WO2009150915A1 - 電解金めっき液及びそれを用いて得られた金皮膜 - Google Patents
電解金めっき液及びそれを用いて得られた金皮膜 Download PDFInfo
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- WO2009150915A1 WO2009150915A1 PCT/JP2009/058846 JP2009058846W WO2009150915A1 WO 2009150915 A1 WO2009150915 A1 WO 2009150915A1 JP 2009058846 W JP2009058846 W JP 2009058846W WO 2009150915 A1 WO2009150915 A1 WO 2009150915A1
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- gold
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- plating solution
- gold plating
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- 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
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- 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
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- 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
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- 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
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
Definitions
- the present invention relates to an electrolytic gold plating solution having a specific composition and a gold coating on a nickel coating obtained using the electrolytic gold plating solution.
- Gold plating on the nickel coating is widely used in the field of electronic and electrical parts because gold has excellent corrosion resistance, mechanical properties, electrical properties, etc., and nickel has excellent heat resistance as a base metal. ing. Among them, hard gold plating alloyed with metals such as cobalt and nickel makes use of its high hardness and excellent wear resistance to make contact joints such as connectors such as connectors and contact members such as switches. Widely used as gold plating.
- This method is an electrolytic gold plating technique generally referred to as nickel barrier plating.
- nickel barrier part a part that does not require gold plating
- the parts such as silicon rubber are mechanically pressed down so that the gold plating solution and the part to be plated cannot be in contact with each other. This is a method of providing a portion (nickel barrier portion).
- Patent Document 1 discloses a gold plating bath that keeps a gold cobalt plating solution weakly acidic and adds hexamethylenetetramine to suppress deposition of a gold plating film on unnecessary portions. It is disclosed.
- this technique cannot be said to have sufficient performance in the selectivity of gold deposition, and since reducing hexamethylenetetramine is added to the gold plating bath, the gold is a gold plating bath. It is very uneconomical that gold deposits on the shaft part of the pump for circulating the plating solution and stops the pump, or gold is consumed in addition to the plating reaction. It was not practical.
- the present invention has been made in view of the above-mentioned background art, and the problem is that the physical properties of the gold plating film are equivalent to those obtained using a conventional electrolytic gold plating solution, wear resistance,
- An object of the present invention is to provide an electrolytic gold plating solution suitable for nickel barrier plating while maintaining electrical characteristics and the like. In other words, it suppresses gold deposition at “parts that do not require gold plating (nickel barrier part)” that mechanically pressed the member, and good gold deposition occurs at parts that require gold plating, and abnormal gold
- An object of the present invention is to provide an electrolytic gold plating solution capable of producing a stable product without precipitation.
- the inventor proceeds the plating reaction at a high current density (set current density) at the portion where the gold plating solution touches the portion to be plated, and the gold plating solution is plated. Focusing on the fact that the plating reaction proceeds at a low current density in the part that does not touch the part, it was found that an electrolytic gold plating solution should be developed using the difference.
- FIG. 1 shows measurement using a general-purpose electrolytic gold plating solution and an electrolytic gold plating solution having the composition described in Example 1 of the present invention.
- the horizontal axis represents current density (A / dm 2 ), and the vertical axis represents 10 seconds. It is the graph which took the film thickness (micrometer) of the gold film after performing a gold plating process. That is, the gold concentration of a general-purpose electrolytic gold plating solution is adjusted to the gold equivalent concentration (9 g / L) of the electrolytic gold plating solution of Example 1, and the bath temperature is raised to 50 ° C. In this step, gold plating was performed on a primary bright nickel plating film of 2.0 ⁇ m on a 10 mm ⁇ 10 mm copper plate.
- the current density is 1 A / dm 2 , 5 A / dm 2 , 10 A / dm 2 , 20 A / h while stirring the gold plating solution with a pump at a flow rate of 18 L / min from a circular jet port having a diameter of 8 mm.
- dm 2 , 30 A / dm 2 , 40 A / dm 2 , 50 A / dm 2 , 60 A / dm 2 gold plating treatment was performed for 10 seconds each time, and fluorescent X-ray analysis was performed around the center that was gold-plated in a circular shape It is the graph which measured the film thickness of the gold film using the apparatus (the Seiko Instruments Inc. make, SFT9255) according to the conventional method, and plotted the measurement result.
- 0 A / dm 2 to 5 A / dm 2 corresponds to a portion not subjected to gold plating in the nickel barrier plating technology, and a gold film in the low current density region. It was judged that the thinner the film thickness, the better the nickel barrier properties.
- 20 A / dm 2 to 60 A / dm 2 (hereinafter, abbreviated as “high current density region”) in FIG. 1 corresponds to a portion to be subjected to gold plating in the nickel barrier plating technology, and gold in the high current density region It was judged that the thicker the film, the better the nickel barrier properties. See the plot graph of the electrolytic gold plating solution having the composition described in Example 1.
- the characteristics of the electrolytic gold plating solution required for the nickel barrier plating technology are that the gold deposition film thickness in the low current density region is very thin, and in the low current density region. It was found that the difference between the amount of deposited gold and the amount of deposited gold in the high current density region was large, and that the amount of deposited gold in the high current density region where the gold plating film was formed on the product could be secured to the maximum. Then, it was considered that an electrolytic gold plating solution having such characteristics has selectivity for gold deposition and is an electrolytic gold plating solution suitable for nickel barrier plating technology.
- the present inventor has obtained a gold cyanide salt and “a heterocyclic ring having one or more nitrogen atoms in the ring. If the gold film is formed using an electrolytic gold plating solution containing a compound, a heterocyclic compound in which one or more nitro groups are substituted on the carbon atom in the ring as an essential component, the above-mentioned problems are solved. Then, the present inventors have solved the above problems, found that gold deposition in the low current density region of the gold plating film is suppressed, and that stable products can be produced without abnormal gold deposition, and the present invention has been completed.
- the present invention relates to a gold cyanide salt as a gold source, a heterocyclic compound having one or more nitrogen atoms in the ring, and one or more nitro groups substituted on the carbon atoms in the ring; It is intended to provide an electrolytic gold plating solution characterized by containing.
- the present invention further provides the above electrolytic gold plating solution containing a cobalt salt, a nickel salt and / or an iron salt.
- the present invention provides a gold film at a current density of 5 A / dm 2 when the current density is set to 5 A / dm 2 and 40 A / dm 2 using a jet jet plating apparatus and plating is performed for 10 seconds.
