WO2007040046A1 - Etchant for nickel-chromium alloy - Google Patents

Etchant for nickel-chromium alloy Download PDF

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Publication number
WO2007040046A1
WO2007040046A1 PCT/JP2006/318576 JP2006318576W WO2007040046A1 WO 2007040046 A1 WO2007040046 A1 WO 2007040046A1 JP 2006318576 W JP2006318576 W JP 2006318576W WO 2007040046 A1 WO2007040046 A1 WO 2007040046A1
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WIPO (PCT)
Prior art keywords
nickel
chromium alloy
etching
copper
etching solution
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PCT/JP2006/318576
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French (fr)
Japanese (ja)
Inventor
Kiichi Tanimoto
Nobuo Kobayashi
Original Assignee
Ebara-Udylite Co., Ltd.
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Publication date
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Priority to JP2007538690A priority Critical patent/JPWO2007040046A1/en
Publication of WO2007040046A1 publication Critical patent/WO2007040046A1/en

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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
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/28—Acidic compositions for etching iron group 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
    • 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
    • C23F1/26—Acidic compositions for etching refractory 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
    • 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
    • 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
    • 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
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/388—Improvement of the adhesion between the insulating substrate and the metal by the use of a metallic or inorganic thin film adhesion layer

Definitions

  • the present invention relates to an etching solution for a nickel-chromium alloy. More specifically, the nickel-chromium alloy layer is removed, and the etching capability does not decrease even if the copper concentration in the solution increases during the etching.
  • the present invention relates to an etching solution for a chromium alloy and a method for etching a nickel-chromium alloy using the same. Background art
  • a 10 to 50 nm dissimilar metal layer is formed on a polyimide film by sputtering, then copper sputtering of 50 to 100 nm is performed, and a copper film of about 10 m is formed on the copper sputtered film.
  • the underlying dissimilar metal layer, which forms the adhesion layer, is called the seed layer or the noble layer, and a nickel-chromium alloy is often used for this purpose. It is for improvement.
  • the adhesion between the polyimide resin and the copper layer is improved by the effect of the seed layer, a new problem has arisen.
  • the nickel-chromium alloy layer is not sufficiently etched with the conventional etching solution for removing the copper layer, and the nickel-chromium alloy layer may remain after the wiring is formed, causing a short circuit between the wirings. There was a thing.
  • Patent Document 1 Japanese Unexamined Patent Application Publication No. 2004-190054
  • the present invention provides an etching solution for a nickel chromium alloy that can sufficiently remove the nickel chromium alloy layer and that does not decrease the etching ability even if the copper concentration in the solution becomes high during the etching. Let it be an issue. Means for solving the problem
  • the present invention provides the following components (a) to (c)
  • the present invention is a method for etching a nickel-chromium alloy, characterized in that the above-mentioned nickel-chromium alloy etching solution is allowed to act on the nickel-chromium alloy.
  • the etching solution for nickel-chromium alloy of the present invention does not decrease the etching property with respect to the nickel-chromium alloy even when the concentration of copper in the solution becomes high during etching, and the strength and etching property with respect to copper also increase. It is a thing. Accordingly, the nickel-chromium alloy etching solution of the present invention can be used, for example, for efficiently removing the nickel-chromium alloy remaining in the removed portion of the copper layer in the production of a printed wiring board.
  • the sulfuric acid or sulfonic acid compound as the component (a) used in the etching solution for nickel chromium alloy of the present invention includes sulfuric acid, methane sulfonic acid, ethane sulfone.
  • examples include acids, alkane sulfonic acids such as hydroxymethane sulfonic acid and hydroxyethane sulfonic acid or derivatives thereof, and sulfonic acid compounds such as phenol sulfonic acid or derivatives thereof.
  • the content of these components ( a ) in the etching solution is particularly preferably 0.5 to 3N, preferably 0.2 to 4N as the acid concentration. In addition, the effect may not be obtained if the acid concentration is S0.2N or less, and if it is 4N or more, the effect depending on the added concentration may not be obtained.
  • hydrochloric acid or chlorine compound which is component (b) of the etching solution of the present invention hydrochloric acid or sodium chloride, sodium chloride, potassium salt, ammonium salt, calcium salt
  • examples include chlorine compounds such as lithium chloride, copper chloride, nickel chloride, iron chloride, zinc chloride, tin chloride, and lead chloride.
  • the content of these components (b) in the etching solution is particularly preferably 5 to 30 gZL, preferably 1 to 50 gZL as the chlorine concentration. If the chlorine concentration is less than lgZL, the effect may not be obtained. If the chlorine concentration is more than 50 gZL, the effect corresponding to the added concentration may not be obtained, and the etching amount for copper may further increase.
  • examples of the nitrite as the component (c) of the etching solution of the present invention include nitrites such as sodium nitrite, potassium nitrite, ammonium nitrite and calcium nitrite.
  • the content of these components (c) in the etching solution is preferably 1 mgZL to 5 gZL, particularly preferably 5 mgZL to lgZL as nitrite ions. Note that if the nitrite ion concentration is 1 mgZL or less, the effect may not be obtained, and if it is 5 gZL or more, the removal effect may decrease, and the force and the etching amount for copper may increase.
  • the etching agent of the present invention is produced by mixing the components (a) to (c) described above according to a conventional method.
