JPS6217033B2 - - Google Patents

Info

Publication number
JPS6217033B2
JPS6217033B2 JP7364083A JP7364083A JPS6217033B2 JP S6217033 B2 JPS6217033 B2 JP S6217033B2 JP 7364083 A JP7364083 A JP 7364083A JP 7364083 A JP7364083 A JP 7364083A JP S6217033 B2 JPS6217033 B2 JP S6217033B2
Authority
JP
Japan
Prior art keywords
tin
nickel alloy
copper
mol
etching
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.)
Expired
Application number
JP7364083A
Other languages
Japanese (ja)
Other versions
JPS58193372A (en
Inventor
Takeshi Tsunohashi
Kazuo Fukunaga
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nitto Denko Corp
Original Assignee
Nitto Electric Industrial Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Nitto Electric Industrial Co Ltd filed Critical Nitto Electric Industrial Co Ltd
Priority to JP7364083A priority Critical patent/JPS58193372A/en
Publication of JPS58193372A publication Critical patent/JPS58193372A/en
Publication of JPS6217033B2 publication Critical patent/JPS6217033B2/ja
Granted legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/30—Acidic compositions for etching other metallic material
    • 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
    • H05K3/02—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding
    • H05K3/06—Apparatus or processes for manufacturing printed circuits in which the conductive material is applied to the surface of the insulating support and is thereafter removed from such areas of the surface which are not intended for current conducting or shielding the conductive material being removed chemically or electrolytically, e.g. by photo-etch process
    • H05K3/067—Etchants

Landscapes

  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • ing And Chemical Polishing (AREA)

Description

【発明の詳細な説明】 本発明はスズ−ニツケル合金のエツチング液に
関し、特に、スズ−ニツケル合金と銅とが共存す
る場合に、選択的にスズ−ニツケル合金のみをエ
ツチングすることができるエツチング液に関す
る。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an etching solution for a tin-nickel alloy, and in particular, an etching solution that can selectively etch only the tin-nickel alloy when the tin-nickel alloy and copper coexist. Regarding.

絶縁支持体の少なくとも片面に抵抗膜が形成さ
れ、その抵抗膜の上に銅のような高導電層が接合
されている積層材料から、抵抗付きプリント回路
基板を製作することは既に知られている。近年、
上記の抵抗膜としてニツケル電気メツキ膜、ニツ
ケル−リン電気メツキ膜、ニツケル−モリブデン
電気メツキ膜等が用いられ、或いは提案されてい
るが、これらの電気メツキ膜は一般に物性、作業
性等の面において尚、多くの問題を有している。 It is already known to produce resistive printed circuit boards from laminated materials, in which a resistive film is formed on at least one side of an insulating support, and a highly conductive layer, such as copper, is bonded onto the resistive film. . recent years,
Nickel electroplated films, nickel-phosphorous electroplated films, nickel-molybdenum electroplated films, etc. have been used or proposed as the above-mentioned resistive films, but these electroplated films generally have poor physical properties, workability, etc. However, it has many problems.

そこで、本発明者らは抵抗膜としてスズ−ニツ
ケル合金メツキ膜を抵抗膜とする抵抗付きプリン
ト回路基板を先に開発し、特許出願した（特願昭
52−140525号）。その出願中に詳細に説明されて
いるように、銅箔にスズ−ニツケル合金をメツキ
し、次にこの合金メツキ膜上にエポキシ樹脂含浸
ガラス布等の絶縁支持体を接着して積層板を製作
し、この積層板に導体と抵抗のパターンに応じて
エツチング等の加工を施こして、抵抗付きプリン
ト回路基板が製作される。スズ−ニツケル合金膜
は、一般に、還元剤としてヒドラジン水和物や次
亜リン酸ソーダ等を用いる化学メツキ法、或いは
フツ化ナトリウムや酸性フツ化アンモニウム等を
用いるフツ化物浴、ピロリン酸第一スズやピロリ
ン酸カリウム等を用いるピロリン酸浴からの電気
メツキ法等により、銅箔上に形成される。プリン
ト回路基板における抵抗膜としてスズ−ニツケル
合金メツキ膜を形成するときには、膜厚及びメツ
キ浴組成を最も制御しやすい電気メツキ法が好ま
しく、特にフツ化物浴を用いる方法は、メツキ浴
組成の広い範囲にわたつて、実質的にスズとニツ
ケルとの等原子比、即ち、スズが64〜70重量％の
合金組成が得られる点から特に好ましい。 Therefore, the present inventors first developed a printed circuit board with a resistor using a tin-nickel alloy plating film as a resistive film, and filed a patent application (patent application).
52-140525). As detailed in that application, a laminate is fabricated by plating a tin-nickel alloy onto a copper foil and then bonding an insulating support such as an epoxy resin-impregnated glass cloth onto the alloy plating film. Then, a printed circuit board with a resistor is manufactured by performing etching or other processing on this laminate according to the pattern of the conductor and resistor. Tin-nickel alloy films are generally produced using chemical plating methods using hydrazine hydrate, sodium hypophosphite, etc. as reducing agents, fluoride baths using sodium fluoride, acidic ammonium fluoride, etc., or stannous pyrophosphate. It is formed on copper foil by electroplating from a pyrophosphate bath using potassium pyrophosphate or the like. When forming a tin-nickel alloy plating film as a resistive film on a printed circuit board, the electroplating method is preferred because it is the easiest to control the film thickness and plating bath composition.In particular, the method using a fluoride bath allows for a wide range of plating bath compositions. This is particularly preferred since an alloy composition having a substantially equiatomic ratio of tin and nickel, ie, 64 to 70% by weight of tin, can be obtained.

