JP2008174774A - Reduction precipitation type electroless gold plating liquid for palladium film - Google Patents
Reduction precipitation type electroless gold plating liquid for palladium film Download PDFInfo
- Publication number
- JP2008174774A JP2008174774A JP2007007766A JP2007007766A JP2008174774A JP 2008174774 A JP2008174774 A JP 2008174774A JP 2007007766 A JP2007007766 A JP 2007007766A JP 2007007766 A JP2007007766 A JP 2007007766A JP 2008174774 A JP2008174774 A JP 2008174774A
- Authority
- JP
- Japan
- Prior art keywords
- gold plating
- palladium
- electroless
- plating film
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000007747 plating Methods 0.000 title claims abstract description 217
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 239000010931 gold Substances 0.000 title claims abstract description 119
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 119
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 84
- 238000001556 precipitation Methods 0.000 title abstract description 10
- 239000007788 liquid Substances 0.000 title abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 100
- 239000000243 solution Substances 0.000 claims abstract description 80
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 50
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 38
- 239000008139 complexing agent Substances 0.000 claims abstract description 21
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000004020 conductor Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 8
- XWGJFPHUCFXLBL-UHFFFAOYSA-M rongalite Chemical compound [Na+].OCS([O-])=O XWGJFPHUCFXLBL-UHFFFAOYSA-M 0.000 claims abstract description 6
- 150000002344 gold compounds Chemical class 0.000 claims abstract description 5
- 230000008021 deposition Effects 0.000 claims description 34
- DETXZQGDWUJKMO-UHFFFAOYSA-N 2-hydroxymethanesulfonic acid Chemical compound OCS(O)(=O)=O DETXZQGDWUJKMO-UHFFFAOYSA-N 0.000 claims description 20
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims description 18
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 150000002941 palladium compounds Chemical class 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 150000002429 hydrazines Chemical class 0.000 abstract description 5
- 238000004381 surface treatment Methods 0.000 abstract description 3
- 230000002349 favourable effect Effects 0.000 abstract 1
- DXRFSTNITSDOKK-UHFFFAOYSA-N formaldehyde;sulfurous acid Chemical class O=C.OS(O)=O DXRFSTNITSDOKK-UHFFFAOYSA-N 0.000 abstract 1
- 238000000151 deposition Methods 0.000 description 35
- 150000003863 ammonium salts Chemical class 0.000 description 16
- 238000000034 method Methods 0.000 description 16
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- 159000000001 potassium salts Chemical class 0.000 description 11
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- 238000006073 displacement reaction Methods 0.000 description 6
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- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
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- 239000004471 Glycine Substances 0.000 description 3
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- 239000003054 catalyst Substances 0.000 description 3
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- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 description 3
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 3
- 229960002989 glutamic acid Drugs 0.000 description 3
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 3
- 150000007522 mineralic acids Chemical class 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 3
- 238000010979 pH adjustment Methods 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- 229960003330 pentetic acid Drugs 0.000 description 3
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 3
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- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 3
- 238000005476 soldering Methods 0.000 description 3
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- FUSNOPLQVRUIIM-UHFFFAOYSA-N 4-amino-2-(4,4-dimethyl-2-oxoimidazolidin-1-yl)-n-[3-(trifluoromethyl)phenyl]pyrimidine-5-carboxamide Chemical compound O=C1NC(C)(C)CN1C(N=C1N)=NC=C1C(=O)NC1=CC=CC(C(F)(F)F)=C1 FUSNOPLQVRUIIM-UHFFFAOYSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
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- BGRDGMRNKXEXQD-UHFFFAOYSA-N Maleic hydrazide Chemical compound OC1=CC=C(O)N=N1 BGRDGMRNKXEXQD-UHFFFAOYSA-N 0.000 description 2
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- BIVUUOPIAYRCAP-UHFFFAOYSA-N aminoazanium;chloride Chemical compound Cl.NN BIVUUOPIAYRCAP-UHFFFAOYSA-N 0.000 description 2
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- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- XTFKWYDMKGAZKK-UHFFFAOYSA-N potassium;gold(1+);dicyanide Chemical compound [K+].[Au+].N#[C-].N#[C-] XTFKWYDMKGAZKK-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 1
- 235000019345 sodium thiosulphate Nutrition 0.000 description 1
- VMDSWYDTKFSTQH-UHFFFAOYSA-N sodium;gold(1+);dicyanide Chemical compound [Na+].[Au+].N#[C-].N#[C-] VMDSWYDTKFSTQH-UHFFFAOYSA-N 0.000 description 1
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 description 1
- UOULCEYHQNCFFH-UHFFFAOYSA-M sodium;hydroxymethanesulfonate Chemical compound [Na+].OCS([O-])(=O)=O UOULCEYHQNCFFH-UHFFFAOYSA-M 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
- 150000003585 thioureas Chemical class 0.000 description 1
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- Electrodes Of Semiconductors (AREA)
- Manufacturing Of Printed Wiring (AREA)
- Parts Printed On Printed Circuit Boards (AREA)
- Chemically Coating (AREA)
Abstract
Description
本発明は、パラジウム皮膜上に直接金めっき皮膜を析出させることが可能な還元析出型無電解金めっき液に関する。 The present invention relates to a reduction deposition type electroless gold plating solution capable of depositing a gold plating film directly on a palladium film.
電子部品、特にプリント配線板において、金ワイヤー、アルミワイヤー等のボンディングやハンダ付けを行う際に、接合箇所の導体部分に対する表面処理として、無電解ニッケルめっき皮膜を形成した後、金めっき皮膜を形成することがある。この処理は、金めっき皮膜によってニッケルめっき皮膜の表面を保護して高いハンダ接合強度を発揮させるとともに、良好なハンダ濡れ性を確保することを目的とするものである。 When bonding or soldering gold wires, aluminum wires, etc. on electronic parts, especially printed wiring boards, after forming an electroless nickel plating film as a surface treatment for the conductor part of the joint, form a gold plating film There are things to do. The purpose of this treatment is to protect the surface of the nickel plating film with a gold plating film to exhibit high solder joint strength and to ensure good solder wettability.
この場合、通常、１〜１０μｍ程度の無電解ニッケルめっき皮膜を形成した後、置換析出型の金めっき液を用いて０．０３〜０．１μｍ程度の金めっき皮膜を形成しており、更に、金ワイヤーボンディングにおける優れた耐熱性を付与することなどを目的として、厚さ０．２〜１μｍ程度の厚付け金めっき皮膜を置換めっき法又は還元めっき法によって形成することがある。 In this case, usually, after forming an electroless nickel plating film of about 1 to 10 μm, a gold plating film of about 0.03 to 0.1 μm is formed using a displacement deposition type gold plating solution, For the purpose of imparting excellent heat resistance in gold wire bonding, a thick gold plating film having a thickness of about 0.2 to 1 μm may be formed by a displacement plating method or a reduction plating method.
しかしながら、上記した方法では、置換めっき法で金めっき皮膜を形成する際に、下地のニッケルめっき皮膜との電位差によって金めっきが析出するために、ニッケルめっき皮膜の表面が浸食されるという問題点がある。この様なニッケルめっき皮膜の浸食は、ハンダ付け性やボンディング性の低下の原因となり、更に、液の汚染の原因ともなる。 However, the above-described method has a problem in that when the gold plating film is formed by the displacement plating method, the surface of the nickel plating film is eroded because gold plating is deposited due to a potential difference from the underlying nickel plating film. is there. Such erosion of the nickel plating film causes deterioration of solderability and bonding property, and further causes contamination of the liquid.
