JP2018009229A - Treatment method of chemical liquid for reduction, and treatment method of copper foil used for printed wiring board - Google Patents
Treatment method of chemical liquid for reduction, and treatment method of copper foil used for printed wiring board Download PDFInfo
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本発明は、銅箔を還元処理する際に使用する還元剤を含有する薬液（還元用薬液）を処理する方法、及びプリント配線板に用いる銅箔の処理方法に関する。 The present invention relates to a method for treating a chemical solution (reducing chemical solution) containing a reducing agent that is used when a copper foil is subjected to a reduction treatment, and a method for treating a copper foil used for a printed wiring board.
プリント配線板に使用される銅箔は、配線板との密着性（高い接着強度）が要求される。密着性は銅箔表面の粗度を大きくすることにより向上させることができる。また、プリント配線板の高密度化に伴い、銅箔表面を平坦化することが要求される。しかし、銅箔表面を平坦化するには粗度を小さくする必要があるため、結果として密着性が低下するという問題がある。 The copper foil used for the printed wiring board is required to have adhesion (high adhesive strength) with the wiring board. Adhesion can be improved by increasing the roughness of the copper foil surface. In addition, as the printed wiring board becomes denser, it is required to flatten the surface of the copper foil. However, since it is necessary to reduce the roughness in order to flatten the surface of the copper foil, there is a problem that the adhesion is lowered as a result.
密着性及び平坦化の双方の要求を満たす手法として、酸化・還元を利用した銅箔の処理方法がある。この方法は、酸化剤を含有する薬液にプリコンディショニングした銅箔を浸漬して酸化させ、銅箔表面に酸化銅の凹凸を形成する。次に、還元剤を含有する薬液に酸化させた銅箔を浸漬し、酸化銅を還元することで表面の凹凸を調整して表面の粗さを整える。このような方法によりプリント配線板への密着性を保ちつつ、高密度化の要求にも耐えうる銅箔を提供することが可能となる。これらに関連する技術は、たとえば、特許文献１または特許文献２に記載されている。 There is a copper foil processing method using oxidation / reduction as a technique that satisfies both the requirements of adhesion and planarization. This method immerses and oxidizes a preconditioned copper foil in a chemical solution containing an oxidizing agent to form copper oxide irregularities on the surface of the copper foil. Next, the oxidized copper foil is immersed in a chemical solution containing a reducing agent, and the surface roughness is adjusted by adjusting the surface irregularities by reducing the copper oxide. With such a method, it is possible to provide a copper foil that can withstand the demand for higher density while maintaining adhesion to the printed wiring board. Technologies related to these are described in, for example, Patent Document 1 or Patent Document 2.
ところで、酸化銅の還元処理を行った還元剤を含有する薬液は、その性能が経時的に劣化することが知られている。一方、還元剤が高価であるため、還元剤を含有する薬液は長寿命化が求められている。 By the way, it is known that the performance of a chemical solution containing a reducing agent that has been subjected to reduction treatment of copper oxide deteriorates with time. On the other hand, since the reducing agent is expensive, the chemical solution containing the reducing agent is required to have a long life.
本発明の目的は、還元用薬液の経時劣化を抑え、還元用薬液の寿命を長くすることが可能な方法を提供することにある。 An object of the present invention is to provide a method capable of suppressing the deterioration of a reducing chemical solution over time and extending the life of the reducing chemical solution.
本発明者は、未使用の還元用薬液及び使用済みの還元用薬液について、それぞれの薬液中に含まれる還元剤の濃度を経時的に測定した。その結果、未使用の還元用薬液では還元剤の濃度に変化が見られなかった。一方、使用済みの還元用薬液では、銅箔の還元処理を行っていないにも関わらず還元剤の濃度が経時的に減少するということが明らかとなった。具体的には、未使用の還元用薬液は１００日以上経過しても還元剤の濃度に変化が見られなかった。一方、使用済みの還元用薬液中の還元剤の濃度は、１２０日経過後では初期濃度に対して７％にまで減少（９３％減）しているという結果が得られた。 This inventor measured the density | concentration of the reducing agent contained in each chemical | medical solution over time about the unused chemical | medical agent for reduction, and the used chemical | medical agent for reduction. As a result, there was no change in the concentration of the reducing agent in the unused reducing chemical. On the other hand, it has been clarified that the concentration of the reducing agent decreases with time in the used reducing chemical solution even though the copper foil is not reduced. Specifically, no change was found in the concentration of the reducing agent even after 100 days or more of the unused reducing chemical solution. On the other hand, the results showed that the concentration of the reducing agent in the used reducing chemical solution decreased to 7% (down 93%) from the initial concentration after 120 days.