- the above electrolytic gold plating solution in which the thickness of the gold film is 0.1 ⁇ m or less and the thickness of the gold film at 40 A / dm 2 is at least 5 times the thickness of the gold film at 5 A / dm 2 To do.
- the present invention also provides a gold film obtained by performing electrolytic gold plating on a nickel film using the above electrolytic gold plating solution.
- a gold film obtained by using a conventional electrolytic gold plating solution has low current density while maintaining excellent mechanical properties such as wear resistance, corrosion resistance, and electrical properties.
- the gold deposition rate in the region is very slow, and the gold deposition rate in the high current density region can be very fast (this performance is hereinafter referred to as “gold selective deposition performance”).
- the difference between the thickness and the gold deposition film thickness in the high current density region can be increased.
- Nickel barrier parts that are mechanically pressed by a member such as silicon rubber, and parts that are not pressed down (parts that require gold plating).
- Nickel barriers required for contact members such as connectors of electronic devices in recent years It can be suitably applied to plating technology.
- the present invention contains at least a gold cyanide salt as a gold source, and further “a heterocyclic compound having one or more nitrogen atoms in the ring, wherein one or more nitro groups are substituted on the carbon atoms in the ring. It is an electrolytic gold plating solution characterized by containing “a heterocyclic compound” as an essential component.
- the “electrolytic gold plating solution” of the present invention also includes “electrolytic gold alloy plating solution”.
- the “gold film” of the present invention includes “gold alloy film”. That is, a metal other than gold may be contained.
- the electrolytic gold plating solution of the present invention when used for hard gold plating, it further contains a cobalt salt, a nickel salt and / or an iron salt. That is, in addition to the gold cyanide salt as a gold source, it contains any one or more of a cobalt salt, a nickel salt, and an iron salt.
- the electrolytic gold plating solution of the present invention must contain a gold cyanide salt.
- the gold cyanide salt is used as a gold source for the electrolytic gold plating solution of the present invention.
- the gold cyanide salt is not limited to one type, and two or more types can be used in combination.
- the gold cyanide salt alkali metal gold cyanide or ammonium gold cyanide is preferable.
- the gold valence (oxidation number) of the gold cyanide salt may be monovalent or trivalent, but monovalent is preferable from the viewpoint of gold deposition efficiency. That is, the first cyanide gold salt is preferable.
- the gold cyanide salt include, for example, first gold sodium cyanide, first gold potassium cyanide, first gold ammonium cyanide, second gold sodium cyanide, second gold potassium cyanide, cyanide. Secondary gold ammonium and the like can be mentioned. Among these, from the viewpoints of plating performance such as gold deposition efficiency, cost, availability, etc., primary gold sodium cyanide, primary gold potassium cyanide, and primary gold ammonium cyanide are preferable, and further similar viewpoints. To 1st potassium gold cyanide is particularly preferred.
- the content of the gold cyanide salt in the electrolytic gold plating solution of the present invention is not particularly limited, and is usually 0.05 g / L to 50 g / L, preferably 0, as metal gold with respect to the entire electrolytic gold plating solution. 0.5 g / L to 30 g / L, particularly preferably 1 g / L to 20 g / L. If the content of the gold cyanide salt in the electrolytic gold plating solution is too small, golden gold plating may be difficult. On the other hand, when the content of metal gold in the electrolytic gold plating solution is too large, there is no particular problem with the performance of the electrolytic gold plating solution, but gold cyanide salt is a very expensive metal. It may be uneconomical to store in the state of being contained.
- the gold cyanide salt specifies the form present in the electrolytic gold plating solution of the present invention, but as a raw material to be dissolved in the preparation of the electrolytic gold plating solution of the present invention, It is preferable to use a gold cyanide salt.
- the electrolytic gold plating solution of the present invention includes a “heterocyclic compound having at least one nitrogen atom in the ring and having at least one nitro group substituted on the carbon atom in the ring” (hereinafter, in parentheses).
- a specific heterocyclic compound Is abbreviated as “specific heterocyclic compound” as an essential component.
- a specific heterocyclic compound By containing a specific heterocyclic compound, it is possible to reduce the thickness of the gold deposit in the low current density region while maintaining the excellent high corrosion resistance, mechanical properties, electrical properties, etc. of the conventional electrolytic gold plating film. The difference between the gold deposited film thickness in the current density region and the gold deposited film thickness in the high current density region can be greatly increased. That is, by containing a specific heterocyclic compound, an electrolytic gold plating solution excellent in gold selective deposition performance can be obtained, and an electrolytic gold plating solution optimal for nickel barrier plating is realized.
- the heterocyclic ring in the specific heterocyclic compound is not particularly limited, and may be aromatic or non-aromatic. However, the aromatic ring has better plating. It is preferable in terms of performance, availability, etc., and in particular that the above-described effects are exhibited.
- the heteroatoms other than the carbon atoms constituting the heterocycle and examples include nitrogen, oxygen, sulfur, etc., but at least one of the heteroatoms must be a nitrogen atom.
- Arbitrary substituents may be substituted on the carbon atom in the heterocyclic ring as long as the effects of the present invention are not impaired. It is essential that at least one of the substituents for the carbon atom in the heterocycle is a nitro group.
- the substituent other than the nitro group include an alkyl group, a hydroxy group, and a phenyl group.
- the number of nitro groups substituted on carbon atoms in the heterocyclic ring is not particularly limited as long as it is 1 or more, but 1 to 3 is preferable, and 1 to 2 is particularly preferable.
- the specific heterocyclic compound include, for example, pyrrole, imidazole, pyrazole, triazole, tetrazole, oxazole, isoxazole, indole, pyridine, pyridazine, pyrimidine, pyrazine, uracil, cytosine, thymine, adenine, guanine, Preferred examples include those in which one or more nitro groups are substituted on the carbon atoms constituting the ring of quinoline, isoquinoline, oxaline, isoxaline, acridine, cinnosoline or morpholine.
- the content of the specific heterocyclic compound is not particularly limited, but is preferably 10 ppm to 50000 ppm, more preferably 50 ppm to 30000 ppm, and particularly preferably 100 ppm to 10000 ppm with respect to the entire electrolytic gold plating solution. .
- the said numerical value shows those total content. If the content of the specific heterocyclic compound in the electrolytic gold plating solution is too small, gold deposition may not be suppressed when the plating is performed in a low current density region, or the appearance of the gold film may be deteriorated. On the other hand, when there is too much content, the further increase of the said effect of this invention cannot be expected, and it may become uneconomical.
