JPH0377877B2 - - Google Patents
Info
- Publication number
- JPH0377877B2 JPH0377877B2 JP13118988A JP13118988A JPH0377877B2 JP H0377877 B2 JPH0377877 B2 JP H0377877B2 JP 13118988 A JP13118988 A JP 13118988A JP 13118988 A JP13118988 A JP 13118988A JP H0377877 B2 JPH0377877 B2 JP H0377877B2
- Authority
- JP
- Japan
- Prior art keywords
- etching
- weight
- acid
- acetylene alcohol
- alkylene oxide
- 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
Links
- 238000005530 etching Methods 0.000 claims description 35
- 239000000654 additive Substances 0.000 claims description 15
- 230000000996 additive effect Effects 0.000 claims description 14
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 claims description 10
- -1 acetylene alcohol Chemical compound 0.000 claims description 7
- 230000001737 promoting effect Effects 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- 239000007864 aqueous solution Substances 0.000 claims description 6
- 229960003280 cupric chloride Drugs 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 238000000034 method Methods 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 4
- 238000005187 foaming Methods 0.000 description 4
- 125000002947 alkylene group Chemical group 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 239000003945 anionic surfactant Substances 0.000 description 2
- SUMDYPCJJOFFON-UHFFFAOYSA-N isethionic acid Chemical compound OCCS(O)(=O)=O SUMDYPCJJOFFON-UHFFFAOYSA-N 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- KVGOXGQSTGQXDD-UHFFFAOYSA-N 1-decane-sulfonic-acid Chemical compound CCCCCCCCCCS(O)(=O)=O KVGOXGQSTGQXDD-UHFFFAOYSA-N 0.000 description 1
- KDKIWFRRJZZYRP-UHFFFAOYSA-N 1-hydroxypropane-2-sulfonic acid Chemical compound OCC(C)S(O)(=O)=O KDKIWFRRJZZYRP-UHFFFAOYSA-N 0.000 description 1
- ZWLIPWXABAEXNY-UHFFFAOYSA-N 2-hydroxydecane-1-sulfonic acid Chemical compound CCCCCCCCC(O)CS(O)(=O)=O ZWLIPWXABAEXNY-UHFFFAOYSA-N 0.000 description 1
- HSXUNHYXJWDLDK-UHFFFAOYSA-N 2-hydroxypropane-1-sulfonic acid Chemical compound CC(O)CS(O)(=O)=O HSXUNHYXJWDLDK-UHFFFAOYSA-N 0.000 description 1
- YEGPVWSPNYPPIK-UHFFFAOYSA-N 4-hydroxybutane-1-sulfonic acid Chemical compound OCCCCS(O)(=O)=O YEGPVWSPNYPPIK-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910001413 alkali metal ion Inorganic materials 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- QDHFHIQKOVNCNC-UHFFFAOYSA-N butane-1-sulfonic acid Chemical compound CCCCS(O)(=O)=O QDHFHIQKOVNCNC-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- CCIVGXIOQKPBKL-UHFFFAOYSA-M ethanesulfonate Chemical compound CCS([O-])(=O)=O CCIVGXIOQKPBKL-UHFFFAOYSA-M 0.000 description 1
- KDKYADYSIPSCCQ-UHFFFAOYSA-N ethyl acetylene Natural products CCC#C KDKYADYSIPSCCQ-UHFFFAOYSA-N 0.000 description 1
- 229940098779 methanesulfonic acid Drugs 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- TVDSBUOJIPERQY-UHFFFAOYSA-N prop-2-yn-1-ol Chemical compound OCC#C TVDSBUOJIPERQY-UHFFFAOYSA-N 0.000 description 1
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Landscapes
- ing And Chemical Polishing (AREA)
Description
（産業上の利用分野）
本発明は、塩化第二鉄又は塩化第二銅エツチン
グ剤水溶液に添加してエツチング効果を向上、促
