JPH0379778A - Copper etching solution composition and etching method - Google Patents
Copper etching solution composition and etching methodInfo
- Publication number
- JPH0379778A JPH0379778A JP21542889A JP21542889A JPH0379778A JP H0379778 A JPH0379778 A JP H0379778A JP 21542889 A JP21542889 A JP 21542889A JP 21542889 A JP21542889 A JP 21542889A JP H0379778 A JPH0379778 A JP H0379778A
- Authority
- JP
- Japan
- Prior art keywords
- etching
- soln
- etching solution
- copper
- hydrogen peroxide
- 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.)
- Pending
Links
- 238000005530 etching Methods 0.000 title claims abstract description 86
- 229910052802 copper Inorganic materials 0.000 title claims description 20
- 239000010949 copper Substances 0.000 title claims description 20
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 19
- 239000000203 mixture Substances 0.000 title claims description 14
- 238000000034 method Methods 0.000 title claims description 11
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000012964 benzotriazole Substances 0.000 claims abstract description 12
- CMGDVUCDZOBDNL-UHFFFAOYSA-N 4-methyl-2h-benzotriazole Chemical compound CC1=CC=CC2=NNN=C12 CMGDVUCDZOBDNL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229920001223 polyethylene glycol Polymers 0.000 claims abstract description 6
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims abstract description 3
- 150000001298 alcohols Chemical class 0.000 claims abstract 2
- 239000007788 liquid Substances 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 150000002500 ions Chemical class 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- -1 monoarsenic peroxide Chemical class 0.000 description 19
- 239000000460 chlorine Substances 0.000 description 14
- 229910052801 chlorine Inorganic materials 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 125000003944 tolyl group Chemical group 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 description 1
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- COUNCWOLUGAQQG-UHFFFAOYSA-N copper;hydrogen peroxide Chemical compound [Cu].OO COUNCWOLUGAQQG-UHFFFAOYSA-N 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
Landscapes
- ing And Chemical Polishing (AREA)
- Manufacturing Of Printed Circuit Boards (AREA)
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野］
本発明は、プリント回路基板の製造等に使用される銅の
エツチング液組成物およびエツチング方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a copper etching solution composition and an etching method used for manufacturing printed circuit boards and the like.
［従来の技術］
従来、銅のエツチングは、電子部品等、特にプリント回
路基板の製造に欠くことができないプロセスである。[Prior Art] Traditionally, copper etching has been an indispensable process in the manufacture of electronic components, particularly printed circuit boards.
この銅のエツチング液としては、■塩化第二鉄系、■塩
１ヒ銅系、■過硫酸アンモニウム系、■塩素酸ナトリウ
ム系が知られているが最近、Ｏ工価格で廃液の処理が容
易であり、かつ取り扱いの容易さ、および使用後のエツ
チング液からの銅の回収や硫酸の再利用が比較的容易な
ことから、硫酸と過酸１ヒ水素からなるエツチング液系
がプリント回路基板の製造に多用されるようになってき
た。プリント回路基板のエツチングでは、エツチング速
度が一定でないと、エツチングにより形成された銅回路
が更にサイドエツチングされ、個々の回路の回路幅が不
均一となるため、エツチング速度を一定にする必要があ
る。しかしながら、この硫酸と過酸化水素からなるエツ
チング液系の使用前あるいは使用中に塩素イオンが２
ＰＰｆｌ１以上混入してくると、エツチング速度が大幅
に低下するという問題がある。Known etching solutions for this copper include ferric chloride, cupric chloride, ammonium persulfate, and sodium chlorate. Etching solution systems consisting of sulfuric acid and monoarsenic peroxide are used in the manufacture of printed circuit boards because they are easy to handle, and it is relatively easy to recover copper from etching solutions after use and reuse sulfuric acid. It has come to be widely used. When etching a printed circuit board, if the etching speed is not constant, the copper circuit formed by etching will be further side-etched, resulting in uneven circuit widths of individual circuits, so it is necessary to keep the etching speed constant. However, before or during use of this etching solution system consisting of sulfuric acid and hydrogen peroxide, 2 chloride ions are released.
When PPfl1 or more is mixed in, there is a problem that the etching speed is significantly reduced.
