JPH0151559B2 - - Google Patents
Info
- Publication number
- JPH0151559B2 JPH0151559B2 JP25837285A JP25837285A JPH0151559B2 JP H0151559 B2 JPH0151559 B2 JP H0151559B2 JP 25837285 A JP25837285 A JP 25837285A JP 25837285 A JP25837285 A JP 25837285A JP H0151559 B2 JPH0151559 B2 JP H0151559B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- palladium
- plating layer
- titanium
- metal plating
- 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 85
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 30
- 239000010970 precious metal Substances 0.000 claims description 27
- 239000000463 material Substances 0.000 claims description 20
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 19
- 239000010936 titanium Substances 0.000 claims description 19
- 229910052719 titanium Inorganic materials 0.000 claims description 19
- 229910052763 palladium Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 11
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 23
- 229910000510 noble metal Inorganic materials 0.000 description 17
- 239000000243 solution Substances 0.000 description 17
- 229910052759 nickel Inorganic materials 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000005856 abnormality Effects 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 description 4
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 2
- DFPAKSUCGFBDDF-UHFFFAOYSA-N Nicotinamide Chemical compound NC(=O)C1=CC=CN=C1 DFPAKSUCGFBDDF-UHFFFAOYSA-N 0.000 description 2
- 229910001252 Pd alloy Inorganic materials 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 235000003270 potassium fluoride Nutrition 0.000 description 2
- 239000011698 potassium fluoride Substances 0.000 description 2
- 235000013024 sodium fluoride Nutrition 0.000 description 2
- 239000011775 sodium fluoride Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229910000925 Cd alloy Inorganic materials 0.000 description 1
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- OVKMDTVKFLNYRN-UHFFFAOYSA-N [Cd].[Cu].[Au] Chemical compound [Cd].[Cu].[Au] OVKMDTVKFLNYRN-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- WTEOIRVLGSZEPR-UHFFFAOYSA-N boron trifluoride Chemical compound FB(F)F WTEOIRVLGSZEPR-UHFFFAOYSA-N 0.000 description 1
- WUKWITHWXAAZEY-UHFFFAOYSA-L calcium difluoride Chemical compound [F-].[F-].[Ca+2] WUKWITHWXAAZEY-UHFFFAOYSA-L 0.000 description 1
- 229910001634 calcium fluoride Inorganic materials 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- AQEDFGUKQJUMBV-UHFFFAOYSA-N copper;ethane-1,2-diamine Chemical compound [Cu].NCCN AQEDFGUKQJUMBV-UHFFFAOYSA-N 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- MSNOMDLPLDYDME-UHFFFAOYSA-N gold nickel Chemical compound [Ni].[Au] MSNOMDLPLDYDME-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 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
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229960003966 nicotinamide Drugs 0.000 description 1
- 235000005152 nicotinamide Nutrition 0.000 description 1
- 239000011570 nicotinamide Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 235000007686 potassium Nutrition 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007790 scraping Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- PTLRDCMBXHILCL-UHFFFAOYSA-M sodium arsenite Chemical compound [Na+].[O-][As]=O PTLRDCMBXHILCL-UHFFFAOYSA-M 0.000 description 1
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 210000004243 sweat Anatomy 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Electroplating Methods And Accessories (AREA)
Description
【発明の詳細な説明】
本発明はチタン系素材への貴金属メツキ方法に
関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for plating titanium-based materials with precious metals.
チタン系素材は軽量で耐食性に優れるため従来
より各種の分野で用いられているが、近年、金属
製の眼鏡フレームや腕時計外装部品等の材料とし
ての利用が高まるにつれて、より美麗な外観の製
品とするために、チタン系素材の表面に貴金属メ
ツキを施すための種々の試みが行われている。 Titanium-based materials have traditionally been used in a variety of fields due to their light weight and excellent corrosion resistance, but in recent years, as their use as materials for metal eyeglass frames and wristwatch exterior parts has increased, titanium-based materials have become increasingly popular for products with a more beautiful appearance. To this end, various attempts have been made to plate the surface of titanium-based materials with precious metals.