このようなスズ−ニツケル合金膜は、メツキ組
成の安定性にすぐれるほか、所謂平滑性、均一電
着性等にもすぐれるため、抵抗膜として極めてす
ぐれるものである反面、耐食性が著しく大きいた
めに、銅箔上に形成されたスズ−ニツケル合金の
みを選択的にエツチングするときに困難が生じ
る。 Such a tin-nickel alloy film has excellent stability of plating composition, so-called smoothness, and uniform electrodeposition properties, so it is extremely excellent as a resistive film, but on the other hand, it has extremely high corrosion resistance. This creates difficulties when selectively etching only the tin-nickel alloy formed on the copper foil.

スズ−ニツケル合金膜を抵抗回路として有する
抵抗付きプリント回路基板の製作を例にとつて、
より詳細に説明する。第４図乃至第１２図はかか
る抵抗付きプリント回路基板の製作工程図であ
り、各図において左側は平面図、右側は断面図を
示す。 Taking as an example the production of a printed circuit board with a resistor that has a tin-nickel alloy film as a resistor circuit,
This will be explained in more detail. 4 to 12 are manufacturing process diagrams of such a printed circuit board with a resistor, and in each figure, the left side shows a plan view and the right side shows a sectional view.

先ず、第３図に示すように、エポキシ樹脂含浸
ガラス布のような絶縁支持体３上にスズ−ニツケ
ル合金膜２と銅箔１とをこの順に有する積層材料
を製作し、第４図に示すように、上記積層材料の
表面をフオトレジスト４にて被覆する。次いで、
導体領域と抵抗領域の両者の組合せパターンを有
するフオトマスクを介してフオトレジストを露光
させ、現像することにより、第５図に示すよう
に、銅箔１上に上記パターン領域に対応してレジ
スト４を残した中間材料を得る。この後、レジス
トで被覆されていない領域の銅箔１をエツチング
除去して、第６図に示すように、レジスト被覆さ
れていない領域において、スズ−ニツケル合金膜
２を露出させ、次いで、この領域のスズ−ニツケ
ル合金膜２をもエツチング除去して、第７図に示
すように、絶縁支持体３を表面に露出させる。次
に、残存するレジスト４を除去し、第９図に示す
ように、前記組合せパターンに対応する領域に銅
箔１を露出させた中間材料を得、上記領域、即
ち、銅箔１上を新たにフオトレジストで被覆した
後、前記と同様にして導体パターンを用いて導体
領域にレジスト４を残す。このようにして第９図
に示す中間材料を得る。次いで、この中間材料に
おいて、レジスト被覆されていない領域の銅箔１
をエツチング除去して、第１０図に示すように、
上記領域にスズ−ニツケル合金膜２を露出させ、
この後に残存するレジスト４を除去すれば、第１
１図に示すように、上記した導体パターンに対応
する銅箔１からなる導体回路と、抵抗パターンに
対応するスズ−ニツケル合金膜２からなる抵抗回
路がそれぞれに絶縁支持体３上に形成される。 First, as shown in FIG. 3, a laminated material having a tin-nickel alloy film 2 and a copper foil 1 in this order on an insulating support 3 such as an epoxy resin-impregnated glass cloth is manufactured, and then as shown in FIG. The surface of the laminated material is coated with a photoresist 4 as shown in FIG. Then,
By exposing the photoresist to light through a photomask having a combination pattern of both conductor areas and resistance areas and developing it, a resist 4 is formed on the copper foil 1 corresponding to the pattern area, as shown in FIG. Obtain the remaining intermediate material. Thereafter, the copper foil 1 in the area not covered with the resist is removed by etching to expose the tin-nickel alloy film 2 in the area not covered with the resist, as shown in FIG. The tin-nickel alloy film 2 is also etched away to expose the insulating support 3 on the surface as shown in FIG. Next, the remaining resist 4 is removed to obtain an intermediate material in which the copper foil 1 is exposed in the area corresponding to the combination pattern, as shown in FIG. After coating with photoresist, resist 4 is left in the conductor area using a conductor pattern in the same manner as described above. In this way, the intermediate material shown in FIG. 9 is obtained. Next, in this intermediate material, the copper foil 1 in the area not covered with resist is
As shown in Fig. 10,
exposing the tin-nickel alloy film 2 in the above region;
If the remaining resist 4 is removed after this, the first
As shown in FIG. 1, a conductor circuit made of copper foil 1 corresponding to the above-described conductor pattern and a resistance circuit made of tin-nickel alloy film 2 corresponding to the resistance pattern are formed on an insulating support 3, respectively. .