例えば、水道水中に含まれる塩素イオンは５０〜２５０
ｐｐｍもあるため、水道水で洗浄したエツチング装置に
エツチング液を入れただけで、塩素イオンは２ ｐｐｍ
を越える。これによって、エツチング速度を大幅に落と
すことになる。従って、エツチング装置の洗浄も、プリ
ント回路基板の前処理も塩素イオンの入らない純水を使
用する必要がある。さらに、塩化銅系のエツチング液を
使用していた装置を、硫酸と過酸化水素からなるエツチ
ング液系に切り換える場合、いくら純水で洗浄したとし
ても塩素イオンが残存するという理由により、−度、塩
化銅系のエツチング液を使用した装置では、硫酸と過酸
化水素からなるエツチング液系の使用は実質上不可能で
あった。For example, the chlorine ions contained in tap water are 50 to 250.
ppm, so if you just put the etching solution into an etching device that has been cleaned with tap water, the chlorine ions will be 2 ppm.
exceed. This significantly reduces the etching speed. Therefore, it is necessary to use pure water that does not contain chlorine ions for cleaning the etching equipment and pre-treating printed circuit boards. Furthermore, when switching from an etching solution based on copper chloride to an etching solution based on sulfuric acid and hydrogen peroxide, chlorine ions remain no matter how much pure water is used for cleaning. In an apparatus using a copper chloride-based etching solution, it was virtually impossible to use an etching solution system consisting of sulfuric acid and hydrogen peroxide.
［発明が解決しようとする問題点］
この問題を解決するために硝酸銀を添加することによっ
て塩素イオンを塩化銀として排除する方法が考えられは
したが、銀イオンの添加はエツチング液組成物である過
酸化水素を異常に不安定にし、期待するエツチング速度
の回復がみられない。本発明者らは、特願昭６３−６６
７０９号に才３いて、硫酸と過酸化水素からなる銅のエ
ツチング液系に塩素イオンが混入することによるエツチ
ング速度の低下を防止することができ、また塩素イオン
が混入してエツチング速度を低下をしたエツチング液を
ある程度回復させることができるベン′ゾ°トリアソ゛
−ルおよび／またトリルトリアゾ−ルを含有させたＩＰ
Ｊのエッチングン夜組戒↑勿およびエツチング方法を開
示している。[Problems to be Solved by the Invention] In order to solve this problem, a method of eliminating chloride ions as silver chloride by adding silver nitrate has been considered, but the addition of silver ions is not possible in the etching solution composition. Hydrogen peroxide becomes abnormally unstable and the expected etching rate does not recover. The inventors of the present invention have applied for patent application No. 63-66.
In No. 709, it is possible to prevent a decrease in the etching rate due to the contamination of chlorine ions in a copper etching solution system consisting of sulfuric acid and hydrogen peroxide, and also to prevent a decrease in the etching rate due to the contamination of chlorine ions. An IP containing benzotriasol and/or tolyltriazole that can recover the etching solution to some extent.
J's etching night group precepts↑museum and etching methods are disclosed.
しかしながら、このベンゾトリアゾールおよび７／′ま
たトリルトリアゾールを含有させたエツチング溶液は、
ある程度塩素イオンに対する回復力はあるが、これらの
含有されたエツチング液だけでは塩素イオンの影響を完
全に取り除くことはできない。また、ベンゾトリアゾー
ルおよび／またはトリルトリアゾールの添加量を塩素イ
オン２〜３０ｐｐｍに対して１００〜２５００ｐｐｍの
範囲で添加する必要があった。However, this etching solution containing benzotriazole and 7/' also tolyltriazole
Although there is a certain degree of resilience against chlorine ions, the effects of chlorine ions cannot be completely removed by the etching solutions that contain them. Further, it was necessary to add benzotriazole and/or tolyltriazole in an amount of 100 to 2500 ppm relative to 2 to 30 ppm of chlorine ions.
