JPH06220697A - Plating method - Google Patents
Plating methodInfo
- Publication number
- JPH06220697A JPH06220697A JP36118592A JP36118592A JPH06220697A JP H06220697 A JPH06220697 A JP H06220697A JP 36118592 A JP36118592 A JP 36118592A JP 36118592 A JP36118592 A JP 36118592A JP H06220697 A JPH06220697 A JP H06220697A
- Authority
- JP
- Japan
- Prior art keywords
- plating
- water washing
- vibration
- stirring
- vibrating
- 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.)
- Granted
Links
Abstract
Description
【０００１】[0001]
【技術分野】本発明は、めっき方法に関する。TECHNICAL FIELD The present invention relates to a plating method.
【０００２】[0002]
【従来技術】めっきは、めっきの前処理段階、めっき処
理段階、めっきの後処理段階より構成されるが現実に
は、たとえば銅めっき（このときは前段のみ）およびニ
ッケルめっき（全工程が必要）を例にとると、有機溶剤
脱脂−煮沸脱脂−水洗−電解脱脂−一次水洗−二次水洗
−銅ストライク−銅めっき−回収−一次水洗−二次水洗
−酸中和−一次水洗−二次水洗−ニッケルめっき−回収
−一次水洗−二次水洗−中和−水洗−湯洗−乾燥という
多数の工程を必要としている。このように多数の工程が
必要となる最大の原因は各処理液と被めっき物との均一
な接触が充分に行われていない点にある。しかも、脱脂
処理に用いる有機溶剤の代表であるトリクロロエチレン
は公害発生源としてマークされている存在であり、これ
を使用しない方法の出現が強く望まれている。また、小
物のめっきには、バレルめっき法が使用されている。こ
のバレルめっき法はバレルにその容積の１／２〜１／３
の小物を入れ、バレルを回転させながら脱脂、水洗めっ
き、水洗などを行うことにより、小物のめっきを効率よ
く行う方法として実用化されている。しかしながら、バ
レルを回転させているにもかかわらず、その中の小物は
なかなか均一にめっき液等と接触することが困難であ
り、とくに袋穴のあるものとか、複雑な形状のものなど
にはこの傾向が著しい。その対策としてめっき液の充分
な撹拌が必要とされているが、ここにもいろいろの問題
点が存在している。撹拌手段としては、ポンプによる循
環撹拌があり、これはめっき液を酸化させることがない
点では好ましい手段ではあるが、撹拌効率が悪いので、
実用性に乏しい。エアレーションも有効な撹拌手段では
あるが、めっき液を酸化させるので、青化浴においては
炭酸塩を生成するなどの問題点があり、めっき装置にエ
アレーション手段を組みこむことができない。2. Description of the Related Art Plating is composed of a pre-treatment step of plating, a plating treatment step, and a post-treatment step of plating, but in reality, for example, copper plating (in this case only the previous step) and nickel plating (all steps are required) For example, organic solvent degreasing-boiling degreasing-water washing-electrolytic degreasing-primary water washing-secondary water washing-copper strike-copper plating-recovery-primary water washing-secondary water washing-acid neutralization-primary water washing-secondary water washing -Nickel plating-Recovery-Primary water washing-Secondary water washing-Neutralization-Water washing-Hot water washing-Drying are required. The greatest reason why such a large number of steps are required is that the uniform contact between each processing solution and the object to be plated is not performed sufficiently. Moreover, trichloroethylene, which is a typical organic solvent used for degreasing treatment, is marked as a pollution source, and the emergence of a method that does not use this is strongly desired. Barrel plating is used for plating small items. This barrel plating method uses 1 / 2-1 / 3 of the volume of the barrel.
It has been put into practical use as a method for efficiently plating small items by putting the small items in, and performing degreasing, washing plating, and washing while rotating the barrel. However, even though the barrel is rotated, it is difficult for the small items inside to contact the plating solution etc. evenly, especially for those with bag holes or complicated shapes. The tendency is remarkable. As a countermeasure, it is necessary to sufficiently stir the plating solution, but there are various problems here as well. As a stirring means, there is circulation stirring by a pump, which is a preferable means in that it does not oxidize the plating solution, but since the stirring efficiency is poor,
Practicality is poor. Aeration is also an effective stirring means, but since it oxidizes the plating solution, it has problems such as generation of carbonates in the blueing bath, and it is impossible to incorporate aeration means in the plating apparatus.
【０００３】[0003]
【目的】本発明の目的の第一は、めっき法において、被
めっき物とめっき液や脱脂液などの液体との接触を充分
に行うために有効な方法を提供する点にある。本発明の
目的の第二は、有機溶剤を使用する必要のない新しいめ
っき方法を提供する点にある。[Object] A first object of the present invention is to provide an effective method in the plating method for sufficiently bringing the object to be plated into contact with a liquid such as a plating solution or a degreasing solution. The second object of the present invention is to provide a new plating method which does not require the use of an organic solvent.