しかしながらチタン系素材上に直接貴金属メツ
キを施した場合、貴金属メツキ層のチタン系素材
への密着性が悪く、美麗な外観光沢を損なうこと
なく良好な貴金属メツキを施すことはきわめて困
難であつた。このため従来はチタン系素材の表面
に貴金属メツキが可能なニツケル張りを行つた
後、貴金属メツキを施したり、ニツケルメツキを
施した後、貴金属メツキを施す方法（例えば、特
開昭59−162296号等）等が採用されているがニツ
ケルは薬品に侵され易い欠点があるため、耐食性
に優れた製品とするためには貴金属メツキ層の厚
さをかなり厚くする必要があり、この結果製品が
非常に高価なものとなるという問題があつた。ま
たこのような方法により貴金属メツキを施した製
品の場合、使用中に貴金属メツキ層の一部が摩耗
したり傷付いたりして貴金属メツキ層下層のニツ
ケルメツキ層が露出すると、ニツケルメツキ層が
汗等により腐食されて貴金属メツキ層が剥落する
という大きな欠点があつた。 However, when noble metal plating is applied directly onto a titanium-based material, the adhesion of the noble metal plating layer to the titanium-based material is poor, and it is extremely difficult to apply good noble metal plating without impairing the beautiful appearance and gloss. For this reason, conventional methods have been to apply nickel plating, which can be plated with precious metals, to the surface of titanium-based materials, and then apply precious metal plating, or to apply nickel plating, and then to apply precious metal plating (for example, JP-A No. 59-162296, etc.). ) etc., but nickel has the disadvantage of being easily attacked by chemicals, so in order to make a product with excellent corrosion resistance, it is necessary to make the precious metal plating layer considerably thicker, and as a result, the product becomes very There was a problem that it was expensive. In addition, in the case of products plated with precious metals using this method, if part of the precious metal plating layer is worn or scratched during use and the nickel plating layer below the precious metal plating layer is exposed, the nickel plating layer may be damaged by sweat, etc. A major drawback was that the precious metal plating layer would peel off due to corrosion.
本発明は上記の欠点に鑑みなされたもので、チ
タン系素材の上に密着性、耐食性に優れた貴金属
メツキ層を確実かつ安価に施す方法を提供するこ
とを目的とする。 The present invention was made in view of the above-mentioned drawbacks, and an object of the present invention is to provide a method for reliably and inexpensively applying a noble metal plating layer with excellent adhesion and corrosion resistance on a titanium-based material.
即ち本発明はチタン系素材を弗化物を含有する
処理液で処理した後、パラジウムストライクメツ
キを施し、次いでこの上に更に貴金属メツキを施
すことを特徴とするチタン系素材への貴金属メツ
キ方法を要旨とする。 That is, the present invention provides a method for plating a titanium-based material with a precious metal, which is characterized by treating the titanium-based material with a treatment solution containing fluoride, applying palladium strike plating, and then further applying precious metal plating thereon. shall be.
本発明においてチタン系素材としてはチタン及
びチタン合金が用いられ、チタン合金としては例
えばTi−3Al−5Cr、Ti−5Al−2Cr−2Mo、Ti−
7Al−5Cr、Ti−2.5Al−16V、Ti−15Mo−5Zr−
3Al、Ti−4Al−4Mn等が挙げられる。 In the present invention, titanium and titanium alloys are used as titanium-based materials, and examples of titanium alloys include Ti-3Al-5Cr, Ti-5Al-2Cr-2Mo, Ti-
7Al−5Cr, Ti−2.5Al−16V, Ti−15Mo−5Zr−
Examples include 3Al and Ti-4Al-4Mn.
