WO2010024099A1 - Liquide de placage d'or dur - Google Patents

Liquide de placage d'or dur Download PDF

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Publication number
WO2010024099A1
WO2010024099A1 PCT/JP2009/063931 JP2009063931W WO2010024099A1 WO 2010024099 A1 WO2010024099 A1 WO 2010024099A1 JP 2009063931 W JP2009063931 W JP 2009063931W WO 2010024099 A1 WO2010024099 A1 WO 2010024099A1
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WO
WIPO (PCT)
Prior art keywords
plating
acid
hard gold
plating solution
gold plating
Prior art date
Application number
PCT/JP2009/063931
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English (en)
Japanese (ja)
Inventor
理恵 菊池
新吾 渡邊
Original Assignee
日本エレクトロプレイテイング・エンジニヤース株式会社
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Filing date
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Application filed by 日本エレクトロプレイテイング・エンジニヤース株式会社 filed Critical 日本エレクトロプレイテイング・エンジニヤース株式会社
Priority to US13/055,038 priority Critical patent/US20110127168A1/en
Priority to CN200980133847.4A priority patent/CN102131962B/zh
Priority to KR1020117004292A priority patent/KR101275886B1/ko
Publication of WO2010024099A1 publication Critical patent/WO2010024099A1/fr

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Classifications

    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
    • 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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials

