JP2002115074A - Method and equipment for plating using ph-controlled plating solution - Google Patents
Method and equipment for plating using ph-controlled plating solutionInfo
- Publication number
- JP2002115074A JP2002115074A JP2000308819A JP2000308819A JP2002115074A JP 2002115074 A JP2002115074 A JP 2002115074A JP 2000308819 A JP2000308819 A JP 2000308819A JP 2000308819 A JP2000308819 A JP 2000308819A JP 2002115074 A JP2002115074 A JP 2002115074A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- ion exchange
- solution
- plating solution
- exchange membrane
- 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- Withdrawn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
- 238000007747 plating Methods 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims description 15
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 21
- 150000002500 ions Chemical class 0.000 claims abstract description 13
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 238000005342 ion exchange Methods 0.000 claims abstract description 9
- 238000009792 diffusion process Methods 0.000 claims abstract description 6
- 238000010979 pH adjustment Methods 0.000 claims abstract description 6
- 230000008595 infiltration Effects 0.000 claims abstract description 4
- 238000001764 infiltration Methods 0.000 claims abstract description 4
- 239000000126 substance Substances 0.000 claims abstract description 4
- -1 titanium ions Chemical class 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 abstract description 8
- 239000003456 ion exchange resin Substances 0.000 abstract description 8
- 229920003303 ion-exchange polymer Polymers 0.000 abstract description 8
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 56
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 24
- 229910001453 nickel ion Inorganic materials 0.000 description 12
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 11
- JOYRKODLDBILNP-UHFFFAOYSA-N Ethyl urethane Chemical compound CCOC(N)=O JOYRKODLDBILNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000003011 anion exchange membrane Substances 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000007423 decrease Effects 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007772 electroless plating Methods 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000006276 transfer reaction Methods 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
(57)【要約】
【課題】 イオン交換樹脂の再生処理を必要とせず、
還元剤の補給も必要とせず、イオンの移動に電圧を使用
することもなしに、連続して長時間、めっき液のｐＨを
所定の範囲に維持しながらめっきする。
【解決手段】 化学拡散浸透によりイオンが流通される
ようにイオン交換膜を備えたｐＨ調整部の該イオン交換
膜の両側に、それぞれ、めっき槽で使用されためっき液
の一部とｐＨ調整液を導入し、イオン交換膜を介してイ
オン交換することにより、ｐＨ調整した後のめっき液を
めっき槽にもどし、めっき槽中のめっき液を所定のｐＨ
に維持してめっきする。
(57) [Abstract] [Problem] It does not require regeneration treatment of ion exchange resin.
Plating is performed while maintaining the pH of the plating solution within a predetermined range continuously for a long time without requiring replenishment of a reducing agent or using voltage for transferring ions. SOLUTION: A part of a plating solution used in a plating tank and a pH adjusting solution are respectively provided on both sides of the ion exchange membrane of a pH adjusting unit provided with an ion exchange membrane so that ions are circulated by chemical diffusion infiltration. Is introduced, and the plating solution after the pH adjustment is returned to the plating tank by ion exchange through an ion exchange membrane, and the plating solution in the plating tank is adjusted to a predetermined pH.
And plating.
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、めっき液のｐＨを
所定の範囲に制御してめっきする方法およびそのための
設備に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for plating by controlling the pH of a plating solution within a predetermined range, and a facility for plating.
【０００２】[0002]
【従来の技術】めっきのプロセスに於いて、めっき液の
ｐＨを所定の範囲に制御することは、めっきの品質に重
要な影響があり、ｐＨを所定の範囲に制御する方法につ
いて、従来から種々検討されてきた。例えば、特公昭５
８−２４５１９号公報には、電解ニッケルめっき液のｐ
Ｈ調整について次のように記載されている。電気ニッケ
ルめっきの場合、陰極でのニッケルの析出は１００％で
はないため、所定の時間めっきを行うと、めっき液中の
ニッケルイオンが増加し、このイオンが酸と反応する結
果、ｐＨが所定の値より大きくなる。このｐＨを所定の
値にまで小さくするために、めっき液をイオン交換塔に
導いて、ニッケルイオンを吸着除去する。そして、イオ
ン交換塔のイオン交換樹脂がこれらで飽和した場合に
は、別途、イオン交換樹脂を硫酸や塩酸と反応させてニ
ッケルイオンを回収し、イオン交換樹脂を再生させる。2. Description of the Related Art In a plating process, controlling the pH of a plating solution within a predetermined range has an important effect on plating quality, and various methods for controlling the pH within a predetermined range have been conventionally used. Has been considered. For example,
Japanese Patent Application Laid-Open No. 8-24519 discloses that p of electrolytic nickel plating solution is used.