  • the nitrite of component (c) contained in the etching solution of the present invention The nitrite ion produced is low in stability and is naturally consumed, so it cannot be used for a long time. Therefore, it is preferable to add nitric acid or a nitric acid compound as the component (d) and an iron (III) compound as the component (e) to the etching solution.
  • nitrite ions are generated as a side reaction during the etching process, so that the etching agent can be used for a long time.
  • the nitric acid or nitric acid compound of component (d) added to the etching solution of the present invention includes nitric acid or nitric acid such as sodium nitrate, potassium nitrate, ammonium nitrate, copper nitrate, nickel nitrate, lead nitrate, etc. ⁇ composites.
  • the content of these components (d) in the etching solution is particularly preferably 5 to 50 gZL, preferably 2 to: LOOgZL as nitric acid.
  • the nitric acid concentration is 2 gZL or less, the effect may not be obtained, and if it is 10 gZL or more, the removal effect is not changed, and the amount of etching with respect to copper may increase.
  • component (e) iron (III) compound added to the etching solution of the present invention salt iron (III), iron nitrate (III), iron sulfate (III), ammonium iron nitrate (III) etc. are mentioned.
  • the content of these components ( e ) in the etching solution is preferably 5 mgZL to 2 gZL, preferably 1 mgZL to 10 gZL as iron. If the iron concentration is less than lmgZL, the effect may not be obtained. If the iron concentration is more than lOgZL, the removal effect may be reduced, and the etching amount for copper may be increased.
  • components such as an organic acid and a surfactant can be added to the etching solution of the present invention to the extent that the effects of the present invention are not impaired.
  • the etching solution of the present invention thus obtained can be etched by acting on a nickel-chromium alloy.
  • the nickel-chrome alloy to be etched with the etching solution of the present invention may have any composition, but an alloy having a chromium content of 15 to 25% by mass is particularly preferable.
  • the nickel-chromium alloy is preferably formed on a resin such as polyimide resin by sputtering or the like. Further, a copper layer is once formed on the nickel-chromium alloy layer, and then the copper layer is formed. Particularly preferred is a nickel-chromium alloy remaining in the portion from which copper has been removed, and a nickel-chromium alloy remaining in the vicinity of the end of the copper wiring of the printed wiring board is preferred.
  • a processing method and temperature for allowing the etching solution of the present invention to act on a nickel-chromium alloy The conditions such as time are not particularly limited, but examples of the processing method include a method of immersing in an etching solution or a method of spraying an etching solution with a spray.
  • the treatment temperature is preferably 20 to 60 ° C, particularly preferably 30 to 50 ° C. Note that the effect may not be obtained at a processing temperature of 20 ° C or lower, and the temperature of 60 ° C or higher is not preferable because the removal effect does not change and the etching force and the etching amount for copper may increase.
  • the treatment time is preferably 20 seconds to 3 minutes, particularly preferably 30 seconds to 2 minutes.
  • the removability of the nickel-chromium alloy may be insufficient in less than 20 seconds, and if it is longer than 3 minutes, the removal effect will not change, and the rinsing force and the etching amount for copper may be increased. It ’s not.
  • ⁇ 2 were prepared by a conventional method, and their etching amount, nickel chromium alloy layer removability, and etching solution stability were investigated.
  • the copper-clad laminate and copper coupons, nichrome alloy plate (chromium 20 mass 0/0) nickel - were chromium specimen. These test pieces are immersed in the test solutions prepared above (45 to 1 ° C and 1 minute of the test product) and the mass difference before and after treatment of each test piece. Was used to calculate the etching amount. The results are shown in Table 3.
  • a nickel - chromium (chromium content of 20 mass 0/0) alloy layer is 15nm is formed, then, the copper layer was lOOnm formed. Copper sulfate plating was further performed on the copper layer formed by sputtering to form a copper layer of 10 / zm. Thereafter, a wiring pattern of L / S 30/30 m was formed on the polyimide film by the subtractive method, and this was used as a test piece. A nickel-chromium alloy layer remained around 3-5 ⁇ m around the copper wiring formed by this subtractive method. After the specimen was treated, the residual state of the nickel chrome alloy layer was observed with a transmission electron microscope (SEM) and evaluated according to the following evaluation criteria. The results are also shown in Table 3.
  • SEM transmission electron microscope
  • a copper-clad laminate was immersed in each test solution and dissolved until the amount of copper in each test solution was 0.5 gZL, and each test solution was in the same state as was etched several times. Next, the etching amount and the nickel chromium alloy layer removal property were evaluated by the same method as in the above (1) and (2). The results are also shown in Table 3.
  • the etching solution of the present invention containing at least components (a) to (c) has a nickel-chromium etching amount larger than the copper etching amount, and has a nickel-chromium alloy.
  • the removability of the layer was high.
  • the etching liquid of the present invention containing the components (a) to (e) has a nickel chrome etching amount larger than the copper etching amount even in a continuous state where the copper concentration is high, and the nickel-chromium alloy layer Removability was high.
  • the nickel-chromium alloy etching solution of the present invention can efficiently remove the nickel-chromium alloy without damaging the copper wiring in the production of the flexible printed wiring board. It can be suitably used for the production of a wiring board.

