JPS648716B2 - - Google Patents
Info
- Publication number
- JPS648716B2 JPS648716B2 JP17812581A JP17812581A JPS648716B2 JP S648716 B2 JPS648716 B2 JP S648716B2 JP 17812581 A JP17812581 A JP 17812581A JP 17812581 A JP17812581 A JP 17812581A JP S648716 B2 JPS648716 B2 JP S648716B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- nickel
- satin
- electrodeposit
- plating solution
- 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.)
- Expired
Links
- 238000007747 plating Methods 0.000 claims description 60
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 54
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 239000000654 additive Substances 0.000 claims description 18
- 230000000996 additive effect Effects 0.000 claims description 17
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 14
- 239000011118 polyvinyl acetate Substances 0.000 claims description 14
- 229920002432 poly(vinyl methyl ether) polymer Polymers 0.000 claims description 9
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 5
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000002659 electrodeposit Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- 239000007788 liquid Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 12
- 239000000203 mixture Substances 0.000 description 12
- 239000002245 particle Substances 0.000 description 9
- 238000006116 polymerization reaction Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 5
- 239000004327 boric acid Substances 0.000 description 5
- 229910001369 Brass Inorganic materials 0.000 description 4
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 4
- 239000010951 brass Substances 0.000 description 4
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000012190 activator Substances 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 2
- OVQABVAKPIYHIG-UHFFFAOYSA-N n-(benzenesulfonyl)benzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NS(=O)(=O)C1=CC=CC=C1 OVQABVAKPIYHIG-UHFFFAOYSA-N 0.000 description 2
- 150000001451 organic peroxides Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical class CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 description 1
- -1 nonionic Chemical group 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 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
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- HRQDCDQDOPSGBR-UHFFFAOYSA-M sodium;octane-1-sulfonate Chemical compound [Na+].CCCCCCCCS([O-])(=O)=O HRQDCDQDOPSGBR-UHFFFAOYSA-M 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 239000000080 wetting agent Substances 0.000 description 1
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Description
【発明の詳細な説明】
本発明は酸性の電気ニツケルめつき液や電気ニ
ツケル合金めつき液に添加されて良好な梨地状電
着物を与える梨地状めつき用添加剤に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an additive for satin-like plating that is added to an acidic electronickel plating solution or an electric nickel alloy plating solution to give a good satin-like electrodeposit.
従来、梨地状ニツケル電着物を得る方法として
は、電気ニツケルめつき液に不溶性の無機非電導
性粒子を懸濁させ、ニツケルの電析に際してこの
粒子を共析させることにより、ニツケル電着物に
粗面を形成し、梨地状効果を与える方法が知られ
ている（特公昭43−405号）。しかし、この方法
は、めつき液の保寸管理が困難であり、めつき液
が汚れた時に活性炭処理を行なう場合、不溶性粒
子を別してから行なわなければならないなどの
面倒もある上、得られた電着物は指紋がつき易い
という問題もあり、更に被めつき物の低電流密度
部分が梨地状になり難い等の欠点がある。また、
この方法はバレルめつきが行ない難い。 Conventionally, the method for obtaining a satin-like nickel electrodeposit is to suspend insoluble inorganic non-conductive particles in an electrolytic nickel plating solution, and eutectoidize the particles during nickel electrodeposition, thereby adding coarseness to the nickel electrodeposit. A method of forming a surface to give a satin-like effect is known (Special Publication No. 43-405). However, with this method, it is difficult to maintain the size of the plating solution, and when treating the plating solution with activated carbon when it becomes dirty, insoluble particles must be separated before treatment. Electrodeposited materials also have the problem of being susceptible to fingerprints, and furthermore have the disadvantage that low current density areas of the deposited material are difficult to form a matte finish. Also,
This method makes barrel plating difficult.
