JPH10158869A - Chemical polishing liquid for iron-nickel alloy or iron-nickel-cobalt alloy and chemical polishing method therefor - Google Patents
Chemical polishing liquid for iron-nickel alloy or iron-nickel-cobalt alloy and chemical polishing method thereforInfo
- Publication number
- JPH10158869A JPH10158869A JP33015996A JP33015996A JPH10158869A JP H10158869 A JPH10158869 A JP H10158869A JP 33015996 A JP33015996 A JP 33015996A JP 33015996 A JP33015996 A JP 33015996A JP H10158869 A JPH10158869 A JP H10158869A
- Authority
- JP
- Japan
- Prior art keywords
- chemical polishing
- iron
- nickel
- alloy
- acid
- 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.)
- Withdrawn
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
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は４２アロイに代表さ
れる鉄−ニッケル系合金、コバルトに代表される鉄−ニ
ッケル−コバルト系合金を平滑性のある光沢面に付与し
うる過酸化水素と硫酸を主成分とし、光沢強化剤を含有
することを特徴とする化学研磨液及び化学研磨方法に関
する。鉄−ニッケル系合金又は鉄−ニッケル−コバルト
系合金は電子部品のリードフレーム材料や半導体素子材
料に広く利用されてきている。これらの合金は電子部品
として素材より加工し製造する場合、圧延、切断、パン
チング等の機械加工時にバリや表面荒れ等が発生し、
又、ガラス封着時の熱処理において酸化スケールが生成
する為、後工程のメッキ、ボンディング、樹脂封止等で
密着性不良や機能性低下が生ずる。この為、これらの後
工程の前処理としてバフ研磨やバレル研磨などの機械研
磨あるいは電気的溶解を利用する電解研磨が行なわれて
いるが形状の複雑な品物や小さな品物あるいは変形しや
すい品物に対しては、適用が困難であり、生産性も著し
く低下する。従って、前処理としては化学研磨が主に利
用され酸化スケールを除去し、かつバリを除去し光沢あ
る平滑面に仕上げている。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to hydrogen peroxide and sulfuric acid which can provide an iron-nickel alloy represented by 42 alloy and an iron-nickel-cobalt alloy represented by cobalt to a smooth glossy surface. And a chemical polishing method characterized by containing a gloss enhancing agent. BACKGROUND ART Iron-nickel alloys or iron-nickel-cobalt alloys have been widely used as lead frame materials for electronic components and semiconductor element materials. When these alloys are processed and manufactured from raw materials as electronic components, burrs and surface roughness occur at the time of machining such as rolling, cutting, and punching,
In addition, since an oxide scale is generated in the heat treatment at the time of sealing the glass, poor adhesion and reduced functionality are caused by plating, bonding, resin sealing, and the like in a later step. For this reason, mechanical polishing such as buffing or barrel polishing or electrolytic polishing using electric melting is performed as a pretreatment of these post-processes, but for articles having complicated shapes, small articles or articles which are easily deformed. Therefore, application is difficult, and productivity is significantly reduced. Therefore, chemical polishing is mainly used as a pretreatment to remove oxide scale, remove burrs, and finish a glossy smooth surface.
【０００２】[0002]
【従来の技術】従来、鉄−ニッケル系合金又は鉄−ニッ
ケル−コバルト系合金の化学研磨液としては、塩酸、硝
酸、酒石酸の混合液（特開昭５３−４７３３５）、酢
酸、硝酸、燐酸の混合液（特開昭６０−１９０５８１）
が提案されている。しかしながらこれらの硝酸を含有す
る混合液では有害なＮＯｘガスが発生するため、作業環
境性に問題があり、これらの合金を良好光沢に研磨でき
ないものであった。一方、過酸化水素を用いた処理液と
して、過酸化水素、有機酸又は無機酸にセレン化合物含
有を特徴とする化学的溶解液（特公昭５３−３２７６
８）、又、過酸化水素、弗酸及び／又は重弗酸イオンを
含有する化学的溶解処理方法（特公昭５９−２７４８）
が提案されている。しかしながら、これらの処理液では
毒性の強いセレン化合物や排水規制の厳しい弗素を含有
しているもので作業安全上、排水処理上好ましいもので
はなかった。2. Description of the Related Art Conventionally, as a chemical polishing liquid for an iron-nickel alloy or an iron-nickel-cobalt alloy, a mixed solution of hydrochloric acid, nitric acid and tartaric acid (JP-A-53-47335), acetic acid, nitric acid and phosphoric acid are used. Mixed liquid (JP-A-60-190581)
Has been proposed. However, since a harmful NOx gas is generated in the mixed solution containing these nitric acids, there is a problem in working environment, and these alloys cannot be polished with good gloss. On the other hand, as a treatment solution using hydrogen peroxide, a chemical solution characterized by containing a selenium compound in hydrogen peroxide, an organic acid or an inorganic acid (JP-B-53-3276)
8) Also, a chemical dissolution treatment method containing hydrogen peroxide, hydrofluoric acid and / or bifluoric acid ions (Japanese Patent Publication No. 59-2748)
Has been proposed. However, these treatment liquids contain highly toxic selenium compounds and fluorine with strict wastewater regulations, which are not preferable in terms of work safety and wastewater treatment.