【０００４】[0004]
【構成】本発明は、めっきの前処理段階、めっき処理段
階およびめっき後の処理段階のすべての処理段階におけ
る少なくともその一工程で振動撹拌を行うことを特徴と
するめっき方法に関する。本発明の１つの好ましい態様
は、めっきの前処理段階における煮沸脱脂工程、水洗工
程；めっきの処理段階におけるめっき工程；めっきの後
処理段階における水洗工程、必要に応じて酸中和工程、
水洗工程の各工程において振動撹拌を行なうめっき方法
である。本発明は、振動撹拌手段を採用していることに
より、めっきの前処理段階において有機溶剤による脱脂
工程を省略しても、有機溶剤による脱脂工程を含む従来
法に較べて優るとも劣らない効果を発揮する。特にめっ
き対象物がバレルに充填された複数の物品とくに多数の
小物類である場合、すなわち、バレルめっきの場合に
は、本発明方法は特に顕著な効果を奏する。バレルは外
周に多数の小孔が設けられてはいるが、そのなかにおけ
る液体の流動は極めて悪く、ほとんど流動していないの
が実状である。ところが驚くべきことに振動撹拌を行な
うと、バレル内の液体が見事に流動し、新しい液体が、
それぞれの小物に充分接触できるようになったのであ
る。The present invention relates to a plating method characterized by vibrating and agitating in at least one step of all pretreatment steps of plating, a plating treatment step and a treatment step after plating. One preferred embodiment of the present invention is a boiling degreasing step in a pretreatment step of plating, a water washing step; a plating step in a treatment step of plating; a water washing step in a posttreatment step of plating, and optionally an acid neutralization step,
This is a plating method in which vibration stirring is performed in each step of the water washing step. The present invention, by adopting the vibrating stirring means, even if the degreasing step by the organic solvent is omitted in the pretreatment step of plating, the effect is not inferior to the conventional method including the degreasing step by the organic solvent. Demonstrate. In particular, when the object to be plated is a plurality of articles filled in the barrel, particularly a large number of small articles, that is, in the case of barrel plating, the method of the present invention exerts a particularly remarkable effect. Although the barrel has a large number of small holes on its outer circumference, the liquid flow in the barrel is extremely poor, and in reality, it hardly flows. However, surprisingly, when vibrating and stirring, the liquid in the barrel flows nicely and new liquid
It came to be able to fully contact each small item.
【０００５】振動撹拌は、１５〜６０Ｈｚ、好ましくは
２０〜４０Ｈｚでの振動を発生させる、振動モータによ
る振動を液中の振動板に伝え、液体にこの振動を伝える
ことにもとづく本発明者が開発した新しい撹拌手段であ
り、その基本的考え方は特開平３−２７５１３０号公報
に開示したとおりであり、また、その変形撹拌手段は特
願平４−２８６５４４号として平成４年９月１４日に出
願している。この振動撹拌は、振動板による振動が系全
体に伝えられると、スクリューによる撹拌に較べて系全
体がすみやかに均一化されることは驚くべきことであ
り、この現象は、液体系のみならず、粉体、粒体系にお
いても同様であり、おが屑中に着色おが屑を加えた実験
でも立証できているところである。なお、振動板の振幅
は、２〜３０ｍｍ好ましくは、１０〜１５ｍｍである。Vibratory agitation produces vibrations at 15 to 60 Hz, preferably 20 to 40 Hz. The vibration generated by a vibration motor is transmitted to a diaphragm in the liquid and developed by the present inventor based on transmitting this vibration to the liquid. The basic idea of the new stirring means is as disclosed in JP-A-3-275130, and the modified stirring means is filed on September 14, 1992 as Japanese Patent Application No. 4-286544. is doing. It is surprising that this vibration agitation, when vibration by the vibrating plate is transmitted to the entire system, makes the entire system promptly homogenized as compared with stirring by a screw, and this phenomenon is not limited to liquid systems. The same is true for powders and granules, and it is being verified in an experiment in which colored sawdust was added to sawdust. The amplitude of the diaphragm is 2 to 30 mm, preferably 10 to 15 mm.
【０００６】振動撹拌の手段は、前記公報や明細書記載
のものでもよいが、処理槽の底部寄りに設けた振動板の
一個所または２個所を振動軸に連結してウチワであおぐ
ように振動させることもできる。液槽が四角形のときは
振動板の一辺の両端部に振動軸を一本づつ二本設けても
よいが、辺の中央に一本設けることもできる。また振動
板の一つの角部に一本の振動軸を設けてもよい。振動軸
をとりつけた辺の対角辺あるいは振動軸をとりつけた角
部以外の角部は固定軸により支持する。固定軸には弾性
体、たとえば、ゴム、スプリング、空気バネ等を介して
振動板を固定することが好ましいが、振動板自体の弾力
にたよることも可能である。図１にその一具体例を示
す。振動モーターに任意の手段で連結した振動伝達棒５
を介して振動棒１，２を設け、この振動棒１、２にはゴ
ム片８，９を用いて振動板６を固定する一方、固定棒
３，４には、振動板６の振動を支持する支持用ゴム片１
０，１１を固定し、これに振動板６を連結する。振動板
６は、支持用ゴム片１０，１１を支点として振動伝達棒
１，２の上下動にあわせて扇をあおぐように振動するの
でこれを槽中におさえることにより、液体、粉体、粒体
等の混合撹拌を行うことができる。The vibrating and agitating means may be those described in the above-mentioned publications and specifications, but one or two portions of the vibrating plate provided near the bottom of the processing tank are connected to the vibrating shaft to vibrate with a punch. You can also let it. When the liquid tank has a quadrangular shape, two vibration shafts may be provided at both ends of one side of the vibration plate, but one vibration axis may be provided at the center of the side. Further, one vibration shaft may be provided at one corner of the diaphragm. The diagonal side of the side to which the vibration axis is attached or the corners other than the corner to which the vibration axis is attached are supported by the fixed shaft. The vibrating plate is preferably fixed to the fixed shaft via an elastic body such as rubber, a spring, or an air spring, but it is also possible to rely on the elastic force of the vibrating plate itself. FIG. 1 shows a specific example thereof. Vibration transmission rod 5 connected to the vibration motor by any means
The vibrating rods 1 and 2 are provided through the vibrating rods 1 and 2, and the vibrating plate 6 is fixed to the vibrating rods 1 and 2 by using rubber pieces 8 and 9, while the vibration of the vibrating plate 6 is supported on the fixing rods 3 and 4. Supporting rubber piece 1
0 and 11 are fixed, and the diaphragm 6 is connected thereto. The vibrating plate 6 vibrates with the supporting rubber pieces 10 and 11 as a fulcrum so as to open and close the fan in accordance with the vertical movement of the vibration transmitting rods 1 and 2. Mixing and stirring of the body and the like can be performed.