従つて、スズ−ニツケル合金膜をエツチング除
去するときに、銅が攻撃されてはならないことが
明らかである。即ち、スズ−ニツケル合金のため
のエツチング液は、銅に対しては腐食性をもたな
いことが要求される。例えば、上記のような抵抗
付きプリント回路基板の製作において、スズ−ニ
ツケル合金用のエツチング液が銅に対しても腐食
作用を有する場合には、第６図から第７図への工
程において、合金抵抗膜２をエツチングする際
に、表面をレジスト４で被覆されている銅箔１も
その側面からエツチングされ、従つて、得られる
回路基板の寸法精度が低く、また、抵抗素子の抵
抗値の精度も低くなるからである。 It is therefore clear that the copper must not be attacked when etching away the tin-nickel alloy film. That is, etching solutions for tin-nickel alloys are required to be non-corrosive to copper. For example, in the production of printed circuit boards with resistors as described above, if the etching solution for tin-nickel alloys also has a corrosive effect on copper, in the process from FIG. 6 to FIG. When etching the resistive film 2, the copper foil 1 whose surface is covered with the resist 4 is also etched from its side surfaces, resulting in low dimensional accuracy of the resulting circuit board and low accuracy of the resistance value of the resistive element. This is because it also becomes lower.

しかし、スズ−ニツケル合金は、ニツケル−リ
ン合金用のアンモニア・キレート系の銅のエツチ
ング液によりエツチングされないことからも明ら
かように、一般に、多くの化学薬品に対して銅よ
りも安定である。例えば、厚さ25μ以上のスズ−
ニツケル合金膜は、モネルメタルと銀との中間、
ほぼインコネルに匹敵する耐食性を有するといわ
れている。 However, tin-nickel alloys are generally more stable than copper to many chemicals, as evidenced by their inability to be etched by ammonia chelate-based copper etchants for nickel-phosphorus alloys. For example, tin with a thickness of 25μ or more
Nickel alloy film is intermediate between monel metal and silver.
It is said to have corrosion resistance comparable to Inconel.

本発明者らは、スズ−ニツケル合金メツキ膜を
抵抗膜とする抵抗付きプリント回路基板の製作に
おいて、上記合金メツキ膜を選択的にエツチング
除去するために、従来は、先ず、塩酸水に浸漬
し、次いで硫酸と硝酸との混酸に浸漬する方法を
採用していた。しかし、このエツチング液は、銅
の共存下におけるスズ−ニツケル合金メツキ膜の
選択エツチング性が必ずしも満足できるものでは
なかつたので、更に鋭意研究を行なつた結果、リ
ン酸、ピロリン酸若しくは亜リン酸の加熱水溶液
又は融解液と、ある種の酸化剤とからなるエツチ
ング液が、銅との共存下において、銅を実質的に
腐食することなく、スズ−ニツケル合金のみを選
択的にエツチングすることを見出して本発明に到
達したものである。 The present inventors discovered that in the production of a printed circuit board with a resistor using a tin-nickel alloy plating film as a resistive film, in order to selectively remove the alloy plating film, conventionally, first immersion in hydrochloric acid water was performed. Next, a method was adopted in which the material was immersed in a mixed acid of sulfuric acid and nitric acid. However, this etching solution did not necessarily have satisfactory selective etching properties for tin-nickel alloy plating films in the coexistence of copper.As a result of further intensive research, we found that phosphoric acid, pyrophosphoric acid, or phosphorous acid It has been shown that an etching solution consisting of a heated aqueous solution or molten liquid and a certain oxidizing agent selectively etches only the tin-nickel alloy in the coexistence of copper without substantially corroding the copper. This discovery led to the present invention.

