JP2962598B2 - Microporous chrome plating method - Google Patents
Microporous chrome plating methodInfo
- Publication number
- JP2962598B2 JP2962598B2 JP17477091A JP17477091A JP2962598B2 JP 2962598 B2 JP2962598 B2 JP 2962598B2 JP 17477091 A JP17477091 A JP 17477091A JP 17477091 A JP17477091 A JP 17477091A JP 2962598 B2 JP2962598 B2 JP 2962598B2
- Authority
- JP
- Japan
- Prior art keywords
- plating
- titanium oxide
- fine particles
- hydroxide
- conductive fine
- 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 - Lifetime
Links
- 238000007747 plating Methods 0.000 title claims description 98
- 238000000034 method Methods 0.000 title claims description 36
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 88
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 51
- 229910052759 nickel Inorganic materials 0.000 claims description 44
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 42
- 239000010419 fine particle Substances 0.000 claims description 32
- 229910052804 chromium Inorganic materials 0.000 claims description 27
- 239000011651 chromium Substances 0.000 claims description 27
- 238000005260 corrosion Methods 0.000 claims description 16
- 230000007797 corrosion Effects 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 8
- 229910052782 aluminium Inorganic materials 0.000 claims description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 239000000654 additive Substances 0.000 claims 2
- 230000000996 additive effect Effects 0.000 claims 2
- 239000000126 substance Substances 0.000 claims 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 20
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 14
- 239000002002 slurry Substances 0.000 description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 12
- 229910004298 SiO 2 Inorganic materials 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 8
- 229910010413 TiO 2 Inorganic materials 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 8
- 239000011248 coating agent Substances 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000000576 coating method Methods 0.000 description 6
- 239000008119 colloidal silica Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- 239000000460 chlorine Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- 239000004327 boric acid Substances 0.000 description 3
- 159000000007 calcium salts Chemical class 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 3
- RRIWRJBSCGCBID-UHFFFAOYSA-L nickel sulfate hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-]S([O-])(=O)=O RRIWRJBSCGCBID-UHFFFAOYSA-L 0.000 description 3
- 229940116202 nickel sulfate hexahydrate Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 150000007513 acids Chemical class 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- -1 and C. a Inorganic materials 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 1
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 description 1
- 229910052580 B4C Inorganic materials 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 239000005977 Ethylene Substances 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
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- RNFNDJAIBTYOQL-UHFFFAOYSA-N chloral hydrate Chemical compound OC(O)C(Cl)(Cl)Cl RNFNDJAIBTYOQL-UHFFFAOYSA-N 0.000 description 1
- 229960002327 chloral hydrate Drugs 0.000 description 1
- PBKYWJHTOHRLDS-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni].[Ni] PBKYWJHTOHRLDS-UHFFFAOYSA-N 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical compound [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 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
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 229960004279 formaldehyde Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- HEWDOWUUTBCVJP-UHFFFAOYSA-N naphthalene-1,6-disulfonic acid Chemical compound OS(=O)(=O)C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 HEWDOWUUTBCVJP-UHFFFAOYSA-N 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005086 pumping Methods 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
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 1
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229940077386 sodium benzenesulfonate Drugs 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 description 1
- NQFKJZVOGHJWTD-UHFFFAOYSA-M sodium;pyridine-2-sulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=N1 NQFKJZVOGHJWTD-UHFFFAOYSA-M 0.000 description 1
- 150000003455 sulfinic acids Chemical class 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は、マイクロポーラスクロ
ムめっき方法に関し、さらに詳細には、非電導性微粒子
を分散したニッケルめっき浴でめっきを行ない、次いで
クロムめっきを施すことにより高耐食性ニッケル−クロ
ムめっきを得るマイクロポーラスクロムめっき方法に関
する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a microporous chromium plating method, and more particularly, to a highly corrosion-resistant nickel-chromium plating method in which plating is performed in a nickel plating bath in which non-conductive fine particles are dispersed and then chromium plating is performed. The present invention relates to a microporous chrome plating method for obtaining plating.
【０００２】[0002]
【従来の技術】非電導性微粒子を分散したニッケルめっ
き浴でめっきを行ない、非電導性粒子をニッケル被膜中
に共析せしめ、次いでこれにクロムめっきを施すことに
よりクロム被膜層に多くの微孔を形成せしめ、これによ
り優れた耐食性を得ることは、マイクロポーラスクロム
めっきとして古くから知られている。また、ニッケルめ
っき浴中に分散させる非電導性微粒子の量を変化させる
ことによって、鏡面光沢から梨地までのめっきの外観を
調製することも広く行われている。2. Description of the Related Art Plating is carried out in a nickel plating bath in which non-conductive fine particles are dispersed, the non-conductive particles are co-deposited in a nickel film, and then chromium plating is applied to the chromium film layer to form many fine holes. The formation of chromium and thereby obtaining excellent corrosion resistance has long been known as microporous chrome plating. It is also widely practiced to adjust the appearance of plating from specular gloss to satin by changing the amount of non-conductive fine particles dispersed in a nickel plating bath.