［発明の構成］
本発明者らは、前記の問題を解決するため、鋭意研究し
た結果、酸性過酸化水素の銅エツチング溶液に対する有
効な安定化添加剤としての低級飽和脂肪族アルコール（
米国特許
第３５９７２９０号）およびモノまたはポリ形のエチレ
ングリコール類（米国特許
第３７７３５７８号）のいずれかである公知の系にベン
ゾトリアゾールおよび／またはトリルトリアゾールを単
独または併用して添加することで、塩素イオンの影響を
完全に除き、エツチング速度を回復させることを見出し
た。しかもこれらの相乗効果により、従来のベンゾトリ
アゾールおよび／またはトリルトリアゾールの添加量を
少なくすることができることをも見出し、本発明を完成
するに至った。[Structure of the Invention] In order to solve the above-mentioned problem, the present inventors have conducted extensive research and found that a lower saturated aliphatic alcohol (
The addition of benzotriazole and/or tolyltriazole, alone or in combination, to known systems, either U.S. Pat. No. 3,597,290) and mono- or polyethylene glycols (U.S. Pat. No. 3,773,578) It has been found that the influence of ions can be completely removed and the etching rate can be restored. Furthermore, the inventors have also discovered that due to these synergistic effects, it is possible to reduce the amount of conventional benzotriazole and/or tolyltriazole added, and have completed the present invention.
すなわち、本発明は、硫酸、過酸化水素。That is, the present invention uses sulfuric acid and hydrogen peroxide.
アルコール類からなるエツチング液に、ベンゾトリアゾ
ールおよび／またはトリルトリアゾールを含有させたこ
とからなる銅のエツチング液組成物、およびこのエツチ
ング液組成物を用いる銅のエツチング方法である。本発
明によって、硫酸と過酸１ヒ水素からなるエツチング液
系に塩素イオンが混入することによって起こるエツチン
グ速度の低下を、完全に防止すること、および銅のエツ
チング速度を回復させることが可能となる。The present invention provides a copper etching liquid composition comprising benzotriazole and/or tolyltriazole added to an alcohol-based etching liquid, and a copper etching method using this etching liquid composition. According to the present invention, it is possible to completely prevent a decrease in the etching rate caused by the mixing of chlorine ions into an etching solution system consisting of sulfuric acid and monoarsenic peroxide, and to restore the etching rate of copper. .
本発明の銅のエツチング液組成物において、−１えば使
用されるエツチング液の主成分である硫酸の濃度範囲は
、５〜２５容量パーセントであり、より好ましくは８〜
１６容量パーセントである。この硫酸は市販の約９８パ
ーセント濃度のものを使用する。過酸化水素系の濃度範
囲は３〜２０容量パーセントであり、より好ましくは６
〜１２容量パーセントである。この過酸化水素は市販の
約３５パーセントのものを使用する。低級飽和脂肪族ア
ルコール類は、例えばメタノール。In the copper etching solution composition of the present invention, -1, for example, the concentration range of sulfuric acid, which is the main component of the etching solution used, is 5 to 25 volume percent, more preferably 8 to 25 percent by volume.
16% by volume. The commercially available sulfuric acid with a concentration of about 98% is used. The concentration range of the hydrogen peroxide system is 3 to 20 volume percent, more preferably 6
~12 volume percent. About 35% commercially available hydrogen peroxide is used. Examples of lower saturated aliphatic alcohols include methanol.
エタノール、ｎ−プロパツール、イソプロパツール、ブ
タノールであり、これらを０．１〜５．０容量パーセン
ト、好ましくは０．２〜２、Ｏ容量パーセント含有する
ものである。また、モノまたはポリ形のいずれかのエチ
レングリコール類を０゜１〜・５，０容景パーセント、
好ましくは０．２〜２．０容量パーセントを単独または
併用して添加することができる。また、ベンゾトリアゾ
ールおよび／またはトリル斗リアゾールの濃度範囲は、
５０〜・２５０００ｐｐｔｎであり、好ましくは１５０
〜１０００’Ｏｐｐｍである。酸性過酸化水素の銅エツ
チング液に対する有効な安定化添加剤である低級飽和脂
肪族アルコールおよび／またはモノまたはポリ形のエチ
レングリコールのみを使用した場合は、塩素イオンに対
しての影響を改良する効果はあるものの、エツチング速
度を完全に元にもどすことはできない。このため、ベン
ゾ１〜リアゾールおよび／またはトリルトリアゾールを
ｆＪＦ用する使用法が不可欠である。Ethanol, n-propanol, isopropanol, butanol, containing 0.1 to 5.0 volume percent, preferably 0.2 to 2, O volume percent. In addition, 0.1 to 5.0 volume percent of ethylene glycol, either mono or poly,
Preferably, 0.2 to 2.0 volume percent can be added alone or in combination. In addition, the concentration range of benzotriazole and/or tolyl-diazole is
50 to 25,000 pptn, preferably 150
~1000'Oppm. An effective stabilizing additive for acidic hydrogen peroxide copper etching solutions, the effect of improving the effect on chloride ions when using only lower saturated aliphatic alcohols and/or ethylene glycol in mono or poly form However, the etching speed cannot be completely restored. For this reason, the use of benzo-1-lyazole and/or tolyltriazole as fJF is essential.
