JPH08192015A - Method of filtering alkaline electrolyte containing copper - Google Patents
Method of filtering alkaline electrolyte containing copperInfo
- Publication number
- JPH08192015A JPH08192015A JP7019895A JP1989595A JPH08192015A JP H08192015 A JPH08192015 A JP H08192015A JP 7019895 A JP7019895 A JP 7019895A JP 1989595 A JP1989595 A JP 1989595A JP H08192015 A JPH08192015 A JP H08192015A
- Authority
- JP
- Japan
- Prior art keywords
- filter
- filter aid
- cellulose
- filled
- containing copper
- 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.)
- Withdrawn
Links
- 238000001914 filtration Methods 0.000 title claims abstract description 49
- 239000010949 copper Substances 0.000 title claims abstract description 38
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 37
- 239000003792 electrolyte Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229920002678 cellulose Polymers 0.000 claims abstract description 44
- 239000001913 cellulose Substances 0.000 claims abstract description 44
- 239000004744 fabric Substances 0.000 claims abstract description 26
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000012670 alkaline solution Substances 0.000 claims abstract description 7
- 238000007747 plating Methods 0.000 claims description 41
- 239000008151 electrolyte solution Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 6
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims description 3
- 229940005657 pyrophosphoric acid Drugs 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims 2
- 239000000243 solution Substances 0.000 abstract description 9
- 239000002585 base Substances 0.000 abstract description 7
- 238000005406 washing Methods 0.000 abstract description 7
- 239000003513 alkali Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052799 carbon Inorganic materials 0.000 abstract 4
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000002245 particle Substances 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 21
- 238000004140 cleaning Methods 0.000 description 10
- 230000000694 effects Effects 0.000 description 5
- RSJOBNMOMQFPKQ-UHFFFAOYSA-L copper;2,3-dihydroxybutanedioate Chemical compound [Cu+2].[O-]C(=O)C(O)C(O)C([O-])=O RSJOBNMOMQFPKQ-UHFFFAOYSA-L 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 238000000862 absorption spectrum Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 3
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 3
- 239000000835 fiber Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 239000005909 Kieselgur Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000010425 asbestos Substances 0.000 description 2
- 229910000365 copper sulfate Inorganic materials 0.000 description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000002265 prevention Effects 0.000 description 2
- 229910052895 riebeckite Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012209 synthetic fiber Substances 0.000 description 2
- 229920002994 synthetic fiber Polymers 0.000 description 2
- 229920003002 synthetic resin Polymers 0.000 description 2
- 239000000057 synthetic resin Substances 0.000 description 2
- MIDXCONKKJTLDX-UHFFFAOYSA-N 3,5-dimethylcyclopentane-1,2-dione Chemical compound CC1CC(C)C(=O)C1=O MIDXCONKKJTLDX-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229920000875 Dissolving pulp Polymers 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 239000004677 Nylon Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229920001131 Pulp (paper) Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000013736 caramel Nutrition 0.000 description 1
- 238000005256 carbonitriding Methods 0.000 description 1
- 238000005255 carburizing Methods 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229920001778 nylon Polymers 0.000 description 1
- -1 polyethylene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Landscapes
- Filtration Of Liquid (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Filtering Materials (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、銅めっき浴の濾過方法
に係わり、特にセルロース系濾過助剤を充填した濾布フ
ィルターを用いて銅を含むアルカリ性電解液を濾過する
方法における一時的な濾過圧上昇を抑えるためのセルロ
ース系濾過助剤の処理に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for filtering a copper plating bath, and more particularly to a temporary filtration in a method for filtering an alkaline electrolyte containing copper using a filter cloth filter filled with a cellulosic filter aid. The present invention relates to treatment of a cellulosic filter aid to suppress pressure rise.
【０００２】[0002]
【従来の技術】銅めっきは、古くからニッケルまたはニ
ッケル−クロムめっきの下地めっき、鉄鋼、亜鉛ダイカ
ス等の下地めっき、浸炭防止めっき、浸炭窒化防止めっ
き等として使われてきた。最近では、プリント基板のス
ルーホールめっきなど電子工業への応用が盛んになって
きた。2. Description of the Related Art Copper plating has been used for a long time as a base plating of nickel or nickel-chromium plating, a base plating of steel, zinc die-cast, etc., a carburizing prevention plating, a carbonitriding prevention plating and the like. Recently, applications to the electronic industry such as through-hole plating of printed circuit boards have become popular.
【０００３】銅めっき浴としては、硫酸銅めっき浴が１
８世紀初期から使われている。しかし、酒石酸系めっき
浴、ピロリン酸系めっき浴、シアン系めっき浴といった
アルカリ性銅めっき浴が、緻密なめっき被膜が得られる
ことや均一電着性に優れることから、最近では広く使わ
れるようになった。As the copper plating bath, there is one copper sulfate plating bath.