【０００３】マイクロポーラスクロムめっき方法を行な
うための非電導性微粒子としては、Ａｌ、Ｍｇ、Ｂ、Ｃ
ａ、Ｂａ、Ｓｒの浴不溶性硅酸塩、Ｂａ、Ｓｒ、Ｃａの
燐酸塩、炭酸塩、硫酸塩、しゅう酸塩および弗化物、炭
酸ニッケル、炭化硅素、炭化硼素、炭化チタニウム、二
酸化硅素、酸化マンガン、酸化チタン、酸化ジルコニウ
ム、酸化アルミニウム、酸化セレン、酸化第二鉄、酸化
クロム、窒化硼素、硫酸亜鉛、硫化亜鉛、硫化カドミウ
ム、硅化鉄がすでに特公昭３８−２２１１９号（耐食性
に優れたしゅす状（梨地）ニッケル−クロムめっき方
法）に開示されている。[0003] Non-conductive fine particles for performing the microporous chrome plating method include Al, Mg, B, and C.
a, Ba, Sr bath-insoluble silicates, Ba, Sr, Ca phosphates, carbonates, sulfates, oxalates and fluorides, nickel carbonate, silicon carbide, boron carbide, titanium carbide, silicon dioxide, oxidation Manganese, titanium oxide, zirconium oxide, aluminum oxide, selenium oxide, ferric oxide, chromium oxide, boron nitride, zinc sulfate, zinc sulfide, cadmium sulfide, and iron silicide have already been disclosed in Japanese Patent Publication No. 38-22119 (corresponding to corrosion resistance). (A matte (nickel) nickel-chromium plating method).
【０００４】現在、工業的に広く行われているマイクロ
ポーラスクロムめっき法で用いられている非電導性微粒
子はコロイダルシリカであるが、この方法で十分な耐食
性を得るためには、マイクロポアー（微孔）の数が１
０,０００個／ｃｍ2以上であることが必要であるとされ
ており、十分な耐食性を得るためには、２０ｇ／ｌ以上
のコロイダルシリカを共析ニッケルめっき浴に添加する
必要がある。At present, non-conductive fine particles used in the microporous chromium plating method widely used in industry are colloidal silica. However, in order to obtain sufficient corrosion resistance by this method, it is necessary to use a micropore (micropore). 1 hole
It is said that the number is required to be not less than 000 / cm 2 , and to obtain sufficient corrosion resistance, it is necessary to add 20 g / l or more of colloidal silica to the eutectoid nickel plating bath.
【０００５】ところで、一般にニッケルめっきでは、良
好なめっきの状態を保つために定期的な活性炭によるめ
っき浴の浄化が必要になるが、このとき、この共析ニッ
ケルめっきでは非電導性微粒子をろ過除去しなくてはな
らない。 したがって、できるかぎり少ない非電導性微
粒子添加量で十分な共析量が得られることが望ましい
が、コロイダルシリカによる場合、この面からは十分満
足できるものとはいえない。Generally, in nickel plating, it is necessary to periodically clean the plating bath with activated carbon in order to maintain a good plating state. At this time, the eutectoid nickel plating removes non-conductive fine particles by filtration. I have to do it. Therefore, it is desirable that a sufficient amount of eutectoid be obtained with the addition of as little non-conductive fine particles as possible. However, colloidal silica is not sufficiently satisfactory from this aspect.
【０００６】前記の非電導性微粒子のうち、酸化チタン
は安価な工業材料であり、この点でマイクロポーラスク
ロムめっき用微粒子として好適であるが、その比重が比
較的大きく、ニッケルめっき浴中で沈降しやすいため、
ニッケルめっき浴中での分散性が悪く、均一に共析しに
くいという欠点、特に被めっき物の下面における共析量
が少なくなり、微孔数が少なくなるという欠点があっ
た。[0006] Among the above non-conductive fine particles, titanium oxide is an inexpensive industrial material, and is suitable as microporous chromium plating fine particles in this regard. However, titanium oxide has a relatively large specific gravity and is precipitated in a nickel plating bath. Easy to do,
There is a disadvantage that the dispersibility in the nickel plating bath is poor and it is difficult to uniformly eutect, and in particular, the amount of eutectoid on the lower surface of the object to be plated is small and the number of micropores is small.
【０００７】酸化チタンの上記欠点を解消することを目
的として、酸化チタンとカルシウム塩を併用することに
より、酸化チタンのニッケルめっき浴中における分散を
均一化する方法が報告されている（特公平２−４０７５
６号）が、この方法のカルシウム塩による酸化チタンの
分散効果は疑問視されており、また、カルシウム塩を用
いることからめっき槽内における析出、電流効率の低
下、クロムめっき層への持ち込み等の問題が派生し、実
用的なものとはいえない。For the purpose of overcoming the above-mentioned drawbacks of titanium oxide, there has been reported a method of using titanium oxide and a calcium salt in combination to make titanium oxide uniform in a nickel plating bath (Japanese Patent Publication No. Hei 2 (1994)). -4075
No. 6), however, the dispersing effect of titanium oxide by the calcium salt in this method has been questioned, and since the calcium salt is used, precipitation in the plating tank, reduction in current efficiency, and carry-in to the chromium plating layer, etc. The problem arises and is not practical.
【０００８】[0008]
【発明が解決しようとする課題】したがって、より少な
い量の非電導性微粒子の使用により従来と同程度または
それ以上の耐食性を示すマイクロポーラスクロムめっき
方法の開発が望まれていた。Therefore, it has been desired to develop a microporous chromium plating method which exhibits the same or higher corrosion resistance as the conventional one by using a smaller amount of non-conductive fine particles.
【０００９】[0009]
【課題を解決するための手段】本発明者らは、酸化チタ
ンに着目し、そのマイクロポーラスクロムめっき用非電
導性微粒子としての欠点を解消すべく鋭意研究を行なっ
た結果、酸化チタンの表面をアルミニウムの水酸化物あ
るいは含水酸化物またはアルミニウムの水酸化物あるい
は含水酸化物と、けい素の水酸化物あるいは含水酸化物
とでコーティングすることによりその目的が達成される
ことを見出し、本発明を完成した。Means for Solving the Problems The present inventors have paid attention to titanium oxide, and have conducted intensive studies to eliminate the disadvantages of the non-conductive fine particles for microporous chromium plating. The present inventors have found that the object can be achieved by coating with aluminum hydroxide or hydrated oxide or aluminum hydroxide or hydrated oxide, and silicon hydroxide or hydrated oxide. completed.