進するエツチング促進添加剤に関するものであ
る。
（従来の技術）
従来エツチング技術は産業用電子機器の急速な
発展にともない広い需要対応と、さらに高度な精
密処理対応が要求されている。
エツチング速度は塩化第二鉄または塩化第二銅
濃度とそのエツチング温度に起因することは知ら
れている。しかし、高濃度になると、逆にエツチ
ング速度を低下させることも知られ、その管理に
多大の労力を要し、精密度を要求される用途への
展開は限界を有する。一方温度には設備的な制約
があり、例えば塩化ビニル製スプレー設備の場合
40〜50℃が、その限界で実用的濃度、温度レベル
でのエツチング速度の向上が強く要望されてい
る。処理条件に限定のある場合、目的効果を効率
的に発揮し得る手段として界面活性剤の添加が有
用である。
界面活性剤はその湿潤、浸透作用からエツチン
グ促進および精密処理に有用である。
（発明が解決しようとする課題）
しかしながらエツチング促進を目的とする界面
活性剤は比較的高濃度レベルの塩化第二鉄または
塩化第二銅水溶液に安定に溶解し、エツチング促
進、精密処理の発現および操作上、問題となる発
泡の抑制が要求される。
ほとんどのアニオン界面活性剤、ノニオン界面
活性剤、カチオン界面活性剤および両性界面活性
剤はエツチング液への溶解安定性が劣り溶解安定
性に優れた一部アニオン界面活性剤も、発泡等の
問題を有する。
この発明は、このような従来の問題点に着目し
てなされたものである。すなわち、本発明は塩化
第二鉄又は塩化第二銅水溶液に(a)アセチレンアル
コール又はそのアルキレンオキシド付加物及び(b)
アルカンスルホン酸、アルカンスルホン酸塩、ア
ルカノールスルホン酸又はアルカノールスルホン
酸塩から成るエツチング促進添加剤を0.05〜５重
量％添加使用すること、さらにはアセチレンアル
コール又はそのアルキレンオキシド付加物をエツ
チング促進添加剤中５〜50重量％、アルカンスル
ホン酸、アルカンスルホン酸塩、アルカノールス
ルホン酸又はアルカノールスルホン酸塩をエツチ
ング促進添加剤中50〜95重量％で構成する事を特
徴とするエツチング促進添加剤を新たに提供する
ものである。
（課題を解決するための手段）
本発明に使用するアセチレンアルコールあるい
はアセチレンアルコールアルキレンオキシド付加
物は分子内にアセチレン結合（炭素三重結合）を
持つ不飽和アルコール、プロパルギルアルコー
ル、ブチンジオール等が挙げられ、アルキレンオ
キシド付加物はアセチレンアルコールにエチレン
オキシド、プロピレンオキシド、ブチレンオキシ
ド等を付加重合せしめ得られるものである。
アルカンスルホン酸はメタンスルホン酸、エタ
ンスルホン酸、プロパンスルホン酸、ブタンスル
ホン酸、デカンスルホン酸等でアルカノールスル
ホン酸は２−ヒドロキシエタン−１−スルホン
酸、２−ヒドロキシプロパン−１−スルホン酸、
１−ヒドロキシプロパン−２−スルホン酸、４−
ヒトロキシブタン−１−スルホン酸、２−ヒドロ
キシデカン−１−スルホン酸等でそれ等の塩はナ
トリウム、カリウム等アルカリ金属イオン又はア
ンモニウム等である。
（作用）
本発明エツチング促進添加剤を添加することに
より多くの界面活性剤には観られない優れた溶解
安定性とともに湿潤性、浸透性の向上が計られエ
ツチングスピードの向上、精密処理性の向上がみ
られ、さらには界面活性剤に基因する発泡は実用
上問題とならない。
（実施例）
１ エツチング効果(1)
塩化第二銅50％水溶液に第１表に示すエツチ
ング促進添加剤を1.0％添加し40℃に保持、15
分後の銅板テストピースのエツチング減量を次
式により表わす。
エツチング減量（％）エツチング前テストピース重
量−エツチング後テストピース重量／エツチング前テス
トピース重量×100
２ エツチング効果(2)
塩化第二鉄50％水溶液に第２表に示すエツチ
ング促進添加剤を2.5％添加したエツチング液
を45℃に保持、スプレー圧2.5Kg／cm2にて噴霧
20分後のステンレステストピース（アクリル系
レジストを塗布後所定パターン紫外線露光した
10cm×10cm片）のエツチング性を以下基準によ
り評価した。
基準
◎ 100％均質貫通孔が得られその仕上り性は
スムーズ。
○ 100％均質貫通孔が得られその仕上り性は
ほぼスムーズ。
△ 80〜95％レベルの貫通孔が得られる。
× 75％以下レベルの貫通孔が得られる。
(Field of Industrial Application) The present invention relates to an etching promoting additive that is added to an aqueous solution of a ferric chloride or cupric chloride etching agent to improve and promote the etching effect. (Conventional Technology) With the rapid development of industrial electronic equipment, conventional etching technology is required to meet a wide range of demands and to support even more advanced precision processing. It is known that the etching rate depends on the ferric chloride or cupric chloride concentration and the etching temperature. However, it is known that a high concentration conversely reduces the etching speed, requiring a great deal of effort to manage it, which limits its application to applications that require precision. On the other hand, there are equipment restrictions on temperature; for example, in the case of vinyl chloride spray equipment,