- the specific heterocyclic compound specifies the form present in the electrolytic gold plating solution of the present invention, but is a raw material to be dissolved in the preparation of the electrolytic gold alloy plating solution of the present invention. As above, it is preferable to use the above-mentioned specific heterocyclic compound.
- ⁇ Cobalt salt, nickel salt, iron salt> in the electrolytic gold alloy plating solution of the present invention, in addition to the gold cyanide salt and the above-mentioned specific heterocyclic compound, a cobalt salt, a nickel salt and / or an iron salt are further used in combination for the nickel barrier plating. It is preferable because an electrolytic gold plating solution capable of forming a hard gold film is obtained.
- the above cobalt salt, nickel salt or iron salt precipitates (eutectoid) with gold in the gold plating film on the nickel plating film, forms a hard gold film, and is necessary for contact members such as connectors of electronic components. High hardness and high wear resistance can be realized.
- cobalt salt, nickel salt and iron salt are preferably water-soluble.
- Said cobalt salt, nickel salt, and / or iron salt are not limited to use of 1 type in each metal salt, but 2 or more types can be used together.
- the metal salt of a different metal is not limited to 1 type, but 2 or more types can be used together.
- cobalt salt for example, cobalt sulfate, cobalt chloride, cobalt nitrate, cobalt carbonate, cobalt phthalocyanine cobalt, stearic acid cobalt, ethylenediamine tetraacetic acid disodium cobalt, naphthenic acid cobalt, boric acid borate, thiocyanic acid cobalt , Cobalt sulfamate, cobalt acetate, cobalt citrate, cobalt hydroxide, cobalt oxalate, cobalt phosphate, etc. have good plating performance, ease of dissolution in water, ease of eutectoid deposition on gold film, From the viewpoint of easy availability and low cost, it is preferable.
- the nickel salt is not particularly limited.
- nickel sulfate, nickel acetate, nickel chloride, nickel borate, nickel benzoate, nickel oxalate, nickel naphthenate, nickel oxide, nickel phosphate, nickel stearate, tartaric acid Nickel, nickel thiocyanate, nickel amidosulfate, nickel carbonate, nickel citrate, nickel formate, nickel cyanide, nickel hydroxide, nickel nitrate, nickel octoate, etc. have good plating performance, easy dissolution in water, From the viewpoints of eutectoid deposition on the gold film, availability, low cost, etc., it is preferable.
- the iron salt is not particularly limited.
- Ferrous iron, ferrous gluconate, ferric ethylenediaminetetraacetate, ferrous nitrate, ferric nitrate, etc. have good plating performance, ease of dissolution in water, and ease of eutectoid deposition on gold film From the viewpoint of availability, low cost, etc., it is preferable.
- the content of the cobalt salt, nickel salt, and iron salt in the electrolytic gold plating solution of the present invention is not particularly limited, but as a metal (in terms of metal), preferably 1 ppm to It is 50000 ppm, more preferably 10 ppm to 30000 ppm, and particularly preferably 50 ppm to 10000 ppm.
- the said numerical value shows those total content. If the content is too small, the amount of eutectoid on the gold film is too small, and sufficient hardness may not be obtained. On the other hand, if the content is too high, the amount of eutectoid on the gold film will increase too much, which may cause poor color tone of the gold film, increase in contact resistance, and further increase in hardness may not be expected. is there.
- the electrolytic gold plating solution of the present invention if necessary, a buffering agent for keeping the pH of the electrolytic gold plating solution constant, a conductive salt for ensuring the conductivity of the electrolytic gold plating solution, Metal ion sequestering agent to remove the influence when impurity metals are mixed in the electrolytic gold plating solution, surfactant to improve the pinhole removal of the gold coating or electrolytic gold plating solution, gold coating A brightening agent or the like for smoothing the surface can be appropriately used.
- the buffer contained in the electrolytic gold plating solution of the present invention as needed is not particularly limited as long as it is a known buffer, but is not limited to inorganic acids such as boric acid and phosphoric acid; citric acid, tartaric acid, malic acid And oxycarboxylic acids such as These may be used alone or in combination of two or more.
- inorganic acids such as boric acid and phosphoric acid
- citric acid, tartaric acid, malic acid And oxycarboxylic acids such as These may be used alone or in combination of two or more.
- the content of the buffer in the electrolytic gold plating solution of the present invention is not particularly limited, but is usually 1 g / L to 500 g / L, preferably 10 g / L to 100 g / L, based on the entire electrolytic gold plating solution. . If the content of the buffering agent in the electrolytic gold plating solution is too small, the buffering effect may be difficult to be exhibited. On the other hand, if the content is too large, the buffering effect may not be increased and it may be uneconomical.
- the conductive salt contained in the electrolytic gold plating solution of the present invention as needed is not particularly limited as long as it is a known conductive salt, but is not limited to inorganic acids such as sulfates, nitrates, and phosphates; oxalic acid, succinic acid Examples thereof include carboxylic acids such as acid, glutaric acid, malonic acid, citric acid, tartaric acid and malic acid. These may be used alone or in combination of two or more.
- the content of the conductive salt in the electrolytic gold plating solution of the present invention is not particularly limited, but is usually 1 g / L to 500 g / L, preferably 10 g / L to 100 g / L with respect to the entire electrolytic gold plating solution. . If the content of the conductive salt in the electrolytic gold plating solution is too small, the conductive effect may be difficult to be exhibited. On the other hand, if the content is too large, the buffering effect may not be increased and it may be uneconomical. It is also possible to share the same component as the buffer.
- the sequestering agent contained as necessary in the electrolytic gold plating solution of the present invention is not particularly limited as long as it is a known sequestering agent, but aminocarboxylic acids such as iminodiacetic acid, nitrilotriacetic acid, ethylenediaminetetraacetic acid, etc. Acid-based chelating agents; phosphonic acid-based chelating agents such as hydroxyethylidene diphosphonic acid, nitrilomethylene phosphonic acid, and ethylenediaminetetramethylene phosphonic acid. These may be used alone or in combination of two or more.
- the content of the sequestering agent in the electrolytic gold plating solution of the present invention is not particularly limited, but is usually 0.1 g / L to 100 g / L, preferably 0.5 g / L, based on the entire electrolytic gold plating solution. ⁇ 50 g / L. If the content of the sequestering agent in the electrolytic gold plating solution is too small, the effect of removing the influence of the impurity metal may be difficult to exert. On the other hand, if the content is too large, the effect of removing the influence of the impurity metal is increased. May not be seen and may be uneconomical.