【００１０】すなわち、本発明は非電導性微粒子を分散
したニッケルめっき浴中でめっきをし、次いでクロムめ
っきを行うことにより耐食性に優れたマイクロポーラス
クロムめっきを得る方法において、非電導性微粒子とし
てアルミニウム（およびけい素）の水酸化物あるいは含
水酸化物でコーティングされた酸化チタンを用いること
を特徴とするマイクロポーラスクロムめっき方法を提供
するものである。That is, the present invention relates to a method for obtaining microporous chromium plating having excellent corrosion resistance by plating in a nickel plating bath in which nonconductive fine particles are dispersed and then performing chromium plating. It is intended to provide a microporous chromium plating method characterized by using titanium oxide coated with (or silicon) hydroxide or hydrated oxide.
【００１１】本発明方法の実施に用いる非電導性微粒子
を分散したニッケルめっき浴（以下「共析ニッケルめっ
き浴」ということがある）は、非電導性微粒子としてア
ルミニウムの水酸化物あるいは含水酸化物（以下、「Ａ
ｌ2Ｏ3」と略称することがある）またはＡｌ2Ｏ3とけい
素の水酸化物あるいは含水酸化物（以下「ＳｉＯ2」と
略称することがある）でコーティングされた酸化チタン
（以下、この酸化チタンを「アルミナコート酸化チタ
ン」ということがある）を用いる以外は、従来のマイク
ロポーラスクロムめっき法の共析ニッケルめっき浴と同
様な組成のものを利用することができる。The nickel plating bath (hereinafter sometimes referred to as “eutectoid nickel plating bath”) in which non-conductive fine particles are dispersed for use in the method of the present invention is a hydroxide or hydrated oxide of aluminum as the non-conductive fine particles. (Hereafter, "A
l 2 O 3 ) or titanium oxide (hereinafter abbreviated as “SiO 2 ”) coated with Al 2 O 3 and silicon hydroxide or hydrated oxide (hereinafter sometimes abbreviated as “SiO 2 ”). Except for using titanium oxide (sometimes referred to as “alumina-coated titanium oxide”), those having the same composition as the eutectoid nickel plating bath of the conventional microporous chromium plating method can be used.
【００１２】すなわち、従来ワット浴として知られてい
る浴を基本とし、これにアルミナコート酸化チタンを加
え、更に必要に応じて、適切な光沢剤、湿潤剤等を添加
することにより調製することができる。That is, it can be prepared by adding an alumina-coated titanium oxide to a bath conventionally known as a watt bath, and further adding an appropriate brightener, a wetting agent and the like, if necessary. it can.
【００１３】アルミナコート酸化チタンは、酸化チタン
微粒子の表面をＡｌ2Ｏ3またはＡｌ2Ｏ3とＳｉＯ2とで
被覆したもので、例えば、酸化チタンスラリーにアルミ
ン酸塩水溶液（及び必要により珪酸塩溶液）を添加し、
これに酸性化合物あるいはアルカリ性化合物を添加して
中和し、被覆剤を水酸化物あるいは含水酸化物として酸
化チタンの表面に沈澱させるか、あるいはアルミン酸塩
水溶液（及び必要により珪酸塩溶液）と、酸性化合物あ
るいはアルカリ性化合物を所定のｐＨを保って同時に添
加することなどによって調製される。 また、このアル
ミナコート酸化チタンは、現在、工業的に生産されてお
り、容易に入手できるので、これを用いても良い。 ア
ルミナコート酸化チタンは、その粒径が０.０１〜５μ
ｍ程度のものを利用することが好ましい。Alumina-coated titanium oxide is obtained by coating the surface of titanium oxide fine particles with Al 2 O 3 or Al 2 O 3 and SiO 2. For example, an aluminate aqueous solution (and silicate if necessary) is added to a titanium oxide slurry. Solution)
This is neutralized by adding an acidic compound or an alkaline compound, and the coating agent is precipitated on the surface of titanium oxide as a hydroxide or a hydrated oxide, or an aluminate aqueous solution (and a silicate solution if necessary), It is prepared by simultaneously adding an acidic compound or an alkaline compound while maintaining a predetermined pH. Moreover, since this alumina-coated titanium oxide is currently industrially produced and can be easily obtained, it may be used. Alumina-coated titanium oxide has a particle size of 0.01 to 5 μm.
It is preferable to use those having a size of about m.
【００１４】共析ニッケルめっき浴中へのアルミナコー
ト酸化チタンの添加量は、０.０５ｇ／ｌ程度以上、好
ましくは０.１ｇ／ｌ程度の少量で十分な耐食効果が得
られるが、逆に添加量が多すぎるとアルミナコート酸化
チタンの共析量が増え、めっき外観に曇を生ずることが
あるので、特に均一な鏡面外観を望む場合は、添加量を
５ｇ／ｌ以下にすることが好ましい。The addition of alumina-coated titanium oxide to the eutectoid nickel plating bath is not less than about 0.05 g / l, preferably about 0.1 g / l. If the addition amount is too large, the eutectoid amount of the alumina-coated titanium oxide increases and the plating appearance may be fogged. Therefore, in particular, when a uniform mirror-like appearance is desired, the addition amount is preferably 5 g / l or less. .
【００１５】このアルミナコート酸化チタンは、粉末状
態のまま共析ニッケルめっき浴中へ加えても良いが、必
要に応じて、これに水やワットニッケルめっき浴を加
え、界面活性剤、分散剤等を加え、更に必要に応じて撹
拌、超音波等の分散手段により調製した懸濁液として用
いても良い。The alumina-coated titanium oxide may be added to the eutectoid nickel plating bath in a powder state. However, if necessary, water or a nickel plating bath may be added thereto to add a surfactant, a dispersant, etc. And, if necessary, may be used as a suspension prepared by dispersing means such as stirring and ultrasonic waves.
