JPH06192844A - Electroless plating method - Google Patents
Electroless plating methodInfo
- Publication number
- JPH06192844A JPH06192844A JP34716392A JP34716392A JPH06192844A JP H06192844 A JPH06192844 A JP H06192844A JP 34716392 A JP34716392 A JP 34716392A JP 34716392 A JP34716392 A JP 34716392A JP H06192844 A JPH06192844 A JP H06192844A
- Authority
- JP
- Japan
- Prior art keywords
- electroless plating
- plating solution
- electroless
- temperature
- plated
- 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 abstract description 116
- 238000000034 method Methods 0.000 title claims description 21
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000011261 inert gas Substances 0.000 claims abstract description 17
- 239000007789 gas Substances 0.000 claims abstract description 12
- 238000007747 plating Methods 0.000 abstract description 48
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 10
- 239000001257 hydrogen Substances 0.000 abstract description 10
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 22
- 229910052802 copper Inorganic materials 0.000 description 22
- 239000010949 copper Substances 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 16
- 239000000758 substrate Substances 0.000 description 13
- 239000007788 liquid Substances 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- 229910052759 nickel Inorganic materials 0.000 description 7
- 229910001873 dinitrogen Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229910001431 copper ion Inorganic materials 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 239000003002 pH adjusting agent Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002926 oxygen Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229940113115 polyethylene glycol 200 Drugs 0.000 description 1
- 230000001603 reducing effect Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
Landscapes
- Chemically Coating (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、表面処理の分野で用い
られる無電解メッキ法に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroless plating method used in the field of surface treatment.
【０００２】[0002]
【従来の技術】近年無電解メッキでは、例えば、無電解
メッキの反応に伴って、被メッキ物の表面より発生する
水素は、還元作用を有しているので、水素が滞留する箇
所で無電解メッキ液中に金属の析出を起こしてしまう等
の問題があり、無電解メッキ液槽内の無電解メッキ液の
品質安定化のために、攪拌操作が重要視されている。例
えば、特開昭５４−１２１２３３では酸素を含む気体の
供給による攪拌が開示されている。これに対し、供給さ
れた酸素が過剰になると、無電解メッキ液に溶解されな
い酸素が被メッキ物表面に接触し、被メッキ物表面の酸
化により金属の析出むらを起こす。この解決法として、
特開昭４−３７６には遮蔽板を用いる方法が開示されて
いる。しかし、上記方法では、遮蔽板の設置で逆に発生
した水素の放出を妨げるため、無電解メッキ液の品質の
安定には不十分である。2. Description of the Related Art In recent years, in electroless plating, for example, hydrogen generated from the surface of an object to be plated due to the reaction of electroless plating has a reducing action, and therefore, electroless plating occurs at the place where hydrogen stays. There is a problem such as metal precipitation in the plating solution, and the stirring operation is considered important in order to stabilize the quality of the electroless plating solution in the electroless plating solution tank. For example, Japanese Patent Laid-Open No. 54-121233 discloses stirring by supplying a gas containing oxygen. On the other hand, when the supplied oxygen becomes excessive, oxygen that is not dissolved in the electroless plating solution comes into contact with the surface of the object to be plated, and the surface of the object to be plated is oxidized to cause uneven deposition of metal. The solution is
Japanese Patent Application Laid-Open No. 4-376 discloses a method using a shield plate. However, the above method is not sufficient for stabilizing the quality of the electroless plating solution because it hinders the release of hydrogen generated conversely when the shielding plate is installed.
【０００３】従来の酸素による析出むらは、外気の温度
が低い際に多く見られる。これは、供給された酸素が被
メッキ物の表面の温度を低下し、メッキの析出より酸化
反応の進行が早いためと推察される。[0003] Conventional precipitation unevenness due to oxygen is often seen when the temperature of the outside air is low. It is speculated that this is because the supplied oxygen lowers the temperature of the surface of the object to be plated, and the oxidation reaction proceeds faster than the deposition of the plating.
【０００４】[0004]
【発明が解決しようとする課題】本発明は上記の事実に
鑑みてなされたもので、その目的とするところは、メッ
キ反応に伴って発生する水素を無電解メッキ液から放出
を容易にし、被メッキ物表面に均一なメッキ被膜を形成
し、外観が良好な無電解メッキ法を提供することにあ
る。SUMMARY OF THE INVENTION The present invention has been made in view of the above facts, and an object of the present invention is to facilitate release of hydrogen generated by a plating reaction from an electroless plating solution. An object of the present invention is to provide an electroless plating method in which a uniform plating film is formed on the surface of a plated product and the appearance is good.
