WO2010004856A1 - Catalyst-imparting liquid for palladium plating - Google Patents

Catalyst-imparting liquid for palladium plating Download PDF

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Publication number
WO2010004856A1
WO2010004856A1 PCT/JP2009/061277 JP2009061277W WO2010004856A1 WO 2010004856 A1 WO2010004856 A1 WO 2010004856A1 JP 2009061277 W JP2009061277 W JP 2009061277W WO 2010004856 A1 WO2010004856 A1 WO 2010004856A1
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Prior art keywords
catalyst
copper
palladium
based metal
gold
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PCT/JP2009/061277
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French (fr)
Japanese (ja)
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茂樹 清水
隆治 高崎
歓三 清原
健児 吉羽
良典 小暮
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日本高純度化学株式会社
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Priority to JP2010519714A priority Critical patent/JP5567478B2/en
Publication of WO2010004856A1 publication Critical patent/WO2010004856A1/en

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    • 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
    • H05K3/24—Reinforcing the conductive pattern
    • H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1827—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment only one step pretreatment
    • C23C18/1831—Use of metal, e.g. activation, sensitisation with noble metals
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/0716—Metallic plating catalysts, e.g. for direct electroplating of through holes; Sensitising or activating metallic plating catalysts
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/07—Treatments involving liquids, e.g. plating, rinsing
    • H05K2203/0703—Plating
    • H05K2203/072—Electroless plating, e.g. finish plating or initial plating

Definitions

  • the present invention relates to a catalyst application liquid for electroless reduction palladium plating, and more particularly to a catalyst application liquid having a specific composition used when electroless reduction palladium plating is performed on a copper-based metal.
  • solder joints of electronic materials in which conductor circuits are formed of copper-based metals are exposed, the copper-based metal surfaces are oxidized by heat treatment before solder joints, resulting in poor solder joints. Therefore, a surface treatment in which a nickel film of about 5 ⁇ m is formed on a metal surface of a copper-based conductor circuit and a gold film of about 0.05 ⁇ m is further formed on the metal surface by electroless plating has been widely put into practical use.
  • a surface treatment is performed by sequentially forming a palladium film by electroless palladium plating on a copper-based conductor circuit and then a gold film by electroless gold plating on the palladium film without forming a nickel film.
  • Patent Documents 1 and 2 the films formed by these known surface treatment methods have a problem that voids are generated in the solder near the joint when solder balls are joined. If voids are present in the solder joint, the conductor area as an electrical contact is reduced, so that a sufficient function as an electrical joint terminal could not be achieved.
  • the present invention has been made in view of the above-described background art, and the problem is that when performing electroless reduction palladium plating directly on a copper-based metal, there is no fine wiring bridge, and there is no film thickness unevenness. Electroless reduced palladium that can form a film that does not generate voids in solder when it is soldered onto a plated film that has been electrolessly plated with gold after electroless reduced palladium plating. It is in providing the catalyst provision liquid for plating.
  • Japanese Patent No. 2649750 discloses a method of activating with a catalyst application liquid containing a palladium compound.
  • Japanese Patent Application Laid-Open No. 2003-082468 discloses a method of activation with a catalyst-providing solution containing at least one compound selected from gold, silver, palladium, ruthenium, rhodium, platinum, and copper compounds. ing.
  • a catalyst-providing solution containing at least one compound selected from gold, silver, palladium, ruthenium, rhodium, platinum, and copper compounds.
  • these examples are provided with a catalyst using a water-soluble palladium compound, and a commercially available catalyst application solution for electroless reduction plating generally contains a water-soluble palladium compound.
  • the present inventor has conducted extensive studies on a catalyst-providing liquid that activates only a copper-based metal. As a result, at least (a) a water-soluble gold compound and (b) a nitrogen atom are present.
  • the catalyst imparting solution containing two or more 5-membered heterocyclic compounds and (c) a chelating agent having an iminodiacetic acid structure is used, the resulting electroless reduced palladium-plated film.
  • the film thickness is uniform, and the generation of voids is remarkably suppressed when soldered onto a plating film that has been subjected to electroless gold plating following electroless reduced palladium plating. As a result, the present invention has been completed.
  • the present invention is a catalyst-providing liquid for performing electroless reduction palladium plating on a copper-based metal, comprising a water-soluble gold compound and a five-membered ring structure having two or more nitrogen atoms as constituent components.
  • the present invention provides a catalyst-providing liquid characterized by containing a heterocyclic compound having a chelating agent having an iminodiacetic acid structure.
  • the present invention provides a method for producing a palladium plating film on a copper-based metal, characterized in that electroless reduction palladium plating is performed on the copper-based metal using the above-described catalyst imparting solution, Further, the present invention provides a palladium plating film on a copper-based metal obtained by performing electroless reduction palladium plating on a copper-based metal using the above catalyst-providing liquid.
  • the present invention also provides a palladium plating film on a copper-based metal, characterized in that it has gold of 3 ⁇ 10 ⁇ 5 g / cm 2 or less on a copper-based metal and is formed thereon.
  • the copper is characterized in that it is formed by depositing gold of 3 ⁇ 10 ⁇ 5 g / cm 2 or less on a copper-based metal using the above-described catalyst-providing liquid.
  • the present invention provides a palladium plating film on a base metal.
  • the present invention provides a palladium / gold plating on a copper-based metal, characterized by performing electroless reduction palladium plating on a copper-based metal and subsequently performing electroless gold plating using the above-described catalyst-providing solution.
  • the present invention provides a method for producing a film, and is obtained by performing electroless reduction palladium plating on a copper-based metal, followed by electroless gold plating, using the above-described catalyst imparting solution.
  • a palladium / gold plating film on a copper-based metal is provided.
  • the expression “palladium / gold” means that a gold film exists on the palladium film
  • the expression “copper / palladium / gold” means that the palladium film exists on the copper-based metal. , which means that a gold film exists on it.
  • the above-mentioned problems can be solved and the above-mentioned problems can be solved, and a uniform electroless reduced palladium plating film having no film thickness unevenness can be obtained on a copper-based metal. Even in this case, an electroless reduced palladium plating film having no bridge and no precipitation can be formed. Moreover, when electroless gold plating is performed on the palladium film and solder ball bonding is performed, generation of voids in the solder can be suppressed.
  • mapping analysis photograph (150 times) which shows the criterion judged as "defect” by the evaluation method of the bridge
  • SEM photograph (2000 times) which shows the judgment standard judged with "the absence” by the evaluation method of generation of a void, and is a SEM photograph (2000 times) of Example 4.
  • SEM photograph (2000 times) which shows the judgment standard judged with "it is” by the evaluation method of generation of a void, and is a SEM photograph (2000 times) of comparative example 1.
  • the present invention relates to a catalyst applying liquid for performing electroless reduction palladium plating on a copper-based metal.
  • the “copper-based metal” is used for ordinary conductor circuit formation and is not particularly limited as long as it contains copper, and includes copper alone or a copper alloy. Moreover, there is no limitation in particular as metals other than copper in a copper alloy, if the said effect of this invention is acquired.
  • the “copper-based metal” is preferably copper alone or a copper alloy containing 60% by mass or more of copper, and particularly preferably copper alone or a copper alloy containing 80% by mass or more of copper.
  • “electroless reduced palladium plating” refers to a plating step in which palladium alone or palladium alloy containing palladium is deposited by various reducing agents.
  • the element other than palladium constituting the palladium alloy is not particularly limited, and examples thereof include phosphorus (P), boron (B), carbon (C), sulfur (S), lead (Pb), and bismuth (Bi). .
  • One or more elements other than palladium are used to form a palladium alloy together with palladium.
  • the palladium plating layer in the present invention is preferably “palladium alone or a palladium alloy” containing preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of palladium. It is preferable because the effect can be obtained more.
  • the catalyst-providing liquid of the present invention contains at least (a) a water-soluble gold compound, (b) a heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms, and (c) an iminodiacetic acid structure. It is essential to contain a chelating agent.
  • the “water-soluble gold compound” in the present invention is particularly limited as long as it is a gold compound that is soluble in water so that the concentration in the catalyst-providing solution is suitable. Specific examples include gold cyanide, gold chloride, gold sulfite, gold thiosulfate, and the like. Preferred is a gold cyanide salt in view of the stability of the gold compound and the availability of chemicals, and particularly preferred is a first gold cyanide salt or a second gold cyanide salt.
  • the counter cation is not particularly limited, but an alkali metal salt is preferable as a catalyst-adding solution, and a potassium salt is particularly preferable.
  • the concentration of the “water-soluble gold compound” is not particularly limited, but is preferably 10 ppm or more and 2000 ppm or less, and particularly preferably 20 ppm or more and 1000 ppm or less, in terms of gold based on the total amount of the catalyst application liquid. If the concentration of the “water-soluble gold compound” is too high, the gold may precipitate in the catalyst-providing solution, resulting in instability as a catalyst-providing solution. If it is too small, the catalytic ability is incomplete. There is a case where non-deposition of electrolytic reduction palladium plating occurs.
  • the catalyst-providing liquid of the present invention does not substantially contain a water-soluble platinum group element compound.
  • the platinum group element include ruthenium, rhodium, palladium, osmium, iridium, and platinum.
  • voids may be generated in the solder when soldered as described above.
  • heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms includes elements other than carbon.
  • heterocycle having a 5-membered ring structure may be a heterocycle that is a condensed aromatic ring by condensing with an aromatic ring such as a benzene ring, a naphthalene ring, or another heterocycle.
  • the “other heterocycle” does not need to have two or more nitrogen atoms or a 5-membered ring.
  • heterocyclic ring of the “heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms” there are no particular limitations on the heterocyclic ring of the “heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms”.
  • imidazole ring, pyrazole ring, purine ring, 1,2,3-triazole ring, 1, Examples include 2,4-triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, benzimidazole ring, and benztriazole ring.
  • the substituent bonded to the heterocycle is not particularly limited, but an amino group, an alkyl group, an alkylamino group, and the like are preferable. Of these, amino groups are particularly preferred.
  • examples of the “heterocyclic compound having a 5-membered ring structure having two or more nitrogen atoms” include pyrazole, 3-aminopyrazole, 4-aminopyrazole, 5-aminopyrazole, imidazole, 2-aminoimidazole, 4 -Aminoimidazole, 5-aminoimidazole, purine, 2-aminopurine, 6-aminopurine, 1,2,3-triazole, 4-amino-1,2,3-triazole, 5-amino-1,2,3 -Triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-1,2,4-triazole, tetrazole, 5-aminotetrazole, 2-amino-1,3, 4-thiadiazole, 2-aminobenzimidazole, benztriazole or the like, or an alkyl-substituted product thereof is preferable And the like to. These are used alone or in combination.
  • imidazole 2-aminoimidazole, 4-aminoimidazole, 5-aminoimidazole, 1,2,4-triazole, 3-amino-1,2,4 are particularly preferable for obtaining the effects of the present invention.
  • -Triazole 5-aminotetrazole and the like.
  • the concentration of the “heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms” is not particularly limited, but is preferably 10 ppm or more and 10,000 ppm or less, and particularly 50 ppm or more and 5000 ppm or less with respect to the entire catalyst-providing liquid. preferable. If the concentration is too high, precipitates may be generated. If the concentration is too low, voids may easily occur during solder ball bonding.
  • imino 2 capable of dissolving a copper-based metal constituting a copper-based conductor circuit or the like in a catalyst-providing solution. It preferably has an acetic acid structure.
  • a chelating agent having an iminodiacetic acid structure as an essential component, it is possible to promote uniform dissolution of the copper-based metal in the catalyst-providing liquid and to prevent the copper-based metal from reprecipitating, The application of catalyst nuclei can be performed uniformly and reliably, and the occurrence of bridging of the fine wiring due to metal adhesion to the insulator between the fine wirings can be prevented.
  • chelating agent having an iminodiacetic acid structure examples include, for example, ethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and triethylenetetramine.
  • examples include 6-acetic acid, dicarboxymethyl glutamic acid, propanediamine tetraacetic acid, 1,3-diamino-2-hydroxylpropane tetraacetic acid, and the like, or water-soluble salts thereof.
  • water-soluble salt Sodium salt, potassium salt, ammonium salt, etc. are mentioned. These are used alone or in combination of two or more.
  • acetic acid units in that the action of stably dissolving the copper-based metal is strong.
  • water-soluble salts are mentioned.
  • the “chelating agent having an iminodiacetic acid structure” in the present invention is preferably used in the range of 1 g / L to 100 g / L, more preferably 2 g / L to 60 g / L with respect to the entire catalyst-providing liquid. Particularly preferred is 3 g / L to 40 g / L.
  • concentration of the chelating agent is too large, it may be precipitated in the catalyst-providing liquid, and when it is too small, the catalyst activation on the copper-based metal surface may be insufficient.
  • the catalyst-imparting solution of the present invention can contain a pH buffering agent and the like as appropriate, if necessary.
  • the pH buffer is not particularly limited as long as it can alleviate fluctuations in pH without adversely affecting the properties of the catalyst-providing liquid. Regardless of whether it is an organic substance or an inorganic substance, an acid or a salt thereof may be added as appropriate. Specific examples include inorganic acids such as boric acid, phosphoric acid, and pyrophosphoric acid; organic acids such as citric acid, acetic acid, malic acid, succinic acid, and tartaric acid; or salts thereof.
  • the catalyst-providing liquid of the present invention is preferably pH 3 or more and pH 9 or less, particularly preferably pH 4 or more and pH 8 or less.
  • a commercially available catalyst-providing solution for electroless reduction plating containing palladium is in the vicinity of pH 1, which is significantly different from the preferred pH range of the catalyst-providing solution of the present invention. If the pH is too low, gold may be deposited, which may result in instability as a catalyst-imparting solution, and if the pH is too high, catalyst activity may be reduced and electroless reduced palladium plating may not proceed easily.
  • the treatment temperature of the catalyst imparting solution of the present invention is preferably 10 ° C. or more and 95 ° C. or less, and particularly preferably 20 ° C. or more and 90 ° C. or less. Further, the treatment time of the catalyst applying liquid of the present invention is preferably from 5 seconds to 15 minutes, particularly preferably from 10 seconds to 10 minutes.
  • the amount of catalyst core metal supported in the catalyst application liquid of the present invention is 0.05 to 3 mg / dm 2 (0.05 ⁇ 10 ⁇ 5 to 3 ⁇ 10 ⁇ 5). g / cm 2 ), preferably 0.1 to 2 mg / dm 2 (0.1 ⁇ 10 ⁇ 5 to 2 ⁇ 10 ⁇ 5 g / cm 2 ). Within this range, the effects of the present invention described above are easily obtained. That is, one embodiment of the present invention is “a copper-based metal having 3 mg / dm 2 or less (3 ⁇ 10 ⁇ 5 g / cm 2 or less) of gold on a copper-based metal and formed thereon.
  • “Palladium plating film on metal” is preferable because it has the above-mentioned effect. “Palladium plating film on copper-based metal having 3 ⁇ 10 ⁇ 5 g / cm 2 or less of gold on the copper-based metal and formed thereon” There is the effect of the present invention as long as this configuration is satisfied.
  • gold plating in order to be able to confirm the color tone of the deposited metal visually, that is, to say “gold plating”, about 6 mg / dm 2 (6 ⁇ 10 ⁇ 5 g / cm 2 , thickness 30 nm)
  • gold plating about 6 mg / dm 2 (6 ⁇ 10 ⁇ 5 g / cm 2 , thickness 30 nm)
  • the amount of precipitation described above is necessary, and normal displacement gold plating is deposited on the order of 12 mg / dm 2 (12 ⁇ 10 ⁇ 5 g / cm 2 , thickness 60 nm) or more. That is, the catalyst-providing liquid of the present invention deposits a significantly smaller amount of gold on a copper-based metal compared to substitutional electroless gold plating.
  • the catalyst application liquid of the present invention selectively activates a copper-based metal such as a copper-based conductor circuit formed on a printed circuit board, for example. It is used to selectively form only on a copper-based metal such as a conductor circuit.
  • the “copper-based conductor circuit” is formed by forming a circuit with a copper-based metal on a base material that is an insulator such as glass epoxy, ceramic, or polyimide.
  • the method for forming a copper-based metal circuit is not particularly limited, and examples thereof include plating, vapor deposition, and lamination of a Cu plate.
  • the pretreatment step in the case of using the catalyst application liquid of the present invention is not particularly limited, and may be performed according to a pretreatment method before applying the catalyst application liquid, which is performed by normal electroless plating.
  • the electroless reduced palladium plating solution is not particularly limited and can be used. Examples thereof include those containing a water-soluble palladium compound, formic acid or a formic acid derivative, and a nitrogen-containing complexing agent. Other examples include water-soluble palladium compounds, amine compounds, organic compounds containing divalent sulfur, and compounds containing hypophosphorous acid compounds or borohydride compounds.
  • the palladium film formed using the catalyst-providing liquid of the present invention is preferably “palladium alone or a palladium alloy” containing 80% by mass or more of palladium, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. It is preferable for the effect of the present invention to be obtained more.
  • the film thickness of the palladium film is not particularly limited, but is preferably 0.03 ⁇ m to 1 ⁇ m, and particularly preferably 0.05 ⁇ m to 0.5 ⁇ m.
  • the plating conditions for electroless reduced palladium plating are not particularly limited and may be normal conditions.
  • the solder wettability after heat treatment may not be good.
  • electroless gold plating should be performed, and a gold plating film with good solder wettability should be applied. Forming on the outermost surface is preferable in that the effect of the present invention can be obtained more.
  • the thickness of the gold film is not particularly limited, but is preferably 0.03 ⁇ m to 0.3 ⁇ m, particularly preferably 0.05 ⁇ m to 0.1 ⁇ m.
  • the electroless gold plating conditions are not particularly limited and may be normal conditions.
  • Examples 1-6 Preparation of catalyst application liquid>
  • the water-soluble gold compound shown in Table 1 is 100 ppm in mass with respect to the entire catalyst-providing liquid in terms of metal gold, and (b) a hetero compound having a five-membered ring structure with two or more nitrogen atoms shown in Table 1.
  • the ring compound is 500 ppm by mass with respect to the entire catalyst-providing liquid
  • the chelating agent having (c) iminodiacetic acid structure shown in Table 1 is 20 g / L with respect to the entire catalyst-applying liquid. Dissolved.
  • each catalyst provision liquid was adjusted so that it might become pH 5.0.
  • a sodium hydroxide aqueous solution was used to raise the pH
  • hydrochloric acid was used to lower the pH.
  • Comparative Examples 1 and 2 As Comparative Example 1, a “catalyst-providing solution for electroless reduction nickel plating (KAT-450, manufactured by Uemura Kogyo Co., Ltd.)” containing commercially available palladium was used in a state of normal use. Further, as Comparative Example 2, a “catalyst imparting solution for electroless reduced nickel plating (ICP Axela, manufactured by Okuno Seiyaku Co., Ltd.)” containing commercially available palladium was used in a normal use state.
  • KAT-450 manufactured by Uemura Kogyo Co., Ltd.
  • ICP Axela manufactured by Okuno Seiyaku Co., Ltd.
  • Comparative Examples 3-20 The compound shown in the leftmost column of Table 1 is 100 ppm by mass with respect to the entire catalyst application liquid in terms of metal, and those specified to be contained in Table 1 include the heterocyclic compound shown in Table 1 in the entire catalyst application liquid.
  • the chelating agent shown in Table 1 was dissolved in pure water so as to be 20 g / L with respect to the entire catalyst application liquid.
  • each catalyst provision liquid was prepared by adjusting to pH shown in Table 1. For pH adjustment, an aqueous sodium hydroxide solution was used to raise the pH, and hydrochloric acid was used to lower the pH.
  • an evaluation substrate was prepared separately from the evaluation, and in addition to the above-described catalyst applying solution and electroless reduced palladium plating solution, a known electroless displacement gold plating solution (IM- GOLDPC (manufactured by Nippon High Purity Chemical Co., Ltd.) was used, and electroless reduced palladium and then electroless displacement gold plating were performed in the steps shown in Table 3. The evaluation method was evaluated.
  • IM- GOLDPC manufactured by Nippon High Purity Chemical Co., Ltd.
  • Evaluation board 1 An evaluation substrate having the configuration shown in FIGS. 1 and 2 was produced. Circular copper pads with a diameter of 0.76 mm are arranged in a grid pattern on a polyimide resin substrate 40 mm long x 40 mm wide x 1.0 mm thick, and each copper pad is surrounded by a photo solder resist. The one coated with is used. Each copper pad is formed of copper having a thickness of 12 ⁇ m, the thickness of the photo solder resist is 20 ⁇ m, and the diameter of the opening of the solder ball pad is 0.62 mm.
  • Evaluation board 2 The evaluation board
  • the film thickness of the electroless reduced palladium film formed on the copper of the solder ball pad of the evaluation board 1 was measured at 10 points using a fluorescent X-ray film thickness meter (SEA5120, manufactured by Seiko Instruments Inc.), and the average film
  • the deposition uniformity of electroless reduced palladium plating was evaluated by comparing the thickness, maximum film thickness, and minimum film thickness. A sample having a very small minimum film thickness was evaluated as “precipitation unevenness”. All the measured values were 0.00 ⁇ m and evaluated as “no precipitation”. The results are shown in Table 4.
  • the copper wiring of the evaluation board 2 is scanned with a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.) (hereinafter abbreviated as “SEM”) and an energy dispersive X-ray analyzer (EMAX EX-220, manufactured by HORIBA).
  • SEM scanning electron microscope
  • EMAX EX-220 an energy dispersive X-ray analyzer
  • the evaluation substrate 1 to which the solder balls are fused is cut into a size of about 15 mm ⁇ 15 mm so that the operation is easy, and is placed in a mold for cold embedding resin. (No. 105, manufactured by Marumoto Struers) and its curing agent were poured and cured. The cured sample was polished using a SiC polishing paper and a polishing machine, and the cross section was exposed so that the cross section of the joint between the solder ball and the ball pad could be seen.
  • a water-soluble gold compound of the present invention (b) a heterocyclic compound in which the nitrogen atom has two or more five-membered ring structures, and (c) an iminodiacetic acid structure.
  • the catalyst application liquid containing a chelating agent as an essential component has sufficient catalytic action for electroless reduction palladium plating on a copper-based conductor circuit, and does not have a fine wiring bridge and forms a uniform palladium plating film. Furthermore, it was found that the film formed by electroless gold plating after electroless reduced palladium plating was free of voids in the solder when solder balls were bonded onto the film. (Examples 1 to 6).
  • Comparative Examples 1 to 10 which do not contain a water-soluble gold compound
  • Comparative Examples 1 to 5 having a low pH of 1.0 have no fine wiring bridge and form a uniform palladium plating film. Although it was possible, extremely large voids were generated during soldering. In Comparative Examples 6 to 10 having a pH of 5.0 close to the neutral pH range, the catalyst could not be activated uniformly, and deposition unevenness of the palladium plating film occurred.
  • the catalyst-providing liquid for electroless reduced palladium plating of the present invention can provide an electroless reduced palladium plated film having no film thickness unevenness and no bridge on a copper-based metal, and solder ball bonding Since generation of voids at the time can also be suppressed, it is widely used in all fields where solder joints of copper-based conductor circuits are used.