このため、ニッケルめっき皮膜の保護等を目的として、無電解ニッケルめっき皮膜と置換金めっき皮膜との間に、中間層として無電解パラジウムめっき皮膜を形成する方法が提案されている（下記特許文献１参照）。この方法は、中間層としてパラジウムめっき皮膜を形成することによって、置換金めっき液によるニッケルめっき皮膜の浸食を抑制しようとするものである。しかしながら、無電解パラジウムめっき皮膜が薄い場合や、被めっき物に欠陥部が存在したり、形状が複雑な場合などには、パラジウムめっき皮膜の析出が不十分となって、ニッケルめっき皮膜の露出部分が生じることがある。この様な場合には、ニッケルはパラジウムより卑な金属であるために、一部でもニッケルめっき皮膜が露出すると、この部分のニッケルが優先的に溶解してニッケル表面が浸食され、ハンダ付け性低下の原因となる。 For this reason, a method of forming an electroless palladium plating film as an intermediate layer between the electroless nickel plating film and the displacement gold plating film has been proposed for the purpose of protecting the nickel plating film (Patent Document 1 below). reference). This method intends to suppress erosion of the nickel plating film by the displacement gold plating solution by forming a palladium plating film as an intermediate layer. However, when the electroless palladium plating film is thin, or there are defects in the object to be plated or the shape is complicated, the deposition of the palladium plating film becomes insufficient, and the exposed part of the nickel plating film May occur. In such a case, since nickel is a base metal than palladium, if even a part of the nickel plating film is exposed, the nickel in this part will be preferentially dissolved and the nickel surface will be eroded, reducing solderability. Cause.
また、ワイヤーボンディング時の耐熱性を向上させるために、０．２〜１μｍ程度の厚付け金めっき皮膜を形成することがあるが、置換析出型金めっき液を用いる場合には、厚膜化が困難である。また、還元析出型の金めっきを行う場合には、通常、ニッケル皮膜やパラジウム皮膜上に直接析出しないので、置換析出型金めっき液を用いて薄い金めっき皮膜を形成した後、還元析出型金めっき液を用いて厚膜化を行うことが必要である。例えば、下記特許文献２には、端子の銅箔部分に無電解ニッケル、置換パラジウム又は無電解パラジウム、置換金めっき及び無電解金めっきを順次形成する方法が記載されているが、この方法では、金めっき皮膜の形成に２工程を要するので、処理作業が煩雑となる。
本発明は、上記した従来技術の現状に鑑みてなされたものであり、その主な目的は、パラジウム皮膜上に直接析出が可能であり、プリント配線板の導体回路の表面処理に特に有用な還元析出型の無電解金めっき液を提供することである。 The present invention has been made in view of the current state of the prior art described above, and its main purpose is that it can be directly deposited on a palladium film, and is particularly useful for surface treatment of a conductor circuit of a printed wiring board. It is to provide a deposition type electroless gold plating solution.
本発明者は、上記した目的を達成すべく鋭意研究を重ねてきた。その結果、ホルムアルデヒド重亜硫酸類、ロンガリット又はヒドラジン類という特定の化合物を還元剤として含む還元析出型の無電解金めっき液によれば、置換析出型の金めっきを行うことなく、パラジウム皮膜上に金めっき皮膜を直接形成可能であることを見出した。そして、プリント配線板の導体部分に無電解ニッケルめっき皮膜を形成し、無電解パラジウムめっき皮膜を形成した後、上記した特定の還元剤を含む無電解金めっき液を用いて金めっき皮膜を形成する方法によれば、パラジウムめっき皮膜の膜厚が薄い場合であっても、下地のニッケルめっき皮膜を浸食することなく、金めっき皮膜を形成することが可能であり、しかも置換析出型の金めっきを行うことなく、簡略化された処理工程によって、厚付けの金めっき皮膜を形成することが可能となることを見出し、ここに本発明を完成するに至った。 The present inventor has intensively studied to achieve the above-described object. As a result, according to the reduction deposition type electroless gold plating solution containing a specific compound such as formaldehyde bisulfite, Rongalite or hydrazine as a reducing agent, gold is deposited on the palladium film without performing substitution deposition type gold plating. It has been found that a plating film can be formed directly. And after forming an electroless nickel plating film in the conductor part of a printed wiring board and forming an electroless palladium plating film, a gold plating film is formed using the above-mentioned electroless gold plating solution containing a specific reducing agent. According to the method, even when the palladium plating film is thin, it is possible to form a gold plating film without eroding the underlying nickel plating film, and to perform substitution deposition type gold plating. It has been found that a thick gold plating film can be formed by a simplified processing step without performing the present invention, and the present invention has been completed here.
即ち、本発明は、下記のパラジウム皮膜用還元析出型無電解金めっき液、及びプリント配線板を提供するものである。
１． 水溶性金化合物、還元剤及び錯化剤を含有する水溶液からなる無電解金めっき液であって、還元剤として、ホルムアルデヒド重亜硫酸類、ロンガリット及びヒドラジン類からなる群から選ばれた少なくとも一種の化合物を含有することを特徴とする、パラジウム皮膜上に直接金めっき皮膜を形成するために用いる還元析出型無電解金めっき液。
２． プリント配線板の導体部分に、無電解ニッケルめっき皮膜、無電解パラジウムめっき皮膜及び無電解金めっき皮膜が順次形成されたプリント配線板であって、該無電解金めっき皮膜が、上記項１に記載された還元析出型無電解金めっき液を用いて形成されたものである、プリント配線板。
３． 無電解パラジウムめっき皮膜が、パラジウム化合物、還元剤及び錯化剤を含有する水溶液からなり、該還元剤が、蟻酸及びその塩からなる群から選ばれた少なくとも一種である無電解パラジウムめっき液から形成されたものである上記項２に記載のプリント配線板。
That is, the present invention provides the following reduced deposition type electroless gold plating solution for a palladium film and a printed wiring board.
1. An electroless gold plating solution comprising an aqueous solution containing a water-soluble gold compound, a reducing agent and a complexing agent, wherein the reducing agent is at least one compound selected from the group consisting of formaldehyde bisulfite, Rongalite and hydrazine A reduction deposition type electroless gold plating solution used for forming a gold plating film directly on a palladium film, characterized in that
2. Item 2. A printed wiring board in which an electroless nickel plating film, an electroless palladium plating film, and an electroless gold plating film are sequentially formed on a conductor portion of the printed wiring board, wherein the electroless gold plating film is the item 1 described above. A printed wiring board which is formed using the reduced deposition type electroless gold plating solution.
3. The electroless palladium plating film is made of an aqueous solution containing a palladium compound, a reducing agent, and a complexing agent, and the reducing agent is formed from an electroless palladium plating solution that is at least one selected from the group consisting of formic acid and salts thereof. Item 3. The printed wiring board according to Item 2 above.