【０００５】[0005]
【課題を解決するための手段】本発明の請求項１に係る
無電解メッキ法は、溶存酸素を含む無電解メッキ液槽内
の無電解メッキ液中に、無電解メッキの液温より３０℃
低い温度以上から無電解メッキの液温より１０℃高い温
度以下迄の温度範囲の不活性ガスを被メッキ物の下方よ
り散気することを特徴とする。In the electroless plating method according to claim 1 of the present invention, the temperature of the electroless plating solution in the electroless plating solution containing dissolved oxygen is 30 ° C. higher than the temperature of the electroless plating solution.
It is characterized in that an inert gas in a temperature range from a low temperature or higher to a temperature 10 ° C. or higher higher than the liquid temperature of electroless plating is diffused from below the object to be plated.
【０００６】本発明の請求項２に係る無電解メッキ法
は、無電解メッキ液槽内の無電解メッキ液中に、無電解
メッキの液温より上下１０℃の温度範囲の酸素を含む気
体を被メッキ物の下方より散気することを特徴とする。In the electroless plating method according to the second aspect of the present invention, a gas containing oxygen in a temperature range of 10 ° C. above and below the temperature of the electroless plating solution is added to the electroless plating solution in the electroless plating solution bath. It is characterized in that air is diffused from below the object to be plated.
【０００７】[0007]
【作用】本発明の請求項１に係る無電解メッキ法は、不
活性ガスの温度を無電解メッキの液温より３０℃低い温
度以上で、無電解メッキの液温より１０℃高い温度以下
の温度範囲に限定することにより、気体の接触による被
メッキ物の表面の温度が低下するのを防ぐことによっ
て、被メッキ物表面に析出する金属被膜のむらを防ぎ、
且つ、不活性ガスはメッキ反応には影響を与えずに無電
解メッキ液の攪拌効果をあげ、さらに、被メッキ物の下
方より散気することで、発生する水素を滞留させること
なく無電解メッキ液より放出させる。In the electroless plating method according to the first aspect of the present invention, the temperature of the inert gas is not less than 30 ° C. lower than the liquid temperature of the electroless plating and not higher than 10 ° C. higher than the liquid temperature of the electroless plating. By limiting the temperature range, it is possible to prevent the temperature of the surface of the object to be plated from lowering due to the contact of gas, thereby preventing the unevenness of the metal film deposited on the surface of the object to be plated,
In addition, the inert gas improves the stirring effect of the electroless plating solution without affecting the plating reaction, and further diffuses air from the lower side of the object to be plated so that the generated hydrogen does not stay and the electroless plating is not retained. Release from liquid.
【０００８】本発明の請求項２に係る無電解メッキ法
は、酸素を含む気体の温度を無電解メッキの液温より上
下１０℃の温度範囲に限定することにより、気体の接触
による被メッキ物の表面の温度が低下するのを防ぐこと
によって、被メッキ物の表面のむらを防ぎ、さらに、被
メッキ物の下方より散気することで、発生する水素を滞
留させることなく無電解メッキ液より放出させる。In the electroless plating method according to claim 2 of the present invention, the temperature of the gas containing oxygen is limited to a temperature range of 10 ° C. above and below the liquid temperature of the electroless plating, so that the object to be plated by the contact of the gas By preventing the temperature of the surface of the plate from lowering, the unevenness of the surface of the object to be plated is prevented, and by diffusing from below the object to be plated, the generated hydrogen is released from the electroless plating solution without retaining. Let
【０００９】以下、本発明を詳細に説明する。本発明の
請求項１に係る無電解メッキ法を図１に基づいて説明す
る。The present invention will be described in detail below. An electroless plating method according to claim 1 of the present invention will be described with reference to FIG.
【００１０】図１は本発明の一実施例に係る無電解メッ
キ法に使用する無電解メッキ装置のブロック図である。FIG. 1 is a block diagram of an electroless plating apparatus used in an electroless plating method according to an embodiment of the present invention.
