WO2011145508A1 - 封孔処理剤および封孔処理方法 - Google Patents
封孔処理剤および封孔処理方法 Download PDFInfo
- Publication number
- WO2011145508A1 WO2011145508A1 PCT/JP2011/060951 JP2011060951W WO2011145508A1 WO 2011145508 A1 WO2011145508 A1 WO 2011145508A1 JP 2011060951 W JP2011060951 W JP 2011060951W WO 2011145508 A1 WO2011145508 A1 WO 2011145508A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- gold
- sealing
- ppm
- sealing agent
- plating
- Prior art date
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/48—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 not containing phosphates, hexavalent chromium compounds, fluorides or complex fluorides, molybdates, tungstates, vanadates or oxalates
- C23C22/52—Treatment of copper or alloys based thereon
-
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
-
- 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
-
- 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
- H05K3/22—Secondary treatment of printed circuits
- H05K3/28—Applying non-metallic protective coatings
- H05K3/282—Applying non-metallic protective coatings for inhibiting the corrosion of the circuit, e.g. for preserving the solderability
Definitions
- the present invention relates to a sealing agent, particularly a sealing agent used for a member having gold or gold alloy plating formed on a base material having a surface made of copper or a copper alloy, and a sealing method using the same. About.
- copper or an alloy containing copper is used as a base material or wiring material for many electronic components (connectors, switches, printed circuit boards, etc.) because of its high conductivity.
- copper alloys used for this purpose include brass, phosphor bronze, titanium copper, and beryllium copper.
- Such a material having a surface made of copper or a copper alloy (hereinafter referred to as a “copper-based material”) has high internal conductivity, but the surface portion may have reduced conductivity due to oxidation or the like. .
- an electronic component made of a copper-based material is generally plated with gold or a metal (for example, Rh) having excellent corrosion resistance and conductivity as in the case of gold or an alloy of these metals (“gold plating” in the present invention).
- gold plating in the present invention.
- gold plating In order to perform gold plating, first, usually nickel plating is performed as a base plating, and then strike gold plating using an alkaline bath or an acidic bath is performed. On the gold plating thus formed, solder plating may be performed by spot plating (partial plating) as necessary.
- a member having a copper-based material as a base material and having a surface plated with gold is referred to as a gold-plated member.
- Patent Documents 1 and 2 a method is adopted in which a sealing agent is applied to the gold-plated member to cover the pinholes and suppress deterioration in corrosion resistance.
- a sealing agent techniques for using benzotriazole and mercaptobenzothiazole in combination have been proposed (Patent Documents 1 and 2).
- such a pore-sealing agent has a high pKa of 7 to 8 in mercaptobenzothiazole, it cannot be used unless the pH is substantially 9 or higher. Adjustment of the pH of such a sealing agent is generally performed with NaOH, KOH, alcohol amine, etc., and these components remain on the surface of the gold-plated member to form a copper base material. There is a concern that the material is corroded (for example, when NaOH remains, it reacts with the exposed metal Cu to form CuOH). If the sealing agent becomes a corrosion source, the meaning of sealing treatment is lost.
- the present invention has an object to provide a sealing agent that functions satisfactorily even when the liquid composition is neutral to acidic, and a sealing method for a gold-plated member using the sealing agent.
- the present invention provided to solve the above problems is a pore-sealing agent comprising an acidic or neutral aqueous liquid composition containing an inhibitor, wherein the inhibitor is benzotriazole and 2-carboxyl. It is a sealing agent containing methylthiobenzothiazole.
- the above sealing agent preferably has a pH of 3.0 or more.
- the above-mentioned sealing agent preferably has a benzotriazole content of 10 ppm to 1000 ppm and a 2-carboxymethylthiobenzothiazole content of 10 ppm to 1000 ppm.
- Another aspect of the present invention is a sealing treatment method for a member in which gold or gold alloy plating is performed on a base material having a surface made of copper or a copper alloy, and the above (1) to (3)
- a sealing treatment method comprising the step of subjecting the member to electrolytic treatment using the sealing treatment agent described in any one of the above.
- the alkaline corrosion material remains essentially on the surface of the gold plating member, a gold plating member having excellent corrosion resistance can be obtained stably.
- An electronic component made of such a gold-plated member does not easily increase contact resistance over a long period of time.
- Gold-plated member The member which the sealing agent which concerns on this invention makes object is a gold-plated member.
- Gold-plated members have inevitably have pinholes due to recent demands for reducing production costs. For this reason, the gold-plated member after the gold plating process exposes the copper-based material as the base material from this pinhole.
- the exposed copper-based material is referred to as an exposed copper-based material.
- the sealing treatment agent according to the present invention comprises benzotriazole as a component that suppresses corrosion by adsorbing to an exposed copper-based material in an inhibitor, that is, a gold-plated member.
