製造方法は、電解メッキ浴に陰極として銅箔を配置し、前記銅薄箔の表面に黒化メッキ層を形成させることにより電磁波遮蔽用表面処理銅箔を製造する方法において、Co及び陰極における水素発生を抑制する酸化剤を含む電解メッキ浴を使用して前記銅箔表面に黒色のCo酸化物メッキ層を形成させることを特徴とする。
前記酸化剤は、KNO3、NH4NO3、HNO3、NaNO3、NH4ClO3、KClO3、NaClO3及びKMO4から成る群から選択される少なくとも1種であってもよい
前記酸化剤の濃度は、1〜40g/lであることが好ましい。
更に、前記電解メッキ浴にNi及びFeから成る群から選択される少なくとも1種の金属イオンが含まれることが好ましい。
前記電解メッキ浴中Co、Ni及びFeの金属成分総濃度が1〜80g/lであることが好ましい。
一方、前記Co酸化物メッキ層を形成する前に、更に、銅箔の表面に微細銅粒子層を析出形成させる段階を含むことが好ましい。
更に、前記Co酸化物メッキ層の表面に電解クロメート層を形成する段階を含むことが好ましい。
更に、メッキ層が形成された表面の裏面にZn又はZn合金で構成されたメッキ被膜層を形成する段階を含むことが好ましい。
In order to achieve the above object, the method for producing a blackened surface-treated copper foil for electromagnetic wave shielding according to the present invention comprises disposing a copper foil as a cathode in an electrolytic plating bath and forming a blackened plating layer on the surface of the copper thin foil. Forming a black Co oxide plating layer on the surface of the copper foil using an electrolytic plating bath containing an oxidizing agent that suppresses hydrogen generation at Co and the cathode. It is characterized by making it.
The oxidizing agent may be at least one selected from the group consisting of KNO 3 , NH 4 NO 3 , HNO 3 , NaNO 3 , NH 4 ClO 3 , KClO 3 , NaClO 3 and KMO 4. The concentration of is preferably 1 to 40 g / l.
Furthermore, it is preferable that the electrolytic plating bath contains at least one metal ion selected from the group consisting of Ni and Fe.
The total concentration of Co, Ni and Fe metal components in the electrolytic plating bath is preferably 1 to 80 g / l.
On the other hand, before forming the Co oxide plating layer, it is preferable to further include a step of forming a fine copper particle layer on the surface of the copper foil.
Furthermore, it is preferable to include a step of forming an electrolytic chromate layer on the surface of the Co oxide plating layer.
Furthermore, it is preferable to include a step of forming a plating film layer made of Zn or a Zn alloy on the back surface of the surface on which the plating layer is formed.
以下、本発明を詳しく説明する。
本発明の対象となる電磁波遮蔽用銅箔は広幅生産が可能な電解銅箔であって、銅箔の厚さは1〜35μmであり、好ましくは6〜18μmである。表面粗度(Rz:DIN)は0.1〜2.0μmであり、好ましくは、0.5〜1.5μmである。表面粗度が0.1μmより小さい場合、透明基材との接着性が十分でないようになり、電磁波遮蔽体の信頼性が低下され、2.0μmより大きい場合、エッチングによって回路を形成した後に、銅箔が接着されている透明基材の表面の凹凸が大きくなり、これに因り表示画面の曇りが大きくなるので好ましくない。
銅箔の黒化表面処理は、黒色を誘発する金属が含まれた電解メッキ浴において銅箔を陰極に配置し、前記陰極の銅箔表面上に前記金属メッキ層を析出させることにより行われる。黒色を誘発すると知られた金属としては、Cu、Cr、Co等があるが、Cuは完全な黒色を導出できるが、追後銅箔回路パターン形成時銅箔回路側に浸透して回路パターンを損傷させる問題があり、Crは銅箔回路形成時のエッチング性に問題を起こすため、本発明に適用することが難しい。従って、製品損傷防止、製造工程上の問題点等を考慮すると、Coが最も適当な金属である。
Hereinafter, the present invention will be described in detail.