The H adjustment is described as follows. In the case of electro-nickel plating, nickel deposition at the cathode is not 100%. Therefore, when plating is carried out for a predetermined time, nickel ions in the plating solution increase, and as a result of this ion reacting with acid, the pH becomes a predetermined value Greater than the value. In order to reduce the pH to a predetermined value, the plating solution is guided to an ion exchange tower to absorb and remove nickel ions. Then, when the ion exchange resin of the ion exchange tower is saturated with these, the ion exchange resin is separately reacted with sulfuric acid or hydrochloric acid to recover nickel ions and regenerate the ion exchange resin.
【０００３】また、特開昭５６−１１２５００号公報に
は、めっき浴の組成を安定に保つ方法として、可溶性陽
極を用いる電気めっきに於いて、可溶性陽極とは別に不
溶性補助陽極を用いる方法が開示されている。この方法
は、不溶性補助陽極を通じてめっき電流の一部を流し、
可溶性陽極からの金属の溶出量を減らすことにより、め
っき液中の金属濃度の上昇を抑え、めっき液のｐＨが大
きくならないようにするものである。さらに、特開平３
−５９１４３号公報には、無電解めっき液の管理装置と
して、陽イオン交換膜と陰イオン交換膜とを用いて、溶
液槽を、陽イオン膜側、陰イオン膜側、中間槽の３槽に
区切り、陽イオン側、陰イオン側にそれぞれ設けられた
電極間に交流定電流パルスを流すことにより、中間槽に
めっきに必要なイオンを選択的に補充するという方法が
開示されている。Japanese Patent Application Laid-Open No. 56-112500 discloses a method for maintaining a stable composition of a plating bath by using an insoluble auxiliary anode separately from a soluble anode in electroplating using a soluble anode. Have been. This method involves passing a portion of the plating current through an insoluble auxiliary anode,
By reducing the amount of metal eluted from the soluble anode, an increase in the metal concentration in the plating solution is suppressed, and the pH of the plating solution is not increased. Further, Japanese Unexamined Patent Application Publication No.
JP-A-59143 discloses that a solution tank is divided into three tanks: a cation membrane side, an anion membrane side, and an intermediate tank, using a cation exchange membrane and an anion exchange membrane as a device for managing an electroless plating solution. A method is disclosed in which an AC constant current pulse is applied between electrodes provided on a partition, a cation side, and an anion side, respectively, to selectively replenish ions required for plating in an intermediate tank.
【０００４】[0004]
【発明が解決しようとする課題】しかし、これらの方法
には、それぞれ、次のような問題がある。特公昭５８−
２４５１９号公報に開示された方法では、ニッケルイオ
ンを除去するときに、還元剤も、ある程度除去されるた
め、還元剤の補給が必要になる他、イオン交換樹脂がニ
ッケルイオンで飽和されると、それ以上はニッケルイオ
ンを吸着除去することが出来なくなり、別途、ニッケル
イオンで飽和されたイオン交換樹脂からニッケルイオン
を回収して、イオン交換樹脂を再生させる処理が必要に
なる。特開昭５６−１１２５００号公報、特開平３−５
９１４３号公報の方法は、いずれも、イオンを移動させ
るのに電圧をかけており、電源設備が必要となる上、め
っき液に塩素イオンが含くまれている場合、陽極近傍
で、塩素ガスが発生し、作業環境が悪化する問題もあ
る。However, each of these methods has the following problems. Tokiko Sho 58-
According to the method disclosed in Japanese Patent No. 24519, when the nickel ions are removed, the reducing agent is also removed to some extent. Therefore, it is necessary to supply the reducing agent, and when the ion exchange resin is saturated with the nickel ions, After that, nickel ions cannot be adsorbed and removed, and it is necessary to separately recover nickel ions from the ion exchange resin saturated with nickel ions and regenerate the ion exchange resin. JP-A-56-112500, JP-A-3-5500
In each of the methods disclosed in Japanese Patent No. 9143, a voltage is applied to move ions, power supply equipment is required, and when a plating solution contains chlorine ions, chlorine gas is supplied near the anode. This causes a problem that the working environment deteriorates.
