JPS6231070B2 - - Google Patents
Info
- Publication number
- JPS6231070B2 JPS6231070B2 JP17135781A JP17135781A JPS6231070B2 JP S6231070 B2 JPS6231070 B2 JP S6231070B2 JP 17135781 A JP17135781 A JP 17135781A JP 17135781 A JP17135781 A JP 17135781A JP S6231070 B2 JPS6231070 B2 JP S6231070B2
- Authority
- JP
- Japan
- Prior art keywords
- copper
- acid
- hydrogen peroxide
- solution
- soft 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
Links
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 35
- 229910052802 copper Inorganic materials 0.000 claims description 35
- 239000010949 copper Substances 0.000 claims description 35
- 239000002253 acid Substances 0.000 claims description 12
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 11
- 239000011707 mineral Substances 0.000 claims description 11
- 238000005530 etching Methods 0.000 claims description 10
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 150000008107 benzenesulfonic acids Chemical class 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 16
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 14
- 238000007747 plating Methods 0.000 description 13
- 235000010755 mineral Nutrition 0.000 description 9
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- RPAJSBKBKSSMLJ-DFWYDOINSA-N (2s)-2-aminopentanedioic acid;hydrochloride Chemical class Cl.OC(=O)[C@@H](N)CCC(O)=O RPAJSBKBKSSMLJ-DFWYDOINSA-N 0.000 description 5
- DIZBQMTZXOUFTD-UHFFFAOYSA-N 2-(furan-2-yl)-3h-benzimidazole-5-carboxylic acid Chemical compound N1C2=CC(C(=O)O)=CC=C2N=C1C1=CC=CO1 DIZBQMTZXOUFTD-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- -1 chlorine ions Chemical class 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 150000002989 phenols Chemical class 0.000 description 5
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WQGWDDDVZFFDIG-UHFFFAOYSA-N pyrogallol Chemical compound OC1=CC=CC(O)=C1O WQGWDDDVZFFDIG-UHFFFAOYSA-N 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 235000019270 ammonium chloride Nutrition 0.000 description 3
- 150000001805 chlorine compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- SRSXLGNVWSONIS-UHFFFAOYSA-N benzenesulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC=C1 SRSXLGNVWSONIS-UHFFFAOYSA-N 0.000 description 2
- 229940092714 benzenesulfonic acid Drugs 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229940079877 pyrogallol Drugs 0.000 description 2
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- AXZKCQSGDARVRL-UHFFFAOYSA-N 2-hydroxy-5-methylbenzenesulfonic acid Chemical compound CC1=CC=C(O)C(S(O)(=O)=O)=C1 AXZKCQSGDARVRL-UHFFFAOYSA-N 0.000 description 1
- BRIXOPDYGQCZFO-UHFFFAOYSA-N 4-ethylphenylsulfonic acid Chemical compound CCC1=CC=C(S(O)(=O)=O)C=C1 BRIXOPDYGQCZFO-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- OATNQHYJXLHTEW-UHFFFAOYSA-N benzene-1,4-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=C(S(O)(=O)=O)C=C1 OATNQHYJXLHTEW-UHFFFAOYSA-N 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XEMZLVDIUVCKGL-UHFFFAOYSA-N hydrogen peroxide;sulfuric acid Chemical compound OO.OS(O)(=O)=O XEMZLVDIUVCKGL-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 235000002639 sodium chloride Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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
- C23F1/18—Acidic compositions for etching copper or alloys thereof
-
- 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
- H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
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
本発明は、銅のソフトエツチング剤に関するも
のである。
プリント配線板を作製するに際し、回路の精密
化に伴い、銅張積層板に孔あけ等の加工をした
後、これに無電解銅メツキをはじめとする種々の
メツキ加工を行なうことが多くなつている。この
場合、銅張積層板の銅ハク表面の酸化被膜や汚れ
を取り除き、表面を荒らし、無電解メツキの密着
性を向上させるため表面をごく浅く腐シヨクさせ
る、いわゆるソフトエツチングという工程があ
り、この工程は不可欠で重要なものである。
このソフトエツチング剤としては、従来、過硫
酸アンモニウムが広く用いられているが、液寿命
が短く、頻繁に建浴する必要があり、廃液処理に
も問題があつた。
このような欠点を排除するために、発明者らは
鉱酸（塩酸を除く−−以下単に鉱酸と称す）、過