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  • 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)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

Disclosed is an etchant for nickel-chromium alloys which is capable of sufficiently remove a nickel-chromium alloy layer and does not deteriorate in etching ability even when the copper concentration in the etchant is increased during etching. The etchant for nickel-chromium alloys is characterized by containing the following components (a)-(c). (a) sulfuric acid or a sulfonic acid compound (b) hydrochloric acid or a chlorine compound (c) a nitrite

Description

明 細 書  Specification
ニッケル—クロム合金用エッチング液  Etching solution for nickel-chromium alloy
技術分野  Technical field
[0001] 本発明はニッケル—クロム合金用エッチング液に関し、更に詳細には、ニッケル— クロム合金層を除去し、かつ、エッチング中に液中の銅濃度が増加してもエッチング 能力が低下しないニッケル クロム合金用エッチング液およびこれを利用した-ッケ ル—クロム合金のエッチング方法に関する。 背景技術  [0001] The present invention relates to an etching solution for a nickel-chromium alloy. More specifically, the nickel-chromium alloy layer is removed, and the etching capability does not decrease even if the copper concentration in the solution increases during the etching. The present invention relates to an etching solution for a chromium alloy and a method for etching a nickel-chromium alloy using the same. Background art
[0002] 従来、フレキシブルプリント配線板は、ポリイミドフィルムと銅箔とを接着剤により張り 合わせた、いわゆる 3層 CCL (銅張積層板)材が主流であった。この 3層 CCL材に使 用される接着剤は通常エポキシ系のもので、厚さと柔軟性の低さが問題であつた。  Conventionally, a so-called three-layer CCL (copper-clad laminate) material in which a polyimide film and a copper foil are bonded together with an adhesive has been mainly used as a flexible printed wiring board. Adhesives used for these three-layer CCL materials are usually epoxy-based, and problems with thickness and low flexibility.
[0003] 近年、電子機器類の小型化が進み、フレキシブルプリント配線板に対して、これま で以上の高密度化や柔軟性 ·屈曲性が要求されてきているが、上記問題点により、 3 層 CCL材では対応が困難となっている。  [0003] In recent years, electronic devices have been miniaturized, and flexible printed wiring boards have been required to have higher density, flexibility, and flexibility, but due to the above problems, 3 It is difficult to handle with layer CCL material.
[0004] それら問題点の解決のため、接着剤を使用せずに直接ポリイミドフィルムと銅層を 密着させた、いわゆる 2層 CCL材が開発されている。 2層 CCL材の製法にはいくつ かあるが、基板の薄膜ィ匕および配線パターンの高密度化には、スパッタ法が最も有 利とされている。  [0004] In order to solve these problems, a so-called two-layer CCL material has been developed in which a polyimide film and a copper layer are directly adhered without using an adhesive. There are several methods for producing a two-layer CCL material, but sputtering is the most advantageous method for increasing the density of the substrate thin film and wiring pattern.
[0005] スパッタ法の工程は、ポリイミドフィルム上に 10〜50nmの異種金属層をスパッタで 形成してから、 50〜100nmの銅スパッタを行い、さらにこの銅スパッタ膜上に 10 m 程度の銅めつき層を形成するというものである、下地の異種金属層は、シード層ある いはノ リア層と呼ばれ、これにはニッケル一クロム合金が使用される場合が多いが、 その目的は密着性向上のためである。  [0005] In the sputtering method, a 10 to 50 nm dissimilar metal layer is formed on a polyimide film by sputtering, then copper sputtering of 50 to 100 nm is performed, and a copper film of about 10 m is formed on the copper sputtered film. The underlying dissimilar metal layer, which forms the adhesion layer, is called the seed layer or the noble layer, and a nickel-chromium alloy is often used for this purpose. It is for improvement.
[0006] シード層の効果により、ポリイミド榭脂と銅層との密着性は向上するものの、新たな 問題が生じていた。すなわち、ニッケル クロム合金層は、銅層を除去するための従 来のエッチング液では十分にエッチングされず、ニッケル一クロム合金層が配線形成 後も残存することがあり、配線間で短絡等が起こることがあった。 [0007] 上記した問題に対し、ニッケル一クロム合金層をエッチングする技術として、 -ッケ ル、クロム若しくはニッケル 'クロム合金を溶解する酸成分と、銅イオン捕捉機能を有 する銅エッチング抑制成分とを含むエッチング液が知られている（特許文献 1)。しか し、このエッチング液ではエッチング液中の銅濃度が高くなると、ニッケル—クロム合 金に対するエッチング性は低下すると共に、銅に対するエッチング性が高くなり、銅 配線に対するダメージも大きくなると言う問題があった。 [0006] Although the adhesion between the polyimide resin and the copper layer is improved by the effect of the seed layer, a new problem has arisen. In other words, the nickel-chromium alloy layer is not sufficiently etched with the conventional etching solution for removing the copper layer, and the nickel-chromium alloy layer may remain after the wiring is formed, causing a short circuit between the wirings. There was a thing. [0007] To solve the above problems, as a technique for etching a nickel-chromium alloy layer, an acid component that dissolves a nickel, chromium, or nickel 'chromium alloy, and a copper etching inhibiting component that has a copper ion trapping function An etching solution containing benzene is known (Patent Document 1). However, with this etchant, there is a problem that when the copper concentration in the etchant increases, the etchability with respect to the nickel-chromium alloy decreases, the etchability with respect to copper increases, and the damage to the copper wiring also increases. .