【０００７】以下の実施例は、銅めっきの上にニッケル
めっきを行う態様を説明するものであるが、本発明は、
この実施例により限定されることなく、亜鉛、すず、
銅、ニッケル、クロム、銀、金など各種金属、合金類の
めっきにすべて顕著な効果を奏するものである。The following examples explain the mode of nickel plating on copper plating.
Without being limited by this example, zinc, tin,
It has a remarkable effect on plating of various metals and alloys such as copper, nickel, chrome, silver and gold.
【０００８】[0008]
実施例１ （工程） （１）煮沸脱脂（振動撹拌付）、（２）水洗（振動撹拌
付）、（３）一般水洗、（４）銅ストライク、（５）銅
めっき（振動撹拌付）、（６）回収（振動撹拌付）、
（７）水洗（振動撹拌付）、（８）一般水洗、（９）酸
中和（振動撹拌付）、（１０）水洗（振動撹拌付）、
（１１）ニッケルめっき（振動撹拌付）、（１２）回収
（振動撹拌付）、（１３）水洗（振動撹拌付）、（１
４）一般湯洗、（１５）乾燥よりなる１５工程。Example 1 (Process) (1) Boiling degreasing (with vibration stirring), (2) Water washing (with vibration stirring), (3) General water washing, (4) Copper strike, (5) Copper plating (with vibration stirring), (6) Recovery (with vibration stirring),
(7) Water washing (with vibration stirring), (8) General water washing, (9) Acid neutralization (with vibration stirring), (10) Water washing (with vibration stirring),
(11) Nickel plating (with vibration stirring), (12) Recovery (with vibration stirring), (13) Washing with water (with vibration stirring), (1
15 steps consisting of 4) general hot water washing and (15) drying.
【０００９】（撹拌手段）本実施例で使用する振動撹拌
手段を設けためっき装置を図２〜５に示す。めっき工程
以外で使用するときは図２で示す電極２７は不要であ
る。振動撹拌手段は、振動モーター２６で発生した振動
を振動枠２３、振動棒２１を介して振動羽根群２２、２
２……に伝える。振動羽根群は図２、３に明示されてい
るように槽２９の両側に設置する。振動モーター２６よ
りの振動が槽２９本体に影響しないようにするため、振
動枠２３はスプリング２４と台座２５を介して本体に取
付けられている。振動羽根は、水平であってもよいがや
ゝ傾斜をつけて取付けることが好ましい。傾斜の程度は
水平方向を基準にして０〜４５゜、好ましくは１０〜２
０゜の角度で取付けることが好ましい。本実施例では１
５゜でセットした。振動羽根の幅は特に制限はないが３
０ｍｍ以上程度あれば充分その効力を発揮する。通常３
０〜１００ｍｍ、好ましくは５０〜８０ｍｍ程度であ
る。撹拌羽根同士の間隔はとくに制限はないが通常１０
〜８０ｍｍ、好ましくは３０〜４０ｍｍであり、本実施
例では３５ｍｍ間隔とした。また、左右の振動羽根２２
の位置は、同一の高さでもよいが、やゝずらせた位置に
設けることもできる。最上位の振動羽根は液面から約１
００ｍｍ下の位置にすることが好ましい。これより上に
設けるとその振幅により多少異なるが、液が飛び散るの
で好ましくない。最下位の振動羽根は底から約５０ｍｍ
上の位置とすることが好ましい。本発明の振動羽根は幅
８０ｍｍ、長さ４００ｍｍ、間隔３５ｍｍとした。(Stirring Means) FIGS. 2 to 5 show a plating apparatus provided with a vibrating stirring means used in this embodiment. The electrode 27 shown in FIG. 2 is unnecessary when used in a process other than the plating process. The vibrating agitation unit applies the vibration generated by the vibrating motor 26 to the vibrating blade groups 22, 2 via the vibrating frame 23 and the vibrating rod 21.
Tell 2 ……. The vibrating blade groups are installed on both sides of the tank 29 as clearly shown in FIGS. The vibration frame 23 is attached to the main body via a spring 24 and a pedestal 25 so that the vibration from the vibration motor 26 does not affect the main body of the tank 29. The vibrating blade may be horizontal, but it is preferable to attach it with a slight inclination. The degree of inclination is 0 to 45 ° with respect to the horizontal direction, preferably 10 to 2
It is preferable to mount at an angle of 0 °. In this embodiment, 1
I set it at 5 degrees. The width of the vibrating blade is not particularly limited, but 3
If it is about 0 mm or more, its effect is sufficiently exhibited. Usually 3
It is 0 to 100 mm, preferably about 50 to 80 mm. The distance between the stirring blades is not particularly limited, but is usually 10
.About.80 mm, preferably 30 to 40 mm, and in this embodiment, the interval is 35 mm. In addition, the left and right vibrating blades 22
The positions may be at the same height, but they can be provided at slightly offset positions. The uppermost vibrating blade is about 1 from the liquid surface.
It is preferable to set it at a position below 00 mm. If it is provided above this, the liquid will be scattered, although it is somewhat different depending on the amplitude, which is not preferable. The lowest vibrating blade is about 50 mm from the bottom
The upper position is preferable. The vibrating blade of the present invention has a width of 80 mm, a length of 400 mm, and an interval of 35 mm.