【００１６】アルミナコート酸化チタンを用いる共析ニ
ッケルめっきも、従来の非電導微粒子共析ニッケルめっ
きとほぼ同様の条件で行なうことができ、めっき浴の撹
拌についても、空気攪拌や、プロペラ攪拌、ポンプ攪拌
等の機械攪拌を採用することができる。Eutectoid nickel plating using alumina-coated titanium oxide can be performed under substantially the same conditions as conventional non-conductive fine particle eutectoid nickel plating. The stirring of the plating bath is also performed by air stirring, propeller stirring, and pumping. Mechanical stirring such as stirring can be employed.
【００１７】本発明における共析ニッケルめっきのため
の好ましい条件を示せば次の通りである。 Preferred conditions for the eutectoid nickel plating in the present invention are as follows.
【００１８】共析ニッケルめっきの上に施される
クロムめっきも、従来のマイクロポーラスクロムめっき
法で採用されている浴組成および条件で行なうことがで
きる。例えば、サージェント浴やケイフッ化浴等の一般
に利用されている浴を使用し、通常行われている条件で
実施することができる。 このクロムめっきの膜厚は、
一般には、０.０１〜１.０μｍとすることが好ましい。The chromium plating applied on the eutectoid nickel plating can also be performed with the bath composition and conditions employed in the conventional microporous chromium plating method. For example, a commonly used bath such as a Sargent bath or a fluorinated silicon bath is used, and the reaction can be carried out under ordinary conditions. The film thickness of this chrome plating is
Generally, it is preferable that the thickness be 0.01 to 1.0 μm.
【００１９】本発明方法を適用することのできる被めっ
き素材には特に制限はなく、鉄鋼、亜鉛、アルミニウ
ム、銅、銅合金その他の金属素地やＡＢＳ樹脂その他の
プラスチック素地上に、通常の方法により前処理をした
のち、必要であれば、銅などの下地めっきを施したもの
のいずれをも採用することができる。The material to be plated to which the method of the present invention can be applied is not particularly limited, and is applied to a metal substrate such as steel, zinc, aluminum, copper, a copper alloy or the like or an ABS resin or other plastic substrate by a usual method. After the pretreatment, if necessary, any of those subjected to a base plating of copper or the like can be adopted.
【００２０】これら上記被めっき素材は、一般には、直
接、または銅めっきの後、通常の光沢ニッケルめっきま
たは半光沢ニッケル−光沢ニッケルめっきが施され、更
に本発明のマイクロポーラスクロムめっきが施される。These materials to be plated are generally subjected to ordinary bright nickel plating or semi-bright nickel-bright nickel plating directly or after copper plating, and further to the microporous chrome plating of the present invention. .
【００２１】このうち光沢ニッケルめっき浴には、公知
の光沢剤、例えば一次光沢剤として、１,５−１,６−又
は２,５−ナフタリンジスルホン酸ソーダ、１,３,６−
ナフタリントリスルホン酸ソーダ、ベンゼンスルホン酸
ソーダ及びサッカリン酸ソーダなどの芳香族スルホンイ
ミド類、及びスルフィン酸類が単独又は組み合わせて使
用され、また、光沢・レベリングを付与する目的で、
１,４−ブチンジオールを代表とするアセチレン系不飽
和アルコール及びその誘導体、及びビニルスルホン酸ソ
ーダ、アリルスルホン酸ソーダなどのエチレン系不飽和
スルホン酸塩、あるいは、ピリジン系スルホン酸ソーダ
塩が使用される。 またこれらに代えて、#６１０、#６
３（荏原ユージライト(株)製）等の市販の光沢ニッケル
用光沢剤を利用しても良い。Among these, the bright nickel plating bath contains a known brightener, for example, sodium 1,5-1,6- or 2,5-naphthalene disulfonate, 1,3,6-
Sodium naphthalene trisulfonate, aromatic sulfonimides such as sodium benzenesulfonate and sodium saccharinate, and sulfinic acids are used alone or in combination, and for the purpose of imparting gloss and leveling,
Acetylene unsaturated alcohols and their derivatives represented by 1,4-butynediol and ethylene unsaturated sulfonates such as sodium vinyl sulfonate and sodium allyl sulfonate, or sodium pyridine sulfonate are used. You. Instead of these, # 610, # 6
A commercially available brightening agent for bright nickel such as No. 3 (manufactured by Ebara Ujilight Co., Ltd.) may be used.
【００２２】また、半光沢ニッケルめっきには、イオウ
共析量が少なく、電位の貴な半光沢ニッケルめっき層を
形成するために用いられる公知ニッケルめっき浴のいず
れをも採用することができ、このために利用できる光沢
剤としては、抱水クロラール、ホルマリン、クマリン等
を挙げることができる。 またこれらに代えて、例え
ば、Ｎ２Ｅ、ＢＴＬ（荏原ユージライト(株)製）などの
市販のものを利用することもできる。For the semi-bright nickel plating, any known nickel plating bath used for forming a semi-bright nickel plating layer having a small sulfur eutectoid and a noble potential can be used. Examples of the brightener that can be used include chloral hydrate, formalin, coumarin and the like. In place of these, commercially available products such as N2E and BTL (manufactured by Ebara Uzilite Co., Ltd.) can also be used.
【００２３】[0023]
【作用】本発明のマイクロポーラスクロムめっき方法で
は、従来使用されているコロイダルシリカに比べ少量の
アルミナコート酸化チタンを添加することにより、従来
と同様またはそれ以上の耐食性を得ることができるが、
これは、Ａｌ2Ｏ3のコーティングにより酸化チタンが＋
に帯電し、陰極である被めっき物に共析しやすくなるた
めと考えられる。According to the microporous chromium plating method of the present invention, the same or higher corrosion resistance can be obtained by adding a small amount of alumina-coated titanium oxide as compared with conventionally used colloidal silica.