【００１１】図１に示す如く、本発明を用いた無電解メ
ッキ装置は無電解メッキ槽（２）を備え、この無電解メ
ッキ槽（２）は、無電解メッキ液が満たされ、ホルダー
（９）で保持した被メッキ物（８）を無電解メッキ液中
に浸漬して無電解メッキを施すものである。As shown in FIG. 1, the electroless plating apparatus using the present invention is provided with an electroless plating tank (2), which is filled with an electroless plating solution and is held in a holder (9). The object to be plated (8) held in () is immersed in an electroless plating solution for electroless plating.
【００１２】この無電解メッキ装置は、不活性ガス用の
ボンベ（４）を備え、この不活性ガスの温度を調整する
温度調整器（６）を備える。そして、無電解メッキ液槽
（２）内の被メッキ物（８）より下方に上記不活性ガス
を無電解メッキ液に散気する散気管（３）が設けられて
いる。This electroless plating apparatus comprises a cylinder (4) for an inert gas and a temperature controller (6) for adjusting the temperature of this inert gas. A diffusing pipe (3) for diffusing the inert gas into the electroless plating solution is provided below the object to be plated (8) in the electroless plating solution tank (2).
【００１３】さらに、上記無電解メッキ装置は、無電解
メッキ液中に酸素を溶存させる補給槽（１０）を備え
る。そして、空気を取り込む送風機（１１）を備え、補
給槽（１０）内には無電解メッキ液に上記空気に含まれ
ている酸素を供給する散気管（１４）が設けられてい
る。空気中の酸素を供給する散気管（１４）をメッキ液
槽（２）ではなく補給槽（１０）内に設けると、メッキ
反応に伴い被メッキ物（８）の表面から発生する水素の
影響を受けずに、適切な酸素溶存濃度にできるので有用
である。Further, the electroless plating apparatus comprises a replenishing tank (10) for dissolving oxygen in the electroless plating solution. An air blower (11) for taking in air is provided, and a diffusing pipe (14) for supplying oxygen contained in the air to the electroless plating solution is provided in the replenishment tank (10). When the diffuser pipe (14) for supplying oxygen in the air is provided in the replenishment tank (10) instead of the plating solution tank (2), the influence of hydrogen generated from the surface of the object to be plated (8) due to the plating reaction is affected. It is useful because the oxygen dissolved concentration can be adjusted to an appropriate level without receiving it.
【００１４】次に本発明の無電解メッキ法について図１
に基づいて説明する。上記無電解メッキ液槽（２）に
は、メッキを施すための無電解メッキ液が満たされてい
る。この無電解メッキ液は公知の各種無電解メッキ液が
用いられ、例えば無電解銅メッキ、無電解ニッケルメッ
キが挙げられる。上記無電解メッキ液の温度は一般に５
０℃〜９０℃に保持される。Next, the electroless plating method of the present invention will be described with reference to FIG.
It will be described based on. The electroless plating solution tank (2) is filled with an electroless plating solution for plating. As this electroless plating solution, various known electroless plating solutions are used, and examples thereof include electroless copper plating and electroless nickel plating. The temperature of the electroless plating solution is generally 5
It is maintained at 0 ° C to 90 ° C.
【００１５】本発明においては、不活性ガスを無電解メ
ッキ液槽（２）内の無電解メッキ液に供給する。この不
活性ガスとしては、メッキ反応には影響を与えないガス
であり、例えば窒素、アルゴン等が挙げられる。ボンベ
（４）より供給された上記不活性ガスは、温度調整器
（６）で温度を無電解メッキの液温より３０℃低い温度
〜無電解メッキの液温より１０℃高い温度範囲に調整さ
れる。上記不活性ガスの温度をこの範囲に限定すると、
上記不活性ガスと接触しても被メッキ物（８）の表面の
温度が低下しないので、表面に析出する金属被膜のむら
を起こさない。In the present invention, an inert gas is supplied to the electroless plating solution in the electroless plating solution tank (2). The inert gas is a gas that does not affect the plating reaction, and examples thereof include nitrogen and argon. The temperature of the above-mentioned inert gas supplied from the cylinder (4) is adjusted by the temperature controller (6) to a temperature range which is 30 ° C. lower than the liquid temperature of the electroless plating to 10 ° C. higher than the liquid temperature of the electroless plating. It When the temperature of the inert gas is limited to this range,
Since the temperature of the surface of the object to be plated (8) does not drop even when it comes into contact with the above-mentioned inert gas, the unevenness of the metal film deposited on the surface does not occur.