- the surfactant contained as necessary in the electrolytic gold plating solution of the present invention is not particularly limited as long as it is a known surfactant, and is a nonionic surfactant, an anionic surfactant, an amphoteric surfactant. Alternatively, a cationic surfactant is used. These may be used alone or in combination of two or more.
- Nonionic surfactants include ether type nonionic surfactants such as noniphenol polyalkoxylate, ⁇ -naphthol polyalkoxylate, dibutyl- ⁇ -naphthol polyalkoxylate, styrenated phenol polyalkoxylate; octylamine polyalkoxy Examples thereof include amine-type nonionic surfactants such as rate, hexynylamine polyalkoxylate, and linoleylamine polyalkoxylate.
- anionic surfactant examples include alkyl sulfates such as sodium lauryl sulfate; polyoxyethylene alkyl ether sulfates such as sodium polyoxyethylene nonyl ether sulfate; polyoxyethylene alkyl phenyl ether sulfates; It is done.
- amphoteric surfactants examples include 2-undecyl-1-carboxymethyl-1-hydroxyethylimidazolium betaine, N-stearyl-N, N-dimethyl-N-carboxymethylbetaine, and lauryldimethylamine oxide.
- Examples of the cationic surfactant include lauryl trimethyl ammonium salt, lauryl dimethyl ammonium betaine, lauryl pyridinium salt, oleyl imidazolium salt, stearyl amine acetate and the like.
- the content of the surfactant in the electrolytic gold plating solution of the present invention is preferably 0.01 g / L to 20 g / L with respect to the entire electrolytic gold plating solution, as long as the desired performance is exhibited.
- the content is not particularly limited.
- the brightener contained as necessary in the electrolytic gold plating solution of the present invention is not particularly limited as long as it is a well-known brightener, and examples thereof include amine compounds having a pyridine skeleton. These may be used alone or in combination of two or more.
- Examples of the amine compound having a pyridine skeleton include 2-aminopyridine, 3-aminopyridine, 4-aminopyridine and the like.
- the content of the brightener in the electrolytic gold plating solution of the present invention is preferably 0.01 g / L to 20 g / L with respect to the entire electrolytic gold plating solution.
- the content is not limited.
- the electrolytic gold plating solution of the present invention when used, when a current density is set to 5 A / dm 2 and 40 A / dm 2 using a jet-jet plating apparatus and plating is performed for 10 seconds, the current density is 5 A / dm.
- the film thickness of the gold film at 2 can be 0.1 ⁇ m or less, and the film thickness of the gold film at 40 A / dm 2 can be 5 times or more the film thickness of the gold film at 5 A / dm 2 .
- the film thickness of the gold film at a current density of 5 A / dm 2 can be 0.08 ⁇ m or less, and the film thickness of the gold film at 40 A / dm 2 can be reduced to the film thickness of the gold film at 5 A / dm 2 . Can be more than 7 times.
- the electrolytic gold plating solution of the present invention has the above composition, and the current density is set to 5 A / dm 2 and 40 A / dm 2 using the jet jet plating apparatus, and the plating treatment is performed for 10 seconds respectively.
- the film thickness of the gold film at a current density of 5 A / dm 2 is 0.1 ⁇ m or less, and the film thickness of the gold film at 40 A / dm 2 is equal to the film thickness of the gold film at 5 A / dm 2 .
- the electrolytic gold plating solution is preferably 5 times or more.
- the gold film thickness at a current density of 5 A / dm 2 is 0.08 ⁇ m or less, and the gold film thickness at 40 A / dm 2 is 5 A / dm 2.
- an electrolytic gold plating solution having a thickness of 7 times or more.
- the electrolytic gold plating solution of the present invention can be particularly suitably used for the above-described nickel barrier plating technique.
- the “electrolytic gold plating solution” of the present invention includes “electrolytic gold alloy plating solution”.
- the “gold film” of the present invention includes “gold alloy film”. That is, you may contain metals other than gold
- the concentration of gold (gold purity) in the “gold film” is not particularly limited, but the gold content is preferably 95% by mass or more based on the entire “gold film”. In order to obtain the above, 97 mass% to 99.99 mass% is more preferable, and 99 mass% to 99.9 mass% is particularly preferable.
- the plating conditions of the electrolytic gold plating solution of the present invention described above are not particularly limited, but the temperature conditions are preferably 20 ° C. to 90 ° C., particularly preferably 30 ° C. to 70 ° C.
- the pH of the plating solution is preferably pH 2.0 to pH 9.0, particularly preferably pH 3.0 to pH 8.0.
- the film thickness of the gold film obtained by performing electrolytic plating using the electrolytic gold plating solution of the present invention is not particularly limited, but is preferably 0.01 ⁇ m to 20 ⁇ m, particularly preferably 0.05 ⁇ m to 5 ⁇ m.
- a thin gold plating process called flash gold plating with a thickness of about 0.01 ⁇ m to 0.05 ⁇ m is performed for the purpose of improving the adhesion between the gold film and the underlying metal. Then, it is common to perform a thick gold plating process to a desired film thickness.
- the electrolytic gold plating solution of the present invention can be suitably used for the thick gold plating treatment at this time, but it is possible to perform flash gold plating even when the thick gold plating treatment is performed with the electrolytic gold plating solution of the present invention.
- a commercially available flash gold plating solution or the electrolytic gold plating solution of the present invention can be appropriately used for flash gold plating.
- the electrolytic gold plating solution of the present invention is preferably used for the nickel barrier plating technique described above. Therefore, when performing electrolytic gold plating using the electrolytic gold plating solution of the present invention, it is preferable to form a nickel plating film as a base plating treatment.
- the nickel plating solution at this time is not particularly limited, but a watt bath, a sulfamine bath, a nickel bromide bath and the like that are generally used are suitable. Moreover, a pit inhibitor, a primary brightener, and a secondary brightener can be added to the nickel plating solution used as needed.
- the method of using the nickel plating solution is not particularly limited and is used according to a conventional method.
- the thickness of the nickel plating film is not particularly limited, but is preferably 0.1 ⁇ m to 20 ⁇ m, and particularly preferably 0.5 ⁇ m to 5 ⁇ m.
- the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples as long as the gist thereof is not exceeded.
- concentration in the composition of electrolytic gold plating solution is a numerical value of the density
- the “comparative compound” hexamethylenetetramine, a benzene ring compound in which one or more nitro groups are substituted on the carbon atom in the ring, and a heterocyclic compound in which the nitro group is not substituted are used.
