JPH04323380A - Electroless plating method - Google Patents
Electroless plating methodInfo
- Publication number
- JPH04323380A JPH04323380A JP9242291A JP9242291A JPH04323380A JP H04323380 A JPH04323380 A JP H04323380A JP 9242291 A JP9242291 A JP 9242291A JP 9242291 A JP9242291 A JP 9242291A JP H04323380 A JPH04323380 A JP H04323380A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- tank
- plating solution
- solution
- recovered
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000007772 electroless plating Methods 0.000 title claims description 23
- 238000000034 method Methods 0.000 title claims description 23
- 238000007747 plating Methods 0.000 claims abstract description 114
- 238000000909 electrodialysis Methods 0.000 claims abstract description 16
- 239000002351 wastewater Substances 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims description 104
- 239000007788 liquid Substances 0.000 claims description 34
- 239000000654 additive Substances 0.000 claims description 15
- 229910021645 metal ion Inorganic materials 0.000 claims description 13
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 239000008139 complexing agent Substances 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002699 waste material Substances 0.000 abstract description 19
- 238000009825 accumulation Methods 0.000 abstract description 8
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000004140 cleaning Methods 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 238000000502 dialysis Methods 0.000 description 7
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 229910001431 copper ion Inorganic materials 0.000 description 3
- 229910001453 nickel ion Inorganic materials 0.000 description 3
- 239000003002 pH adjusting agent Substances 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 1
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 1
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- SDVHRXOTTYYKRY-UHFFFAOYSA-J tetrasodium;dioxido-oxo-phosphonato-$l^{5}-phosphane Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)P([O-])([O-])=O SDVHRXOTTYYKRY-UHFFFAOYSA-J 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】この発明は、無電解めっき法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention This invention relates to electroless plating.
【0002】0002
【従来の技術】無電解めっき法は、いかなる形状の材質
にも均一な皮膜形成が可能であり、種々の電気的・機械
的特性を付与できる表面処理技術として、近年見直され
つつあり、その使用量は年々増大の傾向にある。しかし
ながら、電気めっきに比べ老廃物(反応生成物)が蓄積
しやすく、皮膜の品質を一定に保つことが難しい。従来
、老廃物の蓄積による品質低下を防止するため、使用中
のめっき液の一部をバッチ的に新めっき液に置き換える
ことが行われているが、新めっき液の置き換えに伴い取
り出される古いめっき液は有害成分を含む処理困難な廃
液であり、結構な量でもあることから問題となっていた
。[Prior Art] Electroless plating is being reconsidered in recent years as a surface treatment technology that can form a uniform film on any shape of material and can impart various electrical and mechanical properties. The amount tends to increase year by year. However, compared to electroplating, waste products (reaction products) tend to accumulate, making it difficult to maintain constant film quality. Conventionally, in order to prevent quality deterioration due to the accumulation of waste products, part of the plating solution in use has been replaced with new plating solution in batches. The liquid is a difficult-to-process waste liquid that contains harmful components, and the amount of the liquid is quite large, which has posed a problem.
【0003】電気透析法を利用して廃液から有価成分を
回収してしまうことも考えられるが、めっき原液に電気
透析法でそのまま処理すると、さらに濃縮される(H2
Oも移行してしまう)ために、装置配管内やイオン交
換膜に含有成分の析出というトラブルが起こり、事実上
、利用することができない。[0003] It is possible to recover valuable components from the waste liquid using electrodialysis, but if the plating stock solution is directly treated with electrodialysis, it will be further concentrated (H2
(O also migrates), this causes problems such as precipitation of the contained components in the equipment piping and on the ion exchange membrane, making it practically unusable.
【0004】0004
【発明が解決しようとする課題】この発明は、上記事情
に鑑み、めっき液中の老廃物蓄積の抑制と廃液発生量低
減を容易に実現することのできる無電解めっき法を提供
することを課題とする。[Problems to be Solved by the Invention] In view of the above circumstances, an object of the present invention is to provide an electroless plating method that can easily suppress the accumulation of waste products in the plating solution and reduce the amount of waste solution generated. shall be.