【０００３】[0003]
【発明が解決しようとする課題】本発明はこれらの従来
の化学研磨液及び化学研磨方法の欠点である作業環境、
排水処理性の改善を目的とするものでＮＯｘガス等の有
害ガスの発生がなく、排水処理に悪影響を与える弗素、
有害物を含まない鉄−ニッケル系合金又は鉄−ニッケル
−コバルト系合金の化学研磨液及び化学研磨方法を提供
するものである。更に、鉄−ニッケル系合金又は鉄−ニ
ッケル−コバルト系合金の表面に均一な光沢面を付与
し、かつ平滑面に仕上げる化学研磨液及び化学研磨方法
を提供するものである。SUMMARY OF THE INVENTION The present invention provides a work environment, which is a disadvantage of these conventional chemical polishing solutions and chemical polishing methods.
The purpose is to improve wastewater treatment, and there is no generation of harmful gases such as NOx gas, and fluorine which has an adverse effect on wastewater treatment.
An object of the present invention is to provide a chemical polishing liquid and a chemical polishing method for an iron-nickel alloy or an iron-nickel-cobalt alloy containing no harmful substances. It is another object of the present invention to provide a chemical polishing liquid and a chemical polishing method for imparting a uniform glossy surface to the surface of an iron-nickel alloy or an iron-nickel-cobalt alloy and finishing the surface to be smooth.
【０００４】[0004]
【課題を解決するための手段】本発明者らは鉄−ニッケ
ル系合金又は鉄−ニッケル−コバルト系合金の化学研磨
において、作業環境や排水に悪影響を及ぼす硝酸、弗
酸、弗化物、セレン化合物などを含まない環境にやさし
い化学研磨剤および化学研磨方法を鋭意研究の結果、過
酸化水素に従来では考えられない高い濃度の硫酸を含有
することにより、従来と殆ど変わらない処理時間で化学
研磨できることを見い出し、更に光沢強化剤を添加する
ことにより、従来と殆ど同等な光沢性、平滑性が得られ
ることを見い出した。DISCLOSURE OF THE INVENTION The present inventors have found that in chemical polishing of an iron-nickel alloy or an iron-nickel-cobalt alloy, nitric acid, hydrofluoric acid, fluoride, and selenium compound which adversely affect the working environment and drainage. As a result of intensive research on environmentally friendly chemical polishing agents and chemical polishing methods that do not contain such substances, the fact that hydrogen peroxide contains a high concentration of sulfuric acid, which is unlikely to be considered in the past, can be chemically polished in almost the same processing time as conventional. It was found that glossiness and smoothness almost equivalent to those of the prior art can be obtained by further adding a gloss enhancing agent.
【０００５】すなわち本発明に係わる化学研磨液は過酸
化水素８５〜２００ｇ／ｌ、硫酸１００〜８３０ｇ／ｌ
を基本成分とする混合液よりなる鉄−ニッケル系合金又
は鉄−ニッケル−コバルト系合金の化学研磨液である。
好ましくは、光沢強化剤として下記の（Ａ）、（Ｂ）、
（Ｃ）の１種以上を０．０１〜５０ｇ／ｌ含有する。さ
らに化学研磨方法として、処理温度２０〜６０℃、及び
処理時間１０秒〜１０分で化学研磨することを特徴とす
る。 （Ａ）カチオン系、ノニオン系、両性から選ばれた界面
活性剤の１種以上。 （Ｂ）アルコール類又はエーテル類の１種以上。 （Ｃ）有機酸又は化合物の１種以上。That is, the chemical polishing liquid according to the present invention contains 85 to 200 g / l of hydrogen peroxide and 100 to 830 g / l of sulfuric acid.