【００１０】（めっき対象物とめっき法）Ｌ字状をした
接極子（幅約７ｍｍ，全長約３０ｍｍ）（目視により油
汚れが多く付着していた）をバレルめっき法によりめっ
きした。 （煮沸脱脂）苛性ソーダ、炭酸ソーダ、りん酸ソーダ、
トリポリリン酸ソーダおよび界面活性剤を含有する水溶
液を使用、液温；７０℃、浸漬時間；５分。 （銅めっき浴） シアン化銅 ４６．２ｇ／リットル シアン化ナトリウム ３５ｇ／リットル 炭酸ナトリウム ２６．５ｇ／リットル 遊離シアン分 １３．５ｇ／リットル 電流密度 ０．３Ａ／ｄｍ2 電解時間 ９０分 ｐＨ １２．３ 温度 ５０℃ 銅メッキ膜厚 １２±２μ 有機光沢剤 ５リットル／Ｍ バレル ３５０φ×５００Ｌ 穴径５ｍ／ｍ
φ 槽寸法 ７００×５００×７００Ｈ（２０
０リットル） バレル数 ３連 （ニッケルめっき浴） 硫酸ニッケル ２４３．６ｇ／リットル 塩化ニッケル ４８．５ｇ／リットル ホウ酸 ３４．２ｇ／リットル 電流密度 ０．４Ａ／ｄｍ2 電解時間 ３０分 ｐＨ ４．８ 温度 ４８℃ ニッケル膜厚 ２±０．５μ 有機光沢剤 ８リットル／Ｍ バレル ３５０φ×５００Ｌ 穴径５ｍ／ｍ
φ 槽寸法 ６００×１，２００×７００（４
３０リットル） バレル数 ２連(Object to be plated and plating method) An L-shaped armature (width: about 7 mm, total length: about 30 mm) (a large amount of oil stain was visually observed) was plated by the barrel plating method. (Boiling degreasing) caustic soda, sodium carbonate, sodium phosphate,
An aqueous solution containing sodium tripolyphosphate and a surfactant was used, liquid temperature: 70 ° C., immersion time: 5 minutes. (Copper plating bath) Copper cyanide 46.2 g / liter Sodium cyanide 35 g / liter Sodium carbonate 26.5 g / liter Free cyanide content 13.5 g / liter Current density 0.3 A / dm 2 Electrolysis time 90 minutes pH 12.3 Temperature 50 ℃ Copper plating film thickness 12 ± 2μ Organic brightener 5 liter / M Barrel 350φ × 500L Hole diameter 5m / m
φ tank size 700 × 500 × 700H (20
0 liters) Number of barrels 3 (nickel plating bath) Nickel sulfate 243.6 g / liter Nickel chloride 48.5 g / liter Boric acid 34.2 g / liter Current density 0.4 A / dm 2 Electrolysis time 30 minutes pH 4.8 Temperature 48 ° C Nickel film thickness 2 ± 0.5μ Organic brightener 8 liters / M barrel 350φ × 500L Hole diameter 5m / m
φ tank size 600 × 1,200 × 700 (4
30 liters) 2 barrels
【００１１】比較例１ 実施例１と同レベルのめっきを達成するためには、従来
の工程は次の通り２２工程が必要である。 （工程） （１）有機溶剤脱脂、（２）煮沸脱脂、（３）水洗、
（４）電解脱脂、（５）一次水洗、（６）二次水洗、
（７）銅ストライク、（８）銅めっき、（９）回収、
（１０）一次水洗、（１１）二次水洗、（１２）酸中
和、（１３）一次水洗、（１４）二次水洗、（１５）ニ
ッケルめっき、（１６）回収、（１７）一次水洗、（１
８）二次水洗、（１９）中和、（２０）水洗、（２１）
湯洗、（２２）乾燥 （めっき対象物とめっき法）実施例と同一。 （有機溶剤脱脂）実施例と同一。 （煮沸脱脂）振動撹拌のかわりに浸漬方法（撹拌なし）
を用いた以外は、実施例と同一。 （銅めっき浴）と（ニッケル浴）いずれも振動撹拌にか
わる積極的撹拌を行わなかった（バレルめっきの場合は
エアレーションを行ってもバレルが邪魔をして全く効果
がないことが知られている。）以外は実施例１と同一。Comparative Example 1 In order to achieve the same level of plating as in Example 1, the following 22 conventional processes are required. (Process) (1) Organic solvent degreasing, (2) Boiling degreasing, (3) Washing with water,
(4) Electrolytic degreasing, (5) Primary water washing, (6) Secondary water washing,
(7) Copper strike, (8) Copper plating, (9) Recovery,
(10) Primary water washing, (11) Secondary water washing, (12) Acid neutralization, (13) Primary water washing, (14) Secondary water washing, (15) Nickel plating, (16) Recovery, (17) Primary water washing, (1
8) Secondary water washing, (19) Neutralization, (20) Water washing, (21)
Washing with hot water, (22) Drying (plating target and plating method) Same as the example. (Organic solvent degreasing) Same as the example. (Boiling degreasing) Immersion method instead of vibration stirring (no stirring)
Same as the example except that was used. Neither (copper plating bath) nor (nickel bath) was vigorously stirred instead of vigorous stirring. (In the case of barrel plating, it is known that even if aeration is performed, the barrel interferes and there is no effect. .) But the same as Example 1.