また、使用済みの還元用薬液を分析したところ、薬液中に酸化銅等の銅化合物が含まれていることが判った。 Moreover, when the used chemical | medical agent for a reduction | restoration was analyzed, it turned out that copper compounds, such as a copper oxide, are contained in the chemical | medical solution.
以上より、使用済みの還元用薬液中に存在する銅化合物が還元剤と反応することにより、還元用薬液の経時的な劣化が生じていると考えられる。本発明は、これらの知見に基づき完成されたものである。すなわち、本発明者は、還元処理に使用した使用済み薬液から銅化合物を取り除くことで薬液の経時劣化を抑え、長寿命化を可能とすることを見出した。 From the above, it is considered that the deterioration of the chemical solution for reduction with time is caused by the reaction of the copper compound present in the used chemical solution for reduction with the reducing agent. The present invention has been completed based on these findings. That is, the present inventor has found that removing the copper compound from the used chemical solution used for the reduction treatment suppresses the deterioration of the chemical solution over time and enables a long life.
上記目的を達成するための主たる発明は、酸化処理された銅箔の表面を還元処理する際に使用する還元用薬液の処理方法であって、前記還元処理に使用した後の還元用薬液中に存在する銅化合物を除去する除去工程を有することを特徴とする還元用薬液の処理方法である。
本発明の他の特徴については、本明細書の記載により明らかにする。
The main invention for achieving the above object is a method for treating a reducing chemical solution used for reducing the surface of an oxidized copper foil, wherein the reducing chemical solution used in the reducing treatment is used in the reducing chemical solution. It is the processing method of the chemical | medical solution for a reduction | restoration characterized by having the removal process which removes the copper compound which exists.
Other features of the present invention will become apparent from the description of this specification.
本発明の処理方法は、還元用薬液の経時劣化を抑え、還元用薬液の寿命を長くすることができる。 The treatment method of the present invention can suppress the deterioration of the reducing chemical solution over time and extend the life of the reducing chemical solution.
＝＝開示の概要＝＝
本明細書の記載により、上記の主たる発明の他、少なくとも以下の事項が明らかとなる。
== Summary of disclosure ==
In addition to the main invention described above, at least the following matters will become apparent from the description of the present specification.
すなわち、前記除去工程は、前記還元処理に使用した後の還元用薬液をろ過することにより行われることを特徴とする還元用薬液の処理方法が明らかとなる。また、前記除去工程は、前記還元処理に使用した後の還元用薬液を遠心分離し、その上澄みを回収することにより行われることを特徴とする還元用薬液の処理方法が明らかとなる。薬液中の銅化合物は、これらろ過や遠心分離といった方法により除去することができる。 That is, the reducing chemical solution processing method is characterized in that the removing step is performed by filtering the reducing chemical solution used for the reduction treatment. In addition, the reducing chemical solution processing method is characterized in that the removing step is performed by centrifuging the reducing chemical solution used for the reduction treatment and collecting the supernatant. The copper compound in the chemical solution can be removed by such methods as filtration and centrifugation.