こｌしらの添加剤は、エツチング液中の過酸化水素の安
定性にも影響せず、本発明のエツチング速度が低下する
ことなく使用できる。更に、エツチング中において、塩
素イオンが増加することにより、エツチング速度が低下
する場合は、本発明の化合物類を補充することでエツチ
ング速度を回復することができる。これらの化合物の相
乗効果の（幾横については不明瞭ではあるが、本発明の
組成物は産業上、非常に有効な銅のエツチング４（１成
物である。These additives do not affect the stability of hydrogen peroxide in the etching solution and can be used without reducing the etching rate of the present invention. Furthermore, during etching, if the etching rate decreases due to an increase in chloride ions, the etching rate can be restored by supplementing the compounds of the present invention. Although the extent of the synergistic effect of these compounds is unclear, the composition of the present invention is an industrially very effective copper etching composition.
［実施例］
以下に本発明を比較例および実施例により詳しく説明す
るが、この発明の範囲は本実施例の記載の態４．１に限
定されるものではない。[Example] The present invention will be explained in detail below using comparative examples and examples, but the scope of the present invention is not limited to mode 4.1 described in this example.
比’Ｉ！２ ｆｎＪ オＪ：び実施ｍｌ比１ｆｔ２ （
ψ１（１）として、スプレー式エツチング装置［ツルミ
ニ業株式会社製］に硫酸１２容量パーセント、過酸化水
素８容量パーセントおよび蒸留水８０容量パーセントか
らなるエツチング液６０リットルを仕込み、ガラスエポ
キシ銅基板（６２ｍｍＸ ６２ｍｍ、銅の厚さ１８μ）
をエツチング液の吐出に対して、垂直方向にセットして
、エツチング液の吐出圧力を１．５ｋｇ／ｃｍ’、温度
は５０±１℃の条件下で、塩素イオンを含まない状態で
のエツチング速度を、エツチング液が噴射し始めてから
完全に銅が溶解するまでの時間で測定した。比較例（２
）として」１記と同じ装置および条（’ＩＦで塩素イオ
ン（過酸化水素の分解に対して不活性な塩ｆヒナトリウ
ムを使用した）を１５ｐｐｍ添加した場合のエツチング
速度を測定した。ratio'I! 2 fnJ OJ: and implementation ml ratio 1ft2 (
As ψ1 (1), 60 liters of etching solution consisting of 12 volume percent sulfuric acid, 8 volume percent hydrogen peroxide, and 80 volume percent distilled water was charged into a spray etching device [manufactured by Tsurumi Gyo Co., Ltd.], and a glass epoxy copper substrate (62 mm 62mm, copper thickness 18μ)
was set perpendicular to the discharge of the etching solution, the discharge pressure of the etching solution was 1.5 kg/cm', the temperature was 50±1°C, and the etching rate was determined in the absence of chlorine ions. was measured as the time from when the etching solution started to be sprayed until the copper was completely dissolved. Comparative example (2
) The etching rate was measured using the same equipment and method as in Section 1 (IF) when 15 ppm of chlorine ions (the salt f arsenium, which is inert to the decomposition of hydrogen peroxide, was used) was added.
比較１の１（３〉〜（７）として、比較例（２）のエツ
チング液にｎ−プロパツール、ポリエチレングリコール
（平均分子量４００）、ベンゾトリアゾール及びトリル
１〜リアゾールの有効量を単独で、または１１−プロパ
ツールとポリエチレングリコール・の有効量を併用して
それぞれのエツチング速度を測定した。As 1(3) to (7) of Comparative Example 1, effective amounts of n-propanol, polyethylene glycol (average molecular weight 400), benzotriazole, and tolyl to lyazole were added to the etching solution of Comparative Example (2) alone or Effective amounts of 11-propertool and polyethylene glycol were used in combination to measure their respective etching rates.