Is a chemical polishing solution of an iron-nickel alloy or an iron-nickel-cobalt alloy composed of a mixed solution containing as a basic component.
Preferably, the following (A), (B),
It contains 0.01 to 50 g / l of one or more kinds of (C). Further, as a chemical polishing method, a chemical polishing is performed at a processing temperature of 20 to 60 ° C. and a processing time of 10 seconds to 10 minutes. (A) One or more surfactants selected from cationic, nonionic and amphoteric. (B) One or more alcohols or ethers. (C) one or more organic acids or compounds.
【０００６】[0006]
【発明の実施の形態】本発明の適用対象は鉄−ニッケル
系合金又は鉄−ニッケル−コバルト系合金の化学研磨で
ある。ここに鉄−ニッケル系合金又は鉄−ニッケル−コ
バルト系合金は通常含有される不純物量以上のクロムを
含まない材料に限定される。他の金属は含有されても良
いが、好ましくは通常の不純物レベル以下である。DESCRIPTION OF THE PREFERRED EMBODIMENTS The object of the present invention is chemical polishing of an iron-nickel alloy or an iron-nickel-cobalt alloy. Here, the iron-nickel-based alloy or the iron-nickel-cobalt-based alloy is limited to a material that does not contain chromium in excess of the amount of impurities usually contained. Other metals may be included but are preferably below normal impurity levels.
【０００７】本発明の鉄−ニッケル系合金又は鉄−ニッ
ケル−コバルト系合金の化学研磨液の構成成分、有効成
分量及び化学研磨方法を説明する。過酸化水素は８５〜
２００ｇ／ｌが好ましく、更に好ましくは１００〜１５
０ｇ／ｌである。硫酸は１００〜８３０ｇ／ｌが好まし
く、更に好ましくは３００〜７００ｇ／ｌである。過酸
化水素８５ｇ／ｌ未満では完全に光沢研磨領域から外れ
ることになり、無光沢の仕上がりになる。又２００ｇ／
ｌを超えると過酸化水素の自然分解が多く、不安定な研
磨液となる。硫酸１００ｇ／ｌ未満では溶解量が増大
し、光沢性が低下する。又８３０ｇ／ｌを超えると過酸
化水素の安定性が低下する。なお、このように硫酸を高
濃度で使用することは従来まったく着想されなかったこ
とは上に述べた通りである。The components, effective components, and the chemical polishing method of the chemical polishing solution of the iron-nickel alloy or the iron-nickel-cobalt alloy of the present invention will be described. 85-80 hydrogen peroxide
200 g / l is preferable, and 100 to 15 is more preferable.
0 g / l. Sulfuric acid is preferably 100 to 830 g / l, more preferably 300 to 700 g / l. If the amount of hydrogen peroxide is less than 85 g / l, it will completely fall out of the gloss polishing region, resulting in a matte finish. 200g /
If it exceeds 1, the spontaneous decomposition of hydrogen peroxide is large, resulting in an unstable polishing liquid. If the amount of sulfuric acid is less than 100 g / l, the amount of dissolution increases and the gloss decreases. If it exceeds 830 g / l, the stability of hydrogen peroxide decreases. As described above, the use of sulfuric acid at a high concentration has not been conceived at all.
【０００８】光沢強化剤は必須ではないが、対象とする
被研磨材料と光沢強化剤の組み合わせによっては効果が
期待できる。例えば、以下の実施例で述べるように、鉄
−ニッケル系合金では限られた数の光沢強化剤が有効で
あるが、鉄−ニッケル−コバルト系合金の場合にはより
多くの光沢強化剤が有効に作用することが分かった。光
沢強化剤の含有量は０．０１〜５０ｇ／ｌが好ましく、
更に好ましくは０．１〜３０ｇ／ｌである。光沢強化剤
０．０１ｇ／ｌ未満では光沢化に効果が劣り、５０ｇ／
ｌを超えるとピンホールが発生し、平滑性が低下する。
化学研磨の処理温度は２０〜６０℃が好ましく、更に好
ましくは３０〜５０℃である。２０℃未満では研磨速度
が遅く良好な光沢が得にくく、６０℃を超えると過酸化
水素の安定性が低下する。処理時間は１０秒〜１０分が
好ましく、更に好ましくは３０秒〜５分である。１０秒
未満では研磨速度が遅く、良好な光沢が得にくく、１０
分を超えると表面が荒れ、光沢性が低下する。Although a gloss enhancer is not essential, an effect can be expected depending on the combination of the material to be polished and the gloss enhancer. For example, as described in the examples below, a limited number of gloss enhancers are effective with iron-nickel based alloys, but more gloss enhancers are effective with iron-nickel-cobalt based alloys. It was found to work. The content of the gloss enhancer is preferably 0.01 to 50 g / l,
More preferably, it is 0.1 to 30 g / l. If the gloss enhancer is less than 0.01 g / l, the effect on gloss is inferior, and 50 g / l
If it exceeds 1, a pinhole is generated and the smoothness is reduced.