- the content is not particularly limited as long as it functions as an inhibitor. If it is less than 10 ppm, depending on the area of the pin hole of the gold plating, it may be difficult to cover all of the exposed copper-based material. If it exceeds 1000 ppm, although it depends on the treatment conditions (particularly temperature) of the sealing agent and the content of other components, undissolved components are produced and there is a concern that the appearance of the product may be deteriorated. Considering productivity and the like, it is preferably 50 ppm or more and 500 ppm or less, and more preferably 70 ppm or more and 300 ppm or less.
- the sealing agent according to the present invention includes 2-carboxymethylthiobenzothiazole (hereinafter abbreviated as “ABT”) as an inhibitor. Since the pKa of ABT is as low as 4.62, it can be stably dissolved even if the sealing agent is neutral to acidic.
- ABT 2-carboxymethylthiobenzothiazole
- the content of ABT is not particularly limited as long as it functions as an inhibitor. If it is less than 10 ppm, depending on the area of the pin hole of the gold plating, it may be difficult to cover all of the exposed copper-based material. If it exceeds 1000 ppm, although it depends on the treatment conditions (particularly temperature) of the sealing agent and the content of other components, undissolved components are produced and there is a concern that the appearance of the product may be deteriorated. Considering productivity and the like, it is preferably 50 ppm or more and 500 ppm or less, and more preferably 70 ppm or more and 300 ppm or less. If it is 100 ppm or more, the function can be performed stably.
- the sealing agent according to the present invention contains the above-described inhibitor, the liquidity is neutral or acidic, that is, the pH is 7 or less.
- the preferred pH is 3 to 7. Within this range, the inhibitor can be stably adsorbed on the exposed copper-based material. A more preferred pH is 5-7.
- pH may be less than 3, when it is too low, there is a concern that the gold-plated member itself is affected by acid.
- the sealing agent according to the present invention may contain any other components as long as the inhibitor comprises the above components and the liquidity satisfies the above requirements.
- a surfactant and / or an amine compound may be contained.
- the surfactant contained in the emulsion component remaining on the surface of the gold-plated member will penetrate the corrosion-causing substance to the bottom of the pinhole unless sufficient cleaning is performed after the sealing treatment. There is. In this case, the causative substance reaches the exposed copper material and corrodes it. On the other hand, excessive cleaning may be a hindrance to the coating of the exposed copper-based material with benzotriazole and ABT. Therefore, when the sealing component according to the present invention contains an emulsion component, it is necessary to optimize the cleaning process after the sealing treatment.
- Sealing treatment method By bringing the above-mentioned sealing treatment agent into contact with the gold-plated member, the inhibitor is adsorbed on the exposed copper-based material in the gold-plated member, and the sealing treatment is performed.
- the contact method of this sealing agent is not particularly limited.
- a typical example is a dipping treatment in which a gold plating member is immersed in a bath of a sealing treatment agent.
- a spray treatment in which a fluid containing a sealing treatment agent is brought into contact with the gold plating member, and impregnation with a sealing treatment agent are impregnated. The process etc. which contact sponge etc. with a gold plating member are illustrated.
- Electrolytic treatment may be performed in which the sealing agent is an electrolytic solution and is brought into electrical contact with the gold plating member.
- the electrolytic pattern is arbitrary and may be direct current or alternating current, but direct current electrolysis is preferred. In the case of direct current electrolysis, anodic electrolysis using a gold-plated member as an anode is preferable from the viewpoint of increasing the inhibitor adsorption efficiency.
- the electrolysis conditions are not particularly limited, but the voltage is preferably 0.001 to 5.0 V, and more preferably 0.05 to 3.0 V.
- the current density is preferably 10 to 40 mA / dm 2 , more preferably 15 to 30 mA / dm 2, and particularly preferably 25 to 30 mA / dm 2 .
- the temperature of the sealing treatment liquid in the sealing treatment and the contact time between the gold plating member and the sealing treatment solution are determined according to the contact method, the presence / absence of electrolysis, the pinhole level of the gold plating member, the material / shape of the gold plating member, etc. It is set as appropriate in consideration. As an example, it is 5 seconds at 50 ° C.
- the gold-plated member after being brought into contact with the sealing treatment liquid is washed as necessary, usually with water.
- the content of the inhibitor is 1000 ppm or less, cleaning is not necessary because it does not become a contamination source of the gold-plated member without cleaning.
- the inhibitor on the surface of the gold-plated member is preferable because it can sufficiently interact with the exposed copper-based material.
- a substrate having the following material and shape was prepared.
- the above-mentioned base material was subjected to base plating and top plating in the following process to obtain a gold-plated member.