また従来、温度40〜75℃において微細分散状の
エマルジヨンを生成するエチレンオキサイド、プ
ロピレンオキサイド化合物をめつき液に添加し、
めつき時に液温を上げて液を懸濁させた状態でめ
つきを行なうことにより、梨地状ニツケル電着物
を得る方法も知られている（特公昭46−644号）
が、この方法はめつき作業が難かしく、正常な電
着物を得るのに細心の注意が必要であり、まため
つき液の周期的な活性炭処理が要求され、管理が
面到である。更に、この方法は、めつき液中のエ
マルジヨン粒子の凝集が起り易く、凝集した粒子
によるピツトが生じ易い上、アニオン活性剤等の
有機不純物の混入に対して敏感であり、これらが
混入した場合には良好な梨地状電着物が得られ
ず、はなはだしい場合はサテン状とならず、光沢
電着になる。また更に、この方法は、めつきの低
電流密度部分が黒くなり、低電流密度部分が梨地
状になり難いという欠点もあり、またこの故にこ
の方法はバレルめつきに不向きである。 In addition, conventionally, ethylene oxide and propylene oxide compounds, which form finely dispersed emulsions at temperatures of 40 to 75°C, are added to the plating solution.
It is also known to obtain a satin-like nickel electrodeposit by raising the liquid temperature during plating and plating with the liquid suspended (Special Publication No. 46-644).
However, this method is difficult to perform plating work, requires great care to obtain normal electrodeposit, and requires periodic treatment of the plating solution with activated carbon, requiring careful management. Furthermore, this method is prone to agglomeration of emulsion particles in the plating solution, which tends to cause pits due to the agglomerated particles, and is sensitive to the contamination of organic impurities such as anionic activators; In some cases, a good satin-like electrodeposit cannot be obtained, and in cases where the electrodeposition is extremely satin-like, the result is a glossy electrodeposit. Furthermore, this method has the disadvantage that the low current density part of the plating becomes black and the low current density part is difficult to become satin-like, and for this reason, this method is not suitable for barrel plating.
本発明者らは、上記事情に鑑み、良好な梨地状
電着物を与える添加剤について鋭意研究を行なつ
た結果、酸性の電気ニツケル又はニツケル合金め
つき液にポリ酢酸ビニルの部分けん化物又はポリ
ビニルメチルエーテルを添加することにより、高
電流密度部分から低電流密度部分に至るまで良好
な梨地状電着物が得られ、バレルめつきが可能で
ある上、上記化合物を添加しためつき液は懸濁粒
子の凝集が起こりにくく、また有機不純物に対し
ても比較的鈍感であり、めつき作業、めつき液管
理も容易であることを知見し、本発明をなすに至
つたものである。 In view of the above circumstances, the present inventors have conducted extensive research on additives that provide a good satin-like electrodeposit, and have found that partially saponified polyvinyl acetate or polyvinyl acetate is added to an acidic electric nickel or nickel alloy plating solution. By adding methyl ether, a good satin-like electrodeposit can be obtained from the high current density area to the low current density area, and barrel plating is possible, and the tamping solution containing the above compound can be used as a suspension. The inventors have discovered that particle agglomeration is less likely to occur, that they are relatively insensitive to organic impurities, and that plating work and plating solution management are easy, and the present invention has been developed.
以下、本発明につき更に詳しく説明する。 The present invention will be explained in more detail below.
本発明の梨地状めつき用の添加剤は、ポリ酢酸
ビニルの部分けん化物又はポリビニルメチルエー
テルを主成分とするものである。 The additive for satin-like plating of the present invention is mainly composed of partially saponified polyvinyl acetate or polyvinyl methyl ether.