Definitions

  • the present invention relates to a hard gold plating technique, and more particularly to a hard gold plating solution for performing hard gold plating and hard gold alloy plating suitable for forming contact materials for electronic devices such as connectors.
  • the hard gold plating in the present application refers to either hard gold plating or hard gold alloy plating, and a plating solution for performing hard gold plating is referred to as a hard gold plating solution.
  • gold plating has been used for electronic devices and electronic parts for reasons such as excellent electrical properties and corrosion resistance of gold, and has been widely used for applications that protect the surface of connection terminals such as electronic parts.
  • Gold plating is used as a surface treatment for electronic components such as electrode terminals of semiconductor elements, leads formed on resin films, and connectors for connecting electronic devices.
  • Patent Document 1 Patent Document 2
  • copper or copper alloy is generally used as the material.
  • nickel plating is applied to the surface of copper or copper alloy
  • Hard gold plating is applied to the surface of the nickel plating.
  • the gold-cobalt alloy plating solution in this prior art deposits a gold alloy plating film only at a desired location on an electronic component such as a connector, and suppresses the deposition at an unnecessary location, thereby producing a hard gold system. Plating can be performed.
  • the present invention has been made in the background as described above, and an object of the present invention is to provide a hard gold plating solution that can be selectively subjected to partial plating and is suitable for electronic parts such as connectors.
  • the present invention is characterized in that a hard gold plating solution containing a soluble gold salt or gold complex, a conductive salt, and a chelating agent contains an aromatic compound having one or more nitro groups. Selective partial plating treatment by hard gold plating when an aromatic compound having one or more nitro groups is contained in a hard gold plating solution containing a soluble gold salt or gold complex, a conductive salt, and a chelating agent. Is possible.
  • the hard gold plating solution according to the present invention preferably contains at least one metal salt of a cobalt salt, a nickel salt, and a silver salt. With these metal salts, the plating film can be made into a gold alloy and the film can be hardened.
  • the hard gold plating solution according to the present invention may contain a polyethyleneimine organic additive instead of a metal salt such as a cobalt salt, a nickel salt, or a silver salt.
  • a polyethyleneimine organic additive such as a cobalt salt, a nickel salt, or a silver salt.
  • the polyethyleneimine those having various molecular weights can be used, and any structure such as a linear structure or a branched structure can be used.
  • this organic additive the plating film is hardened in the same manner as the addition of the metal salt.
  • a soluble gold salt or a gold complex can be used as the gold ion source.
  • potassium potassium cyanide, potassium potassium cyanide, ammonium gold cyanide, potassium chloride gold, potassium chloride chloride, sodium chloride chloride, sodium chloride chloride, thiosulfuric acid Gold potassium, sodium gold thiosulfate, potassium gold sulfite, sodium gold sulfite, and combinations of two or more thereof can be used.
  • Particularly preferable is potassium gold cyanide.
  • the gold concentration in the hard gold plating solution of the present invention is preferably in the range of 1 g / L to 20 g / L in terms of gold. If it is less than 1 g / L, it becomes difficult to process at a high current density, and high-speed plating tends to be difficult. If the amount exceeds 20 g / L, the amount of gold taken out from the plating solution (a slight amount of plating solution is attached to the connector to be plated, etc., and is taken out to the next process. For example, several drops of plating solution are taken out. This is because the higher the gold concentration, the greater the amount of gold lost from the plating solution), which increases the manufacturing cost.
  • a more preferable gold salt concentration is 2 g / L to 16 g / L in terms of gold.
  • a soluble cobalt compound can be used as the cobalt source.
  • cobalt sulfate, cobalt chloride, cobalt carbonate, cobalt sulfamate, cobalt gluconate, and combinations of two or more thereof can be used.
  • it is an inorganic cobalt salt, especially cobalt sulfate.
  • the concentration of this cobalt salt in the plating solution is preferably in the range of 0.05 g / L to 10 g / L in terms of cobalt. If it is less than 0.05 g / L, the amount of eutectoid of cobalt in the plating film decreases, and it becomes difficult to improve the hardening of the hard gold plating. Moreover, when it exceeds 10 g / L, it will become the tendency for stability of a plating solution to fall. A more preferable cobalt salt concentration is 0.1 g / L to 3 g / L in terms of cobalt.
  • a soluble nickel compound can be used as the nickel source.
  • nickel sulfate, nickel chloride, nickel carbonate, nickel sulfamate, nickel gluconate, and combinations of two or more thereof can be used.
  • nickel sulfate is particularly preferred.
  • the concentration of this nickel salt in the plating solution is preferably in the range of 0.05 g / L to 30 g / L in terms of nickel. If it is less than 0.05 g / L, the amount of eutectoid of nickel in the plating film is lowered, and the hard gold plating tends to be hardened. Moreover, when it exceeds 30 g / L, it will become the tendency for stability of a plating solution to fall. A more preferable nickel concentration is 0.1 g / L to 20 g / L in terms of nickel.
  • the hard gold plating solution according to the present invention contains a silver salt
  • a soluble silver compound can be used as the silver source.
  • silver cyanide and its salt, silver chloride, silver carbonate, silver nitrate and combinations of two or more thereof can be used. Particularly preferred is silver cyanide.
  • the concentration of this silver salt in the plating solution is preferably in the range of 0.05 g / L to 100 g / L in terms of silver. If it is less than 0.05 g / L, the amount of silver eutectoid in the plating film decreases, and it becomes difficult to improve the hardening of the hard gold plating. Moreover, when it exceeds 100 g / L, it will become the tendency for stability of a plating solution to fall. A more preferable silver concentration is 0.1 g / L to 50 g / L in terms of silver.
  • the concentration of the organic additive in the plating solution is preferably 0.1 g / L to 300 g / L. If it is less than 0.1 g / L, the hardening of the hard gold plating tends to be impossible to improve, and if it exceeds 300 g / L, the stability of the plating solution tends to be lowered. A more preferred concentration is 1 g / L to 200 g / L.
  • an organic compound or an inorganic compound can be used as the conductive salt in the hard gold plating solution of the present invention.
  • the organic compound include citric acid, tartaric acid, adipic acid, malic acid, succinic acid, lactic acid,
  • carboxylic acids such as benzoic acid and salts thereof, and compounds containing phosphonic acid groups and salts thereof.
  • Inorganic compounds include alkali metal salts such as phosphoric acid, sulfurous acid, nitrous acid, nitric acid, sulfuric acid, ammonium salts, and cyanide. Examples include alkali and ammonium cyanide. A combination of two or more of these can also be used.
