JPS647153B2 - - Google Patents
Info
- Publication number
- JPS647153B2 JPS647153B2 JP9479785A JP9479785A JPS647153B2 JP S647153 B2 JPS647153 B2 JP S647153B2 JP 9479785 A JP9479785 A JP 9479785A JP 9479785 A JP9479785 A JP 9479785A JP S647153 B2 JPS647153 B2 JP S647153B2
- Authority
- JP
- Japan
- Prior art keywords
- base material
- film
- electroless plating
- black
- nickel
- 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
- 239000000463 material Substances 0.000 claims description 37
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 34
- 238000007772 electroless plating Methods 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 18
- 229910052759 nickel Inorganic materials 0.000 claims description 17
- 238000007254 oxidation reaction Methods 0.000 claims description 15
- 230000003647 oxidation Effects 0.000 claims description 14
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 10
- 229910052698 phosphorus Inorganic materials 0.000 claims description 10
- 239000011574 phosphorus Substances 0.000 claims description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 239000011593 sulfur Substances 0.000 claims description 9
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 21
- 238000011282 treatment Methods 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 238000005299 abrasion Methods 0.000 description 7
- 229910018104 Ni-P Inorganic materials 0.000 description 4
- 229910018536 Ni—P Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000003638 chemical reducing agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 238000007654 immersion Methods 0.000 description 3
- 229910000159 nickel phosphate Inorganic materials 0.000 description 3
- JOCJYBPHESYFOK-UHFFFAOYSA-K nickel(3+);phosphate Chemical compound [Ni+3].[O-]P([O-])([O-])=O JOCJYBPHESYFOK-UHFFFAOYSA-K 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 229910052749 magnesium Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003973 paint Substances 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 229910001379 sodium hypophosphite Inorganic materials 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 235000011150 stannous chloride Nutrition 0.000 description 2
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000002048 anodisation reaction Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- RYGMFSIKBFXOCR-AHCXROLUSA-N copper-60 Chemical compound [60Cu] RYGMFSIKBFXOCR-AHCXROLUSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000002075 main ingredient Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 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
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012811 non-conductive material Substances 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 1
- 229940081974 saccharin Drugs 0.000 description 1
- 235000019204 saccharin Nutrition 0.000 description 1
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052711 selenium Inorganic materials 0.000 description 1
- 239000011669 selenium Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- HELHAJAZNSDZJO-OLXYHTOASA-L sodium L-tartrate Chemical compound [Na+].[Na+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O HELHAJAZNSDZJO-OLXYHTOASA-L 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 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
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000001433 sodium tartrate Substances 0.000 description 1
- 229960002167 sodium tartrate Drugs 0.000 description 1
- 235000011004 sodium tartrates Nutrition 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- POWFTOSLLWLEBN-UHFFFAOYSA-N tetrasodium;silicate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-][Si]([O-])([O-])[O-] POWFTOSLLWLEBN-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229940001496 tribasic sodium phosphate Drugs 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemically Coating (AREA)
- Chemical Treatment Of Metals (AREA)
- Other Surface Treatments For Metallic Materials (AREA)
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は金属又はプラスチツク等の母材表面に
黒色被膜を形成する黒色被膜形成方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for forming a black film on the surface of a base material such as metal or plastic.
この種の被膜形成方法としては、従来、塗装の
他、電気メツキ法による黒色クロメート、黒色ク
ロム、黒色ニツケル膜の形成等があつた。ところ
が、塗装によるものでは耐摩耗性が悪いため傷が
つき易く、また電気メツキ法による黒色クロメー
ト被膜は耐蝕性が悪く塩水等により白色のさびが
発生し易く、更には黒色クロムや黒色ニツケル被
膜も耐蝕性及び耐摩耗性において不十分であると
いう欠点がある。また、母材を陽極酸化法により
多孔質化した後黒色塗料を浸透させる方法もある
が、これでは母材がアルミニウムやマグネシウム
等に限られる上、耐侯性に劣るという問題があ
る。
In addition to painting, conventional methods for forming this type of film include forming black chromate, black chromium, and black nickel films by electroplating. However, paint-based coatings have poor abrasion resistance and are easily scratched, and black chromate coatings made by electroplating have poor corrosion resistance and are susceptible to white rust when exposed to salt water, etc. Furthermore, black chromium and black nickel coatings It has the disadvantage of being insufficient in corrosion resistance and abrasion resistance. Another method is to make the base material porous by anodic oxidation and then infiltrate it with black paint, but this method limits the base material to aluminum, magnesium, etc., and has the problem of poor weather resistance.