本発明においてはチタン系素材をまず弗化物を
含有する処理液にて処理するが、通常この処理に
先だつてチタン系素材をアルカリ等により脱脂洗
浄する。弗化物を含有する処理液としては弗化物
を0.1〜20wt％含有するPH6.0以下の溶液が好まし
い。上記弗化物としては例えば酸性弗化アンモニ
ウム、ケイ弗酸、ホウ弗酸、弗化カルシウム、弗
化カリウム、弗化ナトリウム、ケイ弗化カリウ
ム、酸性弗化カリウム、酸性弗化ナトリウム、弗
化水素酸等が挙げられる。弗化物を含有する処理
液による処理は、チタン系素材を該処理液に浸漬
することにより行われるが、処理液の温度１〜60
℃、浸漬時間10〜300秒程度の条件で処理するこ
とが好ましい。 In the present invention, the titanium-based material is first treated with a treatment liquid containing fluoride, but usually prior to this treatment, the titanium-based material is degreased and cleaned with an alkali or the like. As the treatment liquid containing fluoride, a solution containing 0.1 to 20 wt% of fluoride and having a pH of 6.0 or less is preferable. Examples of the above fluorides include acidic ammonium fluoride, fluorosilicic acid, boric fluoride, calcium fluoride, potassium fluoride, sodium fluoride, potassium silicofluoride, acidic potassium fluoride, acidic sodium fluoride, and hydrofluoric acid. etc. Treatment with a treatment solution containing fluoride is performed by immersing the titanium-based material in the treatment solution, but the temperature of the treatment solution is 1 to 60°C.
It is preferable to perform the treatment under conditions such as temperature and immersion time of about 10 to 300 seconds.
弗化物含有処理液で処理を行つたチタン系素材
には次いでパラジウムストライクメツキが施され
る。パラジウムストライクメツキ工程に用いられ
るメツキ液としては通常のパラジウムメツキに用
いられると同様のメツキ液が使用される。パラジ
ウムストライクメツキは、溶液温度20〜80℃、電
流密度0.1〜5A／ｄm2、メツキ時間10〜300秒程
度の条件で行い、厚さ0.1〜1μ程度に形成するこ
とが好ましい。 The titanium-based material treated with the fluoride-containing treatment liquid is then plated with palladium strike plating. The plating liquid used in the palladium strike plating process is the same as that used in ordinary palladium plating. Palladium strike plating is preferably carried out at a solution temperature of 20 to 80° C., a current density of 0.1 to 5 A/dm 2 , and a plating time of about 10 to 300 seconds, and is preferably formed to a thickness of about 0.1 to 1 μm.
尚、本発明におけるパラジウムストライクメツ
キは、パラジウム−ニツケル、パラジウム−コバ
ルト等のパラジウム合金メツキであつてもよい。
本発明者等はパラジウム合金メツキでもストライ
クメツキ析出物のパラジウム含有率が30％以上あ
れば、パラジウムストライクメツキと変らない効
果を有することを実験的に確かめた。 The palladium strike plating in the present invention may be a palladium alloy plating such as palladium-nickel or palladium-cobalt.
The present inventors have experimentally confirmed that palladium alloy plating has the same effect as palladium strike plating if the palladium content of the strike plating precipitate is 30% or more.
本発明においてはパラジウムストライクメツキ
を施した後、この上に更に貴金属メツキを施す。
この貴金属メツキ工程に用いられるメツキ液は単
一の貴金属を含有するものでも異なる２種以上の
貴金属を含有するものでもよい。貴金属メツキ液
としては通常の貴金属メツキに用いられると同様
のメツキ液が使用される。上記貴金属メツキは溶
液温度40〜60℃、電流密度0.2〜1.0A／ｄm2で１
〜10分の条件で行うことにより0.2〜5μの貴金属
メツキ層を形成することができる。 In the present invention, after palladium strike plating is applied, noble metal plating is further applied thereon.
The plating solution used in this noble metal plating step may contain a single noble metal or two or more different noble metals. As the noble metal plating solution, a plating solution similar to that used for ordinary noble metal plating is used. The above precious metal plating is performed at a solution temperature of 40 to 60℃ and a current density of 0.2 to 1.0A/ dm2 .
A noble metal plating layer of 0.2 to 5μ can be formed by performing the process for ~10 minutes.