The processing temperature of the chemical polishing is preferably from 20 to 60 ° C, more preferably from 30 to 50 ° C. If the temperature is lower than 20 ° C., the polishing rate is low and it is difficult to obtain good gloss. If the temperature is higher than 60 ° C., the stability of hydrogen peroxide decreases. The processing time is preferably from 10 seconds to 10 minutes, more preferably from 30 seconds to 5 minutes. If it is less than 10 seconds, the polishing rate is low, and it is difficult to obtain good gloss.
If it exceeds minutes, the surface becomes rough and the gloss is reduced.
【０００９】［界面活性剤（Ａ）］本発明では界面活性
剤（Ａ）としては次のものが使用できる。カチオン系界
面活性剤としては、オクタデシルトリメチルアンモニウ
ムクロライド、ドデシルトリメチルアンモニウムクロラ
イド、ヘキサデシルトリメチルアンモニウムクロライ
ド、パーフルオロアルキルトリメチルアンモニウムクロ
ライドなどのアルキルトリメチルアンモニウムクロライ
ド及びジアルキルジメチルアンモニウムクロライドなど
の４級アンモニウムクロライドなどが挙げられる。[Surfactant (A)] In the present invention, the following can be used as the surfactant (A). Examples of the cationic surfactant include quaternary ammonium chlorides such as octadecyltrimethylammonium chloride, dodecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, alkyltrimethylammonium chloride such as perfluoroalkyltrimethylammonium chloride, and dialkyldimethylammonium chloride. Can be
【００１０】ノニオン系界面活性剤としては、ポリオキ
シエチレンラウリルアミン、ポリオキシエチレンステア
リルアミンなどのポリオキシエチレンアルキルアミン
類、ポリオキシエチレンオレイルエーテル、ポリオキシ
エチレンセチルエーテル、ポリオキシエチレンステアリ
ルエーテルなどのポリオキシエチレンアルキルエーテル
類、ポリオキシエチレンノニルフェニルエーテル、ポリ
オキシエチレンオクチルフェニルエーテルなどのポリオ
キシエチレンアルキルフェニルエーテル類、ポリオキシ
エチレンモノラウレート、ポリオキシエチレンモノステ
アレート、ポリオキシエチレンモノオレエートなどのポ
リオキシエチレン脂肪酸エステル類、ソルビタンモノラ
ウレート、ソルビタンモノパルミテート、ソルビタンモ
ノステアレートなどのソルビタンエステル類、ポリオキ
シエチレンオキシプロピレンブロックポリマーなどが挙
げられる。Examples of the nonionic surfactant include polyoxyethylene alkylamines such as polyoxyethylene laurylamine and polyoxyethylene stearylamine, and polyoxyethylene oleyl ether, polyoxyethylene cetyl ether and polyoxyethylene stearyl ether. Polyoxyethylene alkyl phenyl ethers such as polyoxyethylene alkyl ethers, polyoxyethylene nonyl phenyl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene monolaurate, polyoxyethylene monostearate, polyoxyethylene monooleate Polyoxyethylene fatty acid esters, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, etc. Sorbitan esters, polyoxyethylene polyoxypropylene block polymers.
【００１１】両性界面活性剤としては、ジメチルアルキ
ルベタイン型、アルキルグリシン型、アミドベタイン
型、イミダゾリン型が挙げられる。Examples of the amphoteric surfactant include dimethyl alkyl betaine type, alkyl glycine type, amido betaine type and imidazoline type.