また銅箔の表面を洗浄するプリコンディショニング工程、前記プリコンディショニング工程が行われた銅箔の表面を酸化用薬液により酸化する酸化処理工程、及び前記酸化工程が行われた前記銅箔を還元用薬液により還元する還元処理工程を有する、プリント配線板に用いる銅箔の処理方法であって、前記還元処理工程に使用した後の還元用薬液に存在する銅化合物を除去する除去工程を更に有し、前記還元処理工程は、除去工程で銅化合物が除去された前記還元用薬液を再利用することを特徴とするプリント配線板に用いる銅箔の処理方法が明らかとなる。このような処理方法によれば、経時劣化の少ない還元用薬液を繰り返し使用することができる。 Also, a preconditioning step for cleaning the surface of the copper foil, an oxidation treatment step for oxidizing the surface of the copper foil subjected to the preconditioning step with an oxidizing chemical solution, and a chemical solution for reducing the copper foil subjected to the oxidation step A method for treating a copper foil used in a printed wiring board having a reduction treatment step to reduce by the step, further comprising a removal step of removing a copper compound present in the reducing chemical after being used in the reduction treatment step, In the reduction treatment step, a copper foil treatment method for use in a printed wiring board, in which the reducing chemical solution from which the copper compound has been removed in the removal step is reused, becomes clear. According to such a treatment method, a reducing chemical solution with little deterioration with time can be used repeatedly.
＝＝実施形態＝＝
プリント配線板等の基板に使用される銅箔の処理方法は、従来から知られている様々な手法を用いることが可能である。一般的な銅箔の処理方法は、主に「プリコンディショニング工程」、「酸化処理工程」、「還元処理工程」を含む。
== Embodiment ==
As a method for treating a copper foil used for a substrate such as a printed wiring board, various conventionally known methods can be used. A general copper foil treatment method mainly includes a “preconditioning step”, an “oxidation treatment step”, and a “reduction treatment step”.
［プリコンディショニング工程］
プリコンディショニング工程は、アルカリ溶液による脱脂や酸による洗浄を行い、銅箔の表面を予備的に洗浄する工程である。
[Preconditioning process]
The preconditioning step is a step of preliminarily cleaning the surface of the copper foil by performing degreasing with an alkaline solution or cleaning with an acid.
アルカリ溶液による脱脂は、たとえば、銅箔を液温２０〜６０℃、２０〜６０ｇ／Ｌの水酸化ナトリウム（ＮａＯＨ）溶液中に２〜３０分間浸漬した後、水洗することにより行う。酸による洗浄は、たとえば、銅箔を液温２０〜５０℃、５〜２０重量％の硫酸に１〜５分間浸漬した後、水洗することにより行う。 Degreasing with an alkaline solution is performed, for example, by immersing the copper foil in a 20 to 60 g / L sodium hydroxide (NaOH) solution at a liquid temperature of 20 to 60 ° C. for 2 to 30 minutes and then washing with water. Washing with an acid is performed, for example, by immersing the copper foil in 5 to 20 wt% sulfuric acid at a liquid temperature of 20 to 50 ° C. for 1 to 5 minutes and then washing with water.
［酸化処理工程］
酸化処理工程は、酸化剤を含有する薬液（酸化用薬液）と接触させる方法、またはアルカリ性の電解液を用いて陽極酸化処理を行う方法によって銅箔の表面を酸化させ、酸化銅（ＣｕＯ）の凹凸を形成する工程である。
[Oxidation treatment process]
In the oxidation treatment step, the surface of the copper foil is oxidized by a method of contacting with a chemical solution (oxidation chemical solution) containing an oxidant or a method of anodizing using an alkaline electrolyte, and copper oxide (CuO) This is a step of forming irregularities.
酸化剤としては、亜塩素酸ナトリウム、次亜塩素酸ナトリウム、塩素酸カリウム、過塩素酸カリウム等を用いることができる。また、酸化用薬液は、酸化剤、アルカリ性化合物（水酸化ナトリウム、水酸化カリウム等）、及び溶媒（純水等）を含む液体である。酸化用薬液は、各種の添加剤（たとえば、リン酸三ナトリウム十二水和物のようなリン酸塩）を添加してもよい。 As the oxidizing agent, sodium chlorite, sodium hypochlorite, potassium chlorate, potassium perchlorate and the like can be used. The oxidizing chemical solution is a liquid containing an oxidizing agent, an alkaline compound (such as sodium hydroxide or potassium hydroxide), and a solvent (such as pure water). Various additives (for example, phosphates such as trisodium phosphate dodecahydrate) may be added to the oxidizing chemical solution.