【００１６】そして、無電解メッキ液槽（２）内の散気
管（３）により上記不活性ガスを無電解メッキ液に散気
する。散気管（３）が無電解メッキ液槽（２）内の被メ
ッキ物（８）より下方に設けられているので、メッキ反
応の進行に伴って発生した水素を効率的に無電解メッキ
液より放出する。上記散気管（３）としては、微細分化
して不活性ガスを無電解メッキ液に散気するため、例え
ば中空多孔質のフッソ樹脂製散気管、中空多孔質のセラ
ミック製散気管等が挙げられる。Then, the inert gas is diffused into the electroless plating solution by the diffuser pipe (3) in the electroless plating solution tank (2). Since the air diffuser pipe (3) is provided below the object to be plated (8) in the electroless plating solution tank (2), hydrogen generated by the progress of the plating reaction can be efficiently transferred from the electroless plating solution. discharge. The air diffuser (3) is, for example, a hollow porous fluorine-containing resin air diffuser, a hollow porous ceramic air diffuser, or the like, because it finely differentiates and diffuses an inert gas into the electroless plating solution. .
【００１７】本発明においては、無電解メッキ液は溶存
酸素が含まれている。この酸素の溶解は補給槽（１０）
内で行われ、補給槽（１０）内に設けられた散気管（１
４）により酸素を無電解メッキ液に供給し、所望の溶存
酸素濃度とする。この酸素としては、例えば酸素ボンベ
等の純粋な酸素を利用してもよいし、送風機（１１）で
空気を取り入れ、この空気中の酸素を利用してもよい。
上記補給槽（１０）内の所望の溶存酸素を含んだ無電解
メッキ液と無電解メッキ液槽（２）内の無電解メッキ液
はポンプ（１２）を介して適宜循環する。In the present invention, the electroless plating solution contains dissolved oxygen. This dissolution of oxygen is a replenishment tank (10)
Diffusing pipe (1) installed inside the replenishment tank (10)
Oxygen is supplied to the electroless plating solution according to 4) to obtain a desired dissolved oxygen concentration. As this oxygen, for example, pure oxygen such as an oxygen cylinder may be used, or air in the blower (11) may be taken in and oxygen in the air may be used.
The electroless plating solution containing the desired dissolved oxygen in the replenishment tank (10) and the electroless plating solution in the electroless plating solution tank (2) are appropriately circulated via a pump (12).
【００１８】本発明の請求項２に係る無電解メッキ法を
図２に基づいて説明する。図２は本発明の一実施例に係
る無電解メッキ法に使用する無電解メッキ装置のブロッ
ク図である。The electroless plating method according to claim 2 of the present invention will be described with reference to FIG. FIG. 2 is a block diagram of an electroless plating apparatus used in the electroless plating method according to an embodiment of the present invention.
【００１９】図２に示す如く、この無電解メッキ槽
（２）は無電解メッキ液が満たされ、ホルダー（９）で
保持した被メッキ物（８）を無電解メッキ液中に浸漬し
て無電解メッキを施す。As shown in FIG. 2, the electroless plating bath (2) is filled with the electroless plating solution, and the object to be plated (8) held by the holder (9) is immersed in the electroless plating solution to remove the electroless plating solution. Apply electrolytic plating.
【００２０】この無電解メッキ装置は、酸素を含む気体
として空気を取り込む送風機（１１）を備え、この空気
の温度を調整する温度調整器（６）を備える。そして、
無電解メッキ液槽（２）内の被メッキ物（８）より下方
に上記空気を無電解メッキ液に散気する散気管（３）が
設けられている。This electroless plating apparatus comprises a blower (11) for taking in air as a gas containing oxygen and a temperature controller (6) for adjusting the temperature of this air. And
An air diffuser pipe (3) for diffusing the air into the electroless plating solution is provided below the object to be plated (8) in the electroless plating solution tank (2).