本発明の無電解金めっき液は、水溶性金化合物、還元剤及び錯化剤を必須成分として含有する水溶液からなる還元析出型の金めっき液であり、非シアン浴及びシアン浴のいずれでも良い。本発明の無電解金めっき液は、ホルムアルデヒド重亜硫酸類、ロンガリット及びヒドラジン類からなる群から選ばれた少なくとも一種の化合物を還元剤として含有することを特徴とするものであり、パラジウム皮膜上に金めっき皮膜を直接形成するために用いられるものである。以下、本発明の還元析出型無電解金めっき液について具体的に説明する。 The electroless gold plating solution of the present invention is a reduction precipitation type gold plating solution comprising an aqueous solution containing a water-soluble gold compound, a reducing agent and a complexing agent as essential components, and may be either a non-cyan bath or a cyan bath. . The electroless gold plating solution of the present invention is characterized in that it contains at least one compound selected from the group consisting of formaldehyde bisulfite, Rongalite and hydrazine as a reducing agent, and a gold film is formed on the palladium film. It is used for directly forming a plating film. Hereinafter, the reduction precipitation type electroless gold plating solution of the present invention will be specifically described.
還元析出型無電解金めっき液
本発明の還元析出型無電解金めっき液では、水溶性金化合物としては、めっき液に可溶性であって、所定の濃度の水溶液が得られるものであれば特に限定なく使用できる。例えば、亜硫酸金カリウム、亜硫酸金ナトリウム、亜硫酸金アンモニウム、シアン化金カリウム、シアン化金ナトリウム、シアン化金アンモニウム等を用いることができる。水溶性金塩は１種単独又は２種以上混合して用いることができる。水溶性金塩の含有量は、０．１〜２０ｇ／Ｌ程度とすることが好ましく、０．３〜５ｇ／Ｌ程度とすることがより好ましい。
Reduced deposition type electroless gold plating solution In the reduced deposition type electroless gold plating solution of the present invention, the water-soluble gold compound is particularly limited as long as it is soluble in the plating solution and can obtain an aqueous solution of a predetermined concentration. Can be used without For example, potassium gold sulfite, sodium gold sulfite, gold ammonium sulfite, potassium gold cyanide, sodium gold cyanide, ammonium gold cyanide and the like can be used. The water-soluble gold salt can be used alone or in combination of two or more. The content of the water-soluble gold salt is preferably about 0.1 to 20 g / L, and more preferably about 0.3 to 5 g / L.
錯化剤としては公知の錯化剤を使用できる。例えばエチレンジアミン、ジエチレントリアミン等のアミン類；エチレンジアミンジ酢酸、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸等のアミノポリカルボン酸、これらのナトリウム塩、カリウム塩、アンモニウム塩等；グリシン、アラニン、イミノジ酢酸、ニトリロトリ酢酸、Ｌ−グルタミン酸、Ｌ−グルタミン酸２酢酸、Ｌ−アスパラギン酸、タウリン等のアミノ酸類、これらのアンモニウム塩、カリウム塩、ナトリウム塩等；アミノトリメチレンホスホン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、エチレンジアミンテトラメチレンホスホン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等を用いることができる。錯化剤は１種単独又は２種以上混合して用いることができる。錯化剤としては、特に、エチレンジアミンが好ましい。錯化剤の含有量は、０．５〜１００ｇ／Ｌ程度とすることが好ましく、５〜５０ｇ／Ｌ程度とすることがより好ましい。 A known complexing agent can be used as the complexing agent. For example, amines such as ethylenediamine and diethylenetriamine; aminopolycarboxylic acids such as ethylenediaminediacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, sodium salts, potassium salts and ammonium salts thereof; glycine, alanine, iminodiacetic acid, nitrilotriacetic acid, L Amino acids such as glutamic acid, L-glutamic acid diacetic acid, L-aspartic acid, taurine, ammonium salts, potassium salts, sodium salts thereof; aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, Ethylenediaminetetramethylene phosphonic acid, ammonium salts, potassium salts, sodium salts thereof and the like can be used. Complexing agents can be used alone or in combination of two or more. As the complexing agent, ethylenediamine is particularly preferable. The complexing agent content is preferably about 0.5 to 100 g / L, more preferably about 5 to 50 g / L.
本発明の還元析出型無電解金めっき液は、ホルムアルデヒド重亜硫酸類、ロンガリット及びヒドラジン類からなる群から選ばれた少なくとも一種の化合物を還元剤として含有することを特徴とするものである。この様な特定の化合物を還元剤とする無電解金めっき液によれば、無電解パラジウムめっき皮膜、電解パラジウムめっき皮膜などの各種のパラジウム皮膜上に、置換析出型金めっきを行うことなく、金めっき皮膜を直接形成することができる。この様な特定の還元剤を用いる場合に、パラジウム皮膜上に、還元析出型の無電解金めっき皮膜を直接形成できることは、従来全く知られていない新規な発見事項である。 The reduction deposition type electroless gold plating solution of the present invention is characterized in that it contains at least one compound selected from the group consisting of formaldehyde bisulfite, longalite and hydrazine as a reducing agent. According to the electroless gold plating solution using such a specific compound as a reducing agent, the gold is deposited on the various palladium films such as the electroless palladium plated film and the electrolytic palladium plated film without performing substitution deposition type gold plating. A plating film can be directly formed. When such a specific reducing agent is used, the ability to directly form a reduced deposition type electroless gold plating film on the palladium film is a novel discovery that has not been known at all.
上記還元剤の内で、ホルムアルデヒド重亜硫酸類としては、ホルムアルデヒド重亜硫酸の他に、ホルムアルデヒド重亜硫酸のアンモニウム塩、カリウム塩、ナトリウム塩等の可溶性塩を用いることができる。 Among the reducing agents, as formaldehyde bisulfite, in addition to formaldehyde bisulfite, soluble salts such as ammonium salt, potassium salt and sodium salt of formaldehyde bisulfite can be used.
また、ヒドラジン類としては、ヒドラジン；硫酸ヒドラジン、塩酸ヒドラジン等のヒドラジン塩；ピラゾール類、トリアゾール類、ヒドラジド類等のヒドラジン誘導体等を用いることができる。これらの内で、ピラゾール類としては、ピラゾールの他に、３，５−ジメチルピラゾール、３−メチル−５−ピラゾロン等のピラゾール誘導体を用いることができる。トリアゾール類としては、４−アミノ−１，２，４−トリアゾール、１，２，３−トリアゾール等を用いることができる。ヒドラジド類としては、アジピン酸ヒドラジド、マレイン酸ヒドラジド、カルボヒドラジド等を用いることができる。ヒドラジン類としては、特に、硫酸ヒドラジン、塩酸ヒドラジン、アジピン酸ヒドラジド、マレイン酸ヒドラジド、カルボヒドラジド等が好ましい。 Examples of hydrazines that can be used include hydrazine; hydrazine salts such as hydrazine sulfate and hydrazine hydrochloride; hydrazine derivatives such as pyrazoles, triazoles, and hydrazides. Among these, as pyrazoles, pyrazole derivatives such as 3,5-dimethylpyrazole and 3-methyl-5-pyrazolone can be used in addition to pyrazole. As triazoles, 4-amino-1,2,4-triazole, 1,2,3-triazole and the like can be used. As the hydrazides, adipic acid hydrazide, maleic acid hydrazide, carbohydrazide and the like can be used. As the hydrazines, hydrazine sulfate, hydrazine hydrochloride, adipic hydrazide, maleic hydrazide, carbohydrazide and the like are particularly preferable.