以下に実施例を挙げて本発明を更に詳細に説明
する。 The present invention will be explained in more detail with reference to Examples below.
実施例 １
メツキ合金製眼鏡フレームをアルカリ脱脂した
後、該フレームを酸性弗化アンモニウム20ｇ／
、スルフアミン酸150ｇ／、界面活性剤（フ
ルオロアルキルカルボン酸ナトリウム）0.1ｇ／
を含有するPH0.8の15℃の水溶液中に30秒間浸
漬して処理した後水洗した。次いで金属換算量で
５ｇ／となる塩化パラジウム、塩化アンモニウ
ム150ｇ／を含有する溶液をアンモニア水でPH
10.0に調整した後、これにニコチン酸アミド10
ｇ／を含有させ、これを70℃に加温した溶液中
で、白金電極を陽極として、電流密度1.5A／ｄ
m2で60秒間パラジウムストライクメツキを施した
後、ただちに水洗した。次いで金属換算量５ｇ／
となる亜硫酸金ナトリウム、金属換算量で３
ｇ／となるエチレンジアミンパラジウム、金属
換算量で0.01ｇ／となるエチレンジアミン銅、
EDTA・２ナトリウム塩80ｇ／、添加剤（亜
ヒ酸ナトリウム）0.02ｇ／を含有するPH10.5の
50℃のメツキ液中で白金電極を陽極として電流密
度0.6A／ｄm2で３分間メツキを行なつたところ、
0.9μ厚の金−パラジウムメツキ層を有する外観美
麗な光沢のある眼鏡フレームが得られた。このフ
レームを200℃にて乾燥後、90度折り曲げ試験及
びキヤス試験10サイクルを行つたが、貴金属メツ
キ層が剥離する等の異常は全く確認されず、良好
な貴金属メツキが施されていることが確認され
た。Example 1 After degreasing an eyeglass frame made of a metal alloy with alkali, the frame was treated with 20g/20g of acidic ammonium fluoride.
, sulfamic acid 150g/, surfactant (sodium fluoroalkylcarboxylate) 0.1g/
The sample was treated by immersing it in an aqueous solution of pH 0.8 at 15°C for 30 seconds, followed by washing with water. Next, a solution containing 5 g/metal equivalent of palladium chloride and 150 g/ammonium chloride was PHed with aqueous ammonia.
After adjusting to 10.0, add nicotinamide 10 to this
In a solution heated to 70°C, a current density of 1.5 A/d was applied using a platinum electrode as an anode.
Palladium strike plating was applied for 60 seconds at m 2 and immediately washed with water. Next, metal equivalent amount 5g/
Sodium gold sulfite, metal equivalent amount is 3
Ethylenediamine palladium which is 0.01g/ in terms of metal, ethylenediamine copper which is 0.01g/
PH10.5 containing EDTA disodium salt 80g/, additive (sodium arsenite) 0.02g/
When plating was performed for 3 minutes in a plating solution at 50°C with a platinum electrode as an anode and a current density of 0.6A/ dm2 ,
A glossy eyeglass frame with a beautiful appearance and a gold-palladium plating layer with a thickness of 0.9 μm was obtained. After drying this frame at 200℃, we conducted 10 cycles of a 90-degree bending test and a casing test, but no abnormalities such as peeling of the precious metal plating layer were observed, indicating that the precious metal plating was in good condition. confirmed.
比較例 １
実施例１と同様の眼鏡フレームを、硫酸ニツケ
ル150ｇ／、塩化ニツケル150ｇ／、ホウ酸40
ｇ／含有し、リン酸でPH0.5に調整した55℃の
メツキ液中でニツケル電極を陽極として電流密度
5A／ｄm2にて60秒間ニツケルメツキを行つた。
次いでニツケルメツキ層の上に実施例１と同様の
条件で金−パラジウムメツキを施し、0.9μ厚の金
−パラジウムメツキ層を形成した。この眼鏡フレ
ームは外観美麗な光沢を有し、90度折り曲げ試験
においても異常は認められなかつたが、キヤス試
験５サイクルでは下層のニツケルメツキ層がキヤ
ス試験液により腐食され、表面の貴金属メツキ層
が剥落する異常が発生した。Comparative Example 1 Eyeglass frames similar to those in Example 1 were prepared using 150 g of nickel sulfate, 150 g of nickel chloride, and 40 g of boric acid.
g/containing current density using a nickel electrode as an anode in a plating solution at 55°C adjusted to pH 0.5 with phosphoric acid.