【0005】[0005]
【課題を解決するための手段】前記課題を解決するため
、この発明にかかる無電解めっき法では、無電解めっき
液を満たしためっき液槽で被処理物にめっきを施した後
、めっき済みの被処理物を水洗するようにする方法にお
いて、前記めっき液槽に継続的に新めっき液を供給する
とともに、新めっき液の供給に伴いめっき液槽からオー
バーフローする余剰めっき液と前記水洗で出る廃水とを
混合し、この混合液から電気透析により有価成分の回収
液を得て、この回収液を前記めっき液槽に供給する構成
をとっている。[Means for Solving the Problems] In order to solve the above problems, in the electroless plating method according to the present invention, after plating the workpiece in a plating solution tank filled with an electroless plating solution, In a method in which the object to be treated is washed with water, a new plating solution is continuously supplied to the plating solution tank, and surplus plating solution overflows from the plating solution tank as the new plating solution is supplied and waste water generated from the washing. The system is configured such that a valuable component recovery solution is obtained from this mixed solution by electrodialysis, and this recovery solution is supplied to the plating solution tank.
【0006】以下、図面を参照しながら、この発明の無
電解めっき法を具体的に説明する。図1は、この発明に
かかる無電解めっき法の一例を適用した無電解メッキシ
ステムをあらわすブロック図である。めっき液槽1には
、浸漬される被処理物(被めっき物)にめっきを施すた
めの無電解めっき液が満たされている。この無電解めっ
き液には、金属イオンと金属イオンの錯体と還元剤、p
H調整剤や添加剤などが含まれているが、めっき反応に
よって消耗される金属イオン、還元剤、pH調整剤、添
加剤等はコントローラ5で補給される。この発明で使わ
れる無電解めっき液としては、限定されるものではない
が、具体的には下記の組成のものが例示される。[0006] The electroless plating method of the present invention will be specifically explained below with reference to the drawings. FIG. 1 is a block diagram showing an electroless plating system to which an example of the electroless plating method according to the present invention is applied. The plating solution tank 1 is filled with an electroless plating solution for plating a processed object (an object to be plated) to be immersed. This electroless plating solution contains metal ions, a complex of metal ions, a reducing agent, p
Although it contains an H adjuster and additives, the metal ions, reducing agent, pH adjuster, additives, etc. that are consumed by the plating reaction are replenished by the controller 5. Although the electroless plating solution used in this invention is not limited, specifically, those having the following compositions are exemplified.
【0007】
(A) 無電
解銅めっき液 硫酸銅五水和物(金属イオン用)
・・・10g/リットル
エチレンジアミン四酢酸二ナトリウム(錯化剤)・・・
30g/リットル 水酸化ナトリウム(pH調整剤)
・・・pH12.8とす
る量 ホルマリン溶液−35%(還元剤)
・・・5mリットル/リットル イオ
ウ系添加剤(安定用)
・・・少量 界面活性剤
・・・少量 浴温条件
・・
・65℃ (B)
無電解ニンケル−りんめっき液 硫酸ニッケル六
水和物(金属イオン用) ・・・30g
/リットル 次亞りん酸ナトリウム(還元剤)
・・・30g/リットル グ
リシン(錯化剤)
・・・20g/リットル クエン
酸ナトリウム(錯化剤)
・・・20g/リットル 水酸化ナトリウム(p
H調整剤) ・・・pH5
.5 とする量 鉛系添加剤(安定用)
・・・少量
界面活性剤
・・・少量 浴温条件
・・・90℃めっき槽1には新
液タンク2からポンプ6等により一定量の新めっき液が
継続的に供給される。新めっき液の継続的供給の形態は
、常に流し続ける連続供給と所定時間おきに所定量ずつ
流す間欠供給とがあるが、前者の連続供給の方が好まし
い。新めっき液の供給量は、例えば、1時間あたり、め
っき液槽1の容量の1/20程度である。(A) Electroless copper plating solution Copper sulfate pentahydrate (for metal ions)
...10g/liter
Disodium ethylenediaminetetraacetate (complexing agent)...