40 to 50°C is the limit, and there is a strong desire to improve the etching rate at a practical concentration and temperature level. When there are limitations on treatment conditions, addition of a surfactant is useful as a means of efficiently achieving the desired effect. Surfactants are useful for promoting etching and precision processing due to their wetting and penetrating effects. (Problems to be Solved by the Invention) However, surfactants for the purpose of promoting etching are stably dissolved in a relatively high concentration level of ferric chloride or cupric chloride aqueous solution. Suppression of foaming, which is a problem in operation, is required. Most anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric surfactants have poor dissolution stability in etching solutions, and some anionic surfactants that have excellent dissolution stability may also cause problems such as foaming. have This invention was made by focusing on such conventional problems. That is, the present invention provides (a) acetylene alcohol or its alkylene oxide adduct and (b) a ferric chloride or cupric chloride aqueous solution.
Addition of 0.05 to 5% by weight of an etching promoting additive consisting of alkanesulfonic acid, alkanesulfonate, alkanolsulfonic acid or alkanolsulfonate, and further adding acetylene alcohol or its alkylene oxide adduct to the etching promoting additive. A new etching accelerating additive characterized by comprising 50 to 50% by weight of alkanesulfonic acid, alkanesulfonate, alkanolsulfonic acid, or alkanolsulfonate in the etching accelerating additive. It is something to do. (Means for Solving the Problems) The acetylene alcohol or acetylene alcohol alkylene oxide adduct used in the present invention includes unsaturated alcohols having an acetylene bond (carbon triple bond) in the molecule, propargyl alcohol, butyne diol, etc. Alkylene oxide adducts are obtained by addition polymerizing ethylene oxide, propylene oxide, butylene oxide, etc. to acetylene alcohol. Alkanesulfonic acids include methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, decanesulfonic acid, etc.Alkanolsulfonic acids include 2-hydroxyethane-1-sulfonic acid, 2-hydroxypropane-1-sulfonic acid,
1-hydroxypropane-2-sulfonic acid, 4-
Hydroxybutane-1-sulfonic acid, 2-hydroxydecane-1-sulfonic acid, etc., and their salts include alkali metal ions such as sodium and potassium, or ammonium. (Function) By adding the etching accelerating additive of the present invention, excellent dissolution stability not seen in many surfactants as well as improved wettability and permeability are achieved, resulting in improved etching speed and precision processability. Furthermore, foaming caused by surfactants does not pose a practical problem. (Example) 1. Etching effect (1) Add 1.0% of the etching accelerating additive shown in Table 1 to a 50% cupric chloride aqueous solution and maintain at 40°C for 15 minutes.
The etching loss of the copper plate test piece after 5 minutes is expressed by the following formula. Etching weight loss (%) Weight of test piece before etching - Weight of test piece after etching / Weight of test piece before etching x 100 2 Etching effect (2) Add 2.5% of the etching promoting additive shown in Table 2 to a 50% aqueous solution of ferric chloride. The added etching solution was maintained at 45℃ and sprayed at a spray pressure of 2.5Kg/ cm2.