- pH was adjusted with 20 mass% potassium hydroxide aqueous solution and a citric acid, the bath temperature of the electrolytic gold plating solution was set to 50 degreeC, and the following evaluation was performed.
- Example 11 An electrolytic gold plating solution was prepared in the same manner as in Example 1 except that no metal salt other than a gold salt such as a cobalt salt, a nickel salt, or an iron salt was contained, and electrolytic gold plating was performed in the same manner as in Example 1. The following evaluation was performed.
- a gold salt such as a cobalt salt, a nickel salt, or an iron salt
- Electrolytic gold plating was performed on a primary bright nickel plating film of 2.0 ⁇ m on a 10 mm ⁇ 10 mm copper plate in the steps shown in Table 2. did. Electrolytic gold plating is carried out by stirring the electrolytic gold plating solution from a circular jet port having a diameter of 8 mm at a flow rate of 18 L / min with a pump (hereinafter referred to as “jet jet gold plating method”), and a current density of 5 A. Electrolytic gold plating was performed for 10 seconds each at two levels of / dm 2 and 40 A / dm 2 .
- the primary bright nickel plating film was plated to a thickness of 2.0 ⁇ m using the following electrolytic nickel plating solution A. That is, commercially available nickel sulfamate plating solution (manufactured by Murata Co., Ltd., SN Conque (trade name)) 500 mL / L, commercially available nickel chloride 10 g / L, commercially available boric acid 30 g / L, and pit inhibitor (Ebara Eugelite Co., Ltd.) The product was made at a concentration of 2 mL / L, made by company, pit inhibitor # 82 (trade name) to obtain “electrolytic nickel plating solution A”.
- the thickness of the gold film was measured according to a conventional method using a fluorescent X-ray analyzer (SFT 9255, manufactured by Seiko Instruments Inc.) in the vicinity of the center subjected to electrolytic gold plating in a circular shape. The results are shown in Table 3.
- a gold film having a gold film thickness of 0.1 ⁇ m or less when subjected to electrolytic gold plating at a current density of 5 A / dm 2 was determined to be an electrolytic gold plating solution optimal for nickel barrier plating technology having excellent gold selective deposition performance.
- the result is shown in Table 3 as “good” when 0.1 ⁇ m or less and “bad” when thicker than 0.1 ⁇ m.
- a gold film having a gold film thickness of 5 times or more than the gold film thickness when electrolytic gold plating treatment is performed at a current density of 5 A / dm 2 when gold plating is performed at a current density of 40 A / dm 2 is used.
- the electrolytic gold plating solution was judged to be optimal for nickel barrier plating technology with excellent selective deposition performance. 5 times or more is “good”, less than 5 times is “bad”, and the results are shown in Table 3.
- ⁇ Method for measuring gold purity of gold film> Using the electrolytic gold plating solution prepared in each example and each comparative example, a cathode current density of 40 A / min was applied on a primary bright nickel plating film of 2.0 ⁇ m on a 10 mm ⁇ 10 mm copper plate in the steps shown in Table 2. An electrolytic gold plating film of 50 ⁇ m was prepared at dm 2 by a jet-jet gold plating method, and a copper material and a nickel plating film were dissolved in nitric acid to prepare a gold foil.
- the gold foil was dissolved in 20 mL of aqua regia and quantitative analysis of Cu, Ni, Co, and Fe as impurity elements was performed with an ICP emission spectroscopic analyzer (Seiko Instruments Inc., SPS3000). The gold purity was calculated from the deposited gold mass and the impurity mass. The results are shown in Table 3. In Table 3, “%” indicates “mass%”.
- each electrolytic gold plating solution has a gold equivalent concentration of 9 g / L. Then, the bath temperature was raised to 50 ° C., and gold plating was performed on 2.0 ⁇ m of the primary bright nickel plating film on the 10 mm ⁇ 10 mm copper plate in the process described in Table 2 above.
- the current density is 1 A / dm 2 , 5 A / dm 2 , 10 A / dm 2 , 15 A / dm 2 (only the electrolytic gold plating solution of Example 1), 20 A / dm by the jet jet gold plating method. 2 , 30 A / dm 2 , 40 A / dm 2 , 50 A / dm 2 , 60 A / dm 2 , followed by electrolytic gold plating for 10 seconds each, and the gold was plated in the vicinity of the center by the above method. The film thickness of the film was measured. A graph plotting the measurement results is shown in FIG.
- the film thickness of the gold film was very thin. Has formed.
- the electrolytic gold plating solution of Example 1 may form a gold film having a film thickness equal to or greater than that of a general-purpose electrolytic gold plating solution. did it.
- the low current density region corresponds to a portion not subjected to gold plating
- the high current density region is considered to correspond to a portion subjected to gold plating.
- the thinner the gold film in the density region the better the nickel barrier properties the thicker the gold film in the high current density region. Therefore, the electrolytic gold plating solution of Example 1 containing the specific heterocyclic compound has “excellent performance adapted to the nickel barrier plating technique” because of the properties shown in FIG. 1 and the above reasons.
- the portion where the electrolytic gold plating is not desired (nickel barrier portion) (the portion where the silicon rubber member was pressed) was always 0.05 ⁇ m even at the edge portion. Only the following gold film was formed, but the gold film with an average of 0.67 ⁇ m was formed over the entire area where the electrolytic gold plating was desired (the part where the silicon rubber member was not pressed). Also, only a gold film of 0.03 ⁇ m or less was always formed on the side surface of the portion where the silicon rubber member was pressed. Even though the nickel barrier portion was an edge, almost no gold film was formed, so no solder bleeding was observed.
- the gold film thickness at a current density of 5 A / dm 2 is 0.1 ⁇ m or less, and the gold film at a current density of 5 A / dm 2 is used.
- the ratio of the film thickness to the gold film thickness at a current density of 40 A / dm 2 is 1: 5 or more, and the gold selective deposition performance is all “good”, which is optimal for nickel barrier plating. It turned out to be a liquid.
- the gold films obtained using the electrolytic gold plating solutions of the present invention of Examples 1 to 11 had excellent mechanical properties such as wear resistance, corrosion resistance, and electrical properties.
- the gold alloy films obtained using the electrolytic gold alloy plating solutions of Examples 1 to 10 had excellent mechanical properties such as wear resistance.
- the film thickness of the gold film at a current density of 5 A / dm 2 is much higher than 0.1 ⁇ m, and the film of the gold film at a current density of 5 A / dm 2 is used.