従つて、本発明の目的は、一般的には、スズ−
ニツケル合金のエツチング液を提供することを目
的とし、特に、銅との共存下において、スズ−ニ
ツケル合金を選択的にエツチングすることのでき
るエツチング液を提供することを目的とする。特
に、本発明は、銅上にスズ−ニツケル合金が積層
された積層材料から、銅を実質的に腐食させるこ
となく、スズ−ニツケル合金を選択的にエツチン
グ除去することができるエツチング液を提供する
ことを目的とし、従つて、本発明はまた、絶縁支
持体の少なくとも片面にスズ−ニツケル合金膜を
有し、その上に銅層を有する積層材料から、スズ
−ニツケル合金膜を選択的にエツチング除去し
て、抵抗付きプリント回路基板を製造するのに好
適に用いることができるスズ−ニツケル合金用の
エツチング液を提供することを目的とする。 Therefore, the object of the present invention is to generally
The object of the present invention is to provide an etching solution for nickel alloys, and particularly to provide an etching solution that can selectively etch tin-nickel alloys in the presence of copper. In particular, the present invention provides an etching solution that can selectively remove tin-nickel alloy from a laminated material in which tin-nickel alloy is laminated on copper without substantially corroding the copper. Therefore, the present invention also provides a method for selectively etching a tin-nickel alloy film from a laminated material having a tin-nickel alloy film on at least one side of an insulating support and a copper layer thereon. It is an object of the present invention to provide an etching solution for tin-nickel alloys that can be removed and suitably used for manufacturing printed circuit boards with resistors.

本発明によるスズ−ニツケル合金用のエツチン
グ液は、0.1モル／以上のリン酸、0.05モル／
以上のピロリン酸、又は0.1モル／以上の亜
リン酸と、硝酸銀、銅塩、過酸化物及び酸素酸塩
から選ばれる少なくとも１種の酸化剤とを含有す
ることを特徴とし、好ましくは、0.2モル／以
上のリン酸、0.1モル／以上のピロリン酸、又
は0.2モル／以上の亜リン酸と、硝酸銀、銅
塩、過酸化物及び酸素酸塩から選ばれる少なくと
も１種の酸化剤とを含有する。尚、以下におい
て、上記リン酸、ピロリン酸及び亜リン酸をリン
酸類と総称する。 The etching solution for tin-nickel alloys according to the invention comprises phosphoric acid of 0.1 mole or more, 0.05 mole of
It is characterized by containing the above pyrophosphoric acid or 0.1 mole or more of phosphorous acid and at least one oxidizing agent selected from silver nitrate, copper salt, peroxide, and oxyacid, preferably 0.2 Contains mol/or more of phosphoric acid, 0.1 mol/or more of pyrophosphoric acid, or 0.2 mol/or more of phosphorous acid, and at least one oxidizing agent selected from silver nitrate, copper salts, peroxides, and oxyacids. do. In addition, below, the said phosphoric acid, pyrophosphoric acid, and phosphorous acid are collectively called phosphoric acids.

本発明においては、上記エツチング液における
リン酸類の濃度は、下限が規定されるが、上限は
何ら規定されず、これらリン酸類の飽和水溶液及
び融解液（即ち、濃度100％）もまたエツチング
液として用いられる。従つて、本発明において、
リン酸類の濃度を規定する「以上」なる語は、リ
ン酸類の飽和水溶液及び融解液を含むとして理解
されるべきである。 In the present invention, the lower limit of the concentration of phosphoric acids in the etching solution is defined, but the upper limit is not defined at all, and saturated aqueous solutions and melted solutions (i.e., 100% concentration) of these phosphoric acids can also be used as etching solutions. used. Therefore, in the present invention,
The term "above" defining the concentration of phosphoric acids should be understood to include saturated aqueous solutions and melts of phosphoric acids.

本発明によるエツチング液は、上記のようなリ
ン酸類と硝酸銀、銅塩、過酸化物及び酸素酸塩か
ら選ばれる少なくとも１種の酸化剤とを含有する
ことにより、比較的低温で、且つ、短時間に、銅
を実質的に腐食することなく、スズ−ニツケル合
金を選択的にエツチングすることができる。 The etching solution according to the present invention contains the above-mentioned phosphoric acids and at least one oxidizing agent selected from silver nitrate, copper salt, peroxide, and oxyacid, so that it can be etched at a relatively low temperature and in a short period of time. In time, the tin-nickel alloy can be selectively etched without substantially corroding the copper.