ここで、ポリ酢酸ビニルの部分けん化物として
は、けん化度65〜90％、重合度１〜2200のものが
好適に使用し得るが、特に重合度１〜550のもの
がより好ましく、重合度１〜550のものを用いる
ことによつてより良好な梨地状電着物が得られ
る。なお、低重合度の部分けん化ポリ酢酸ビニル
を得るには、酢酸ビニルの重合度を低く押えるよ
うな合成法によるか、高重合度の部分けん化ポリ
酢酸ビニルを過マンガン酸カリウム等で酸化分解
する方法が採用し得る。具体的には、ポリ酢酸ビ
ニルの部分けん化物として、日本合成化学工業
（株）社製ゴーセノールKH−20、ゴーセノール
KH−17、これらの過マンガン酸カリウム等によ
る酸化分解物が使用し得る。また、ポリビニルメ
チルエーテルとしては、重合度10〜100、分子量
600〜6000のものが好適に使用し得、例えば比較
的高分子量のものとしてBASF社製のLutonal
M40、東京化成社製のポリビニルメチルエーテル
（30％水溶液の粘度が25℃で3400cpのもの）等が
用いられ、またビニルメチルエーテルより有機過
酸化物を触媒として合成した比較的低分子量のも
のも好ましく用いられ得る。 Here, as the partially saponified polyvinyl acetate, those having a degree of saponification of 65 to 90% and a degree of polymerization of 1 to 2,200 can be suitably used, but those having a degree of polymerization of 1 to 550 are particularly preferable, and those having a degree of polymerization of 1 to 2,200 are preferably used. A better satin-like electrodeposit can be obtained by using one having a particle size of 550 to 550. In addition, in order to obtain partially saponified polyvinyl acetate with a low degree of polymerization, it is necessary to use a synthesis method that keeps the degree of polymerization of vinyl acetate low, or to oxidize and decompose partially saponified polyvinyl acetate with a high degree of polymerization using potassium permanganate, etc. method can be adopted. Specifically, as a partially saponified product of polyvinyl acetate, Gohsenol KH-20 manufactured by Nippon Gohsen Kagaku Kogyo Co., Ltd., Gohsenol
KH-17, oxidized decomposition products of these with potassium permanganate, etc. can be used. In addition, polyvinyl methyl ether has a polymerization degree of 10 to 100 and a molecular weight of
600 to 6000 can be suitably used, for example, Lutonal manufactured by BASF is a relatively high molecular weight one.
M40, polyvinyl methyl ether manufactured by Tokyo Kasei Co., Ltd. (viscosity of 30% aqueous solution is 3400 cp at 25°C), etc. are used, and relatively low molecular weight products synthesized from vinyl methyl ether using an organic peroxide as a catalyst are also used. It can be preferably used.
なお、本発明添加剤は上述した化合物の１種又
は２種以上を含有し得る。 Note that the additive of the present invention may contain one or more of the above-mentioned compounds.
本発明の添加剤は、特に通常PH2.5〜６の酸性
電気ニツケルめつき液、ニツケル−コバルト、ニ
ツケル−鉄等のニツケル合金めつき液、に添加さ
れて梨地状電着物を与える。この場合、めつき液
としては、ワツト浴、硫酸浴、高塩化浴、スルフ
アミン酸浴等、公知の浴組成のものが用いられ得
る。 The additive of the present invention is particularly added to an acidic electronickel plating solution, which usually has a pH of 2.5 to 6, or a nickel alloy plating solution such as nickel-cobalt or nickel-iron to give a satin-like electrodeposit. In this case, the plating solution may be one having a known bath composition, such as a Watt bath, a sulfuric acid bath, a high chloride bath, or a sulfamic acid bath.
例えば、特に制限されないが、ワツトタイプの
ニツケルめつき液として下記組成のものが使用さ
れ得る。 For example, although not particularly limited, the following composition may be used as a Watt type nickel plating solution.
組 成
Ni2+ 20〜160ｇ／
CO2+ ０〜100 〃
Fe2+ ０〜100 〃
NiCl2・6H2O ０〜200 〃
H3BO3 20〜 60 〃
PH 2.5〜 ６ 〃
めつき条件
陰極電流密度（Dk）0.01〜20A／ｄm2
液 温 20〜75℃
撹 拌 カソードロツカー又は静止、
空気撹拌も可能
但し、添加剤としてポリ酢酸ビニルの部分けん
化物を用いる場合は、硼酸が存在しているとゲル
化し易いため、硼酸を使用しないか、硼酸の代り
に酢酸、クエン酸やこれらの塩等の緩衝剤を使用
することが望ましい。 Composition Ni 2+ 20~160g/ CO 2+ 0~100 〃 Fe 2+ 0~100 〃 NiCl 2・6H 2 O 0~200 〃 H 3 BO 3 20~ 60 〃 PH 2.5~ 6 〃 Plating conditions Cathode Current density (Dk) 0.01 to 20 A/dm Two liquids Temperature 20 to 75°C Stirring Cathode rocker or stationary, air stirring is also possible. However, when partially saponified polyvinyl acetate is used as an additive, boric acid may be present. Since it is easy to gel when exposed to water, it is preferable not to use boric acid or to use a buffer such as acetic acid, citric acid, or a salt thereof in place of boric acid.