【００１２】［アルコール又はエーテル類（Ｂ）］本発
明で使用できるアルコール類（Ｂ）としては、メタノー
ル、エタノール、プロパノール、２−プロパノール、１
−ブタノールなどの脂肪族一価アルコール、エチレング
リコール、プロピレングリコール、ブチレングリコール
などの脂肪族二価アルコール、グリセリンなどの脂肪族
三価アルコール、フェノール、キシレノール、クレゾー
ルなどの芳香族一価アルコール、カテコール、レゾルシ
ン、ヒドロキノンなどの芳香族三価アルコール、ピロガ
ロールなどの芳香族酸化アルコール、ポリエチレングリ
コール、ポリプロピレングリコール、ポリビニルアルコ
ールが挙げられる。エーテル類としてはエチレングリコ
ールモノメチルエーテル、エチレングリコールモノエチ
ルエーテル、エチレングリコールモノプロピルエーテ
ル、エチレングリコールモノブチルエーテルなどのエチ
レングリコールモノアルキルエーテル類、プロピレング
リコールモノメチルエーテル、プロピレングリコールモ
ノエチルエーテルなどのプロピレングリコールモノアル
キルエーテル類、ジエチレングリコールモノメチルエー
テル、ジエチレングリコールモノエチルエーテル、ジエ
チレングリコールモノブチルエーテルなどのジエチレン
グリコールモノアルキルエーテル類、ジプロピレングリ
コールモノメチルエーテル、ジプロピレングリコールモ
ノエチルエーテル、ジプロピレングリコールモノブチル
エーテルなどのジプロピレングリコールモノアルキルエ
ーテル類、トリエチレングリコールモノメチルエーテ
ル、トリプロピレングリコールモノメチルエーテルなど
が挙げられる。[Alcohol or ether (B)] The alcohol (B) usable in the present invention includes methanol, ethanol, propanol, 2-propanol,
-Aliphatic monohydric alcohols such as butanol, aliphatic dihydric alcohols such as ethylene glycol, propylene glycol, butylene glycol, aliphatic trihydric alcohols such as glycerin, phenol, xylenol, aromatic monohydric alcohols such as cresol, catechol, Examples include aromatic trihydric alcohols such as resorcinol and hydroquinone, aromatic oxidized alcohols such as pyrogallol, polyethylene glycol, polypropylene glycol, and polyvinyl alcohol. Examples of ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and ethylene glycol monobutyl ether, and propylene glycol monoalkyl such as propylene glycol monomethyl ether and propylene glycol monoethyl ether. Ethers, diethylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol such as dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether -Alkyl ethers, triethylene glycol monomethyl ether, tripropylene glycol monomethyl ether.
【００１３】［有機酸又はその化合物（Ｃ）］本発明で
使用できる有機酸又はその化合物（Ｃ）としては、蟻
酸、酢酸、プロピオン酸、ｎ−酪酸、イソ−酪酸、吉草
酸、イソ吉草酸、アクリル酸、３−ブテン酸、メタクリ
ル酸などの脂肪族モノカルボン酸類及びこの化合物、蓚
酸、マロン酸、コハク酸、ダルタル酸、アジピン酸、ピ
メリン酸、スベリン酸、マレイン酸、フマル酸などの脂
肪族ジカルボン酸類及びこの化合物、グリコール酸、乳
酸、２−ヒドロキシ酪酸、グリセリン酸、リンゴ酸、酒
石酸、クエン酸などの脂肪族オキシカルボン酸類及びそ
の化合物、安息香酸、フタル酸、イソフタル酸などの芳
香族カルボン酸及びこの化合物、ヒドロキシ安息香酸、
サリチル酸、没食子酸などの芳香族ヒドロキシカルボン
酸類及びこの化合物、メタンスルホン酸、エタンスルホ
ン酸などの脂肪族スルホン酸類及びこの化合物、ベンゼ
ンスルホン酸、トルエンスルホン酸、フェノールスルホ
ン酸などの芳香族スルホン酸類及びこの化合物が挙げら
れる。[Organic acid or its compound (C)] The organic acid or its compound (C) which can be used in the present invention includes formic acid, acetic acid, propionic acid, n-butyric acid, iso-butyric acid, valeric acid, isovaleric acid , Acrylic acid, 3-butenoic acid, aliphatic monocarboxylic acids such as methacrylic acid and the like, and fats such as oxalic acid, malonic acid, succinic acid, daltaric acid, adipic acid, pimelic acid, suberic acid, maleic acid and fumaric acid Aliphatic dicarboxylic acids and their compounds, glycolic acid, lactic acid, 2-hydroxybutyric acid, glyceric acid, malic acid, tartaric acid, citric acid and other aliphatic oxycarboxylic acids and their compounds, benzoic acid, phthalic acid, isophthalic acid and other aromatic compounds Carboxylic acid and this compound, hydroxybenzoic acid,
Salicylic acid, aromatic hydroxycarboxylic acids such as gallic acid and this compound, methanesulfonic acid, aliphatic sulfonic acids such as ethanesulfonic acid and this compound, benzenesulfonic acid, toluenesulfonic acid, aromatic sulfonic acids such as phenolsulfonic acid and This compound is exemplified.
