JP2013084680A - Etchant for transparent conductive thin film laminate - Google Patents
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Abstract
Description
本発明は、透明導電性薄膜積層体のエッチング液及びそのエッチング液を使用するエッチング方法に関する。 The present invention relates to an etching solution for a transparent conductive thin film laminate and an etching method using the etching solution.
透明導電性薄膜は、透明であるにもかかわらず導電性を有する薄膜であり、インジウムとスズの酸化物（ＩＴＯ）を代表例とする薄膜である。
ＩＴＯの様な透明導電性薄膜は可視光線透過率が高く、抵抗値が比較的低いことが特徴であるが、近年透明導電性薄膜を利用した回路の高密度化への要求が高くなると、可視光線透過率を維持しつつ、抵抗値のより低い透明金属薄膜との積層体が必要となり、銀又は銀合金を使用した特開２００１−５２５２９のような積層体が開発されている。
ＩＴＯの様な透明導電性薄膜のエッチング液としては、例えば特開２０００−３０９８８８のような塩酸、りん酸、カルボン酸及び界面活性剤からなる組成や、特開２００３−３０６６７６のようなシュウ酸及びカルボン酸からなる組成が公開されている。しかし、このような処理液では、前述した透明金属薄膜のエッチングは困難であり、透明金属薄膜を用いた透明導電性積層体のエッチングは不可能である。
また、透明導電性積層体のエッチングとしては、特開２００４−１５６０７０のような、りん酸、硝酸、酢酸を含有するエッチング液や、特開２００２−１５７９２９のようなドライエッチング法が紹介されている。
しかし、りん酸や酢酸は排水処理性に大きな問題を抱えており、硝酸によるエッチングではエッチング速度が速いため、エッチングレジスト下の透明導電性薄膜を浸食するいわゆるアンダーカットが発生しやすい。
一方ドライエッチングは装置が高価で、毒性の強いガスを使用し、また大量生産に不向きであるという欠点を有する。
The transparent conductive thin film is a thin film having conductivity despite being transparent, and is a thin film having an oxide of indium and tin (ITO) as a representative example.
A transparent conductive thin film such as ITO is characterized by a high visible light transmittance and a relatively low resistance value. However, in recent years, as the demand for higher density of circuits using the transparent conductive thin film increases, visible A laminate with a transparent metal thin film having a lower resistance value is required while maintaining light transmittance, and a laminate such as JP-A-2001-52529 using silver or a silver alloy has been developed.
As an etching solution for a transparent conductive thin film such as ITO, for example, a composition comprising hydrochloric acid, phosphoric acid, carboxylic acid and a surfactant as disclosed in JP 2000-309888, oxalic acid as described in JP 2003-306676, and A composition comprising a carboxylic acid is disclosed. However, with such a treatment solution, it is difficult to etch the transparent metal thin film described above, and it is impossible to etch the transparent conductive laminate using the transparent metal thin film.
As etching of the transparent conductive laminate, an etching solution containing phosphoric acid, nitric acid and acetic acid as disclosed in JP-A No. 2004-156070 and a dry etching method such as JP-A No. 2002-157929 have been introduced. .
However, phosphoric acid and acetic acid have a serious problem in wastewater treatment, and etching with nitric acid has a high etching rate, so that a so-called undercut that erodes the transparent conductive thin film under the etching resist is likely to occur.
On the other hand, dry etching has the disadvantages that the apparatus is expensive, uses a highly toxic gas, and is unsuitable for mass production.
従って、本発明の課題は、透明導電性薄膜積層体をエッチングする際に、アンダーカット無くエッチングでき、排水処理性に負担のかからないウェットエッチング液を提供することにある。 Accordingly, an object of the present invention is to provide a wet etching solution that can be etched without undercut when the transparent conductive thin film laminate is etched, and does not impose a burden on wastewater treatment.