  • the concentration of the conductive salt in the plating solution is preferably in the range of 0.1 g / L to 300 g / L. A more preferred concentration is 1 g / L to 200 g / L.
  • a carboxyl group-containing compound such as citric acid, potassium citrate, sodium citrate, tartaric acid, oxalic acid and succinic acid, a phosphonic acid group or a salt thereof is contained in the molecule.
  • the phosphonic acid group containing compound etc. which have can be used.
  • the phosphonic acid group-containing compound for example, aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, diethylenetriaminepentamethylenephosphonic acid and the like have a plurality of phosphonic acid groups in the molecule.
  • nitrogen compounds such as ammonia, ethylenediamine, and triethanolamine, can also be used with a carboxyl group-containing compound as an auxiliary chelating agent.
  • a chelating agent can also use 2 or more types of combinations.
  • the concentration of this chelating agent in the plating solution is preferably in the range of 0.1 g / L to 300 g / L. When the amount is less than 0.1 g / L, the chelating action tends not to work, and when the amount exceeds 300 g / L, the chelating solution tends not to be dissolved. A more preferred concentration is 1 g / L to 200 g / L.
  • the aromatic compound having one or more nitro groups in the hard gold plating solution of the present invention dinitrobenzoic acid, nitrobenzoic acid, and nitrobenzenesulfonic acid can be used.
  • dinitrobenzoic acid, nitrobenzoic acid, and nitrobenzenesulfonic acid can be used.
  • these aromatic compounds are added to the plating solution, selective partial plating treatment is possible, and precipitation of hard gold plating on unnecessary portions is effectively suppressed.
  • the concentration of the aromatic compound having one or more nitro groups in the plating solution is preferably in the range of 0.01 g / L to 30 g / L. If it is less than 0.01 g / L, deposition of gold alloy plating on unnecessary portions tends to occur. On the other hand, if it exceeds 30 g / L, the plating deposition amount is excessively suppressed as a whole, and it becomes difficult to perform hard gold plating on a necessary portion. A more preferred concentration is 0.05 g / L to 15 g / L.
  • the hard gold plating solution in the present invention can contain a pH adjusting agent, a buffering agent and the like in addition to the above basic composition.
  • a pH adjuster alkali metal hydroxides such as potassium citrate and potassium hydroxide, or acidic substances such as citric acid and phosphoric acid can be used.
  • acidic substances such as citric acid and phosphoric acid
  • buffer citric acid, tartaric acid, oxalic acid, succinic acid, phosphoric acid, sulfurous acid, or a salt thereof can be used.
  • the above-described hard gold plating solution according to the present invention preferably has a plating solution pH of 3 or more as a plating treatment condition, and is preferably performed at a solution temperature of 5 ° C. to 90 ° C. If the pH is less than 3, cyan gas is likely to be generated. More preferable plating conditions are pH 4 or more and a liquid temperature of 20 ° C. to 70 ° C. About the current density at the time of a plating process, the applicable range is wide and it can select an optimal current density value according to conditions, such as a plating target object, a plating apparatus, and a plating solution flow rate.
  • the hard gold plating solution according to the present invention is particularly applicable to high current density plating treatment conditions such as high-speed plating treatment.
  • the hard gold plating solution according to the present invention it is possible to perform hard gold plating only on necessary portions of electronic parts such as connectors.
  • hard gold plating is performed on the surface of the base plated with nickel, it is possible to selectively perform partial plating.
  • Example 1 the result of examining the electrodeposition characteristics by conducting a hull cell test using dinitrobenzoic acid as an aromatic compound having one or more nitro groups will be described.
  • the composition of the hard gold plating solution was as follows.
  • the hull cell test uses a commercially available hull cell tester (manufactured by Yamamoto Kakin Tester Co., Ltd.), and the substrate to be plated is nickel-plated (thickness 70 mm, width 100 mm, thickness 0.3 mm) on a brass hull cell plate. 10 ⁇ m) was used on both sides.
  • the plating treatment time was 30 seconds, and the energization current was 3A. During the plating process, the plating solution was vigorously stirred.
  • Hull cell evaluation was performed by measuring the plating film thickness of nine places of the plated hull cell plate.
  • Nine locations on this Hull cell plate are the portion about 2 cm above the bottom of the Hull cell plate that touches the inner bottom surface of the Hull cell tester (the portion that has been immersed in the plating solution). Selected.
  • the plating film thickness was measured with a fluorescent X-ray film thickness measuring instrument (manufactured by SII Nanotechnology Co., Ltd.).
  • the approximate current density value at each of the nine points (Nos. 1 to 9) where the film thickness was measured is 1 is 0.3 A / dm 2 , No. 1 2 is 1 A / dm 2 , No. 2 3 is 2 A / dm 2 , No.
  • Table 1 also shows the results of a blank hard gold plating solution to which dinitrobenzoic acid is not added for comparison.
  • the numbers 1 to 9 shown in Table 1 indicate the measurement points at nine locations on the Hull cell plate, and the results of the hyphen row are the results of the blank hard gold plating solution.
  • 1 g / L, 5 g / L Are the results of the hard gold-based plating solution containing dinitrobenzoic acid at that concentration (the same applies to the table of film thickness measurement results of the hull cell plate shown below). As can be seen from the results of the film thickness measurement on the surface of the Hull cell plate, it was found that the addition of dinitrobenzoic acid sharply decreased the plating film thickness on the low current density side.
  • Example 2 nitrobenzoic acid was used as an aromatic compound having one or more nitro groups.
  • the composition of the hard gold plating solution of Example 2 is the same as that of Example 1, except that nitrobenzoic acid is used instead of dinitrobenzoic acid of Example 1. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. Table 2 shows the results of measuring the film thickness at each point according to Example 2.
  • Example 3 nitrobenzenesulfonic acid was used as an aromatic compound having one or more nitro groups.
  • the composition of the hard gold plating solution of Example 3 is the same as that of Example 1, except that nitrobenzenesulfonic acid is used instead of dinitrobenzoic acid of Example 1. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. Table 3 shows the results of measuring the film thickness at each point according to Example 3.
  • Example 4 the results of examining the electrodeposition characteristics of a high-speed partial plating test using dinitrobenzoic acid as an aromatic compound having one or more nitro groups will be described.
  • the composition of the gold-cobalt alloy hard gold plating solution was as follows.
  • this groove portion Since this groove portion has a mask above it, it becomes a low current density portion during electrolysis as compared with a circular exposed portion without a mask. Therefore, when plating is performed by this high-speed partial plating apparatus, it is an ideal plating process that only the circular portion is plated and the groove portion is not plated.
  • Plating conditions were adjusted to a flow rate of 15 L / min and a current density of 50 A / dm 2 to form a gold-cobalt alloy plating film having a thickness of 0.5 ⁇ m.