- the ratio between the thickness and the gold film thickness at a current density of 40 A / dm 2 is less than 1: 5, and the difference between the gold film thickness in the low current density area and the gold film thickness in the high current density area is small. , All showed poor gold selective deposition performance and were not suitable for nickel barrier plating.
- the electrolytic gold plating solution is suitable for nickel barrier plating.
- the electrolytic gold plating solutions of Examples 1 to 11 were found to be suitable for nickel barrier plating.
- the gold film obtained using the electrolytic gold plating solution of the present invention has excellent mechanical properties, corrosion resistance, and electrical properties, and further has excellent gold selective deposition performance. It is ideal for nickel barrier plating that has been put to practical use in the past, and it is possible to apply nickel barrier plating to connectors with complicated shapes and miniaturized connectors that have been considered extremely difficult until now. It is widely used in this field.
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Abstract
Description
本発明の電解金めっき液は、シアン化金塩を含有することが必須である。該シアン化金塩は、本発明の電解金めっき液の金源として用いられる。シアン化金塩は、1種の使用に限定されず2種以上を併用することができる。
本発明の電解金めっき液には、「環中に窒素原子を1個以上有し、該環中の炭素原子にニトロ基が1個以上置換している複素環式化合物」(以下、括弧内を「特定複素環式化合物」と略記することがある)を必須成分として含有する。特定複素環式化合物を含有することにより、従来の電解金めっき皮膜の優れた高耐食性、機械特性、電気特性等を維持したままで、低電流密度域での金析出膜厚を小さくでき、低電流密度域での金析出膜厚と高電流密度域での金析出膜厚の差を非常に大きくできる。すなわち、特定複素環式化合物を含有することにより、金選択析出性能に優れた電解金めっき液を得ることができ、ニッケルバリアめっきに最適な電解金めっき液が実現される。
本発明の電解金合金めっき液は、シアン化金塩、上記の特定複素環式化合物に加えて、更に、コバルト塩、ニッケル塩及び/又は鉄塩を併用することが、ニッケルバリアめっきに最適な硬質金皮膜を形成できる電解金めっき液が得られるために好ましい。
本発明の電解金めっき液には、上記の成分以外に必要に応じて、電解金めっき液のpHを一定に保つための緩衝剤、電解金めっき液の導電性を確保するための電導塩、電解金めっき液中に不純物金属が混入した場合に影響を除去するための金属イオン封鎖剤、金皮膜のピンホール除去若しくは電解金めっき液の泡切れを良好にするための界面活性剤、金皮膜を平滑にするための光沢剤等を、適宣含有させて用いることができる。
本発明の電解金めっき液を用いれば、ジェット噴流式めっき装置を用いて、電流密度を5A/dm2と40A/dm2に設定してそれぞれ10秒間めっき処理をした場合、電流密度5A/dm2での金皮膜の膜厚を0.1μm以下にでき、かつ40A/dm2での金皮膜の膜厚を、5A/dm2での金皮膜の膜厚の5倍以上にできる。更には、電流密度5A/dm2での金皮膜の膜厚を0.08μm以下にもでき、40A/dm2での金皮膜の膜厚を、5A/dm2での金皮膜の膜厚の7倍以上にもできる。
前述した通り、本発明の「電解金めっき液」には、「電解金合金めっき液」も含まれる。また、本発明の「金皮膜」には、「金合金皮膜」も含まれる。すなわち、コバルト、ニッケル、鉄等の金以外の金属を含有していてもよい。金以外の金属は、ニッケルめっき皮膜上の金めっき皮膜中に金と共析し、ニッケルバリアめっきに最適な硬質金皮膜を形成し、電子部品のコネクター等の接点部材に必要とされる高硬度や高耐摩耗性等を実現させることができる。
上記した本発明の電解金めっき液のめっき条件は特に限定されるものではないが、温度条件としては、20℃~90℃であることが好ましく、特に好ましくは30℃~70℃である。また、めっき液のpHはpH2.0~pH9.0であることが好ましく、特に好ましくは、pH3.0~pH8.0である。
本発明の電解金めっき液が、ニッケルバリアめっき技術に要求される優れた金選択析出性能を示す作用・原理は明らかではなく、本発明は以下の作用・原理の範囲に限定されるものではないが、以下のことが考えられる。すなわち、特に低電流密度域では、シアン化金塩中の金が還元されて金属金になるより、特定複素環式化合物が置換基として有するニトロ基が還元されてニトロソ基になる方が支配的となり、低電流密度域では金の析出が抑えられ、その結果、優れた金選択析出性能を示すようになったと考えられる。
実施例1~10、比較例1~12
電解金めっき液全体に対して、シアン化金カリウムを金換算で9g/L、表1に示す各実施例及び各比較例に記載のコバルト塩、ニッケル塩又は鉄塩を金属換算で200ppm、特定複素環式化合物若しくはその比較化合物を1000ppm、電導塩と緩衝剤を兼ねた成分としてクエン酸を100g/Lとなるように溶解し、pHを4.3に調整して電解金めっき液とした。
コバルト塩、ニッケル塩、鉄塩等の金塩以外の金属塩を含有しない以外は、実施例1と同様に電解金めっき液を調製し、実施例1と同様に電解金めっきを施し、同様に以下に記載の評価を行った。
各実施例及び各比較例で調製した電解金めっき液を用いて、表2に示す工程にて、10mm×10mmの銅板上の1次光沢ニッケルめっき皮膜2.0μm上に、電解金めっきを施した。電解金めっきは、口径8mmの円状の噴流口から毎分18Lの流量で電解金めっき液をポンプにより噴流攪拌しながら(以下、「ジェット噴流式金めっき法」とする)、電流密度を5A/dm2、40A/dm2の2水準で各10秒間ずつ電解金めっき処理した。
円状に電解金めっき処理された中心付近を、蛍光X線分析装置(セイコーインスツルメンツ株式会社製、SFT9255)を使用して、常法に従って金皮膜の膜厚を測定した。結果を表3に示す。