本発明者らは上記課題を解決すべく、鋭意検討を重ねた結果、硫酸、過酸化水素、および含窒素化合物を含有するエッチング液により、アンダーカット無くエッチングでき、排水処理性に負担のかからないことを見いだすことができた。
すなわち、本発明は硫酸、過酸化水素および含窒素化合物を含有する透明導電性薄膜及び透明導電性薄膜と金属薄膜を含む積層膜のエッチング液組成物に関する。また、透明性導電性薄膜が、スズドーピングのインジウム酸化物（ＩＴＯ）、亜鉛ドーピングのインジウム酸化物（ＩＺＯ）、ガリウムドーピングの酸化亜鉛（ＧＺＯ）、及びアルミニウムドーピングの酸化亜鉛（ＡＺＯ）である、前記エッチング液に関する。
また、透明導電性薄膜積層体が、前記透明性導電薄膜および金属薄膜による積層体である前記エッチング液に関する。
また、銀又は銀合金からなる金属薄膜を使用した透明導電性薄膜積層体の前記エッチング液に関する。
また、前記エッチング液を使用して、エッチングする方法に関する。
As a result of intensive studies to solve the above-mentioned problems, the present inventors can etch without undercut with an etching solution containing sulfuric acid, hydrogen peroxide, and a nitrogen-containing compound, and do not impose a burden on wastewater treatment performance. I was able to find.
That is, the present invention relates to a transparent conductive thin film containing sulfuric acid, hydrogen peroxide and a nitrogen-containing compound, and an etching solution composition for a laminated film including the transparent conductive thin film and a metal thin film. The transparent conductive thin film is tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), gallium-doped zinc oxide (GZO), and aluminum-doped zinc oxide (AZO). The present invention relates to the etching solution.
Further, the present invention relates to the etching solution, wherein the transparent conductive thin film laminate is a laminate of the transparent conductive thin film and the metal thin film.
Moreover, it is related with the said etching liquid of the transparent conductive thin film laminated body which uses the metal thin film which consists of silver or a silver alloy.
The present invention also relates to a method for etching using the etching solution.
本発明のエッチング液の組成物は、透明導電性薄膜及び透明導電性積層体をアンダーカット無くエッチングすることができる。また、酢酸やシュウ酸などキレート性の有機酸を使用しなくともよいため、排水処理性が良好である。 The composition of the etching solution of the present invention can etch a transparent conductive thin film and a transparent conductive laminate without undercutting. Moreover, since it is not necessary to use a chelating organic acid such as acetic acid or oxalic acid, the wastewater treatment property is good.
以下に、本発明の実施の形態について詳述する。
本発明のエッチング液の組成物は、硫酸、過酸化水素、含窒素化合物の含有を特徴としているｐＨ７．０未満の処理液であり、透明導電性薄膜はこのような液によってエッチングされるものであればいずれを用いても良い。好適にはＩＴＯ、ＩＺＯ、ＧＺＯ及びＡＺＯが挙げられる。