30g/liter Sodium hydroxide (pH adjuster)
...Amount to adjust pH to 12.8 Formalin solution - 35% (reducing agent)
...5ml/liter Sulfur-based additive (for stability)
...small amount surfactant
...small amount Bath temperature conditions
・・・
・65℃ (B)
Electroless nickel phosphor plating solution Nickel sulfate hexahydrate (for metal ions)...30g
/liter Sodium hypophosphate (reducing agent)
...30g/liter glycine (complexing agent)
...20g/liter sodium citrate (complexing agent)
...20g/liter Sodium hydroxide (p
H adjuster) ・・・pH5
.. 5 Amount of lead-based additive (for stabilization)
...a small amount
surfactant
...small amount Bath temperature conditions
... A fixed amount of new plating solution is continuously supplied to the 90° C. plating tank 1 from the new solution tank 2 by a pump 6 or the like. Continuous supply of new plating solution can be divided into two types: continuous supply, which continues to flow all the time, and intermittent supply, which flows a predetermined amount at predetermined time intervals; however, the former continuous supply is preferable. The amount of fresh plating solution supplied is, for example, about 1/20 of the capacity of the plating solution tank 1 per hour.
【0008】新めっき液の供給に伴いめっき液槽1から
オーバーフローする余剰めっき液は、余剰液タンク3で
受けられる。ついで、この余剰めっき液の一部または全
部と、被処理物洗浄工程で発生する洗浄タンク7内の洗
浄廃水(被処理物がめっき液槽1から持ち出すめっき液
を含むのでめっき液を希釈したものに相当する)を透析
タンク8に投入混合し、この混合液を電気透析装置4に
かけて金属イオンや金属イオンの錯体や還元剤などの有
価成分の回収液を得る。洗浄廃水中の有価成分も回収で
きる。洗浄廃水を加えて一旦は薄められるが電気透析で
濃縮されな適度な状態となる。この場合、加熱し水分を
蒸発させる濃縮操作を併用してもよいが、回収液を不安
定化させる場合があるので注意を要する。Surplus plating solution overflowing from the plating solution tank 1 due to the supply of new plating solution is received in a surplus solution tank 3. Next, some or all of this surplus plating solution is combined with cleaning waste water in the cleaning tank 7 generated in the process of cleaning the object to be treated (a diluted plating solution since the object to be treated contains the plating solution taken out from the plating solution tank 1). (equivalent to) are charged into a dialysis tank 8 and mixed, and this mixed solution is passed through an electrodialyzer 4 to obtain a recovered solution containing valuable components such as metal ions, metal ion complexes, and reducing agents. Valuable components in cleaning wastewater can also be recovered. It is diluted once by adding washing waste water, but it is not concentrated by electrodialysis and becomes a suitable state. In this case, a concentration operation in which water is evaporated by heating may also be used, but care must be taken as this may destabilize the recovered liquid.
【0009】なお、無電解めっき液が高アルカリ性のも
のであって、透析で使われるイオン交換膜が侵されやす
いなどの問題点がある場合には、余剰めっき液と洗浄廃
水の混合時にpH調整を行ってもよい。電気透析により
回収された金属イオン、錯化剤、還元剤等の有価成分を
含む回収液をめっき液槽1に一定量順次供給していくこ
とによって、廃液量の低減化がなされるわけであるが、
このままの状態でめっき液槽1に供給したのでは、
■「金属イオンと錯化剤との濃度被、あるいは、還元剤
の濃度が適当範囲を越えるところまで変化する」、■「
添加剤の一部が電気透析の際に抜き取られている場合に
は、めっき液中のの添加剤濃度のバランスが崩れる」な
どのために、めっき皮膜の物性が変動したり、めっき液
成分の分解が起こり大量の廃液を生ずる恐れのある場合
がある。[0009] If the electroless plating solution is highly alkaline and has problems such as easily corroding the ion exchange membrane used in dialysis, the pH should be adjusted when mixing the excess plating solution and cleaning waste water. You may do so. The amount of waste liquid is reduced by sequentially supplying a fixed amount of the recovered liquid containing valuable components such as metal ions, complexing agents, and reducing agents to the plating solution tank 1 recovered by electrodialysis. but,
If the plating solution was supplied to tank 1 in this state,
■“The concentration of the metal ion and complexing agent or the concentration of the reducing agent changes to a point that exceeds the appropriate range.”■”
If some of the additives are removed during electrodialysis, the balance of the additive concentration in the plating solution will be disrupted, resulting in changes in the physical properties of the plating film and changes in the plating solution components. Decomposition may occur and large amounts of waste liquid may be generated.