This is because the coating of Al 2 O 3 titanium oxide +
This is presumed to be due to the fact that it is easily charged and is likely to be eutectoid on the object to be plated as the cathode.
【００２４】[0024]
【発明の効果】アルミナコート酸化チタンを非電導性微
粒子として用いると、コロイダルシリカに比べ、ニッケ
ルめっきでの共析量が増加し、このあとに施すクロムめ
っきで生ずる微孔数も増加する。 このため、十分な耐
食性を得るために従来の方法では２０ｇ／ｌ以上の非電
導性微粒子を必要としたが、本発明方法では０.１ｇ／
ｌ程度の少量で十分な効果が得られる。更に、Ａｌ2Ｏ3
とＳｉＯ2の双方でコーティングしたアルミナコート酸
化チタンを用いると、共析ニッケルめっき浴中における
分散性が改善され、より高い耐食性が得られる。According to the present invention, when alumina-coated titanium oxide is used as the non-conductive fine particles, the amount of eutectoid in nickel plating increases and the number of micropores generated in chromium plating thereafter increases as compared with colloidal silica. For this reason, in order to obtain sufficient corrosion resistance, the conventional method requires non-conductive fine particles of 20 g / l or more, but the method of the present invention requires 0.1 g / l.
A sufficient effect can be obtained with a small amount of about l. Further, Al 2 O 3
And the use of alumina-coated titanium oxide coated with both SiO 2, an improved dispersibility in eutectoid nickel plating bath, a higher corrosion resistance can be obtained.
【００２５】このように本発明方法は、少ない微粒子の
添加により高い耐食性が得られるので、高い耐食性が要
求される物品、例えば自動車部品や屋外利用品のめっき
方法として優れているばかりでなく、その浴の浄化等も
容易であるので、工業的にも有利なものである。As described above, the method of the present invention can obtain high corrosion resistance by adding a small amount of fine particles. Therefore, the method is not only excellent as a plating method for articles requiring high corrosion resistance, for example, automobile parts and products for outdoor use. Since it is easy to purify the bath, it is industrially advantageous.
【００２６】[0026]
【実施例】次に、参考例および実施例を挙げ、本発明を
更に詳しく説明するが、本発明はこれら実施例になんら
制約されるものではない。EXAMPLES Next, the present invention will be described in more detail with reference to Reference Examples and Examples, but the present invention is not limited to these Examples.
【００２７】参 考 例 １ 塩素法ルチル形二酸化チタンの水性スラリー（ＴｉＯ2
として３００ｇ／ｌ）を７０℃に加熱し、これにアルミ
ン酸ナトリウム水溶液をＡｌ2Ｏ3として３.５％（Ｔｉ
Ｏ2 重量基準）添加して１０分間撹拌し、その後硫酸を
ゆっくり添加してスラリ−のｐＨを７.０とした。１時
間熟成してＡｌ2Ｏ3を二酸化チタン粒子表面に被覆させ
た。 この被覆後のスラリーを濾過、洗浄した後、１５
０℃で乾燥しパルベライザーミルで粉砕し、アルミナコ
ート酸化チタンＡを得た。REFERENCE EXAMPLE 1 Aqueous slurry of rutile titanium dioxide by chlorine method (TiO 2
Was heated to 70 ° C., and an aqueous solution of sodium aluminate was added thereto as Al 2 O 3 at 3.5% (Ti
(Based on O 2 weight) and stirred for 10 minutes, after which sulfuric acid was slowly added to bring the pH of the slurry to 7.0. After aging for 1 hour, Al 2 O 3 was coated on the surface of the titanium dioxide particles. After filtering and washing the slurry after coating, 15
It was dried at 0 ° C. and pulverized with a pulverizer mill to obtain alumina-coated titanium oxide A.
【００２８】参 考 例 ２ 塩素法ルチル形二酸化チタンの水性スラリー（ＴｉＯ2
として３００ｇ／ｌ）のｐＨを、水酸化ナトリウム水溶
液で１１に調製し、次いでスラリー温度を７０℃に加温
した後、ケイ酸ナトリウム水溶液をＳｉＯ2として５.０
％（ＴｉＯ2重量基準）添加した。 引き続きスラリー温
度を９０℃に加温した後、硫酸をゆっくり添加してスラ
リーのｐＨを７.０とした。１時間熟成した後、アルミ
ン酸ナトリウム水溶液をＡｌ2Ｏ3として３.０％（Ｔｉ
Ｏ2重量基準）添加して、１０分間撹拌し、硫酸をゆっ
くり添加してスラリーのｐＨ７.０とし、１時間熟成し
てＡｌ2Ｏ3およびＳｉＯ2を二酸化チタン粒子表面に被
覆させた。この被覆処理後のスラリーを濾過、洗浄した
後、１５０℃で乾燥し、次いでパルベライザーミルで粉
砕し、アルミナコート酸化チタンＢを得た。REFERENCE EXAMPLE 2 Aqueous slurry of rutile titanium dioxide by chlorine method (TiO 2
PH was adjusted to 11 with an aqueous solution of sodium hydroxide, and then the slurry was heated to 70 ° C., and then the aqueous solution of sodium silicate was converted to 5.0 as SiO 2.
% (Based on TiO 2 weight). Subsequently, the slurry temperature was raised to 90 ° C., and sulfuric acid was slowly added to adjust the pH of the slurry to 7.0. After aging for 1 hour, the aqueous solution of sodium aluminate was converted to Al 2 O 3 by 3.0% (Ti
O 2 by weight) were added, and stirred for 10 minutes, and pH7.0 slurry was slowly added sulfuric acid, was coated in 1 hour aging to Al 2 O 3 and SiO 2 the titanium dioxide particle surface. The slurry after the coating treatment was filtered and washed, dried at 150 ° C., and then pulverized with a pulverizer mill to obtain alumina-coated titanium oxide B.