本発明の目的は、母材の種類を問わず、優れた
耐蝕性、耐摩耗性及び耐侯性等の特性を有する黒
色被膜を形成することができる黒色被膜形成方法
を提供するにある。
An object of the present invention is to provide a method for forming a black film that can form a black film having excellent characteristics such as corrosion resistance, abrasion resistance, and weather resistance, regardless of the type of base material.
本発明は、酸化触媒を含有せる無電解メツキ液
により母材に７％以下のリンを含むニツケル膜又
はコバルト膜を形成し、この後、母材表面を酸化
処理するようにしたところに特徴を有するもので
ある。
The present invention is characterized in that a nickel film or cobalt film containing 7% or less phosphorus is formed on a base material using an electroless plating solution containing an oxidation catalyst, and then the surface of the base material is oxidized. It is something that you have.
即ち、還元剤として次亜リン酸塩や亜リン酸等
を用いた無電解メツキ液により母材表面に例えば
ニツケルの無電解メツキを施すと、母材表面に
Ni―Ｐ合金膜が形成されることが知られており、
そのリン濃度は一般に液成分やメツキ条件を適宜
選定することにより従来８〜12％に調整されてい
た。ところが、本発明者はこのNi―Ｐ合金膜に
関する種々の研究の結果、無電解メツキにより形
成したリンを含むニツケル膜にあつては、リン濃
度が７％以上の場合はNi―Ｐ合金が非晶質構造
となつて安定化し、７％以下の場合には過飽和固
溶体を形成するために黒色化を伴う酸化反応が生
じ易くなることを見出した。本発明は、斯かる知
験に基き完成されたものであつて、無電解メツキ
液中に予め酸化触媒を含有せしめておいて母材に
７％以下（最も好ましくは１〜５％）のリン濃度
のニツケル膜又はコバルト膜を形成すると共に、
この後、酸化処理によりニツケル膜又はコバルト
膜表面を酸化することにより、ニツケル膜又はコ
バルト膜の表面を安定化すると同時にこれを黒色
化するようにしたものである。 That is, when electroless plating of nickel, for example, is applied to the surface of a base material using an electroless plating solution using hypophosphite, phosphorous acid, etc. as a reducing agent, the surface of the base material becomes
It is known that a Ni-P alloy film is formed.
The phosphorus concentration has conventionally been adjusted to 8 to 12% by appropriately selecting liquid components and plating conditions. However, as a result of various studies regarding this Ni-P alloy film, the present inventor found that in a phosphorous-containing nickel film formed by electroless plating, the Ni-P alloy is non-functional when the phosphorus concentration is 7% or more. It has been found that it becomes a crystalline structure and becomes stable, and when it is 7% or less, an oxidation reaction accompanied by blackening is likely to occur because a supersaturated solid solution is formed. The present invention has been completed based on such knowledge, and involves pre-containing an oxidation catalyst in the electroless plating solution and adding 7% or less (most preferably 1 to 5%) of phosphorus to the base material. While forming a high concentration nickel film or cobalt film,
Thereafter, the surface of the nickel film or cobalt film is oxidized by oxidation treatment, thereby stabilizing the surface of the nickel film or cobalt film and turning it black at the same time.
以下本発明を母材を鉄系とした場合に適用され
る第１実施例につき第１図及び第２図を参照して
説明する。
A first embodiment of the present invention in which the base material is iron-based will be described below with reference to FIGS. 1 and 2.