酸化水素溶液に注目した。しかしこの鉱酸、過酸
化水素溶液は、銅の溶解速度が速く、銅表面の粗
化もそれほどなされず、さらに溶解に際し、過酸
化水素の無効分解により銅表面から酸素の気泡が
発生し一部それらが銅表面に付着すること等によ
り均一な表面が得られにくい。又これらの気泡は
ミストの飛散へとつながり作業環境の悪化等種々
の問題があつた。
本発明者らは、これらの問題を解決するため鋭
意研究した結果、鉱酸、過酸化水素溶液において
過酸化水素の無効分解による銅表面かからの気泡
の発生を抑制するとともに銅の溶解速度を抑制
し、銅表面を粗化できる本発明に到達した。
すなわち、本発明は、鉱酸、過酸化水素からな
る液に、過酸化水素の無効分解による銅表面から
の気泡の発生の抑制、銅の溶解速度抑制、表面粗
化の目的でフエノール類およびベンゼンスルホン
酸類から選ばれた化合物を１種又は２種以上添加
することを特徴とする、銅のソフトエツチング剤
である。この溶液において遊離塩素イオンを適量
添加すれば、さらに銅の溶解速度を抑制し、希望
する溶解速度が得られるとともに、銅の表面はさ
らに粗化される。
本発明で使用する鉱酸および過酸化水素の濃度
範囲は、１〜500ｇ／であり、フエノール類、
ベンゼンスルホン酸類の濃度範囲は、0.1〜100
ｇ／である。また遊離塩素イオンの濃度範囲
は、0.1〜1000ppmであり、処理温度は、５〜60
℃である。各成分の好ましい濃度および好ましい
処理温度の設定は、作業性、経済性の観点から、
鉱酸10〜300ｇ／、過酸化水素10〜300ｇ／、
フエノール類、ベンゼンスルホン酸類１〜50ｇ／
、遊離塩素イオン0.1〜200ppmであり、処理温
度は20〜40℃である。
本発明に使用する鉱酸としては、硫酸、硝酸、
リン酸等があげられ、これらの混酸も使用でき
る。
フエノール類としては、フエノール、３・５−
キシレール、カテコール、レゾルシン、ヒドロキ
ノン、ピロガロールがあり、ベンゼンスルホン酸
類としては、ベンゼンスルホン酸、スルホサリチ
ル酸、Ｐ−ベンゼンジスルホン酸、１−エチル−
４−スルホベンゼン、Ｐ−フエノールスルホン
酸、Ｐ−クレゾールスルホン酸、Ｐ−トルエンス
ルホン酸、等であるが、過酸化水素−硫酸溶液に
おいてある程度の溶解度を有するものでなければ
ならない。
また、これらのフエノール類およびベンゼンス
ルホン酸類は、過酸化水素の安定剤としても作用
し、本発明を一層有用ならしめるものである。
遊離塩素イオンとしては、過酸化水素−鉱酸溶
液に可溶性の塩化物あるいは、実質的に液中で塩
素イオンを遊離する無機、有機化合物で、過酸化
水素の分解に対して不活性な塩化物を使用するこ
とが望ましく、この意味からもごく一般的な塩化
物である塩化ナトリウム、塩化カリウム、塩化ア
ンモニウム、および塩酸等が適当である。
銅のソフトエツチングは、本発明のソフトエツ
チング剤に無電解銅メツキ前の銅張積層板を浸せ
きすることによつて行ない得る。
本発明によれば、数十秒〜数分の処理により銅
表面を粗化し、その後活性化処理を施し、無電解
銅メツキを行なえば、充分な密着強度が得られ
る。
また、過酸化水素の安定性が良いため、使用中
途液を２〜３週間放置しても効力を失する事なく
使用できる。また、エツチング処理によつて消耗
された溶液成分を適宜補充する等の方法によりコ
ントロールされた状態で連続的な処理も可能であ
る。
さらに、操作が簡単であること、鉱酸、過酸化
水素を基本成分とするため銅の回収が容易である
こと公害問題を引き起こすことのないこと等実用
上多くの価値を有するソフトエツチング剤を提供
するものである。
以下に本発明を参考例および実施例により詳し
く説明する。
参考例 １
過酸化水素60ｇ／、硫酸200ｇ／の組成液
に、フエノール10ｇ／を添加した液、Ｐ−フエ
ノールスルホン酸10ｇ／を添加した液、Ｐ−ト
ルエンスルホン酸10ｇ／を添加した液、カテコ
ールを添加した液、および無添加の液、以上五種
の液に、銅張積層板を30℃にてそれぞれ浸せきし
たときの30分間におけるガス発生量を測定したと
ころ、第一表のような結果となつた。
The present invention relates to a soft etching agent for copper. When producing printed wiring boards, as circuits become more precise, it is becoming increasingly common to perform various plating processes, including electroless copper plating, after drilling holes and other processes on copper-clad laminates. There is. In this case, there is a process called soft etching that removes the oxide film and dirt from the copper surface of the copper clad laminate, roughens the surface, and etches the surface very shallowly to improve the adhesion of electroless plating. Processes are essential and important. Conventionally, ammonium persulfate has been widely used as this soft etching agent, but the solution life is short, it is necessary to prepare a bath frequently, and there are also problems in waste liquid treatment. In order to eliminate such drawbacks, the inventors focused on mineral acids (excluding hydrochloric acid--hereinafter simply referred to as mineral acids) and hydrogen peroxide solutions. However, this mineral acid and hydrogen peroxide solution dissolves copper at a fast rate and does not roughen the copper surface much. Furthermore, during dissolution, oxygen bubbles are generated from the copper surface due to the ineffective decomposition of hydrogen peroxide. Due to their adhesion to the copper surface, it is difficult to obtain a uniform surface. Furthermore, these bubbles lead to the scattering of mist, resulting in various problems such as deterioration of the working environment. As a result of intensive research to solve these problems, the present inventors have succeeded in suppressing the generation of bubbles from the copper surface due to the ineffective decomposition of hydrogen peroxide in mineral acid and hydrogen peroxide solutions, and increasing the dissolution rate of copper. We have arrived at the present invention, which can suppress and roughen the copper surface. That is, the present invention adds phenols and benzene to a solution consisting of a mineral acid and hydrogen peroxide for the