It has been used since the early 8th century. However, alkaline copper plating baths such as tartaric acid-based plating baths, pyrophosphoric acid-based plating baths, and cyan-based plating baths have become widely used recently because of the ability to obtain a dense plating film and excellent throwing power. It was
【０００４】ところで、めっき浴は時間と共に固形の電
解生成物や汚物が浮遊し、めっき面をざらつかせたり、
光沢度を劣化させ、まためっき浴の電気抵抗も増加させ
るので、めっき浴から電解液を循回させての濾過が必要
である。近代的なめっき技術は、濾過に大きく依存して
いるといっても過言ではない。めっきの欠陥の大部分は
濾過の不備に関連している。By the way, in the plating bath, solid electrolytic products and dirt are suspended over time, and the plating surface is roughened.
Since it deteriorates the glossiness and increases the electric resistance of the plating bath, it is necessary to circulate the electrolytic solution from the plating bath for filtration. It is no exaggeration to say that modern plating technology relies heavily on filtration. Most of the plating defects are associated with defective filtration.
【０００５】液体のみを通し、固体を表面上に捕捉する
という濾過作用を実現するために、濾材として合成繊維
等の濾布を使用する濾布フィルターが最も広く使用され
ている。通常、工業めっきプロセスにおいて、濾布だけ
の濾過では微細な粒子による濾布の目詰りが起りやすい
ため、濾過助剤を使用する。濾過助剤は、微粒子をその
表面に吸着・凝集せしめそれらが一体となって濾布の濾
過面に堆積して圧縮性の少ないそして通過性の良い濾滓
層を形成し、濾布の目詰まりを防止する役目をなす。濾
過助剤としては、珪藻土、活性炭、石綿、合成樹脂、セ
ルロース等が用いられる。このうち、濾過助剤の安定
性、フィルターの寿命、濾過精度、価格等の点からアル
カリ性銅めっき浴からのアルカリ性電解液に対しては、
セルロースが最も優れた濾過助剤である。セルロース系
濾過助剤は、パルプ製造プロセスで製造され、繊維長を
グレード毎に所定の大きさに揃えたものが市販されてい
る。Filter cloth filters, which use a filter cloth made of synthetic fiber or the like as a filter medium, are most widely used in order to realize a filtering action of passing only a liquid and trapping a solid on the surface. Usually, in the industrial plating process, a filter aid is used because filtration of only the filter cloth tends to cause clogging of the filter cloth with fine particles. The filter aid adsorbs and agglomerates fine particles on the surface of the filter aid and deposits them on the filter surface of the filter cloth to form a filter cake layer with low compressibility and good permeability, which causes clogging of the filter cloth. Play a role in preventing As the filter aid, diatomaceous earth, activated carbon, asbestos, synthetic resin, cellulose or the like is used. Among them, from the viewpoint of stability of filter aid, filter life, filtration accuracy, price, etc., for alkaline electrolyte from alkaline copper plating bath,
Cellulose is the best filter aid. Cellulose-based filter aids are manufactured by a pulp manufacturing process, and fiber lengths of each grade are made commercially available in a predetermined size.
【０００６】[0006]
【発明が解決しようとする課題】しかし、セルロースに
は若干の可溶成分が存在し、これがメッキ浴に混入する
ことは避けられなかった。しかも、濾過助剤を充填し、
アルカリ性電解液を通流した直後に、一時的なフィルタ
ーの濾過圧上昇が起こり、フィルター寿命が極端に短く
なることがあった。本発明の課題は、こうしたセルロー
ス系濾過助剤に伴う問題を解決することである。However, some soluble components are present in cellulose, and it is unavoidable that these are mixed in the plating bath. Moreover, it is filled with a filter aid,
Immediately after flowing through the alkaline electrolyte, the filtration pressure of the filter temporarily increased, which sometimes shortened the filter life extremely. An object of the present invention is to solve the problems associated with such cellulosic filter aids.
【０００７】[0007]
【課題を解決するための手段】前記課題を解決するた
め、本発明者等が鋭意検討した結果、活性炭を多量に添
加することで一時的な濾過圧上昇を防ぐことができるこ
とを見いだした。この場合、活性炭に吸着した成分は比
較的高分子量のセルロースであることもまた判明した。
更には、市販のセルロース系濾過助剤を、アルカリ水溶
液で予備洗浄すれば、活性炭に吸着する成分のほとんど
が除去できることもわかった。[Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have made earnest studies, and as a result, have found that a temporary increase in filtration pressure can be prevented by adding a large amount of activated carbon. In this case, it was also found that the component adsorbed on the activated carbon was relatively high molecular weight cellulose.
Further, it was found that most of the components adsorbed on the activated carbon can be removed by pre-washing a commercially available cellulose-based filter aid with an alkaline aqueous solution.