【００１２】[0012]
【表１】 [Table 1]
【００１３】[0013]
（１）残留油分について、 １，１，１−トリクロルエタンのような有機溶剤を使用
しないにも拘らず、有機溶剤を使用した従来法に較べて
優るとも劣らない脱脂効果を挙げている。また、煮沸脱
脂工程には、界面活性剤が存在することに伴い泡立ちが
問題となるが、振動撹拌によるときは不思議とほとんど
泡立ちがなく、また被めっき物表面からの油の離脱も極
めてスムースである。(1) Regarding the residual oil content, despite not using an organic solvent such as 1,1,1-trichloroethane, a degreasing effect which is not inferior to the conventional method using an organic solvent is mentioned. Also, in the boiling degreasing process, foaming becomes a problem due to the presence of a surfactant, but when vibrating and stirring, there is almost no foaming, and the oil can be removed from the surface of the plated object very smoothly. is there.
【００１４】（２）水洗効率について 表１にみられるとおり、本発明の水洗効果は比較例と較
べて抜群である。比較例は一次、二次と二回に分けて水
洗しているのに対して、実施例では一回の水洗で充分で
あり、かつその水洗効果も表１のデータからみて約３〜
８倍である。(2) Washing efficiency As shown in Table 1, the washing effect of the present invention is outstanding as compared with the comparative example. In the comparative example, the washing is performed twice in the primary and secondary steps, whereas in the example, one washing is sufficient, and the washing effect is about 3 to 10 in view of the data in Table 1.
8 times.
【００１５】（３）電流効率、電流密度への影響につい
て、 電流密度を上げると生産性が上がるから電流密度を上げ
ることはたいへん好ましいことであるが、電流密度をあ
げてゆくとある段階で過電流となり、製品にヤケやコゲ
が生じ、まためっき中にガスが発生し製品にピットが生
じたりする。ところが、振動撹拌を採用すると製品に、
ヤケ、コゲ、ピットが発生する限界となる電流密度が従
来法に較べて大幅に上昇した。(3) Concerning the influence on the current efficiency and the current density, it is very preferable to increase the current density because increasing the current density will increase the productivity. It becomes an electric current, burns and burns occur on the product, and gas is generated during plating to cause pits on the product. However, if vibration agitation is adopted,
The current density, which is the limit of burns, kogation, and pits, increased significantly compared to the conventional method.
【００１６】[0016]
【表２】 [Table 2]
【表３】 [Table 3]
【表４】 [Table 4]
【表５】 [Table 5]
【００１７】（４）省スペース、省エネルギー高生産性
について、 実施例と比較例をみれば明らかなとおり、従来法に較べ
て本発明は工程数が大幅に少なくなる結果、省スペー
ス、省エネルギー、高生産性を達成することができた。
同一生産高を達成するのに実施例は比較例の約１／３の
時間ですむ。(4) Space-saving, energy-saving High productivity As is clear from Examples and Comparative Examples, the present invention has a significantly smaller number of steps as compared with the conventional method, resulting in space-saving, energy-saving and high productivity. We were able to achieve productivity.
The embodiment takes about 1/3 the time of the comparative example to achieve the same output.
【００１８】（５）炭酸塩について 比較例では、銅めっき浴中に多量の炭酸塩が生じるた
め、これを取り除く作業が必要である。比較例の場合は
多量の炭酸塩が発生するだけでなく、槽壁等に固着する
から、これを除去するのが大変である。これに対して、
実施例においては、ある程度の炭酸塩が発生している
が、槽壁に固着せず、系中に分散しているので濾過によ
り簡単に分離できる。(5) Carbonate In the comparative example, since a large amount of carbonate is generated in the copper plating bath, it is necessary to remove it. In the case of the comparative example, not only a large amount of carbonate is generated, but it also adheres to the tank wall, etc., so it is difficult to remove this. On the contrary,
In the examples, a certain amount of carbonate is generated, but since it does not adhere to the tank wall and is dispersed in the system, it can be easily separated by filtration.
【００１９】（６）光沢剤の使用量について、 下記の表に示すとおり、実施例では比較例に較べて有機
光沢剤の使用量が１／２〜１／３に減少した。(6) Concerning the amount of the brightening agent used, as shown in the table below, the amount of the organic brightening agent used in the examples was reduced to 1/2 to 1/3 as compared with the comparative example.
【表６】 [Table 6]
【表７】 [Table 7]
【００２０】（７）ニッケルめっき浴におけるホウ酸の
働きについて、 ホウ酸は、めっきが行われている周辺領域の水素イオン
消費を補い、めっき面の物性向上に役立つ重要な試薬で
あり、とくにニッケルめっきにおいてはめっき浴中での
ホウ酸の不均一に基因する焦げ、ざらつき等が発生しや
すい。ところが、本発明によれば、このような不都合は
全く発生しない。(7) Regarding the function of boric acid in the nickel plating bath Boric acid is an important reagent that supplements the consumption of hydrogen ions in the peripheral region where plating is performed and helps improve the physical properties of the plated surface, and especially nickel. In plating, scorching and roughness due to unevenness of boric acid in the plating bath are likely to occur. However, according to the present invention, such inconvenience does not occur at all.
【００２１】（８）本発明により形成されためっき面
は、柔軟性に富み、内部応力が低いという優れた物性を
有する。ニッケルめっき面について測定した結果は次の
とおりである。(8) The plated surface formed according to the present invention has excellent physical properties such as high flexibility and low internal stress. The results of measurement on the nickel-plated surface are as follows.
【表８】 （９）めっき不良率を低減させたニッケルめっきのさい
の不良率は次のとおりである。[Table 8] (9) The defective rate of nickel plating in which the defective plating rate is reduced is as follows.
【表９】 （１０） めっき膜厚のバラツキが著しく少なくなっ
た。これを銅めっき膜について測定したデータをつぎに
示す。[Table 9] (10) The variation in plating film thickness was significantly reduced. The data obtained by measuring this on a copper plating film are shown below.