The copper foil for electromagnetic wave shielding which is the object of the present invention is an electrolytic copper foil capable of wide production, and the thickness of the copper foil is 1 to 35 μm, preferably 6 to 18 μm. The surface roughness (Rz: DIN) is 0.1 to 2.0 μm, preferably 0.5 to 1.5 μm. If the surface roughness is less than 0.1 μm, the adhesion with the transparent substrate is not sufficient, the reliability of the electromagnetic wave shield is reduced, and if greater than 2.0 μm, after forming the circuit by etching, Unevenness on the surface of the transparent base material to which the copper foil is bonded increases, which is not preferable because cloudiness of the display screen increases.
The blackened surface treatment of the copper foil is performed by placing the copper foil on the cathode in an electrolytic plating bath containing a metal that induces blackness, and depositing the metal plating layer on the copper foil surface of the cathode. There are Cu, Cr, Co, etc. that are known to induce black color, but Cu can derive a complete black color, but it penetrates into the copper foil circuit side at the time of copper foil circuit pattern formation later, and the circuit pattern is There is a problem of damage, and Cr causes a problem in etching property when forming a copper foil circuit, so that it is difficult to apply to the present invention. Accordingly, Co is the most suitable metal in consideration of product damage prevention, manufacturing process problems, and the like.
Coメッキ層が黒色を呈するためには、限界電流密度辺りで電解メッキして、銅箔表面上にCo3O4、CoOOH、CoOのような酸化物の形態で析出されなければならない。しかし、前述のとおり、このような黒化メッキ層は表面に斑が生じるか、表面から粉末が付いて出る残渣発生の問題がある。黒化メッキ層に斑や残渣が発生する主な理由は、陰極から発生する水素の発生態様が銅箔表面に従って均一でないからであると思われる。即ち、メッキ過程で陰極である銅箔表面ではCoが酸化され析出されるとともに、水素(H2)が発生するようになるが、このような水素が発生する部分のメッキ厚さは残り部分の厚さと微細な差異を見せる。このため、全体の銅箔表面を眺望した時、周囲部に比べて水素が発生しないか水素発生態様が異なる部分は斑に見えるようになる。また、前記のようなメッキの不均一性に因り銅箔の製造過程中に表面から部分的にメッキ粒子が脱落される等残渣が発生するようになる。
従って、メッキ層が形成された銅箔の表面粗度が全体的には電磁波遮蔽用銅箔に使用可能な範囲内にあるとしても、前記のように不均一な外観を有する銅箔は製品不良を招くようになる問題がある。
In order for the Co plating layer to exhibit a black color, it must be electroplated around the limit current density and deposited on the copper foil surface in the form of oxides such as Co 3 O 4 , CoOOH, and CoO. However, as described above, such a blackened plating layer has a problem of generation of residue on the surface, or generation of a residue attached with powder from the surface. It seems that the main reason why spots and residues are generated in the blackened plating layer is that the generation mode of hydrogen generated from the cathode is not uniform according to the copper foil surface. That is, during the plating process, Co is oxidized and deposited on the surface of the copper foil, which is the cathode, and hydrogen (H 2 ) is generated. Shows small differences in thickness. For this reason, when the whole copper foil surface is looked at, the part which hydrogen does not generate | occur | produce compared with the surrounding part, or a hydrogen generating aspect differs will become visible. Further, due to the non-uniformity of plating as described above, residues such as plating particles are partially dropped from the surface during the manufacturing process of the copper foil.
Therefore, even if the surface roughness of the copper foil on which the plating layer is formed is within the range that can be used for the copper foil for electromagnetic wave shielding as a whole, the copper foil having a non-uniform appearance as described above is a defective product. There is a problem that will invite.