  • Second Embodiment In this embodiment, the results of investigating the plating characteristics of a hard gold plating solution of a gold-nickel alloy will be described.
  • Table 5 also shows the results of a blank hard gold plating solution to which dinitrobenzoic acid is not added for comparison.
  • Table 5 shows the results of a blank hard gold plating solution to which dinitrobenzoic acid is not added for comparison.
  • nitrobenzoic acid was added, the plating film thickness on the low current density side was abruptly reduced as in the case of the first embodiment. And when the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed.
  • hard gold plating was also performed on the back side of the hull cell plate, but it was found that when dinitrobenzoic acid was added, the back side was hardly plated.
  • Example 6 nitrobenzoic acid was used as an aromatic compound having one or more nitro groups.
  • the composition of the hard gold plating solution of Example 6 is the same as that of Example 5 except that nitrobenzoic acid is used instead of dinitrobenzoic acid of Example 5. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. Table 6 shows the results of measuring the film thickness at each point according to Example 6.
  • Example 7 nitrobenzenesulfonic acid was used as an aromatic compound having one or more nitro groups.
  • the composition of the hard gold plating solution of Example 7 is the same as that of Example 5, except that nitrobenzenesulfonic acid is used instead of dinitrobenzoic acid of Example 5. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. Table 7 shows the results of measuring the film thickness at each point according to Example 7.
  • Example 8 As in Example 4, the electrodeposition characteristics were examined by conducting a high-speed partial plating test using dinitrobenzoic acid as an aromatic compound having one or more nitro groups. Will be described.
  • the composition of the gold-nickel alloy hard gold plating solution was as follows.
  • test sample, equipment, plating conditions, etc. for the high-speed partial plating test were the same as in Example 4.
  • Example 8 when the plating state when the concentration of dinitrobenzoic acid in the plating solution was changed was observed in appearance, as the amount of dinitrobenzoic acid added increased, the groove portion was not plated. Turned out to be.
  • Example 8 the results of investigating the average plating film thickness of the groove portions as in Example 4 are shown in Table 8. This film thickness investigation was performed in the same manner as in Example 4 above.
  • Potassium cyanide 50g / L Dinitrobenzoic acid 1g / L, 5g / L pH 12 Liquid temperature 20 °C
  • Table 9 also shows the results of a blank hard gold plating solution to which dinitrobenzoic acid is not added for comparison.
  • Table 9 shows the results of a blank hard gold plating solution to which dinitrobenzoic acid is not added for comparison.
  • nitrobenzoic acid was added, the plating film thickness on the low current density side was abruptly reduced as in the case of the first embodiment.
  • the addition amount was 5 g / L, it turned out that the plating by the side of a low current density is further suppressed.
  • dinitrobenzoic acid was added, there was almost no plating treatment on the back side of the hull cell plate.
  • Example 10 nitrobenzoic acid was used as an aromatic compound having one or more nitro groups.
  • the composition of the hard gold plating solution of Example 10 is the same as that of Example 9, except that nitrobenzoic acid is used instead of dinitrobenzoic acid of Example 10. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. In Table 10, the result of having measured the film thickness of each point in Example 10 is shown.
  • Example 11 nitrobenzenesulfonic acid was used as an aromatic compound having one or more nitro groups.
  • the composition of the hard gold plating solution of Example 11 is the same as that of Example 9, except that nitrobenzenesulfonic acid is used instead of dinitrobenzoic acid of Example 9. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. In Table 11, the result of having measured the film thickness of each point in Example 11 is shown.
  • Example 12 As in Example 4, the electrodeposition characteristics were examined by conducting a high-speed partial plating test using dinitrobenzoic acid as an aromatic compound having one or more nitro groups. Will be described.
  • the composition of the gold-silver alloy hard gold plating solution was as follows.
  • Potassium cyanide 50g / L Dinitrobenzoic acid 0.5 g / L, 1.0 g / L, 1.5 g / L, 2.0 g / L, 3.0g / L, 5.0g / L pH 12 Liquid temperature 20 °C
  • test sample, equipment, plating conditions, etc. for the high-speed partial plating test were the same as in Example 4.
  • Example 12 the results of investigating the average plating film thickness of the groove portions as in Example 4 are shown in Table 12. This film thickness investigation was performed in the same manner as in Example 4 above.
  • Table 13 also shows the results of a blank hard gold plating solution to which dinitrobenzoic acid was not added for comparison.
  • Table 13 shows the results of a blank hard gold plating solution to which dinitrobenzoic acid was not added for comparison.
  • Example 14 nitrobenzoic acid was used as an aromatic compound having one or more nitro groups.
  • the composition of the hard gold plating solution of Example 14 is the same as that of Example 13, except that nitrobenzoic acid is used instead of dinitrobenzoic acid of Example 13. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. In Table 14, the result of having measured the film thickness of each point in Example 13 is shown.
  • Example 15 nitrobenzenesulfonic acid was used as an aromatic compound having one or more nitro groups.
  • the composition of the hard gold plating solution of Example 15 is the same as that of Example 13 except that nitrobenzenesulfonic acid is used instead of dinitrobenzoic acid of Example 9. Further, the Hull cell test conditions and the evaluation thereof were the same as those in Example 1. Table 15 shows the results of measuring the film thickness at each point in Example 15.
  • Example 16 as in Example 4, the electrodeposition characteristics were examined by performing a high-speed partial plating test using dinitrobenzoic acid as an aromatic compound having one or more nitro groups. Will be described.
  • the composition of the hard gold plating solution was as follows.
  • Potassium cyanide potassium 12g / L (8g / L in terms of gold) Polyethyleneamine 10g / L Citric acid 150g / L Dinitrobenzoic acid 0.5 g / L, 1.0 g / L, 1.5 g / L, 2.0 g / L, 3.0g / L, 5.0g / L pH 7 Liquid temperature 65 °C
  • test sample, equipment, plating conditions, etc. for the high-speed partial plating test were the same as in Example 4.
  • Example 16 when the plating state when the concentration of dinitrobenzoic acid in the plating solution was changed was observed in appearance, as the amount of dinitrobenzoic acid added increased, the groove portion was not plated. Turned out to be.
  • Example 16 the result of investigating the average plating film thickness of the groove portion as in Example 4 is shown in Table 16. This film thickness investigation was performed in the same manner as in Example 4 above.
  • the present invention it is possible to perform hard gold plating only on a necessary portion of an electronic component such as a connector.
  • hard gold plating is performed on the surface of the base plated with nickel, partial plating can be selectively performed.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

