JPH0153352B2 - - Google Patents
Info
- Publication number
- JPH0153352B2 JPH0153352B2 JP14675182A JP14675182A JPH0153352B2 JP H0153352 B2 JPH0153352 B2 JP H0153352B2 JP 14675182 A JP14675182 A JP 14675182A JP 14675182 A JP14675182 A JP 14675182A JP H0153352 B2 JPH0153352 B2 JP H0153352B2
- Authority
- JP
- Japan
- Prior art keywords
- bath
- electroless
- boron
- nickel
- complexing agent
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 72
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 52
- UORVGPXVDQYIDP-UHFFFAOYSA-N borane Chemical compound B UORVGPXVDQYIDP-UHFFFAOYSA-N 0.000 claims description 52
- 229910052796 boron Inorganic materials 0.000 claims description 52
- 229910052759 nickel Inorganic materials 0.000 claims description 36
- 239000008139 complexing agent Substances 0.000 claims description 28
- 229910000085 borane Inorganic materials 0.000 claims description 26
- 239000002244 precipitate Substances 0.000 claims description 24
- -1 vanadyl ions Chemical class 0.000 claims description 20
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
- 238000001556 precipitation Methods 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000003623 enhancer Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 238000000151 deposition Methods 0.000 claims description 12
- 150000002500 ions Chemical class 0.000 claims description 12
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 claims description 11
- 150000002148 esters Chemical group 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 230000008021 deposition Effects 0.000 claims description 7
- 230000001965 increasing effect Effects 0.000 claims description 7
- 239000000872 buffer Substances 0.000 claims description 6
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- 230000002708 enhancing effect Effects 0.000 claims description 5
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 claims description 5
- 150000001412 amines Chemical group 0.000 claims description 4
- 150000001732 carboxylic acid derivatives Chemical group 0.000 claims description 4
- 229910000352 vanadyl sulfate Inorganic materials 0.000 claims description 4
- 229940041260 vanadyl sulfate Drugs 0.000 claims description 3
- IPCAPQRVQMIMAN-UHFFFAOYSA-L zirconyl chloride Chemical compound Cl[Zr](Cl)=O IPCAPQRVQMIMAN-UHFFFAOYSA-L 0.000 claims description 3
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 claims description 2
- 125000005287 vanadyl group Chemical group 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims 1
- 125000004122 cyclic group Chemical group 0.000 claims 1
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 150000007513 acids Chemical class 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 5
- 239000004310 lactic acid Substances 0.000 description 4
- 235000014655 lactic acid Nutrition 0.000 description 4
- 238000007747 plating Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- UCMIRNVEIXFBKS-UHFFFAOYSA-N beta-alanine Chemical compound NCCC(O)=O UCMIRNVEIXFBKS-UHFFFAOYSA-N 0.000 description 2
- 150000001735 carboxylic acids Chemical class 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- MTCFGRXMJLQNBG-REOHCLBHSA-N (2S)-2-Amino-3-hydroxypropansäure Chemical compound OC[C@H](N)C(O)=O MTCFGRXMJLQNBG-REOHCLBHSA-N 0.000 description 1
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- QEVGZEDELICMKH-UHFFFAOYSA-N Diglycolic acid Chemical compound OC(=O)COCC(O)=O QEVGZEDELICMKH-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 description 1
- 239000004471 Glycine Substances 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 description 1
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 description 1