Nickel plating was performed at 5 A/dm 2 for 60 seconds.
Next, gold-palladium plating was applied on the nickel plating layer under the same conditions as in Example 1 to form a gold-palladium plating layer with a thickness of 0.9 μm. This eyeglass frame had a beautiful gloss appearance, and no abnormality was observed in the 90 degree bending test, but in 5 cycles of the cast test, the lower nickel plating layer was corroded by the cast test liquid, and the precious metal plating layer on the surface peeled off. An abnormality has occurred.
比較例 ２
弗化物を含有する処理液による処理を行わなか
つた他は実施例１と同様の方法でメツキ処理し、
金−パラジウムメツキ層を形成したが、金−パラ
ジウムメツキ層の密着性がきわめて悪く、90度折
り曲げ試験により表面の貴金属メツキ層が簡単に
剥落した。Comparative Example 2 Plating treatment was carried out in the same manner as in Example 1, except that the treatment with the treatment liquid containing fluoride was not performed.
Although a gold-palladium plating layer was formed, the adhesion of the gold-palladium plating layer was extremely poor, and the noble metal plating layer on the surface easily peeled off during a 90 degree bending test.
比較例 ３
パラジウムストライクメツキ工程を行わなかつ
た他は実施例１と同様の方法でメツキ処理し、金
−パラジウムメツキ層を形成したが、金−パラジ
ウムメツキ層の密着性がきわめて悪く、90度折り
曲げ試験により表面の貴金属メツキ層が簡単に剥
落した。Comparative Example 3 A gold-palladium plating layer was formed by plating in the same manner as in Example 1, except that the palladium strike plating step was not performed, but the adhesion of the gold-palladium plating layer was extremely poor, and it was bent at 90 degrees. During the test, the precious metal plating layer on the surface easily peeled off.
実施例 ２
実施例１と同様にして弗化物を含有する処理液
で処理した後、パラジウムストライクメツキを施
した眼鏡フレームに白金電極を陽極としてパラジ
ウム−ニツケル合金メツキ（メツキ液温度35℃、
電流密度2A／ｄm2）、金−ニツケル合金メツキ
（メツキ液温度60℃、電流密度1.5A／ｄm2）、金
−銅−カドミウム合金メツキ（メツキ液温度55
℃、電流密度2A／ｄm2）、純金メツキ（メツキ液
温度50℃、電流密度1.0A／ｄm2）、ロジウムメツ
キ（メツキ液温度43℃、電流密度2A／ｄm2）を
各々0.3μ、1.0μ、2.0μ厚に形成したところ、いず
れも90度折り曲げ試験、キヤス試験10サイクルに
よる異常が認められず、貴金属メツキ層が密着性
に優れるとともに、貴金属メツキ層の厚さに関係
なく耐食性に優れていることが認められた。Example 2 After treatment with a treatment solution containing fluoride in the same manner as in Example 1, palladium-nickel alloy plating was performed using a platinum electrode as an anode on a palladium strike-plated eyeglass frame (plating solution temperature: 35°C,
Current density 2A/ dm2 ), gold-nickel alloy plating (plating liquid temperature 60℃, current density 1.5A/ dm2 ), gold-copper-cadmium alloy plating (plating liquid temperature 55
℃, current density 2A/dm 2 ), pure gold plating (plating liquid temperature 50℃, current density 1.0A/dm 2 ), rhodium plating (plating liquid temperature 43℃, current density 2A/dm 2 ) 0.3 μ and 1.0, respectively. When formed to a thickness of μ and 2.0μ, no abnormalities were observed in either the 90 degree bending test or 10 cycles of the scraping test, indicating that the precious metal plating layer has excellent adhesion and excellent corrosion resistance regardless of the thickness of the precious metal plating layer. It was recognized that
以上説明したように、本発明はチタン系素材を
弗化物を含有する処理液で処理した後、パラジウ
ムストライクメツキを施し、次いでこの上に更に
貴金属メツキを施す方法を採用したことにより、
貴金属メツキを施す前にニツケルメツキを施さず
とも、密着性に優れた美麗な光沢の貴金属メツキ
層を確実に形成することができる。しかも本発明
方法は貴金属メツキ層の下層にニツケルメツキ層
を形成しないため、本発明方法により貴金属メツ
キを施した製品は、貴金属メツキ層の厚さに関係
なく優れた耐食性を有し、従来の方法のように貴
金属メツキ層を必要以上に厚く形成する必面がな
い。しかも本発明方法により貴金属メツキを行つ