より具体的には次のエッチング液、及びエッチング方法を提供する。
（１）硫酸、過酸化水素及び含窒素化合物を含有することを特徴とする、透明導電性薄膜及び透明導電性薄膜積層体のエッチングに用いられるｐＨ７．０未満のエッチング液。
（２）上記（１）において含窒素化合物がＲ1Ｒ2Ｒ3Ｎで表されるアミン（Ｒ1〜Ｒ3はそれぞれ水素、−ＣnＨ2n+1（ｎ＝１〜８）で表されるアルキル基、−ＣnＨ2n+1（ｎ＝３〜８）で表される分岐アルキル基、−ＣnＨ2n-1（ｎ＝５〜８）で表されるシクロアルキル基、前記アルキル基、分岐アルキル基若しくはシクロアルキル基の１つまたは複数の水素を−ＯＨに置換したもの、１つまたは複数のＣ−Ｃ単結合を二重結合または三重結合に置換したものから選択される）、５〜８員環を有するラクタム（Ｎと結合する水素が前記アルキル基または分岐アルキル基で置換されているものを含む）、Ｒ1−ＣＯＮＲ2Ｒ3で表されるアミド（Ｒ1〜Ｒ3はそれぞれ水素、−ＣnＨ2n+1（ｎ＝１〜８）で表されるアルキル基、−ＣnＨ2n+1（ｎ＝３〜８）で表される分岐アルキル基、前記アルキル基、分岐アルキル基の１つまたは複数の水素を−ＯＨに置換したもの、１つまたは複数のＣ−Ｃ単結合を二重結合または三重結合に置換したものから選択される）、Ｒ1Ｒ2Ｎ−〔（ＣＨ2）m−ＮＨ−〕n−（ＣＨ2）m−ＮＲ3Ｒ4（ｍ：２〜５、ｎ：０〜８、Ｒ1〜Ｒ4はそれぞれ水素、−ＣnＨ2n+1（ｎ＝１〜６）で表されるアルキル基、−ＣnＨ2n+1（ｎ＝３〜６）で表される分岐アルキル基、前記アルキル基および分岐アルキル基の１つまたは複数の水素を−ＯＨに置換したものから選択される）で表されるポリアルキレンポリアミン、Ｒ1−ＣＮで表されるニトリル（Ｒ1は−ＣnＨ2n+1（ｎ＝１〜８）で表されるアルキル基、−ＣnＨ2n+1（ｎ＝３〜８）で表される分岐アルキル基、前記アルキル基、分岐アルキル基の１つまたは複数の水素を−ＯＨまたは−ＣＮに置換したもの、１つまたは複数のＣ−Ｃ単結合を二重結合または三重結合に置換したものから選択される）、オキサジン（Ｎと結合する水素が前記アルキル基または分岐アルキル基で置換されているものを含む）、テトラヒドロオキサジン（Ｎと結合する水素が前記アルキル基または分岐アルキル基で置換されているものを含む）から選択される少なくとも１種であるエッチング液。
（３）上記（１）又は（２）において、フッ化物イオン以外のハロゲン化物イオンを含まないことを特徴とするエッチング液。
（４）上記（１）〜（３）の何れかにおいて、フッ化物イオンを含まないことを特徴とするエッチング液。
（５）上記（１）〜（４）の何れかにおいて、透明導電性薄膜が、スズドーピングのインジウム酸化物（ＩＴＯ）、亜鉛ドーピングのインジウム酸化物（ＩＺＯ）、ガリウムドーピングの酸化亜鉛（ＧＺＯ）、又はアルミニウムドーピングの酸化亜鉛（ＡＺＯ）であるエッチング液。
（６）上記（１）〜（４）の何れかにおいて、透明導電性薄膜積層体が、上記（５）で示される透明導電性薄膜および金属薄膜による積層体であるエッチング液。
（７）上記（１）〜（６）の何れかにおいて、金属薄膜が、銀又は銀合金である、エッチング液。
（８）上記（１）〜（７）の何れかのエッチング液を使用してエッチングを行う方法。
Hereinafter, embodiments of the present invention will be described in detail.
The composition of the etching solution of the present invention is a treatment solution having a pH of less than 7.0, characterized by containing sulfuric acid, hydrogen peroxide, and a nitrogen-containing compound, and the transparent conductive thin film is etched by such a solution. Any of them may be used. Suitable examples include ITO, IZO, GZO and AZO.
More specifically, the following etching liquid and etching method are provided.
(1) An etching solution having a pH of less than 7.0, which is used for etching a transparent conductive thin film and a transparent conductive thin film laminate, comprising sulfuric acid, hydrogen peroxide, and a nitrogen-containing compound.