- ROHFNLRQFUQHCH-YFKPBYRVSA-N L-leucine Chemical compound CC(C)C[C@H](N)C(O)=O ROHFNLRQFUQHCH-YFKPBYRVSA-N 0.000 description 1
- KZSNJWFQEVHDMF-BYPYZUCNSA-N L-valine Chemical compound CC(C)[C@H](N)C(O)=O KZSNJWFQEVHDMF-BYPYZUCNSA-N 0.000 description 1
- ROHFNLRQFUQHCH-UHFFFAOYSA-N Leucine Natural products CC(C)CC(N)C(O)=O ROHFNLRQFUQHCH-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 1
- MTCFGRXMJLQNBG-UHFFFAOYSA-N Serine Natural products OCC(N)C(O)=O MTCFGRXMJLQNBG-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- KZSNJWFQEVHDMF-UHFFFAOYSA-N Valine Natural products CC(C)C(N)C(O)=O KZSNJWFQEVHDMF-UHFFFAOYSA-N 0.000 description 1
- YDONNITUKPKTIG-UHFFFAOYSA-N [Nitrilotris(methylene)]trisphosphonic acid Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CP(O)(O)=O YDONNITUKPKTIG-UHFFFAOYSA-N 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 235000001014 amino acid Nutrition 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000001450 anions Chemical class 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
- 235000003704 aspartic acid Nutrition 0.000 description 1
- 229940000635 beta-alanine Drugs 0.000 description 1
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 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
- YJROYUJAFGZMJA-UHFFFAOYSA-N boron;morpholine Chemical compound [B].C1COCCN1 YJROYUJAFGZMJA-UHFFFAOYSA-N 0.000 description 1
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- OWBTYPJTUOEWEK-UHFFFAOYSA-N butane-2,3-diol Chemical compound CC(O)C(C)O OWBTYPJTUOEWEK-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- YPTUAQWMBNZZRN-UHFFFAOYSA-N dimethylaminoboron Chemical compound [B]N(C)C YPTUAQWMBNZZRN-UHFFFAOYSA-N 0.000 description 1
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007772 electroless plating Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- 235000013922 glutamic acid Nutrition 0.000 description 1
- 239000004220 glutamic acid Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- DKPHLYCEFBDQKM-UHFFFAOYSA-H hexapotassium;1-phosphonato-n,n-bis(phosphonatomethyl)methanamine Chemical compound [K+].[K+].[K+].[K+].[K+].[K+].[O-]P([O-])(=O)CN(CP([O-])([O-])=O)CP([O-])([O-])=O DKPHLYCEFBDQKM-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- YACKEPLHDIMKIO-UHFFFAOYSA-N methylphosphonic acid Chemical compound CP(O)(O)=O YACKEPLHDIMKIO-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- SKVFQANNTIZUQZ-UHFFFAOYSA-N n-[2-[bis[hydroxy(methoxy)phosphoryl]amino]ethyl]-n-[hydroxy(methoxy)phosphoryl]-methoxyphosphonamidic acid Chemical compound COP(O)(=O)N(P(O)(=O)OC)CCN(P(O)(=O)OC)P(O)(=O)OC SKVFQANNTIZUQZ-UHFFFAOYSA-N 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical compound [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- WSHYKIAQCMIPTB-UHFFFAOYSA-M potassium;2-oxo-3-(3-oxo-1-phenylbutyl)chromen-4-olate Chemical compound [K+].[O-]C=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 WSHYKIAQCMIPTB-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- 239000004474 valine Substances 0.000 description 1
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical class [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 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
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
Description
【発明の詳細な説明】
本発明は、一般に、ホウ素含量が高い無電解ニ
ツケルホウ素析出物に関する。さらに詳しくは、
使用する浴は、PHが比較的低くかつ温度が比較的
低いボラン還元浴であり、前記浴はジルコニルイ
オンおよび／またはバナジルイオンの源を含める
ことにより、高い百分率のホウ素を析出する。DETAILED DESCRIPTION OF THE INVENTION The present invention generally relates to electroless nickel boron deposits with high boron content. For more details,
The bath used is a borane reducing bath with relatively low pH and relatively low temperature, said bath containing a source of zirconyl and/or vanadyl ions to precipitate a high percentage of boron.