【0010】したがって、このような恐れのある場合に
は、めっき液1内での成分バランスを崩さないように、
電気透析後の回収液をめっき槽に供給する前に、回収液
中の金属イオン、錯化剤、還元剤および添加剤(さらに
は必要に応じてpH調整剤)の濃度を新めっき液に合わ
せる濃度調整を調整器9で行うようにすることが望まし
い。勿論、このような濃度調整を行わずに回収液を直に
新液タンク2あるいはめっき液槽1に供給するようにす
ることができるが、この場合にはコントローラ5に必要
な濃度調整機能を付加し、濃度調整を行うようにするこ
とが望ましい。[0010] Therefore, in cases where there is such a possibility, in order not to disturb the component balance in the plating solution 1,
Before supplying the recovered solution after electrodialysis to the plating tank, adjust the concentrations of metal ions, complexing agents, reducing agents, and additives (and pH adjuster if necessary) in the recovered solution to the new plating solution. It is desirable that the concentration be adjusted by the adjuster 9. Of course, it is possible to directly supply the recovered liquid to the new liquid tank 2 or the plating liquid tank 1 without performing such concentration adjustment, but in this case, the necessary concentration adjustment function is added to the controller 5. However, it is desirable to adjust the density.
【0011】回収液は、単独で供給してもよいし、ある
程度の比率で新めっき液と平行して供給してもよい。具
体的には、新液タンク2に回収液を投入混合し新めっき
液の一部にしてめっき液槽1に投入するようにしてもよ
い。また、回収液の供給がめっき浴温度の変動を引き起
こさないように、回収液をめっき液槽1に供給する前に
めっき浴温度と同程度の温度に温めるようにしてもよい
。[0011] The recovered solution may be supplied alone or in parallel with the new plating solution at a certain ratio. Specifically, the recovered liquid may be added to the new liquid tank 2 and mixed, and then added to the plating liquid tank 1 as part of the new plating liquid. Further, the recovered liquid may be heated to a temperature comparable to the plating bath temperature before being supplied to the plating liquid tank 1 so that the supply of the recovered liquid does not cause fluctuations in the plating bath temperature.
【0012】0012
【作用】請求項1、2記載の無電解めっき法では、めっ
き液槽に継続的に新めっき液が供給され老廃物の蓄積が
抑えられるため、被処理物に対し適切なめっきが行える
。それに、新めっき液の供給に伴いめっき液槽からオー
バーフローする余剰めっき液は水洗で出る廃水と混合さ
れ、有価成分の回収液としてめっき液槽に供給されるた
め、廃液発生量を抑えることができる。余剰めっき液は
水洗で出る廃水で薄めており、過度の濃縮で装置配管内
やイオン交換膜に析出物によるトラブルが発生しないた
め、有価成分の回収液を得るための電気透析も何らの困
難なく行える。水洗で出る廃水中の有価成分も回収でき
るという利点もある。In the electroless plating method according to claims 1 and 2, new plating solution is continuously supplied to the plating solution tank and accumulation of waste products is suppressed, so that the object to be treated can be appropriately plated. In addition, excess plating solution that overflows from the plating solution tank when new plating solution is supplied is mixed with wastewater from washing and supplied to the plating solution tank as valuable component recovery solution, reducing the amount of waste solution generated. . Excess plating solution is diluted with wastewater from washing, and excessive concentration will not cause trouble due to precipitates in the equipment piping or on the ion exchange membrane, so electrodialysis to obtain a recovered solution for valuable components can be performed without any difficulty. I can do it. Another advantage is that valuable components in the wastewater produced during washing can also be recovered.
【0013】請求項2記載の無電解めっき法では、回収
液をめっき槽に供給する前に、回収液中の金属イオン、
錯化剤、還元剤および添加剤の濃度を新めっき液に合わ
せる濃度調整を行うため、めっき皮膜の物性変動やめっ
き液槽内の成分変動を十分に抑えることができる。[0013] In the electroless plating method according to claim 2, before the recovered liquid is supplied to the plating tank, metal ions in the recovered liquid,
Since the concentrations of the complexing agent, reducing agent, and additives are adjusted to match the new plating solution, changes in the physical properties of the plating film and changes in the components in the plating solution tank can be sufficiently suppressed.