まず、母材をオルソ珪酸ナトリウム
（2Na2O・SiO2）の30g／液により例えば50〜
70℃で脱脂処理する。この後、HClの500ml／
液により酸洗し、次いで無電解メツキ液により母
材表面にリン濃度が７％以下（最も好ましくは１
〜５％）のニツケル膜を形成する。無電解メツキ
液は、硫酸ニツケル30ｇ／、酒石酸ナトリウム
30ｇ／及び還元剤としての次亜リン酸ナトリウ
ム15ｇ／を主成分とし、その他PH調整剤、緩
衝剤、光沢剤等の補助成分を有する。ここで、本
実施例では、酸化処理をより迅速たらしめるため
各種の光沢剤の中から特にイオウを含んだサツカ
リン（C7H5NO3S）又はそのナトリウム塩等の誘
導体を選定することにより、無電解メツキ液中に
酸化触媒として作用するイオウを含有させてい
る。この無電解メツキは、例えば液温度90℃の下
で母材を液中に約15分間浸漬することにより行な
う。このようにしてニツケル膜を母材表面に形成
した後に、母材を酸化処理する。酸化処理は、例
えば塩酸100ml／の溶液中に母材を浸漬する化
学的酸化法、或は所定の液中で陽極酸化させる陽
極酸化法により行なう。これにより、第２図に示
すように、母材１の表面にNi―Ｐの過飽和固溶
体として形成されていたニツケル膜２表面が酸化
してニツケルのリン酸塩被膜３が形成され、表面
が安定化すると同時に、黒色化される。この後、
水洗・乾燥すれば全工程が完了する。 First, the base material is treated with 30g/liquid of sodium orthosilicate (2Na 2 O・SiO 2 ), for example,
Degrease at 70℃. After this, 500ml of HCl/
The surface of the base material is pickled with an electroless plating solution, and then the phosphorus concentration is 7% or less (most preferably 1%).
~5%) to form a nickel film. Electroless plating solution is nickel sulfate 30g/sodium tartrate.
The main ingredients are 30g/ and 15g/ of sodium hypophosphite as a reducing agent, and other auxiliary ingredients such as a PH adjuster, buffering agent, and brightening agent. Here, in this example, in order to make the oxidation treatment more rapid, saccharin (C 7 H 5 NO 3 S) containing sulfur or its derivatives such as sodium salts were selected from among various brightening agents. , the electroless plating solution contains sulfur that acts as an oxidation catalyst. This electroless plating is performed, for example, by immersing the base material in the liquid for about 15 minutes at a liquid temperature of 90°C. After the nickel film is thus formed on the surface of the base material, the base material is oxidized. The oxidation treatment is carried out, for example, by a chemical oxidation method in which the base material is immersed in a solution of 100 ml of hydrochloric acid, or by an anodization method in which it is anodized in a predetermined solution. As a result, as shown in Fig. 2, the surface of the nickel film 2, which had been formed as a supersaturated solid solution of Ni-P on the surface of the base material 1, is oxidized and a nickel phosphate film 3 is formed, making the surface stable. At the same time, it becomes black. After this,
The entire process is completed by washing and drying.
上記実施例によれば、母材１の表面に形成され
た黒色のリン酸塩被膜３は極めて安定であるか
ら、耐蝕性、耐侯性及び耐摩耗性等の諸特性に優
れ、特に耐摩耗性はビツカース硬度でHv500以上
の値を得ることができる。しかも、無電解メツキ
の後に酸化処理を行なうという極めて簡単な工程
で黒色被膜を形成できるから、設備費が安価に済
むと共に、大量生産が可能で、総じてコストダウ
ンを図ることができる。このようにして形成した
黒色被膜は、その優れた耐蝕性、耐侯性及び耐摩
耗性等の諸特性を生かして、金属表面の防食を兼
ねた装飾処理（例えば車両のシリンダキーの装飾
処理）或は太陽熱利用機器の熱吸収面の表面処
理、更には遠赤外線ヒーターの輻射面形成処理等
に広く適用することができるものである。 According to the above embodiment, the black phosphate film 3 formed on the surface of the base material 1 is extremely stable, so it has excellent properties such as corrosion resistance, weather resistance, and abrasion resistance, and in particular, the abrasion resistance. can obtain a value of Hv500 or more on the Bitkers hardness. Moreover, since the black film can be formed by an extremely simple process of performing oxidation treatment after electroless plating, equipment costs are low, mass production is possible, and overall costs can be reduced. The black film formed in this way takes advantage of its excellent properties such as corrosion resistance, weather resistance, and abrasion resistance, and can be used for decorative treatments that also serve as corrosion protection for metal surfaces (for example, decorative treatments for vehicle cylinder keys). This method can be widely applied to surface treatment of heat absorption surfaces of solar heat utilization equipment, and further to treatment for forming radiation surfaces of far-infrared heaters.