本発明は、Coを含む全体メッキ浴に水素発生抑制剤としての酸化剤を添加して陰極における水素発生を抑制することにより、陰極における水素発生態様を均一化することにより、均一な外観の黒化メッキ層を有する黒化表面処理銅箔を得ることができることにその特徴がある。前記酸化剤は水素の発生を抑制するので水素発生で生成され得る斑を防止するとともに、電解液中のCoを酸化させる。
このような酸化剤物質としては、KNO3、NH4NO3、HNO3、NaNO3、NH4ClO3、KClO3、NaClO3、KMO4等があり、この中一つ以上を電解メッキ浴に所定量含ませると均一な外観の黒化表面処理銅箔を得ることができる。
具体的なメッキ過程は、例えば、Ir電極を陽極に使用し、陰極を銅箔にしてメッキを行うことによりなり、銅箔表面に形成されたCo黒化メッキ層はCo3O4、CoOOH、CoOのような酸化物の形態になっている。電解メッキ浴に含まれるCoの濃度は1〜80g/lから選ぶことができるが、最も効率良く黒化メッキ層が形成できる濃度は20〜60g/lである。酸化剤の濃度は、1〜40g/lが適当であり、最も適切な濃度は1〜15g/lである。酸化剤の濃度が1g/lを下回ると、水素発生抑制効果が殆ど無くなるばかりでなく、黒色の酸化メッキ層を得ることができないし、40g/lを超えるとCoが度を過ぎて酸化され却ってメッキ層の残渣発生(粉落)が更に甚だしくなるからである。
The present invention adds a oxidant as a hydrogen generation inhibitor to the entire plating bath containing Co to suppress hydrogen generation at the cathode, thereby uniformizing the hydrogen generation mode at the cathode, thereby achieving a uniform black appearance. It is characterized in that a blackened surface-treated copper foil having a plated layer can be obtained. The oxidant suppresses the generation of hydrogen, thereby preventing spots that can be generated by hydrogen generation and oxidizing Co in the electrolyte.
Examples of such an oxidant material include KNO 3 , NH 4 NO 3 , HNO 3 , NaNO 3 , NH 4 ClO 3 , KClO 3 , NaClO 3 , KMO 4, etc., and one or more of them are used as an electrolytic plating bath. When a predetermined amount is included, a blackened surface-treated copper foil having a uniform appearance can be obtained.
The specific plating process includes, for example, plating using an Ir electrode as an anode and a cathode as a copper foil, and the Co blackening plating layer formed on the surface of the copper foil includes Co 3 O 4 , CoOOH, It is in the form of an oxide such as CoO. The concentration of Co contained in the electrolytic plating bath can be selected from 1 to 80 g / l, but the concentration at which the blackened plating layer can be formed most efficiently is 20 to 60 g / l. The concentration of the oxidizing agent is suitably 1 to 40 g / l, and the most suitable concentration is 1 to 15 g / l. When the concentration of the oxidizing agent is less than 1 g / l, not only the effect of suppressing hydrogen generation is almost lost, but also a black oxide plating layer cannot be obtained, and when it exceeds 40 g / l, Co is excessively oxidized and rejected. This is because the generation of residue (powder) in the plating layer becomes more serious.
工業的に経済的なメッキ浴の電流密度は0.1〜60A/dm2であり、特に5〜25A/dm2の電流密度が好ましい。電流密度が0.1A/dm2未満であれば望む黒色のメッキ層を得ることができないし、60A/dm2以上では黒色メッキ層と銅箔との間の接着強度が劣り剥離現像が発生するからである。
メッキ浴のpHは2.5〜5.5範囲であるのが好ましく、特に、3.0〜4.0範囲の pHが好ましい。pHが2.5未満である場合、メッキされた黒化層が溶け出るようになり、pHが5.5以上である場合には黒化表面処理されない反対側面が変色される問題がある。前記pHは硫酸とKOHを添加して調節することができる。
また、メッキ時間は1〜20秒範囲で可能であるが、電流密度、電解液濃度等を考慮して前記範囲以外も可能である。
一方、銅箔の剥離強度を向上させ透明基材との接着性を向上させるためにCo外の他の金属成分も電解浴に含ませることができる。銅箔の特性を害せず、剥離強度を向上させる元素としては、Ni、Feが適当である。前記金属成分とCoとを合わせた電解液中の金属成分濃度も1〜80g/l範囲にあるものがメッキ効率性の側面で好ましい。
Current density industrially economical plating baths are 0.1~60A / dm 2, in particular current density of 5~25A / dm 2 is preferred. If the current density is less than 0.1 A / dm 2 , the desired black plating layer cannot be obtained, and if it is 60 A / dm 2 or more, the adhesive strength between the black plating layer and the copper foil is poor and peeling development occurs. Because.