【００２１】次に上記無電解メッキ法の酸素を含む気体
の散気について説明する。本発明においては、酸素を含
む気体として空気を無電解メッキ液槽（２）内の無電解
メッキ液に散気する。送風機（１１）より取り入れた上
記空気は、温度調整器（６）で温度を無電解メッキの液
温の上下１０℃の温度範囲に調整される。上記空気の温
度をこの範囲に限定すると、上記空気と接触しても被メ
ッキ物（８）の表面の温度が低下しないので、表面に析
出する金属被膜のむらを起こさない。無電解メッキ液槽
（２）内の散気管（３）により上記空気を無電解メッキ
液に散気する。この散気で、無電解メッキ液に空気中の
酸素が溶解する。Next, the diffusion of the gas containing oxygen by the electroless plating method will be described. In the present invention, air as a gas containing oxygen is diffused into the electroless plating solution in the electroless plating solution tank (2). The temperature of the air taken in from the blower (11) is adjusted by the temperature controller (6) to a temperature range of 10 ° C. above and below the liquid temperature of the electroless plating. When the temperature of the air is limited to this range, the temperature of the surface of the object to be plated (8) does not drop even if it comes into contact with the air, so that the unevenness of the metal film deposited on the surface does not occur. The air is diffused into the electroless plating solution by the diffuser pipe (3) in the electroless plating solution tank (2). Oxygen in the air is dissolved in the electroless plating solution by this air diffusion.
【００２２】また、請求項１及び２にかかる発明におい
て、無電解メッキ液槽（２）内の無電解メッキ液は、金
属イオン濃度、還元剤の濃度、ｐＨ値等を測定し、メッ
キ反応に伴って変化する無電解メッキ液の組成を維持す
るため、新たに金属イオン化合物、金属イオンの還元
剤、ｐＨ調整剤を適宜無電解メッキ液に補給する。Further, in the invention according to claims 1 and 2, the electroless plating solution in the electroless plating solution tank (2) measures metal ion concentration, reducing agent concentration, pH value, etc., for the plating reaction. In order to maintain the composition of the electroless plating solution which changes with it, a new metal ion compound, a metal ion reducing agent and a pH adjuster are newly added to the electroless plating solution.
【００２３】[0023]
実施例１ 図１に示す無電解メッキ装置を用いて無電解銅メッキを
行った。無電解メッキ液槽（２）に下記無電解銅メッキ
液を満たした。なお、この無電解銅メッキ液にｐＨ調整
剤としてＮａＯＨを加え、ｐＨを測定したところｐＨは
１２．０であった。被メッキ物（８）としてキャタリス
トーアクセレータ法によってＰｄ核を付与した２００ｍ
ｍ角のガラスエポキシ樹脂基板を１０枚、ホルダー
（９）に１０ｍｍ間隔でセットしこの無電解銅メッキ液
に浸漬した。無電解メッキ液槽（２）中の無電解銅メッ
キ液の銅イオン濃度、ＨＣＨＯ濃度、ｐＨ値を測定し、
メッキ反応に伴い、上記濃度やｐＨが一定となるよう銅
イオン、ＨＣＨＯ、ＮａＯＨを補給した。Example 1 Electroless copper plating was performed using the electroless plating apparatus shown in FIG. An electroless plating bath (2) was filled with the following electroless copper plating liquid. When pH was measured by adding NaOH as a pH adjuster to this electroless copper plating solution, the pH was 12.0. 200m with Pd nuclei added as catalyst (8) by catalyst-accelerator method
Ten m-square glass epoxy resin substrates were set in a holder (9) at intervals of 10 mm and immersed in this electroless copper plating solution. Measure the copper ion concentration, HCHO concentration, and pH value of the electroless copper plating solution in the electroless plating solution tank (2),
With the plating reaction, copper ions, HCHO, and NaOH were replenished so that the above concentration and pH would be constant.