(2) In the above (1), the nitrogen-containing compound is an amine represented by R 1 R 2 R 3 N (R 1 to R 3 are each represented by hydrogen and —C n H 2n + 1 (n = 1 to 8)). An alkyl group, a branched alkyl group represented by —C n H 2n + 1 (n = 3 to 8), a cycloalkyl group represented by —C n H 2n-1 (n = 5 to 8), One or more hydrogens of an alkyl group, branched alkyl group or cycloalkyl group substituted with —OH, or one or more C—C single bonds substituted with double bonds or triple bonds ), A lactam having a 5- to 8-membered ring (including those in which the hydrogen bonded to N is substituted with the alkyl group or the branched alkyl group), an amide represented by R 1 —CONR 2 R 3 (R 1 to R 3 each represents hydrogen, -C n H 2n + 1 ( n = 1~8) with an alkyl group represented, -C n H 2n + 1 a branched alkyl group represented by n = 3 to 8), wherein one or more hydrogens of the alkyl group or branched alkyl group are substituted with —OH, and one or more CC single bonds are double bonds Or selected from those substituted with a triple bond), R 1 R 2 N — [(CH 2 ) m —NH—] n — (CH 2 ) m —NR 3 R 4 (m: 2 to 5, n: 0 to 8, R 1 to R 4 are each represented by hydrogen, an alkyl group represented by —C n H 2n + 1 (n = 1 to 6), or —C n H 2n + 1 (n = 3 to 6). A branched alkyl group selected from the group consisting of the above alkyl group and one or more hydrogens of the branched alkyl group substituted with —OH), a nitrile represented by R 1 —CN ( R 1 is an alkyl group represented by -C n H 2n + 1 (n = 1~8), represented by -C n H 2n + 1 (n = 3~8) min From an alkyl group, one or more hydrogens of the alkyl group or branched alkyl group substituted with -OH or -CN, or one or more CC single bonds substituted with double bonds or triple bonds Selected), oxazine (including those in which hydrogen bonded to N is substituted with the alkyl group or branched alkyl group), tetrahydrooxazine (hydrogen bonded to N is substituted with the alkyl group or branched alkyl group) An etchant that is at least one selected from the group consisting of:
(3) In the above (1) or (2), an etching solution characterized by not containing halide ions other than fluoride ions.
(4) In any one of the above (1) to (3), an etching solution characterized by not containing fluoride ions.
(5) In any one of the above (1) to (4), the transparent conductive thin film is made of tin-doped indium oxide (ITO), zinc-doped indium oxide (IZO), or gallium-doped zinc oxide (GZO). Or an etchant that is aluminum doped zinc oxide (AZO).
(6) The etching solution according to any one of (1) to (4), wherein the transparent conductive thin film laminate is a laminate of the transparent conductive thin film and metal thin film shown in (5) above.
(7) The etching solution according to any one of the above (1) to (6), wherein the metal thin film is silver or a silver alloy.
(8) A method of performing etching using the etching solution according to any one of (1) to (7) above.
透明導電性膜と共に積層体を構成する金属薄膜は、単体としての比抵抗が低い銀またはその合金が好適である。銀合金としてはＡｇ−Ｐｄ−Ｃｕ、Ａｇ−Ｐｄ、Ａｇ−Ｃｕ−Ａｕ、Ａｇ−Ｒｕ−Ｃｕ、Ａｇ−Ｒｕ−Ａｕなどがあり、特にＡｇ−Ｐｄ−Ｃｕ（ＡＰＣ）が好適である。 The metal thin film constituting the laminate together with the transparent conductive film is preferably silver or an alloy thereof having a low specific resistance as a simple substance. Examples of the silver alloy include Ag-Pd-Cu, Ag-Pd, Ag-Cu-Au, Ag-Ru-Cu, and Ag-Ru-Au, and Ag-Pd-Cu (APC) is particularly preferable.
本発明のエッチング液の組成の濃度は以下の通りである。
硫酸の濃度は、好ましくは０．０１〜５．０重量％、さらに好ましくは０．０５〜１．０重量％である。硫酸濃度が高い場合は透明導電性膜のアンダーカットの進行が懸念され、低い場合はエッチング速度が極端に低下する。
過酸化水素濃度は、好ましくは０．０５〜５．０重量％、さらに好ましくは０．１〜１．０重量％である。
過酸化水素濃度が高い場合はアンダーカットの進行が懸念され、低い場合はエッチング速度が極端に低下する。
含窒素化合物の濃度は、好ましくは０．０１〜５．０重量％である。含窒素化合物が低い場合はアンダーカット抑制効果が充分得られない。含窒素化合物濃度がこれ以上に上昇しても、効果は大きく得られないばかりか、コスト面で不利が生ずる。
The concentration of the composition of the etching solution of the present invention is as follows.