【０００８】この知見に基づいて、本発明は、基本的
に、（１）セルロース系濾過助剤を充填した濾布フィル
ターを用い、銅を含むアルカリ性電解液を濾過する方法
において、予めアルカリ水溶液で予備洗浄したセルロー
ス系濾過助剤をフィルターに充填することを特徴とする
銅を含むアルカリ性電解液を濾過方法並びに（２）セル
ロース系濾過助剤を充填した濾布フィルターを用い、銅
を含むアルカリ性電解液を濾過する方法において、活性
炭を該セルロース系濾過助剤と混合させることを特徴と
する銅を含むアルカリ性電解液を濾過方法を提供する。
更に、状況によっては、（１）と（２）とを併用して、
セルロース系濾過助剤を予めアルカリ水溶液で予備洗浄
しそして活性炭を該セルロース系濾過助剤と混合させる
こともできる。Based on this finding, the present invention basically provides (1) a method for filtering an alkaline electrolyte containing copper using a filter cloth filter filled with a cellulosic filter aid, in advance with an alkaline aqueous solution. A method for filtering an alkaline electrolytic solution containing copper, characterized in that a pre-washed cellulosic filter aid is filled in a filter, and (2) an alkaline electrolysis containing copper using a filter cloth filter filled with a cellulose filter aid. In a method for filtering a liquid, there is provided a method for filtering an alkaline electrolytic solution containing copper, characterized in that activated carbon is mixed with the cellulosic filter aid.
Furthermore, depending on the situation, by using (1) and (2) together,
It is also possible to pre-wash the cellulosic filter aid with an aqueous alkaline solution beforehand and to mix the activated carbon with the cellulosic filter aid.
【０００９】活性炭を該セルロース系濾過助剤と混合さ
せるには、（Ａ）活性炭を該セルロース系濾過助剤に添
加して充填する方法及び（Ｂ）活性炭を充填した後にセ
ルロース系濾過助剤を充填する方法及び（Ｃ）アルカリ
性溶液又は銅を含むアルカリ性電解液を充填液として用
い、前記充填液を循環させながら、セルロース系濾過助
剤を充填した後活性炭を充填する方法がある。銅を含む
アルカリ性電解液の例は、酒石酸系めっき浴、ピロリン
酸系めっき浴、シアン系めっき浴のいずれかからの電解
液である。In order to mix the activated carbon with the cellulosic filter aid, (A) a method of adding activated carbon to the cellulosic filter aid and filling it, and (B) adding activated carbon and then adding the cellulosic filter aid. There are a method of filling and a method (C) of using an alkaline solution or an alkaline electrolyte containing copper as a filling solution, and then filling the cellulosic filter aid with the activated carbon after circulating the filling solution. An example of the alkaline electrolyte containing copper is an electrolyte from a tartaric acid-based plating bath, a pyrophosphoric acid-based plating bath, or a cyan-based plating bath.
【００１０】[0010]
【作用】本発明の最大の特徴は、セルロース系濾過助剤
を充填した濾布フィルターを用いて銅を含むアルカリ性
電解液を濾過する方法において、セルロース系濾過助剤
を使用するに当たって、予めセルロース系濾過助剤を洗
浄するか活性炭を混合することにより、電解液中から可
溶性セルロースを除去することにある。すなわち、活性
炭を多量に添加することでセルロース成分を活性炭に吸
着せしめ、また市販のセルロース系濾過助剤をアルカリ
水溶液でこれら成分を予備洗浄することにより、セルロ
ースの可溶成分を除去することができる。一時的な濾過
圧上昇が無くなる理由を解明するため、銅を含まない電
解液を作製し、これにセルロースを溶解してみたが、一
時的な濾過圧上昇は発生せず、また、活性炭処理により
可溶性セルロースを除去しても、一時的な濾過圧上昇は
発生しない。また、溶解したセルロース系濾過助剤が活
性炭に吸着されることを確認するため、セルロース系濾
過助剤を１０％水酸化ナトリウムに溶解し、活性炭処理
前後で液中に含まれるセルロースの濃度を測定した。分
析方法は、溶解パルプ分析法の１０％水酸化ナトリウム
溶解度測定方法｛日本分析化学会編：分析化学便覧（改
訂四版）、ｐ１０９１（１９９１）・丸善｝に従った。
その結果、活性炭を多量に（セルロース系濾過助剤の４
倍量以上）使用しても、溶解したセルロースの６３％市
価吸着しないことが分かった。この結果から、活性炭処
理により、比較的高分子のセルロースのみが除去されて
いると推定される。これらのことから、電解液中で銅と
比較的高分子である可溶性セルロースが結合し、微細な
粒子を作るために一時的な濾過圧上昇が起るものと推定
される。フィルターの濾過圧上昇が一時的であるのは、
電解液中に溶解したセルロースが時間と共に加水分解
し、銅と結合できるセルロースの可溶成分が減少するた