The pH of the plating bath is preferably in the range of 2.5 to 5.5, and particularly preferably in the range of 3.0 to 4.0. When the pH is less than 2.5, the plated blackened layer starts to melt, and when the pH is 5.5 or more, there is a problem that the opposite side surface that is not treated with the blackened surface is discolored. The pH can be adjusted by adding sulfuric acid and KOH.
The plating time can be in the range of 1 to 20 seconds, but other than the above range is also possible in consideration of the current density, the electrolyte concentration, and the like.
On the other hand, other metal components other than Co can be included in the electrolytic bath in order to improve the peel strength of the copper foil and improve the adhesion to the transparent substrate. Ni and Fe are suitable as elements that improve the peel strength without impairing the properties of the copper foil. The metal component concentration in the electrolyte solution combining the metal component and Co is preferably in the range of 1 to 80 g / l from the viewpoint of plating efficiency.
また、反射率を小さくし、透明基材との接着性を向上させるために黒化メッキを行う前に、銅箔の表面に微細銅粒子層を析出付着させることができる。析出された銅粒子はアンカー(anchor)役割をして透明基材に銅箔を積層させる時、剥離強度を上昇させて接着性を向上させ、外光を乱反射させ反射率を劣らせる。
微細銅粒子層の形成は、プリント配線板用銅箔に使用される粗化処理を利用して行うことができる。粗化処理は硫酸銅メッキ浴で行うことが普通であり、粗化処理時の銅粒子の付着量は0.1〜10g/m2範囲が好ましく、更に好ましい範囲は0.5〜8g/m2である。
微細銅粒子層形成、黒化メッキ層形成の全ての表面処理工程に亘って表面粗度は前述のとおり、Rz(DIN規格)で0.1〜2.0μm以内に保持されるべきである。
上述の微細銅粒子層形成条件、黒化メッキ条件の範囲内で表面処理する場合、表面粗度を前記範囲以内に保持することができる。
一方、本発明の銅箔に電解クロメート(chromate)処理等の防錆処理をすることができる。また、黒化メッキを行わない側の表面にZn又はZn合金からなるメッキ被膜を形成すると、電磁波遮蔽体製造のための加熱工程で加熱変色を防ぐことができる。
In addition, a fine copper particle layer can be deposited on the surface of the copper foil before performing blackening plating in order to reduce the reflectance and improve the adhesion to the transparent substrate. The deposited copper particles act as an anchor, and when the copper foil is laminated on the transparent substrate, the peel strength is increased to improve the adhesion, and the external light is irregularly reflected to deteriorate the reflectance.
Formation of a fine copper particle layer can be performed using the roughening process used for the copper foil for printed wiring boards. The roughening treatment is usually performed in a copper sulfate plating bath, and the amount of copper particles deposited during the roughening treatment is preferably in the range of 0.1 to 10 g / m 2 , and more preferably in the range of 0.5 to 8 g / m. 2 .
As described above, the surface roughness should be kept within 0.1 to 2.0 μm in Rz (DIN standard) over the entire surface treatment process of forming the fine copper particle layer and blackening plating layer.
When the surface treatment is performed within the range of the above-described fine copper particle layer forming conditions and blackening plating conditions, the surface roughness can be maintained within the above ranges.
On the other hand, the copper foil of the present invention can be subjected to rust prevention treatment such as electrolytic chromate treatment. Further, when a plating film made of Zn or a Zn alloy is formed on the surface not subjected to blackening plating, heating discoloration can be prevented in the heating process for manufacturing the electromagnetic wave shielding body.
以下、本発明を実施例により具体的に説明する。しかし、以下の実施例は専ら本発明を説明するためのものであって、本発明の要旨に基づいて本発明の範囲が以下の実施例に限定されないことは当業者にとって自明である。 Hereinafter, the present invention will be specifically described by way of examples. However, the following examples are only for explaining the present invention, and it is obvious to those skilled in the art that the scope of the present invention is not limited to the following examples based on the gist of the present invention.