Abstract

A catalyst-imparting liquid is provided.  When electroless reductional palladium plating is conducted directly on a copper-based-conductor circuit material, the catalyst-imparting liquid enables an even coating film free from thickness unevenness to be deposited without bridging fine wiring lines.  When the electroless reductional palladium plating is followed by electroless gold plating and then by soldering to the resultant deposit, a coating film having no voids can be formed.  The catalyst-imparting liquid is used for conducting electroless reductional palladium plating on a copper-based metal.  The catalyst-imparting liquid is characterized by containing, as constituent ingredients, a water-soluble gold compound, a heterocyclic compound having a five-membered ring structure including two or more nitrogen atoms, and a chelating agent having an iminodiacetic acid structure.  Also provided are: a process for producing a palladium deposit on a copper-based metal, characterized by using the catalyst-imparting liquid to conduct electroless reductional palladium plating on the copper-based metal; and a palladium deposit produced on a copper-based metal by the process.

Description

パラジウムめっき用触媒付与液Catalyst plating solution for palladium plating
　本発明は、無電解還元パラジウムめっき用の触媒付与液に関し、更に詳しくは、銅系金属の上に無電解還元パラジウムめっきを行う際に用いる、特定の組成をもった触媒付与液に関する。 The present invention relates to a catalyst application liquid for electroless reduction palladium plating, and more particularly to a catalyst application liquid having a specific composition used when electroless reduction palladium plating is performed on a copper-based metal.
　銅系金属により導体回路を形成した電子材料のはんだ接合部は、銅系導体回路が露出した状態であると、はんだ接合前の熱処理により銅系金属表面が酸化して、はんだ接合不良を発生してしまうため、銅系導体回路の金属表面上に５μｍ程度のニッケル皮膜、更にその上に０．０５μｍ程度の金皮膜をそれぞれ無電解めっきにより形成する表面処理が広く実用化されている。 If the solder joints of electronic materials in which conductor circuits are formed of copper-based metals are exposed, the copper-based metal surfaces are oxidized by heat treatment before solder joints, resulting in poor solder joints. Therefore, a surface treatment in which a nickel film of about 5 μm is formed on a metal surface of a copper-based conductor circuit and a gold film of about 0.05 μm is further formed on the metal surface by electroless plating has been widely put into practical use.
　しかし、近年の電子材料の小型化・高密度化に対応するためには、はんだ接合信頼性が低いことや、無電解ニッケルめっきが微細配線への追従性が悪く、本来はめっきを行ないたくない微細配線間の絶縁体部に析出してしまうブリッジと呼ばれる基板配線不良等が問題となっていた。 However, in order to cope with the recent downsizing and higher density of electronic materials, the reliability of solder joints is low, and electroless nickel plating has poor followability to fine wiring, so we do not want to perform plating originally Substrate wiring defects called bridges that precipitate on the insulator between fine wirings have been problematic.
　これらの問題を解決する方法としては、ニッケル皮膜を形成することなく、銅系導体回路上に無電解パラジウムめっきによるパラジウム皮膜、次いでパラジウム皮膜上に無電解金めっきによる金皮膜を順次形成する表面処理が開示されている（特許文献１～２）。しかし、これらの公知の表面処理方法により形成した皮膜は、はんだボール接合をした際に、接合部近傍のはんだ内にボイドが発生してしまうという問題点があった。はんだ接合部内にボイドが存在すると、電気接点としての導体面積が小さくなるため、電気接合端子としては十分な機能を果たせていなかった。 As a method for solving these problems, a surface treatment is performed by sequentially forming a palladium film by electroless palladium plating on a copper-based conductor circuit and then a gold film by electroless gold plating on the palladium film without forming a nickel film. Is disclosed (Patent Documents 1 and 2). However, the films formed by these known surface treatment methods have a problem that voids are generated in the solder near the joint when solder balls are joined. If voids are present in the solder joint, the conductor area as an electrical contact is reduced, so that a sufficient function as an electrical joint terminal could not be achieved.
　近年の電子材料の小型化・高密度化に対応するため、銅系導体回路上にパラジウム皮膜及び金皮膜を順次形成させる表面処理法の工業化が強く望まれているが、上記した公知技術では不十分であり、工業化には至っていなかった。 In order to cope with the recent downsizing and higher density of electronic materials, industrialization of a surface treatment method for sequentially forming a palladium film and a gold film on a copper-based conductor circuit is strongly desired. It was enough and it was not industrialized.
特開平５－３２７１８７号公報JP-A-5-327187 特開２００５－３１７７２９号公報JP 2005-317729 A
　本発明は上記背景技術に鑑みてなされたものであり、その課題は、銅系金属の上に直接無電解還元パラジウムめっきを行う際に、微細配線のブリッジがなく、膜厚ムラがなく均一な皮膜であり、無電解還元パラジウムめっきに続いて無電解金めっきを行なっためっき皮膜上にはんだ接合した際に、はんだ内にボイドを発生させない皮膜を形成することを可能とする、無電解還元パラジウムめっき用の触媒付与液を提供することにある。 The present invention has been made in view of the above-described background art, and the problem is that when performing electroless reduction palladium plating directly on a copper-based metal, there is no fine wiring bridge, and there is no film thickness unevenness. Electroless reduced palladium that can form a film that does not generate voids in solder when it is soldered onto a plated film that has been electrolessly plated with gold after electroless reduced palladium plating. It is in providing the catalyst provision liquid for plating.
　本発明者は、銅系導体回路素材の上に何も処理を行なわずに直接無電解還元パラジウムめっきを行なうと、無電解還元パラジウムのめっき反応進行開始が非常に遅く、たとえ反応が開始したとしても進行開始が疎らなため、膜厚ムラが発生するので実用上不十分な皮膜形成になってしまうことを見出した。従って、無電解還元パラジウムの反応開始を促進するために銅系導体回路の表面を活性化させてから無電解還元パラジウムめっきを行なうことが必須であることを見出した。 When the present inventor directly electrolessly reduced palladium plating without any treatment on the copper-based conductor circuit material, the start of the electroless reduced palladium plating reaction was very slow, even if the reaction started However, it has been found that since the start of progress is sparse, film thickness unevenness occurs, resulting in a practically insufficient film formation. Accordingly, it has been found that in order to promote the reaction initiation of electroless reduced palladium, it is essential to perform electroless reduced palladium plating after activating the surface of the copper-based conductor circuit.
　一方、一般に無電解還元めっきを行なうために銅系金属の表面を活性化する方法としては、特許第２６４９７５０号にはパラジウム化合物を含有する触媒付与液にて活性化する方法が開示されている。 On the other hand, as a method for activating the surface of a copper-based metal in order to perform electroless reduction plating in general, Japanese Patent No. 2649750 discloses a method of activating with a catalyst application liquid containing a palladium compound.
　また、特開２００３－０８２４６８号公報には、金、銀、パラジウム、ルテニウム、ロジウム、白金、銅の化合物から選ばれた少なくとも一種の化合物を含有する触媒付与液にて活性化する方法が開示されている。しかしながら、これらの実施例は、水溶性パラジウム化合物にて触媒付与が行われており、また、市販の無電解還元めっき用触媒付与液は水溶性パラジウム化合物を含有するものが一般的である。 Japanese Patent Application Laid-Open No. 2003-082468 discloses a method of activation with a catalyst-providing solution containing at least one compound selected from gold, silver, palladium, ruthenium, rhodium, platinum, and copper compounds. ing. However, these examples are provided with a catalyst using a water-soluble palladium compound, and a commercially available catalyst application solution for electroless reduction plating generally contains a water-soluble palladium compound.
　しかし、本発明者は、公知の水溶性パラジウム化合物を含有し、パラジウムを触媒核として付与する方法の触媒付与液を使用してパラジウム皮膜を形成すると、金めっき後にはんだ接合をした際に、はんだ内にボイドが発生してしまい、本発明における上記課題の解決には至らないことを見出した（比較例３～比較例９）。 However, the present inventor, when containing a known water-soluble palladium compound and forming a palladium film using a catalyst applying liquid of a method of applying palladium as a catalyst nucleus, It has been found that voids are generated in the interior of the substrate, and that the above-described problems in the present invention cannot be solved (Comparative Examples 3 to 9).
　そこで、本発明者は、上記の課題を解決すべく、銅系金属のみを活性化させる触媒付与液について鋭意検討を重ねた結果、少なくとも（ａ）水溶性の金化合物、（ｂ）窒素原子が２個以上の５員環構造を有するヘテロ環化合物、及び、（ｃ）イミノ２酢酸構造を有するキレート剤、を含有する触媒付与液を使用すると、得られた無電解還元パラジウムめっきを行なった皮膜が、微細配線のブリッジがなく、膜厚も均一なものであり、また無電解還元パラジウムめっきに続いて無電解金めっきを行なっためっき皮膜上にはんだ接合した際にボイドの発生が著しく抑制されることを見出して、本発明を完成するに至った。 Therefore, in order to solve the above problems, the present inventor has conducted extensive studies on a catalyst-providing liquid that activates only a copper-based metal. As a result, at least (a) a water-soluble gold compound and (b) a nitrogen atom are present. When the catalyst imparting solution containing two or more 5-membered heterocyclic compounds and (c) a chelating agent having an iminodiacetic acid structure is used, the resulting electroless reduced palladium-plated film However, there is no fine wiring bridge, the film thickness is uniform, and the generation of voids is remarkably suppressed when soldered onto a plating film that has been subjected to electroless gold plating following electroless reduced palladium plating. As a result, the present invention has been completed.
　すなわち、本発明は、銅系金属の上に無電解還元パラジウムめっきを行うための触媒付与液であって、構成成分として、水溶性の金化合物、窒素原子が２個以上の５員環構造を有するヘテロ環化合物、及び、イミノ２酢酸構造を有するキレート剤を含有することを特徴とする触媒付与液を提供するものである。 That is, the present invention is a catalyst-providing liquid for performing electroless reduction palladium plating on a copper-based metal, comprising a water-soluble gold compound and a five-membered ring structure having two or more nitrogen atoms as constituent components. The present invention provides a catalyst-providing liquid characterized by containing a heterocyclic compound having a chelating agent having an iminodiacetic acid structure.
　また、本発明は、上記の触媒付与液を用い、銅系金属の上に無電解還元パラジウムめっきを行うことを特徴とする銅系金属上のパラジウムめっき皮膜の製造方法を提供するものであり、また、上記の触媒付与液を用い、銅系金属の上に無電解還元パラジウムめっきを行って得られたことを特徴とする銅系金属上のパラジウムめっき皮膜を提供するものである。 In addition, the present invention provides a method for producing a palladium plating film on a copper-based metal, characterized in that electroless reduction palladium plating is performed on the copper-based metal using the above-described catalyst imparting solution, Further, the present invention provides a palladium plating film on a copper-based metal obtained by performing electroless reduction palladium plating on a copper-based metal using the above catalyst-providing liquid.
　また、本発明は、銅系金属の上に３×１０－５ｇ／ｃｍ２以下の金を有し、その上に形成されてなることを特徴とする銅系金属上のパラジウムめっき皮膜を提供するものであり、また、上記の触媒付与液を用い、銅系金属の上に３×１０－５ｇ／ｃｍ２以下の金を付着させ、その上に形成されてなることを特徴とする銅系金属上のパラジウムめっき皮膜を提供するものである。 The present invention also provides a palladium plating film on a copper-based metal, characterized in that it has gold of 3 × 10 −5 g / cm 2 or less on a copper-based metal and is formed thereon. In addition, the copper is characterized in that it is formed by depositing gold of 3 × 10 −5 g / cm 2 or less on a copper-based metal using the above-described catalyst-providing liquid. The present invention provides a palladium plating film on a base metal.