【０００５】[0005]
【課題を解決するための手段】本発明は、イオン交換樹
脂の再生処理を必要とせず、還元剤の補給も必要とせ
ず、イオンの移動に電圧を使用することもなしに、長時
間、めっき液のｐＨを所定の範囲に維持しながらめっき
することを目的とするもので、化学拡散浸透によりイオ
ンが流通されるようにイオン交換膜を備えたｐＨ調整部
の該イオン交換膜の両側に、それぞれ、めっき槽で使用
されためっき液の一部とｐＨ調整液を導入し、イオン交
換膜を介してイオン交換することにより、ｐＨ調整した
後のめっき液をめっき槽にもどし、めっき槽中のめっき
液を所定のｐＨに維持してめっきすることを特徴とす
る。SUMMARY OF THE INVENTION The present invention does not require regeneration treatment of an ion exchange resin, does not require replenishment of a reducing agent, and does not use a voltage for the transfer of ions. It is intended to perform plating while maintaining the pH of the solution in a predetermined range, and on both sides of the ion exchange membrane of the pH adjustment unit having an ion exchange membrane so that ions are circulated by chemical diffusion infiltration, A part of the plating solution used in the plating tank and the pH adjusting solution are introduced, and the pH adjusted plating solution is returned to the plating tank by ion exchange through an ion exchange membrane. The plating is performed while maintaining the plating solution at a predetermined pH.
【０００６】[0006]
【発明の実施の形態】図に基づいて、以下に本発明の内
容を説明する。図１は本発明を示す概念図であり、ｐＨ
調整部１はイオン交換膜８を備えている。イオン交換膜
８としては、たとえば、陰イオン交換膜で、旭硝子社製
ＡＭＰ（強塩基性陰イオン交換膜）、ＡＭＶ（耐アル
カリ性陰イオン交換膜）などが好適に使用できる。イオ
ン交換膜８の面積は、めっき液に対して、０．００１〜
２０ｍ2／リットルであることが好ましい。イオン交換
膜８の面積が０．００１ｍ2／リットルより大きけれ
ば、イオン交換効率が実用的レベルになり、２０ｍ2／
リットルより小さい範囲で、設備コストに対するイオン
交換効率が良好と言える。DESCRIPTION OF THE PREFERRED EMBODIMENTS The contents of the present invention will be described below with reference to the drawings. FIG. 1 is a conceptual diagram illustrating the present invention, wherein pH
The adjusting unit 1 includes an ion exchange membrane 8. As the ion exchange membrane 8, for example, an anion exchange membrane such as AMP (strongly basic anion exchange membrane) and AMV (alkali-resistant anion exchange membrane) manufactured by Asahi Glass Co., Ltd. can be suitably used. The area of the ion exchange membrane 8 ranges from 0.001 to
It is preferably 20 m 2 / liter. If the area of the ion exchange membrane 8 is larger than 0.001 m 2 / liter, the ion exchange efficiency becomes a practical level, and 20 m 2 / liter.
In a range smaller than 1 liter, it can be said that the ion exchange efficiency with respect to the equipment cost is good.