実施例1
表面粗度(Rz)が2μm以下、厚さ10μmである電解銅箔を100g/l硫酸において、5秒間浸漬し酸洗処理後純水で洗浄した後に、通常的にshiny面と称する銅箔表面に下の条件で黒化メッキ処理を行った。黒化メッキ処理後、黒化処理面にCr防錆処理を行った。電解浴組成;Co金属イオン濃度40g/l(Coは硫酸コバルト形態でメッキ浴に添加される)、KNO3濃度2g/l、緩衝液(H3BO3)濃度30g/l
電解液pH;3.5、
電解液の温度:25℃、電流密度;10A/dm2、メッキ時間;4秒。
Example 1
An electrolytic copper foil having a surface roughness (Rz) of 2 μm or less and a thickness of 10 μm is immersed in 100 g / l sulfuric acid for 5 seconds, pickled, washed with pure water, and then generally referred to as a shiny surface. The blackening plating process was performed under the following conditions. After the blackening plating treatment, the blackening treatment surface was subjected to Cr rust prevention treatment. Electrolytic bath composition: Co metal ion concentration 40 g / l (Co is added to the plating bath in the form of cobalt sulfate), KNO 3 concentration 2 g / l, buffer solution (H 3 BO 3 ) concentration 30 g / l
Electrolyte pH: 3.5,
Electrolyte temperature: 25 ° C., current density: 10 A / dm 2 , plating time: 4 seconds.
実施例2
実施例1と同一な条件で銅箔の表面を前処理した後、通常的にshiny面と称する銅箔表面に下の条件で黒化メッキ処理を実施した。黒化メッキ処理後、黒化処理面にCr防錆処理を実施した。電解浴組成;Co金属イオン濃度40g/l(Coは硫酸コバルト形態でメッキ浴に添加される)、KNO3濃度2g/l、緩衝液(H3BO3)濃度30g/l
電解液 pH;3.5,
電解液の温度;25℃、電流密度;20A/dm2、メッキ時間;2.5秒
Example 2
After pretreating the surface of the copper foil under the same conditions as in Example 1, the blackening plating treatment was carried out on the surface of the copper foil, which is usually referred to as a shiny surface, under the following conditions. After the blackening plating treatment, the blackening treatment surface was subjected to Cr rust prevention treatment. Electrolytic bath composition: Co metal ion concentration 40 g / l (Co is added to the plating bath in the form of cobalt sulfate), KNO 3 concentration 2 g / l, buffer solution (H 3 BO 3 ) concentration 30 g / l
Electrolyte pH: 3.5,
Electrolyte temperature: 25 ° C., current density: 20 A / dm 2 , plating time: 2.5 seconds
実施例3
銅付着量を1.5g/m2にして微細銅粒子層を形成し、実施例2と同一な条件で黒化メッキ処理及び防錆処理をした。
Example 3
A fine copper particle layer was formed with a copper adhesion amount of 1.5 g / m 2 , and blackening plating treatment and rust prevention treatment were performed under the same conditions as in Example 2.
実施例4
実施例1と同一な条件で銅箔の表面を前処理した後、通常的にshiny面と称する銅箔表面に下の条件で黒化メッキ処理を実施した。黒化メッキ処理後、黒化処理面にCr防錆処理を実施した。電解浴組成;Co金属イオン濃度35g/l(Coは硫酸コバルト形態でメッキ浴に添加される)、Ni金属イオン濃度(硫酸ニッケル形態でメッキ浴に添加される)8g/l、KNO3濃度2g/l、緩衝液(H3BO3)濃度30g/l
電解液pH;3.5,
電解液の温度;25℃、電流密度;10A/dm2、メッキ時間;4秒。
Example 4
After pre-treating the surface of the copper foil under the same conditions as in Example 1, a blackening plating process was performed on the copper foil surface, usually referred to as a shiny surface, under the following conditions. After the blackening plating treatment, the blackening treatment surface was subjected to Cr rust prevention treatment. Electrolytic bath composition: Co metal ion concentration 35 g / l (Co is added to the plating bath in the form of cobalt sulfate), Ni metal ion concentration (added to the plating bath in the form of nickel sulfate) 8 g / l, KNO 3 concentration 2 g / L, buffer (H 3 BO 3 ) concentration 30 g / l
Electrolyte pH: 3.5,
Electrolyte temperature: 25 ° C., current density: 10 A / dm 2 , plating time: 4 seconds.
実施例5
Niイオンの代わりにFeイオンを8g/l添加したことの外には実施例4と同一な条件で黒化メッキ処理及び防錆処理を行った。
Example 5
A blackening plating treatment and a rust prevention treatment were performed under the same conditions as in Example 4 except that 8 g / l of Fe ions were added instead of Ni ions.