[0008] 特許文献 1：特開 2004— 190054号公報  [0008] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2004-190054
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0009] 従って、本発明はニッケル クロム合金層の除去が十分に行え、更に、エッチング 中に液中の銅濃度が高くなつてもエッチング能力が低下しないニッケル クロム合金 用エッチング液を提供することを課題とする。 課題を解決するための手段 [0009] Accordingly, the present invention provides an etching solution for a nickel chromium alloy that can sufficiently remove the nickel chromium alloy layer and that does not decrease the etching ability even if the copper concentration in the solution becomes high during the etching. Let it be an issue. Means for solving the problem
[0010] 本発明者らは、ニッケル—クロム合金のエッチング剤に関し、鋭意研究を行った結 果、従来の硫酸、塩酸等力 なるエッチング液に亜硝酸塩を添加することにより、上 記課題が解決できることを見出し、本発明を完成させた。 [0010] As a result of intensive studies on the etching agent for nickel-chromium alloys, the present inventors have solved the above-mentioned problems by adding nitrite to conventional etching solutions of sulfuric acid and hydrochloric acid. The present invention has been completed by finding out what can be done.
[0011] すなわち、本発明は 次の成分 (a)〜(c)  That is, the present invention provides the following components (a) to (c)
(a)硫酸またはスルホン酸ィ匕合物  (a) Sulfuric acid or sulfonic acid compound
(b)塩酸または塩素化合物  (b) Hydrochloric acid or chlorine compounds
(c)亜硝酸塩  (c) Nitrite
を含有することを特徴とするニッケル一クロム合金用エッチング液である。  An etching solution for nickel-chromium alloy, characterized in that
[0012] また、本発明はニッケル一クロム合金に、上記ニッケル一クロム合金用エッチング液 を作用させることを特徴とするニッケル一クロム合金のエッチング方法である。 [0012] Further, the present invention is a method for etching a nickel-chromium alloy, characterized in that the above-mentioned nickel-chromium alloy etching solution is allowed to act on the nickel-chromium alloy.
発明の効果  The invention's effect
[0013] 本発明のニッケル クロム合金用エッチング液は、エッチング中に液中の銅濃度が 高くなつても、ニッケル クロム合金に対するエッチング性は低下せず、し力も、銅に 対するエッチング性も上昇しな 、ものである。 [0014] 従って、本発明のニッケル一クロム合金用エッチング液は、例えば、プリント配線板 の製造において、銅層の除去部分に残存するニッケル クロム合金を効率よく除去 するために利用できるものである。 [0013] The etching solution for nickel-chromium alloy of the present invention does not decrease the etching property with respect to the nickel-chromium alloy even when the concentration of copper in the solution becomes high during etching, and the strength and etching property with respect to copper also increase. It is a thing. Accordingly, the nickel-chromium alloy etching solution of the present invention can be used, for example, for efficiently removing the nickel-chromium alloy remaining in the removed portion of the copper layer in the production of a printed wiring board.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0015] 本発明のニッケル クロム合金用エッチング液 (以下、単に「エッチング液」という） に用いられる成分 (a)である硫酸またはスルホン酸ィ匕合物としては、硫酸またはメタン スルホン酸、エタンスルホン酸、ヒドロキシメタンスルホン酸、ヒドロキシエタンスルホン 酸等のアルカンスルホン酸またはその誘導体、フヱノールスルホン酸またはその誘導 体等のスルホン酸ィ匕合物が挙げられる。これら成分 (a)のエッチング液における含有 量は、酸濃度として、 0.2〜4Nが好ましぐ 0.5〜3Nが特に好ましい。なお、酸濃度 力 S0.2N以下では効果が得られないことがあり、 4N以上では添加濃度に応じた効果 が得られないことがある。 [0015] The sulfuric acid or sulfonic acid compound as the component (a) used in the etching solution for nickel chromium alloy of the present invention (hereinafter simply referred to as "etching solution") includes sulfuric acid, methane sulfonic acid, ethane sulfone. Examples include acids, alkane sulfonic acids such as hydroxymethane sulfonic acid and hydroxyethane sulfonic acid or derivatives thereof, and sulfonic acid compounds such as phenol sulfonic acid or derivatives thereof. The content of these components ( a ) in the etching solution is particularly preferably 0.5 to 3N, preferably 0.2 to 4N as the acid concentration. In addition, the effect may not be obtained if the acid concentration is S0.2N or less, and if it is 4N or more, the effect depending on the added concentration may not be obtained.
[0016] また、本発明のエッチング液の成分 (b)である塩酸または塩素化合物としては、塩 酸または塩ィ匕ナトリウム、塩ィ匕カリウム、塩ィ匕アンモ-ゥム、塩ィ匕カルシウム、塩化リチ ゥム、塩化銅、塩化ニッケル、塩化鉄、塩化亜鉛、塩化スズ、塩化鉛等の塩素化合物 が挙げられる。これら成分 (b)のエッチング液における含有量は、塩素濃度として 1〜 50gZLが好ましぐ 5〜30gZLが特に好ましい。なお、塩素濃度が lgZL以下では 効果が得られないことがあり、 50gZL以上では添加濃度に応じた効果が得られない こともあり、更に銅に対するエッチング量も多くなることがある。  [0016] Further, as the hydrochloric acid or chlorine compound which is component (b) of the etching solution of the present invention, hydrochloric acid or sodium chloride, sodium chloride, potassium salt, ammonium salt, calcium salt, Examples include chlorine compounds such as lithium chloride, copper chloride, nickel chloride, iron chloride, zinc chloride, tin chloride, and lead chloride. The content of these components (b) in the etching solution is particularly preferably 5 to 30 gZL, preferably 1 to 50 gZL as the chlorine concentration. If the chlorine concentration is less than lgZL, the effect may not be obtained. If the chlorine concentration is more than 50 gZL, the effect corresponding to the added concentration may not be obtained, and the etching amount for copper may further increase.