【０００７】めっきの種類により、めっきが進むととも
に、めっき液のｐＨが小さくなるめっきと、めっき液の
ｐＨが大きくなるめっきとがある。例えば、チタンイオ
ンを還元剤とするめっき液の場合は、めっきが進むとと
もにめっき液のｐＨは小さくなり、水素発生が盛んな水
酸化ホウ素ナトリウムを還元剤とするめっき液の場合
は、めっきが進むとともにめっき液のｐＨは大きくな
る。めっき液のｐＨが小さくなる場合には、ｐＨ調整液
としては、水酸化リチウム、水酸化ナトリウム、水酸化
カリウムなどの、濃度が１〜５０重量％のアルカリ性水
溶液を使用することが好ましい。アルカリ性水溶液の濃
度が小さすぎては、濃度差がつきにくく、ＯＨ- イオン
の拡散速度が遅く、イオン交換の効率が悪く、アルカリ
性水溶液の濃度が大きすぎては、作業の安全上、問題が
生じるおそれがある。また、イオン交換膜としては、耐
アルカリ性の陰イオン交換膜を使用することが好まし
い。めっき液のｐＨが大きくなる場合には、ｐＨ調整液
としては、塩酸、硫酸などの、濃度が１〜５０重量％の
酸性水溶液を使用することが好ましい。酸の濃度が小さ
すぎては、濃度差がつきにくく、Ｈ+ イオンの拡散速度
が遅くなり、イオン交換の効率が悪く、酸の濃度が大き
すぎては、作業の安全上、問題が生じるおそれがある。
また、イオン交換膜としては、耐酸性の陰イオン交換膜
を使用することが好ましい。[0007] Depending on the type of plating, there are plating in which the pH of the plating solution decreases as plating progresses, and plating in which the pH of the plating solution increases. For example, in the case of a plating solution using titanium ions as a reducing agent, the pH of the plating solution decreases as plating progresses, and in the case of a plating solution using sodium borohydride, which actively generates hydrogen, plating proceeds. At the same time, the pH of the plating solution increases. When the pH of the plating solution decreases, it is preferable to use an alkaline aqueous solution having a concentration of 1 to 50% by weight, such as lithium hydroxide, sodium hydroxide, or potassium hydroxide, as the pH adjusting solution. If the concentration of the alkaline aqueous solution is too low, the difference in concentration is hardly obtained, the diffusion rate of OH - ions is slow, the efficiency of ion exchange is low, and if the concentration of the alkaline aqueous solution is too high, problems occur in work safety. There is a risk. It is preferable to use an alkali-resistant anion exchange membrane as the ion exchange membrane. When the pH of the plating solution increases, it is preferable to use an acidic aqueous solution such as hydrochloric acid or sulfuric acid having a concentration of 1 to 50% by weight as the pH adjusting solution. If the acid concentration is too low, the difference in concentration is hard to be made, the diffusion rate of H + ions is slow, the efficiency of ion exchange is low, and if the acid concentration is too high, problems may occur on work safety. There is.
Further, it is preferable to use an acid-resistant anion exchange membrane as the ion exchange membrane.
【０００８】ｐＨ調整部１のイオン交換膜８の図１に於
ける右側６にめっき槽からのめっき液の一部を導入し、
左側７にｐＨ調整液を導入すると、イオン交換膜の両側
にイオンの濃度勾配ができ、この濃度勾配を下げる方向
へイオンが移行される。A part of the plating solution from the plating tank is introduced into the ion exchange membrane 8 of the pH adjusting section 1 on the right side 6 in FIG.
When the pH adjusting solution is introduced into the left side 7, an ion concentration gradient is formed on both sides of the ion exchange membrane, and the ions are transferred in a direction to decrease the concentration gradient.
【０００９】めっきをすることにより、めっき液のｐＨ
が小さくなる場合には、ｐＨ調整液としてアルカリ性水
溶液を使用するので、めっきをすることによりｐＨが小
さくなっためっき液に、アルカリ水溶液からＯＨ- が移
行し、ｐＨが大きくなる。めっきをすることにより、め
っき液のｐＨが大きくなる場合には、ｐＨ調整液として
酸性水溶液を使用するので、めっきをすることによりｐ
Ｈが大きくなっためっき液にＨ+ が移行し、ｐＨが小さ
くなる。こうしてｐＨが調整されためっき液をめっき槽
にもどすことにより、めっき槽中のめっき液のｐＨを所
定の範囲に維持することができる。[0009] By plating, the pH of the plating solution
If the decrease is due to the use of an alkaline aqueous solution as a pH adjusting solution, the plating solution pH is reduced by the plating, OH alkali aqueous solution - is shifted, pH increases. When the pH of the plating solution is increased by plating, an acidic aqueous solution is used as the pH adjusting solution.
H + is transferred to the plating solution in which H is increased, and the pH is decreased. By returning the plating solution whose pH has been adjusted to the plating tank, the pH of the plating solution in the plating tank can be maintained in a predetermined range.
【００１０】[0010]
【実施例】（実施例１）表１に、チタンイオンを還元剤
として使用するニッケルの無電解めっきのめっき液の組
成を示す。EXAMPLES (Example 1) Table 1 shows the composition of a plating solution for electroless plating of nickel using titanium ions as a reducing agent.