Stainless steel test piece after 20 minutes (after applying acrylic resist, exposed to UV light in a specified pattern)
The etching properties of the 10 cm x 10 cm pieces were evaluated according to the following criteria. Criteria ◎ 100% homogeneous through holes are obtained and the finish is smooth. ○ 100% homogeneous through holes are obtained and the finish is almost smooth. △ A through hole of 80-95% level is obtained. × Through holes of 75% or less level can be obtained.
【表】【table】
【表】【table】
【表】
（発明の効果）
以上の結果より、本発明品はエツチング液への
溶解安定性と濡れ性改善をはかり、エツチング効
率の向上と精密処理をはかることができ、且つエ
ツチング促進添加剤、即ち、界面活性剤に起因す
る発泡を実用上、問題とならない程度まで抑制
し、実用的、極めて優れたエツチング促進添加剤
を提供することができる。[Table] (Effects of the Invention) From the above results, the product of the present invention can improve dissolution stability and wettability in etching solutions, improve etching efficiency and perform precision processing, and also contains an etching accelerating additive, That is, it is possible to suppress foaming caused by surfactants to such an extent that it does not pose a practical problem, and to provide an extremely excellent etching accelerating additive for practical use.
Claims (1)
ルコールアルキレンオキシド付加物及び (b) アルカンスルホン酸、アルカンスルホン酸
塩、アルカノールスルホン酸又はアルカノール
スルホン酸塩を必須成分とするエツチング促進
添加剤。 ２ アセチレンアルコール又は、アセチレンアル
コールアルキレンオキシド付加物がエツチング促
進添加剤中５重量％以上50重量％以下で、アルカ
ンスルホン酸、アルカンスルホン酸塩、アルカノ
ールスルホン酸又はアルカノールスルホン酸塩が
エツチング促進添加剤中50重量％以上95重量％以
下であることを特徴とする請求項１記載のエツチ
ング促進添加剤。 ３ 塩化第二鉄又は塩化第二銅水溶液に請求項１
記載の添加剤を添加使用することを特徴とするエ
ツチング処理法。[Scope of Claims] 1. An etching promoting additive containing (a) an acetylene alcohol or an acetylene alcohol alkylene oxide adduct and (b) an alkanesulfonic acid, an alkanesulfonate, an alkanolsulfonic acid, or an alkanolsulfonate as essential components. 2. Acetylene alcohol or acetylene alcohol alkylene oxide adduct is 5% by weight or more and 50% by weight or less in the etching-promoting additive, and alkanesulfonic acid, alkanesulfonate, alkanolsulfonic acid, or alkanolsulfonate is in the etching-promoting additive. The etching accelerating additive according to claim 1, characterized in that the content is 50% by weight or more and 95% by weight or less. 3 Claim 1 for ferric chloride or cupric chloride aqueous solution
An etching treatment method characterized by using the additives described above.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13118988A JPH01301869A (en) | 1988-05-27 | 1988-05-27 | Etching accelerating additive |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13118988A JPH01301869A (en) | 1988-05-27 | 1988-05-27 | Etching accelerating additive |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01301869A JPH01301869A (en) | 1989-12-06 |
| JPH0377877B2 true JPH0377877B2 (en) | 1991-12-11 |
Family
ID=15052100
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13118988A Granted JPH01301869A (en) | 1988-05-27 | 1988-05-27 | Etching accelerating additive |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01301869A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4428995B2 (en) | 2003-12-03 | 2010-03-10 | 関東化学株式会社 | Etching solution composition for metal film |
| EP2010477A4 (en) * | 2006-04-27 | 2012-05-30 | Intezyne Technologies Inc | Poly (ethylene glycol) containing chemically disparate endgroups |
| JP2016017209A (en) * | 2014-07-08 | 2016-02-01 | メック株式会社 | Etching agent and replenishing liquid |
-
1988
- 1988-05-27 JP JP13118988A patent/JPH01301869A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01301869A (en) | 1989-12-06 |
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