酸化処理工程は、たとえば亜塩素酸ナトリウム１０〜２００ｇ／Ｌ、リン酸三ナトリウム塩十二水和物５〜６０ｇ／Ｌ、水酸化ナトリウム５〜５０ｇ／Ｌを含む薬液に、銅箔を液温４０〜９５℃、１〜１０分間浸漬することにより行う。 In the oxidation treatment step, for example, a copper foil is added to a chemical solution containing sodium chlorite 10 to 200 g / L, trisodium phosphate dodecahydrate 5 to 60 g / L, and sodium hydroxide 5 to 50 g / L. It is carried out by dipping at 40 to 95 ° C. for 1 to 10 minutes.
電解液に用いるアルカリ性化合物としては、水酸化ナトリウム、水酸化カリウム等を用いることができる。たとえば、水酸化ナトリウムを用いる場合、電解液に含まれる水酸化ナトリウム１００〜３００ｇ／Ｌ、液温６０〜９５℃、陽極電流密度０．５〜３Ａ／ｄｍ2、処理時間２〜３０分間の条件で酸化処理工程を行う。 As an alkaline compound used for the electrolytic solution, sodium hydroxide, potassium hydroxide, or the like can be used. For example, when sodium hydroxide is used, sodium hydroxide contained in the electrolyte is 100 to 300 g / L, liquid temperature is 60 to 95 ° C., anode current density is 0.5 to 3 A / dm 2 , and treatment time is 2 to 30 minutes. An oxidation treatment process is performed.
［還元処理工程］
還元処理工程は、還元剤を含有する薬液（還元用薬液）を用いて銅箔に形成された酸化銅を還元させ、凹凸を調整する工程である。
[Reduction treatment process]
The reduction treatment step is a step of adjusting the unevenness by reducing the copper oxide formed on the copper foil using a chemical solution (reducing chemical solution) containing a reducing agent.
還元剤としては、ジメチルアミンボラン（ＤＭＡＢ）、ジボラン、水素化ホウ素ナトリウム、ヒドラジン等を用いることができる。また、還元用薬液は、還元剤、アルカリ性化合物（水酸化ナトリウム、水酸化カリウム等）、及び溶媒（純水等）を含む液体である。 As the reducing agent, dimethylamine borane (DMAB), diborane, sodium borohydride, hydrazine and the like can be used. The reducing chemical solution is a liquid containing a reducing agent, an alkaline compound (such as sodium hydroxide or potassium hydroxide), and a solvent (such as pure water).
還元処理工程は、たとえばジメチルアミンボラン２〜５０ｇ／Ｌ、水酸化ナトリウム等を用いてｐＨを９以上に調整した薬液に、銅箔を液温２０〜６０℃、２秒〜５分間浸漬することにより行う。 In the reduction treatment step, the copper foil is immersed in a chemical solution having a pH adjusted to 9 or more using, for example, dimethylamine borane 2 to 50 g / L, sodium hydroxide or the like, at a liquid temperature of 20 to 60 ° C. for 2 seconds to 5 minutes. To do.
なお、上記各工程で使用される薬液は、繰り返し使われる。 In addition, the chemical | medical solution used at each said process is used repeatedly.
［除去工程］
本実施形態における銅箔の処理方法は、更に除去工程を有する。除去工程は、還元処理に使用した後の還元用薬液（使用済み薬液）中に存在する銅化合物を除去する工程である。
[Removal process]
The processing method of the copper foil in this embodiment has a removal process further. A removal process is a process of removing the copper compound which exists in the chemical | medical agent for reduction (used chemical | medical solution) after using for a reduction process.
上述の通り、還元剤を含有する薬液を使用して還元処理を行った場合、使用済み薬液中には銅化合物（たとえば、酸化処理された銅箔表面の酸化銅が一部脱落したもの）が含まれている。従って、そのままの状態で放置すれば還元剤と銅化合物とが反応し、使用済み薬液中の還元剤の濃度が経時的に減少する（還元用薬液が劣化する）と考えられる。 As described above, when the reduction treatment is performed using a chemical solution containing a reducing agent, a copper compound (for example, copper oxide on the surface of the oxidized copper foil partially dropped) is contained in the used chemical solution. include. Therefore, if left as it is, it is considered that the reducing agent and the copper compound react and the concentration of the reducing agent in the used chemical solution decreases with time (the chemical solution for reduction deteriorates).