比較例1
前記実施例と同一な条件で電解銅箔表面を前処理した後、下記の条件で黒化処理メッキを実施した。黒化メッキ処理後、黒化処理面にCr防錆処理を実施した。電解浴組成;Co金属イオン濃度40g/l(Coは硫酸コバルト形態でメッキ浴に添加される)、緩衝液(H3BO3)濃度30g/l、その他微量元素等。
電解液pH;3.5、
電解液の温度;25℃、電流密度;20A/dm2、メッキ時間;2.5秒。
Comparative Example 1
After pre-treating the surface of the electrolytic copper foil under the same conditions as in the above example, blackening plating was performed under the following conditions. After the blackening plating treatment, the blackening treatment surface was subjected to Cr rust prevention treatment. Electrolytic bath composition: Co metal ion concentration 40 g / l (Co is added to the plating bath in the form of cobalt sulfate), buffer solution (H 3 BO 3 ) concentration 30 g / l, and other trace elements.
Electrolyte pH: 3.5,
Electrolyte temperature: 25 ° C., current density: 20 A / dm 2 , plating time: 2.5 seconds.
比較例2
前記実施例と同一な条件で電解銅箔表面を前処理した後、下記の条件で黒化処理メッキを実施した。黒化メッキ処理後、黒化処理面にCr防錆処理を実施した。電解浴組成;Co金属イオン濃度30g/l(Coは硫酸コバルト形態でメッキ浴に添加される)、Ni金属イオン濃度(硫酸ニッケル形態でメッキ浴に添加される)8g/l、緩衝液(H3BO3)濃度30g/l、その他微量元素等。
電解液pH;3.5、
電解液の温度;25℃、電流密度;20A/dm2、メッキ時間;4秒。
Comparative Example 2
After pre-treating the surface of the electrolytic copper foil under the same conditions as in the above example, blackening plating was performed under the following conditions. After the blackening plating treatment, the blackening treatment surface was subjected to Cr rust prevention treatment. Electrolytic bath composition: Co metal ion concentration 30 g / l (Co is added to the plating bath in the form of cobalt sulfate), Ni metal ion concentration (added to the plating bath in the form of nickel sulfate) 8 g / l, buffer solution (H 3 BO 3 ) Concentration 30 g / l, other trace elements, etc.
Electrolyte pH: 3.5,
Electrolyte temperature: 25 ° C., current density: 20 A / dm 2 , plating time: 4 seconds.
下記表1は前記実施例及び比較例による表面処理銅箔の斑発生有無、擦ることによる残渣発生(粉落)有無、剥離強度を測定した結果を表したものである。
表1に示すように、電解メッキ浴に酸化剤が含まれなかった比較例1及び2は表面上に斑と残渣が発生している。しかし、本発明の実施例は斑及び残渣が発生しなかったことを分かる。
また、黒化メッキ処理前に微細銅粒子層を形成させた実施例3は、微細銅粒子層を形成しない各対応される条件の実施例2に比べて剥離強度が上昇したことを分かる。また、黒化メッキ層にNiとFeとがそれぞれ追加的に含まれた実施例4と実施例5とが前記成分等が含まれない実施例1及び2より更に高い剥離強度を有することを分かる。
前記のような均一な外観を有する本発明の表面処理銅箔をPETのような絶縁性透明基材に積層して製造される複合材料で電磁波遮蔽体を製造すると、表示画面の解像図が優秀なプラズマデイスプレーパネルを製造することができ、その不良率も顕著に低くすることができるようになる。
As shown in Table 1, in Comparative Examples 1 and 2 in which the oxidant was not contained in the electrolytic plating bath, spots and residues were generated on the surface. However, it can be seen that the examples of the present invention did not produce spots and residues.
In addition, it can be seen that Example 3 in which the fine copper particle layer was formed before the blackening plating treatment increased the peel strength as compared with Example 2 in each of the corresponding conditions in which the fine copper particle layer was not formed. Further, it can be seen that Example 4 and Example 5 in which Ni and Fe are additionally included in the blackened plating layer have higher peel strength than Examples 1 and 2 in which the above components and the like are not included. .