第３図は母材を銅系とした場合に適用される第
２実施例を示す工程流れ図で、前記第１実施例と
の相違は、酸洗と無電解メツキとの間に活性化処
理を行なうようにした点にある。この活性化処理
は、二塩化鉛（PdCl2）３ｇ／、二塩化すず
（SnCl2）30ｇ／及び塩酸100〜200ml／から
なる液中に母材を浸漬することにより行われる。 FIG. 3 is a process flowchart showing the second embodiment applied when the base material is copper-based. The difference from the first embodiment is that an activation treatment is performed between pickling and electroless plating. The point is that I decided to do it. This activation treatment is carried out by immersing the base material in a solution consisting of 3 g of lead dichloride (PdCl 2 ), 30 g of tin dichloride (SnCl 2 ), and 100 to 200 ml of hydrochloric acid.
第４図は母材をアルミニウム又はマグネシウム
系とした場合に適用される第３実施例の工程流れ
図を示す。前記第１実施例との相違は、無電解メ
ツキを行なう前に、第１実施例と同様の脱脂処理
後、炭酸ナトリウム25ｇ／、第３リン酸ナトリ
ウム25ｇ／の溶液中に60〜80℃で母材を浸漬し
ながらの電解脱脂と、硝酸500ml／溶液による
酸洗と、塩化亜鉛0.5ｇ／、シアン化ナトリウ
ム0.5ｇ／及び水酸化ナトリウム10ｇ／の溶
液中に母材を浸漬することによる亜鉛置換処理
と、硫酸銅240ｇ／及び硫酸60ｇ／の溶液中
に母材を常温で１分間浸漬する銅ストライク処理
と、硫酸100ml／による酸洗とを順に行なうよ
うにしたところにある。 FIG. 4 shows a process flowchart of the third embodiment, which is applied when the base material is aluminum or magnesium based. The difference from the first embodiment is that, before electroless plating, after the same degreasing treatment as in the first embodiment, a solution of 25 g of sodium carbonate and 25 g of tribasic sodium phosphate was added at 60 to 80°C. Electrolytic degreasing while immersing the base material, pickling with nitric acid 500ml/solution, and zinc immersion by immersing the base material in a solution of 0.5g/zinc chloride, 0.5g/sodium cyanide, and 10g/sodium hydroxide. The replacement treatment, the copper strike treatment in which the base material is immersed in a solution of 240 g of copper sulfate and 60 g of sulfuric acid for 1 minute at room temperature, and pickling with 100 ml of sulfuric acid are performed in this order.
第５図は母材がABS樹脂等のプラスチツク或
はセラミツク等の非導電材である場合に適用され
る第４実施例を示す工程流れ図である。前記第１
実施例との相違は、脱脂処理後、母材を硫酸400
ml／、三酸化クロム400ｇ／の溶液中に70℃
で15分間浸漬するエツチング処理と、二塩化鉛３
ｇ／、二塩化すず30ｇ／、塩酸100〜200ml／
の溶液中に常温で２分浸漬する触媒付与処理
と、硫酸30ml／の溶液中に浸漬する活性化処理
とを順に実行し、且つ無電解メツキ液を、塩化ニ
ツケル（NiCl2）15〜30ｇ／、クエン酸ナトリ
ウム50ｇ／、還元剤としての次亜リン酸ナトリ
ウム20ｇ／、塩化アンモニウム40ｇ／から調
整して水素イオン濃度をPH8.3〜9.3にすると共
に、35〜38℃のこの無電解メツキ液中に母材を約
５分間浸漬するようにした点にある。 FIG. 5 is a process flowchart showing a fourth embodiment applied when the base material is plastic such as ABS resin or non-conductive material such as ceramic. Said first
The difference from the example is that after degreasing, the base material was treated with 400% sulfuric acid.