【００２９】参 考 例 ３ 硫酸法ルチル形二酸化チタンの水性スラリー（ＴｉＯ2
として２５０ｇ／ｌ）を６０℃に加熱し、アルミン酸ナ
トリウム水溶液をＡｌ2Ｏ3として３.０％（ＴｉＯ2重量
基準）添加して、１０分間撹拌した。次いでケイ酸ナト
リウム水溶液をＳｉＯ2として４.０％（ＴｉＯ2重量基
準）添加し、１０分間撹拌後、硫酸をゆっくり添加して
スラリーのｐＨを７.０とした。その後再びアルミン酸
ナトリウム水溶液をＡｌ2Ｏ3として２.０％（ＴｉＯ2重
量基準）添加し、１０分間撹拌後硫酸をゆっくり添加し
てスラリーのｐＨ７.０とし、１時間熟成してＡｌ2Ｏ3
およびＳｉＯ2を二酸化チタン粒子表面に被覆させた。
この被覆処理後のスラリーを濾過、洗浄した後、１５０
℃で乾燥し、次いでパルベライザーミルで粉砕し、アル
ミナコート酸化チタンＣを得た。REFERENCE EXAMPLE 3 Aqueous slurry of rutile titanium dioxide by sulfuric acid method (TiO 2
Was heated to 60 ° C., and an aqueous solution of sodium aluminate was added in an amount of 3.0% (based on TiO 2 weight) as Al 2 O 3 and stirred for 10 minutes. Then, 4.0% (based on TiO 2 weight) of an aqueous solution of sodium silicate was added as SiO 2 , and after stirring for 10 minutes, sulfuric acid was slowly added to adjust the pH of the slurry to 7.0. Followed by the addition of 2.0% aqueous sodium aluminate solution as Al 2 O 3 again (TiO 2 by weight), was slowly added After stirring for 10 minutes sulfate and pH7.0 the slurry was aged for 1 hour Al 2 O Three
And SiO 2 were coated on the surface of the titanium dioxide particles.
After filtering and washing the slurry after the coating treatment, 150
C. and then pulverized with a pulverizer mill to obtain alumina-coated titanium oxide C.
【００３０】実 施 例 １ 下記記載の共析ニッケルめっき浴に非電導性微粒子とし
てアルミナコート酸化チタンＡ（平均粒径０.２５μ
ｍ、Ａｌ2Ｏ3でコーティング、９５％ＴｉＯ2）を０.５
ｇ／ｌ添加し、下記条件でめっきを行った。 なお、試
料板は、垂直（条件Ａ）および有効面が４５゜下向き
（条件Ｂ）となるようにセットした。EXAMPLE 1 Alumina-coated titanium oxide A (average particle size 0.25 μm) was used as nonconductive fine particles in a eutectoid nickel plating bath described below.
m, coated with Al 2 O 3 , 95% TiO 2 ) 0.5
g / l was added and plating was performed under the following conditions. The sample plate was set so as to be vertical (condition A) and the effective surface was directed downward by 45 ° (condition B).
【００３１】＜試料＞鋼 板（１００×５０×０.３ｍ
ｍ） <Sample> Steel plate (100 × 50 × 0.3 m)
m)
【００３２】 （注） * 半光沢ニッケルめっき浴組成： 硫酸ニッケル６水塩 ３００ｇ／ｌ 塩化ニッケル６水塩 ４５ｇ／ｌ ホ ウ 酸 ４５ｇ／ｌ Ｂ−ｍｕ（荏原ユージライト(株)製） １０ｍｌ／ｌ ＢＴＬ（荏原ユージライト(株)製） １.５ｍｌ／ｌ ｐＨ ４.０(Note) * Semi-bright nickel plating bath composition: nickel sulfate hexahydrate 300 g / l nickel chloride hexahydrate 45 g / l boric acid 45 g / l B-mu (manufactured by Ebara Uzilite Co., Ltd.) 10 ml / l BTL (manufactured by Ebara Ujilight Co., Ltd.) 1.5 ml / l pH 4.0
【００３３】 ** 光沢ニッケルめっき浴組成： 硫酸ニッケル６水塩 ３００ｇ／ｌ 塩化ニッケル６水塩 ６０ｇ／ｌ ホ ウ 酸 ４５ｇ／ｌ #６１０（荏原ユージライト(株)製） ５ｍｌ／ｌ #６３（荏原ユージライト(株)製） １０ｍｌ／ｌ ｐＨ ４.０** Bright nickel plating bath composition: Nickel sulfate hexahydrate 300 g / l Nickel chloride hexahydrate 60 g / l Boric acid 45 g / l # 610 (manufactured by Ebara Uzilite Co., Ltd.) 5 ml / l # 63 ( Ebara Ujilight Co., Ltd.) 10ml / l pH 4.0
【００３４】 *** 共析ニッケルめっき浴組成（非電導性微粒子を除く）： 硫酸ニッケル６水塩 ３００ｇ／ｌ 塩化ニッケル６水塩 ６０ｇ／ｌ ホ ウ 酸 ４５ｇ／ｌ ＤＮ−３０１（荏原ユージライト(株)製） ５ｍｌ／ｌ ＤＮ−３０３（荏原ユージライト(株)製） １０ｍｌ／ｌ ｐＨ ４.０*** Eutectoid nickel plating bath composition (excluding non-conductive fine particles): Nickel sulfate hexahydrate 300 g / l Nickel chloride hexahydrate 60 g / l Boric acid 45 g / l DN-301 (Ebara Uzilite 5 ml / l DN-303 (manufactured by Ebara Uzilite Co., Ltd.) 10 ml / l pH 4.0
【００３５】 + クロムめっき浴 無水クロム酸 ２５０ｇ／ｌ 三価クロム ３ｇ／ｌ 硫 酸 ２.５ｇ／ｌ+ Chromium plating bath Chromic anhydride 250 g / l Trivalent chromium 3 g / l Sulfuric acid 2.5 g / l
【００３６】実 施 例 ２ 実施例１の共析ニッケルめっき浴に非電導性微粒子とし
てアルミナコート酸化チタンＢ（平均粒径０.２５μ
ｍ、Ａｌ2Ｏ3およびＳｉＯ2でコーティング、９０％Ｔ
ｉＯ2）を０.５ｇ／ｌ添加し、実施例１と同じ条件でめ
っきを行った。Example 2 In the eutectoid nickel plating bath of Example 1, alumina-coated titanium oxide B (average particle size 0.25 μm) was used as non-conductive fine particles.