めと考えられる。The greatest feature of the present invention is that when a cellulosic filter aid is used in a method for filtering an alkaline electrolyte containing copper using a filter cloth filter filled with a cellulosic filter aid, the cellulosic filter aid is used in advance. The purpose is to remove soluble cellulose from the electrolytic solution by washing the filter aid or mixing activated carbon. That is, the soluble component of cellulose can be removed by adding a large amount of activated carbon to cause the activated carbon to adsorb the cellulose component, and preliminarily washing the commercially available cellulose-based filter aid with an alkaline aqueous solution. . In order to elucidate the reason why the temporary increase in filtration pressure disappeared, we prepared an electrolyte solution containing no copper and dissolved cellulose in this solution, but no temporary increase in filtration pressure occurred. Removal of soluble cellulose does not cause a temporary rise in filtration pressure. In addition, in order to confirm that the dissolved cellulose-based filter aid is adsorbed on the activated carbon, the cellulose-based filter aid is dissolved in 10% sodium hydroxide and the concentration of cellulose contained in the liquid is measured before and after the activated carbon treatment. did. The analysis method was in accordance with the 10% sodium hydroxide solubility measurement method of the dissolving pulp analysis method (edited by the Japan Society for Analytical Chemistry: Analytical Chemistry Handbook (Revised Fourth Edition), p1091 (1991) Maruzen}.
As a result, a large amount of activated carbon (4% of the cellulosic filter aid
It was found that 63% of the dissolved cellulose was not adsorbed at a market value even when used. From this result, it is presumed that only the relatively high molecular weight cellulose was removed by the activated carbon treatment. From these facts, it is estimated that copper and soluble cellulose, which is a relatively high polymer, are bound to each other in the electrolytic solution to form fine particles, which causes a temporary increase in filtration pressure. The rise in filtration pressure of the filter is temporary,
It is considered that the cellulose dissolved in the electrolytic solution hydrolyzes with time, and the soluble component of cellulose that can bind to copper decreases.
【００１１】可溶性セルロースが、銅と結合することを
確認するため、シアン化銅めっき浴１リットルに５０ｇ
のセルロース系濾過助剤を加え、８０℃で１時間放置
後、濾過した。濾過後、室温で放置すると、沈殿物が発
生したので濾別し、沈殿物を十分水洗した。沈殿を真空
デシケータで２４時間乾燥後、ＫＢｒ法により赤外吸収
スペクトルを測定した。また、比較のために、濾過助剤
そのものを同様にして赤外吸収スペクトルを測定した。
その結果、前記沈殿物と濾過助剤そのものの赤外吸収ス
ペクトルは、ほぼ同一であることがわかった。In order to confirm that soluble cellulose binds to copper, 50 g per 1 liter of a copper cyanide plating bath is used.
The cellulosic filter aid was added, and the mixture was allowed to stand at 80 ° C. for 1 hour and then filtered. After filtration, when left at room temperature, a precipitate was generated. Therefore, the precipitate was separated by filtration and washed thoroughly with water. The precipitate was dried with a vacuum desiccator for 24 hours, and the infrared absorption spectrum was measured by the KBr method. For comparison, the infrared absorption spectrum was measured in the same manner as the filter aid itself.
As a result, it was found that the infrared absorption spectra of the precipitate and the filter aid themselves were almost the same.