そこで、本実施形態においては、使用済みの還元用薬液中から銅化合物を除去する処理を行う。この処理により、還元剤の濃度の減少を抑制できるため、還元用薬液の寿命を延ばすことが可能となる。銅化合物を除去された還元用薬液は還元処理工程で再利用される。 Therefore, in the present embodiment, a treatment for removing the copper compound from the used reducing chemical solution is performed. This treatment can suppress a reduction in the concentration of the reducing agent, thereby extending the life of the reducing chemical solution. The reducing chemical solution from which the copper compound has been removed is reused in the reduction treatment step.
銅化合物を除去する具体的な方法は、ろ過又は遠心分離、及びそれらの組み合わせが可能である。 Specific methods for removing the copper compound can be filtration or centrifugation, and combinations thereof.
ろ過は、濾紙やフィルターを使用して行うことができる。濾紙は、たとえば、桐山ロート用濾紙（桐山製作所製）を使用することができる。銅化合物の粒径等を考慮し、桐山ロート用濾紙Ｎｏ．４（保留粒子径１μｍ。桐山製作所製）を使用することが好ましい。フィルターは、市販の様々なフィルターを使用することができる。たとえば、フィルターカートリッジＳＲＬ−００５（株式会社ロキテクノ製）を使用することが好ましい。なお、濾紙やフィルターは、銅化合物の粒子を捕捉することができれば、上述の濾紙やフィルターに限られない。たとえば、大量の還元用薬液（数トン）をろ過する場合には、その量に合ったフィルター等を用いる。 Filtration can be performed using filter paper or a filter. As the filter paper, for example, filter paper for Kiriyama funnel (manufactured by Kiriyama Seisakusho) can be used. In consideration of the particle size of the copper compound, the filter paper for Kiriyama funnel No. 4 (retained particle diameter 1 μm, manufactured by Kiriyama Seisakusho) is preferably used. Various commercially available filters can be used as the filter. For example, it is preferable to use a filter cartridge SRL-005 (manufactured by Loki Techno Co., Ltd.). Note that the filter paper and the filter are not limited to the above-described filter paper and filter as long as the copper compound particles can be captured. For example, when a large amount of chemical solution for reduction (several tons) is filtered, a filter suitable for the amount is used.
ろ過は１μｍ以下の濾過精度を有することが好ましい。 The filtration preferably has a filtration accuracy of 1 μm or less.
遠心分離は、遠心分離機を用いて還元用薬液と薬液中に存在する銅化合物を遠心分離する。遠心分離機は、たとえば、テーブルトップ遠心機５４２０（クボタ商事株式会社製）のような小型サイズのものから、工業用の大型遠心分離機のようなものまで薬液の量に応じて様々なものを使用することができる。遠心分離機は、テーブルトップ遠心機５４２０（クボタ商事株式会社製）のようなバッチ式でも、横型連続式遠心分離機Ｈ−８００（株式会社コクサン製）のような連続式でも使用することができる。 Centrifugation uses a centrifuge to centrifuge the reducing chemical and the copper compound present in the chemical. Various centrifuges can be used depending on the amount of the chemical solution, from a small size such as a table top centrifuge 5420 (manufactured by Kubota Shoji Co., Ltd.) to a large industrial centrifuge. Can be used. The centrifuge can be used in a batch type such as a table top centrifuge 5420 (manufactured by Kubota Corporation) or a continuous type such as a horizontal continuous centrifuge H-800 (manufactured by Kokusan Co., Ltd.). .
遠心分離は、２２００×ｇ以上の遠心力で行うことが好ましい。 Centrifugation is preferably performed with a centrifugal force of 2200 × g or more.
また、ろ過と遠心分離を組み合わせてもよい。たとえば、最初に濾紙を用いて使用済み薬液中の銅化合物をろ過し、その後、遠心分離を行って更に銅化合物を除去する。このように、異なる除去方法を組み合わせることにより、使用済み還元用薬液中に存在する銅化合物をより確実に除去することが可能となる。 Moreover, you may combine filtration and centrifugation. For example, the copper compound in the spent chemical solution is first filtered using a filter paper, and then the centrifugal separation is performed to further remove the copper compound. Thus, it becomes possible to remove the copper compound which exists in the used chemical | medical solution for a reduction more reliably by combining a different removal method.