ml/, 70℃ in a solution of chromium trioxide 400g/
Etching treatment by soaking in water for 15 minutes and lead dichloride 3
g/, tin dichloride 30g/, hydrochloric acid 100-200ml/
A catalyst application treatment of immersion in a solution of 2 minutes at room temperature and an activation treatment of immersion in a solution of 30 ml of sulfuric acid were carried out in sequence, and the electroless plating solution was immersed in a solution of 15 to 30 g of nickel chloride (NiCl 2 ). , sodium citrate 50g/, sodium hypophosphite 20g/ as a reducing agent, ammonium chloride 40g/ to adjust the hydrogen ion concentration to PH8.3-9.3, and this electroless plating solution at 35-38℃. The main point is that the base material is immersed in the water for about 5 minutes.
上記第２乃至第４の各実施例のようにしても、
第１実施例と同様に、無電解メツキにより形成し
たリン濃度が７％以下のニツケル膜の表面を酸化
して安定なニツケルのリン酸塩被膜を形成できる
ので、母材表面に耐蝕性、耐侯性及び耐摩耗性等
の諸特性に優れた黒色被膜を形成することができ
る。 Even if it is as in each of the second to fourth embodiments,
As in the first embodiment, a stable nickel phosphate film can be formed by oxidizing the surface of a nickel film with a phosphorus concentration of 7% or less formed by electroless plating, thereby providing corrosion and weather resistance to the surface of the base material. It is possible to form a black film with excellent properties such as hardness and abrasion resistance.
尚、上記各実施例では、母材表面に無電解メツ
キによりニツケル膜を形成するようにしたが、本
発明はこれに限らず、無電解メツキ液中のニツケ
ル塩に代えてコバルト塩を含ませて母材表面に７
％以下のリン濃度のコバルト膜を形成することに
より、前記各実施例と同様に諸特性に優れた黒色
被膜を形成することができる。本法の特徴の一つ
は、イオウのアノード反応極作用を触媒作用とし
て利用し、リン酸塩皮膜の形成を著しく迅速・容
易にした点にあるが、酸化触媒としては、光沢剤
に含まれるイオウを利用するに限らず、イオウを
含まない光沢剤を使用する場合には無電解メツキ
液中にイオウを含んだ化合物を含有させるように
しても良い。この場合イオウ濃度はppmオーダー
が適当である。更には、酸化触媒としては、イオ
ウに限らず、亜鉛、カドミウム、水銀、タリウ
ム、すず、鉛、リン、ヒ素、アンチモン、ビスマ
ス、セレン等であつても良い。 In each of the above embodiments, a nickel film was formed on the surface of the base material by electroless plating, but the present invention is not limited to this. 7 on the base material surface
By forming a cobalt film having a phosphorus concentration of % or less, it is possible to form a black film having excellent properties as in each of the above embodiments. One of the characteristics of this method is that it uses the anode reaction electrode action of sulfur as a catalyst, making the formation of a phosphate film extremely quick and easy. In addition to using sulfur, if a brightener that does not contain sulfur is used, a compound containing sulfur may be included in the electroless plating solution. In this case, the appropriate sulfur concentration is on the order of ppm. Furthermore, the oxidation catalyst is not limited to sulfur, but may also be zinc, cadmium, mercury, thallium, tin, lead, phosphorus, arsenic, antimony, bismuth, selenium, or the like.
本発明は以上述べたように、酸化触媒を含有せ
る無電解メツキ液により母材に７％以下のリンを
含むニツケル膜又はコバルト膜を形成し、この
後、母材表面を酸化処理するようにしたところに
特徴を有するものであつて、この結果、ニツケル
膜又はコバルト膜の表面を酸化により安定化する
と同時に黒色化できるので、母材の種類を問わず
且つ安価に、耐蝕性、耐摩耗性及び耐侯性等の諸
特性に優れた黒色被膜を形成することができると
いう著効を奏するものである。
As described above, the present invention involves forming a nickel film or a cobalt film containing 7% or less of phosphorus on a base material using an electroless plating solution containing an oxidation catalyst, and then oxidizing the surface of the base material. As a result, the surface of the nickel film or cobalt film can be stabilized by oxidation and at the same time be blackened, so it can be made to have corrosion resistance and wear resistance regardless of the type of base material and at low cost. It also has the remarkable effect of being able to form a black film with excellent properties such as weather resistance.