　また、本発明は、上記の触媒付与液を用い、銅系金属の上に無電解還元パラジウムめっきを行い、続いて無電解金めっきを行うことを特徴とする銅系金属上のパラジウム／金めっき皮膜の製造方法を提供するものであり、また、上記の触媒付与液を用い、銅系金属の上に無電解還元パラジウムめっきを行い、続いて無電解金めっきを行って得られたことを特徴とする銅系金属上のパラジウム／金めっき皮膜を提供するものである。 In addition, the present invention provides a palladium / gold plating on a copper-based metal, characterized by performing electroless reduction palladium plating on a copper-based metal and subsequently performing electroless gold plating using the above-described catalyst-providing solution. The present invention provides a method for producing a film, and is obtained by performing electroless reduction palladium plating on a copper-based metal, followed by electroless gold plating, using the above-described catalyst imparting solution. A palladium / gold plating film on a copper-based metal is provided.
　本発明において、「パラジウム／金」という表現は、パラジウム皮膜の上に金皮膜が存在するという意味であり、「銅／パラジウム／金」という表現は、銅系金属の上にパラジウム皮膜が存在し、その上に金皮膜が存在するという意味である。 In the present invention, the expression “palladium / gold” means that a gold film exists on the palladium film, and the expression “copper / palladium / gold” means that the palladium film exists on the copper-based metal. , Which means that a gold film exists on it.
　本発明によれば、上記問題点を解消し上記課題を解決し、銅系金属の上に膜厚ムラがない均一な無電解還元パラジウムめっき皮膜を得ることができ、銅系導体回路が微細配線であってもブリッジがなく、未析出もない無電解還元パラジウムめっき皮膜を形成することができる。また、そのパラジウム皮膜上に無電解金めっきを行ない、はんだボール接合を行なった際に、はんだ内のボイドの発生を抑制することができる。 According to the present invention, the above-mentioned problems can be solved and the above-mentioned problems can be solved, and a uniform electroless reduced palladium plating film having no film thickness unevenness can be obtained on a copper-based metal. Even in this case, an electroless reduced palladium plating film having no bridge and no precipitation can be formed. Moreover, when electroless gold plating is performed on the palladium film and solder ball bonding is performed, generation of voids in the solder can be suppressed.
実施例及び比較例で使用した評価基板１の平面図である。It is a top view of the evaluation board | substrate 1 used by the Example and the comparative example. 実施例及び比較例で使用した評価基板１の断面図である。It is sectional drawing of the evaluation board | substrate 1 used by the Example and the comparative example. 実施例及び比較例で使用した評価基板２の平面図である。It is a top view of the evaluation board | substrate 2 used by the Example and the comparative example. 実施例及び比較例で使用した評価基板２の断面図である。It is sectional drawing of the evaluation board | substrate 2 used by the Example and the comparative example. 微細配線のブリッジの評価方法で「良好」と判定される判定基準を示すマッピング分析写真（１５０倍）であり、実施例１のマッピング分析写真（１５０倍）である。It is the mapping analysis photograph (150 times) which shows the criterion judged as "good" by the evaluation method of the bridge | bridging of fine wiring, and is the mapping analysis photograph (150 times) of Example 1. FIG. 微細配線のブリッジの評価方法で「不良」と判定される判定基準を示すマッピング分析写真（１５０倍）であり、比較例６のマッピング分析写真（１５０倍）である。It is the mapping analysis photograph (150 times) which shows the criterion judged as "defect" by the evaluation method of the bridge | bridging of fine wiring, and is the mapping analysis photograph (150 times) of the comparative example 6. ボイドの発生の評価方法で「無し」と判定される判定基準を示すＳＥＭ写真（２０００倍）であり、実施例４のＳＥＭ写真（２０００倍）である。It is a SEM photograph (2000 times) which shows the judgment standard judged with "the absence" by the evaluation method of generation of a void, and is a SEM photograph (2000 times) of Example 4. ボイドの発生の評価方法で「有り」と判定される判定基準を示すＳＥＭ写真（２０００倍）であり、比較例１のＳＥＭ写真（２０００倍）である。It is a SEM photograph (2000 times) which shows the judgment standard judged with "it is" by the evaluation method of generation of a void, and is a SEM photograph (2000 times) of comparative example 1.
　以下、本発明について説明するが、本発明は、以下の具体的形態に限定されるものではなく、技術的思想の範囲内で任意に変形することができる。 Hereinafter, the present invention will be described, but the present invention is not limited to the following specific embodiments, and can be arbitrarily modified within the scope of the technical idea.
　本発明は、銅系金属の上に無電解還元パラジウムめっきを行うための触媒付与液に係るものである。本発明において、「銅系金属」とは、通常の導体回路形成に用いられるものであり銅を含有していれば特に限定はなく、銅単独又は銅合金が含まれる。また、銅合金における銅以外の金属としては、本発明の上記効果が得られるものであれば特に限定はない。「銅系金属」としては、好ましくは、銅単独又は銅を６０質量％以上含有する銅合金であり、特に好ましくは、銅単独又は銅を８０質量％以上含有する銅合金である。 The present invention relates to a catalyst applying liquid for performing electroless reduction palladium plating on a copper-based metal. In the present invention, the “copper-based metal” is used for ordinary conductor circuit formation and is not particularly limited as long as it contains copper, and includes copper alone or a copper alloy. Moreover, there is no limitation in particular as metals other than copper in a copper alloy, if the said effect of this invention is acquired. The “copper-based metal” is preferably copper alone or a copper alloy containing 60% by mass or more of copper, and particularly preferably copper alone or a copper alloy containing 80% by mass or more of copper.
　本発明において、「無電解還元パラジウムめっき」とは、パラジウム単独又はパラジウムを含有するパラジウム合金を各種還元剤により析出させるめっき工程のことである。パラジウム合金を構成するパラジウム以外の元素としては特に限定はないが、リン（Ｐ）、ホウ素（Ｂ）、炭素（Ｃ）、硫黄（Ｓ）、鉛（Ｐｂ）、ビスマス（Ｂｉ）等が挙げられる。上記パラジウム以外の元素は、１種又は２種以上がパラジウムと共にパラジウム合金を構成するために用いられる。 In the present invention, “electroless reduced palladium plating” refers to a plating step in which palladium alone or palladium alloy containing palladium is deposited by various reducing agents. The element other than palladium constituting the palladium alloy is not particularly limited, and examples thereof include phosphorus (P), boron (B), carbon (C), sulfur (S), lead (Pb), and bismuth (Bi). . One or more elements other than palladium are used to form a palladium alloy together with palladium.
　本発明におけるパラジウムめっき層は、パラジウムを好ましくは８０質量％以上、より好ましくは９０質量％以上、特に好ましくは９５質量％以上含有する「パラジウム単独又はパラジウム合金」であることが、上記本発明の効果がより得られる等のために好ましい。 The palladium plating layer in the present invention is preferably “palladium alone or a palladium alloy” containing preferably 80% by mass or more, more preferably 90% by mass or more, and particularly preferably 95% by mass or more of palladium. It is preferable because the effect can be obtained more.
　本発明の触媒付与液には、少なくとも、（ａ）水溶性の金化合物、（ｂ）窒素原子が２個以上の５員環構造を有するヘテロ環化合物、及び、（ｃ）イミノ２酢酸構造を有するキレート剤を含有することが必須である。 The catalyst-providing liquid of the present invention contains at least (a) a water-soluble gold compound, (b) a heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms, and (c) an iminodiacetic acid structure. It is essential to contain a chelating agent.
（ａ）水溶性の金化合物について
　本発明における「水溶性の金化合物」は、触媒付与液中の濃度が好適になるように水に溶解する程度の水溶性を有する金化合物であれば特に限定はないが、具体的には、例えば、シアン化金塩、塩化金塩、亜硫酸金塩、チオ硫酸金塩等が挙げられる。好ましくは、金化合物の安定性及び薬品の入手の容易さ等の点でシアン化金塩であり、特に好ましくは、シアン化第１金塩又はシアン化第２金塩である。対カチオンは特に限定はないが、触媒付与液を調製する際に加えるものとしては、アルカリ金属塩が好ましく、なかでもカリウム塩が特に好ましい。 (A) Water-soluble gold compound The “water-soluble gold compound” in the present invention is particularly limited as long as it is a gold compound that is soluble in water so that the concentration in the catalyst-providing solution is suitable. Specific examples include gold cyanide, gold chloride, gold sulfite, gold thiosulfate, and the like. Preferred is a gold cyanide salt in view of the stability of the gold compound and the availability of chemicals, and particularly preferred is a first gold cyanide salt or a second gold cyanide salt. The counter cation is not particularly limited, but an alkali metal salt is preferable as a catalyst-adding solution, and a potassium salt is particularly preferable.
　「水溶性の金化合物」を含有する触媒付与液を用いることによって、触媒付与液が中性ｐＨ域に近くても液安定性が良好であり、銅系金属の上に膜厚ムラがない均一な無電解還元パラジウムめっき皮膜を得ることができる。 By using a catalyst-providing liquid containing a “water-soluble gold compound”, liquid stability is good even when the catalyst-providing liquid is close to the neutral pH range, and there is no film thickness unevenness on the copper-based metal. An electroless reduced palladium plating film can be obtained.
　上記「水溶性の金化合物」の濃度は特に限定はないが、触媒付与液全体に対して、金換算の質量で、好ましくは１０ｐｐｍ以上２０００ｐｐｍ以下であり、特に好ましくは２０ｐｐｍ以上１０００ｐｐｍ以下である。「水溶性の金化合物」の濃度が大きすぎる場合は、金が触媒付与液中で析出する等、触媒付与液として不安定になる場合があり、小さすぎる場合は、触媒能が不完全で無電解還元パラジウムめっきの未析出が起きる場合がある。 The concentration of the “water-soluble gold compound” is not particularly limited, but is preferably 10 ppm or more and 2000 ppm or less, and particularly preferably 20 ppm or more and 1000 ppm or less, in terms of gold based on the total amount of the catalyst application liquid. If the concentration of the “water-soluble gold compound” is too high, the gold may precipitate in the catalyst-providing solution, resulting in instability as a catalyst-providing solution. If it is too small, the catalytic ability is incomplete. There is a case where non-deposition of electrolytic reduction palladium plating occurs.
　特に限定はないが、本発明の触媒付与液には実質的に水溶性白金族元素化合物を含有しないことが好ましい。白金族元素とは、具体的には、ルテニウム、ロジウム、パラジウム、オスミウム、イリジウム、白金等である。例えば、水溶性白金族元素化合物である水溶性パラジウム化合物を用いると、上記した通り、はんだ接合した際に、はんだ内にボイドが発生する場合がある。 Although there is no particular limitation, it is preferable that the catalyst-providing liquid of the present invention does not substantially contain a water-soluble platinum group element compound. Specific examples of the platinum group element include ruthenium, rhodium, palladium, osmium, iridium, and platinum. For example, when a water-soluble palladium compound, which is a water-soluble platinum group element compound, is used, voids may be generated in the solder when soldered as described above.
（ｂ）窒素原子が２個以上の５員環構造を有するヘテロ環化合物について
　本発明における「窒素原子が２個以上の５員環構造を有するヘテロ環化合物」とは、炭素以外の元素を有する芳香族性をもつ環（以下、「ヘテロ環」と略記する）を有する化合物であって、５員環構造を有し、その５員環を形成している原子のうち２個以上が窒素原子である構造を持つ化合物をいう。すなわち、「窒素原子が２個以上の５員環構造を有するヘテロ環化合物」とは、「『窒素原子が２個以上の５員環構造を有する』ヘテロ環化合物」をいう。 (B) About a heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms The “heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms” in the present invention includes elements other than carbon. A compound having an aromatic ring (hereinafter abbreviated as “heterocycle”) having a five-membered ring structure, and two or more of the atoms forming the five-membered ring are nitrogen atoms A compound having a structure of That is, “a heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms” means “a heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms”.