[0017] 更に、本発明のエッチング液の成分 (c)である亜硝酸塩としては、亜硝酸ナトリウム 、亜硝酸カリウム、亜硝酸アンモ-ゥム、亜硝酸カルシウム等の亜硝酸塩が挙げられ る。これら成分 (c)のエッチング液における含有量は、亜硝酸イオンとして lmgZL〜 5gZLが好ましぐ 5mgZL〜lgZLが特に好ましい。なお、亜硝酸イオン濃度が 1 mgZL以下では効果が得られないことがあり、 5gZL以上では逆に除去効果が低下 することもあり、し力も、銅に対するエッチング量も多くなることがある。  Furthermore, examples of the nitrite as the component (c) of the etching solution of the present invention include nitrites such as sodium nitrite, potassium nitrite, ammonium nitrite and calcium nitrite. The content of these components (c) in the etching solution is preferably 1 mgZL to 5 gZL, particularly preferably 5 mgZL to lgZL as nitrite ions. Note that if the nitrite ion concentration is 1 mgZL or less, the effect may not be obtained, and if it is 5 gZL or more, the removal effect may decrease, and the force and the etching amount for copper may increase.
[0018] 本発明のエッチング剤は、上記した成分 (a)ないし (c)を常法に従って混合すること により製造される。しかし、本発明のエッチング液に含有される成分 (c)の亜硝酸塩 力 生じる亜硝酸イオンは安定性が低ぐ自然消耗するため長期間使用できない場 合があるので、上記エッチング液中に更に成分 (d)としての硝酸または硝酸化合物 および成分 (e)としての鉄 (III)化合物を添加することが好ま 、。これら成分を添加し た場合、エッチング処理時の副反応として亜硝酸イオンが発生するため、エッチング 剤の長期間の使用が可能となる。 [0018] The etching agent of the present invention is produced by mixing the components (a) to (c) described above according to a conventional method. However, the nitrite of component (c) contained in the etching solution of the present invention The nitrite ion produced is low in stability and is naturally consumed, so it cannot be used for a long time. Therefore, it is preferable to add nitric acid or a nitric acid compound as the component (d) and an iron (III) compound as the component (e) to the etching solution. When these components are added, nitrite ions are generated as a side reaction during the etching process, so that the etching agent can be used for a long time.
[0019] 本発明のエッチング液に添加される成分 (d)の硝酸または硝酸ィ匕合物としては、硝 酸または硝酸ナトリウム、硝酸カリウム、硝酸アンモニゥム、硝酸銅、硝酸ニッケル、硝 酸鉛等の硝酸ィ匕合物が挙げられる。これら成分 (d)のエッチング液における含有量 は、硝酸として 2〜： LOOgZLが好ましぐ 5〜50gZLが特に好ましい。なお、硝酸濃 度が 2gZL以下では効果が得られないことがあり、 lOOgZL以上では逆に除去効果 が変わらないだけでなぐ銅に対するエッチング量も多くなることがあるので好ましくな い。 [0019] The nitric acid or nitric acid compound of component (d) added to the etching solution of the present invention includes nitric acid or nitric acid such as sodium nitrate, potassium nitrate, ammonium nitrate, copper nitrate, nickel nitrate, lead nitrate, etc.匕 composites. The content of these components (d) in the etching solution is particularly preferably 5 to 50 gZL, preferably 2 to: LOOgZL as nitric acid. In addition, if the nitric acid concentration is 2 gZL or less, the effect may not be obtained, and if it is 10 gZL or more, the removal effect is not changed, and the amount of etching with respect to copper may increase.
[0020] また、本発明のエッチング液に添加される成分 (e)の鉄 (III)化合物としては、塩ィ匕 鉄 (III)、硝酸鉄 (III)、硫酸鉄 (III)、硝酸アンモニゥム鉄 (III)等が挙げられる。これら 成分 (e)のエッチング液における含有量は、鉄として lmgZL〜10gZLが好ましぐ 5mgZL〜2gZLが特に好ましい。なお、鉄濃度が lmgZL以下では効果が得られ ないことがあり、 lOgZL以上では逆に除去効果が低下することもあり、しかも、銅に 対するエッチング量も多くなることがあるので好ましくない。 [0020] Further, as the component (e) iron (III) compound added to the etching solution of the present invention, salt iron (III), iron nitrate (III), iron sulfate (III), ammonium iron nitrate (III) etc. are mentioned. The content of these components ( e ) in the etching solution is preferably 5 mgZL to 2 gZL, preferably 1 mgZL to 10 gZL as iron. If the iron concentration is less than lmgZL, the effect may not be obtained. If the iron concentration is more than lOgZL, the removal effect may be reduced, and the etching amount for copper may be increased.
[0021] 更に、本発明のエッチング液には、本発明の効果を損なわない程度で、有機酸や 界面活性剤等の成分を添加することができる。  Furthermore, components such as an organic acid and a surfactant can be added to the etching solution of the present invention to the extent that the effects of the present invention are not impaired.