各実施例及び各比較例で調製した電解金めっき液を用いて、表2に示す工程にて、10mm×10mmの銅板上の1次光沢ニッケルめっき皮膜2.0μm上に、陰極電流密度40A/dm2にて50μmの電解金めっき皮膜をジェット噴流式金めっき法で作成し、硝酸にて銅素材及びニッケルめっき皮膜を溶解して金箔を作成した。作成した金箔の重量を測った後、金箔を王水20mLに溶解させ、ICP発光分光分析装置(セイコーインスツルメンツ株式会社製、SPS3000)にて、不純物元素として、Cu、Ni、Co、Feの定量分析を行い、析出金質量と不純物質量から金純度を算出した。結果を表3に示す。表3中、「%」は「質量%」を示す。
汎用の「特定複素環式化合物を含有していない電解金めっき液」と「本発明の上記実施例1の電解金めっき液」を用い、何れの電解金めっき液も金換算の濃度9g/Lとし、浴温を50℃に昇温して、上記した表2記載の工程で、10mm×10mmの銅板上の1次光沢ニッケルめっき皮膜2.0μm上に金めっきを施した。金めっきは、上記ジェット噴流式金めっき法により、電流密度を1A/dm2、5A/dm2、10A/dm2、15A/dm2(実施例1の電解金めっき液のみ)、20A/dm2、30A/dm2、40A/dm2、50A/dm2、60A/dm2と変化させて10秒間ずつ電解金めっきをし、円状に金めっき処理された中心付近を上記した方法で金皮膜の膜厚を測定した。測定結果をプロットしたグラフを図1に示す。
実施例1及び比較例1で調製した電解金めっき液を用いて、表2に示す工程にて、高精度コネクターの銅上に1次光沢ニッケルめっき皮膜2.0μmを施した。次いで、その上に、図2に示すように、電解金めっきを施したくない部分(ニッケルバリア-部分)のみに、常法に従ってシリコンゴム部材を押しつけて、50℃で平均の陰極電流密度40A/dm2にて10秒間、電解金めっき皮膜をジェット噴流式金めっき法で作成した。上記で用いたニッケルバリアめっき技術におけるコネクターの形態を図2に示し、実施例1で調製した電解金めっき液を用いたときの、図2に対応した位置の膜厚分布を図3に示す。
本発明の電解金めっき液を使用した実施例1~実施例11は、電流密度5A/dm2での金膜厚が何れも0.1μm以下であり、かつ電流密度5A/dm2での金皮膜の膜厚と電流密度40A/dm2での金皮膜の膜厚の比が何れも1:5以上であり、金選択析出性能は全てが「良」で、ニッケルバリアめっきに最適な金めっき液であることが分かった。
Claims (15)
- 金源としてのシアン化金塩と、環中に窒素原子を1個以上有し、該環中の炭素原子にニトロ基が1個以上置換している複素環式化合物とを含有することを特徴とする電解金めっき液。
- 更に、コバルト塩、ニッケル塩及び/又は鉄塩を含有する請求項1に記載の電解金めっき液。
- 該シアン化金塩が、シアン化第1金ナトリウム、シアン化第1金カリウム、シアン化第1金アンモニウム、シアン化第2金ナトリウム、シアン化第2金カリウム又はシアン化第2金アンモニウムである請求項1に記載の電解金めっき液。
- 該複素環式化合物が、ピロール、イミダゾール、ピラゾール、トリアゾール、テトラゾール、オキサゾール、イソオキサゾール、インドール、ピリジン、ピリダジン、ピリミジン、ピラジン、ウラシル、シトシン、チミン、アデニン、グアニン、キノリン、イソキノリン、キサリン、イソキサリン、アクリジン、シンノソリン又はモルホリンの炭素原子にニトロ基が1個以上置換しているものである請求項1に記載の電解金めっき液。
- 該複素環式化合物が、ピロール、イミダゾール、ピラゾール、トリアゾール、テトラゾール、オキサゾール、イソオキサゾール、インドール、ピリジン、ピリダジン、ピリミジン、ピラジン、ウラシル、シトシン、チミン、アデニン、グアニン、キノリン、イソキノリン、キサリン、イソキサリン、アクリジン、シンノソリン又はモルホリンの炭素原子にニトロ基が1個以上置換しているものである請求項2に記載の電解金めっき液。
- 該複素環式化合物が、ニトロピロール、ジニトロピロール、ニトロイミダゾール、ジニトロイミダゾール、ニトロピラゾール、ジニトロピラゾール、ニトロトリアゾール、ジニトロトリアゾール、ニトロテトラゾール、ニトロオキサゾール、ジニトロオキサゾール、ニトロイソオキサゾール、ジニトロイソオキサゾール、ニトロインドール、ニトロピリジン、ジニトロピリジン、ニトロピリダジン、ジニトロピリダジン、ニトロピリミジン、ジニトロピリミジン、ニトロピラジン、ジニトロピラジン、ニトロウラシル、ニトロシトシン、ニトロチミン、ニトロアデニン、ニトログアニン、ニトロキノリン、ジニトロキノリン、ニトロイソキノリン、ジニトロイソキノリン、ニトロキサリン、ジニトロイソキサリン、ニトロアクリジン、ニトロシンノソリン、ジニトロシンノソリン、ニトロモルホリン又はジニトロモルホリンである請求項1に記載の電解金めっき液。
- 該複素環式化合物が、ニトロピロール、ジニトロピロール、ニトロイミダゾール、ジニトロイミダゾール、ニトロピラゾール、ジニトロピラゾール、ニトロトリアゾール、ジニトロトリアゾール、ニトロテトラゾール、ニトロオキサゾール、ジニトロオキサゾール、ニトロイソオキサゾール、ジニトロイソオキサゾール、ニトロインドール、ニトロピリジン、ジニトロピリジン、ニトロピリダジン、ジニトロピリダジン、ニトロピリミジン、ジニトロピリミジン、ニトロピラジン、ジニトロピラジン、ニトロウラシル、ニトロシトシン、ニトロチミン、ニトロアデニン、ニトログアニン、ニトロキノリン、ジニトロキノリン、ニトロイソキノリン、ジニトロイソキノリン、ニトロキサリン、ジニトロイソキサリン、ニトロアクリジン、ニトロシンノソリン、ジニトロシンノソリン、ニトロモルホリン又はジニトロモルホリンである請求項2に記載の電解金めっき液。
- 該コバルト塩が、硫酸コバルト、塩化コバルト、硝酸コバルト、炭酸コバルト、フタロシアニンコバルト、ステアリン酸コバルト、エチレンジアミン4酢酸二ナトリウムコバルト、ナフテン酸コバルト、ホウ酸コバルト、チオシアン酸コバルト、スルファミン酸コバルト、酢酸コバルト、クエン酸コバルト、水酸化コバルト、シュウ酸コバルト又はリン酸コバルトである請求項2に記載の電解金めっき液。
- 該ニッケル塩が、硫酸ニッケル、酢酸ニッケル、塩化ニッケル、ホウ酸ニッケル、安息香酸ニッケル、シュウ酸ニッケル、ナフテン酸ニッケル、酸化ニッケル、リン酸ニッケル、ステアリン酸ニッケル、酒石酸ニッケル、チオシアン酸ニッケル、アミド硫酸ニッケル、炭酸ニッケル、クエン酸ニッケル、ギ酸ニッケル、シアン化ニッケル、水酸化ニッケル、硝酸ニッケル又はオクタン酸ニッケルである請求項2に記載の電解金めっき液。
- 該鉄塩が、硫酸第1鉄、硫酸第2鉄、塩化第1鉄、塩化第2鉄、クエン酸第1鉄、クエン酸第2鉄、ギ酸第2鉄、次亜リン酸第2鉄、ナフテン酸第2鉄、ステアリン酸第2鉄、ピロリン酸第2鉄、酒石酸第1鉄、酒石酸第2鉄、チオシアン酸第1鉄、チオシアン酸第2鉄、フマル酸第1鉄、グルコン酸第1鉄、エチレンジアミン四酢酸鉄、硝酸第1鉄又は硝酸第2鉄である請求項2に記載の電解金めっき液。
- ジェット噴流式めっき装置を用いて、電流密度を5A/dm2と40A/dm2に設定してそれぞれ10秒間めっき処理をした場合、電流密度5A/dm2での金皮膜の膜厚が0.1μm以下であり、かつ40A/dm2での金皮膜の膜厚が、5A/dm2での金皮膜の膜厚の5倍以上である請求項1乃至請求項10の何れかの請求項に記載の電解金めっき液。
- 請求項1乃至請求項10の何れかの請求項に記載の電解金めっき液を用いてニッケル皮膜上に電解金めっきを行うことによって得られたことを特徴とする金皮膜。