【００２４】無電解銅メッキ液の条件 ・ＣｕＳＯ4 ・５Ｈ2 Ｏ−−−−−−１０ｇ／リットル ・ＥＤＴＡ２Ｎａ２Ｈ2 Ｏ−−−−−３０ｇ／リットル ・ＨＣＨＯ−−−−−−−−−−−−１．８ｇ／リット
ル ・シアン系添加剤−−−−−−−−−１０ｍｇ／リット
ル ・ポリエチレングリコール−−−−−２００ｍｇ／リッ
トル ・ｐＨ−−−−−−−−−−−−−−１２．０ ・液温−−−−−−−−−−−−−−６０℃ ・比重−−−−−−−−−−−−−−１．０８０ 不活性ガスとして、ボンベ（４）の窒素ガスを用いた。
上記窒素ガスの温度を温度調整器（６）で６０±５℃と
なるよう加温した。多孔質セラミック製の散気管（３）
を無電解メッキ液槽（２）内の上記被メッキ物（８）よ
り下方に設け、上記窒素ガスを無電解メッキ液に散気し
た。一方無電解銅メッキ液の補給槽（１０）内に散気管
（１４）を設け、酸素として送風機（１１）で空気を取
り入れ、この空気を補給槽（１０）内の無電解銅メッキ
液に供給した。そして、無電解メッキ液槽（２）内の無
電解銅メッキ液と補給槽（１０）内の無電解銅メッキ液
をポンプ（１２）を介して循環した。無電解メッキ液槽
（２）内の無電解銅メッキ液の溶存酸素濃度は０．５ｐ
ｐｍの一定値に保持した。上記無電解銅メッキを４時間
施し、４時間目に処理した基板を測定用の試料とした。[0024] The conditions · CuSO 4 · 5H 2 of an electroless copper plating solution O ------ 10g / liter · EDTA2Na2H 2 O ----- 30g / liter · HCHO ---------- --1.8 g / liter Cyan-based additive ---- 10 mg / liter Polyethylene glycol --- 200 mg / liter-pH -------- -12.0-Liquid temperature --------------- 60 degreeC-Specific gravity ------------------ 1.080 As an inert gas, a cylinder (4 ) Nitrogen gas was used.
The temperature of the nitrogen gas was heated to 60 ± 5 ° C. with a temperature controller (6). Air diffuser made of porous ceramic (3)
Was provided below the object to be plated (8) in the electroless plating solution tank (2), and the nitrogen gas was diffused into the electroless plating solution. On the other hand, an air diffuser pipe (14) is provided in the replenishment tank (10) for the electroless copper plating solution, air is taken in by the blower (11) as oxygen, and this air is supplied to the electroless copper plating solution in the replenishment tank (10). did. Then, the electroless copper plating solution in the electroless plating solution tank (2) and the electroless copper plating solution in the replenishment tank (10) were circulated via the pump (12). Dissolved oxygen concentration of electroless copper plating solution in electroless plating solution tank (2) is 0.5p
It was kept at a constant value of pm. The electroless copper plating was applied for 4 hours, and the substrate treated at the 4th hour was used as a sample for measurement.
【００２５】実施例２ 図１に示す無電解メッキ装置を用いて無電解ニッケルメ
ッキを行った。無電解メッキ液槽（２）に下記条件の無
電解ニッケルメッキ液を満たし、実施例１と同様の被メ
ッキ物（８）を用い、無電解ニッケルメッキ液に浸漬し
た。無電解メッキ液槽（２）中の無電解ニッケルメッキ
液のニッケルイオン濃度、次亜燐酸濃度、ｐＨ値を測定
し、メッキ反応に伴い、上記濃度やｐＨが一定となるよ
うニッケルイオン、次亜燐酸ナトリウム、ＮａＯＨ又は
Ｈ2 ＳＯ4 を補給した。Example 2 Electroless nickel plating was performed using the electroless plating apparatus shown in FIG. The electroless plating solution tank (2) was filled with the electroless nickel plating solution under the following conditions, and the same object to be plated (8) as in Example 1 was used and immersed in the electroless nickel plating solution. The nickel ion concentration, hypophosphorous acid concentration, and pH value of the electroless nickel plating solution in the electroless plating bath (2) are measured, and the nickel ion and hypophosphite are adjusted so that the above concentration and pH become constant with the plating reaction. Supplemented with sodium phosphate, NaOH or H 2 SO 4 .