ニツケルおよびホウ素の無電解同時析出は、ニ
ツケルイオン源とボラン還元剤を含む無電解ニツ
ケル浴中に支持体を含めることによつて達成され
る。99.9％のニツケルまでの実質的に純粋なニツ
ケル析出物と比べたとき、析出物の硬度を増大す
るためには、ホウ素含量が比較的高い析出物を形
成することが、しばしば望ましい。しかしなが
ら、伝統的に、ボラン還元浴は、同時析出物中に
形成できるホウ素の百分率を調節する能力に関し
てきびしく制限され、そしてホウ素含量が２重量
％以上程度に比較的高い同時析出物の形成にこと
に不適当である。これらのボラン還元析出物は、
一般に、浴のPHおよび浴のボラン還元剤の安定性
によつて制限される。 Electroless co-deposition of nickel and boron is accomplished by including the support in an electroless nickel bath containing a nickel ion source and a borane reducing agent. It is often desirable to form a precipitate with a relatively high boron content to increase the hardness of the precipitate when compared to substantially pure nickel precipitates up to 99.9% nickel. However, traditionally, borane reducing baths have been severely limited in their ability to control the percentage of boron that can be formed in the co-precipitate, and have been susceptible to the formation of co-precipitates with relatively high boron contents, on the order of 2% by weight or more. It is inappropriate for These borane-reduced precipitates are
Generally limited by the bath PH and the stability of the bath borane reducing agent.
さらに詳しくは、ボラン還元浴のPHが減少する
につれて、ニツケルと同時析出するホウ素の百分
率は増加する。しかしながら、ボランは低いPH値
において加水分解するので、ボラン還元剤は安定
性を失い始め、こうしてPHが４以下に減少するに
つれて、急速に消費される。ホウ素含量が高い析
出物を形成するボラン還元無電解ニツケル浴は低
いPHでなくてはならないが、低いPHの浴はホウ素
還元剤を商業的に許容され得ない過度の速度で消
費する。したがつて、ホウ素還元同時析出物のホ
ウ素含量はPHを低下することによつて増加するこ
とができるが、この能力は、PHが高いホウ素の析
出物を生成するレベルに低下するとき、商業的に
許容しうる速度で消費されるという事実によつて
制限される。一般に、ボラン消費の許容しうるレ
ベルの観点から商業的に生き残れるボラン還元浴
は、５をかなり超えるPHをもつべきである。 More specifically, as the PH of the borane reduction bath decreases, the percentage of boron co-deposited with nickel increases. However, since borane hydrolyzes at low PH values, the borane reducing agent begins to lose stability and is thus rapidly consumed as the PH decreases below 4. Borane-reducing electroless nickel baths that form precipitates with high boron content must have low PH, but low PH baths consume boron reducing agent at excessive rates that are not commercially acceptable. Therefore, although the boron content of boron-reduced co-precipitates can be increased by lowering the PH, this ability is limited by commercial limited by the fact that it is consumed at an acceptable rate. Generally, a commercially viable borane reduction bath in terms of acceptable levels of borane consumption should have a PH well above 5.
ニツケル−ホウ素無電解析出物のホウ素含量
は、ボラン還元剤よりはむしろホウ水素化物のイ
オンを浴中に還元剤として使用することによつて
増加できるが、ホウ水素化物還元浴、このような
浴が13を超えるPHおよび90℃を超える温度におい
て操作されるときにのみ、ホウ素含量の高い析出
物を形成する。これらは比較的きびしい条件であ
り、商業的無電解めつき作業を維持するためには
望ましくない。しかし、ホウ水素化物還元浴を約
12以下のPHに低下させると、この浴は自発的に溶
液分解を起こす。 Although the boron content of the nickel-boron electroless deposit can be increased by using borohydride ions as the reducing agent in the bath, rather than a borane reducing agent, borohydride reducing baths, such baths forms a precipitate with high boron content only when operated at a PH above 13 and a temperature above 90 °C. These are relatively harsh conditions and are undesirable for maintaining commercial electroless plating operations. However, the borohydride reducing bath
When lowered to a pH below 12, this bath undergoes spontaneous solution decomposition.