【００１２】[0012]
【発明の具体的な説明】図１は、従来からの濾布フィル
ターの一例の簡略図である。フィルター１内部には、濾
布２により濾過室３が構成され、濾過電解液を取り出す
ための濾過室出口４はフィルター１の一端から突出して
いる。フィルター１には、反対側に電解液導入のための
入口５が形成されている。濾布は、例示の形態以外に、
長手方向に多数の溝を有する形態等適宜の形態をとるこ
とができ、要は濾過能率を向上するために大きな濾過面
積を持つものとされる。濾布としては、綿布、動物性繊
維、ナイロン、塩化ビニール、ポリエチレン等の合成繊
維、ガラス繊維、セラミック製のものを使用することが
できる。濾過助剤槽６が適宜の配管、ポンプ、弁を介し
てフィルター１に連結されている。濾過助剤槽６には、
珪藻土、活性炭、石綿、合成樹脂、セルロース等が用い
られるが、本発明ではセルロース系のものが装填されて
いる。濾過助剤を使用するためには、最初、濾過助剤の
みの懸濁液が充填され、濾布の濾過面に濾過助剤のプリ
コート層を点線で示すように形成させることが必要であ
る。別様には、電解液と濾過助剤とを混合して供給する
方法もある。濾過助剤は、微粒子をその表面に吸着・凝
集せしめ、それらが一体となって濾布の濾過面に堆積し
て圧縮性の少ないそして通過性の良い濾滓層を形成し、
濾布の目詰まりを防止する役目をなす。ところが、セル
ロース系濾過助剤の場合、アルカリ性電解液に対しては
前述した一時的な濾過圧上昇の問題が生じたのである。DETAILED DESCRIPTION OF THE INVENTION FIG. 1 is a simplified view of an example of a conventional filter cloth filter. Inside the filter 1, a filter chamber 2 is constituted by a filter cloth 2, and a filter chamber outlet 4 for taking out the filtered electrolyte solution projects from one end of the filter 1. An inlet 5 for introducing an electrolytic solution is formed on the opposite side of the filter 1. The filter cloth, in addition to the exemplified form,
It can take any suitable form such as a form having a large number of grooves in the longitudinal direction, and the point is that it has a large filtration area in order to improve the filtration efficiency. As the filter cloth, cotton cloth, animal fibers, synthetic fibers such as nylon, vinyl chloride and polyethylene, glass fibers, and ceramics can be used. A filter aid tank 6 is connected to the filter 1 via appropriate pipes, pumps, and valves. In the filter aid tank 6,
Diatomaceous earth, activated carbon, asbestos, synthetic resin, cellulose, etc. are used, but in the present invention, a cellulosic material is loaded. In order to use the filter aid, it is first necessary to fill it with a suspension of the filter aid alone and to form a precoat layer of filter aid on the filtration surface of the filter cloth as indicated by the dotted line. Alternatively, there is also a method in which the electrolytic solution and the filter aid are mixed and supplied. The filter aid causes fine particles to be adsorbed and aggregated on the surface thereof, and they are integrally deposited on the filter surface of the filter cloth to form a filter layer having low compressibility and good permeability,
It serves to prevent clogging of the filter cloth. However, in the case of the cellulosic filter aid, the above-mentioned problem of temporary increase in filtration pressure occurs with respect to the alkaline electrolyte.
【００１３】セルロース系濾過助剤としては、多くのも
のが市販されており、例えばＦＩＢＲＡ−ＣＥＬ社から
ＢＨ及びＳＷ ＧＲＡＤＥＳとして販売されている。こ
れらは、木材パルプ／セルロースを乾式予備ミルでミリ
サイズに摩砕し、乾式ミルにかけた後、グレード毎の繊
維長分別を行い、製品化したものである。Many cellulosic filter aids are commercially available, for example BH and SW GRADES from FIBRA-CEL. In these products, wood pulp / cellulose is ground into a millimeter size in a dry preliminary mill, and after being subjected to a dry mill, fiber lengths are classified according to grades and commercialized.
【００１４】本発明に従えば、比較的高分子の可溶性セ
ルロースを除去するため、予めセルロース系濾過助剤を
洗浄するか、或いは活性炭と混合せしめられる。According to the invention, the cellulosic filter aid is pre-washed or mixed with activated carbon to remove the relatively high molecular weight soluble cellulose.
【００１５】濾過助剤を予備洗浄する場合は、アルカリ
水溶液、好ましくは水酸化ナトリウム溶液を用い、その
濃度が好ましくは２ｇ／l 以上、より好ましくは４〜４
０ｇ／l の液を用いる。水酸化ナトリウム濃度が２ｇ／
l 未満になると、予備洗浄が不完全となり、一時的な濾
過圧上昇が目立つようになる。また、アルカリ濃度が４
０ｇ／l を超えると、洗浄効果は飽和するばかりでな
く、液の粘性が増加する等で作業性が低下する。洗浄温
度は、使用する電解液の温度より高めとし、洗浄時間は
約１時間程度で十分である。これは、添加直後に可溶性
セルロースの大部分が溶解してしまうためと考えられ
る。もし、低い温度で洗浄する場合は、洗浄時間を延長
するのが望ましい。これは、電解液の温度にもよるが、
例えば、２５℃低い条件で洗浄する場合は、４時間程度
となる。また、使用する電解液温度よりも極端に低い場
合は、洗浄時間を１〜２日間にしないと効果が出ない場
合がある。When the filter aid is preliminarily washed, an alkaline aqueous solution, preferably a sodium hydroxide solution is used, and the concentration thereof is preferably 2 g / l or more, more preferably 4 to 4
A 0 g / l solution is used. Sodium hydroxide concentration is 2g /
If it is less than l, pre-washing is incomplete, and a temporary rise in filtration pressure becomes noticeable. Also, the alkali concentration is 4
If it exceeds 0 g / l, not only the cleaning effect is saturated, but also the viscosity of the liquid increases and the workability deteriorates. The cleaning temperature is higher than the temperature of the electrolytic solution used, and the cleaning time of about 1 hour is sufficient. It is considered that this is because most of the soluble cellulose is dissolved immediately after the addition. If cleaning at low temperature, it is desirable to extend the cleaning time. This depends on the temperature of the electrolyte,
For example, when cleaning is performed at a temperature lower by 25 ° C., it takes about 4 hours. If the temperature of the electrolyte used is extremely low, the effect may not be obtained unless the cleaning time is set to 1 to 2 days.