本発明添加剤を用いる場合、その添加量は0.01
〜10ｇ／、特に0.02〜１ｇ／とすることが好
ましい。 When using the additive of the present invention, the amount added is 0.01
The amount is preferably 10 g/, particularly 0.02 to 1 g/.
また、上述した(1)式の主鎖を有する化合物を主
成分とする本発明添加剤はそれ単独で使用するこ
ともできるが、溶性サツカリンやジベンゼンスル
ホンイミド等のスルホンイミド類、パラトルエン
スルホンアミド等のスルホンアミド類、ナフタリ
ンモノ又はジ又はトリスルホン酸塩、これらの誘
導体等のニツケルめつき、ニツケル合金めつき用
の光沢剤、特に一次光沢剤の１種又は２種以上と
併用することが好ましく、これら光沢剤の添加に
よつてより外観の良好な梨地状電着物を得ること
ができる。なお、これらの光沢剤の添加量は0.1
〜10ｇ／とすることが好ましい。 In addition, the additive of the present invention whose main component is a compound having the main chain of formula (1) described above can be used alone, but it is also possible to use sulfonimides such as soluble saccharin and dibenzenesulfonimide, paratoluenesulfone, etc. Brighteners for nickel plating and nickel alloy plating such as sulfonamides such as amides, naphthalene mono- or di- or trisulfonates, derivatives thereof, etc., especially for use in combination with one or more primary brighteners. are preferable, and by adding these brighteners, it is possible to obtain a satin-like electrodeposit with a better appearance. The amount of these brighteners added is 0.1
It is preferable to set it to 10g/.
また、本発明添加剤を添加しためつき液には、
必要によりオクチルスルホン酸ナトリウム、ラウ
リル硫酸ナトリウム等の湿潤剤或いはピツト防止
剤を適量添加することができる。 In addition, the tamping liquid to which the additive of the present invention has been added includes:
If necessary, a suitable amount of a wetting agent or anti-pitting agent such as sodium octylsulfonate or sodium lauryl sulfate may be added.
本発明の添加剤を用いためつき液より梨地状電
着物を得る場合、そのめつき条件は通常のめつき
条件を採用し得るが、めつき温度はめつき液に添
加された本発明添加剤の曇点以上で、めつき液を
懸濁もしくは乳化状態としてめつきを行なう必要
がある。また、撹拌は必ずしも必要としないが、
カソードロツカーを採用することが好ましい。な
お、陰極電流密度は制限されないが、通常0.01〜
20A／ｄm2の範囲が採用でき、本発明添加剤を用
いることによりこのように低電流密度部分にも良
好な梨地状電着物を与えるので、本発明添加剤は
バレルめつき用としても好適に使用し得る。なお
また、本発明添加剤を用いためつき液は、特公昭
46−644号公報に記載されているようなヒートサ
イクルを行なうことができる。 When obtaining a satin-like electrodeposit from a plating solution using the additive of the present invention, the plating conditions may be those of ordinary plating conditions, but the plating temperature may vary depending on the plating temperature of the plating solution. It is necessary to perform plating with the plating solution in a suspended or emulsified state above the cloud point. Also, although stirring is not necessarily required,
Preferably, a cathode rocker is employed. Note that the cathode current density is not limited, but is usually 0.01~
A range of 20 A/dm 2 can be adopted, and the use of the additive of the present invention provides a good satin-like electrodeposit even in such a low current density area, so the additive of the present invention is also suitable for barrel plating. Can be used. Furthermore, the accumulating liquid using the additive of the present invention is
A heat cycle as described in Japanese Patent No. 46-644 can be performed.
本発明添加剤を用いた梨地状めつきは、従来の
ものと同様にスチール、真鍮、導電化処理を施し
たプラスチツク等の所望の素地に直接、或いは光
沢銅めつきや光沢ニツケルめつき等を施した後に
行なうことができ、素地の種類や下地めつきの種
類は特に制限されない。 Satin-like plating using the additive of the present invention can be applied directly to the desired substrate such as steel, brass, or conductive-treated plastic, as with conventional methods, or by applying bright copper plating, bright nickel plating, etc. This can be done after the coating has been applied, and there are no particular restrictions on the type of base material or the type of base plating.