銅塩として、代表的にはリン酸第二銅、硝酸
銅、酢酸銅、塩化第二銅等を挙げることができ
る。このようにリン酸類と銅塩又は後述する他の
酸化剤とを含有するエツチング液は、エツチング
液が水溶液の場合は、通常、70℃以上、好ましく
は75〜95℃の温度で、また、エツチング液が前記
リン酸類の融解液である場合には、それらの融点
以上、好ましくはそれらの融点乃至95℃の温度
で、それぞれ用いられる。このようなエツチング
液中に、上記した温度範囲において、例えば厚み
0.1μ、シート抵抗値25Ω／□のスズ−ニツケル
合金メツキ膜を有する銅積層板を浸漬すると、数
分以内にスズ−ニツケル合金メツキ膜のみが完全
にエツチング除去され、銅は実質的に腐食されな
い。 Typical copper salts include cupric phosphate, copper nitrate, copper acetate, cupric chloride, and the like. If the etching solution is an aqueous solution, the etching solution containing phosphoric acids and copper salts or other oxidizing agents described below is usually etched at a temperature of 70°C or higher, preferably 75 to 95°C. When the liquid is a melt of the phosphoric acids, it is used at a temperature above their melting points, preferably at a temperature between their melting points and 95°C. In such an etching solution, for example, a thickness of
When a copper laminate with a tin-nickel alloy plating film of 0.1μ and a sheet resistance value of 25Ω/□ is immersed, only the tin-nickel alloy plating film is completely etched away within a few minutes, and the copper is virtually not corroded. .

エツチング液における銅塩の濃度は、用いるリ
ン酸類の種類と銅塩自身の種類とによつて必ずし
も一定しないが、後に例示する他の酸化剤の場合
も含めて、通常、５×10-4〜１×10-1モル／、
好ましくは１×10-3〜５×10-2モル／の範囲内
である。 The concentration of copper salt in the etching solution is not necessarily constant depending on the type of phosphoric acid used and the type of copper salt itself, but it is usually 5 x 10 -4 to 1×10 -1 mol/,
It is preferably within the range of 1×10 −3 to 5×10 −2 mol/.

例えば、リン酸類の水溶液又は融解液とリン酸
第二銅とからなるエツチングの場合は、リン酸第
二銅の濃度は、好ましくは１×10-3〜６×10-3モ
ル／、より好ましくは２×10-3〜5.5×10-3モ
ル／とされる。リン酸第二銅の濃度がこの範囲
以上、例えば、８×10-3モル／以上になると、
スズ−ニツケル合金膜は、おそらくは銅とスズ−
ニツケル合金との電位差に関係する何らかの理由
のために、銅との境界部分のみしかエツチングさ
れない場合があるからである。エツチング液がピ
ロリン酸の水溶液又は融解液とリン酸第二銅とか
らなる場合も上記と同様である。一方、エツチン
グ液が亜リン酸の水溶液、融解液とリン酸第二銅
とからなる場合には、リン酸第二銅の濃度は好ま
しくは、１×10-3〜1.9×10-2モル／、より好
ましくは２×10-3〜1.8×10-2モル／である。 For example, in the case of etching consisting of an aqueous solution or melt of phosphoric acids and cupric phosphate, the concentration of cupric phosphate is preferably 1 x 10 -3 to 6 x 10 -3 mol/, more preferably is 2×10 −3 to 5.5×10 −3 mol/. When the concentration of cupric phosphate exceeds this range, for example, 8 × 10 -3 mol / or more,
The tin-nickel alloy film probably consists of copper and tin.
This is because for some reason related to the potential difference with the nickel alloy, only the boundary with the copper may be etched. The same applies to the case where the etching solution is composed of an aqueous solution or melt of pyrophosphoric acid and cupric phosphate. On the other hand, when the etching solution consists of an aqueous solution or melt of phosphorous acid and cupric phosphate, the concentration of cupric phosphate is preferably 1 x 10 -3 to 1.9 x 10 -2 mol/ , more preferably 2×10 −3 to 1.8×10 −2 mol/.

本発明において好ましく用いられる他の酸化剤
は、臭素酸カリウムのような酸素酸塩や過酸化水
素のような過酸化物である。これらの酸化剤は、
前記した銅塩を含めて、単独で、又は二種以上の
混合物として用いられる。 Other oxidizing agents preferably used in the present invention are oxyacid salts such as potassium bromate and peroxides such as hydrogen peroxide. These oxidants are
Copper salts, including those described above, can be used alone or as a mixture of two or more.