　ヘテロ環を構成する炭素以外の元素としては、窒素のほかは特に限定はなく、酸素、イオウ等が挙げられる。また、「５員環構造を有するヘテロ環」は、ベンゼン環、ナフタリン環、他のヘテロ環等の芳香族環と縮合して縮合芳香族環であるヘテロ環であってもよい。上記「他のヘテロ環」は、窒素原子を２個以上有する必要も、５員環である必要もない。 The elements other than carbon constituting the heterocycle are not particularly limited except nitrogen, and examples thereof include oxygen and sulfur. In addition, the “heterocycle having a 5-membered ring structure” may be a heterocycle that is a condensed aromatic ring by condensing with an aromatic ring such as a benzene ring, a naphthalene ring, or another heterocycle. The “other heterocycle” does not need to have two or more nitrogen atoms or a 5-membered ring.
　「窒素原子が２個以上の５員環構造を有するヘテロ環化合物」のヘテロ環として特に限定はないが、例えば、イミダゾール環、ピラゾール環、プリン環、１，２，３－トリアゾール環、１，２，４－トリアゾール環、テトラゾール環、チアジアゾール環、オキサジアゾール環、ベンズイミダゾール環、ベンズトリアゾール環等が挙げられる。また、ヘテロ環に結合している置換基としては特に限定はないが、アミノ基、アルキル基、アルキルアミノ基等が好ましい。このうち特に好ましいのはアミノ基である。 There are no particular limitations on the heterocyclic ring of the “heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms”. For example, imidazole ring, pyrazole ring, purine ring, 1,2,3-triazole ring, 1, Examples include 2,4-triazole ring, tetrazole ring, thiadiazole ring, oxadiazole ring, benzimidazole ring, and benztriazole ring. In addition, the substituent bonded to the heterocycle is not particularly limited, but an amino group, an alkyl group, an alkylamino group, and the like are preferable. Of these, amino groups are particularly preferred.
　本発明において、「窒素原子が２個以上の５員環構造を有するヘテロ環化合物」としては、ピラゾール、３－アミノピラゾール、４－アミノピラゾール、５－アミノピラゾール、イミダゾール、２－アミノイミダゾール、４－アミノイミダゾール、５－アミノイミダゾール、プリン、２－アミノプリン、６－アミノプリン、１，２，３－トリアゾール、４－アミノ－１，２，３－トリアゾール、５－アミノ－１，２，３－トリアゾール、１，２，４－トリアゾール、３－アミノ－１，２，４－トリアゾール、５－アミノ－１，２，４－トリアゾール、テトラゾール、５－アミノテトラゾール、２－アミノ－１，３，４－チアジアゾール、２－アミノベンズイミダゾール、ベンズトリアゾール等、又はこれらのアルキル置換体が好ましいものとして挙げられる。これらは１種又は２種以上混合して用いられる。 In the present invention, examples of the “heterocyclic compound having a 5-membered ring structure having two or more nitrogen atoms” include pyrazole, 3-aminopyrazole, 4-aminopyrazole, 5-aminopyrazole, imidazole, 2-aminoimidazole, 4 -Aminoimidazole, 5-aminoimidazole, purine, 2-aminopurine, 6-aminopurine, 1,2,3-triazole, 4-amino-1,2,3-triazole, 5-amino-1,2,3 -Triazole, 1,2,4-triazole, 3-amino-1,2,4-triazole, 5-amino-1,2,4-triazole, tetrazole, 5-aminotetrazole, 2-amino-1,3, 4-thiadiazole, 2-aminobenzimidazole, benztriazole or the like, or an alkyl-substituted product thereof is preferable And the like to. These are used alone or in combination.
　なかでも、前記本発明の効果を得るために特に好ましくは、イミダゾール、２－アミノイミダゾール、４－アミノイミダゾール、５－アミノイミダゾール、１，２，４－トリアゾール、３－アミノ－１，２，４－トリアゾール、５－アミノテトラゾール等である。 Of these, imidazole, 2-aminoimidazole, 4-aminoimidazole, 5-aminoimidazole, 1,2,4-triazole, 3-amino-1,2,4 are particularly preferable for obtaining the effects of the present invention. -Triazole, 5-aminotetrazole and the like.
　「窒素原子が２個以上の５員環構造を有するヘテロ環化合物」の濃度は特に限定はないが、触媒付与液全体に対して、質量で１０ｐｐｍ以上１００００ｐｐｍ以下が好ましく、５０ｐｐｍ以上５０００ｐｐｍ以下が特に好ましい。かかる濃度が大きすぎる場合は、沈殿物が生成する場合があり、小さすぎる場合は、はんだボール接合時にボイド発生が起こり易くなる場合がある。 The concentration of the “heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms” is not particularly limited, but is preferably 10 ppm or more and 10,000 ppm or less, and particularly 50 ppm or more and 5000 ppm or less with respect to the entire catalyst-providing liquid. preferable. If the concentration is too high, precipitates may be generated. If the concentration is too low, voids may easily occur during solder ball bonding.
（ｃ）イミノ２酢酸構造を有するキレート剤について
　本発明における「イミノ２酢酸構造を有するキレート剤」としては、銅系導体回路等を構成する銅系金属を触媒付与液中に溶解可能なイミノ２酢酸構造を有するものであることが好ましい。イミノ２酢酸構造を有するキレート剤を必須成分として含有させることによって、銅系金属の触媒付与液への均一な溶解を促進するとともに、銅系金属が再析出するのを防止することができるため、触媒核の付与を均一かつ確実に行なうことができ、また微細配線間の絶縁体への金属付着による微細配線のブリッジ発生を防止することができる。 (C) About the chelating agent having an iminodiacetic acid structure As the “chelating agent having an iminodiacetic acid structure” in the present invention, imino 2 capable of dissolving a copper-based metal constituting a copper-based conductor circuit or the like in a catalyst-providing solution. It preferably has an acetic acid structure. By containing a chelating agent having an iminodiacetic acid structure as an essential component, it is possible to promote uniform dissolution of the copper-based metal in the catalyst-providing liquid and to prevent the copper-based metal from reprecipitating, The application of catalyst nuclei can be performed uniformly and reliably, and the occurrence of bridging of the fine wiring due to metal adhesion to the insulator between the fine wirings can be prevented.
　本発明における「イミノ２酢酸構造を有するキレート剤」としては、具体的には、例えば、エチレンジアミン４酢酸、ヒドロキシエチルイミノ２酢酸、ニトリロ３酢酸、ヒドロキシエチルエチレンジアミン３酢酸、ジエチレントリアミン５酢酸、トリエチレンテトラミン６酢酸、ジカルボキシメチルグルタミン酸、プロパンジアミン４酢酸、１，３－ジアミノ－２－ヒドロキシルプロパン４酢酸等、又はこれらの水溶性塩が挙げられる。水溶性塩としては特に限定はないが、ナトリウム塩、カリウム塩、アンモニウム塩等が挙げられる。これらは１種又は２種以上を混合して用いられる。 Specific examples of the “chelating agent having an iminodiacetic acid structure” in the present invention include, for example, ethylenediaminetetraacetic acid, hydroxyethyliminodiacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, and triethylenetetramine. Examples include 6-acetic acid, dicarboxymethyl glutamic acid, propanediamine tetraacetic acid, 1,3-diamino-2-hydroxylpropane tetraacetic acid, and the like, or water-soluble salts thereof. Although there is no limitation in particular as water-soluble salt, Sodium salt, potassium salt, ammonium salt, etc. are mentioned. These are used alone or in combination of two or more.
　これらの中でも、好ましくは銅系金属を安定に溶解させる作用が強い点で、酢酸ユニットを３個以上含有するものである。具体的には、例えば、エチレンジアミン４酢酸、ニトリロ３酢酸、ヒドロキシエチルエチレンジアミン３酢酸、ジエチレントリアミン５酢酸、トリエチレンテトラミン６酢酸、プロパンジアミン４酢酸、１，３－ジアミノ－２－ヒドロキシルプロパン４酢酸等又はこれらの水溶性塩が挙げられる。 Among these, it is preferable to contain three or more acetic acid units in that the action of stably dissolving the copper-based metal is strong. Specifically, for example, ethylenediaminetetraacetic acid, nitrilotriacetic acid, hydroxyethylethylenediaminetriacetic acid, diethylenetriaminepentaacetic acid, triethylenetetraminehexaacetic acid, propanediaminetetraacetic acid, 1,3-diamino-2-hydroxylpropanetetraacetic acid, etc. These water-soluble salts are mentioned.
　本発明における「イミノ２酢酸構造を有するキレート剤」は、触媒付与液全体に対して、１ｇ／Ｌ～１００ｇ／Ｌの範囲で用いられることが好ましく、２ｇ／Ｌ～６０ｇ／Ｌがより好ましく、３ｇ／Ｌ～４０ｇ／Ｌが特に好ましい。キレート剤の濃度が大きすぎる場合には、触媒付与液中に析出する場合があり、小さすぎる場合には、銅系金属表面の触媒活性化が不十分の場合がある。 The “chelating agent having an iminodiacetic acid structure” in the present invention is preferably used in the range of 1 g / L to 100 g / L, more preferably 2 g / L to 60 g / L with respect to the entire catalyst-providing liquid. Particularly preferred is 3 g / L to 40 g / L. When the concentration of the chelating agent is too large, it may be precipitated in the catalyst-providing liquid, and when it is too small, the catalyst activation on the copper-based metal surface may be insufficient.
　本発明の触媒付与液には、必要に応じて、ｐＨ緩衝剤等を適宜選択して含有させることができる。ｐＨ緩衝剤としては、触媒付与液の特性に悪影響を与えることなくｐＨの変動を緩和できるものであれば特に限定はない。有機物か無機物かを問わず、酸又はその塩を適宜配合して加えてもよい。具体的には、ホウ酸、リン酸、ピロリン酸等の無機酸；クエン酸、酢酸、リンゴ酸、コハク酸、酒石酸等の有機酸；又はそれらの塩等が挙げられる。 The catalyst-imparting solution of the present invention can contain a pH buffering agent and the like as appropriate, if necessary. The pH buffer is not particularly limited as long as it can alleviate fluctuations in pH without adversely affecting the properties of the catalyst-providing liquid. Regardless of whether it is an organic substance or an inorganic substance, an acid or a salt thereof may be added as appropriate. Specific examples include inorganic acids such as boric acid, phosphoric acid, and pyrophosphoric acid; organic acids such as citric acid, acetic acid, malic acid, succinic acid, and tartaric acid; or salts thereof.
　本発明の触媒付与液は、ｐＨ３以上ｐＨ９以下であることが好ましく、ｐＨ４以上ｐＨ８以下であることが特に好ましい。市販のパラジウムを含有する無電解還元めっき用触媒付与液はｐＨ１付近であり、本発明の触媒付与液の好ましいｐＨ範囲とは大幅に異なっている。ｐＨが低すぎると、金が析出する等、触媒付与液として不安定になる場合があり、ｐＨが高すぎると、触媒活性が落ち、無電解還元パラジウムめっきが進行しにくくなる場合がある。 The catalyst-providing liquid of the present invention is preferably pH 3 or more and pH 9 or less, particularly preferably pH 4 or more and pH 8 or less. A commercially available catalyst-providing solution for electroless reduction plating containing palladium is in the vicinity of pH 1, which is significantly different from the preferred pH range of the catalyst-providing solution of the present invention. If the pH is too low, gold may be deposited, which may result in instability as a catalyst-imparting solution, and if the pH is too high, catalyst activity may be reduced and electroless reduced palladium plating may not proceed easily.
　本発明の触媒付与液の処理温度は、１０℃以上９５℃以下が好ましく、特に好ましくは２０℃以上９０℃以下である。また、本発明の触媒付与液の処理時間は、５秒以上１５分以下が好ましく、特に好ましくは１０秒以上１０分以下である。 The treatment temperature of the catalyst imparting solution of the present invention is preferably 10 ° C. or more and 95 ° C. or less, and particularly preferably 20 ° C. or more and 90 ° C. or less. Further, the treatment time of the catalyst applying liquid of the present invention is preferably from 5 seconds to 15 minutes, particularly preferably from 10 seconds to 10 minutes.
　本発明の触媒付与液の触媒核金属の担持量、すなわち銅系金属上に付与される金の量は、０．０５～３ｍｇ／ｄｍ２（０．０５×１０－５～３×１０－５ｇ／ｃｍ２）が好ましく、０．１～２ｍｇ／ｄｍ２（０．１×１０－５～２×１０－５ｇ／ｃｍ２）が特に好ましい。この範囲のときに、前記した本発明の効果が得られ易い。すなわち、本発明の態様の１つである「銅系金属の上に３ｍｇ／ｄｍ２以下（３×１０－５ｇ／ｃｍ２以下）の金を有し、その上に形成されてなる銅系金属上のパラジウムめっき皮膜」は、前記効果を有しているため好ましい。「銅系金属の上に３×１０－５ｇ／ｃｍ２以下の金を有し、その上に形成されてなる銅系金属上のパラジウムめっき皮膜」は、それ自体でこれまでにない構成であり、この構成さえ満たせば、前記した本発明の効果を奏する。 The amount of catalyst core metal supported in the catalyst application liquid of the present invention, that is, the amount of gold applied on the copper-based metal is 0.05 to 3 mg / dm 2 (0.05 × 10 −5 to 3 × 10 −5). g / cm 2 ), preferably 0.1 to 2 mg / dm 2 (0.1 × 10 −5 to 2 × 10 −5 g / cm 2 ). Within this range, the effects of the present invention described above are easily obtained. That is, one embodiment of the present invention is “a copper-based metal having 3 mg / dm 2 or less (3 × 10 −5 g / cm 2 or less) of gold on a copper-based metal and formed thereon. “Palladium plating film on metal” is preferable because it has the above-mentioned effect. “Palladium plating film on copper-based metal having 3 × 10 −5 g / cm 2 or less of gold on the copper-based metal and formed thereon” There is the effect of the present invention as long as this configuration is satisfied.