【表１０】 [Table 10]
【００２２】[0022]
【効果】本発明は、従来法に較べて大幅に工程数を少な
くすることができ、省エネルギーを達成でき、生産効果
が著しく向上した。とくに、本発明によれば有機溶剤の
使用を回避することができるので、公害問題解決に寄与
する点が大である。また、本発明によるめっき物は従来
法によるものに較べて物性が著しく向上している。[Effect] According to the present invention, the number of steps can be significantly reduced as compared with the conventional method, energy saving can be achieved, and the production effect is remarkably improved. In particular, according to the present invention, it is possible to avoid the use of an organic solvent, which is a great point in solving the pollution problem. Further, the physical properties of the plated product according to the present invention are remarkably improved as compared with those obtained by the conventional method.
【図１】本発明のめっき方法に用いる新規な振動撹拌装
置を示す斜視図である。FIG. 1 is a perspective view showing a novel vibration stirrer used in a plating method of the present invention.
【図２】本発明の実施例に用いた撹拌装置の上面図であ
る。FIG. 2 is a top view of a stirring device used in an example of the present invention.
【図３】本発明の実施例に用いた撹拌装置の側面図であ
る。FIG. 3 is a side view of a stirring device used in an example of the present invention.
【図４】本発明の実施例に用いた撹拌装置のもう一方の
側からみた側面図である。FIG. 4 is a side view of the stirring device used in the example of the present invention as seen from the other side.
【図５】本発明の実施例に用いた撹拌装置の要部のみの
斜視図である。FIG. 5 is a perspective view of only a main part of a stirring device used in an example of the present invention.
１ 振動棒 ２ 振動棒 ３ 固定棒 ４ 固定棒 ５ 振動伝達棒 ６ 振動板 ７ 槽底部 ８ 支持用ゴム片 ９ 支持用ゴム片 １０ 支持用ゴム片 １１ 支持用ゴム片 ２１ 振動棒 ２２ 振動羽根 ２３ 振動枠 ２４ スプリング ２５ 台座 ２６ 振動モーター ２７ 電極 ２８ 加熱用電極 ２９ 槽 ３０ バレル 1 Vibration Rod 2 Vibration Rod 3 Fixed Rod 4 Fixed Rod 5 Vibration Transmission Rod 6 Vibration Plate 7 Tank Bottom 8 Supporting Rubber Piece 9 Supporting Rubber Piece 10 Supporting Rubber Piece 11 Supporting Rubber Piece 21 Vibration Rod 22 Vibrating Blade 23 Vibration Frame 24 Spring 25 Pedestal 26 Vibration motor 27 Electrode 28 Heating electrode 29 Tank 30 Barrel
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成６年３月２日[Submission date] March 2, 1994
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００２[Name of item to be corrected] 0002
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００２】[0002]
【従来技術】めっきは、めっきの前処理段階、めっき処
理段階、めっきの後処理段階より構成されるが現実に
は、たとえば銅めっき（このときは前段のみ）およびニ
ッケルめっき（全工程が必要）を例にとると、有機溶剤
脱脂−煮沸脱脂−水洗−電解脱脂−一次水洗−二次水洗
−銅ストライク−銅めっき−回収−一次水洗−二次水洗
−酸中和−一次水洗−二次水洗−ニッケルめっき−回収
−一次水洗−二次水洗−中和−水洗−湯洗−乾燥という
多数の工程を必要としている。このように多数の工程が
必要となる最大の原因は各処理液と被めっき物との均一
な接触が充分に行われていない点にある。しかも、脱脂
処理に用いる有機溶剤の代表であるトリクロロエチレン
は公害発生源としてマークされている存在であり、これ
を使用しない方法の出現が強く望まれている。また、小
物のめっきには、バレルめっき法が使用されている。こ
のバレルめっき法はバレルにその容積の１／２〜１／３
の小物を入れ、バレルを回転させながら脱脂、水洗、め
っき、水洗などを行うことにより、小物のめっきを効率
よく行う方法として実用化されている。しかしながら、
バレルを回転させているにもかかわらず、その中の小物
はなかなか均一にめっき液等と接触することが困難であ
り、とくに袋穴のあるものとか、複雑な形状のものなど
にはこの傾向が著しい。その対策としてめっき液の充分
な撹拌が必要とされているが、ここにもいろいろの問題
点が存在している。撹拌手段としては、ポンプによる循
環撹拌があり、これはめっき液を酸化させることがない
点では好ましい手段ではあるが、撹拌効率が悪いので、
実用性に乏しい。エアレーションも有効な撹拌手段では
あるが、めっき液を酸化させるので、青化浴においては
炭酸塩を生成するなどの問題点があり、めっき装置にエ
アレーション手段を組みこむことができない。2. Description of the Related Art Plating is composed of a pre-treatment step of plating, a plating treatment step, and a post-treatment step of plating, but in reality, for example, copper plating (in this case only the previous step) and nickel plating (all steps are required) For example, organic solvent degreasing-boiling degreasing-water washing-electrolytic degreasing-primary water washing-secondary water washing-copper strike-copper plating-recovery-primary water washing-secondary water washing-acid neutralization-primary water washing-secondary water washing -Nickel plating-Recovery-Primary water washing-Secondary water washing-Neutralization-Water washing-Hot water washing-Drying are required. The greatest reason why such a large number of steps are required is that the uniform contact between each processing solution and the object to be plated is not performed sufficiently. Moreover, trichloroethylene, which is a typical organic solvent used for degreasing treatment, is marked as a pollution source, and the emergence of a method that does not use this is strongly desired. Barrel plating is used for plating small items. This barrel plating method uses 1 / 2-1 / 3 of the volume of the barrel.