本発明によれば、ボラン還元無電解析出浴から
無電解ニツケル−ホウ素析出物の約２％のホウ素
を超える高いホウ素百分率として認識されている
ものを達成し、そしてホウ水素化物イオンの使用
を回避しかつそれに関連する高いPHおよび高い温
度の条件を回避する、方法が発見された。本発明
による浴は、ボラン還元であり、そして比較的適
度の温度および適度のPHを含む。このような本発
明による浴は、ボラン還元浴内にジルコニルイオ
ンおよび／またはバナジルイオンの源を含む。 According to the present invention, we achieve what is recognized as a high boron percentage in excess of about 2% boron in electroless nickel-boron deposits from borane-reducing electroless deposition baths, and avoid the use of borohydride ions. A method has been discovered that avoids the high PH and high temperature conditions associated therewith. The bath according to the invention is borane reducing and contains relatively moderate temperature and moderate PH. Such a bath according to the invention comprises a source of zirconyl ions and/or vanadyl ions within a borane reduction bath.
したがつて、本発明によれば、ニツケル−ホウ
素析出物が比較的高いホウ素含量を有することに
よつて特徴づけられる、改良された無電解ニツケ
ル浴、製品および方法を提供することである。 Accordingly, it is an object of the present invention to provide improved electroless nickel baths, products and methods in which the nickel-boron deposit is characterized by a relatively high boron content.
本発明の他の目的は、ボラン還元剤を含有し、
そして比較的高い重量百分率のホウ素を有する析
出物を形成する、改良された無電解ニツケル析出
浴である。 Another object of the invention is to contain a borane reducing agent,
and an improved electroless nickel deposition bath that forms a deposit having a relatively high weight percentage of boron.
本発明の他の目的は、適度のPHと比較的適度な
温度を有する浴が２重量％程度を超えるホウ素含
量を有するニツケル−ホウ素同時析出物を形成す
る、改良された無電解析出系である。 Another object of the present invention is an improved electroless deposition system in which a bath having a moderate PH and a relatively moderate temperature forms a nickel-boron co-precipitate having a boron content on the order of 2% by weight. .
本発明の他の目的は、実質的に純粋な無電解ニ
ツケル析出物のそれより増大した硬度を有するニ
ツケル析出物を析出するための、改良された無電
解浴である。 Another object of the present invention is an improved electroless bath for depositing nickel deposits having increased hardness than that of substantially pure electroless nickel deposits.
本発明のこれらの目的および他の目的は、以後
の詳細な説明から明らかとなるであろう。 These and other objects of the invention will become apparent from the detailed description that follows.
本発明によれば、ニツケル−ホウ素析出物を支
持体上に形成し、そしてホウ素析出増進剤例えば
ジルコニルイオン、バナジルイオンまたはそれら
の組み合わせ、ならびにホウ素還元剤およびニツ
ケル源を含む、無電解ニツケル浴が提供される。
他の典型的な無電解ニツケル浴成分、たとえば、
錯化剤、安定剤、緩衝剤などを含むことができ
る。 According to the present invention, an electroless nickel bath is provided in which a nickel-boron deposit is formed on a support and includes a boron deposition enhancer such as zirconyl ions, vanadyl ions or a combination thereof, and a boron reducing agent and a nickel source. provided.
Other typical electroless nickel bath components, e.g.
Complexing agents, stabilizers, buffers, etc. can be included.