　金めっきにおいて、目視で析出金属の色調が確認可能であるためには、すなわち「金めっき」といえるためには、６ｍｇ／ｄｍ２（６×１０－５ｇ／ｃｍ２、厚さ３０ｎｍ）程度以上の析出量が必要であり、通常の置換金めっきは、１２ｍｇ／ｄｍ２（１２×１０－５ｇ／ｃｍ２、厚さ６０ｎｍ）程度以上付着されている。すなわち、本発明の触媒付与液は、置換無電解金めっきに比べて大幅に少量の金を銅系金属上に付着させるものである。従って、本発明の触媒付与液による「触媒核金属の付与」は、付着量の点から「無電解金めっき」とは明確に区別される。また、本発明の触媒付与液によって付与された金は、金皮膜を形成している必要はない。 In gold plating, in order to be able to confirm the color tone of the deposited metal visually, that is, to say “gold plating”, about 6 mg / dm 2 (6 × 10 −5 g / cm 2 , thickness 30 nm) The amount of precipitation described above is necessary, and normal displacement gold plating is deposited on the order of 12 mg / dm 2 (12 × 10 −5 g / cm 2 , thickness 60 nm) or more. That is, the catalyst-providing liquid of the present invention deposits a significantly smaller amount of gold on a copper-based metal compared to substitutional electroless gold plating. Therefore, “application of catalyst core metal” by the catalyst application liquid of the present invention is clearly distinguished from “electroless gold plating” in terms of the amount of adhesion. Moreover, the gold | metal | money provided with the catalyst provision liquid of this invention does not need to form the gold film.
　本発明の触媒付与液は、例えば、プリント基板上に形成された銅系導体回路等の銅系金属を選択的に触媒活性化するものであり、後に行なわれる無電解還元パラジウムめっきを、銅系導体回路等の銅系金属の上にのみ選択的に形成するために用いられるものである。 The catalyst application liquid of the present invention selectively activates a copper-based metal such as a copper-based conductor circuit formed on a printed circuit board, for example. It is used to selectively form only on a copper-based metal such as a conductor circuit.
　ここで、「銅系導体回路」とは、ガラスエポキシ、セラミック、ポリイミド等の絶縁体である素地基材に、銅系金属で回路形成したものである。銅系金属の回路形成の方法は特に限定はないが、めっき、蒸着、Ｃｕ板のラミネート等が挙げられる。 Here, the “copper-based conductor circuit” is formed by forming a circuit with a copper-based metal on a base material that is an insulator such as glass epoxy, ceramic, or polyimide. The method for forming a copper-based metal circuit is not particularly limited, and examples thereof include plating, vapor deposition, and lamination of a Cu plate.
　本発明の触媒付与液を用いる場合の前処理工程は特に限定はなく、通常の無電解めっきで行われる、触媒付与液適用前の前処理方法に従えばよい。 The pretreatment step in the case of using the catalyst application liquid of the present invention is not particularly limited, and may be performed according to a pretreatment method before applying the catalyst application liquid, which is performed by normal electroless plating.
　無電解還元パラジウムめっき液に関しては特に限定はなく全て使用できる。例えば、水溶性のパラジウム化合物、蟻酸若しくは蟻酸誘導体、及び窒素含有錯化剤を含有するものが挙げられる。他にも、水溶性のパラジウム化合物、アミン化合物、２価の硫黄を含有する有機化合物、及び次亜リン酸化合物若しくは水素化ホウ素化合物を含有するもの等が挙げられる。 The electroless reduced palladium plating solution is not particularly limited and can be used. Examples thereof include those containing a water-soluble palladium compound, formic acid or a formic acid derivative, and a nitrogen-containing complexing agent. Other examples include water-soluble palladium compounds, amine compounds, organic compounds containing divalent sulfur, and compounds containing hypophosphorous acid compounds or borohydride compounds.
　前記した、本発明における「無電解還元パラジウムめっき」の定義に従って、パラジウム以外の金属化合物を含有することができる。本発明の触媒付与液を用いて形成されるパラジウム皮膜は、パラジウムを好ましくは８０質量％以上、より好ましくは９０質量％以上、特に好ましくは９５質量％以上含有する「パラジウム単独又はパラジウム合金」であることが、上記本発明の効果がより得られる等のために好ましい。 According to the definition of “electroless reduced palladium plating” in the present invention described above, a metal compound other than palladium can be contained. The palladium film formed using the catalyst-providing liquid of the present invention is preferably “palladium alone or a palladium alloy” containing 80% by mass or more of palladium, more preferably 90% by mass or more, and particularly preferably 95% by mass or more. It is preferable for the effect of the present invention to be obtained more.
　「銅／パラジウム」において、パラジウム皮膜の膜厚は特に限定はないが、０．０３μｍ～１μｍが好ましく、０．０５μｍ～０．５μｍが特に好ましい。無電解還元パラジウムめっきのめっき条件は特に限定はなく通常の条件でよい。 In “copper / palladium”, the film thickness of the palladium film is not particularly limited, but is preferably 0.03 μm to 1 μm, and particularly preferably 0.05 μm to 0.5 μm. The plating conditions for electroless reduced palladium plating are not particularly limited and may be normal conditions.
　特に限定はないが、無電解還元パラジウムめっきを行なった後は無電解金めっきを行なうことが好ましい。最表面がパラジウムめっき皮膜であると加熱処理後のはんだ濡れ性が良くない場合があり、はんだ濡れ性を維持するためには、無電解金めっきを行ない、はんだ濡れ性が良好な金めっき皮膜を最表面に形成させることが、本発明の効果がより得られる点で好ましい。 Although there is no particular limitation, it is preferable to perform electroless gold plating after electroless reduction palladium plating. If the outermost surface is a palladium plating film, the solder wettability after heat treatment may not be good. To maintain the solder wettability, electroless gold plating should be performed, and a gold plating film with good solder wettability should be applied. Forming on the outermost surface is preferable in that the effect of the present invention can be obtained more.
　「銅／パラジウム／金」において、金皮膜の膜厚は特に限定はないが、０．０３μｍ～０．３μｍが好ましく、０．０５μｍ～０．１μｍが特に好ましい。無電解金めっきのめっき条件は特に限定はなく通常の条件でよい。 In “copper / palladium / gold”, the thickness of the gold film is not particularly limited, but is preferably 0.03 μm to 0.3 μm, particularly preferably 0.05 μm to 0.1 μm. The electroless gold plating conditions are not particularly limited and may be normal conditions.
　以下に、実施例及び比較例を挙げて本発明を更に具体的に説明するが、本発明は、その要旨を超えない限りこれらの実施例に限定されるものではない。 Hereinafter, 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.
実施例１～６
＜触媒付与液の調製＞
　表１に示す（ａ）水溶性の金化合物を、金属金換算で触媒付与液全体に対して質量で１００ｐｐｍ、表１に示す（ｂ）窒素原子が２個以上の５員環構造を有するヘテロ環化合物を、触媒付与液全体に対して質量で５００ｐｐｍ、表１に示す（ｃ）イミノ２酢酸構造を有するキレート剤を、触媒付与液全体に対して２０ｇ／Ｌ、となるように純水に溶解させた。次いでｐＨ５．０になるように調整して各触媒付与液を調製した。なお、ｐＨ調整は、ｐＨを上げる時は水酸化ナトリウム水溶液を、下げる時は塩酸を使用した。 Examples 1-6
<Preparation of catalyst application liquid>
(A) The water-soluble gold compound shown in Table 1 is 100 ppm in mass with respect to the entire catalyst-providing liquid in terms of metal gold, and (b) a hetero compound having a five-membered ring structure with two or more nitrogen atoms shown in Table 1. In the pure water, the ring compound is 500 ppm by mass with respect to the entire catalyst-providing liquid, and the chelating agent having (c) iminodiacetic acid structure shown in Table 1 is 20 g / L with respect to the entire catalyst-applying liquid. Dissolved. Subsequently, each catalyst provision liquid was adjusted so that it might become pH 5.0. For pH adjustment, a sodium hydroxide aqueous solution was used to raise the pH, and hydrochloric acid was used to lower the pH.
比較例１～２
　比較例１として、市販のパラジウムを含有する「無電解還元ニッケルめっき用の触媒付与液（ＫＡＴ－４５０、上村工業株式会社製）」を、通常の使用状態に調整したものを用いた。また、比較例２として、市販のパラジウムを含有する「無電解還元ニッケルめっき用の触媒付与液（ＩＣＰアクセラ、奥野製薬株式会社製）」を、通常の使用状態に調整したものを用いた。 Comparative Examples 1 and 2
As Comparative Example 1, a “catalyst-providing solution for electroless reduction nickel plating (KAT-450, manufactured by Uemura Kogyo Co., Ltd.)” containing commercially available palladium was used in a state of normal use. Further, as Comparative Example 2, a “catalyst imparting solution for electroless reduced nickel plating (ICP Axela, manufactured by Okuno Seiyaku Co., Ltd.)” containing commercially available palladium was used in a normal use state.
比較例３～２０
　表１の最左欄に示す化合物を、金属換算で触媒付与液全体に対して、質量で１００ｐｐｍ、表１に含有の指定のあるものは、表１に示すヘテロ環化合物を触媒付与液全体に対して質量で５００ｐｐｍ、表１に含有の指定のあるものは、表１に示すキレート剤を、触媒付与液全体に対して２０ｇ／Ｌ、となるように純水に溶解させた。次いで表１に示すｐＨになるよう調整して、各触媒付与液を調製した。ｐＨ調整は、ｐＨを上げる時は水酸化ナトリウム水溶液を、下げる時は塩酸を使用した。 Comparative Examples 3-20
The compound shown in the leftmost column of Table 1 is 100 ppm by mass with respect to the entire catalyst application liquid in terms of metal, and those specified to be contained in Table 1 include the heterocyclic compound shown in Table 1 in the entire catalyst application liquid. On the other hand, in the case of 500 ppm by mass and those specified to be contained in Table 1, the chelating agent shown in Table 1 was dissolved in pure water so as to be 20 g / L with respect to the entire catalyst application liquid. Subsequently, each catalyst provision liquid was prepared by adjusting to pH shown in Table 1. For pH adjustment, an aqueous sodium hydroxide solution was used to raise the pH, and hydrochloric acid was used to lower the pH.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
［評価］
　実施例１～６、比較例１～２０で得られた触媒付与液と、公知の無電解還元パラジウムめっき液（ネオパラブライト、日本高純度化学株式会社製）を使用し、表２に示した工程で無電解還元パラジウムめっきを行ない、得られた無電解還元パラジウムめっき皮膜を、それぞれ以下記載の、＜無電解還元パラジウムめっきの析出均一性の評価方法＞と＜微細配線のブリッジの評価方法＞にて評価を行なった。 [Evaluation]
Steps shown in Table 2 using the catalyst-providing liquids obtained in Examples 1 to 6 and Comparative Examples 1 to 20 and a known electroless reduced palladium plating liquid (Neoparabright, manufactured by Nippon Pure Chemical Co., Ltd.) The electroless reduced palladium plating film was subjected to <Evaluation Method for Deposition Uniformity of Electroless Reduction Palladium Plating> and <Evaluation Method for Fine Wiring Bridge>, respectively, described below. Was evaluated.
　上記２つの評価にて良好であったものは、その評価とは別に評価基板を準備し、上記の触媒付与液、無電解還元パラジウムめっき液に加え、公知の無電解置換金めっき液（ＩＭ－ＧＯＬＤＰＣ、日本高純度化学株式会社製）を使用し、表３に示した工程で無電解還元パラジウム、次いで無電解置換金めっきを行ない、得られためっき皮膜を、それぞれ以下記載の＜ボイドの発生の評価方法＞にて評価を行なった。 If the above two evaluations were good, an evaluation substrate was prepared separately from the evaluation, and in addition to the above-described catalyst applying solution and electroless reduced palladium plating solution, a known electroless displacement gold plating solution (IM- GOLDPC (manufactured by Nippon High Purity Chemical Co., Ltd.) was used, and electroless reduced palladium and then electroless displacement gold plating were performed in the steps shown in Table 3. The evaluation method was evaluated.
＜評価基板の作製＞
評価基板１
　図１及び図２に示した形態の評価基板を作製した。縦４０ｍｍ×横４０ｍｍ×厚さ１．０ｍｍのポリイミド樹脂製の基板に、直径０．７６ｍｍの円形の銅パッドが碁盤目状に配列されているものであって、各銅パッド周辺がフォトソルダーレジストで被覆されているものを用いた。それぞれの銅パッドは厚さ１２μｍの銅により形成され、フォトソルダーレジストの厚さは２０μｍ、はんだボールパッドの開口部の直径は０．６２ｍｍである。 <Production of evaluation substrate>
Evaluation board 1