It has been put to practical use as a method for efficiently plating small items by putting the small items in, and degreasing, washing with water, plating, washing with water while rotating the barrel. However,
Despite rotating the barrel, it is difficult for the small items inside to contact the plating solution etc. evenly, and this tendency tends to occur especially for those with bag holes or complicated shapes. Remarkable. As a countermeasure, it is necessary to sufficiently stir the plating solution, but there are various problems here as well. As a stirring means, there is circulation stirring by a pump, which is a preferable means in that it does not oxidize the plating solution, but since the stirring efficiency is poor,
Practicality is poor. Aeration is also an effective stirring means, but since it oxidizes the plating solution, it has problems such as generation of carbonates in the blueing bath, and it is impossible to incorporate aeration means in the plating apparatus.
【手続補正２】[Procedure Amendment 2]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】０００８[Correction target item name] 0008
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【０００８】[0008]
【実施例】 実施例１ （工程） （１）煮沸脱脂（振動撹拌付）、（２）水洗（振動撹拌
付）、（３）一般水洗、（４）銅ストライク、（５）銅
めっき（振動撹拌付）、（６）回収、（７）水洗（振動
撹拌付）、（８）一般水洗、（９）酸中和（振動撹拌
付）、（１０）水洗（振動撹拌付）、（１１）ニッケル
めっき（振動撹拌付）、（１２）回収、（１３）水洗
（振動撹拌付）、（１４）一般湯洗、（１５）乾燥より
なる１５工程。Examples Example 1 (Process) (1) Boiling degreasing (with vibration stirring), (2) Water washing (with vibration stirring), (3) General water washing, (4) Copper strike, (5) Copper plating (vibration) (With stirring), (6) recovery, (7) water washing (with vibration stirring), (8) general water washing, (9) acid neutralization (with vibration stirring), (10) water washing (with vibration stirring), (11) 15 steps consisting of nickel plating (with vibration stirring), (12) recovery, (13) water washing (with vibration stirring), (14) general hot water washing, and (15) drying.
【手続補正３】[Procedure 3]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】００１０[Correction target item name] 0010
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【００１０】（めっき対象物とめっき法）Ｌ字状をした
接極子（幅約７ｍｍ，全長約３０ｍｍ）（目視により油
汚れが多く付着していた）をバレルめっき法によりめっ
きした。 （煮沸脱脂）苛性ソーダ、炭酸ソーダ、りん酸ソーダ、
トリポリリン酸ソーダおよび界面活性剤を含有する水溶
液を使用、液温；７０℃、浸漬時間；５分。 （銅めっき浴） シアン化銅 ４６．２ｇ／リットル シアン化ナトリウム ３５ｇ／リットル 炭酸ナトリウム ２６．５ｇ／リットル 遊離シアン分 １３．５ｇ／リットル 電流密度 ５．０Ａ／ｄｍ2 電解時間 ９０分 ｐＨ １２．３ 温度 ５０℃ 銅メッキ膜厚 １２±２μ 有機光沢剤 ５リットル／Ｍ バレル ３５０φ×５００Ｌ 穴径５ｍ／ｍ
φ 槽寸法 ７００×５００×７００Ｈ（２０
０リットル） バレル数 ３連 （ニッケルめっき浴） 硫酸ニッケル ２４３．６ｇ／リットル 塩化ニッケル ４８．５ｇ／リットル ホウ酸 ３４．２ｇ／リットル 電流密度 ５．０Ａ／ｄｍ2 電解時間 ３０分 ｐＨ ４．８ 温度 ４８℃ ニッケル膜厚 ２±０．５μ 有機光沢剤 ８リットル／Ｍ バレル ３５０φ×５００Ｌ 穴径５ｍ／ｍ
φ 槽寸法 ６００×１，２００×７００（４
３０リットル） バレル数 ２連(Object to be plated and plating method) An L-shaped armature (width: about 7 mm, total length: about 30 mm) (a large amount of oil stain was visually observed) was plated by the barrel plating method. (Boiling degreasing) caustic soda, sodium carbonate, sodium phosphate,
An aqueous solution containing sodium tripolyphosphate and a surfactant was used, liquid temperature: 70 ° C., immersion time: 5 minutes. (Copper plating bath) Copper cyanide 46.2 g / liter Sodium cyanide 35 g / liter Sodium carbonate 26.5 g / liter Free cyanide content 13.5 g / liter Current density 5.0 A / dm 2 Electrolysis time 90 minutes pH 12.3 Temperature 50 ℃ Copper plating film thickness 12 ± 2μ Organic brightener 5 liter / M Barrel 350φ × 500L Hole diameter 5m / m
φ tank size 700 × 500 × 700H (20
Number of barrels: 3 (nickel plating bath) Nickel sulfate 243.6 g / liter Nickel chloride 48.5 g / liter Boric acid 34.2 g / liter Current density 5.0 A / dm 2 Electrolysis time 30 minutes pH 4.8 Temperature 48 ° C Nickel film thickness 2 ± 0.5μ Organic brightener 8 liters / M barrel 350φ × 500L Hole diameter 5m / m
φ tank size 600 × 1,200 × 700 (4
30 liters) 2 barrels
Claims (5)
よびめっきの後処理段階のすべての処理段階における少
なくともその一工程で振動撹拌を行うことを特徴とする
めっき方法。1. A plating method, characterized in that vibration stirring is performed in at least one of all of the pretreatment stage of plating, the plating treatment stage and the posttreatment stage of plating.