【００１１】[0011]
【表１】 [Table 1]
【００１２】図１に於いて、めっき槽２に表１に示した
めっき液１００リットルを入れ、ｐＨ調整液槽３に、濃
度２００ｇ／リットルのＮａＯＨ１００リットルを入れ
た。基材としては、ウレタンシートを使用し、シートの
表面に触媒としてＰｄを３０ｍｇ／ｍ2付着させたもの
をめっき槽２に、逐次浸漬して、２ｍ2／ｈの速さで、
ウレタンシートの表面にニッケルめっきをした。めっき
としてウレタンシート表面に付着して、めっき液から取
り除かれるニッケルイオンを補充するため、適宜、めっ
き槽に塩化ニッケルを添加した。In FIG. 1, 100 liters of the plating solution shown in Table 1 were placed in a plating tank 2 and 100 liters of NaOH having a concentration of 200 g / liter were placed in a pH adjusting liquid tank 3. As a substrate, a urethane sheet was used, and 30 mg / m 2 of Pd was adhered as a catalyst to the surface of the sheet, which was sequentially immersed in the plating tank 2 at a speed of 2 m 2 / h,
The surface of the urethane sheet was plated with nickel. Nickel chloride was appropriately added to the plating tank to replenish nickel ions that adhered to the surface of the urethane sheet and were removed from the plating solution as plating.
【００１３】表１に示しためっき液を用いるめっきの場
合、３価のチタンイオンが４価になるときに放出する電
子をニッケルイオンが受け取ってゼロ価のニッケルにな
り、ニッケルが基材の表面に析出する。そして、この電
子の授受反応に対して、Ｐｄが触媒として働く。また、
そして、４価のチタンイオンが３価のチタンイオンにも
どるときにＨ+が発生するため、このめっきの場合、な
んの処置もせずに放置すると、当初８．４だっためっき
液のｐＨが、めっきが進むとともに、ｐＨは８．０にま
で小さくなった。In the case of plating using the plating solution shown in Table 1, nickel ions receive electrons emitted when trivalent titanium ions become tetravalent and become zero-valent nickel, and nickel becomes the surface of the base material. Precipitates out. Pd acts as a catalyst for the electron transfer reaction. Also,
Since H + is generated when the tetravalent titanium ions return to the trivalent titanium ions, if this plating is left without any treatment, the pH of the plating solution, which was initially 8.4, As plating progressed, the pH decreased to 8.0.
【００１４】上記のめっきを実施している間、ポンプ
４、５を適宜ＯＮ、ＯＦＦして、流量を調節しながら、
陰イオン交換膜８を有するｐＨ調整部１の、陰イオン交
換膜の図１に於ける左側７にｐＨ調整液槽からのＮａＯ
Ｈを、右側６にめっき槽からのめっき液を送り込んだ。
そうすると、陰イオン交換膜の両側に、ＯＨ-、Ｃｌ-の
濃度差ができる。ＯＨ -は図の左側７の濃度が濃く、右
側６の濃度が薄い。Ｃｌ-は図の右側６の濃度が濃く、
左側の濃度が薄い。この濃度差を小さくする方向、すな
わち、ＯＨ- は、図の左側７から図の右側６に移行し、
Ｃｌ-は図の右側６から図の左側７に移行する。その結
果、めっきが進むことにより小さくなっていためっき液
のｐＨが９．０〜９．５にまで大きくなった。こうし
て、ｐＨが大きくなっためっき液をめっき槽へもどし
た。このプロセスを繰り返すことにより、本プロセスに
よるめっきを、１ケ月間連続して実施し、その間ずっ
と、めっき液を、ｐＨ８．４±０．１に維持することが
でき、還元剤のチタンイオンの働きにより、ニッケルイ
オンが金属のニッケルになり、ウレタンシート表面への
良好なニッケルめっきが続けられた。また、還元剤とし
てチタンイオンを使用したので、できあがっためっき中
に、還元剤由来の不純物が極めてすくなく、めっきの皮
膜が均一で、その後の電気めっき性に優れためっきがで
きた。また、３価のチタンイオンは、還元して４価にな
っても、電解再生が可能である。なお、Ｃｌ- が増加し
た使用済みのｐＨ調整液は、ｐＨ調整液槽にもどしても
良いし、別の槽に移し、別途、未使用のｐＨ調整液をｐ
Ｈ調整液槽に補充してもよい。While performing the above plating, the pump
While turning on and off 4 and 5 as needed to adjust the flow rate,
Anion exchange of the pH adjustment unit 1 having the anion exchange membrane 8
On the left side 7 of the exchange membrane in FIG.