An evaluation substrate having the configuration shown in FIGS. 1 and 2 was produced. Circular copper pads with a diameter of 0.76 mm are arranged in a grid pattern on a polyimide resin substrate 40 mm long x 40 mm wide x 1.0 mm thick, and each copper pad is surrounded by a photo solder resist. The one coated with is used. Each copper pad is formed of copper having a thickness of 12 μm, the thickness of the photo solder resist is 20 μm, and the diameter of the opening of the solder ball pad is 0.62 mm.
評価基板２
　図３及び図４に示した形態の評価基板を作成した。縦４０ｍｍ×横４０ｍｍ×厚さ１．０ｍｍのポリイミド樹脂製の基板に、幅８０μｍ×厚さ４０μｍの銅配線が幅１２０μｍの間隔をもって配列されているものである。 Evaluation board 2
The evaluation board | substrate of the form shown in FIG.3 and FIG.4 was created. Copper wirings having a width of 80 μm and a thickness of 40 μm are arranged at intervals of 120 μm on a polyimide resin substrate having a length of 40 mm × width of 40 mm × thickness of 1.0 mm.
＜無電解還元パラジウムめっきの析出均一性の評価方法＞
　実施例１～６、比較例１～２０で得られた触媒付与液及び無電解還元パラジウムめっき液を使用し、上記評価基板１と評価基板２を用いて、以下の表２の処理条件で無電解還元パラジウムめっきを行なった。なお、各触媒付与液による処理条件は、触媒核である金属金の担持量が０．６ｍｇ／ｄｍ２（０．６×１０－５ｇ／ｃｍ２）になる条件にて行なった。 <Evaluation method for deposition uniformity of electroless reduced palladium plating>
Using the catalyst-providing solution and electroless reduced palladium plating solution obtained in Examples 1 to 6 and Comparative Examples 1 to 20, the evaluation substrate 1 and the evaluation substrate 2 were used and the treatment conditions shown in Table 2 below were applied. Electrolytic reduction palladium plating was performed. The treatment conditions with each catalyst application liquid were such that the supported amount of metal gold as a catalyst nucleus was 0.6 mg / dm 2 (0.6 × 10 −5 g / cm 2 ).
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
　評価基板１のはんだボールパッドの銅上に形成された無電解還元パラジウム皮膜の膜厚を、蛍光Ｘ線膜厚計（ＳＥＡ５１２０、セイコーインスツルメンツ社製）を使用して、１０点測定し、平均膜厚、最大膜厚及び最小膜厚を比較することで無電解還元パラジウムめっきの析出均一性を評価した。最小膜厚の測定値が極めて小さいものを「析出ムラ」と評価した。全ての測定値が０．００μｍであったものを「析出無」と評価した。結果を表４に示す。 The film thickness of the electroless reduced palladium film formed on the copper of the solder ball pad of the evaluation board 1 was measured at 10 points using a fluorescent X-ray film thickness meter (SEA5120, manufactured by Seiko Instruments Inc.), and the average film The deposition uniformity of electroless reduced palladium plating was evaluated by comparing the thickness, maximum film thickness, and minimum film thickness. A sample having a very small minimum film thickness was evaluated as “precipitation unevenness”. All the measured values were 0.00 μm and evaluated as “no precipitation”. The results are shown in Table 4.
＜微細配線のブリッジの評価方法＞
　評価基板２の銅配線を走査型電子顕微鏡（Ｓ－４３００、日立製作所製）（以下、「ＳＥＭ」と略記する）とエネルギー分散型Ｘ線分析装置（ＥＭＡＸ　ＥＸ－２２０、ＨＯＲＩＢＡ社製）にてパラジウムをマッピング分析することにより、微細配線のブリッジの評価を行なった。 <Evaluation method of bridge of fine wiring>
The copper wiring of the evaluation board 2 is scanned with a scanning electron microscope (S-4300, manufactured by Hitachi, Ltd.) (hereinafter abbreviated as “SEM”) and an energy dispersive X-ray analyzer (EMAX EX-220, manufactured by HORIBA). The mapping of the fine wiring was evaluated by mapping analysis of palladium.
　ポリイミド樹脂上に無電解還元パラジウムの析出がなく、銅配線表面にのみ無電解還元パラジウムめっき皮膜が形成されているものを「良好」と判定し、ポリイミド樹脂上に無電解還元パラジウムの析出が認められたものを「不良」と判定した。結果を表４に示す。また、「良好」判定の判定基準（代表例）として、実施例１の場合のパラジウムのマッピング分析写真を図５に、「不良」判定の判定基準（代表例）として、比較例６の場合のパラジウムのマッピング分析写真を図６に示す。 If the electroless reduced palladium plating is not deposited on the polyimide resin and the electroless reduced palladium plating film is formed only on the copper wiring surface, it is judged as “good”, and the electroless reduced palladium is deposited on the polyimide resin. The result was determined as “bad”. The results are shown in Table 4. Further, as a determination criterion (representative example) of “good” determination, the mapping analysis photograph of palladium in the case of Example 1 is shown in FIG. 5, and as a determination criterion (representative example) of “bad” determination in the case of comparative example 6. A mapping analysis photograph of palladium is shown in FIG.
＜ボイドの発生の評価方法＞
　上記の析出均一性評価とブリッジ評価により良好な結果が得られたものに関しては、新たに別の評価基板１を用意して、はんだボール接合時のボイド発生の評価を行なった。下記表３の処理により、ボールパッド上にパラジウムめっき皮膜、次いで金めっき皮膜を形成した評価基板１を、１７５℃で５時間加熱を行なった。この加熱条件は、基板の実装工程で加わる熱処理を想定したものである。加熱処理後の基板のボールパッドにフラックスを塗布し、直径０．７６ｍｍのＳｎ－Ａｇ－Ｃｕ鉛フリーはんだボールを搭載し、これをリフロー炉装置（ＲＦ－４３０－Ｍ２、株式会社日本パルス技術研究所社製）にて融着させた。 <Void generation evaluation method>
For those for which good results were obtained by the above-described precipitation uniformity evaluation and bridge evaluation, another evaluation substrate 1 was newly prepared to evaluate the generation of voids during solder ball bonding. Evaluation substrate 1 in which a palladium plating film and then a gold plating film were formed on a ball pad by the treatment of Table 3 below was heated at 175 ° C. for 5 hours. This heating condition assumes a heat treatment applied in the substrate mounting process. Flux is applied to the ball pad of the substrate after the heat treatment, and a Sn-Ag-Cu lead-free solder ball with a diameter of 0.76 mm is mounted. (Made by a company).
　はんだボールが融着した評価基板１を、操作がし易いように１５ｍｍ×１５ｍｍ程度の大きさに切断し、冷間埋込樹脂用の成形型に設置し、その成形型に冷間埋込樹脂（Ｎｏ．１０５、丸本ストルアス社製）とその硬化剤を流し込み硬化させた。硬化したサンプルをＳｉＣ研磨紙と研磨機を使用して研磨し、はんだボールとボールパッドの接合部断面が見えるように断面を露出させた。 The evaluation substrate 1 to which the solder balls are fused is cut into a size of about 15 mm × 15 mm so that the operation is easy, and is placed in a mold for cold embedding resin. (No. 105, manufactured by Marumoto Struers) and its curing agent were poured and cured. The cured sample was polished using a SiC polishing paper and a polishing machine, and the cross section was exposed so that the cross section of the joint between the solder ball and the ball pad could be seen.
　露出したはんだボール断面をＳＥＭにて、ボール５個分を観察して、はんだボール内にボイドが観測されなければ「無し」、はんだボール内にボイドが１つでも観測されれば「有り」とした。結果を表４に示す。また、観察された中で一番大きいボイドの直径を表４中に括弧で括って示す。「無し」判定の代表例として、実施例４の場合のＳＥＭ観察写真を図７に、「有り」判定の代表例として、比較例１の場合のＳＥＭ観察写真を図８に示す。 Examine the cross section of the exposed solder ball with SEM for five balls. If no void is observed in the solder ball, “None” is indicated. If even one void is observed in the solder ball, “Yes” is indicated. did. The results are shown in Table 4. Further, the diameter of the largest observed void is shown in parentheses in Table 4. As a representative example of “absence” determination, an SEM observation photograph in the case of Example 4 is shown in FIG. 7, and as a representative example of “existence” determination, an SEM observation photograph in the case of Comparative Example 1 is shown in FIG.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
　表４の結果から判るように、本発明の（ａ）水溶性の金化合物、（ｂ）窒素原子が２個以上の５員環構造を有するヘテロ環化合物、（ｃ）イミノ２酢酸構造を有するキレート剤を必須成分として含有する触媒付与液は、銅系導体回路上に無電解還元パラジウムめっきを行なうに十分な触媒作用を持ち、微細配線のブリッジがなく、かつ均一なパラジウムめっき皮膜を形成することができ、更に無電解還元パラジウムめっきの後、続いて無電解金めっきを行なった皮膜は、その皮膜上に、はんだボール接合をした際に、はんだ内にボイドの発生がないことが判明した（実施例１～実施例６）。 As can be seen from the results in Table 4, (a) a water-soluble gold compound of the present invention, (b) a heterocyclic compound in which the nitrogen atom has two or more five-membered ring structures, and (c) an iminodiacetic acid structure. The catalyst application liquid containing a chelating agent as an essential component has sufficient catalytic action for electroless reduction palladium plating on a copper-based conductor circuit, and does not have a fine wiring bridge and forms a uniform palladium plating film. Furthermore, it was found that the film formed by electroless gold plating after electroless reduced palladium plating was free of voids in the solder when solder balls were bonded onto the film. (Examples 1 to 6).
　一方、水溶性の金化合物を含有しない比較例１～比較例１０の内、ｐＨの低いｐＨ１．０の比較例１～比較例５は微細配線のブリッジがなく、かつ均一なパラジウムめっき皮膜を形成することが可能であるが、はんだ接合の際に極めて大きなボイドが発生した。中性ｐＨ域に近いｐＨ５．０の比較例６～比較例１０は均一に触媒活性化することができず、パラジウムめっき皮膜の析出ムラが発生した。 On the other hand, among Comparative Examples 1 to 10 which do not contain a water-soluble gold compound, Comparative Examples 1 to 5 having a low pH of 1.0 have no fine wiring bridge and form a uniform palladium plating film. Although it was possible, extremely large voids were generated during soldering. In Comparative Examples 6 to 10 having a pH of 5.0 close to the neutral pH range, the catalyst could not be activated uniformly, and deposition unevenness of the palladium plating film occurred.
　また、（ａ）水溶性の金化合物と（ｂ）窒素原子が２個以上の５員環構造を有するヘテロ環化合物を含有しても、（ｃ）イミノ２酢酸構造を有するキレート剤を含有しない比較例１１～比較例１５は、触媒活性化が不十分でありパラジウムめっき皮膜の析出無が発生した。 Moreover, even if it contains (a) a water-soluble gold compound and (b) a heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms, it does not contain (c) a chelating agent having an iminodiacetic acid structure In Comparative Examples 11 to 15, catalyst activation was insufficient and no palladium plating film was deposited.
　また、（ａ）水溶性の金化合物と（ｃ）イミノ２酢酸構造を有するキレート剤を含有しても、（ｂ）窒素原子が２個以上の５員環構造を有するヘテロ環化合物を含有しない比較例１６～比較例２０は、微細配線のブリッジがなく、かつ均一なパラジウムめっき皮膜を形成することが可能であるが、はんだ接合の際に大きなボイドが発生した。 Moreover, even if (a) a water-soluble gold compound and (c) a chelating agent having an iminodiacetic acid structure are contained, (b) a heterocyclic compound having a five-membered ring structure in which two or more nitrogen atoms are contained is not contained. In Comparative Examples 16 to 20, there is no fine wiring bridge and it is possible to form a uniform palladium plating film, but large voids were generated during solder bonding.
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　本発明の無電解還元パラジウムめっき用の触媒付与液は、銅系金属の上に膜厚ムラがなく均一であり、ブリッジがない無電解還元パラジウムめっき皮膜を得ることができ、また、はんだボール接合時のボイドの発生を抑制することもできるので、銅系導体回路のはんだ接合等が用いられるあらゆる分野に広く利用されるものである。 The catalyst-providing liquid for electroless reduced palladium plating of the present invention can provide an electroless reduced palladium plated film having no film thickness unevenness and no bridge on a copper-based metal, and solder ball bonding Since generation of voids at the time can also be suppressed, it is widely used in all fields where solder joints of copper-based conductor circuits are used.
　本願は、２００８年７月８日に出願した日本の特許出願である特願２００８－１７８０５４に基づくものであり、その出願の全ての内容はここに引用し、本発明の明細書の開示として取り込まれるものである。 This application is based on Japanese Patent Application No. 2008-178054 filed on Jul. 8, 2008, the entire contents of which are incorporated herein by reference as the disclosure of the specification of the present invention. It is what