上記した還元剤は、一種単独又は二種以上混合して用いることができる。 The above reducing agents can be used singly or in combination of two or more.
還元剤としては、特に、ホルムアルデヒド重亜硫酸ナトリウム、ロンガリットなどが、金めっき浴の浴安定性が良好である点で好ましい。 As the reducing agent, in particular, sodium formaldehyde bisulfite, Rongalite, etc. are preferable in that the bath stability of the gold plating bath is good.
上記した還元剤の含有量は、０．５〜１００ｇ／Ｌ程度とすることが好ましく、１〜３０ｇ／Ｌ程度とすることがより好ましい。 The content of the reducing agent described above is preferably about 0.5 to 100 g / L, and more preferably about 1 to 30 g / L.
なお、還元剤として、チオ尿素、アスコルビン酸、ジメチルアミンボラン、テトラヒドロホウ素化ナトリウム、次亜リン酸ナトリウム等を併用することも可能であるが、これらの還元剤を単独で用いる場合には、パラジウム皮膜上に、直接均一な金めっき皮膜を形成することはできない。上記したホルムアルデヒド重亜硫酸類、ロンガリット及びヒドラジン類からなる群から選ばれた少なくとも一種の化合物からなる還元剤以外の還元剤を用いる場合には、これらの還元剤の含有量は、例えば、０．１〜５０ｇ／Ｌの範囲とすることができる。 As a reducing agent, thiourea, ascorbic acid, dimethylamine borane, sodium tetrahydroborate, sodium hypophosphite, etc. can be used in combination, but when these reducing agents are used alone, palladium A uniform gold plating film cannot be formed directly on the film. When using a reducing agent other than the reducing agent comprising at least one compound selected from the group consisting of formaldehyde bisulfite, longalite and hydrazine, the content of these reducing agents is, for example, 0.1 It can be in the range of ˜50 g / L.
更に、該無電解金めっき液には、安定剤として、シアン化合物、エチレンジアミン誘導体等の窒素系化合物、チオ尿素誘導体等の硫黄系化合物等を一種単独又は混合して配合することもできる。安定剤の配合量は、例えば、０．０００１ｇ／Ｌ〜２０ｇ／Ｌ程度とすることができる。 Furthermore, the electroless gold plating solution may contain a stabilizer such as a nitrogen compound such as a cyanide compound or an ethylenediamine derivative, or a sulfur compound such as a thiourea derivative, alone or in combination. The blending amount of the stabilizer can be, for example, about 0.0001 g / L to 20 g / L.
本発明の還元析出型無電解金めっき液のｐＨは、４〜９程度とすることが好ましい。ｐＨ調整には、硫酸、リン酸等の無機酸、水酸化ナトリウム、アンモニア水等を使用することができる。ｐＨが低すぎる場合や高すぎる場合には、プリント基板等を被めっき物とする場合に、特にソルダーレジストに対してダメージを与えるため好ましくない。 The pH of the reduced deposition type electroless gold plating solution of the present invention is preferably about 4 to 9. For pH adjustment, inorganic acids such as sulfuric acid and phosphoric acid, sodium hydroxide, aqueous ammonia and the like can be used. If the pH is too low or too high, the printed circuit board or the like is undesirably damaged particularly with respect to the solder resist.
上記した本発明の還元析出型無電解金めっき液によれば、無電解パラジウムめっき皮膜、電解パラジウムめっき皮膜の他、気相法によって形成されたパラジウム皮膜等の各種のパラジウム皮膜上に、置換析出型無電解金めっきを行うことなく、還元析出型の無電解金めっき皮膜を直接形成することができる。 According to the reduction deposition type electroless gold plating solution of the present invention described above, substitution deposition is performed on various palladium films such as an electroless palladium plating film, an electrolytic palladium plating film, and a palladium film formed by a vapor phase method. A reduction precipitation type electroless gold plating film can be formed directly without performing electroless gold plating.
例えば、パラジウム皮膜を形成した被めっき物を、上記した還元析出型の無電解金めっき液中に浸漬することによって、パラジウム皮膜上に金めっき皮膜を直接形成することができる。 For example, the gold plating film can be directly formed on the palladium film by immersing the object to be plated on which the palladium film is formed in the above-described reduction deposition type electroless gold plating solution.
本発明の無電解金めっき液の処理温度は、３５℃〜９５℃程度とすることが好ましく、４５℃〜９０℃程度とすることがより好ましい。 The treatment temperature of the electroless gold plating solution of the present invention is preferably about 35 ° C. to 95 ° C., more preferably about 45 ° C. to 90 ° C.
プリント配線板へのめっき方法
本発明の還元析出型無電解金めっき液は、特に、プリント配線板のパッド部分、回路部分、端子部分等の導体部分を被めっき物として、無電解ニッケルめっき皮膜を形成した後、無電解パラジウムめっき皮膜を形成し、次いで、金めっき皮膜を形成する方法において、金めっき皮膜形成用の無電解金めっき液として、特に有用性が高いめっき液である。
Method of plating on printed wiring board The reduced deposition type electroless gold plating solution of the present invention is particularly suitable for electroless nickel plating film with a conductive part such as a pad part, a circuit part, and a terminal part of the printed wiring board being plated. After forming, in the method of forming an electroless palladium plating film and then forming a gold plating film, the plating solution is particularly useful as an electroless gold plating solution for forming a gold plating film.
上記方法において本発明の還元析出型無電解金めっき液を用いることによって、置換析出型金めっきを行うことなく、パラジウムめっき皮膜上に直接金めっき皮膜を形成することができる。このため、ニッケルめっき皮膜がパラジウムめっき皮膜によって完全に被覆されずニッケルめっき皮膜の露出部分が生じた場合であっても、金めっきの際にニッケル表面が浸食されることがなく、ハンダ付け性の低下が生じることがない。また、還元析出型金めっきだけで厚付け金めっきを行うことができるので、処理工程の簡略化が図られる。 By using the reduced deposition type electroless gold plating solution of the present invention in the above method, a gold plating film can be formed directly on the palladium plating film without performing substitution deposition type gold plating. For this reason, even if the nickel plating film is not completely covered with the palladium plating film and an exposed portion of the nickel plating film is generated, the nickel surface is not eroded during gold plating, and solderability is improved. There is no reduction. Further, since the thick gold plating can be performed only by the reduction precipitation type gold plating, the processing process can be simplified.
プリント配線板としては、例えば、エポキシ樹脂、ポリイミド樹脂等を基材として銅等による導体部分が形成されている基板；ガラス、セラミックス等を基材として銅、銀、タングステン、モリブデンなどによる導体部分が形成されている基板等を使用できる。 As a printed wiring board, for example, a substrate in which a conductor portion made of copper or the like is formed using epoxy resin, polyimide resin or the like as a base material; a conductor portion made of copper, silver, tungsten, molybdenum or the like is made of glass or ceramics as a base material A formed substrate or the like can be used.