[0022] 斯くして得られる本発明のエッチング液は、ニッケル一クロム合金に作用させること によりエッチングすることができる。本発明のエッチング液によりエッチングされる-ッ ケルークロム合金は、どのような組成の合金であってもよいが、特にクロム含量が 15 〜25質量％の合金が好ましい。また、ニッケル—クロム合金はポリイミド榭脂等の榭 脂上にスパッタ等の方法により形成されたものが好ましぐ更に、ニッケル クロム合 金層の上に銅層を一旦形成し、その後、銅層が除去された部分に残存したニッケル クロム合金が好ましぐ特に、プリント配線板の銅配線の端部付近に残留している ニッケル クロム合金が好ましい。  [0022] The etching solution of the present invention thus obtained can be etched by acting on a nickel-chromium alloy. The nickel-chrome alloy to be etched with the etching solution of the present invention may have any composition, but an alloy having a chromium content of 15 to 25% by mass is particularly preferable. The nickel-chromium alloy is preferably formed on a resin such as polyimide resin by sputtering or the like. Further, a copper layer is once formed on the nickel-chromium alloy layer, and then the copper layer is formed. Particularly preferred is a nickel-chromium alloy remaining in the portion from which copper has been removed, and a nickel-chromium alloy remaining in the vicinity of the end of the copper wiring of the printed wiring board is preferred.
[0023] 本発明のエッチング液をニッケル クロム合金に作用させための、処理方法、温度 、時間等の条件は特に制限されないが、例えば処理方法としては、エッチング液に 浸潰する方法あるいはエッチング液をスプレーで噴霧する方法が挙げられる。また、 処理温度は 20〜60°Cが好ましぐ 30〜50°Cが特に好ましい。なお、処理温度が 20 °C以下では効果が得られないことがあり、 60°C以上では逆に除去効果が変わらない だけでなぐし力も、銅に対するエッチング量も多くなることがあるので好ましくない。ま た、処理時間は 20秒〜 3分が好ましぐ 30秒〜 2分が特に好ましい。なお、 20秒以 下ではニッケル クロム合金の除去性が不十分なことがあり、 3分以上だと除去効果 が変わらないだけでなぐし力も、銅に対するエッチング量も多くなることがあるので好 ましくない。 [0023] A processing method and temperature for allowing the etching solution of the present invention to act on a nickel-chromium alloy The conditions such as time are not particularly limited, but examples of the processing method include a method of immersing in an etching solution or a method of spraying an etching solution with a spray. The treatment temperature is preferably 20 to 60 ° C, particularly preferably 30 to 50 ° C. Note that the effect may not be obtained at a processing temperature of 20 ° C or lower, and the temperature of 60 ° C or higher is not preferable because the removal effect does not change and the etching force and the etching amount for copper may increase. . Further, the treatment time is preferably 20 seconds to 3 minutes, particularly preferably 30 seconds to 2 minutes. Note that the removability of the nickel-chromium alloy may be insufficient in less than 20 seconds, and if it is longer than 3 minutes, the removal effect will not change, and the rinsing force and the etching amount for copper may be increased. It ’s not.
実施例  Example
[0024] 以下、実施例を挙げて本発明を説明するが、本発明は何らこれらの実施例に限定 されるものではない。  [0024] Hereinafter, the present invention will be described with reference to examples, but the present invention is not limited to these examples.
[0025] 実 施 例 1 [0025] Example 1
以下の表 1および表 2に記載の組成のエッチング液 (実施品 1〜5および比較品 1 Etching solution having the composition described in Table 1 and Table 2 below (Practical product 1 to 5 and Comparative product 1)
〜2)を常法により作製し、それらのエッチング量、ニッケル クロム合金層除去性お よびエッチング液の安定性を調べた。 ~ 2) were prepared by a conventional method, and their etching amount, nickel chromium alloy layer removability, and etching solution stability were investigated.
[0026] [表 1]  [0026] [Table 1]
Figure imgf000006_0001
Figure imgf000006_0001
* 1 I 中の塩素の量を示す。  * 1 Indicates the amount of chlorine in I.
* * 1 I 中の亜硝酸の量を示す。  * * 1 Indicates the amount of nitrous acid in I.
* * * 1 | 中の鉄の量を示す。  * * * 1 | Indicates the amount of iron.
* * * * 1 I 中の硝酸の量を示す。  * * * * 1 Indicates the amount of nitric acid in I.
[0027] [表 2] 比較品 1 比車父 aa 2 [0027] [Table 2] Comparative Product 1 Ratio Father aa 2
硫酸 硫酸  Sulfuric acid sulfuric acid
1 0質量％ 5質量％  1 0% by mass 5% by mass
塩酸 塩酸  Hydrochloric acid hydrochloric acid
1 0質量％ 1 。質量  10% by weight 1 Mass
チォ尿素 チォク"リコ-ル酸  Thiourea Thioc "Ricolic Acid
1 質量％ 5質量％  1% by mass 5% by mass
[0028] (1)エッチング量の測定 [0028] (1) Measurement of etching amount
銅張積層板を銅試験片とし、ニクロム合金板 (クロム 20質量0 /0)をニッケル—クロム 試験片とした。これら試験片をそれぞれ 45°C、 1分の条件で上記で作成した各試験 液 (実施品 1〜5および比較品 1〜2)に浸漬し、各試験片の処理前後の質量差から 下式によりエッチング量を算出した。その結果を表 3に示した。 The copper-clad laminate and copper coupons, nichrome alloy plate (chromium 20 mass 0/0) nickel - were chromium specimen. These test pieces are immersed in the test solutions prepared above (45 to 1 ° C and 1 minute of the test product) and the mass difference before and after treatment of each test piece. Was used to calculate the etching amount. The results are shown in Table 3.