以上のように、本発明のエツチング液によれ
ば、スズ−ニツケル合金が銅と共存する材料、例
えば、銅上にスズ−ニツケル合金が積層されてい
る積層材料からスズ−ニツケル合金のみを選択的
にエツチング除去することができ、従つて、前記
したように、絶縁支持体上にスズ−ニツケル合金
からなる抵抗膜を有し、その上に銅からなる高導
電材料層を有する積層材料から、前記したような
過程を経て抵抗付きプリント回路基板を製造する
場合に、スズ−ニツケル合金抵抗膜を選択的エツ
チングするのに好適に用いることができる。即
ち、上記積層材料の表面に導体及び抵抗の組合せ
パターンをレジストを用いて形成した後、レジス
ト被覆されていない領域の銅層をエツチング除去
し、次いで、露出しているスズ−ニツケル合金膜
をエツチング除去するときに、本発明によるエツ
チング液を用いるのである。 As described above, the etching solution of the present invention selectively removes only the tin-nickel alloy from a material in which the tin-nickel alloy coexists with copper, such as a laminated material in which the tin-nickel alloy is laminated on copper. Therefore, as described above, from a laminated material having a resistive film made of a tin-nickel alloy on an insulating support and a highly conductive material layer made of copper on top of the resistive film, When manufacturing a printed circuit board with a resistor through such a process, it can be suitably used for selectively etching a tin-nickel alloy resistive film. That is, after forming a combination pattern of a conductor and a resistor on the surface of the laminated material using a resist, the copper layer in the area not covered with the resist is removed by etching, and then the exposed tin-nickel alloy film is etched. The etching solution according to the present invention is used for the removal.

このようにして製造される抵抗付きプリント回
路基板は、前記したように、スズ−ニツケル合金
からなる抵抗膜がメツキそれぞれの安定性、平滑
性、均一電着性にすぐれると共に、抵抗膜のエツ
チング除去に際して銅が実質的に腐食されないの
で、得られる回路基板は寸法精度並びに抵抗素子
の抵抗値の精度において非常にすぐれている。 As mentioned above, the printed circuit board with resistors manufactured in this manner has a resistive film made of a tin-nickel alloy that has excellent plating stability, smoothness, and uniform electrodeposition, as well as excellent etching resistance of the resistive film. Since the copper is not substantially corroded during removal, the resulting circuit board has excellent dimensional accuracy and precision in the resistance values of the resistive elements.

尚、上記の抵抗付きプリント回路基板の製造に
おいて、銅層をエツチング除去し、所望ならば、
５〜20重量％の塩酸に５〜60秒程度浸漬し、水洗
した後に、スズ−ニツケル合金抵抗膜をエツチン
グ除去してもよい。銅のエツチング後、時間の経
過と共に、スズ−ニツケル合金膜の表面に不動態
性の薄膜が形成されるためであると思われるが、
場合によつてはこの不動態性薄膜がスズ−ニツケ
ル合金膜のエツチングを円滑に進行させないこと
があるからである。従つて、銅エツチングの後、
長時間を経過してからスズ−ニツケル合金膜をエ
ツチングする場合には、予め塩酸に浸漬する方が
よいことがある。但し、銅エツチング後に直ちに
スズ−ニツケル合金をエツチングするときは、塩
酸による処理は必要ない。 In addition, in manufacturing the above-mentioned printed circuit board with a resistor, the copper layer is removed by etching, and if desired,
The tin-nickel alloy resistive film may be removed by etching after immersing it in 5 to 20% by weight hydrochloric acid for about 5 to 60 seconds and washing with water. This is thought to be due to the formation of a passive thin film on the surface of the tin-nickel alloy film over time after copper etching.
This is because, in some cases, this passive thin film may not allow the etching of the tin-nickel alloy film to proceed smoothly. Therefore, after copper etching,
When etching a tin-nickel alloy film after a long period of time, it may be better to immerse it in hydrochloric acid in advance. However, when etching the tin-nickel alloy immediately after copper etching, treatment with hydrochloric acid is not necessary.

以下に実施例を挙げて本発明を具体的に説明す
る。尚、以下の実施例においては、第６図に示し
たように、絶縁支持体の全体に厚み約0.1μ、シ
ート抵抗値25Ω／□のスズ−ニツケル合金膜が積
層され、この上に表面がレジスト被覆された導体
領域と抵抗領域の組合せパターンを有する銅箔が
積層されている基板を試料としてエツチング処理
した。 The present invention will be specifically described below with reference to Examples. In the following examples, as shown in FIG. 6, a tin-nickel alloy film with a thickness of about 0.1μ and a sheet resistance of 25Ω/□ is laminated over the entire insulating support, and the surface is A substrate on which copper foil having a combination pattern of a resist-coated conductor region and a resistor region was laminated was used as a sample and etched.

実施例 １ リン酸第二銅を3.23×10-3モル／濃度で含有
する種々の濃度のリン酸、ピロリン酸又は亜リン
酸の83℃の水溶液に試料を浸漬し、絶縁支持体上
に露出しているスズ−ニツケル合金膜をエツチン
グ除去するのに要する時間を調べた。結果を第１
図に示す。尚、第１図において、ピロリン酸の濃
度は横軸目盛（モル／）の１／２である。ま
た、いずれの場合においても、銅は実質的に腐食
されず、外観上、全く変化が認められなかつた。Example 1 A sample was immersed in an aqueous solution of phosphoric acid, pyrophosphoric acid or phosphorous acid at various concentrations at 83°C containing cupric phosphate at a concentration of 3.23×10 -3 mol/concentration and exposed on an insulating support. The time required to remove the tin-nickel alloy film was investigated. Results first
As shown in the figure. In FIG. 1, the concentration of pyrophosphoric acid is 1/2 of the horizontal scale (mol/). Further, in any case, copper was not substantially corroded and no change was observed in its appearance.