【0014】[0014]
【実施例】以下、この発明の実施例について説明する。
勿論、この発明は、下記の実施例に限らない。
−実施例1−
図1に示すシステムに前記の無電解銅めっき液を適用し
、以下の条件でシステムを運転した。[Embodiments] Examples of the present invention will be described below. Of course, this invention is not limited to the following embodiments. - Example 1 - The electroless copper plating solution described above was applied to the system shown in FIG. 1, and the system was operated under the following conditions.
【0015】めっき液槽1には4ターン相当のめっきを
実施しためっき液が入っており、新液タンク2からは1
時間当たりめっき液槽1の容量の1/20に相当する新
めっき液を供給した。また、めっき反応によって消耗す
る銅イオン、HCOH、水酸化ナトリウムはコントロー
ラ5のポンプで補給するようにした。20時間の運転の
後、発生した余剰めっき液と洗浄工程で発生した1次洗
浄廃水を約4:1の割合で混合し、徳山曹達(株)製の
電気透析装置(TS−5−40)によって混合溶液の全
量が80%になるまで透析を行い銅イオン、EDTA、
HCHOの一部を回収した。The plating solution tank 1 contains plating solution equivalent to 4 turns of plating, and the new solution tank 2 contains 1 plating solution.
Fresh plating solution equivalent to 1/20 of the capacity of plating solution tank 1 was supplied per hour. Further, the copper ions, HCOH, and sodium hydroxide consumed by the plating reaction are replenished by the pump of the controller 5. After 20 hours of operation, the surplus plating solution generated and the primary cleaning wastewater generated in the cleaning process were mixed at a ratio of approximately 4:1, and an electrodialysis device (TS-5-40 manufactured by Tokuyama Soda Co., Ltd.) was used. Dialysis is performed until the total volume of the mixed solution becomes 80%, and copper ions, EDTA,
A portion of HCHO was recovered.
【0016】次に、電気透析処理された回収液中の銅イ
オン、EDTA、HCOHの濃度を新めっき液と同様に
なるように濃度調整を行った。なお、透析の際、イオウ
系添加剤が抜き取られてしまったため、イオウ系添加剤
の濃度も新めっき液と同様になるように同時に調整した
。濃度調整の後、新液タンク2に混ぜ込み、引き続きめ
っき処理を実施した。Next, the concentrations of copper ions, EDTA, and HCOH in the electrodialyzed recovered solution were adjusted to be the same as in the new plating solution. In addition, since the sulfur-based additive was extracted during dialysis, the concentration of the sulfur-based additive was also adjusted at the same time so that it was the same as that of the new plating solution. After adjusting the concentration, it was mixed into new liquid tank 2, and plating processing was subsequently performed.
【0017】以上のめっき法を実施することにより、老
廃物の蓄積を抑えつつ、廃液発生量を従来の30%に抑
えることができた。さらに、EDTAのように高価な試
薬を回収し利用できるので、めっき液コストの低減も図
れた。
−実施例2−
電気透析処理により得た回収液を、濃度調整を行わずそ
のまま新液タンク2に混ぜ込んだほかは、実施例1と同
様のめっき処理を行った。By carrying out the above plating method, it was possible to suppress the accumulation of waste products and to suppress the amount of waste liquid generated to 30% of the conventional amount. Furthermore, since expensive reagents such as EDTA can be recovered and used, the cost of plating solution can be reduced. -Example 2- The same plating process as in Example 1 was performed except that the recovered liquid obtained by the electrodialysis process was directly mixed into the new liquid tank 2 without adjusting the concentration.