[0029] [数 1] エッチング量 （n m ) = ~ A ¼ 、 X 1 07 [0029] [Equation 1] Etching amount (nm) = ~ A ¼ , X 1 0 7
( d x S )  (d x S)
△W:処理前後の重量差 (g) △ W: Difference in weight before and after treatment (g)
d :試験片の比重 (gZcm3) d: Specific gravity of the specimen (gZcm 3 )
S :試験片の面積 (cm2) S: area of test piece (cm 2)
[0030] (2)ニッケル クロム合金層除去性  [0030] (2) Nickel-chromium alloy layer removability
ポリイミドフィルムの片面に、スパッタにより、ニッケル—クロム（クロム含量 20質量0 /0 )合金層を 15nm形成し、次いで、銅層を lOOnm形成した。スパッタにより形成され た銅層上に、更に硫酸銅めつきを行い、銅層を 10 /z m形成した。その後サブトラクテ イブ法によりポリイミドフィルム上に、 L/S = 30/30 mの配線パターンを形成し、こ れを試験片とした。なお、このサブトラクティブ法により形成された銅配線の周囲 3〜5 μ mにはニッケル クロム合金層が残留していた。この試験片を処理した後の-ッケ ルークロム合金層の残留状況を透過型電子顕微鏡 (SEM)観察し、以下の評価基 準で評価した。その結果も併せて表 3に示した。 On one side of the polyimide film, by sputtering, a nickel - chromium (chromium content of 20 mass 0/0) alloy layer is 15nm is formed, then, the copper layer was lOOnm formed. Copper sulfate plating was further performed on the copper layer formed by sputtering to form a copper layer of 10 / zm. Thereafter, a wiring pattern of L / S = 30/30 m was formed on the polyimide film by the subtractive method, and this was used as a test piece. A nickel-chromium alloy layer remained around 3-5 μm around the copper wiring formed by this subtractive method. After the specimen was treated, the residual state of the nickel chrome alloy layer was observed with a transmission electron microscope (SEM) and evaluated according to the following evaluation criteria. The results are also shown in Table 3.
[0031] < ニッケル クロム合金層除去評価基準 >  [0031] <Nickel / Chromium Alloy Layer Removal Evaluation Criteria>
( 評価 ） （ 内容 ）  (Evaluation) (Contents)
〇 ： 完全に除去されている Δ ： 大部分が除去されている力 わずかに残留している ○: Completely removed Δ: Mostly removed force Slightly remaining
X ： ほとんどまたはまったく除去されていない  X: little or no removal
[0032] (3)浴の安定性 [0032] (3) Stability of the bath
各試験液に銅張り積層板を浸漬し、各試験液中の銅量が 0.5gZLとなるまで溶解 させ、各試験液がエッチングを数回行ったのと同じ状態とした。次いで、その液で上 記（1)および（2)と同様の方法により、エッチング量およびニッケル クロム合金層除 去性を評価した。その結果も併せて表 3に示した。  A copper-clad laminate was immersed in each test solution and dissolved until the amount of copper in each test solution was 0.5 gZL, and each test solution was in the same state as was etched several times. Next, the etching amount and the nickel chromium alloy layer removal property were evaluated by the same method as in the above (1) and (2). The results are also shown in Table 3.
[0033] (4)結果 [0033] (4) Results
[表 3]  [Table 3]
Figure imgf000008_0001
Figure imgf000008_0001
[0034] 表 3から明らかなように、少なくとも成分 (a)〜(c)を含有する本発明のエッチング液 は、銅エッチング量よりもニッケル一クロムエッチング量が多ぐし力も、ニッケル一クロ ム合金層の除去性が高力つた。また特に、成分 (a)〜（e)を含有する本発明のエッチ ング液は、銅濃度が高い連続状態においても銅エッチング量よりもニッケル クロム エッチング量が多ぐしかも、ニッケル—クロム合金層の除去性が高力つた。  As apparent from Table 3, the etching solution of the present invention containing at least components (a) to (c) has a nickel-chromium etching amount larger than the copper etching amount, and has a nickel-chromium alloy. The removability of the layer was high. In particular, the etching liquid of the present invention containing the components (a) to (e) has a nickel chrome etching amount larger than the copper etching amount even in a continuous state where the copper concentration is high, and the nickel-chromium alloy layer Removability was high.
産業上の利用可能性  Industrial applicability
[0035] 本発明のニッケル一クロム合金用エッチング液は、フレキシブルプリント配線板の製 造において、銅配線に対してダメージを与えず、ニッケル クロム合金を効率よく除 去することができるので、フレキシブルプリント配線板の製造に好適に用いることがで きる。 [0035] The nickel-chromium alloy etching solution of the present invention can efficiently remove the nickel-chromium alloy without damaging the copper wiring in the production of the flexible printed wiring board. It can be suitably used for the production of a wiring board.

Claims

請求の範囲 The scope of the claims
[1] 次の成分 (a)〜（c)  [1] Next ingredients (a) to (c)
(a)硫酸またはスルホン酸ィ匕合物  (a) Sulfuric acid or sulfonic acid compound
(b)塩酸または塩素化合物  (b) Hydrochloric acid or chlorine compounds
(c)亜硝酸塩  (c) Nitrite
を含有することを特徴とするニッケル一クロム合金用エッチング液。  Etching solution for nickel-chromium alloy, characterized by comprising
[2] 更に、成分 (d)および (e) [2] In addition, components (d) and (e)
(d)硝酸または硝酸ィ匕合物  (d) Nitric acid or nitrate compound
(e)鉄 (III)化合物  (e) Iron (III) compound
を含有する請求項第 1項記載のニッケル クロム合金用エッチング液。  The nickel-chromium alloy etching solution according to claim 1, comprising:
[3] エッチング対象力 クロム含量が 15〜25質量％のニッケル—クロム合金である請求 項第 1項または第 2項記載のニッケル クロム合金用エッチング液。 [3] The etching target solution according to claim 1 or 2, which is a nickel-chromium alloy having a chromium content of 15 to 25% by mass.