L'invention concerne un liquide de placage d'or dur qui permet de mettre en œuvre un placage partiel sélectif et convient pour des composants électroniques tels que des connecteurs. Le liquide de placage d'or dur contient un sel d'or ou un complexe d'or soluble, un sel conducteur et un agent chélatant, et est caractérisé en ce qu'il contient aussi un composé aromatique comportant un ou plusieurs groupes azote sélectionné(s) dans le groupe constitué par les acides nitrobenzoïques, les acides dinitrobenzoïques et les acides sulfoniques de nitrobenzène.  Ce liquide de placage d'or dur est également caractérisé en ce qu'il contient en outre au moins un sel métallique sélectionné dans le groupe constitué par les sels de cobalt, les sels de nickel et les sels d'argent, ou, dans une forme de réalisation, un additif organique de polyéthylène imine.
PCT/JP2009/063931 2008-08-25 2009-08-06 Liquide de placage d'or dur WO2010024099A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US13/055,038 US20110127168A1 (en) 2008-08-25 2009-08-06 Hard gold-based plating solution
CN200980133847.4A CN102131962B (zh) 2008-08-25 2009-08-06 硬质金系镀液
KR1020117004292A KR101275886B1 (ko) 2008-08-25 2009-08-06 경질 금계 도금액

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2008-215592 2008-08-25
JP2008215592 2008-08-25
JP2009147253A JP5513784B2 (ja) 2008-08-25 2009-06-22 硬質金系めっき液
JP2009-147253 2009-06-22