【００１６】他方、活性炭をセルロース系濾過助剤と混
合させるには、（Ａ）活性炭を該セルロース系濾過助剤
に添加して充填する方法、（Ｂ）活性炭を充填した後に
セルロース系濾過助剤を充填する方法及び（Ｃ）アルカ
リ性溶液又は銅を含むアルカリ性電解液を充填液として
用い、前記充填液を循環させながら、セルロース系濾過
助剤を充填した後活性炭を充填する方法がある。活性炭
を添加する場合は、活性炭を好ましくは重量比で濾過助
剤量の１／１０以上、より好ましくは１／５〜１／２の
量を添加する。比較的高分子な可溶性セルロースをほぼ
完全に除去するためには、濾過助剤量の１／２以上の添
加量が必要であるが、一時的な濾過圧上昇を抑えるため
には１／１０以上あれば相応の効果がある。濾過助剤量
の１／１０未満の添加量になると、一時的な濾過圧上昇
が目立つようになる。活性炭を充填後にセルロース系濾
過助剤を充填してもあるいはアルカリ性溶液又は銅を含
むアルカリ性電解液を充填液として用い、前記充填液を
循環させながら、セルロース系濾過助剤を充填した後活
性炭を充填しても、同様の効果が得られる。On the other hand, in order to mix the activated carbon with the cellulosic filter aid, (A) the activated carbon is added to the cellulosic filter aid and filled, and (B) the activated carbon is charged and then the cellulosic filter aid is added. And a method in which (C) an alkaline solution or an alkaline electrolyte containing copper is used as a filling solution, and while the filling solution is circulated, a cellulosic filter aid is filled and then activated carbon is filled. When activated carbon is added, the activated carbon is preferably added in a weight ratio of 1/10 or more, and more preferably 1/5 to 1/2 of the amount of the filter aid. In order to remove the relatively high-molecular soluble cellulose almost completely, it is necessary to add 1/2 or more of the amount of the filter aid, but 1/10 or more to suppress the temporary increase in filtration pressure. If there is a corresponding effect. When the amount added is less than 1/10 of the amount of the filter aid, a temporary increase in filtration pressure becomes conspicuous. Even if the cellulosic filter aid is filled after the activated carbon is filled, or an alkaline solution or an alkaline electrolyte containing copper is used as the filling liquid, while the filling liquid is circulated, the cellulosic filter aid is filled and then the activated carbon is filled. However, the same effect can be obtained.
【００１７】濾過助剤を予めセルロース系濾過助剤を洗
浄するか、或いは活性炭と混合せしめるだけで十分の効
果が得られるが、両者を併用して、セルロース系濾過助
剤を予めアルカリ水溶液で予備洗浄しそして上記のよう
に該セルロース系濾過助剤と添加混合させることもでき
る。この場合には、活性炭の添加量を減少することがで
きる。A sufficient effect can be obtained only by previously washing the cellulosic filter aid with the filter aid or mixing it with activated carbon. However, both are used in combination to preliminarily prepare the cellulosic filter aid with an aqueous alkaline solution. It can be washed and admixed with the cellulosic filter aid as described above. In this case, the amount of activated carbon added can be reduced.
【００１８】活性炭としては、市販品を使用すれば十分
である。例えば、武田薬品工業株式会社から薬品賦活炭
として「カルボラフィン」の商品名で販売されている活
性炭を使用することができる。これは、１４３０ｍ3 ／
ｇの比表面積、１．１７ｃｃ／ｇの細孔容積及び３２．
７Åの平均細孔直径を有し、カラメル脱色力：９４〜乃
至９５〜、ｐＨ：５．５〜７．０乃至４．０〜５．４、
Ｃｌ- ：約０．１５％、Ｆｅ+2＋Ｆｅ3+：約０．０９
％、比濾過速度：３０〜８０の特性を有する。もちろ
ん、その他の吸着力に優れた市販活性炭を使用すること
ができる。A commercially available product may be used as the activated carbon. For example, activated carbon sold by Takeda Pharmaceutical Co., Ltd. under the trade name of "carborafine" can be used as the activated carbon. This is 1430 m 3 /
g specific surface area, 1.17 cc / g pore volume and 32.
Caramel decolorizing power: 94-95-, pH: 5.5-7.0-4.0-5.4, having an average pore diameter of 7Å.