The concentration of sulfuric acid is preferably 0.01 to 5.0% by weight, more preferably 0.05 to 1.0% by weight. When the sulfuric acid concentration is high, there is a concern about the progress of undercut of the transparent conductive film, and when it is low, the etching rate is extremely reduced.
The hydrogen peroxide concentration is preferably 0.05 to 5.0% by weight, more preferably 0.1 to 1.0% by weight.
When the hydrogen peroxide concentration is high, there is a concern about the progress of undercut, and when it is low, the etching rate is extremely reduced.
The concentration of the nitrogen-containing compound is preferably 0.01 to 5.0% by weight. When the nitrogen-containing compound is low, an undercut suppressing effect cannot be sufficiently obtained. Even if the concentration of the nitrogen-containing compound is further increased, not only a large effect is obtained, but also a disadvantage is caused in terms of cost.
含窒素化合物は、Ｒ1Ｒ2Ｒ3Ｎで表されるアミン（Ｒ1〜Ｒ3はそれぞれ水素、−ＣnＨ2n-1（n=1〜8）で表されるアルキル基、−ＣnＨ2n+1（ｎ＝３〜８）で表される分岐アルキル基、−ＣｎＨ２ｎ−１（ｎ＝５〜８）で表されるシクロアルキル基、前記アルキル基、分岐アルキル基若しくはシクロアルキル基の１つまたは複数の水素を−ＯＨに置換したもの、１つまたは複数のＣ−Ｃ単結合を二重結合または三重結合に置換したものから選択される）、５〜８員環を有するラクタム（Ｎと結合する水素が前記アルキル基または分岐アルキル基で置換されているものを含む）、Ｒ1−ＣＯＮＲ2Ｒ3で表されるアミド（Ｒ1〜Ｒ3はそれぞれ水素、−ＣnＨ2n+1（ｎ＝１〜８）で表されるアルキル基、−ＣnＨ2n+1（ｎ＝３〜８）で表される分岐アルキル基、前記アルキル基、分岐アルキル基の１つまたは複数の水素を−ＯＨに置換したもの、１つまたは複数のＣ−Ｃ単結合を二重結合または三重結合に置換したものから選択される）、Ｒ1Ｒ2Ｎ−〔（ＣＨ2）m−ＮＨ−〕n−（ＣＨ2）m−ＮＲ3Ｒ4（ｍ：２〜５、ｎ：０〜８、Ｒ1〜Ｒ4はそれぞれ水素、−ＣnＨ2n+1（ｎ＝１〜６）で表されるアルキル基、−ＣｎＨ2n+1（ｎ＝３〜６）で表される分岐アルキル基、前記アルキル基および分岐アルキル基の１つまたは複数の水素を−ＯＨに置換したものから選択される）で表されるポリアルキレンポリアミン、Ｒ1−ＣＮで表されるニトリル（Ｒ1は−ＣnＨ2n+1（ｎ＝１〜８）で表されるアルキル基、−ＣnＨ2n+1（ｎ＝３〜８）で表される分岐アルキル基、前記アルキル基、分岐アルキル基の１つまたは複数の水素を-OHまたは−ＣＮに置換したもの、１つまたは複数のＣ−Ｃ単結合を二重結合または三重結合に置換したものから選択される）、オキサジン（Ｎと結合する水素が前記アルキル基または分岐アルキル基で置換されているものを含む）、テトラヒドロオキサジン（Ｎと結合する水素が前記アルキル基または分岐アルキル基で置換されているものを含む）が好適である。具体的にはアセトアミド、Ｎ，Ｎ−ジメチルアセトアミド、アセトニトリル、アミルアミン、アリルアミン、イソブチルアミン、イソプロパノ−ルアミン、イソプロピルアミン、Ｎ−エチルエタノールアミン、モルホリン、Ｎ−エチルモルホリン、エチレンジアミン、カプロラクタム、ジアミルアミン、ジエタノールアミン、ジエチルアミン、ジエチレントリアミン、シクロヘキシルアミン、ジメチルアミン、テトラエチレンペンタミン、Ｎ，Ｎ，Ｎ’，Ｎ’−テトラメチルエチレンジアミン、トリエタノールアミン、２−ピロリドン、Ｎ−メチルピロリドン、Ｎ−メチルホルムアミド、モノエタノールアミン、モノメチルアミン及びモノエチルアミンが挙げられるがこれに限定されるものではない。アミン、アミド及びラクタムが好ましく、特に好ましくはカプロラクタム、シクロヘキシルアミン、２−ピロリドンである。
含窒素化合物の含有により、過酸化水素の分解反応が抑制されると共に、アンダーカットの抑制が出来る。