【００１４】［発明の作用］本発明の鉄−ニッケル系合
金又は鉄−ニッケル−コバルト系合金の化学研磨液は基
本成分である硫酸を高濃度で使用することが特徴で、こ
れによる特異的効果により、これらの合金表面を平滑あ
る光沢面に仕上げるものである。更に詳細には、本発明
の化学研磨液は硫酸の高濃度での特有の粘性を利用し、
平滑化、光沢化させるもので、この粘性から生ずる拡散
型の抑制により、これらの合金の成分金属の選択的溶解
が抑制され、均一な溶解を促がすことにより、光沢化、
平滑化されると推定される。光沢強化剤はこれらの合金
表面への吸着抑制作用又は化学研磨液への増粘化作用に
より、更に合金成分の溶解速度を調整するとともに、合
金表面のミクロ的な凹部の溶解を抑制しつつ、ミクロ的
な凸部を優先的に溶解させることにより、光沢性、平滑
性を更に向上させると推定される。[Effect of the Invention] The chemical polishing solution of the iron-nickel alloy or the iron-nickel-cobalt alloy of the present invention is characterized by using sulfuric acid which is a basic component at a high concentration, thereby producing a specific effect. Thus, the surface of these alloys is finished to a smooth glossy surface. More specifically, the chemical polishing liquid of the present invention utilizes the specific viscosity at a high concentration of sulfuric acid,
Smoothing and glossing, by suppressing the diffusion type generated from this viscosity, the selective melting of the component metals of these alloys is suppressed, and by promoting uniform melting, glossing,
It is estimated to be smoothed. The gloss enhancer adjusts the dissolution rate of the alloy components further by suppressing the adsorption on these alloy surfaces or increasing the viscosity of the chemical polishing solution, while suppressing the dissolution of microscopic recesses on the alloy surface, It is presumed that the glossiness and smoothness are further improved by preferentially dissolving the microscopic projections.
【００１５】本発明の鉄−ニッケル系合金又は鉄−ニッ
ケル−コバルト系合金の化学研磨液の基本成分は過酸化
水素と硫酸から構成され、化学研磨作業時にＮＯｘガ
ス、塩化水素ガス、弗化水素ガス等の有害ガスが発生し
ないもので、又、排水規制をうける弗素、有害物が含有
されない、作業環境及び排水処理性を改善しうる化学研
磨液及び化学研磨方法である。The basic components of the iron-nickel alloy or the iron-nickel-cobalt alloy chemical polishing liquid of the present invention are composed of hydrogen peroxide and sulfuric acid. During the chemical polishing operation, NOx gas, hydrogen chloride gas and hydrogen fluoride are used. A chemical polishing liquid and a chemical polishing method which do not generate harmful gas such as gas and do not contain fluorine and harmful substances which are subject to wastewater regulation and which can improve work environment and wastewater treatment property.
【００１６】[0016]
【実施例】以下、本発明の効果を実施例・比較例につい
て説明するが、これに限定されるものではない。実施例１〜１０、比較例１〜４ 鉄−ニッケル−コバルト合金であるコバール製の電子部
品、鉄−ニッケル合金である４２アロイ板を試験片に用
い、あらかじめアルカリ脱脂、水洗した後、表−１に示
す本発明の硫酸と過酸化水素から成る各種組成の化学研
磨液に表−１に示す処理温度、処理時間の条件で浸漬
し、水洗、乾燥させ、表面光沢を目視判定する。EXAMPLES The effects of the present invention will be described below with reference to examples and comparative examples, but are not limited thereto. Examples 1 to 10 and Comparative Examples 1 to 4 Kovar electronic components, which are iron-nickel-cobalt alloys, and 42 alloy plates, which are iron-nickel alloys, were subjected to alkali degreasing and water washing in advance using test pieces. It is immersed in the chemical polishing liquid of various compositions comprising sulfuric acid and hydrogen peroxide of the present invention shown in 1 under the conditions of the processing temperature and the processing time shown in Table 1, washed with water and dried, and the surface gloss is visually determined.