Cl − : about 0.15%, Fe +2 + Fe 3+ : about 0.09
%, Specific filtration rate: 30 to 80. Of course, other commercially available activated carbons having excellent adsorptive power can be used.
【００１９】[0019]
【実施例】以下、本発明の効果を示すため幾種かの銅め
っき浴を用いての実施例及び比較例を示す。セルロース
系濾過助剤は、ＦＩＢＲＡ−ＣＥＬ社のＢＨ−４０を使
用した。電解液量は５０リットルであり、濾過助剤は５
００ｇ使用した。濾過圧はフィルターの入口と出口の差
圧を測定した。活性炭による処理を行う場合、活性炭は
武田薬品工業株式会社「カルボラフィン」で、濾過助剤
と全量混合した状態で充填した。また、濾過助剤の予備
洗浄を行う場合、水酸化ナトリウム洗浄液の温度は６０
℃、洗浄時間は１時間とした。結果を第１表に示す。EXAMPLES Examples and comparative examples using several kinds of copper plating baths will be shown below to show the effect of the present invention. As the cellulose-based filter aid, BH-40 manufactured by FIBRA-CEL was used. The amount of electrolyte is 50 liters, and the filter aid is 5
00g was used. As the filtration pressure, the differential pressure between the inlet and the outlet of the filter was measured. When the treatment with activated carbon was carried out, the activated carbon was “Carborafine” manufactured by Takeda Pharmaceutical Co., Ltd., and the activated carbon was filled in a state of being completely mixed with the filter aid. When pre-cleaning the filter aid, the temperature of the sodium hydroxide cleaning solution is 60
C. and the washing time was 1 hour. The results are shown in Table 1.
【００２０】実施例１〜８は酒石酸銅めっき浴を使用す
るものであり、酒石酸銅めっき浴として、硫酸銅（Ｃu
ＳＯ4 ・５Ｈ2 Ｏ）４０ｇ／l 、ロッシェル塩１００ｇ
／l及び水酸化ナトリウム５０ｇ／l の浴を用いた。電
解液の温度は６０℃である。実施例９〜１０はピロリン
酸銅めっき浴を使用するものであり、ピロリン酸銅めっ
き浴として、ピロリン酸銅９０ｇ／l 、ピロリン酸カリ
ウム３３０ｇ／l 、アンモニア１．５ｇ／l の浴を用い
た。実施例１１〜１２はシアン化銅めっき浴を使用する
ものであり、シアン化銅めっき浴として、シアン化第１
銅７０ｇ／l 、シアン化ナトリウム９０ｇ／l 及び水酸
化ナトリウム２０ｇ／l の浴を用いた。実施例１３〜１
４は活性炭使用量及び予備洗浄のアルカリ濃度を低めに
して実施例１〜８の酒石酸銅めっき浴を使用して試験し
たものである。比較例１は、活性炭及び予備アルカリ洗
浄なしで実施例１〜８の酒石酸銅めっき浴を使用して試
験したものである。本発明は一時的な濾過圧上昇を完全
に防止することができ、濾過圧上昇が起こった場合でも
その上昇度比較例に較べて格段に低いことが確認され
る。Examples 1 to 8 use a copper tartrate plating bath, and copper sulfate (Cu) is used as the copper tartrate plating bath.
SO 4 · 5H 2 O) 40g / l, Rochelle salt 100g
A bath of 1 / l and 50 g / l of sodium hydroxide was used. The temperature of the electrolytic solution is 60 ° C. Examples 9 to 10 use a copper pyrophosphate plating bath. As the copper pyrophosphate plating bath, a bath containing 90 g / l of copper pyrophosphate, 330 g / l of potassium pyrophosphate and 1.5 g / l of ammonia was used. . Examples 11 to 12 use a copper cyanide plating bath. As the copper cyanide plating bath, cyanide first
A bath of 70 g / l copper, 90 g / l sodium cyanide and 20 g / l sodium hydroxide was used. Examples 13-1
No. 4 was tested using the copper tartrate plating baths of Examples 1 to 8 with a lower amount of activated carbon and a lower alkali concentration for prewashing. Comparative Example 1 was tested using the copper tartrate plating baths of Examples 1-8 without activated carbon and preliminary alkali cleaning. It is confirmed that the present invention can completely prevent a temporary rise in filtration pressure, and that even if a rise in filtration pressure occurs, the degree of increase is significantly lower than in the comparative example.
【００２１】[0021]
【表１】 [Table 1]
【００２２】[0022]
【発明の効果】以上説明したように、本発明によって銅
を含むアルカリ性めっき浴での一時的な濾過圧上昇が抑
えられ、セルロース系濾過助剤使用する濾布フィルター
に起因するトラブルを防止することが可能になった。As described above, according to the present invention, a temporary increase in filtration pressure in an alkaline plating bath containing copper is suppressed, and troubles caused by a filter cloth filter using a cellulosic filter aid are prevented. Became possible.