実施例 ２ 種々の濃度でリン酸第二銅を含有する5.6モ
ル／のリン酸、5.6モル／の亜リン酸及び2.8
モル／のピロリン酸の83℃の水溶液にそれぞれ
試料を浸漬し、スズ−ニツケル合金膜をエツチン
グ除去するのに要する時間を調べた。結果を第２
図に示す。また、いずれの場合においても、銅は
実質的に腐食されず、外観上、全く変化が認めら
れなかつた。Example 2 5.6 moles/phosphoric acid, 5.6 moles/phosphorous acid and 2.8 moles/containing cupric phosphate at various concentrations
Each sample was immersed in an aqueous solution of 83° C. of pyrophosphoric acid at mol/mole, and the time required to remove the tin-nickel alloy film by etching was investigated. Second result
As shown in the figure. Further, in any case, copper was not substantially corroded and no change was observed in its appearance.

実施例 ３ 9.4モル／のリン酸水溶液に各種の酸化剤を
添加し、83℃に加熱した後、試料を浸漬して、ス
ズ−ニツケル合金膜をエツチング除去するのに要
する時間を調べた。酸化剤の濃度は過酸化水素が
0.0027モル／であるほかはすべて0.004モル／
である。結果を下に示す。Example 3 Various oxidizing agents were added to a 9.4 mol/aqueous phosphoric acid solution, heated to 83°C, and then the samples were immersed to examine the time required to remove the tin-nickel alloy film by etching. The concentration of oxidizing agent is hydrogen peroxide
All are 0.004 mol/ except 0.0027 mol/
It is. The results are shown below.

エツチング所要時間（分） 硝酸銀 ３ 過酸化水素 ８ 臭素酸カリウム ２ 酢酸銅 ４ 塩化第二銅 ５ 硝酸銅 12 また、いずれの場合においても、銅は実質的に
腐食されず、外観上、全く変化が認められなかつ
た。 Required time for etching (minutes) Silver nitrate 3 Hydrogen peroxide 8 Potassium bromate 2 Copper acetate 4 Cupric chloride 5 Copper nitrate 12 In either case, copper is not substantially corroded and there is no change in appearance at all. It was not recognized.

実施例 ４ 9.4モル／のリン酸と4.0×10-3モル／のリ
ン酸第二銅とを含むエツチング液に83℃の温度で
厚み約35μの電解銅箔を10分間浸漬したが、銅箔
の重量減少は0.1％以下であつた。これに対し
て、上記の電解銅箔を2.9モル／の塩酸に25℃
の温度で１分間浸漬し、水洗した後、11.2モル／
の硫酸及び0.7モル／の硝酸とを含む従来の
エツチング水溶液に25℃の温度で10分間浸漬した
ところ、銅箔の重量減少は38.4％にも達した。Example 4 Electrolytic copper foil with a thickness of about 35μ was immersed for 10 minutes at a temperature of 83°C in an etching solution containing 9.4 mol/mol of phosphoric acid and 4.0×10 -3 mol/cupric phosphate, but the copper foil The weight loss was less than 0.1%. On the other hand, the above electrolytic copper foil was added to 2.9 mol/hydrochloric acid at 25°C.
After soaking for 1 minute at a temperature of
When the copper foil was immersed in a conventional etching aqueous solution containing 0.7 mol/mole of sulfuric acid and 0.7 mol/mole of nitric acid at a temperature of 25° C. for 10 minutes, the weight loss of the copper foil reached 38.4%.

【図面の簡単な説明】[Brief explanation of the drawing]

第１図は一定濃度のリン酸第二銅を含有する
種々の濃度のリン酸、亜リン酸又はピロリン酸か
らなるエツチング液とスズ−ニツケル合金膜のエ
ツチング所要時間との関係を示すグラフであり、
第２図は一定濃度のリン酸又は亜リン酸と、種々
の濃度のリン酸第二銅とを含有するエツチング液
とスズ−ニツケル合金膜のエツチング所要時間と
の関係を示すグラフである。また、第３図乃至第
１１図はスズ−ニツケル合金膜を抵抗回路として
有する抵抗付きプリント回路基板の製作工程を示
し、各図において左側は平面図、右側はその断面
図である。 １……銅箔、２……スズ−ニツケル合金膜、３
……絶縁支持体、４……フオトレジスト。 FIG. 1 is a graph showing the relationship between an etching solution consisting of various concentrations of phosphoric acid, phosphorous acid, or pyrophosphoric acid containing a certain concentration of cupric phosphate and the etching time required for a tin-nickel alloy film. ,
FIG. 2 is a graph showing the relationship between an etching solution containing a constant concentration of phosphoric acid or phosphorous acid and various concentrations of cupric phosphate and the time required for etching a tin-nickel alloy film. 3 to 11 show the manufacturing process of a printed circuit board with a resistor having a tin-nickel alloy film as a resistor circuit, and in each figure, the left side is a plan view and the right side is a sectional view thereof. 1...Copper foil, 2...Tin-nickel alloy film, 3
...Insulating support, 4...Photoresist.