H was fed into the plating solution 6 from the plating tank on the right side.
Then, on both sides of the anion exchange membrane, OH-, Cl-of
There is a density difference. OH -Indicates that the density on the left side 7 of the figure is high,
Side 6 has low density. Cl-Indicates that the density on the right side 6 in the figure is high,
The density on the left is light. To reduce this density difference,
Word, OH- Shifts from the left side 7 of the figure to the right side 6 of the figure,
Cl-Shifts from the right side 6 in the figure to the left side 7 in the figure. The result
As a result, the plating solution has become smaller as plating progresses
Increased to 9.0 to 9.5. Like this
And return the plating solution whose pH has increased to the plating tank.
Was. By repeating this process,
Plating for one month in a row.
And maintaining the plating solution at pH 8.4 ± 0.1.
And the action of titanium ion as a reducing agent
On becomes nickel metal, and the urethane sheet surface
Good nickel plating continued. In addition, as a reducing agent
During the plating that was completed because titanium ions were used
In addition, the impurities derived from the reducing agent are extremely
Uniform film and subsequent plating with excellent electroplating properties
Came. Also, trivalent titanium ions are reduced to tetravalent.
However, electrolytic regeneration is possible. In addition, Cl- Increases
Return the used pH adjusting solution to the pH adjusting solution tank.
Good, transfer to another tank, and separate unused pH adjusting solution
The H adjustment liquid tank may be replenished.
【００１５】（比較例１）表１に示した組成のめっき液
１００リットルをめっき槽２に入れ、 基材としては、
ウレタンシートを使用し、シートの表面に触媒としてＰ
ｄを３０ｍｇ／ｍ 2付着させたものをめっき槽２に逐次
浸漬して、２ｍ2／ｈの速さで、ウレタンシートの表面
にニッケルめっきをした。めっきとしてウレタンシート
表面に付着して、めっき液から取り除かれるニッケルイ
オンを補充するため、適宜、めっき槽に塩化ニッケルを
添加した。そして、めっき液にアンモニア水を添加して
ｐＨを調整することを試みたが、めっき液に、無関係な
アンモニウムイオンが蓄積され、８時間で、浴が不安定
となり、ニッケル粉末が析出しはじめ、それ以上めっき
を継続することができなかった。Comparative Example 1 A plating solution having the composition shown in Table 1
100 liters are put into the plating tank 2, and as a base material,
Using a urethane sheet, P
d is 30 mg / m TwoThe adhered material is successively placed in the plating tank 2
2mTwo/ H, urethane sheet surface
Was plated with nickel. Urethane sheet as plating
Nickel ions that adhere to the surface and are removed from the plating solution
If necessary, add nickel chloride to the plating tank
Was added. Then, add ammonia water to the plating solution
Tried to adjust the pH, but unrelated to the plating solution
The bath is unstable in 8 hours due to accumulation of ammonium ions
And the nickel powder starts to precipitate, and further plating
Could not continue.
【００１６】(比較例２)表１に示した組成のめっき液１
００リットルをめっき槽２に入れ、 基材としては、ウ
レタンシートを使用し、シートの表面に触媒としてＰｄ
を３０ｍｇ／ｍ 2付着させたものをめっき槽２に逐次浸
漬して、２ｍ2／ｈの速さで、ウレタンシートの表面に
ニッケルめっきをした。めっきとしてウレタンシート表
面に付着して、めっき液から取り除かれるニッケルイオ
ンを補充するため、適宜、めっき槽に塩化ニッケルを添
加した。そして、めっき液にＮａＯＨを添加してｐＨを
調整することを試みたが、めっき液に、無関係なナトリ
ウムイオンが蓄積され、０．５時間で、浴が不安定とな
り、ニッケル粉末が析出しはじめ、それ以上めっきを継
続することができなかった。Comparative Example 2 Plating solution 1 having the composition shown in Table 1
00 liters into the plating tank 2
Using a urethane sheet, Pd as a catalyst on the surface of the sheet
30 mg / m TwoThe adhered material is sequentially immersed in the plating tank 2
2mTwo/ H at the urethane sheet surface
Nickel plated. Urethane sheet table as plating
Nickel ion that adheres to the surface and is removed from the plating solution
If necessary, add nickel chloride to the plating tank to replenish
Added. Then, NaOH is added to the plating solution to adjust the pH.