而して、本発明の添加剤を用いた梨地状めつき
方法によれば、低電流密度部分は黒くならず、良
好な梨地状電着物を与えるので、複雑な形状の品
物に対しても全体に均一な梨地状外観を有するめ
つき物を得ることができ、また上述したようにバ
レル法によつても良好な梨地状外観を有するめつ
き物を得ることができる。また、本発明添加剤を
含有するめつき液は、懸濁もしくは乳化状態にあ
る場合において、粒子の凝集が起りにくく、従つ
て凝集粒子に基づくピツトが生じ難く、この点か
らも外観、耐食性の良いめつき物が得られ、また
めつき液の安定性も高いものであると共に、有機
不純物、例えばアニオン、非イオン、カチオン活
性剤の混入の影響を受け難く、活性炭処理をひん
ぱんに行なう必要もない。更に、金属塩濃度、液
温の影響も受けにくく、例えばNi濃度として20
〜160ｇ／の範囲で、また液温として20〜75℃
の範囲で作業し得るので、めつき作業管理、めつ
き液管理、保守も容易であり、またこのように金
属塩濃度や液温の影響を受けにくいので、低濃度
浴、低温浴に対しても本発明添加剤を好適に使用
し得る。 According to the satin-like plating method using the additive of the present invention, the low current density portions do not turn black and a good satin-like electrodeposit is obtained, so that even products with complex shapes can be coated over the entire surface. A plated product having a uniform satin-like appearance can be obtained, and a plated product having a good satin-like appearance can also be obtained by the barrel method as described above. Furthermore, when the plating solution containing the additive of the present invention is in a suspended or emulsified state, particle aggregation is less likely to occur, and therefore pits are less likely to occur due to agglomerated particles. It is possible to obtain a matted product, and the stability of the matting solution is high, and it is not easily affected by the contamination of organic impurities such as anionic, nonionic, and cationic activators, and there is no need for frequent activated carbon treatment. . Furthermore, it is less affected by metal salt concentration and liquid temperature, for example, when the Ni concentration is 20
~160g/range and liquid temperature of 20~75℃
Since the work can be performed within the range of The additive of the present invention can also be suitably used.
以下、実施例を示し、本発明を具体的に説明す
るが、本発明は下記の実施例に限定されるもので
はない。 EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples.
実施例 １
下記組成の電気ニツケルめつき液を用い、下記
条件でめつきを行なつた。Example 1 Plating was carried out under the following conditions using an electric nickel plating solution having the following composition.
組成 硫酸ニツケル 300ｇ／
塩化ニツケル 50 〃
クエン酸ナトリウム 30 〃
溶性サツカリン ２ 〃
部分ケン化ポリ酢酸ビニル 0.03〃
PH 4.2〃
条件 カソード 真鍮板
アノード 電気ニツケル板
液 温 55℃
陰極電流密度 4A／ｄm2
撹 拌 カソードロツカー
めつき時間 10分間
部分ケン化ポリ酢酸ビニルとしては、日本合成
化学工業(株)製のゴーセノールKH20を使用した。 Composition Nickel sulfate 300g / Nickel chloride 50 Sodium citrate 30 Soluble saccharin 2 Partially saponified polyvinyl acetate 0.03 PH 4.2 Conditions Cathode Brass plate Anode Electric nickel plate Liquid temperature 55℃ Cathode current density 4A/dm 2 Stirring Cathode locker Plating time: 10 minutes As the partially saponified polyvinyl acetate, Gohsenol KH20 manufactured by Nippon Gosei Kagaku Kogyo Co., Ltd. was used.
得られたニツケル電着物は、平均孔径6μｍで、
平均深さ0.1μｍの凹部を有する完全なつや消しの
梨地状電着物であつた。 The obtained nickel electrodeposit had an average pore diameter of 6 μm,
It was a completely matte satin-like electrodeposit having concavities with an average depth of 0.1 μm.
実施例 ２
実施例１の組成において、部分ケン化ポリ酢酸
ビニルとして、重合度約50でケン化度約76％のポ
リ酢酸ビニルの部分ケン化物0.05ｇ／を用い、
実施例１と同じ条件でめつきを行なつた。Example 2 In the composition of Example 1, as the partially saponified polyvinyl acetate, 0.05 g/partially saponified polyvinyl acetate with a degree of polymerization of about 50 and a degree of saponification of about 76% was used,
Plating was carried out under the same conditions as in Example 1.