【００２６】無電解ニッケルメッキ液の条件 ・ＮｉＳＯ4 ６Ｈ2 Ｏ−−−−−−−−−−−０．１ｍ
ｏｌ／リットル ・Ｃ6 Ｈ5 Ｏ7 Ｎａ3 ２Ｈ2 Ｏ−−−−−−−０．４ｍ
ｏｌ／リットル ・ＮａＨ2 ＰＯ2 Ｈ2 Ｏ−−−−−−−−−−０．１ｍ
ｏｌ／リットル ・ｐＨ−−−−−−−−−−−−−−−−−−５．０ ・液温−−−−−−−−−−−−−−−−−−９０℃ ・メッキ液の比重−−−−−−−−−−−−−１．０６
０ 不活性ガスとして、ボンベ（４）の窒素ガスを用いた。
上記窒素ガスの温度を温度調整器（６）で７０±５℃と
なるよう加温した以外は実施例１と同様にして無電解ニ
ッケルメッキを２時間施し、２時間目に処理した基板を
測定用の試料とした。Conditions of electroless nickel plating solution: NiSO 4 6H 2 O ------- 0.1 m
ol / l · C 6 H 5 O 7 Na 3 2H 2 O ------- 0.4m
ol / liter · NaH 2 PO 2 H 2 O ---------- 0.1m
ol / liter pH −−−−−−−−−−−−−−−−−−− 5.0 Liquid temperature −−−−−−−−−−−−−−−−− 90 ° C. Specific gravity of plating solution --------
0 Nitrogen gas in the cylinder (4) was used as the inert gas.
Electroless nickel plating was performed for 2 hours in the same manner as in Example 1 except that the temperature of the nitrogen gas was heated to 70 ± 5 ° C. by the temperature controller (6), and the substrate treated at the second hour was measured. It was used as a sample for.
【００２７】実施例３ 図２に示す無電解メッキ装置を用いて無電解銅メッキを
行った。無電解銅メッキ液の条件、被メッキ物（８）は
実施例１と同一のものを用いた。Example 3 Electroless copper plating was performed using the electroless plating apparatus shown in FIG. The conditions of the electroless copper plating solution and the object to be plated (8) were the same as in Example 1.
【００２８】そして、酸素を含む気体として空気を送風
機（１１）より取り入れ、温度調整器（６）で６０±５
℃となるよう加温し、多孔質セラミック製の散気管
（３）をメッキ液槽（２）内の上記被メッキ物（８）よ
り下方に設け、上記空気を無電解メッキ液槽（２）の無
電解銅メッキ液に散気した。無電解メッキ液槽（２）内
の無電解銅メッキ液の溶存酸素濃度は４．５ｐｐｍであ
った。上記無電解銅メッキを４時間施し、４時間目に処
理した基板を測定用の試料とした。Then, air as a gas containing oxygen is taken in from the blower (11), and the temperature is adjusted to 60 ± 5 by the temperature controller (6).
The air diffuser pipe (3) made of porous ceramic is heated in the plating solution tank (2) below the object to be plated (8), and the air is supplied to the electroless plating solution tank (2). The electroless copper plating solution was diffused. The dissolved oxygen concentration of the electroless copper plating solution in the electroless plating solution tank (2) was 4.5 ppm. The electroless copper plating was applied for 4 hours, and the substrate treated at the 4th hour was used as a sample for measurement.
【００２９】比較例１ 図２に示す装置を用いて無電解銅メッキを行った。空気
の温度を２０℃とした以外無電解銅メッキ液の条件、被
メッキ物（８）は実施例３と同一のものを用いた。無電
解メッキ液槽（２）内の無電解銅メッキ液の溶存酸素濃
度は４．５ｐｐｍとなった。上記無電解銅メッキを４時
間施し、４時間目に処理した基板を測定用の試料とし
た。Comparative Example 1 Electroless copper plating was performed using the apparatus shown in FIG. The conditions of the electroless copper plating solution and the object to be plated (8) used were the same as in Example 3 except that the air temperature was set to 20 ° C. The dissolved oxygen concentration of the electroless copper plating solution in the electroless plating solution tank (2) was 4.5 ppm. The electroless copper plating was applied for 4 hours, and the substrate treated at the 4th hour was used as a sample for measurement.
【００３０】無電解メッキを施した基板１０枚の試料を
用いて、メッキ被膜の外観、メッキ被膜のばらつきを測
定した。The appearance of the plated coating and variations in the plated coating were measured using samples of 10 substrates which were electroless plated.