The nitrogen-containing compound is an amine represented by R 1 R 2 R 3 N (R 1 to R 3 are each hydrogen, an alkyl group represented by —C n H 2n-1 (n = 1 to 8), —C n H 2n + 1 (n = 3~8) at branched alkyl group represented, the cycloalkyl group represented by -CnH2n-1 (n = 5~8) , the alkyl group, branched alkyl group or cycloalkyl group Or a lactam having a 5- to 8-membered ring, selected from one or more hydrogens of -OH substituted with -OH, one or more CC single bonds substituted with double or triple bonds) (Including those in which hydrogen bonded to N is substituted with the alkyl group or branched alkyl group), amides represented by R 1 —CONR 2 R 3 (R 1 to R 3 are each hydrogen, —C n H An alkyl group represented by 2n + 1 (n = 1 to 8), represented by —C n H 2n + 1 (n = 3 to 8) A branched alkyl group, selected from the alkyl group, one in which one or more hydrogens of the branched alkyl group are substituted with —OH, and one or more C—C single bonds substituted with double bonds or triple bonds. R 1 R 2 N — [(CH 2 ) m —NH—] n — (CH 2 ) m —NR 3 R 4 (m: 2 to 5, n: 0 to 8, R 1 to R 4 are Hydrogen, an alkyl group represented by —C n H 2n + 1 (n = 1 to 6), a branched alkyl group represented by —CnH 2n + 1 (n = 3 to 6), the alkyl group and the branched alkyl, respectively A polyalkylene polyamine represented by R 1 -CN selected from those in which one or more hydrogens of the group are substituted with -OH, and R 1 is -C n H 2n + 1 (n = alkyl group represented by 1~8), -C n H 2n + 1 (n = 3~8) at branched alkyl group represented by the alkyl Or a group in which one or more hydrogens of a branched alkyl group are substituted with —OH or —CN, or one or more C—C single bonds are substituted with double bonds or triple bonds) Oxazine (including those in which hydrogen bonded to N is substituted with the alkyl group or branched alkyl group), tetrahydrooxazine (including hydrogen in which N bonded to hydrogen is substituted with the alkyl group or branched alkyl group) ) Is preferred. Specifically, acetamide, N, N-dimethylacetamide, acetonitrile, amylamine, allylamine, isobutylamine, isopropanolamine, isopropylamine, N-ethylethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, caprolactam, diamylamine, diethanolamine, Diethylamine, diethylenetriamine, cyclohexylamine, dimethylamine, tetraethylenepentamine, N, N, N ′, N′-tetramethylethylenediamine, triethanolamine, 2-pyrrolidone, N-methylpyrrolidone, N-methylformamide, monoethanolamine Monomethylamine and monoethylamine, but are not limited thereto. Amine, amide and lactam are preferable, and caprolactam, cyclohexylamine and 2-pyrrolidone are particularly preferable.