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WO2010024099A1 true WO2010024099A1 (fr) 2010-03-04

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JP (1) JP5513784B2 (fr)
KR (1) KR101275886B1 (fr)
CN (1) CN102131962B (fr)
TW (1) TWI495766B (fr)
WO (1) WO2010024099A1 (fr)

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EP2458036A3 (fr) * 2010-11-25 2013-02-20 Rohm and Haas Electronic Materials LLC Solution de placage d'or

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JP2011021217A (ja) * 2009-07-14 2011-02-03 Ne Chemcat Corp 電解硬質金めっき液及びこれを用いるめっき方法
DE102011114931B4 (de) * 2011-10-06 2013-09-05 Umicore Galvanotechnik Gmbh Verfahren zur selektiveren, elektrolytischen Abscheidung von Gold oder einer Goldlegierung
US20160145756A1 (en) * 2014-11-21 2016-05-26 Rohm And Haas Electronic Materials Llc Environmentally friendly gold electroplating compositions and methods
CN107709628B (zh) 2015-06-26 2020-06-16 美泰乐科技(日本)股份有限公司 用于电解硬质金镀敷液的防置换剂和包含其的电解硬质金镀敷液
TWI575623B (zh) * 2015-12-10 2017-03-21 南茂科技股份有限公司 凸塊結構與其製作方法
JP2017186627A (ja) * 2016-04-07 2017-10-12 小島化学薬品株式会社 硬質金めっき溶液
TWI807443B (zh) * 2016-10-14 2023-07-01 日商上村工業股份有限公司 無電解鍍鎳浴
CN109881223B (zh) * 2019-03-11 2020-02-14 深圳市联合蓝海科技开发有限公司 无氰镀金液及其制备方法和应用
CN110894618A (zh) * 2019-10-10 2020-03-20 深圳市金质金银珠宝检验研究中心有限公司 一种环境友好型表面改性电铸金溶液及其制备方法

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KR101275886B1 (ko) 2013-06-17
KR20110034683A (ko) 2011-04-05
TW201022483A (en) 2010-06-16
TWI495766B (zh) 2015-08-11
JP5513784B2 (ja) 2014-06-04
US20110127168A1 (en) 2011-06-02
CN102131962B (zh) 2014-08-13
CN102131962A (zh) 2011-07-20

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