程、水洗工程；めっき処理段階におけるめっき工程；め
っきの後処理段階における水洗工程、酸中和工程後の水
洗工程の各工程において振動撹拌を行う請求項１記載の
めっき方法。2. Vibratory stirring is performed in each step of a boiling degreasing step in a pretreatment step of plating, a water washing step; a plating step in a plating treatment step; a water washing step in a posttreatment step of plating and a water washing step after an acid neutralization step. The plating method according to claim 1.
程、水洗工程；めっき処理段階におけるめっき工程；め
っきの後処理段階における水洗工程、酸中和工程、水洗
工程の各工程において振動撹拌を行う請求項１記載のめ
っき方法。3. A boiling degreasing step in a pretreatment step of plating, a water washing step; a plating step in a plating treatment step; a water washing step, an acid neutralization step and a water washing step in a posttreatment step of plating. Item 1. The plating method according to Item 1.
る脱脂工程を使用しないものである請求項１、２または
３記載のめっき方法。4. The plating method according to claim 1, 2 or 3, wherein the pretreatment step of the plating does not use a degreasing step with an organic solvent.
の物品である請求項１、２、３または４記載のめっき方
法。5. The plating method according to claim 1, wherein the object to be plated is a plurality of articles filled in a barrel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4361185A JP2707530B2 (en) | 1992-12-28 | 1992-12-28 | Plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4361185A JP2707530B2 (en) | 1992-12-28 | 1992-12-28 | Plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06220697A true JPH06220697A (en) | 1994-08-09 |
| JP2707530B2 JP2707530B2 (en) | 1998-01-28 |
Family
ID=18472543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4361185A Expired - Lifetime JP2707530B2 (en) | 1992-12-28 | 1992-12-28 | Plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2707530B2 (en) |
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| JPH07126896A (en) * | 1993-11-02 | 1995-05-16 | Nippon Techno Kk | Surface treating method and surface treating device used therefor |
| KR100296372B1 (en) * | 1995-12-12 | 2001-09-13 | 후지이 히로시 | Pretreatment method for coating on metal molded article |
| US6322689B1 (en) | 1999-04-02 | 2001-11-27 | Japan Techno Co., Ltd. | Anodizing method and apparatus for performing the same |
| US7338586B2 (en) | 2001-06-25 | 2008-03-04 | Japan Techno Co., Ltd. | Vibratingly stirring apparatus, and device and method for processing using the stirring apparatus |
| US7459071B2 (en) | 2001-05-02 | 2008-12-02 | Japan Techno Co., Ltd. | Hydrogen-oxygen gas generator and method of generating hydrogen-oxygen gas using the generator |
| US7964104B2 (en) | 2003-05-02 | 2011-06-21 | Japan Techno Co., Ltd. | Active antiseptic water or active water-based fluid, and production method and apparatus for the same |
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| WO2010023997A1 (en) | 2008-09-01 | 2010-03-04 | 日本テクノ株式会社 | Liquid material comprising hydrogen and oxygen, regasified gas comprising hydrogen and oxygen produced from the liquid material, process and apparatus for producing the liquid material and regasified gas, and fuel that does not evolve carbon dioxide and comprises the liquid material and regasified gas |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5767192A (en) * | 1980-10-11 | 1982-04-23 | C Uyemura & Co Ltd | High-speed plating method |
| JPS59185873A (en) * | 1983-04-05 | 1984-10-22 | Nec Corp | Ignition system |
| JPH03275130A (en) * | 1990-03-26 | 1991-12-05 | Tokyo Kagaku Sochi Kk | Method and apparatus for agitation of liquid in liquid vessel |
| JPH03294497A (en) * | 1990-04-12 | 1991-12-25 | C Uyemura & Co Ltd | Surface treatment in small hole |
-
1992
- 1992-12-28 JP JP4361185A patent/JP2707530B2/en not_active Expired - Lifetime
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5767192A (en) * | 1980-10-11 | 1982-04-23 | C Uyemura & Co Ltd | High-speed plating method |
| JPS59185873A (en) * | 1983-04-05 | 1984-10-22 | Nec Corp | Ignition system |
| JPH03275130A (en) * | 1990-03-26 | 1991-12-05 | Tokyo Kagaku Sochi Kk | Method and apparatus for agitation of liquid in liquid vessel |
| JPH03294497A (en) * | 1990-04-12 | 1991-12-25 | C Uyemura & Co Ltd | Surface treatment in small hole |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07126896A (en) * | 1993-11-02 | 1995-05-16 | Nippon Techno Kk | Surface treating method and surface treating device used therefor |
| KR100296372B1 (en) * | 1995-12-12 | 2001-09-13 | 후지이 히로시 | Pretreatment method for coating on metal molded article |
| US6322689B1 (en) | 1999-04-02 | 2001-11-27 | Japan Techno Co., Ltd. | Anodizing method and apparatus for performing the same |
| US7459071B2 (en) | 2001-05-02 | 2008-12-02 | Japan Techno Co., Ltd. | Hydrogen-oxygen gas generator and method of generating hydrogen-oxygen gas using the generator |
| US7338586B2 (en) | 2001-06-25 | 2008-03-04 | Japan Techno Co., Ltd. | Vibratingly stirring apparatus, and device and method for processing using the stirring apparatus |
| US7678246B2 (en) | 2001-06-25 | 2010-03-16 | Japan Techno Co., Ltd. | Vibratingly stirring apparatus, and device and method for processing using the stirring apparatus |
| US7964104B2 (en) | 2003-05-02 | 2011-06-21 | Japan Techno Co., Ltd. | Active antiseptic water or active water-based fluid, and production method and apparatus for the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2707530B2 (en) | 1998-01-28 |
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