た製品は、たとえ貴金属メツキ層の一部に傷が付
いたりしても、従来の方法によりメツキされた製
品のように傷の付いた個所から腐食が進んで貴金
属メツキ層が剥落するという虞れがなく、美麗な
外観を長期間に亘つて保持することができる。 As explained above, the present invention employs a method in which a titanium-based material is treated with a treatment solution containing fluoride, then palladium strike plating is applied, and then precious metal plating is applied on top of this.
A noble metal plating layer with excellent adhesion and beautiful luster can be reliably formed without applying nickel plating before applying noble metal plating. Moreover, since the method of the present invention does not form a nickel plating layer below the noble metal plating layer, products plated with precious metals by the method of the present invention have excellent corrosion resistance regardless of the thickness of the precious metal plating layer, and are superior to conventional methods. As such, there is no need to form the noble metal plating layer thicker than necessary. Furthermore, even if a part of the precious metal plating layer is scratched on a product plated with precious metals using the method of the present invention, corrosion will not proceed from the scratched area, unlike products plated using the conventional method. There is no risk that the precious metal plating layer will peel off, and a beautiful appearance can be maintained for a long period of time.
而して本発明によればメツキ系素材の耐食性、
軽量性を損なうことなく密着性に優れた貴金属光
沢を有する外観美麗な製品を安価に提供し得る等
の効果を有する。 According to the present invention, the corrosion resistance of the glazed material,
It has the effect of providing a product with excellent adhesion, noble metal luster, and a beautiful appearance at a low cost without sacrificing lightweight properties.
Claims (1)
理した後、パラジウムストライクメツキを施し、
次いでこの上に更に貴金属メツキを施すことを特
徴とするチタン系素材への貴金属メツキ方法。1 After treating the titanium-based material with a treatment solution containing fluoride, palladium strike plating is applied,
A method for plating a titanium-based material with a precious metal, which is then further coated with a precious metal.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25837285A JPS62120493A (en) | 1985-11-18 | 1985-11-18 | Plating method of noble metal to titanium stock |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP25837285A JPS62120493A (en) | 1985-11-18 | 1985-11-18 | Plating method of noble metal to titanium stock |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS62120493A JPS62120493A (en) | 1987-06-01 |
| JPH0151559B2 true JPH0151559B2 (en) | 1989-11-06 |
Family
ID=17319328
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP25837285A Granted JPS62120493A (en) | 1985-11-18 | 1985-11-18 | Plating method of noble metal to titanium stock |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS62120493A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63310993A (en) * | 1987-06-10 | 1988-12-19 | Bikutoria:Kk | Plating method of noble metal on titanium-base stock |
| CN103981545B (en) * | 2014-05-15 | 2017-01-25 | 张佑锋 | Process for surface treatment of zirconium, titanium and alloy thereof |
-
1985
- 1985-11-18 JP JP25837285A patent/JPS62120493A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS62120493A (en) | 1987-06-01 |
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