Claims (13)

  1. 　銅系金属の上に無電解還元パラジウムめっきを行うための触媒付与液であって、構成成分として、水溶性の金化合物、窒素原子が２個以上の５員環構造を有するヘテロ環化合物、及び、イミノ２酢酸構造を有するキレート剤を含有することを特徴とする触媒付与液。 A catalyst-providing liquid for performing electroless reduction palladium plating on a copper-based metal, as a constituent component, a water-soluble gold compound, a heterocyclic compound having a five-membered ring structure with two or more nitrogen atoms, and The catalyst provision liquid characterized by including the chelating agent which has an imino diacetic acid structure.
  2. 　上記水溶性の金化合物がシアン化金塩である請求項１に記載の触媒付与液。 The catalyst-providing liquid according to claim 1, wherein the water-soluble gold compound is a gold cyanide salt.
  3. 　上記窒素原子が２個以上の５員環構造を有するヘテロ環化合物が、イミダゾール環、ピラゾール環、プリン環、１，２，３－トリアゾール環、１，２，４－トリアゾール環、テトラゾール環、チアジアゾール環、オキサジアゾール環、ベンズイミダゾール環及びベンズトリアゾール環よりなる群から選ばれたヘテロ環を有するものである請求項１又は請求項２に記載の触媒付与液。 The heterocyclic compound having a 5-membered ring structure having two or more nitrogen atoms is an imidazole ring, pyrazole ring, purine ring, 1,2,3-triazole ring, 1,2,4-triazole ring, tetrazole ring, thiadiazole The catalyst-providing liquid according to claim 1 or 2, which has a heterocycle selected from the group consisting of a ring, an oxadiazole ring, a benzimidazole ring, and a benztriazole ring.
  4. 　上記窒素原子が２個以上の５員環構造を有するヘテロ環化合物が、ピラゾール、３－アミノピラゾール、４－アミノピラゾール、５－アミノピラゾール、イミダゾール、２－アミノイミダゾール、４－アミノイミダゾール、５－アミノイミダゾール、プリン、２－アミノプリン、６－アミノプリン、１，２，３－トリアゾール、４－アミノ－１，２，３－トリアゾール、５－アミノ－１，２，３－トリアゾール、１，２，４－トリアゾール、３－アミノ－１，２，４－トリアゾール、５－アミノ－１，２，４－トリアゾール、テトラゾール、５－アミノテトラゾール、２－アミノ－１，３，４－チアジアゾール、２－アミノベンズイミダゾール、ベンズトリアゾール、又はこれらのアルキル置換体である請求項１ないし請求項３の何れかの請求項に記載の触媒付与液。 The heterocyclic compound having a 5-membered ring structure having two or more nitrogen atoms is pyrazole, 3-aminopyrazole, 4-aminopyrazole, 5-aminopyrazole, imidazole, 2-aminoimidazole, 4-aminoimidazole, 5- Aminoimidazole, purine, 2-aminopurine, 6-aminopurine, 1,2,3-triazole, 4-amino-1,2,3-triazole, 5-amino-1,2,3-triazole, 1,2 , 4-triazole, 3-amino-1,2,4-triazole, 5-amino-1,2,4-triazole, tetrazole, 5-aminotetrazole, 2-amino-1,3,4-thiadiazole, 2- The aminobenzimidazole, benztriazole, or an alkyl-substituted product thereof is any one of claims 1 to 3. Catalyst application solution according to Motomeko.
  5. 　上記イミノ２酢酸構造を有するキレート剤が、酢酸ユニットを３個以上含有するキレート剤である請求項１ないし請求項４の何れかの請求項に記載の触媒付与液。 The catalyst-providing liquid according to any one of claims 1 to 4, wherein the chelating agent having an iminodiacetic acid structure is a chelating agent containing three or more acetic acid units.
  6. 　実質的に水溶性白金族元素化合物を含有しない請求項１ないし請求項５の何れかの請求項に記載の触媒付与液。 The catalyst imparting solution according to any one of claims 1 to 5, which contains substantially no water-soluble platinum group element compound.
  7. 　上記触媒付与液のｐＨがｐＨ３以上ｐＨ９以下の範囲である請求項１ないし請求項６の何れかの請求項に記載の触媒付与液。 The catalyst application liquid according to any one of claims 1 to 6, wherein the pH of the catalyst application liquid is in a range of pH 3 or more and pH 9 or less.
  8. 　請求項１ないし請求項７の何れかの請求項に記載の触媒付与液を用い、銅系金属の上に無電解還元パラジウムめっきを行うことを特徴とする銅系金属上のパラジウムめっき皮膜の製造方法。 The production of a palladium plating film on a copper-based metal, characterized in that electroless reduction palladium plating is performed on the copper-based metal using the catalyst-imparting solution according to any one of claims 1 to 7. Method.
  9. 　請求項１ないし請求項７の何れかの請求項に記載の触媒付与液を用い、銅系金属の上に無電解還元パラジウムめっきを行って得られたことを特徴とする銅系金属上のパラジウムめっき皮膜。 Palladium on a copper-based metal obtained by electroless reduction palladium plating on a copper-based metal using the catalyst-providing liquid according to any one of claims 1 to 7. Plating film.
  10. 　銅系金属の上に３×１０－５ｇ／ｃｍ２以下の金を有し、その上に形成されてなることを特徴とする銅系金属上のパラジウムめっき皮膜。 A palladium-plated film on a copper-based metal, having gold of 3 × 10 −5 g / cm 2 or less on the copper-based metal and formed thereon.
  11. 　請求項１ないし請求項７の何れかの請求項に記載の触媒付与液を用い、銅系金属の上に３×１０－５ｇ／ｃｍ２以下の金を付着させ、その上に形成されてなる請求項９又は請求項１０に記載の銅系金属上のパラジウムめっき皮膜。 Using the catalyst-providing liquid according to any one of claims 1 to 7, gold of 3 × 10 −5 g / cm 2 or less is deposited on a copper-based metal, and formed thereon. The palladium plating film on the copper-based metal according to claim 9 or 10.
  12. 　請求項１ないし請求項７の何れかの請求項に記載の触媒付与液を用い、銅系金属の上に無電解還元パラジウムめっきを行い、続いて無電解金めっきを行うことを特徴とする銅系金属上のパラジウム／金めっき皮膜の製造方法。 A copper characterized in that electroless reduced palladium plating is performed on a copper-based metal, followed by electroless gold plating, using the catalyst-imparting solution according to any one of claims 1 to 7. Of producing a palladium / gold plating film on a metallic metal.
  13. 　請求項１ないし請求項７の何れかの請求項に記載の触媒付与液を用い、銅系金属の上に無電解還元パラジウムめっきを行い、続いて無電解金めっきを行って得られたことを特徴とする銅系金属上のパラジウム／金めっき皮膜。
          It was obtained by performing electroless reduction palladium plating on a copper-based metal using the catalyst applying solution according to any one of claims 1 to 7, and subsequently performing electroless gold plating. A palladium / gold plating film on a copper-based metal.
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Cited By (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8231639B2 (en) 2001-11-28 2012-07-31 Aptus Endosystems, Inc. Systems and methods for attaching a prosthesis within a body lumen or hollow organ
JP2013108180A (en) * 2011-11-22 2013-06-06 Samsung Electro-Mechanics Co Ltd Substrate and method for producing the same
US8591637B2 (en) 2010-12-14 2013-11-26 Rohm And Haas Electronic Materials Llc Plating catalyst and method
US8591636B2 (en) 2010-12-14 2013-11-26 Rohm And Haas Electronics Materials Llc Plating catalyst and method
US9023065B2 (en) 2001-11-28 2015-05-05 Aptus Endosystems, Inc. Devices, systems, and methods for supporting tissue and/or structures within a hollow body organ
US9320503B2 (en) 2001-11-28 2016-04-26 Medtronic Vascular, Inc. Devices, system, and methods for guiding an operative tool into an interior body region
US9320589B2 (en) 2001-11-28 2016-04-26 Medtronic Vascular, Inc. Endovascular aneurysm repair system
US9320591B2 (en) 2001-11-28 2016-04-26 Medtronic Vascular, Inc. Devices, systems, and methods for prosthesis delivery and implantation, including the use of a fastener tool
WO2018066217A1 (en) * 2016-10-05 2018-04-12 小島化学薬品株式会社 Electroless palladium/gold plating process
US9968353B2 (en) 2001-06-04 2018-05-15 Medtronic Vascular, Inc. Catheter based fastener implantation apparatus and methods
US10098770B2 (en) 2001-11-28 2018-10-16 Medtronic Vascular, Inc. Endovascular aneurysm devices, systems, and methods
US10194905B2 (en) 2001-11-28 2019-02-05 Medtronic Vascular, Inc. Devices, systems, and methods for endovascular staple and/or prosthesis delivery and implantation
US10444995B2 (en) 2011-09-28 2019-10-15 International Business Machines Corporation Automated selection of functions to reduce storage capacity based on performance requirements
US10941493B2 (en) 2016-06-13 2021-03-09 C. Uyemura & Co., Ltd. Film formation method