第１図及び第２図は本発明の第１実施例を示
し、第１図は工程流れ図、第２図は母材表面の模
式的断面図、第３図乃至第５図は本発明の第２乃
至第４実施例を夫々示す工程流れ図である。
図面中、１は母材、２はニツケル膜、３はニツ
ケルのリン酸塩膜である。
1 and 2 show a first embodiment of the present invention, FIG. 1 is a process flow chart, FIG. 2 is a schematic cross-sectional view of the surface of the base material, and FIGS. 3 to 5 show the first embodiment of the present invention. 3 is a process flowchart showing second to fourth embodiments, respectively. In the drawings, 1 is a base material, 2 is a nickel film, and 3 is a nickel phosphate film.
Claims (1)
材に７％以下のリンを含むニツケル膜又はコバル
ト膜を形成し、この後、母材表面を酸化処理する
ことを特徴とする黒色被膜形成方法。 ２ 酸化触媒はイオウであることを特徴とする特
許請求の範囲第１項に記載の黒色被膜形成方法。[Claims] 1. A method comprising forming a nickel film or a cobalt film containing 7% or less phosphorus on a base material using an electroless plating solution containing an oxidation catalyst, and then oxidizing the surface of the base material. A method for forming a black film. 2. The method for forming a black film according to claim 1, wherein the oxidation catalyst is sulfur.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9479785A JPS61253383A (en) | 1985-05-02 | 1985-05-02 | Formation of black film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9479785A JPS61253383A (en) | 1985-05-02 | 1985-05-02 | Formation of black film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61253383A JPS61253383A (en) | 1986-11-11 |
| JPS647153B2 true JPS647153B2 (en) | 1989-02-07 |
Family
ID=14120059
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9479785A Granted JPS61253383A (en) | 1985-05-02 | 1985-05-02 | Formation of black film |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61253383A (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005014881A2 (en) * | 2003-08-08 | 2005-02-17 | Showa Denko K.K. | Production method of substrate with black film and substrate with black film |
| JP4705776B2 (en) * | 2004-12-17 | 2011-06-22 | 日本カニゼン株式会社 | Method for forming electroless nickel plating film having phosphate coating and film for forming the same |
| JP5186763B2 (en) * | 2006-12-11 | 2013-04-24 | 新日鐵住金株式会社 | Ni-plated steel sheet excellent in slidability and corrosion resistance and method for producing the same |
| JP4599433B2 (en) * | 2008-06-12 | 2010-12-15 | 株式会社ネクスコ東日本パトロール | LED sign |
| JP5747147B2 (en) * | 2010-09-06 | 2015-07-08 | パナソニックＩｐマネジメント株式会社 | Method for forming black composite plating film and member for heating cooker using the formation method on the surface |
| WO2013168528A1 (en) * | 2012-05-09 | 2013-11-14 | 奥野製薬工業株式会社 | BLACKENING TREATMENT SOLUTION FOR BLACK Cr-Co ALLOY PLATING FILM |
| CN105039952B (en) * | 2015-06-29 | 2017-08-25 | 北京鼎臣超导科技有限公司 | A kind of passivation hair blackening liquid and its application for neodymium iron boron magnetic body nickel plating surface |
| JP6688066B2 (en) * | 2015-12-22 | 2020-04-28 | 上村工業株式会社 | Blackening treatment agent and method for producing black film using the same |
| US20230103643A1 (en) * | 2021-10-04 | 2023-04-06 | Applied Materials, Inc. | ADVANCED BARRIER NICKEL OXIDE (BNiO) COATING DEVELOPMENT FOR THE PROCESS CHAMBER COMPONENTS |
| JP2023075461A (en) * | 2021-11-19 | 2023-05-31 | 株式会社 コーア | Plated product, method of manufacturing plated product and plating solution |
| US12522923B2 (en) | 2022-03-11 | 2026-01-13 | Applied Materials, Inc. | Advanced barrier nickel oxide (BNiO) coating development for process chamber components via ozone treatment |
-
1985
- 1985-05-02 JP JP9479785A patent/JPS61253383A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61253383A (en) | 1986-11-11 |
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