次に、本発明の実施例とし、では、同じ装置および条件
で塩素イオンを１５ｐｐｍを含んだエツチング液にベン
ゾトリアゾールまたはトリルＩ・リアゾールの有効量を
添加して、更に、ｎ−プロパツールおよび／またはポリ
エチレングリコール（平均分子量４００）各々２％を添
加してエツチング速度を測定した。結果は表−１に示す
。Next, as an example of the present invention, an effective amount of benzotriazole or tolyl I liazole was added to an etching solution containing 15 ppm of chloride ions using the same equipment and conditions, and further n-propanol and/or Alternatively, 2% of each polyethylene glycol (average molecular weight 400) was added and the etching rate was measured. The results are shown in Table-1.
（以下余白）
［発明の効果コ
以上述べたように本発明の銅のエツチング液組成物およ
びエツチング方法によれば、塩素イオンの影響によるエ
ツチング速度の低下を完全に防ぎ、しかもエツチング中
に塩素イオンが増加してエツチング速度が低下しても、
本発明の化合物類を袖充することによってエツチング速
度を完全に回復させる効果がある。(Left below) [Effects of the Invention] As described above, the copper etching solution composition and etching method of the present invention completely prevent the etching rate from decreasing due to the influence of chlorine ions, and furthermore, the copper etching solution composition and etching method of the present invention completely prevent the etching rate from decreasing due to the influence of chlorine ions. Even if the etching speed decreases due to an increase in
Filling with the compounds of the present invention has the effect of completely restoring the etching rate.
Claims (4)
ング液にベンゾトリアゾールおよび／またはトリルトリ
アゾールを含有させた銅のエッチング液組成物。(1) A copper etching solution composition containing benzotriazole and/or tolyltriazole in an etching solution consisting of sulfuric acid, hydrogen peroxide, and alcohols.
０容量パーセント，低級飽和脂肪族アルコールおよび／
またはモノまたはポリ形のエチレングリコール類０．１
〜５．０重量パーセントからなるエッチング液にベンゾ
トリアゾールおよび／またはトリルトリアゾールを５０
〜２５０００ｐｐｍ含有させた銅のエッチング液組成物
。(2) 5-25 volume percent sulfuric acid, 3-2% hydrogen peroxide
0 volume percent, lower saturated aliphatic alcohol and/or
or mono- or polyethylene glycols 0.1
50% of benzotriazole and/or tolyltriazole in an etching solution consisting of ~5.0% by weight.
A copper etching solution composition containing ~25,000 ppm.
を用いる銅のエッチング方法。(3) A copper etching method using the etching solution composition according to claim 2.
を用いるプリント回路基板のエッチング方法。(4) A method for etching a printed circuit board using the etching liquid composition according to claim 2.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21542889A JPH0379778A (en) | 1989-08-21 | 1989-08-21 | Copper etching solution composition and etching method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP21542889A JPH0379778A (en) | 1989-08-21 | 1989-08-21 | Copper etching solution composition and etching method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0379778A true JPH0379778A (en) | 1991-04-04 |
Family
ID=16672175
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP21542889A Pending JPH0379778A (en) | 1989-08-21 | 1989-08-21 | Copper etching solution composition and etching method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0379778A (en) |
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|---|---|---|---|---|
| JPH0633268A (en) * | 1992-07-16 | 1994-02-08 | Asahi Denka Kogyo Kk | Surface treating method of copper and copper alloy |
| EP0634098A1 (en) * | 1993-07-16 | 1995-01-18 | Reckitt & Colman Inc. | Hydrogen peroxide composition |
| WO1996019097A1 (en) * | 1994-12-12 | 1996-06-20 | Alpha Fry Ltd. | Copper coating |
| US5705089A (en) * | 1992-03-11 | 1998-01-06 | Mitsubishi Gas Chemical Company, Inc. | Cleaning fluid for semiconductor substrate |
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| US6146701A (en) * | 1997-06-12 | 2000-11-14 | Macdermid, Incorporated | Process for improving the adhension of polymeric materials to metal surfaces |
| US6162503A (en) * | 1997-06-12 | 2000-12-19 | Macdermid, Incorporated | Process for improving the adhesion of polymeric materials to metal surfaces |