【００１７】[0017]
【表１】 [Table 1]
【００１８】実施例１１〜１９、比較例５〜９ コバールの電子部品、４２アロイ板を試験片に用い、あ
らかじめアルカリ脱脂、水洗した後、表−２に示す本発
明の光沢強化剤添加有無の各種組成液に４５℃で３０秒
浸漬し、水洗、乾燥させ、表面光沢を目視判定する。評
価結果を表−３に示す。 Examples 11 to 19, Comparative Examples 5 to 9 Kovar electronic components and 42 alloy plates were used as test specimens, which were preliminarily alkali-degreased and washed with water, and as shown in Table 2, whether or not the gloss enhancing agent of the present invention was added. It is immersed in various composition liquids at 45 ° C. for 30 seconds, washed with water and dried, and the surface gloss is visually determined. Table 3 shows the evaluation results.
【００１９】[0019]
【表２】 [Table 2]
【００２０】[0020]
【表３】 [Table 3]
【００２１】[0021]
【発明の効果】本発明に係る鉄−ニッケル系合金又は鉄
−ニッケル−コバルト系合金の化学研磨液及び化学研磨
方法は、比較例に比べ、格段に優れた化学研磨効果を示
し、これらの合金に対して良好な光沢性、平滑性を付与
する。また有害なＮＯｘガス等の発生がなく、排水規制
をうける弗素や有害物等を含まない化学研磨液及び化学
研磨方法を提供することができ、工業上非常に有益であ
る。The chemical polishing solution and the chemical polishing method for the iron-nickel alloy or the iron-nickel-cobalt alloy according to the present invention exhibit a significantly superior chemical polishing effect as compared with the comparative example. Good gloss and smoothness. Further, it is possible to provide a chemical polishing solution and a chemical polishing method that do not generate harmful NOx gas and do not contain fluorine or harmful substances that are subject to drainage regulation, which is industrially very useful.
Claims (3)
００〜８３０ｇ／ｌを成分として含有する、鉄−ニッケ
ル系合金又は鉄−ニッケル−コバルト系合金の化学研磨
液。1. 85 to 200 g / l of hydrogen peroxide, sulfuric acid 1
An iron-nickel-based alloy or an iron-nickel-cobalt-based alloy chemical polishing solution containing from 0.00 to 830 g / l as a component.
（Ｂ）、（Ｃ）の１種以上を０．０１〜５０ｇ／ｌ含有
する請求項１に記載する鉄−ニッケル系合金又は鉄−ニ
ッケル−コバルト系合金の化学研磨液。 （Ａ）カチオン系、ノニオン系、両性から選ばれた界面
活性剤の１種以上。 （Ｂ）アルコール類又はエーテル類の１種以上。 （Ｃ）有機酸又はその化合物の１種以上。2. The following (A) as a gloss enhancer:
The chemical polishing solution for an iron-nickel alloy or the iron-nickel-cobalt alloy according to claim 1, which contains 0.01 to 50 g / l of at least one of (B) and (C). (A) One or more surfactants selected from cationic, nonionic and amphoteric. (B) One or more alcohols or ethers. (C) one or more organic acids or compounds thereof.