得られたニツケル電着物は、平均孔径8μｍで、
平均深さ0.2μｍの凹部を有する完全なつや消しの
梨地状電着物であつた。 The resulting nickel electrodeposit had an average pore diameter of 8 μm,
It was a completely matte satin-like electrodeposit having concavities with an average depth of 0.2 μm.
実施例 ３
実施例１の組成において、部分ケン化ポリ酢酸
ビニルとして、ゴーセノールKH20を過マンガン
酸カリウムにより酸化分解し、重合度約20とした
もの0.05ｇ／を用い、実施例１と同じ条件でめ
つきを行なつた。Example 3 In the composition of Example 1, 0.05 g/g of GOHSENOL KH20 was oxidatively decomposed with potassium permanganate and the degree of polymerization was about 20 as partially saponified polyvinyl acetate, and the same conditions as in Example 1 were used. I performed a ceremonial ceremony.
得られたニツケル電着物は、平均孔径10μｍ
で、平均深さ0.3μｍの凹部を有する完全なつや消
しの梨地状電着物であつた。 The resulting nickel electrodeposit had an average pore diameter of 10 μm.
The electrodeposit was completely matte and satin-like, having concavities with an average depth of 0.3 μm.
実施例 ４
下記組成の電気ニツケルめつき液を用い、下記
条件でめつきを行なつた。Example 4 Plating was carried out under the following conditions using an electric nickel plating solution having the following composition.
組成 硫酸ニツケル 280ｇ／
塩化ニツケル 45 〃
硼 酸 40 〃
溶性サツカリン ２ 〃
ポリビニルメチルエーテル 0.1 〃
PH 4.2 〃
条件 カソード 真鍮板
アノード 電気ニツケル板
液 温 55℃
陰極電流密度 4A／ｄm2
撹 拌 カソードロツカー
めつき時間 10分間
ポリビニルメチルエーテルとしては、BASF社
製Lutonal M40を使用した。 Composition Nickel sulfate 280g / Nickel chloride 45 Boric acid 40 Soluble saccharin 2 Polyvinyl methyl ether 0.1 PH 4.2 Conditions Cathode Brass plate anode Electric nickel plate liquid Temperature 55℃ Cathode current density 4A/dm 2 Stirring Cathode rocker Burning time: 10 minutes As the polyvinyl methyl ether, Lutonal M40 manufactured by BASF was used.
得られたニツケル電着物は、平均孔径8μｍで、
平均深さ0.15μｍの凹部を有する白色のきめ細か
なつや消しの梨地状電着物であつた。 The resulting nickel electrodeposit had an average pore diameter of 8 μm,
It was a white, fine-grained matte satin-like electrodeposit having concavities with an average depth of 0.15 μm.
実施例 ５
実施例４記載の組成において、Lutomal M40
を0.5ｇ／添加し、下記方法によりバレルニツ
ケルめつきを行なつた。Example 5 In the composition described in Example 4, Lutomal M40
0.5g/barrel plating was performed using the following method.
容量10のバレルに１個当り12.6cm2の表面積を
有する鋼球100個を入れ、この鋼球をカソード、
電気ニツケル板をアノードとして液温50℃におい
て60Aの直流を通じ、１分間当り５回転のバレル
回転速度で60分間バレルめつきを行なつた。 Put 100 steel balls each with a surface area of 12.6 cm 2 into a barrel with a capacity of 10, and use these steel balls as cathodes,
Barrel plating was carried out for 60 minutes at a barrel rotation speed of 5 revolutions per minute at a liquid temperature of 50° C. and a direct current of 60 A using an electric nickel plate as an anode.
得られたニツケル電着物は、平均孔径8μｍで、
平均深さ0.15μｍの凹部を有する乳白色の完全な
つや消しの梨地状電着物であつた。 The resulting nickel electrodeposit had an average pore diameter of 8 μm,
It was a milky-white, completely matte satin-like electrodeposit having concavities with an average depth of 0.15 μm.
実施例 ６
下記組成の電気ニツケルめつき液を用い、下記
条件でめつきを行なつた。Example 6 Plating was carried out under the following conditions using an electric nickel plating solution having the following composition.