[4] エッチング対象が、ポリイミド榭脂上に形成されたニッケル—クロム合金である請求 項第 1項ないし第 3項の何れかの項に記載のニッケル クロム合金用エッチング液。 [4] The etching solution for a nickel-chromium alloy according to any one of [1] to [3], wherein the etching target is a nickel-chromium alloy formed on a polyimide resin.
[5] ニッケル—クロム合金に、請求項第 1項ないし第 4項の何れかの項に記載の-ッケ ルークロム合金用エッチング液を作用させることを特徴とするニッケル一クロム合金の エッチング方法。 [5] A nickel-chromium alloy etching method, wherein the nickel-chromium alloy etching solution according to any one of claims 1 to 4 is allowed to act on the nickel-chromium alloy.
[6] ポリイミド榭脂上に順次形成されたニッケル—クロム合金層および銅層から、所定の 配線パターンで銅層を除去した後、露出、残存するニッケル—クロム合金層をエッチ ングするものである請求項第 5項記載のニッケル クロム合金のエッチング方法。  [6] After removing the copper layer with a predetermined wiring pattern from the nickel-chromium alloy layer and copper layer sequentially formed on the polyimide resin, the exposed and remaining nickel-chromium alloy layer is etched. The method for etching a nickel-chromium alloy according to claim 5.
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JP2012144791A (en) * 2011-01-13 2012-08-02 National Institute Of Advanced Industrial Science & Technology Method for patterning electroless nickel alloy film
US8486281B2 (en) 2009-10-05 2013-07-16 Kesheng Feng Nickel-chromium alloy stripper for flexible wiring boards
KR101298766B1 (en) 2011-05-20 2013-08-21 주식회사 익스톨 Etching solution composites for nickel, chrome, and/or nickel-chrome alloy and etching method using the etching solution composites
KR20160005237A (en) * 2014-07-04 2016-01-14 오씨아이 주식회사 Etching composition for metal layer comprising nickel
JP2017017360A (en) * 2011-03-11 2017-01-19 フジフィルム・エレクトロニック・マテリアルズ・ユーエスエイ・インコーポレイテッドＦｕｊｉＦｉｌｍ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＵＳＡ， Ｉｎｃ． Novel etching composition
CN112064027A (en) * 2020-09-14 2020-12-11 深圳市志凌伟业光电有限公司 Etching solution for composite copper film structure
CN112064028A (en) * 2020-09-14 2020-12-11 深圳市志凌伟业光电有限公司 Etching liquid for composite copper film structure
CN112649270A (en) * 2018-09-17 2021-04-13 沈阳市启光科技有限公司 Corrosive agent for dendritic crystal corrosion macroscopic examination

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JP2009161788A (en) * 2007-12-28 2009-07-23 Nihon Kagaku Sangyo Co Ltd Plating method, and plating pretreatment liquid used for the method
US8486281B2 (en) 2009-10-05 2013-07-16 Kesheng Feng Nickel-chromium alloy stripper for flexible wiring boards
JP5911145B2 (en) * 2010-12-03 2016-04-27 株式会社Ｊｃｕ Etching solution maintenance method
WO2012073816A1 (en) * 2010-12-03 2012-06-07 荏原ユージライト株式会社 Method for maintaining etching liquid and system therefor
JPWO2012073816A1 (en) * 2010-12-03 2014-05-19 株式会社Ｊｃｕ Etch solution maintenance method and system therefor
JP2012144791A (en) * 2011-01-13 2012-08-02 National Institute Of Advanced Industrial Science & Technology Method for patterning electroless nickel alloy film
JP2017017360A (en) * 2011-03-11 2017-01-19 フジフィルム・エレクトロニック・マテリアルズ・ユーエスエイ・インコーポレイテッドＦｕｊｉＦｉｌｍ Ｅｌｅｃｔｒｏｎｉｃ Ｍａｔｅｒｉａｌｓ ＵＳＡ， Ｉｎｃ． Novel etching composition
KR101298766B1 (en) 2011-05-20 2013-08-21 주식회사 익스톨 Etching solution composites for nickel, chrome, and/or nickel-chrome alloy and etching method using the etching solution composites
KR101590258B1 (en) 2014-07-04 2016-02-01 오씨아이 주식회사 Etching composition for metal layer comprising nickel
KR20160005237A (en) * 2014-07-04 2016-01-14 오씨아이 주식회사 Etching composition for metal layer comprising nickel
CN112649270A (en) * 2018-09-17 2021-04-13 沈阳市启光科技有限公司 Corrosive agent for dendritic crystal corrosion macroscopic examination
CN112064027A (en) * 2020-09-14 2020-12-11 深圳市志凌伟业光电有限公司 Etching solution for composite copper film structure
CN112064028A (en) * 2020-09-14 2020-12-11 深圳市志凌伟业光电有限公司 Etching liquid for composite copper film structure

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