- 請求項11に記載の電解金めっき液を用いてニッケル皮膜上に電解金めっきを行うことによって得られたことを特徴とする金皮膜。
- 該金皮膜の金純度が95質量%以上である請求項12に記載の金皮膜。
- 該金皮膜の金純度が95質量%以上である請求項13に記載の金皮膜。
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Cited By (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2010077527A (ja) * | 2008-08-25 | 2010-04-08 | Electroplating Eng Of Japan Co | 硬質金系めっき液 |
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JP2014139348A (ja) * | 2008-08-25 | 2014-07-31 | Electroplating Eng Of Japan Co | 硬質金系めっき液 |
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DE102013109400A1 (de) * | 2013-08-29 | 2015-03-05 | Harting Kgaa | Kontaktelement mit Goldbeschichtung |
CN103741180B (zh) * | 2014-01-10 | 2015-11-25 | 哈尔滨工业大学 | 无氰光亮电镀金添加剂及其应用 |
EP2990507A1 (en) * | 2014-08-25 | 2016-03-02 | ATOTECH Deutschland GmbH | Composition, use thereof and method for electrodepositing gold containing layers |
CN106637307B (zh) * | 2017-01-04 | 2019-01-01 | 中国地质大学(武汉) | 一种用于黄金无氰电铸工艺的添加剂 |
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- 2009-05-12 CN CN2009801286107A patent/CN102105623B/zh active Active
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JP2014139348A (ja) * | 2008-08-25 | 2014-07-31 | Electroplating Eng Of Japan Co | 硬質金系めっき液 |
JP2010077527A (ja) * | 2008-08-25 | 2010-04-08 | Electroplating Eng Of Japan Co | 硬質金系めっき液 |
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 |
JP2011122236A (ja) * | 2009-09-25 | 2011-06-23 | Rohm & Haas Electronic Materials Llc | 抗置換硬質金組成物 |
JP2011122192A (ja) * | 2009-12-09 | 2011-06-23 | 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 |
KR101809565B1 (ko) * | 2010-11-25 | 2017-12-15 | 롬 앤드 하스 일렉트로닉 머트어리얼즈 엘엘씨 | 금 도금 용액 |
JP2012112004A (ja) * | 2010-11-25 | 2012-06-14 | Rohm & Haas Denshi Zairyo Kk | 金めっき液 |
JP2013177654A (ja) * | 2012-02-28 | 2013-09-09 | Matex Japan Co Ltd | 電解硬質金めっき液、めっき方法、及び、金−鉄合金被膜の製造方法 |
JP5152943B1 (ja) * | 2012-09-19 | 2013-02-27 | 小島化学薬品株式会社 | 低遊離シアン金塩の製造方法 |
WO2016208340A1 (ja) * | 2015-06-26 | 2016-12-29 | メタローテクノロジーズジャパン株式会社 | 電解硬質金めっき液用置換防止剤及びそれを含む電解硬質金めっき液 |
JPWO2016208340A1 (ja) * | 2015-06-26 | 2018-04-12 | メタローテクノロジーズジャパン株式会社 | 電解硬質金めっき液用置換防止剤及びそれを含む電解硬質金めっき液 |
US10577704B2 (en) | 2015-06-26 | 2020-03-03 | Metalor Technologies Corporation | Electrolytic hard gold plating solution substitution inhibitor and electrolytic hard gold plating solution including same |
KR102670599B1 (ko) * | 2015-06-26 | 2024-05-29 | 이이쟈 가부시키가이샤 | 전해 경질 금 도금액용 치환 방지제 및 그것을 포함하는 전해 경질 금 도금액 |
JPWO2018221089A1 (ja) * | 2017-05-30 | 2020-04-02 | オリエンタル鍍金株式会社 | Pcb端子の製造方法及びpcb端子 |
JPWO2018221087A1 (ja) * | 2017-05-30 | 2020-05-28 | オリエンタル鍍金株式会社 | Pcb端子 |
JP7079016B2 (ja) | 2017-05-30 | 2022-06-01 | オリエンタル鍍金株式会社 | Pcb端子の製造方法及びpcb端子 |
JP2022082619A (ja) * | 2017-05-30 | 2022-06-02 | オリエンタル鍍金株式会社 | Pcb端子の製造方法及びpcb端子 |
JP7117784B2 (ja) | 2017-05-30 | 2022-08-15 | オリエンタル鍍金株式会社 | Pcb端子 |
Also Published As
Publication number | Publication date |
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TWI409367B (zh) | 2013-09-21 |
CN102105623A (zh) | 2011-06-22 |
JP4719822B2 (ja) | 2011-07-06 |
CN102105623B (zh) | 2013-10-02 |
KR101079554B1 (ko) | 2011-11-04 |
KR20110022576A (ko) | 2011-03-07 |
TW201009125A (en) | 2010-03-01 |
JPWO2009150915A1 (ja) | 2011-11-10 |
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