I tried to adjust it, but the plating solution did not
0.5 hours, the bath becomes unstable.
Nickel powder begins to precipitate, and further plating continues.
Could not continue.
【００１７】[0017]
【発明の効果】以上説明したように、本発明のめっき方
法であれば、めっき液に、無関係イオンが蓄積されるこ
ともなく、めっき槽のｐＨを、連続して長時間、所定の
範囲に維持することができ、連続して長時間、良好なめ
っきを継続することができる。As described above, according to the plating method of the present invention, irrelevant ions are not accumulated in the plating solution, and the pH of the plating tank is kept within a predetermined range for a long time continuously. The plating can be maintained and good plating can be continuously performed for a long time.
【図１】本発明のめっき方法を示す概念図。FIG. 1 is a conceptual diagram showing a plating method of the present invention.
１ ｐＨ調整部 ２ めっき槽 ３ ｐＨ調整液槽 ４ ポンプ ５ ポンプ ６ イオン交換膜右側 ７ イオン交換膜左側 ８ イオン交換膜 DESCRIPTION OF SYMBOLS 1 pH adjustment part 2 Plating tank 3 pH adjustment liquid tank 4 Pump 5 Pump 6 Ion exchange membrane right side 7 Ion exchange membrane left side 8 Ion exchange membrane
───────────────────────────────────────────────────── フロントページの続き (72)発明者 稲澤 信二 大阪市此花区島屋１丁目１番３号 住友電 気工業株式会社大阪製作所内 Ｆターム(参考） 4K022 BA14 DA01 DB01 DB25 ────────────────────────────────────────────────── ─── Continued on the front page (72) Inventor Shinji Inazawa 1-3-1 Shimaya, Konohana-ku, Osaka City F-term in Sumitomo Electric Industries, Ltd. Osaka Works 4K022 BA14 DA01 DB01 DB25
Claims (3)
ようにイオン交換膜を備えたｐＨ調整部の該イオン交換
膜の両側に、それぞれ、めっき槽で使用されためっき液
の一部とｐＨ調整液を導入し、イオン交換膜を介してイ
オン交換することにより、ｐＨ調整した後のめっき液を
めっき槽にもどし、めっき槽中のめっき液を所定のｐＨ
に維持してめっきすることを特徴とするめっき方法。Claims: 1. A part of a plating solution used in a plating tank and pH adjustment on both sides of an ion exchange membrane provided with an ion exchange membrane so that ions are circulated by chemical diffusion infiltration. The pH-adjusted plating solution is returned to the plating tank by introducing a solution and performing ion exchange through an ion exchange membrane, and the plating solution in the plating tank is adjusted to a predetermined pH.
A plating method characterized in that plating is performed while maintaining the plating temperature.
るめっき液であることを特徴とする請求項１に記載のめ
っき方法。2. The plating method according to claim 1, wherein the plating solution is a plating solution using titanium ions as a reducing agent.
ようにイオン交換膜を備えたｐＨ調整部を有することを
特徴とするめっき用設備。3. A plating facility comprising a pH adjuster provided with an ion exchange membrane so that ions can be circulated by chemical diffusion infiltration.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000308819A JP2002115074A (en) | 2000-10-10 | 2000-10-10 | Method and equipment for plating using ph-controlled plating solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2000308819A JP2002115074A (en) | 2000-10-10 | 2000-10-10 | Method and equipment for plating using ph-controlled plating solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JP2002115074A true JP2002115074A (en) | 2002-04-19 |
Family
ID=18789073
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2000308819A Withdrawn JP2002115074A (en) | 2000-10-10 | 2000-10-10 | Method and equipment for plating using ph-controlled plating solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2002115074A (en) |
-
2000
- 2000-10-10 JP JP2000308819A patent/JP2002115074A/en not_active Withdrawn
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