purpose of suppressing the generation of bubbles from the copper surface due to ineffective decomposition of hydrogen peroxide, suppressing the dissolution rate of copper, and roughening the surface. This is a copper soft etching agent characterized by adding one or more compounds selected from sulfonic acids. If an appropriate amount of free chlorine ions is added to this solution, the dissolution rate of copper can be further suppressed, a desired dissolution rate can be obtained, and the surface of the copper can be further roughened. The concentration range of mineral acid and hydrogen peroxide used in the present invention is 1 to 500 g/, and phenols,
The concentration range of benzenesulfonic acids is 0.1 to 100
g/. The concentration range of free chlorine ions is 0.1 to 1000 ppm, and the treatment temperature is 5 to 60 ppm.
It is ℃. The preferred concentration of each component and the preferred processing temperature are determined from the viewpoints of workability and economic efficiency.
Mineral acid 10-300g/, Hydrogen peroxide 10-300g/,
Phenols, benzenesulfonic acids 1-50g/
, free chlorine ions are 0.1~200ppm, and the processing temperature is 20~40℃. Mineral acids used in the present invention include sulfuric acid, nitric acid,
Examples include phosphoric acid, and mixed acids thereof can also be used. As phenols, phenol, 3.5-
There are xyler, catechol, resorcinol, hydroquinone, and pyrogallol, and benzenesulfonic acids include benzenesulfonic acid, sulfosalicylic acid, P-benzenedisulfonic acid, and 1-ethyl-
4-sulfobenzene, P-phenolsulfonic acid, P-cresolsulfonic acid, P-toluenesulfonic acid, etc., but they must have a certain degree of solubility in the hydrogen peroxide-sulfuric acid solution. Furthermore, these phenols and benzenesulfonic acids also act as stabilizers for hydrogen peroxide, making the present invention even more useful. Free chlorine ions include chlorides that are soluble in the hydrogen peroxide-mineral acid solution, or chlorides that are inert to the decomposition of hydrogen peroxide and are inorganic or organic compounds that substantially release chlorine ions in the solution. From this point of view, very common chlorides such as sodium chloride, potassium chloride, ammonium chloride, and hydrochloric acid are suitable. Copper soft etching can be carried out by dipping the copper clad laminate before electroless copper plating in the soft etching agent of the present invention. According to the present invention, sufficient adhesion strength can be obtained by roughening the copper surface by treatment for several tens of seconds to several minutes, followed by activation treatment and electroless copper plating. Further, since hydrogen peroxide has good stability, the solution can be used without losing its effectiveness even if the solution is left for 2 to 3 weeks. It is also possible to carry out continuous processing in a controlled manner by appropriately replenishing the solution components consumed by the etching process. Furthermore, we provide a soft etching agent that has many practical values, such as being easy to operate, containing mineral acid and hydrogen peroxide as basic ingredients, making it easy to recover copper, and not causing pollution problems. It is something to do. The present invention will be explained in detail below using reference examples and examples. Reference example 1 A solution containing 60 g of hydrogen peroxide and 200 g of sulfuric acid, a solution containing 10 g of phenol, a solution containing 10 g of P-phenolsulfonic acid, a solution containing 10 g of P-toluenesulfonic acid, and catechol. When copper-clad laminates were immersed in the above five types of liquids at 30°C, with and without additives, the amount of gas generated in 30 minutes was measured, and the results are shown in Table 1. It became.