【００３１】メッキ被膜の外観は目視でムラの有無を検
査した。ムラのなきものは○、ムラが発生したものは×
とした。The appearance of the plated coating was visually inspected for unevenness. If there is no unevenness ○, if there is unevenness ×
And
【００３２】メッキ被膜のばらつきは、被膜の厚さを蛍
光Ｘ線式膜厚計を用い、同一試料の基板で１０か所測定
し、平均、最大、最小を求めた。同一基板の平均値に対
する最大と最小の差の％を計算し「基板内ばらつき」と
し、基板１０枚中の平均値どおしを比較して、全平均に
対する各基板の平均値の最大と最小の差の％を計算し
「基板間のばらつき」とした。結果は表１のとおり、実
施例は外観も良好で、基板内、及び基板間のばらつきも
少なかった。Regarding the variation of the plating film, the thickness of the film was measured at 10 points on the substrate of the same sample using a fluorescent X-ray film thickness meter, and the average, maximum and minimum were obtained. The% difference between the maximum and the minimum of the average value of the same substrate is calculated as "in-substrate variation", and the average values of 10 substrates are compared, and the maximum and minimum of the average value of each substrate with respect to the total average. % Of the difference was calculated and defined as “variation between substrates”. The results are shown in Table 1, and in the examples, the appearance was good, and there was little variation in and between the substrates.
【００３３】[0033]
【表１】 [Table 1]
【００３４】[0034]
【発明の効果】本発明の無電解メッキ法によると、メッ
キ反応に伴って発生する水素の無電解メッキ液からの放
出を容易にし、被メッキ物表面のメッキ被膜の外観が良
好で、メッキ被膜厚さのばらつきの少ない無電解メッキ
が行える。EFFECTS OF THE INVENTION According to the electroless plating method of the present invention, hydrogen generated by the plating reaction can be easily released from the electroless plating solution, and the appearance of the plated coating on the surface of the object to be plated is good. Electroless plating with less variation in thickness can be performed.
【図１】本発明の一実施例に係る無電解メッキ法に使用
する無電解メッキ装置のブロック図である。FIG. 1 is a block diagram of an electroless plating apparatus used in an electroless plating method according to an embodiment of the present invention.
【図２】本発明の一実施例に係る無電解メッキ法に使用
する無電解メッキ装置のブロック図である。FIG. 2 is a block diagram of an electroless plating apparatus used in an electroless plating method according to an embodiment of the present invention.
２ 無電解メッキ液槽 ３ 散気管 ４ ボンベ ６ 温度調節器 ８ 被メッキ物 ９ ホルダー １０ 補給槽 １１ 送風機 １２ ポンプ １４ 散気管 2 Electroless plating liquid tank 3 Air diffuser 4 Cylinder 6 Temperature controller 8 Plated object 9 Holder 10 Replenishment tank 11 Blower 12 Pump 14 Air diffuser
───────────────────────────────────────────────────── フロントページの続き (72)発明者 吉井 靖 大阪府門真市大字門真1048番地松下電工株 式会社内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yasushi Yoshii 1048, Kadoma, Kadoma City, Osaka Prefecture Matsushita Electric Works Co., Ltd.
Claims (2)
電解メッキ液中に、無電解メッキの液温より３０℃低い
温度以上から無電解メッキの液温より１０℃高い温度以
下迄の温度範囲の不活性ガスを被メッキ物の下方より散
気することを特徴とする無電解メッキ法。1. In an electroless plating solution in a bath of electroless plating solution containing dissolved oxygen, from a temperature of 30 ° C. or lower lower than the temperature of the electroless plating to a temperature 10 ° C. or higher higher than the temperature of the electroless plating. An electroless plating method characterized in that an inert gas in a temperature range is diffused from below the object to be plated.
に、無電解メッキの液温より上下１０℃の温度範囲の酸
素を含む気体を被メッキ物の下方より散気することを特
徴とする無電解メッキ法。2. A gas containing oxygen in a temperature range of 10 ° C. above and below the temperature of the electroless plating solution is diffused into the electroless plating solution in the electroless plating solution from below the object to be plated. And electroless plating method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34716392A JPH06192844A (en) | 1992-12-25 | 1992-12-25 | Electroless plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP34716392A JPH06192844A (en) | 1992-12-25 | 1992-12-25 | Electroless plating method |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06192844A true JPH06192844A (en) | 1994-07-12 |
Family
ID=18388344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP34716392A Pending JPH06192844A (en) | 1992-12-25 | 1992-12-25 | Electroless plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06192844A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013216932A (en) * | 2012-04-06 | 2013-10-24 | Hitachi Ltd | Electroless metal plating apparatus |
-
1992
- 1992-12-25 JP JP34716392A patent/JPH06192844A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013216932A (en) * | 2012-04-06 | 2013-10-24 | Hitachi Ltd | Electroless metal plating apparatus |
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