は鉄−ニッケル−コバルト系合金の化学研磨液を使用し
て、鉄−ニッケル系合金又は鉄−ニッケル−コバルト系
合金を、処理温度２０〜６０℃及び処理時間１０秒〜１
０分間処理することを特徴とする化学研磨方法。3. An iron-nickel alloy or an iron-nickel-cobalt alloy is treated with a chemical polishing solution of the iron-nickel alloy or the iron-nickel-cobalt alloy according to claim 1 or 2. 20-60 ° C and processing time 10 seconds-1
A chemical polishing method characterized by treating for 0 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33015996A JPH10158869A (en) | 1996-11-27 | 1996-11-27 | Chemical polishing liquid for iron-nickel alloy or iron-nickel-cobalt alloy and chemical polishing method therefor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP33015996A JPH10158869A (en) | 1996-11-27 | 1996-11-27 | Chemical polishing liquid for iron-nickel alloy or iron-nickel-cobalt alloy and chemical polishing method therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH10158869A true JPH10158869A (en) | 1998-06-16 |
Family
ID=18229483
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP33015996A Withdrawn JPH10158869A (en) | 1996-11-27 | 1996-11-27 | Chemical polishing liquid for iron-nickel alloy or iron-nickel-cobalt alloy and chemical polishing method therefor |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH10158869A (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001049899A3 (en) * | 1999-12-30 | 2002-05-02 | Henkel Kgaa | Brightening/passivating metal surfaces without hazard from emissions of oxides of nitrogen |
| JP2004307972A (en) * | 2003-04-09 | 2004-11-04 | Mitsui Mining & Smelting Co Ltd | Plating pretreatment liquid, and plating pretreatment method |
| US6858097B2 (en) | 1999-12-30 | 2005-02-22 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Brightening/passivating metal surfaces without hazard from emissions of oxides of nitrogen |
| KR100938735B1 (en) * | 2002-05-30 | 2010-01-26 | 미츠비시 가스 가가쿠 가부시키가이샤 | Solution for Detaching Nickel or Nickel Alloy |
| WO2012024300A2 (en) * | 2010-08-16 | 2012-02-23 | Advanced Technology Materials, Inc. | Etching solution for copper or copper alloy |
| WO2013076587A2 (en) * | 2011-09-30 | 2013-05-30 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | Etching agent for copper or copper alloy |
| CN104947113A (en) * | 2015-07-27 | 2015-09-30 | 浙江湖磨抛光磨具制造有限公司 | Environment-friendly metal polishing solution |
| CN111826657A (en) * | 2020-08-19 | 2020-10-27 | 温州奥洋科技有限公司 | Polishing solution for oxidation, coloring and polishing of copper material surface and preparation method thereof |
-
1996
- 1996-11-27 JP JP33015996A patent/JPH10158869A/en not_active Withdrawn
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6858097B2 (en) | 1999-12-30 | 2005-02-22 | Henkel Kommanditgesellschaft Auf Aktien (Henkel Kgaa) | Brightening/passivating metal surfaces without hazard from emissions of oxides of nitrogen |
| WO2001049899A3 (en) * | 1999-12-30 | 2002-05-02 | Henkel Kgaa | Brightening/passivating metal surfaces without hazard from emissions of oxides of nitrogen |
| KR100938735B1 (en) * | 2002-05-30 | 2010-01-26 | 미츠비시 가스 가가쿠 가부시키가이샤 | Solution for Detaching Nickel or Nickel Alloy |
| JP2004307972A (en) * | 2003-04-09 | 2004-11-04 | Mitsui Mining & Smelting Co Ltd | Plating pretreatment liquid, and plating pretreatment method |
| US10570522B2 (en) | 2010-08-16 | 2020-02-25 | Entegris, Inc. | Etching solution for copper or copper alloy |
| WO2012024300A2 (en) * | 2010-08-16 | 2012-02-23 | Advanced Technology Materials, Inc. | Etching solution for copper or copper alloy |
| WO2012024300A3 (en) * | 2010-08-16 | 2012-05-31 | Advanced Technology Materials, Inc. | Etching solution for copper or copper alloy |
| WO2013076587A2 (en) * | 2011-09-30 | 2013-05-30 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | Etching agent for copper or copper alloy |
| US9175404B2 (en) | 2011-09-30 | 2015-11-03 | Advanced Technology Materials, Inc. | Etching agent for copper or copper alloy |
| US9790600B2 (en) | 2011-09-30 | 2017-10-17 | Entegris, Inc. | Etching agent for copper or copper alloy |
| WO2013076587A3 (en) * | 2011-09-30 | 2013-09-19 | アドバンスド テクノロジー マテリアルズ，インコーポレイテッド | Etching agent for copper or copper alloy |
| CN104947113A (en) * | 2015-07-27 | 2015-09-30 | 浙江湖磨抛光磨具制造有限公司 | Environment-friendly metal polishing solution |
| CN111826657A (en) * | 2020-08-19 | 2020-10-27 | 温州奥洋科技有限公司 | Polishing solution for oxidation, coloring and polishing of copper material surface and preparation method thereof |
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