無電解ニッケルめっき皮膜は常法に従って形成することができる。通常は、無電解ニッケルめっき液中に被めっき物を浸漬すればよい。被めっき物が無電解ニッケルめっきに対して触媒活性を有さない場合には、常法に従ってパラジウム核などの金属触媒核を付着させた後、無電解ニッケルめっきを行えばよい。無電解ニッケルめっきの際には、必要に応じて、めっき液の撹拌や被めっき物の揺動を行うことができる。 The electroless nickel plating film can be formed according to a conventional method. Usually, the object to be plated may be immersed in an electroless nickel plating solution. When the object to be plated does not have catalytic activity for electroless nickel plating, electroless nickel plating may be performed after depositing a metal catalyst nucleus such as a palladium nucleus according to a conventional method. During electroless nickel plating, the plating solution can be agitated and the object to be plated can be swung as necessary.
無電解ニッケルめっき液としては、特に限定的ではなく、水溶性ニッケル化合物、還元剤、及び錯化剤を必須成分として含有する水溶液からなる公知の無電解ニッケルめっき液を用いることができる。無電解ニッケルめっき液の一例を挙げると、次の通りである。 The electroless nickel plating solution is not particularly limited, and a known electroless nickel plating solution made of an aqueous solution containing a water-soluble nickel compound, a reducing agent, and a complexing agent as essential components can be used. An example of the electroless nickel plating solution is as follows.
水溶性ニッケル化合物としては、めっき液に可溶性であって、所定の濃度の水溶液が得られるものであれば特に限定なく使用できる。例えば、硫酸ニッケル、塩化ニッケル、スルファミン酸ニッケル、次亜リン酸ニッケル等を用いることができる。水溶性ニッケル化合物は１種単独又は２種以上混合して用いることができる。特に硫酸ニッケルが溶解性が良好である点で好ましい。 The water-soluble nickel compound can be used without particular limitation as long as it is soluble in the plating solution and can obtain an aqueous solution having a predetermined concentration. For example, nickel sulfate, nickel chloride, nickel sulfamate, nickel hypophosphite, or the like can be used. A water-soluble nickel compound can be used individually by 1 type or in mixture of 2 or more types. In particular, nickel sulfate is preferable in terms of good solubility.
水溶性ニッケル化合物の含有量は、０．５〜５０ｇ／Ｌ程度とすることが好ましく、２〜１０ｇ／Ｌ程度とすることがより好ましい。 The content of the water-soluble nickel compound is preferably about 0.5 to 50 g / L, and more preferably about 2 to 10 g / L.
還元剤としては、次亜リン酸、次亜リン酸塩（ナトリウム塩、カリウム塩、アンモニウム塩等）、ジメチルアミンボラン、ヒドラジン等を用いることができる。還元剤の含有量は、０．０１〜１００ｇ／Ｌ程度とすることが好ましく、０．１〜５０ｇ／Ｌとすることがより好ましい。 As the reducing agent, hypophosphorous acid, hypophosphite (sodium salt, potassium salt, ammonium salt, etc.), dimethylamine borane, hydrazine and the like can be used. The content of the reducing agent is preferably about 0.01 to 100 g / L, and more preferably 0.1 to 50 g / L.
錯化剤としては公知の錯化剤を使用できる。例えば、酢酸、蟻酸等のモノカルボン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等；マロン酸、コハク酸、アジピン酸、マレイン酸、フマール酸等のジカルボン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等；リンゴ酸、乳酸、グリコール酸、グルコン酸、クエン酸等のヒドロキシカルボン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等；エチレンジアミンジ酢酸、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸等のアミノポリカルボン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等；グリシン、アラニン、イミノジ酢酸、ニトリロトリ酢酸、Ｌ−グルタミン酸、Ｌ−グルタミン酸２酢酸、Ｌ−アスパラギン酸、タウリン等のアミノ酸類、これらのアンモニウム塩、カリウム塩、ナトリウム塩等；アミノトリメチレンホスホン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、エチレンジアミンテトラメチレンホスホン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等；エチレンジアミン、ジエチレントリアミンなどのアミン化合物等を配合することができる。錯化剤は１種単独又は２種以上混合して用いることができる。錯化剤の配合量は、０．５〜１００ｇ／Ｌ程度とすることが好ましく、５〜５０ｇ／Ｌ程度とすることがより好ましい。 A known complexing agent can be used as the complexing agent. For example, monocarboxylic acids such as acetic acid and formic acid, ammonium salts, potassium salts, sodium salts thereof; dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid, fumaric acid, ammonium salts, potassium salts thereof, Sodium salts, etc .; hydroxycarboxylic acids such as malic acid, lactic acid, glycolic acid, gluconic acid, citric acid, ammonium salts, potassium salts, sodium salts, etc .; aminopolyamines such as ethylenediaminediacetic acid, ethylenediaminetetraacetic acid, diethylenetriaminepentaacetic acid Carboxylic acids, ammonium salts thereof, potassium salts, sodium salts and the like; Glycine, alanine, iminodiacetic acid, nitrilotriacetic acid, L-glutamic acid, L-glutamic acid diacetic acid, L-aspartic acid, taurine and other amino acids, ammonium salts thereof , Mosquito Ammonium salt, sodium salt, etc .; aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, ethylenediaminetetramethylenephosphonic acid, ammonium salts, potassium salts, sodium salts thereof; amine compounds such as ethylenediamine, diethylenetriamine Etc. can be blended. Complexing agents can be used alone or in combination of two or more. The compounding amount of the complexing agent is preferably about 0.5 to 100 g / L, and more preferably about 5 to 50 g / L.
無電解ニッケルめっき液には、その他必要に応じて、通常用いられている各種の添加剤を配合することができる。例えば、安定剤として、硝酸鉛、酢酸鉛等の鉛塩；硝酸ビスマス、酢酸ビスマス等のビスマス塩；チオジグリコール酸等の硫黄化合物等を１種単独又は２種以上混合して添加することができる。安定剤の添加量は、特に限定的ではないが、例えば、０．０１〜１００ｍｇ／Ｌ程度とすることができる。 In addition to the electroless nickel plating solution, various commonly used additives can be blended as necessary. For example, as a stabilizer, lead salts such as lead nitrate and lead acetate; bismuth salts such as bismuth nitrate and bismuth acetate; sulfur compounds such as thiodiglycolic acid may be added singly or in combination of two or more. it can. Although the addition amount of a stabilizer is not specifically limited, For example, it can be set as about 0.01-100 mg / L.
さらに、めっき液の浸透性のために、界面活性剤を配合することができる。界面活性剤としては、ノニオン性、カチオン性、アニオン性、両性等の界面活性剤を１種単独又は２種以上添加することができる。添加量としては、０．１〜１００ｍｇ／Ｌ程度が好ましい。 Furthermore, a surfactant can be blended for the permeability of the plating solution. As the surfactant, nonionic, cationic, anionic, and amphoteric surfactants can be added singly or in combination of two or more. The addition amount is preferably about 0.1 to 100 mg / L.
上記した無電解ニッケルめっき液のｐＨは、２〜９程度であることが好ましく、３〜８程度であることがより好ましい。ｐＨ調整には、硫酸、リン酸等の無機酸、水酸化ナトリウム、アンモニア水等を使用することができる。 The pH of the above electroless nickel plating solution is preferably about 2 to 9, and more preferably about 3 to 8. For pH adjustment, inorganic acids such as sulfuric acid and phosphoric acid, sodium hydroxide, aqueous ammonia and the like can be used.