【0018】但し、この場合には、コントローラにイオ
ウ系の添加剤の分析補給装置を付加し、めっき浴の管理
を行ったが、問題のない範囲でめっき処理が行えた。実
施例1と同様、老廃物の蓄積を抑えつつ、廃液発生量を
従来の30%に抑えることができた。さらに、EDTA
のように高価な試薬を回収し利用できるので、めっき液
コストの低減も図れた。実施例1に比べ、透析により得
た回収液の濃度調整を行わない分、処理が簡略化できる
利点がある。However, in this case, a sulfur-based additive analysis and replenishment device was added to the controller to manage the plating bath, but the plating process could be performed without any problems. As in Example 1, the amount of waste liquid generated was able to be suppressed to 30% of the conventional amount while suppressing the accumulation of waste products. Furthermore, EDTA
Since expensive reagents such as those described above can be recovered and used, the cost of plating solutions can also be reduced. Compared to Example 1, there is an advantage that the processing can be simplified because the concentration of the recovered liquid obtained by dialysis is not adjusted.
【0019】−実施例3−
図1に示すシステムに前記の無電解ニッケル−りんめっ
き液を適用し、以下の条件でシステムを運転した。めっ
き液槽1には4ターン相当のめっきを実施しためっき液
が入っており、新液タンク2からは1時間当たりめっき
液槽1の容量の1/20に相当する新めっき液を供給し
た。また、めっき反応によって消耗するニッケルイオン
、次亜りん酸ナトリウム、水酸化ナトリウムはコントロ
ーラ5のポンプで補給するようにした。Example 3 The electroless nickel-phosphorus plating solution described above was applied to the system shown in FIG. 1, and the system was operated under the following conditions. The plating solution tank 1 contained plating solution that had been used for plating equivalent to four turns, and the new plating solution equivalent to 1/20 of the capacity of the plating solution tank 1 was supplied from the new solution tank 2 per hour. Further, the nickel ions, sodium hypophosphite, and sodium hydroxide consumed by the plating reaction are replenished by the pump of the controller 5.
【0020】20時間の運転の後、発生した余剰めっき
液と洗浄工程で発生した1次洗浄廃水を約4:1の割合
で混合し、電気透析装置(徳山曹達(株)製 ST−
5−40)によって混合溶液の全量が80%になるまで
透析を行いニッケルイオン、クエン酸、グリシン、次亜
りん酸の一部を回収した。次に、電気透析処理された回
収液中のニッケルイオン、クエン酸、グリシン、次亜り
ん酸の濃度を新めっき液と同様になるように濃度調整し
た。なお、透析の際、鉛系添加剤が抜き取られてしまっ
たため、鉛系添加剤の濃度も新めっき液と同様になるよ
うに同時に調整した。濃度調整の後、新液タンク2に混
ぜ込み、引き続きめっき処理を実施した。After 20 hours of operation, the surplus plating solution generated and the primary cleaning wastewater generated in the cleaning process were mixed at a ratio of about 4:1, and an electrodialysis device (ST- manufactured by Tokuyama Soda Co., Ltd.) was used.
5-40) until the total amount of the mixed solution became 80%, and a portion of nickel ions, citric acid, glycine, and hypophosphorous acid were recovered. Next, the concentrations of nickel ions, citric acid, glycine, and hypophosphorous acid in the electrodialyzed recovered solution were adjusted to be the same as in the new plating solution. In addition, since the lead-based additive was extracted during dialysis, the concentration of the lead-based additive was also adjusted at the same time so that it was the same as the new plating solution. After adjusting the concentration, it was mixed into new liquid tank 2, and plating processing was subsequently performed.
【0021】以上のめっき法を実施することにより、老
廃物の蓄積を抑えつつ、廃液発生量を従来の30%に抑
えることができた。さらに、試薬を回収し利用できるの
で、めっき液コストの低減も図れた。By carrying out the above plating method, it was possible to suppress the accumulation of waste products and to suppress the amount of waste liquid generated to 30% of the conventional amount. Furthermore, since the reagents can be recovered and used, the cost of plating solution can be reduced.