【表】
ここで、銅表面の発泡状態は、無添加＞カテコ
ール＞フエノール＞ｐ−フエノールスルホン酸＞
ｐ−トルエンスルホン酸の順であり、Ｐ−トルエ
ンスルホン酸を添加したものは、ほとんど発泡し
なかつた。
参考例 ２
過酸化水素60ｇ／、硫酸200ｇ／、Ｐ−ト
ルエンスルホン酸10ｇ／、Ｐ−フエノールスル
ホン酸５ｇ／の組成液に塩化アンモニウムを
各々０、２、３、４、7ppm添加したときの30℃
における銅の溶解速度は、第二表のような結果と
なつた。[Table] Here, the foaming state of the copper surface is: No additives > Catechol > Phenol > p-phenolsulfonic acid >
p-toluenesulfonic acid was ranked first, and those to which p-toluenesulfonic acid was added hardly foamed. Reference example 2 30 when ammonium chloride was added at 0, 2, 3, 4, and 7 ppm to a composition solution of hydrogen peroxide 60 g/, sulfuric acid 200 g/, P-toluenesulfonic acid 10 g/, and P-phenolsulfonic acid 5 g/ respectively. ℃
The dissolution rate of copper was as shown in Table 2.
【表】
実施例 １
過酸化水素40ｇ／、硫酸200ｇ／、フエノ
ール５ｇ／の組成液に銅張積層板を60秒浸せき
し、電子顕微鏡にて表面状態を観察した所非常に
荒れていた。又、このものに無電解銅メツキを５
μ施し、続いて電解銅メツキを30μ施したもの
は、充分な密着強度をもつていた。
実施例 ２
過酸化水素70ｇ／、硫酸150ｇ／、Ｐ−ト
ルエンスルホン酸20ｇ／、Ｐ−フエノールスル
ホン酸10ｇ／、塩化アンモニウム4PPmからな
る組成液に銅張積層板を90秒浸せきした所、表面
は非常に荒れていた。又、このものに無電解銅メ
ツキおよび電解銅メツキをそれぞれ５μ、および
30μ施したものは、充分な密着強度をもつてい
た。
実施例 ３
過酸化水素60ｇ／、硫酸100ｇ／、硝酸70
ｇ／、Ｐ−トルエンスルホン酸10ｇ／、塩化
ナトリウム3ppmからなる組成液に銅張積層板を
60秒浸せきした所表面は非常に荒れていた。又、
このものに無電解銅メツキおよび電解銅メツキを
それぞれ５μ、30μ施したものは充分な密着強度
をもつていた。
実施例 ４
過酸化水素50ｇ／、硫酸150ｇ／、ヒドロ
キノン５ｇ／、ベンゼンスルホン酸10ｇ／か
らなる組成液に銅張積層板を30秒浸せきし、電子
顕微鏡にて表面状態を観察したところ非常に荒れ
ていた。また、このものに無電解銅メツキ及び電
解銅メツキをそれぞれ５μ及び30μ施したもの
は、充分な密着強度を持つていた。
実施例 ５
過酸化水素50ｇ／、硫酸200ｇ／、ピロガ
ロール２ｇ／、ｐ−クレゾールスルホン酸10
ｇ／からなる組成液に銅張積層板を30秒浸せき
し、電子顕微鏡にて表面状態を観察したところ非
常に荒れていた。また、このものに無電解銅メツ
キ及び電解銅メツキをそれぞれ５μ及び30μ施し
たものは、充分な密着強度を持つていた。[Table] Example 1 A copper-clad laminate was immersed for 60 seconds in a solution containing 40 g of hydrogen peroxide, 200 g of sulfuric acid, and 5 g of phenol, and the surface condition was observed under an electron microscope and found to be extremely rough. Also, electroless copper plating is applied to this item.