無電解ニッケルめっき液による処理温度は、通常、５０〜９５℃程度とすればよく、６０〜９０℃程度とすることが好ましい。 The treatment temperature with the electroless nickel plating solution is usually about 50 to 95 ° C, and preferably about 60 to 90 ° C.
無電解ニッケルめっき皮膜の膜厚は、特に限定的ではないが、０．１〜１５μｍ程度とすることが好ましく、０．２μｍ〜１０μｍ程度とすることがより好ましい。ニッケルめっき液の膜厚が薄すぎる場合には、ニッケルめっきの効果が得られ難く、厚すぎる場合には、一定以上の効果は得られないので、経済的でない。 The film thickness of the electroless nickel plating film is not particularly limited, but is preferably about 0.1 to 15 μm, and more preferably about 0.2 μm to 10 μm. If the thickness of the nickel plating solution is too thin, it is difficult to obtain the effect of nickel plating, and if it is too thick, an effect of a certain level cannot be obtained, which is not economical.
次いで、上記した方法で無電解ニッケルめっき皮膜を形成した後、無電解パラジウムめっき皮膜を形成する。通常、無電解ニッケルめっき皮膜を形成した被めっき物を無電解パラジウムめっき液中に浸漬することによって、無電解パラジウムめっき皮膜を形成することができる。 Subsequently, after forming an electroless nickel plating film by the above-described method, an electroless palladium plating film is formed. Usually, an electroless palladium plating film can be formed by immersing an object on which an electroless nickel plating film is formed in an electroless palladium plating solution.
無電解パラジウムめっき液についても、特に限定はなく、パラジウム化合物、還元剤及び錯化剤を必須成分として含有する水溶液からなる無電解パラジウムめっき液を用いることができる。無電解パラジウムめっき液の一例を挙げると次の通りである。 The electroless palladium plating solution is not particularly limited, and an electroless palladium plating solution comprising an aqueous solution containing a palladium compound, a reducing agent and a complexing agent as essential components can be used. An example of the electroless palladium plating solution is as follows.
まず、パラジウム化合物としては、めっき液に可溶性であって、所定の濃度の水溶液が得られるものであれば特に限定なく使用できる。例えば、硫酸パラジウム、塩化パラジウム、酢酸パラジウム、ジクロロジエチンレジアミンパラジウム、テトラアンミンパラジウムジクロライド等の水溶性パラジウム化合物を用いることができる。また、パラジウム化合物として、パラジウムを溶液化したいわゆるパラジウム溶液を使用することもできる。パラジウム溶液としては、例えば、ジクロロジエチレンジアミンパラジウム溶液やテトラアンミンパラジウムジクロライド溶液等も使用することができる。パラジウム化合物は、１種単独又は２種以上混合して用いることができる。 First, the palladium compound can be used without particular limitation as long as it is soluble in the plating solution and can obtain an aqueous solution having a predetermined concentration. For example, water-soluble palladium compounds such as palladium sulfate, palladium chloride, palladium acetate, dichlorodiethine rediamine palladium, and tetraammine palladium dichloride can be used. Further, as the palladium compound, a so-called palladium solution in which palladium is made into a solution can also be used. As the palladium solution, for example, a dichlorodiethylenediamine palladium solution or a tetraammine palladium dichloride solution can be used. A palladium compound can be used individually by 1 type or in mixture of 2 or more types.
パラジウム化合物の含有量は、パラジウムとして０．１〜３０ｇ／Ｌ程度とすることが好ましく、０．３〜１０ｇ／Ｌ程度とすることがより好ましい。 The content of the palladium compound is preferably about 0.1 to 30 g / L as palladium, and more preferably about 0.3 to 10 g / L.
無電解パラジウムめっきの還元剤としては、蟻酸、次亜リン酸、亜リン酸、これらの塩（ナトリウム塩、カリウム塩、アンモニウム塩等）等を用いることができる。これらの還元剤は、一種単独又は二種以上混合して用いることができる。 As a reducing agent for electroless palladium plating, formic acid, hypophosphorous acid, phosphorous acid, salts thereof (sodium salt, potassium salt, ammonium salt, etc.) and the like can be used. These reducing agents can be used singly or in combination of two or more.
還元剤の含有量は、０．１〜１００ｇ／Ｌ程度とすることが好ましく、１〜５０ｇ／Ｌとすることがより好ましい。 The content of the reducing agent is preferably about 0.1 to 100 g / L, more preferably 1 to 50 g / L.
還元剤としては、特に、蟻酸又はその塩が好ましい。これを使用して得られるパラジウムめっき皮膜は、９９％以上の高純度の皮膜となり、金めっき皮膜との密着性が特に良好となり、更に、ハンダ接合強度も向上する。 As the reducing agent, formic acid or a salt thereof is particularly preferable. The palladium plating film obtained by using this becomes a high-purity film of 99% or more, the adhesion with the gold plating film is particularly good, and the solder joint strength is also improved.
錯化剤としては、公知の錯化剤を使用できる。例えばエチレンジアミン、ジエチレントリアミン等のアミン類；エチレンジアミンジ酢酸、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸等のアミノポリカルボン酸、これらのナトリウム塩、カリウム塩、アンモニウム塩等；グリシン、アラニン、イミノジ酢酸、ニトリロトリ酢酸、Ｌ−グルタミン酸、Ｌ−グルタミン酸２酢酸、Ｌ−アスパラギン酸、タウリン等のアミノ酸類、これらのナトリウム塩、カリウム塩、アンモニウム塩等；アミノトリメチレンホスホン酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、エチレンジアミンテトラメチレンホスホン酸、これらのナトリウム塩、カリウム塩、アンモニウム塩等を配合することができる。錯化剤は１種単独又は２種以上混合して用いることができる。錯化剤の配合量は、０．５〜１００ｇ／Ｌ程度とすることが好ましく、５〜５０ｇ／Ｌ程度とすることがより好ましい。 A known complexing agent can be used as the complexing agent. For example, amines such as ethylenediamine and diethylenetriamine; aminopolycarboxylic acids such as ethylenediaminediacetic acid, ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, sodium salts, potassium salts and ammonium salts thereof; glycine, alanine, iminodiacetic acid, nitrilotriacetic acid, L -Amino acids such as glutamic acid, L-glutamic acid diacetic acid, L-aspartic acid, taurine, sodium salts, potassium salts, ammonium salts thereof; aminotrimethylenephosphonic acid, 1-hydroxyethylidene-1,1-diphosphonic acid, Ethylenediaminetetramethylene phosphonic acid, sodium salts, potassium salts, ammonium salts and the like thereof can be blended. Complexing agents can be used alone or in combination of two or more. The compounding amount of the complexing agent is preferably about 0.5 to 100 g / L, and more preferably about 5 to 50 g / L.
無電解パラジウムめっき液のｐＨは２〜９程度であることが好ましく、３〜８程度であることがより好ましい。ｐＨ調整には、硫酸、リン酸等の無機酸、水酸化ナトリウム、アンモニア水等を使用することができる。 The pH of the electroless palladium plating solution is preferably about 2 to 9, and more preferably about 3 to 8. For pH adjustment, inorganic acids such as sulfuric acid and phosphoric acid, sodium hydroxide, aqueous ammonia and the like can be used.