【0022】[0022]
【発明の効果】請求項1、2記載の無電解めっき法では
、めっき液槽に継続的に新めっき液が供給され老廃物の
蓄積が抑えられるために被処理物に対し適切なめっきが
行え、それに、新めっき液の供給に伴いめっき液槽から
オーバーフローする余剰めっき液は水洗で出る廃水と混
合され有価成分の回収液としてめっき液槽に供給される
ため、廃液発生量を抑えることができ、しかも、余剰め
っき液は水洗で出る廃水で薄められるため過度の濃縮で
装置配管内やイオン交換膜に析出物によるトラブルが発
生することもなく、有価成分の回収液を得るための電気
透析は何らの困難なく行え、非常に実用的である。[Effects of the Invention] In the electroless plating method according to claims 1 and 2, new plating solution is continuously supplied to the plating solution tank, and accumulation of waste products is suppressed, so that appropriate plating can be performed on the object to be processed. In addition, excess plating solution that overflows from the plating solution tank when new plating solution is supplied is mixed with wastewater from washing and supplied to the plating solution tank as a recovery solution for valuable components, reducing the amount of waste solution generated. Moreover, since the excess plating solution is diluted with waste water from washing, there is no problem with precipitates in the equipment piping or on the ion exchange membrane due to excessive concentration, and electrodialysis to obtain the recovered solution of valuable components is not necessary. It can be done without any difficulty and is very practical.
【0023】請求項2記載の無電解めっき法では、上に
加えて、回収液をめっき槽に供給する前に、回収液中の
金属イオン、錯化剤、還元剤および添加剤の濃度を新め
っき液に合わせる濃度調整を行うため、めっき皮膜の物
性変動やめっき液槽内の成分変動を十分に抑えることが
できるという利点がある。In the electroless plating method according to claim 2, in addition to the above, the concentrations of metal ions, complexing agents, reducing agents, and additives in the recovered liquid are refreshed before the recovered liquid is supplied to the plating tank. Since the concentration is adjusted to match the plating solution, there is an advantage that variations in the physical properties of the plating film and variations in the components in the plating solution tank can be sufficiently suppressed.
【図1】図1は、この発明にかかる無電解めっき法を適
用した無電解メッキシステムの一例をあらわすブロック
図である。FIG. 1 is a block diagram showing an example of an electroless plating system to which the electroless plating method according to the present invention is applied.
1 めっき液槽 2 新液タンク 3 余剰液タンク 4 電気透析装置 5 コントローラ 7 洗浄タンク 8 透析タンク 9 調整器 1 Plating solution tank 2 New liquid tank 3 Surplus liquid tank 4 Electrodialysis device 5 Controller 7 Washing tank 8 Dialysis tank 9 Adjuster
Claims (2)
で被処理物にめっきを施した後、めっき済みの被処理物
を水洗するようにする無電解めっき法において、前記め
っき液槽に継続的に新めっき液を供給するとともに、新
めっき液の供給に伴いめっき液槽からオーバーフローす
る余剰めっき液と前記水洗で出る廃水とを混合し、この
混合液から電気透析により有価成分の回収液を得て、こ
の回収液を前記めっき液槽に供給するようにすることを
特徴とする無電解めっき法。[Claim 1] In an electroless plating method in which a workpiece is plated in a plating solution tank filled with an electroless plating solution and the plated workpiece is then washed with water, At the same time, the surplus plating solution that overflows from the plating solution tank due to the supply of the new plating solution is mixed with the waste water generated from the water washing, and valuable components are recovered from this mixed solution by electrodialysis. An electroless plating method characterized in that the collected liquid is supplied to the plating liquid tank.
収液中の金属イオン、錯化剤、還元剤および添加剤の濃
度を新めっき液に合わせる濃度調整を行うようにする請
求項1記載の無電解めっき法。[Claim 2] Before supplying the recovered solution to the plating tank, the concentrations of metal ions, complexing agents, reducing agents, and additives in the recovered solution are adjusted to match the new plating solution. [Claim 1] Electroless plating method as described.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9242291A JPH04323380A (en) | 1991-04-23 | 1991-04-23 | Electroless plating method |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP9242291A JPH04323380A (en) | 1991-04-23 | 1991-04-23 | Electroless plating method |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04323380A true JPH04323380A (en) | 1992-11-12 |
Family
ID=14053988
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP9242291A Pending JPH04323380A (en) | 1991-04-23 | 1991-04-23 | Electroless plating method |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04323380A (en) |
-
1991
- 1991-04-23 JP JP9242291A patent/JPH04323380A/en active Pending
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