| JP2001262374A (en) * | 2000-03-09 | 2001-09-26 | Lg Philips Lcd Co Ltd | Etching agent for copper, method for manufacturing substrate for electronic aperture using the same and electronic apparatus |
| US6383272B1 (en) | 2000-06-08 | 2002-05-07 | Donald Ferrier | Process for improving the adhesion of polymeric materials to metal surfaces |
| US6419784B1 (en) | 2000-06-21 | 2002-07-16 | Donald Ferrier | Process for improving the adhesion of polymeric materials to metal surfaces |
| JP2002266088A (en) * | 2001-03-07 | 2002-09-18 | Yamatoya & Co Ltd | Soft etching agent for copper clad laminate |
| JP2003003283A (en) * | 2001-06-25 | 2003-01-08 | Mitsubishi Gas Chem Co Inc | Surface treatment agent for copper and copper alloy |
| US6544436B2 (en) * | 1996-07-29 | 2003-04-08 | Ebara Dansan Ltd. | Etchant, method for roughening copper surface and method for producing printed wiring board |
| US6554948B1 (en) | 2000-08-22 | 2003-04-29 | Donald Ferrier | Process for improving the adhesion of polymeric materials to metal surfaces |
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1989
- 1989-08-21 JP JP21542889A patent/JPH0379778A/en active Pending
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| JPH0633268A (en) * | 1992-07-16 | 1994-02-08 | Asahi Denka Kogyo Kk | Surface treating method of copper and copper alloy |
| EP0634098A1 (en) * | 1993-07-16 | 1995-01-18 | Reckitt & Colman Inc. | Hydrogen peroxide composition |
| WO1996019097A1 (en) * | 1994-12-12 | 1996-06-20 | Alpha Fry Ltd. | Copper coating |
| US5800859A (en) * | 1994-12-12 | 1998-09-01 | Price; Andrew David | Copper coating of printed circuit boards |
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| US6146701A (en) * | 1997-06-12 | 2000-11-14 | Macdermid, Incorporated | Process for improving the adhension of polymeric materials to metal surfaces |
| US6162503A (en) * | 1997-06-12 | 2000-12-19 | Macdermid, Incorporated | Process for improving the adhesion of polymeric materials to metal surfaces |
| JP2001262374A (en) * | 2000-03-09 | 2001-09-26 | Lg Philips Lcd Co Ltd | Etching agent for copper, method for manufacturing substrate for electronic aperture using the same and electronic apparatus |
| US6503566B2 (en) | 2000-06-08 | 2003-01-07 | Donald Ferrier | Process for improving the adhesion of polymeric materials to metal surfaces |
| US6383272B1 (en) | 2000-06-08 | 2002-05-07 | Donald Ferrier | Process for improving the adhesion of polymeric materials to metal surfaces |
| US6419784B1 (en) | 2000-06-21 | 2002-07-16 | Donald Ferrier | Process for improving the adhesion of polymeric materials to metal surfaces |
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| JP2002266088A (en) * | 2001-03-07 | 2002-09-18 | Yamatoya & Co Ltd | Soft etching agent for copper clad laminate |
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| JP2003003283A (en) * | 2001-06-25 | 2003-01-08 | Mitsubishi Gas Chem Co Inc | Surface treatment agent for copper and copper alloy |
| EP1664382A1 (en) * | 2003-07-14 | 2006-06-07 | Enthone Inc. | Adhesion promotion in printed circuit boards |
| US7232478B2 (en) * | 2003-07-14 | 2007-06-19 | Enthone Inc. | Adhesion promotion in printed circuit boards |
| EP1664382A4 (en) * | 2003-07-14 | 2010-01-20 | Enthone | Adhesion promotion in printed circuit boards |
| US7682432B2 (en) | 2003-07-14 | 2010-03-23 | Enthone Inc. | Adhesion promotion in printed circuit boards |
| US8142840B2 (en) | 2003-07-14 | 2012-03-27 | Enthone Inc. | Adhesion promotion in printed circuit boards |
| US9040117B2 (en) | 2003-07-14 | 2015-05-26 | Enthone Inc. | Adhesion promotion in printed circuit boards |
| CN103451716A (en) * | 2012-05-31 | 2013-12-18 | 际华三五二二装具饰品有限公司 | Plating layer stripping corrosion solution |
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