無電解パラジウムめっき液の処理温度は、３０℃〜９０℃程度、特に４０℃〜８０℃程度であることが好ましい。 The treatment temperature of the electroless palladium plating solution is preferably about 30 ° C to 90 ° C, particularly about 40 ° C to 80 ° C.
無電解パラジウムめっき皮膜の厚さは、０．００１μｍ程度以上であることが好ましく、０．００５μｍ程度以上であることがより好ましく、０．０５μｍ程度以上であることが更に好ましい。パラジウムめっき皮膜の膜厚が薄すぎる場合には、金めっきが均一に析出しないため好ましくない。 The thickness of the electroless palladium plating film is preferably about 0.001 μm or more, more preferably about 0.005 μm or more, and further preferably about 0.05 μm or more. When the thickness of the palladium plating film is too thin, gold plating is not uniformly deposited, which is not preferable.
パラジウムめっき皮膜の膜厚の上限については、特に限定はないが、コストを考慮すれば例えば、２μｍ程度以下とすることが好ましい。また、金めっき皮膜上にハンダ接合を行う場合には、十分なハンダ接合強度を得るためには、パラジウムめっき皮膜の膜厚は、１μｍ程度以下であることが好ましく、０．５μｍ程度以下であることがより好ましい。パラジウム皮膜が厚すぎる場合には、パラジウムめっき皮膜はハンダ中への拡散性が劣るために、ハンダ付けの際に無電解ニッケルめっき皮膜の表面に残存して、ハンダ接合強度の低下の原因となることがあるので好ましくない。上記した本発明の還元析出型無電解金めっき液を用いることにより、パラジウムめっき皮膜が１μｍ以下という非常に薄い場合であっても、下地の無電解ニッケルめっき皮膜を浸食することがないので、ハンダ接合強度の高いめっき皮膜を形成することが可能となる。 The upper limit of the film thickness of the palladium plating film is not particularly limited, but is preferably about 2 μm or less, for example, considering the cost. In addition, when solder bonding is performed on the gold plating film, the film thickness of the palladium plating film is preferably about 1 μm or less, and about 0.5 μm or less in order to obtain sufficient solder bonding strength. It is more preferable. If the palladium film is too thick, the palladium plating film has poor diffusibility into the solder, and therefore remains on the surface of the electroless nickel plating film during soldering, causing a decrease in solder joint strength. This is not preferable. By using the reduced deposition type electroless gold plating solution of the present invention described above, even if the palladium plating film is very thin of 1 μm or less, the underlying electroless nickel plating film is not eroded, so that solder It is possible to form a plating film with high bonding strength.
上記した方法でパラジウムめっき皮膜を形成した後、本発明の還元析出型無電解金めっき液を用いて金めっき皮膜を形成する。通常は、無電解パラジウムめっき皮膜を形成した後、該還元析出型無電解金めっき液中に被めっき物を浸漬することによって、金めっき皮膜を形成することができる。 After forming a palladium plating film by the above-described method, a gold plating film is formed using the reduction deposition type electroless gold plating solution of the present invention. Usually, after forming an electroless palladium plating film, a gold plating film can be formed by immersing an object to be plated in the reduction deposition type electroless gold plating solution.
無電解金めっき液の処理温度は、３５℃〜９５℃程度とすることが好ましく、４５℃〜９０℃程度とすることがより好ましい。 The treatment temperature of the electroless gold plating solution is preferably about 35 ° C to 95 ° C, more preferably about 45 ° C to 90 ° C.
無電解金めっき皮膜の膜厚は、その目的によって適宜選択すればよいが、薄すぎると金めっき膜としての性能が十分に発揮されず、ハンダ性、ワイヤーボンディング性などが劣るものとなる。通常は、０．００１μｍ程度以上の膜厚とすればよい。金めっき皮膜の膜厚の上限については特に限定的ではないが、厚すぎるとコストが高くなるので、この点を考慮して決めればよい。例えば、十分なハンダ接合強度を得るためには、０．３μｍ程度までの厚さとすればよい。また、ワイヤーボンディングにおける耐熱性を向上させるためには、１μｍ程度までの厚さの厚付け金めっき皮膜を形成すればよいが、更に、金めっき皮膜の厚付けも可能である。 The film thickness of the electroless gold plating film may be appropriately selected depending on the purpose. However, if it is too thin, the performance as a gold plating film is not sufficiently exhibited, and the soldering property, wire bonding property and the like are inferior. Usually, the film thickness may be about 0.001 μm or more. The upper limit of the film thickness of the gold plating film is not particularly limited, but if it is too thick, the cost becomes high, and this may be determined in consideration of this point. For example, in order to obtain sufficient solder joint strength, the thickness may be up to about 0.3 μm. Moreover, in order to improve the heat resistance in wire bonding, a thick gold plating film having a thickness of up to about 1 μm may be formed, but it is also possible to thicken the gold plating film.
本発明の無電解金めっき液は、パラジウム皮膜上に金めっき皮膜を直接析出させることが可能な還元析出型の無電解金めっき液である。 The electroless gold plating solution of the present invention is a reduction deposition type electroless gold plating solution capable of directly depositing a gold plating film on a palladium film.
本発明の還元析出型の無電解金めっき液を用いることにより、プリント配線板の導体回路部分にニッケルめっき皮膜、パラジウムめっき皮膜及び金めっき皮膜を積層した構造の多層めっき皮膜を形成する際に、下地のニッケルめっき皮膜を浸食することなく、金めっき皮膜を形成することが可能となる。その結果、ハンダ付け性、ワイヤーボンディング性などに優れためっき皮膜を得ることができる。 By using the reduced deposition type electroless gold plating solution of the present invention, when forming a multilayer plating film having a structure in which a nickel plating film, a palladium plating film and a gold plating film are laminated on a conductor circuit portion of a printed wiring board, A gold plating film can be formed without eroding the underlying nickel plating film. As a result, it is possible to obtain a plating film excellent in solderability, wire bonding property, and the like.
更に、金めっき皮膜の厚付けを行う場合に、還元析出型の金めっきのみで厚付けが可能となり、ワイヤーボンディングにおける耐熱性に優れためっき皮膜を簡単な処理工程によって形成することができる。 Furthermore, when the gold plating film is thickened, it is possible to thicken only by the reduction precipitation type gold plating, and a plating film having excellent heat resistance in wire bonding can be formed by a simple processing step.
以下、実施例を挙げて本発明を更に詳細に説明する。 Hereinafter, the present invention will be described in more detail with reference to examples.
実施例１
以下、本発明の実施例及び比較例において用いためっき液の組成を示す。
（Ｉ）無電解ニッケルめっき液
（１）ニッケル浴Ａ：
硫酸ニッケル・６水和物 ２２．５ｇ／Ｌ
次亜リン酸ナトリウム ２０ ｇ／Ｌ
リンゴ酸 １０ ｇ／Ｌ
コハク酸 １０ ｇ／Ｌ
チオ硫酸ナトリウム ０．２ｍｇ／Ｌ
ｐＨ ４．６（水酸化ナトリウムで調整）
Example 1
Hereinafter, the composition of the plating solution used in the examples and comparative examples of the present invention is shown.