m, coated with Al 2 O 3 and SiO 2 , 90% T
iO 2 ) was added at 0.5 g / l, and plating was performed under the same conditions as in Example 1.
【００３７】実 施 例 ３ 実施例１の共析ニッケルめっき浴に非電導性微粒子とし
てアルミナコート酸化チタンＢを０.１ｇ／ｌ添加し、
実施例１と同じ条件でめっきを行った。Example 3 To the eutectoid nickel plating bath of Example 1 was added 0.1 g / l of alumina-coated titanium oxide B as non-conductive fine particles.
Plating was performed under the same conditions as in Example 1.
【００３８】実 施 例 ４ 実施例１の共析ニッケルめっき浴に非電導性微粒子とし
てアルミナコート酸化チタンＣ（平均粒径０.２５μ
ｍ、Ａｌ2Ｏ3およびＳｉＯ2でコーティング、８８％Ｔ
ｉＯ2）を０.５ｇ／ｌ添加し、実施例１と同じ条件でめ
っきを行った。Example 4 In the eutectoid nickel plating bath of Example 1, alumina-coated titanium oxide C (average particle size 0.25 μm) was used as non-conductive fine particles.
m, coated with Al 2 O 3 and SiO 2 , 88% T
iO 2 ) was added at 0.5 g / l, and plating was performed under the same conditions as in Example 1.
【００３９】実 施 例 ５ 実施例１の共析ニッケルめっき浴に非電導性微粒子とし
てアルミナコート酸化チタンＣを０.１ｇ／ｌ添加し、
実施例１と同じ条件でめっきを行った。EXAMPLE 5 To the eutectoid nickel plating bath of Example 1 was added 0.1 g / l of alumina-coated titanium oxide C as non-conductive fine particles.
Plating was performed under the same conditions as in Example 1.
【００４０】比 較 例 １ 実施例１の共析ニッケルめっき浴に非電導性微粒子とし
て酸化チタン（平均粒径０.２５μｍ、１００％Ｔｉ
Ｏ2）を０.５ｇ／ｌ添加し、実施例１と同じ条件でめっ
きを行った。Comparative Example 1 In the eutectoid nickel plating bath of Example 1, titanium oxide (average particle size 0.25 μm, 100% Ti) was used as non-conductive fine particles.
O 2 ) was added in an amount of 0.5 g / l, and plating was performed under the same conditions as in Example 1.
【００４１】比 較 例 ２ 実施例１の共析ニッケルめっき浴に、非電導性微粒子と
してコロイダルシリカ（ＤＮ−ＭＰ；荏原ユージライト
(株)製）を２５ｇ／ｌおよび分散補助剤（ＤＮ−３０
７；荏原ユージライト(株)製）を添加し、実施例１と同
じ条件でめっきを行った。Comparative Example 2 Colloidal silica (DN-MP; Ebara Uzilite) was added to the eutectoid nickel plating bath of Example 1 as non-conductive fine particles.
25 g / l and a dispersing aid (DN-30)
7; manufactured by EBARA Eugelite Co., Ltd.), and plating was performed under the same conditions as in Example 1.
【００４２】試 験 例 実施例１〜５および比較例１、２でめっきした試料につ
いて、４８時間ＣＡＳＳ試験（ＪＩＳ Ｄ ０２０１ 付
属書 ２による）を行ない、耐食性を調べた。また、こ
の試料について、硫酸銅めっき法による微孔数の測定も
行った。 この結果を次の表に示す。Test Examples The samples plated in Examples 1 to 5 and Comparative Examples 1 and 2 were subjected to a 48-hour CASS test (according to JIS D 0201 Appendix 2) to examine the corrosion resistance. Further, the number of micropores was measured for this sample by a copper sulfate plating method. The results are shown in the following table.