＝＝実施例＝＝
以下の実施例１〜３及び比較例１について、使用済みの還元用薬液中に含まれる銅化合物の量、及び還元用薬液中の還元剤の濃度の経時的な変化を求めた。
== Example ==
About the following Examples 1-3 and Comparative Example 1, the change with time of the quantity of the copper compound contained in the used chemical | medical agent for a reduction | restoration and the density | concentration of the reducing agent in a chemical | medical agent for a reduction | restoration was calculated | required.
全ての実施例及び比較例において、銅箔はＤＲ−ＷＳ（古河電工株式会社製）を用いた。この銅箔（厚み １８μｍ）に対して、以下の処理を行い、使用済みの還元用薬液Ａ〜Ｄを得た。なお、各処理で使用する薬液等は未使用のものを用いている。 In all examples and comparative examples, DR-WS (manufactured by Furukawa Electric Co., Ltd.) was used as the copper foil. The following treatment was performed on this copper foil (thickness: 18 μm) to obtain used reducing chemicals A to D. In addition, the chemical | medical solution etc. which are used by each process use the unused thing.
［アルカリ脱脂処理］
銅箔を、液温５０℃、４０ｇ／Ｌの水酸化ナトリウム水溶液に３分間浸漬した後、水洗を行った。
[Alkaline degreasing treatment]
The copper foil was immersed in a 40 g / L sodium hydroxide aqueous solution at a liquid temperature of 50 ° C. for 3 minutes, and then washed with water.
［酸洗浄処理］
アルカリ脱脂処理を行った銅箔を、液温２５℃、１０重量％の硫酸水溶液に２分間浸漬した後、水洗を行った。
[Acid cleaning treatment]
The copper foil subjected to the alkaline degreasing treatment was immersed in a sulfuric acid aqueous solution having a liquid temperature of 25 ° C. and 10% by weight for 2 minutes, and then washed with water.
［酸化処理］
酸洗浄処理を行った銅箔を、液温８５℃の酸化用薬液に２分間浸漬した後、水洗を行った。
酸化用薬液は以下の成分からなる。
・亜塩素酸ナトリウム（ＮａＣｌＯ2）：９０ｇ／Ｌ
・リン酸三ナトリウム塩十二水和物（Ｎａ3ＰＯ4／１２Ｈ2Ｏ）：１０ｇ／Ｌ
・水酸化ナトリウム（ＮａＯＨ）：１５ｇ／Ｌ
・純水：１Ｌになる量
[Oxidation treatment]
The copper foil subjected to the acid cleaning treatment was immersed in an oxidizing chemical solution having a liquid temperature of 85 ° C. for 2 minutes, and then washed with water.
The oxidizing chemical solution is composed of the following components.
・ Sodium chlorite (NaClO 2 ): 90 g / L
・ Trisodium phosphate dodecahydrate (Na 3 PO 4 / 12H 2 O): 10 g / L
Sodium hydroxide (NaOH): 15 g / L
・ Pure water: 1L
［還元処理］
酸化処理を行った銅箔を、液温５０℃の還元用薬液に２分間浸漬した。なお、還元用薬液に対して０．３６ｍ2／Ｌに相当する量の銅箔を還元処理した。
還元用薬液は以下の成分からなる。
・ジメチルアミンボラン（（ＣＨ3）2ＮＨＢＨ3）：２５ｇ／Ｌ
・水酸化ナトリウム（ＮａＯＨ）：５ｇ／Ｌ
・純水：１Ｌになる量
[Reduction treatment]
The oxidized copper foil was immersed in a reducing chemical solution having a liquid temperature of 50 ° C. for 2 minutes. An amount of copper foil corresponding to 0.36 m 2 / L was reduced with respect to the reducing chemical.
The reducing chemical solution comprises the following components.