組成 硫酸ニツケル 280ｇ／
塩化ニツケル 45 〃
硼 酸 40 〃
溶性サツカリン ２ 〃
ジベンゼンスルホンイミド １ 〃
ポリビニルメチルエーテル 0.05〃
PH 4.2 〃
条件 カソード 鏡面研摩真鍮板
アノード 電気ニツケル板
液 温 55℃
陰極電流密度 4A／ｄm2
撹 拌 カソードロツカー
めつき時間 ５分間
なお、ポリビニルメチルエーテルとしては有機
過酸化物を触媒として合成した比較的低分子量
（平均分子量約1000）を有するものを用いた。 Composition Nickel sulfate 280g / Nickel chloride 45 Boric acid 40 Soluble saccharin 2 Dibenzenesulfonimide 1 Polyvinyl methyl ether 0.05 PH 4.2 Conditions Cathode Mirror polished brass plate anode Electric nickel plate liquid Temperature 55℃ Cathode current Density 4A/ dm 2 stirring Cathode rocker plating time 5 minutes As the polyvinyl methyl ether, one having a relatively low molecular weight (average molecular weight about 1000) synthesized using an organic peroxide as a catalyst was used.
得られたニツケル電着物は、平均孔径10μｍ
で、平均深さ0.2μｍの凹部を有する乳白色のつや
消しの梨地状電着物であつた。 The resulting nickel electrodeposit had an average pore diameter of 10 μm.
It was a milky white, matte, satin-like electrodeposit having concavities with an average depth of 0.2 μm.
実施例 ７
実施例４の電気ニツケルめつき液の一部を取り
出し、これを10℃に冷却し、再び55℃に加温して
元のめつき板を液に戻すというヒートサイクルを
行ない、連続的に１ケ月間ニツケルめつきを行な
つた。Example 7 A heat cycle was performed in which a part of the electric nickel plating solution from Example 4 was taken out, cooled to 10°C, heated again to 55°C, and the original plated plate returned to the liquid. I did nickel plating for a month.
なお、ヒートサイクルにおけるめつき液の循環
速度は１時間当り原めつき液量の1/4とした。ま
た、ポリビニルメチルエーテルの３％水溶液を
1KAH当り約300ml補給した。 The circulation rate of the plating solution during the heat cycle was set to 1/4 of the amount of the original plating solution per hour. In addition, a 3% aqueous solution of polyvinyl methyl ether
Approximately 300ml was replenished per 1KAH.
上記実験の結果、１ケ月間に亘つて一定なつや
消しの梨地状ニツケル電着物が得られた。 As a result of the above experiment, a constant matte satin-like nickel electrodeposit was obtained over a period of one month.
Claims (1)
ルメチルエーテルを主成分としてなることを特徴
とする酸性の電気ニツケルめつき又は電気ニツケ
ル合金めつき用の梨地状めつき用添加剤。1. An additive for satin-like plating for acidic electric nickel plating or electric nickel alloy plating, which is characterized by containing partially saponified polyvinyl acetate or polyvinyl methyl ether as a main component.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17812581A JPS5881988A (en) | 1981-11-06 | 1981-11-06 | Additive for satin finished plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17812581A JPS5881988A (en) | 1981-11-06 | 1981-11-06 | Additive for satin finished plating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5881988A JPS5881988A (en) | 1983-05-17 |
| JPS648716B2 true JPS648716B2 (en) | 1989-02-15 |
Family
ID=16043083
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17812581A Granted JPS5881988A (en) | 1981-11-06 | 1981-11-06 | Additive for satin finished plating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS5881988A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7105082B2 (en) * | 2003-02-27 | 2006-09-12 | Novellus Systems, Inc. | Composition and method for electrodeposition of metal on a work piece |
| US8262894B2 (en) | 2009-04-30 | 2012-09-11 | Moses Lake Industries, Inc. | High speed copper plating bath |
| DK3642396T3 (en) * | 2017-06-23 | 2021-10-11 | Atotech Deutschland Gmbh | NICKEL ELECTROGALVANIZATION BATH FOR SETTING A DECORATIVE NICKEL COATING ON A SURFACE |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5856037B2 (en) * | 1975-07-17 | 1983-12-13 | ソニー株式会社 | Acidic Ni electroplating bath |
-
1981
- 1981-11-06 JP JP17812581A patent/JPS5881988A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5881988A (en) | 1983-05-17 |
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