- Nickel base plating Plating bath Sulfamine bath Film thickness: 1 ⁇ m
- Gold top plating Plating bath Acid bath Film thickness: 0.1 ⁇ m
- Ni—Pd base plating Plating bath Ammonia bath Film thickness: 1 ⁇ m
- Au—Co top plating Plating bath Acid bath Film thickness: 0.1 ⁇ m
- Rh top plating Plating bath Acid bath Film thickness: 0.1 ⁇ m
- a sealing agent having the composition shown in Table 1 was prepared.
- composition of the emulsion in Table 1 was liquid paraffin: 0.04 mass% and nonionic surfactant: a trace amount.
- pH of each sealing agent was adjusted with KOH.
- Sealing treatment was performed under the conditions shown in Table 1 using the above gold-plated member and sealing agent.
- subjected before the numerical value in the column which shows the electrolysis condition of Table 1 means having performed the electrolysis process (all process time is 5 second) by making a gold plating member into an anode.
- the gold-plated member after the treatment is washed with water (submerged in a 25 ° C. water-washing bath for 10 seconds) if necessary and dried (air-dried at 60 ° C.-30% RH). Drying was performed.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- General Chemical & Material Sciences (AREA)
- Electroplating Methods And Accessories (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
- Preventing Corrosion Or Incrustation Of Metals (AREA)
Abstract
Description
その一方で、近年、電子機器にはコストダウンの要請が強く、上述のような金めっきおよび下地めっきにおいても、コストダウンのためにめっきの膜厚を薄くする対応が取られてきている。その結果、下地めっきや金めっきの膜厚が薄くなるにつれて、めっき皮膜上に指数関数的にピンホールが増えるという現象が生じてきている。
そのような封孔処理剤として、ベンゾトリアゾールとメルカプトベンゾチアゾールとを併用する技術が提案されている(特許文献1,2)。
上記の封孔処理剤は、ベンゾトリアゾールの含有量が10ppm以上1000ppm以下、かつ2-カルボキシメチルチオベンゾチアゾールの含有量が10ppm以上1000ppm以下であることが好ましい。
本発明に係る封孔処理剤が対象とする部材は、金めっき部材である。金めっき部材は、昨今の生産コストの低減の要請により、不可避的にピンホールを有するようになってきている。このため、金めっき処理後の金めっき部材は、このピンホールから基材である銅系材料が露出している。以下、この露出部分の銅系材料を露出銅系材料という。
(1)ベンゾトリアゾール
本発明に係る封孔処理剤は、インヒビター、すなわち金めっき部材における露出銅系材料に対して吸着することによりその腐食を抑制する成分として、ベンゾトリアゾールを備える。
本発明に係る封孔処理剤は、インヒビターとして2-カルボキシメチルチオベンゾチアゾール(以下、「ABT」と略記する。)を備える。ABTのpKaは4.62と低いため、封孔処理剤が中性から酸性であっても、安定的に溶解する。
本発明に係る封孔処理剤は、上記のインヒビターを含有するため、液性は中性または酸性、すなわちpHは7以下である。好ましいpHは3~7であり、この範囲であれば安定的にインヒビターを露出銅系材料に吸着させることができる。さらに好ましいpHは5~7である。なお、pHは3未満でもよいが、過度に低い場合には金めっき部材そのものが酸により冒されることが懸念される。
本発明に係る封孔処理剤は、インヒビターが上記の成分からなり、液性が上記の要件を満たす限り、他のいかなる成分を含有していてもよい。特許文献2に記載されるように、界面活性剤および/またはアミン化合物を含有していてもよい。
上記の封孔処理剤を金めっき部材に接触させることにより、金めっき部材における露出銅系材料にインヒビターが吸着し、封孔処理が行われる。
材質:リン青銅(C5210)
形状:幅20mm×長さ25mm×厚さ0.25mm
上記の基材に次の工程で下地めっきおよび上地めっきを施し、金めっき部材とした。
めっき浴:スルファミン浴
膜厚:1μm
(2)金上地めっき
めっき浴:酸性浴
膜厚:0.1μm
(3)Ni-Pd下地めっき
めっき浴:アンモニア浴
膜厚:1μm
(4)Au-Co上地めっき
めっき浴:酸性浴
膜厚:0.1μm
(5)Rh上地めっき
めっき浴:酸性浴
膜厚:0.1μm
表1に示される組成の封孔処理剤を作製した。
上記の金めっき部材および封孔処理剤を用い、表1に示される条件で封孔処理を行った。なお、表1の電解条件を示す欄における数値の前に付された「+」とは、金めっき部材をアノードとして電解処理(処理時間はいずれも5秒間)を行ったことを意味する。処理後の金めっき部材は必要に応じ水洗(25℃水洗浴に10秒間浸漬)を行い乾燥(60℃-30%RHにて風乾)させ、その他は封孔処理後、水洗することなく同様の乾燥を行った。
(1)溶解性
調製した封孔処理剤を目視で観察し、濁りや沈殿の有無について、次の基準で評価した。1と判定された封孔処理剤を合格とした。
1:透明であり、濁りも白濁もない、および
2:濁りまたは沈殿が確認される。