Dimethylamine borane ((CH 3 ) 2 NHBH 3 ): 25 g / L
Sodium hydroxide (NaOH): 5 g / L
・ Pure water: 1L
［除去処理］
実施例１〜３については、以下の方法により、使用済みの還元用薬液Ａ〜Ｃ中から銅化合物を除去する処理を行った。一方、使用済みの還元用薬液Ｄについては、銅化合物を除去する処理を行なっていない（比較例１に相当）。
[Removal processing]
About Examples 1-3, the process which removes a copper compound from used chemical | medical solution A-C for reduction with the following method was performed. On the other hand, about the used chemical | medical solution D for reduction, the process which removes a copper compound is not performed (equivalent to the comparative example 1).
（実施例１）
実施例１は、還元処理を行った後、桐山ロート用濾紙Ｎｏ．４（保留粒子径１μｍ。桐山製作所製）を用いて使用済みの還元用薬液Ａをろ過した。
Example 1
In Example 1, after the reduction treatment, the filter paper No. 1 for Kiriyama funnel was used. The used reducing chemical A was filtered using 4 (retained particle diameter: 1 μm, manufactured by Kiriyama Seisakusho).
（実施例２）
実施例２は、還元処理を行った後、フィルターカートリッジＳＲＬ−００５（株式会社ロキテクノ製）を用いて使用済みの還元用薬液Ｂをろ過した。
(Example 2)
In Example 2, after the reduction treatment, the used chemical solution B for reduction was filtered using a filter cartridge SRL-005 (manufactured by Loki Techno Co., Ltd.).
（実施例３）
実施例３は、還元処理を行った後、テーブルトップ遠心機５４２０（クボタ商事株式会社製）を用いて使用済みの還元用薬液Ｃを遠心分離した後、上澄みを回収した。
(Example 3)
In Example 3, after performing the reduction treatment, the used chemical solution C for reduction was centrifuged using a table top centrifuge 5420 (manufactured by Kubota Corporation), and then the supernatant was collected.
（使用済みの還元用薬液中に含まれる銅化合物の量）
使用済みの還元用薬液に含まれる銅化合物の濃度を銅元素の濃度として測定した。測定は、使用済みの還元用薬液に６０％硝酸を加えて銅化合物を完全に溶解させた後、Ａｇｉｌｅｎｔ ５１００ ＩＰＣ−ＯＥＳ（アジレント・テクノロジー株式会社製）を用いて測定した。なお、使用済みの還元用薬液Ａ〜Ｃについては、上述の除去処理を行った後に、銅化合物の濃度を測定した。以下の表１に示す各実施例の銅化合物の量は、比較例１における銅化合物の濃度を１００とした場合の比較値である。
(Amount of copper compound contained in used reducing chemical)
The concentration of the copper compound contained in the used reducing chemical was measured as the concentration of copper element. The measurement was performed using Agilent 5100 IPC-OES (manufactured by Agilent Technologies) after adding 60% nitric acid to the used reducing chemical solution to completely dissolve the copper compound. In addition, about the used chemical | medical solution A to C for reduction, after performing the above-mentioned removal process, the density | concentration of the copper compound was measured. The amount of the copper compound of each Example shown in Table 1 below is a comparative value when the concentration of the copper compound in Comparative Example 1 is 100.
（還元用薬液中の還元剤の濃度変化）
還元用薬液中の還元剤の濃度変化を求めた。具体的には、まず銅箔を還元処理した直後の還元用薬液Ａ〜Ｄ中の還元剤の濃度を自動滴定装置ＧＴ−２００（株式会社三菱化学アナリテック製）を用い、ヨウ素法の逆滴定により測定し基準値とした。その後、実施例１〜３については上述の除去処理を行った。そして、還元処理を行った日から１６日経過後に還元用薬液Ａ〜Ｄ中の還元剤の濃度を再度測定し、基準値からの変化率を求めた。
(Change in concentration of reducing agent in reducing chemical)
The change in the concentration of the reducing agent in the reducing chemical was determined. Specifically, the concentration of the reducing agent in the reducing chemicals A to D immediately after the reduction of the copper foil is first determined using an automatic titration device GT-200 (manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and back titration by the iodine method. Was used as a reference value. Then, about the Examples 1-3, the above-mentioned removal process was performed. And the density | concentration of the reducing agent in the chemical | medical solutions AD for reduction was measured again 16 days after the day which performed the reduction process, and the rate of change from a reference value was calculated | required.