When an electromagnetic wave shielding body is manufactured with a composite material manufactured by laminating the surface-treated copper foil of the present invention having a uniform appearance as described above on an insulating transparent substrate such as PET, a resolution diagram of a display screen is obtained. An excellent plasma display panel can be manufactured, and the defect rate can be significantly reduced.
以上で説明したとおり、本発明の製造方法によって製造された表面処理銅箔は、反射率が低い黒色の外観を有するので、PDP表示画面の輝度を低下させないという長所がある。
さらに、本発明による表面処理銅箔は、黒色の外観を有しながらも、斑及び残渣が殆どない均一な外観を有するので、これを利用して製造された電磁波遮蔽体用複合材料の不良率が顕著に低くなり、前記複合材料を使用して製造されたPDP表示画面の外観が優秀になる効果がある。
As described above, since the surface-treated copper foil manufactured by the manufacturing method of the present invention has a black appearance with low reflectance, there is an advantage that the luminance of the PDP display screen is not lowered.
Furthermore, since the surface-treated copper foil according to the present invention has a black appearance but a uniform appearance with almost no spots and residues, the defect rate of the composite material for electromagnetic wave shields produced using this Is significantly reduced, and the appearance of the PDP display screen manufactured using the composite material is excellent.
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Cited By (3)
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---|---|---|---|---|
JPS5993984A (en) * | 1982-11-17 | 1984-05-30 | Fuji Electric Co Ltd | Water encapsulated pump device |
WO2013168528A1 (en) * | 2012-05-09 | 2013-11-14 | 奥野製薬工業株式会社 | BLACKENING TREATMENT SOLUTION FOR BLACK Cr-Co ALLOY PLATING FILM |
JP2017505385A (en) * | 2013-12-30 | 2017-02-16 | イルジン マテリアルズ カンパニー リミテッドIljin Materials Co., Ltd. | Copper foil, electrical parts including the same, and battery |
Families Citing this family (2)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2007332418A (en) * | 2006-06-15 | 2007-12-27 | Fukuda Metal Foil & Powder Co Ltd | Surface treated copper foil |
WO2017130869A1 (en) * | 2016-01-29 | 2017-08-03 | 住友金属鉱山株式会社 | Blackening plating solution and method for manufacturing conductive substrate |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
TW230290B (en) * | 1991-11-15 | 1994-09-11 | Nikko Guruder Foreer Kk | |
JP3222002B2 (en) * | 1993-12-27 | 2001-10-22 | 株式会社日鉱マテリアルズ | Copper foil for printed circuit and manufacturing method thereof |
US6497806B1 (en) * | 2000-04-25 | 2002-12-24 | Nippon Denkai, Ltd. | Method of producing a roughening-treated copper foil |
JP3374127B2 (en) * | 2000-11-27 | 2003-02-04 | 古河サーキットフォイル株式会社 | Metal foil, laminated board for circuit boards using it |
-
2004
- 2004-04-02 KR KR1020040023096A patent/KR100604964B1/en active IP Right Grant
-
2005
- 2005-03-31 WO PCT/KR2005/000952 patent/WO2006004299A1/en active Application Filing
- 2005-03-31 JP JP2007506086A patent/JP4326019B2/en active Active
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5993984A (en) * | 1982-11-17 | 1984-05-30 | Fuji Electric Co Ltd | Water encapsulated pump device |
WO2013168528A1 (en) * | 2012-05-09 | 2013-11-14 | 奥野製薬工業株式会社 | BLACKENING TREATMENT SOLUTION FOR BLACK Cr-Co ALLOY PLATING FILM |
US9920416B2 (en) | 2012-05-09 | 2018-03-20 | Okuno Chemical Industries Co., Ltd. | Blackening treatment solution for black Cr—Co alloy plating film |
JP2017505385A (en) * | 2013-12-30 | 2017-02-16 | イルジン マテリアルズ カンパニー リミテッドIljin Materials Co., Ltd. | Copper foil, electrical parts including the same, and battery |
Also Published As
Publication number | Publication date |
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WO2006004299A1 (en) | 2006-01-12 |
KR100604964B1 (en) | 2006-07-26 |
KR20050097831A (en) | 2005-10-10 |
JP4326019B2 (en) | 2009-09-02 |
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