【図１】従来からの濾布フィルターの一例の簡略図であ
る。FIG. 1 is a simplified diagram of an example of a conventional filter cloth filter.
１ フィルター ２ 濾布 ３ 濾過室 ４ 濾過室出口 ５ 電解液入口 ６ 濾過助剤槽 1 Filter 2 Filter Cloth 3 Filtration Chamber 4 Filtration Chamber Outlet 5 Electrolyte Inlet 6 Filter Aid Tank
Claims (6)
ィルターを用い、銅を含むアルカリ性電解液を濾過する
方法において、予めアルカリ水溶液で予備洗浄したセル
ロース系濾過助剤をフィルターに充填することを特徴と
する銅を含むアルカリ性電解液の濾過方法。1. In a method of filtering an alkaline electrolyte containing copper using a filter cloth filter filled with a cellulose-based filter aid, the filter is filled with a cellulose-based filter aid preliminarily washed with an alkaline aqueous solution. A method for filtering an alkaline electrolyte containing copper.
ィルターを用い、銅を含むアルカリ性電解液を濾過する
方法において、セルロース系濾過助剤をフィルターに充
填する際に、活性炭を該セルロース系濾過助剤に添加し
て充填することを特徴とする銅を含むアルカリ性電解液
の濾過方法。2. A method for filtering an alkaline electrolytic solution containing copper using a filter cloth filter filled with a cellulose-based filter aid, wherein activated carbon is added to the cellulose-based filter when the cellulose-based filter aid is filled in the filter. A method for filtering an alkaline electrolyte containing copper, which comprises adding to an auxiliary agent and filling the auxiliary agent.
ィルターを用い、銅を含むアルカリ性電解液を濾過する
方法において、セルロース系濾過助剤をフィルターに充
填する際に、活性炭を充填した後にセルロース系濾過助
剤を充填することを特徴とする銅を含むアルカリ性電解
液の濾過方法。3. A method for filtering an alkaline electrolytic solution containing copper by using a filter cloth filter filled with a cellulose-based filter aid, wherein when the cellulose-based filter aid is loaded into the filter, cellulose is filled after the activated carbon is filled. A method for filtering an alkaline electrolyte containing copper, which comprises filling a system-based filter aid.
ィルターを用い、銅を含むアルカリ性電解液を濾過する
方法において、アルカリ性溶液又は銅を含むアルカリ性
電解液を充填液として用い、前記充填液を循環させなが
ら、セルロース系濾過助剤を充填した後活性炭を充填す
ることを特徴とする銅を含むアルカリ性電解液の濾過方
法。4. A method for filtering an alkaline electrolyte containing copper using a filter cloth filter filled with a cellulosic filter aid, wherein an alkaline solution or an alkaline electrolyte containing copper is used as the filling liquid, and the filling liquid is A method for filtering an alkaline electrolyte containing copper, which comprises charging a cellulosic filter aid and then charging activated carbon while circulating.
溶液で予備洗浄したことを特徴とする請求項２乃至４の
銅を含むアルカリ性電解液の濾過方法。5. The method for filtering an alkaline electrolyte containing copper according to claim 2, wherein the cellulosic filter aid is preliminarily washed with an alkaline aqueous solution.
めっき浴、ピロリン酸系めっき浴、シアン系めっき浴の
いずれかからの電解液であることを特徴とする請求項１
乃至５の銅を含むアルカリ性電解液の濾過方法。6. The electrolytic solution containing copper is an electrolytic solution from any one of a tartaric acid-based plating bath, a pyrophosphoric acid-based plating bath, and a cyan-based plating bath.
5 to a method of filtering an alkaline electrolyte containing copper.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7019895A JPH08192015A (en) | 1995-01-13 | 1995-01-13 | Method of filtering alkaline electrolyte containing copper |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7019895A JPH08192015A (en) | 1995-01-13 | 1995-01-13 | Method of filtering alkaline electrolyte containing copper |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH08192015A true JPH08192015A (en) | 1996-07-30 |
Family
ID=12011940
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7019895A Withdrawn JPH08192015A (en) | 1995-01-13 | 1995-01-13 | Method of filtering alkaline electrolyte containing copper |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH08192015A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001087459A1 (en) * | 2000-05-18 | 2001-11-22 | Mitsui Mining & Smelting Co.,Ltd. | Method for filtration of copper electrolyte solution |
-
1995
- 1995-01-13 JP JP7019895A patent/JPH08192015A/en not_active Withdrawn
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001087459A1 (en) * | 2000-05-18 | 2001-11-22 | Mitsui Mining & Smelting Co.,Ltd. | Method for filtration of copper electrolyte solution |
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