Claims (1)

【特許請求の範囲】 １ 0.1モル／以上のリン酸、0.05モル／以
上のピロリン酸、又は0.1モル／以上の亜リン
酸と、硝酸銀、銅塩、過酸化物及び酸素酸塩から
選ばれる少なくとも１種の酸化剤とを含有するこ
とを特徴とするスズ−ニツケル合金のエツチング
液。 ２ 酸化剤が硝酸銀、リン酸第二銅、ピロリン酸
第二銅、酢酸銅、臭素酸カリウム及び過酸化水素
から選ばれる少なくとも１種であることを特徴と
する特許請求の範囲第１項記載のスズ−ニツケル
合金のエツチング液。 ３ 0.2モル／以上のリン酸と、１×10-3〜６
×10-3モル／のリン酸第二銅とを含有すること
を特徴とする特許請求の範囲第１項記載のスズ−
ニツケル合金のエツチング液。 ４ 0.2モル／以上の亜リン酸と、１×10-3〜
1.9×10-2モル／のリン酸第二銅とを含有する
ことを特徴とする特許請求の範囲第１項記載のス
ズ−ニツケル合金のエツチング液。 ５ 0.1モル／以上のピロリン酸と、１×10-3
〜６×10-3モル／のリン酸第二銅とを含有する
ことを特徴とする特許請求の範囲第１項記載のス
ズ−ニツケル合金のエツチング液。[Scope of Claims] 1 0.1 mole or more of phosphoric acid, 0.05 mole or more of pyrophosphoric acid, or 0.1 mole or more of phosphorous acid, and at least one selected from silver nitrate, copper salts, peroxides, and oxyacids. An etching solution for a tin-nickel alloy, characterized in that it contains one kind of oxidizing agent. 2. The oxidizing agent according to claim 1, wherein the oxidizing agent is at least one selected from silver nitrate, cupric phosphate, cupric pyrophosphate, copper acetate, potassium bromate, and hydrogen peroxide. Etching liquid for tin-nickel alloy. 3 0.2 mol/or more of phosphoric acid and 1×10 -3 to 6
x10 -3 mol/cupric phosphate according to claim 1.
Etching liquid for nickel alloy. 4 0.2 mol/or more of phosphorous acid and 1×10 -3 ~
The etching solution for tin-nickel alloy according to claim 1, characterized in that it contains 1.9×10 -2 mol/cupric phosphate. 5 0.1 mol/or more of pyrophosphoric acid and 1×10 -3
The etching solution for a tin-nickel alloy according to claim 1, characterized in that it contains up to 6×10 -3 mol/cupric phosphate.
JP7364083A 1983-04-25 1983-04-25 Liquid etchant for tin-nickel alloy Granted JPS58193372A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP7364083A JPS58193372A (en) 1983-04-25 1983-04-25 Liquid etchant for tin-nickel alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP7364083A JPS58193372A (en) 1983-04-25 1983-04-25 Liquid etchant for tin-nickel alloy

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
JP1084479A Division JPS55104481A (en) 1979-02-01 1979-02-01 Etching fluid for tin-nickel alloy

Publications (2)

Publication Number Publication Date
JPS58193372A JPS58193372A (en) 1983-11-11
JPS6217033B2 true JPS6217033B2 (en) 1987-04-15

Family

ID=13524089

Family Applications (1)

Application Number Title Priority Date Filing Date
JP7364083A Granted JPS58193372A (en) 1983-04-25 1983-04-25 Liquid etchant for tin-nickel alloy

Country Status (1)

Country Link
JP (1) JPS58193372A (en)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20240044014A1 (en) * 2020-12-15 2024-02-08 Mitsubishi Gas Chemical Company, Inc. Roughening treatment method for stainless steel surface, method for manufacturing roughened stainless steel, and aqueous composition used in said methods
US20240044015A1 (en) * 2020-12-15 2024-02-08 Mitsubishi Gas Chemical Company, Inc. Aqueous composition, stainless steel surface roughening method using same, and method for manufacturing roughened stainless steel

Also Published As

Publication number Publication date
JPS58193372A (en) 1983-11-11

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