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20150024123A1 (en) * 2013-07-16 2015-01-22 Rohm And Haas Electronic Materials Llc Catalysts for electroless metallization containing iminodiacetic acid and derivatives
KR102041850B1 (en) 2019-04-08 2019-11-06 (주)엠케이켐앤텍 Gold-strike plating method corresponding to pretreatment process for electroless palladium plating on copper surface of printed circuit board, composition of gold-strike plating solution and electroless plating method of palladium and gold
JP7285123B2 (en) 2019-04-10 2023-06-01 上村工業株式会社 Gold plating method and plating film
JP6841462B1 (en) * 2020-07-03 2021-03-10 奥野製薬工業株式会社 Catalyst-imparting liquid for electroless plating

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05327187A (en) * 1992-05-18 1993-12-10 Ishihara Chem Co Ltd Printed circuit board and manufacture thereof
JP2003082468A (en) * 2001-09-12 2003-03-19 Okuno Chem Ind Co Ltd Catalyst solution for electroless plating
JP2005317729A (en) * 2004-04-28 2005-11-10 Hitachi Chem Co Ltd Connection terminal, semiconductor package using the same, and method for manufacturing semiconductor package
JP2006312763A (en) * 2005-05-09 2006-11-16 Japan Pure Chemical Co Ltd Substitution type electroless gold plating liquid

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05327187A (en) * 1992-05-18 1993-12-10 Ishihara Chem Co Ltd Printed circuit board and manufacture thereof
JP2003082468A (en) * 2001-09-12 2003-03-19 Okuno Chem Ind Co Ltd Catalyst solution for electroless plating
JP2005317729A (en) * 2004-04-28 2005-11-10 Hitachi Chem Co Ltd Connection terminal, semiconductor package using the same, and method for manufacturing semiconductor package
JP2006312763A (en) * 2005-05-09 2006-11-16 Japan Pure Chemical Co Ltd Substitution type electroless gold plating liquid

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Publication number Priority date Publication date Assignee Title
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US9320591B2 (en) 2001-11-28 2016-04-26 Medtronic Vascular, Inc. Devices, systems, and methods for prosthesis delivery and implantation, including the use of a fastener tool
US10098770B2 (en) 2001-11-28 2018-10-16 Medtronic Vascular, Inc. Endovascular aneurysm devices, systems, and methods
US9808250B2 (en) 2001-11-28 2017-11-07 Medtronic Vascular, Inc. Systems and methods for attaching a prosthesis within a body lumen or hollow organ
US9744021B2 (en) 2001-11-28 2017-08-29 Medtronic Vascular, Inc. Devices, systems, and methods for prosthesis delivery and implantation, including the use of a fastener tool
US10595867B2 (en) 2001-11-28 2020-03-24 Medtronic Vascular, Inc. Systems and methods for attaching a prosthesis within a body lumen or hollow organ
US8685044B2 (en) 2001-11-28 2014-04-01 Aptus Endosystems, Inc. Systems and methods for attaching a prosthesis with a body lumen or hollow organ
US10357230B2 (en) 2001-11-28 2019-07-23 Medtronic Vascular, Inc. Devices, system, and methods for guiding an operative tool into an interior body region
US9023065B2 (en) 2001-11-28 2015-05-05 Aptus Endosystems, Inc. Devices, systems, and methods for supporting tissue and/or structures within a hollow body organ
US10299791B2 (en) 2001-11-28 2019-05-28 Medtronic Vascular, Inc. Endovascular aneurysm repair system
US9320503B2 (en) 2001-11-28 2016-04-26 Medtronic Vascular, Inc. Devices, system, and methods for guiding an operative tool into an interior body region
US9320589B2 (en) 2001-11-28 2016-04-26 Medtronic Vascular, Inc. Endovascular aneurysm repair system
US8231639B2 (en) 2001-11-28 2012-07-31 Aptus Endosystems, Inc. Systems and methods for attaching a prosthesis within a body lumen or hollow organ
US10194905B2 (en) 2001-11-28 2019-02-05 Medtronic Vascular, Inc. Devices, systems, and methods for endovascular staple and/or prosthesis delivery and implantation
US8591636B2 (en) 2010-12-14 2013-11-26 Rohm And Haas Electronics Materials Llc Plating catalyst and method
US20140087062A1 (en) * 2010-12-14 2014-03-27 Rohm And Haas Electronic Materials Llc Plating catalyst and method
US8591637B2 (en) 2010-12-14 2013-11-26 Rohm And Haas Electronic Materials Llc Plating catalyst and method
US9234282B2 (en) * 2010-12-14 2016-01-12 Rohm And Haas Electronic Materials Llc Plating catalyst and method
US8961669B2 (en) * 2010-12-14 2015-02-24 Rohm And Haas Electronic Materials Llc Plating catalyst and method
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