表１に示す銅化合物の量から明らかなように、使用済み還元用薬液に対してろ過や遠心分離を行うことにより、多くの銅化合物を除去できることが分かった。特にフィルターカートリッジを用いた場合（実施例２）、銅化合物をより効率的に除去できることが分かった。 As apparent from the amount of the copper compound shown in Table 1, it was found that many copper compounds can be removed by filtering or centrifuging the used reducing chemical solution. In particular, when a filter cartridge was used (Example 2), it was found that the copper compound can be removed more efficiently.
また、表１に示す還元剤の濃度変化率から明らかなように、比較例１の使用済み還元用薬液Ｄに比べ、銅化合物を除去した使用済み還元用薬液Ａ〜Ｃ（実施例１〜３）の方が還元剤の濃度変化が少ない（還元剤が減少していない）ことが分かった。 Further, as is apparent from the concentration change rate of the reducing agent shown in Table 1, compared with the used reducing chemical solution D of Comparative Example 1, the used reducing chemical solutions A to C (Examples 1 to 3) from which the copper compound was removed. ) Showed less change in the concentration of the reducing agent (the reducing agent was not decreased).
本発明の実施形態及び実施例を説明したが、上記実施形態及び実施例は、例として提示したものであり、発明の範囲を限定することは意図していない。実施形態や実施形態は、発明の範囲や要旨に含まれると同様に、特許請求の範囲に記載された発明とその均等の範囲に含まれるものである。 Although the embodiments and examples of the present invention have been described, the above-described embodiments and examples are presented as examples, and are not intended to limit the scope of the invention. The embodiments and the embodiments are included in the scope of the invention and the gist thereof, and are also included in the invention described in the claims and the equivalents thereof.
Claims (4)
前記還元処理に使用した後の還元用薬液中に存在する銅化合物を除去する除去工程を有することを特徴とする還元用薬液の処理方法。 It is a processing method of a reducing chemical used when reducing the surface of the oxidized copper foil,
A treatment method for a chemical solution for reduction, comprising a removing step of removing a copper compound present in the chemical solution for reduction after being used for the reduction treatment.
前記還元処理工程に使用した後の還元用薬液に存在する銅化合物を除去する除去工程を更に有し、
前記還元処理工程は、除去工程で銅化合物が除去された前記還元用薬液を再利用することを特徴とするプリント配線板に用いる銅箔の処理方法。 A preconditioning step for cleaning the surface of the copper foil, an oxidation treatment step for oxidizing the surface of the copper foil subjected to the preconditioning step with an oxidizing chemical solution, and the copper foil subjected to the oxidizing step with a reducing chemical solution A method for treating a copper foil used for a printed wiring board, comprising a reduction treatment step of reducing,
A further removing step of removing the copper compound present in the reducing chemical after being used in the reduction treatment step;
The said reduction process process reuses the said chemical | medical solution for reduction | restoration from which the copper compound was removed by the removal process, The processing method of the copper foil used for a printed wiring board characterized by the above-mentioned.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0462047A (en) * | 1990-07-02 | 1992-02-27 | Compeq Mfg Co Ltd | Method for bonding copper and resin |
| JPH05247666A (en) * | 1992-03-06 | 1993-09-24 | Hitachi Chem Co Ltd | Surface treatment of steel |
| JP2001295068A (en) * | 2000-04-12 | 2001-10-26 | Hitachi Chem Co Ltd | Surface treating liquid for copper, surface treating method for copper using the same and method for manufacturing printed circuit board |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0462047A (en) * | 1990-07-02 | 1992-02-27 | Compeq Mfg Co Ltd | Method for bonding copper and resin |
| JPH05247666A (en) * | 1992-03-06 | 1993-09-24 | Hitachi Chem Co Ltd | Surface treatment of steel |
| JP2001295068A (en) * | 2000-04-12 | 2001-10-26 | Hitachi Chem Co Ltd | Surface treating liquid for copper, surface treating method for copper using the same and method for manufacturing printed circuit board |
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