By containing the nitrogen-containing compound, the decomposition reaction of hydrogen peroxide is suppressed, and undercut can be suppressed.
処理液のｐＨは７．０未満が好適である。ｐＨが７．０以上のアルカリ性では、透明導電性薄膜のエッチングが困難である。 The pH of the treatment liquid is preferably less than 7.0. When the pH is 7.0 or higher, it is difficult to etch the transparent conductive thin film.
本発明の処理液には、公知の過酸化水素を分解抑制させる添加剤を加えることも可能である。添加剤の例として、フェナセチン、芳香族スルホン酸、芳香族カルボン酸、グリコールエーテル、アゾール類などがあるが、これらに特に限定されるわけではない。
本発明のエッチング液においては、フッ化物イオンを除くハロゲン化物イオンは金属薄膜に使用される銀、又は銀合金と不溶性のハロゲン化銀を形成し、エッチング反応中に下層の透明導電性薄膜のエッチングを直接阻害し、及びエッチング液中で固形物となるため、混入を避けることが望ましい。フッ化物イオンについても、エッチング処理自体には悪影響を与えないものの排水処理性に問題があり環境に負荷を与えるため、やはり混入を避けることが望ましい。
It is also possible to add a known additive that suppresses decomposition of hydrogen peroxide to the treatment liquid of the present invention. Examples of the additive include phenacetin, aromatic sulfonic acid, aromatic carboxylic acid, glycol ether, and azole, but are not particularly limited thereto.
In the etching solution of the present invention, halide ions other than fluoride ions form insoluble silver halide with silver or silver alloy used in the metal thin film, and etch the transparent conductive thin film underneath during the etching reaction. It is desirable to avoid contamination because it directly inhibits and becomes a solid in the etching solution. Although fluoride ions also do not adversely affect the etching process itself, there is a problem with wastewater treatment performance and a burden on the environment, so it is desirable to avoid contamination.
本発明のエッチング液の使用方法としてはバッチ式による浸漬や、スプレー処理などが挙げられるが、これらに特に限定されるものではない。
エッチング液の使用温度は５０℃以下が好ましい。高温では、エッチング速度が過剰になり、アンダーカットのおそれがある上に、過酸化水素の分解が促進される。
Examples of the method of using the etching solution of the present invention include, but are not limited to, batch immersion and spray treatment.
The use temperature of the etching solution is preferably 50 ° C. or less. At high temperatures, the etching rate becomes excessive and there is a risk of undercutting, and the decomposition of hydrogen peroxide is promoted.
＜エッチング試験＞
以下に、実施例と比較例を挙げて本発明を詳細に説明する。本発明はこれら実施例に限定されるものではない。
ガラス基材上の透明導電性薄膜及び透明導電性積層体にドライフィルムフォトレジストを塗布し、現像によりパターン作成して試験片を作成した。その後、エッチング液に浸漬してエッチングした。エッチング液の組成（残部は水）、ｐＨ及び温度を表１に示す。エッチング時間を表２に示す。
<Etching test>
Below, an Example and a comparative example are given and this invention is demonstrated in detail. The present invention is not limited to these examples.
A dry film photoresist was applied to the transparent conductive thin film and the transparent conductive laminate on the glass substrate, and a pattern was created by development to prepare a test piece. Then, it was immersed in an etching solution and etched. Table 1 shows the composition of the etching solution (the balance is water), pH, and temperature. The etching time is shown in Table 2.
評価 ドライフィルムに覆われていない部分の導電率の変化よりエッチング完了時間を測定し、エッチング完了時間の２倍時間におけるドライフィルムパターンの残存率をもって、アンダーカットの評価を行った。結果を表２に示す。○はアンダーカットなし、△はわずかにアンダーカットあり、×は大きいアンダーカットがあったことを示す。なお−ははく離できなかったことを示す。 Evaluation The etching completion time was measured from the change in the conductivity of the portion not covered with the dry film, and the undercut was evaluated based on the remaining rate of the dry film pattern at twice the etching completion time. The results are shown in Table 2. ○ indicates that there is no undercut, Δ indicates that there is a slight undercut, and × indicates that there is a large undercut. In addition,-indicates that peeling was not possible.