JIS C5444-01に準拠し、40℃-85%RH-SO210ppmの雰囲気に金めっき部材を96時間放置した。暴露試験後の金めっき部材を目視で観察し、次の判定基準で評価した。1および2と判定された金めっき部材を合格とした。
2:評価対象面に腐食生成物の痕跡が認められる、
3:評価対象面に腐食生成物が点在する、
4:点状の腐食生成物が評価対象面の半分以上の領域において認められる、および
5:点状の腐食生成物が評価対象面の全領域において認められる。
Claims (4)
- インヒビターを含有する酸性または中性の水系液状組成物からなる封孔処理剤であって、
インヒビターがベンゾトリアゾールおよび2-カルボキシメチルチオベンゾチアゾールを含む封孔処理剤。 - pHが3.0以上である、請求項1記載の封孔処理剤。
- ベンゾトリアゾールの含有量が10ppm以上1000ppm以下、かつ2-カルボキシメチルチオベンゾチアゾールの含有量が10ppm以上1000ppm以下である、請求項1記載の封孔処理剤。
- 銅または銅合金からなる表面を有する基材上に金または金合金めっきが施された部材の封孔処理方法であって、請求項1から3のいずれかに記載される封孔処理剤を用いて前記部材を電解処理するステップを備える封孔処理方法。
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
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CN2011800244797A CN102906312A (zh) | 2010-05-17 | 2011-05-12 | 封孔处理剂以及封孔处理方法 |
KR1020127027696A KR20130069591A (ko) | 2010-05-17 | 2011-05-12 | 봉공처리제 및 봉공처리 방법 |
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JP2010-113545 | 2010-05-17 | ||
JP2010113545A JP5740727B2 (ja) | 2010-05-17 | 2010-05-17 | 封孔処理剤および封孔処理方法 |
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WO2011145508A1 true WO2011145508A1 (ja) | 2011-11-24 |
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JP (1) | JP5740727B2 (ja) |
KR (1) | KR20130069591A (ja) |
CN (1) | CN102906312A (ja) |
TW (1) | TW201207154A (ja) |
WO (1) | WO2011145508A1 (ja) |
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KR101688756B1 (ko) * | 2013-07-24 | 2016-12-21 | 제이엑스금속주식회사 | 전자 부품 및 그 제조 방법 |
CN103606688B (zh) * | 2013-12-02 | 2015-08-19 | 新源动力股份有限公司 | 一种燃料电池金属双极板板表面改性层的无微孔处理方法 |
CN108977868A (zh) * | 2017-05-31 | 2018-12-11 | 比亚迪股份有限公司 | 一种7系铝合金封孔方法 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05311488A (ja) * | 1991-12-25 | 1993-11-22 | Nikko Kinzoku Kk | 金めっき材の封孔処理方法 |
JPH05311489A (ja) * | 1991-12-25 | 1993-11-22 | Nikko Kinzoku Kk | 金めっき材の封孔処理方法 |
JPH07258894A (ja) * | 1994-03-24 | 1995-10-09 | Nikko Kinzoku Kk | 金めっき材の封孔処理方法 |
JPH07258887A (ja) * | 1994-03-24 | 1995-10-09 | Nikko Kinzoku Kk | 金めっき材の封孔処理方法 |
-
2010
- 2010-05-17 JP JP2010113545A patent/JP5740727B2/ja active Active
-
2011
- 2011-05-12 WO PCT/JP2011/060951 patent/WO2011145508A1/ja active Application Filing
- 2011-05-12 CN CN2011800244797A patent/CN102906312A/zh active Pending
- 2011-05-12 KR KR1020127027696A patent/KR20130069591A/ko not_active Application Discontinuation
- 2011-05-16 TW TW100117016A patent/TW201207154A/zh unknown
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH05311488A (ja) * | 1991-12-25 | 1993-11-22 | Nikko Kinzoku Kk | 金めっき材の封孔処理方法 |
JPH05311489A (ja) * | 1991-12-25 | 1993-11-22 | Nikko Kinzoku Kk | 金めっき材の封孔処理方法 |
JPH07258894A (ja) * | 1994-03-24 | 1995-10-09 | Nikko Kinzoku Kk | 金めっき材の封孔処理方法 |
JPH07258887A (ja) * | 1994-03-24 | 1995-10-09 | Nikko Kinzoku Kk | 金めっき材の封孔処理方法 |
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CN102906312A (zh) | 2013-01-30 |
TW201207154A (en) | 2012-02-16 |
KR20130069591A (ko) | 2013-06-26 |
JP2011241428A (ja) | 2011-12-01 |
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