The product that was coated with μ and then electrolytically plated with 30μ had sufficient adhesion strength. Example 2 When a copper-clad laminate was immersed for 90 seconds in a composition solution consisting of 70 g of hydrogen peroxide, 150 g of sulfuric acid, 20 g of P-toluenesulfonic acid, 10 g of P-phenolsulfonic acid, and 4 PPm of ammonium chloride, the surface It was very rough. In addition, 5μ of electroless copper plating and electrolytic copper plating were applied to this product, respectively.
The one coated with 30μ had sufficient adhesion strength. Example 3 Hydrogen peroxide 60g/, sulfuric acid 100g/, nitric acid 70g
Copper-clad laminates were placed in a composition solution consisting of g/g/, P-toluenesulfonic acid 10 g/, and sodium chloride 3 ppm.
After soaking for 60 seconds, the surface was very rough. or,
This material was coated with electroless copper plating and electrolytic copper plating of 5μ and 30μ, respectively, and had sufficient adhesion strength. Example 4 A copper-clad laminate was immersed for 30 seconds in a solution consisting of 50 g of hydrogen peroxide, 150 g of sulfuric acid, 5 g of hydroquinone, and 10 g of benzenesulfonic acid, and the surface condition was observed using an electron microscope. was. In addition, this material was coated with electroless copper plating and electrolytic copper plating of 5μ and 30μ, respectively, and had sufficient adhesion strength. Example 5 Hydrogen peroxide 50g/, sulfuric acid 200g/, pyrogallol 2g/, p-cresolsulfonic acid 10
A copper-clad laminate was immersed in a composition solution consisting of 30 g/g for 30 seconds, and its surface condition was observed using an electron microscope, and it was found to be extremely rough. In addition, this material was coated with electroless copper plating and electrolytic copper plating of 5μ and 30μ, respectively, and had sufficient adhesion strength.
Claims (1)
る溶液に、フエノールおよびベンゼンスルホン酸
類から選ばれた化合物を１種、または２種類以上
添加することを特徴とする銅のソフトエツチング
剤。 ２ 遊離塩素イオンを更に添加することを特徴と
する、特許請求の範囲第１項記載の、銅のソフト
エツチング剤。[Claims] 1. A method for producing copper, characterized in that one or more compounds selected from phenol and benzenesulfonic acids are added to a solution consisting of a mineral acid (excluding hydrochloric acid) and hydrogen peroxide. Soft etching agent. 2. A soft etching agent for copper according to claim 1, characterized in that free chloride ions are further added.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17135781A JPS5873775A (en) | 1981-10-28 | 1981-10-28 | Soft etching agent for copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17135781A JPS5873775A (en) | 1981-10-28 | 1981-10-28 | Soft etching agent for copper |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5873775A JPS5873775A (en) | 1983-05-04 |
| JPS6231070B2 true JPS6231070B2 (en) | 1987-07-06 |
Family
ID=15921681
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17135781A Granted JPS5873775A (en) | 1981-10-28 | 1981-10-28 | Soft etching agent for copper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5873775A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62134871U (en) * | 1986-02-20 | 1987-08-25 | ||
| JPH01132520U (en) * | 1988-02-22 | 1989-09-08 | ||
| JPH0323087U (en) * | 1989-01-06 | 1991-03-11 |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6926922B2 (en) * | 2002-04-09 | 2005-08-09 | Shipley Company, L.L.C. | PWB manufacture |
| DE10313517B4 (en) * | 2003-03-25 | 2006-03-30 | Atotech Deutschland Gmbh | Solution for etching copper, method for pretreating a layer of copper and application of the method |
| CN110528038B (en) * | 2019-10-16 | 2021-09-03 | 中电国基南方集团有限公司 | Method for improving welding performance of copper surface for packaging shell after heat sink gold plating |
-
1981
- 1981-10-28 JP JP17135781A patent/JPS5873775A/en active Granted
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS62134871U (en) * | 1986-02-20 | 1987-08-25 | ||
| JPH01132520U (en) * | 1988-02-22 | 1989-09-08 | ||
| JPH0323087U (en) * | 1989-01-06 | 1991-03-11 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5873775A (en) | 1983-05-04 |
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