以上の結果から、硫酸（好ましくは０．０１〜５．０重量％、さらに好ましくは０．０５〜１．０重量％）、過酸化水素（好ましくは０．０５〜５．０重量％、さらに好ましくは０．１〜１．０重量％）、含窒素化合物（好ましくは０．０１〜５．０重量％）を含有し、かつｐＨ７．０未満のエッチング液は、透明導電性薄膜及び透明導電性薄膜積層体のエッチングにおいて、アンダーカットを生じない優れたエッチング液であることがわかる。 From the above results, sulfuric acid (preferably 0.01 to 5.0% by weight, more preferably 0.05 to 1.0% by weight), hydrogen peroxide (preferably 0.05 to 5.0% by weight, Preferably 0.1 to 1.0% by weight), a nitrogen-containing compound (preferably 0.01 to 5.0% by weight), and an etching solution having a pH of less than 7.0 It can be seen that this is an excellent etching solution that does not cause undercut in etching of the conductive thin film laminate.
＜排水処理試験＞
硫酸０．２重量％、過酸化水素水０．５重量％、εカプロラクタム０．５重量％の本発明処理液に銀イオンを１０００ｍｇ／Ｌ添加した廃液を作成した。この液を１０倍希釈してから、水酸化カルシウムでｐＨを１２．５に調整し、重亜硫酸ナトリウムを０．２ｇ／Ｌ添加して２４時間常温で放置した。その後、硫酸にてｐＨを１０．５に調整し、高分子凝集剤（日本表面化学（株）製Ｗ−８３６）を添加して凝集させ、ろ過を行って排水処理液を作成した。この廃液と排水処理液の分析をおこなった。結果は表３のとおりである。
<Effluent treatment test>
A waste solution was prepared by adding 1000 mg / L of silver ions to the treatment solution of the present invention containing 0.2 wt% sulfuric acid, 0.5 wt% hydrogen peroxide, and 0.5 wt% ε caprolactam. After diluting this solution 10 times, the pH was adjusted to 12.5 with calcium hydroxide, 0.2 g / L of sodium bisulfite was added, and the mixture was allowed to stand at room temperature for 24 hours. Thereafter, the pH was adjusted to 10.5 with sulfuric acid, and a polymer flocculant (W-836 manufactured by Nippon Surface Chemical Co., Ltd.) was added to cause aggregation, followed by filtration to prepare a wastewater treatment solution. The waste liquid and the waste water treatment liquid were analyzed. The results are shown in Table 3.
比較例として、以下のエッチング液の例を考察する。
即ち、特開２００４−１５６０７０に記されているりん酸５４．０質量％、硝酸２．２質量％、酢酸３３．０質量％の排水処理を行う場合は、水酸化カルシウムの添加により不溶性のりん酸カルシウムを生成させて、沈降分離させる必要があり、りん酸量の約１．６３倍にあたるりん酸カルシウムを生成させる事になる。これは、大量の希釈水とスラッジの処理が必要になるため、排水処理は甚だ困難である。
以上より、本発明の処理液は廃水処理性が良好である。
As a comparative example, consider the following etchant examples.
That is, when wastewater treatment of 54.0% by mass of phosphoric acid, 2.2% by mass of nitric acid and 33.0% by mass of acetic acid described in JP-A-2004-156070 is performed, insoluble phosphorus is added by adding calcium hydroxide. Calcium phosphate needs to be generated and precipitated and separated, and calcium phosphate corresponding to about 1.63 times the amount of phosphoric acid is generated. This requires a large amount of dilution water and sludge treatment, and wastewater treatment is extremely difficult.
From the above, the treatment liquid of the present invention has good wastewater treatability.
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