(I) Electroless nickel plating solution (1) Nickel bath A:
Nickel sulfate hexahydrate 22.5g / L
Sodium hypophosphite 20 g / L
Malic acid 10 g / L
Succinic acid 10 g / L
Sodium thiosulfate 0.2mg / L
pH 4.6 (adjusted with sodium hydroxide)
（II）無電解パラジウムめっき液
（１）パラジウム浴Ａ
ジクロロジエチレンジアミンパラジウム溶液 ２ｇ／Ｌ（パラジウムとして）
エチレンジアミン １０ｇ／Ｌ
蟻酸ナトリウム １０ｇ／Ｌ
ｐＨ ６．０
（２）パラジウム浴Ｂ
ジクロロジエチレンジアミンパラジウム溶液 ２ｇ／Ｌ（パラジウムとして）
エチレンジアミン １０ｇ／Ｌ
亜リン酸ナトリウム １０ｇ／Ｌ
ｐＨ ６．０
（３）パラジウム浴Ｃ：
ジクロロジエチレンジアミンパラジウム溶液 ２ｇ／Ｌ（パラジウムとして）
エチレンジアミン １０ｇ／Ｌ
次亜リン酸ナトリウム １０ｇ／Ｌ
ｐＨ ６．０
(II) Electroless palladium plating solution (1) Palladium bath A
Dichlorodiethylenediamine palladium solution 2g / L (as palladium)
Ethylenediamine 10g / L
Sodium formate 10g / L
pH 6.0
(2) Palladium bath B
Dichlorodiethylenediamine palladium solution 2g / L (as palladium)
Ethylenediamine 10g / L
Sodium phosphite 10g / L
pH 6.0
(3) Palladium bath C:
Dichlorodiethylenediamine palladium solution 2g / L (as palladium)
Ethylenediamine 10g / L
Sodium hypophosphite 10g / L
pH 6.0
（III）還元析出型無電解金めっき液
下記金めっき浴Ａ（非シアン浴）を基本浴として、これに、下記表１に示す還元剤をそれぞれ５ｇ／Ｌ添加し、硫酸又は水酸化ナトリウムを用いてｐＨ７．０に調整しためっき浴を用いた。
(III) Reduced deposition type electroless gold plating solution The following gold plating bath A (non-cyan bath) is used as a basic bath, and 5 g / L of the reducing agent shown in Table 1 below is added thereto, and sulfuric acid or sodium hydroxide is added. The plating bath adjusted to pH 7.0 by using was used.
（１）金めっき浴Ａ
エチレンジアミン４酢酸２ナトリウム ２０ｇ／Ｌ
亜硫酸金カリウム ２ｇ／Ｌ（金として）
Ｓ−メチルイソチオ尿素 ０．５ｍｇ／Ｌ
(1) Gold plating bath A
Ethylenediaminetetraacetic acid disodium 20g / L
Potassium gold sulfite 2g / L (as gold)
S-methylisothiourea 0.5mg / L
被めっき物として樹脂基板に銅回路およびレジストを形成したプリント基板を用いた。該プリント基板は、４ｃｍ×６ｃｍの樹脂基板上に、厚さ１８μｍの銅箔を用いて各種の形状の導体回路を形成したものである。 A printed circuit board in which a copper circuit and a resist were formed on a resin substrate was used as an object to be plated. The printed circuit board is obtained by forming various shapes of conductor circuits on a 4 cm × 6 cm resin substrate using a copper foil having a thickness of 18 μm.
まず、被めっき物について、脱脂処理を行った後、過硫酸ナトリウム溶液で０．５μｍ程度のエッチングを行い、触媒付与液（商標名：ＩＣＰアクセラ、奥野製薬工業（株）製）２００ｍｌ／Ｌ中に、室温で１分間浸漬して無電解めっき用触媒を付与した。 First, after the degreasing treatment was performed on the object to be plated, etching of about 0.5 μm was performed with a sodium persulfate solution, and a catalyst application solution (trade name: ICP Axela, manufactured by Okuno Pharmaceutical Co., Ltd.) in 200 ml / L And a catalyst for electroless plating was applied by immersion for 1 minute at room temperature.
その後、無電解ニッケルめっき液として、上記ニッケル浴Ａを用いて、空気攪拌を行いながら、浴温８０℃のめっき液中に被めっき物を２０分間浸漬して、厚さ約５μｍのニッケルめっき皮膜を形成した。 Thereafter, using the above nickel bath A as an electroless nickel plating solution, the object to be plated is immersed in a plating solution having a bath temperature of 80 ° C. for 20 minutes while stirring in the air, and a nickel plating film having a thickness of about 5 μm. Formed.
次いで、下記表１に示す各パラジウムめっき浴中に６０℃で１０分間浸漬して、０．２μｍの無電解パラジウムめっき皮膜を形成した。 Subsequently, it was immersed in each palladium plating bath shown in Table 1 at 60 ° C. for 10 minutes to form a 0.2 μm electroless palladium plating film.
その後、下記表１に示す還元剤を含有する無電解金めっき液を用いて、８０℃の浴温の金めっき浴中に３０分間又は１２０分間浸漬して、金めっき皮膜を形成した。 Then, using the electroless gold plating solution containing the reducing agent shown in the following Table 1, it was immersed in a gold plating bath having a bath temperature of 80 ° C. for 30 minutes or 120 minutes to form a gold plating film.
上記した方法で金めっき皮膜を形成した各試料について、金めっき皮膜の析出状態を目視により判定し、更に、蛍光Ｘ線膜厚測定装置により金めっき皮膜の膜厚を測定した。また、被めっき物において、金めっき皮膜が形成された面積１×４ｃｍの部分について、カッターナイフを用いて金めっき皮膜の表面に切り込みを入れて、１ｍｍ角のマス目を１００個形成し、粘着テープを貼り付けて、垂直方向に引き剥がした。この際に剥離したマス目の数を計測することによって金めっき皮膜の密着性を評価した。 About each sample which formed the gold plating film by the above-mentioned method, the deposition state of the gold plating film was judged visually, and also the film thickness of the gold plating film was measured with a fluorescent X-ray film thickness measuring device. In addition, in the object to be plated, an area of 1 × 4 cm where the gold plating film was formed was cut into the surface of the gold plating film using a cutter knife to form 100 squares of 1 mm square. The tape was applied and peeled off in the vertical direction. At this time, the adhesion of the gold plating film was evaluated by measuring the number of cells peeled off.
以上の結果を下記表１に示す。 The above results are shown in Table 1 below.
以上の結果から明らかなように、ホルムアルデヒド重亜硫酸類、ロンガリット又はヒドラジン類を還元剤として含有する実施例１〜２４の無電解金めっき液によれば、パラジウム皮膜上に均一な金めっき皮膜を形成することができる。特に、下地のパラジウム皮膜が蟻酸ナトリウムを還元剤とするパラジウム浴Ａから形成された皮膜である場合には、厚付けの金めっき皮膜を形成した場合にも、良好な密着性を有する皮膜を形成できる。 As is clear from the above results, according to the electroless gold plating solution of Examples 1 to 24 containing formaldehyde bisulfite, longalite or hydrazine as a reducing agent, a uniform gold plating film is formed on the palladium film. can do. In particular, when the underlying palladium film is a film formed from a palladium bath A using sodium formate as a reducing agent, a film having good adhesion is formed even when a thick gold plating film is formed. it can.
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