【００４３】 [0043]
【００４４】この結果から明らかなように、本発明方法
によれば、少ない非電導性微粒子の使用により、従来法
（比較例２）と同様な優れた耐食性を得ることができ
る。 以 上As is apparent from the results, according to the method of the present invention, excellent corrosion resistance similar to that of the conventional method (Comparative Example 2) can be obtained by using a small amount of non-conductive fine particles. that's all
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｃ２５Ｄ 5/14 Ｃ２５Ｄ 5/14 (72)発明者 畑中 竜彦 神奈川県藤沢市善行坂１−１−６ 荏原 ユージライト株式会社中央研究所内 (72)発明者 和田 仁志 神奈川県藤沢市善行坂１−１−６ 荏原 ユージライト株式会社中央研究所内 (72)発明者 小澤 学 愛知県豊田市トヨタ町１番地 トヨタ自 動車株式会社内 (72)発明者 鈴木 滋 愛知県豊田市大林町３−189 (72)発明者 奥田 晴夫 三重県四日市市石原町１番地 石原産業 株式会社技術研究所内 (72)発明者 高橋 英雄 三重県四日市市石原町１番地 石原産業 株式会社技術研究所内 (56)参考文献 特開 昭49−76734（ＪＰ，Ａ) 特公 平２−40756（ＪＰ，Ｂ２) 特公 昭38−22119（ＪＰ，Ｂ１) (58)調査した分野(Int.Cl.6，ＤＢ名) C25D 15/02 C25D 15/00 C25D 5/14 ────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. 6 Identification code FI C25D 5/14 C25D 5/14 (72) Inventor Tatsuhiko Hatanaka 1-1-6 Yoshiyukizaka, Fujisawa-shi, Kanagawa EBARA Eugerite Co., Ltd. Inside the research institute (72) Inventor Hitoshi Wada 1-1-6 Yoshiyukizaka, Fujisawa-shi, Kanagawa Ebara Ujilight Co., Ltd.Central research institute (72) Inventor Manabu Ozawa 1 Toyota-cho, Toyota-shi, Aichi Prefecture Inside Toyota Motor Corporation ( 72) Inventor Shigeru Suzuki 3-189 Obayashi-cho, Toyota City, Aichi Prefecture No. 1 Ishihara Sangyo R & D Co., Ltd. (56) References JP-A-49-76734 (JP, A) JP 2-40756 (JP, B2) JP-B-38-22119 (JP, B1) (58) Field surveyed (Int. Cl. 6 , DB name) C25D 15/02 C25D 15/00 C25D 5/14
Claims (6)
き浴中でめっきをし、次いでクロムめっきを行うことに
より耐食性に優れたマイクロポーラスクロムめっきを得
る方法において、非電導性微粒子としてアルミニウムの
水酸化物あるいは含水酸化物でコーティングされた酸化
チタンを用いることを特徴とするマイクロポーラスクロ
ムめっき方法。In a method for obtaining microporous chromium plating having excellent corrosion resistance by plating in a nickel plating bath in which non-conductive fine particles are dispersed, and then performing chromium plating, aluminum hydroxide is used as the non-conductive fine particles. A microporous chrome plating method using titanium oxide coated with a substance or a hydrated oxide.
酸化物あるいは含水酸化物でコーティングされた酸化チ
タンの量が、０.０５〜５ｇ／ｌであることを特徴とす
る請求項第１項記載の方法。2. The method according to claim 1, wherein the amount of titanium oxide coated with aluminum hydroxide or hydrated oxide in the nickel plating bath is 0.05 to 5 g / l. Method.
き浴中でめっきをし、次いでクロムめっきを行うことに
より耐食性に優れたマイクロポーラスクロムめっきを得
る方法において、非電導性微粒子としてアルミニウムの
水酸化物あるいは含水酸化物と、けい素の水酸化物ある
いは含水酸化物とでコーティングされた酸化チタンを用
いることを特徴とするマイクロポーラスクロムめっき方
法。3. A method for obtaining microporous chromium plating having excellent corrosion resistance by plating in a nickel plating bath in which non-conductive fine particles are dispersed and then performing chromium plating, wherein aluminum is used as non-conductive fine particles. A microporous chromium plating method characterized by using titanium oxide coated with a substance or a hydrated oxide and a silicon hydroxide or a hydrated oxide.
酸化物あるいは含水酸化物と、けい素の水酸化物あるい
は含水酸化物とでコーティングされた酸化チタンの量が
０.０５〜５ｇ／ｌであることを特徴とする請求項第３
項記載の方法。4. The amount of titanium oxide coated with a hydroxide or hydrated oxide of aluminum and a hydroxide or hydrated oxide of silicon in a nickel plating bath is 0.05 to 5 g / l. 3. The method according to claim 1, wherein
The method described in the section.
化物でコーティングされた酸化チタンを含有するマイク
ロポーランスクロムめっき用添加剤。5. An additive for microporous chromium plating containing titanium oxide coated with a hydroxide or hydrated oxide of aluminum.
酸化物と、けい素の水酸化物あるいは含水酸化物とでコ
ーティングされた酸化チタンを含有するマイクロポーラ
ンスクロムめっき用添加剤。6. An additive for microporous chromium plating comprising titanium oxide coated with a hydroxide or hydrated oxide of aluminum and a hydroxide or hydrated oxide of silicon.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17477091A JP2962598B2 (en) | 1991-06-20 | 1991-06-20 | Microporous chrome plating method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP17477091A JP2962598B2 (en) | 1991-06-20 | 1991-06-20 | Microporous chrome plating method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04371597A JPH04371597A (en) | 1992-12-24 |
| JP2962598B2 true JP2962598B2 (en) | 1999-10-12 |
Family
ID=15984370
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP17477091A Expired - Lifetime JP2962598B2 (en) | 1991-06-20 | 1991-06-20 | Microporous chrome plating method |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2962598B2 (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4494309B2 (en) * | 2005-08-05 | 2010-06-30 | 柿原工業株式会社 | Method for improving corrosion resistance of copper-free nickel-chromium resin plating |
| DE102014207778B3 (en) * | 2014-04-25 | 2015-05-21 | Kiesow Dr. Brinkmann GmbH & Co. KG | Use of a mixture for use in a plating bath or plating bath to produce a bright nickel plating, and to a method of making an article having a bright nickel plating |
| EP3940119A4 (en) * | 2019-03-12 | 2022-08-10 | JCU Corporation | Microporous plating solution and method of using this plating solution to perform microporous plating on object to be plated |
| US20210040637A1 (en) * | 2019-08-08 | 2021-02-11 | Jcu International, Inc. | Chromium plating product and method for producing the same |
| JP6945761B1 (en) * | 2021-06-16 | 2021-10-06 | 株式会社Ｊｃｕ | Additives for composite plating solutions |
-
1991
- 1991-06-20 JP JP17477091A patent/JP2962598B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04371597A (en) | 1992-12-24 |
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