ホウ素析出増進剤は、浴中のホウ素還元剤へ追
加の安定性を付与すると同時に、また適度なPH値
においてホウ素析出能力を増大すると、信じられ
る。ジルコニルイオンホウ素析出増進剤は、浴
へ、ジルコニルイオン（ZrO++）を遊離する化合
物、たとえば、塩化ジルコニルハ水和物
（ZrOCl2・8H2O）によつて加えられる。バナジ
ルイオン（VO++）ホウ素析出増進剤は、硫酸バ
ナジルまたはオキシ硫酸バナジウム（VOSO4・
2H2O）または他のバナジル塩のような化合物に
より、ならびにナトリウムメタバナデートのよう
なバナデートにより、供給することができ、前記
バナデートは浴内の有機化合物を酸化し、それは
還元されてバナジルイオンを浴内に供給する。 It is believed that the boron deposition enhancer provides additional stability to the boron reducing agent in the bath while also increasing boron deposition ability at moderate PH values. Zirconyl ion boron precipitation enhancers are added to the bath by compounds that liberate zirconyl ions (ZrO ++ ), such as zirconyl chloride hahydrate (ZrOCl 2 .8H 2 O). Vanadyl ion (VO ++ ) boron precipitation enhancer is vanadyl sulfate or vanadium oxysulfate ( VOSO4 .
2H 2 O) or other vanadyl salts, as well as by vanadates such as sodium metavanadate, which oxidizes organic compounds in the bath, which are reduced to vanadyl ions. is supplied into the bath.
ホウ素析出増進剤は、特定の増進剤がホウ素の
析出百分率を増加する下限と、経済性および浴の
安定性を考慮して決定される上限とを有する濃度
において、浴内へ含められる。増進剤は、本発明
に従い、少なくとも約0.0005モル／の濃度で含
められる。浴内のホウ素析出増進剤の典型的な濃
度は、少なくとも0.0005モル／、好ましくは少
なくとも約0.0007モル／、最も好ましくは少な
くともよく0.001モル／である。通常、これら
のホウ素析出増進剤を0.5モル／を超える浴濃
度で含める必要はなく、好ましくはその濃度は
0.1モル／以下である。 The boron precipitation enhancer is included in the bath at a concentration that has a lower limit at which the particular enhancer will increase the percent boron precipitation and an upper limit determined by economics and bath stability considerations. Enhancing agents are included in accordance with the present invention at a concentration of at least about 0.0005 mol/ml. Typical concentrations of boron precipitation enhancer in the bath are at least 0.0005 mole/, preferably at least about 0.0007 mole/, and most preferably at least well 0.001 mole/. Typically, it is not necessary to include these boron precipitation enhancers at bath concentrations greater than 0.5 mol/l, and preferably the concentration is
It is 0.1 mol/or less.
本発明による浴中に利用するボラン還元剤は、
浴可溶性ボラン源、たとえば、アミンボラン、低
級アルキル置換アミンボラン、および窒素含有複
素環式ボランたとえばピリジンおよびモルホリン
ボランを含有する。一般に、アルキルアミンボラ
ン、ことにジメチルアミンボランは好ましい。こ
れらの浴内の還元剤の濃度は、適切な還元を実施
するために十分でありかつまた浴内のニツケル陽
イオンの還元にコスト的に効率よい濃度である。
典型的な最小濃度は、少なくとも約0.001モル／
、より通常少なくとも0.005モル／であるが、
１モル／程度に多くを含めることができるが、
通常約0.1モル／以下を含めることが必要であ
る。 The borane reducing agent utilized in the bath according to the present invention is
Contains bath-soluble borane sources such as amine borane, lower alkyl substituted amine borane, and nitrogen-containing heterocyclic borane such as pyridine and morpholine borane. In general, alkylamine borane, especially dimethylamine borane, is preferred. The concentration of reducing agent in these baths is sufficient to effect adequate reduction and is also cost effective for reducing the nickel cations within the bath.
Typical minimum concentrations are at least about 0.001 mole/
, more usually at least 0.005 mol/, but
Although a large amount can be contained in 1 mol/degree,
It is usually necessary to include about 0.1 mole or less.
これらの浴のためのニツケル源は、浴可溶性ニ
ツケル源、たとえば、硫酸塩、塩化物、スルフア
ミン酸塩、または無電解ニツケル系と適合性の他
の陰イオンである。利用する濃度は、無電解ニツ
ケルめつき浴に典型的であり、約0.001モル／
〜約0.5モル／の間程度である。 The nickel source for these baths is a bath-soluble nickel source, such as sulfate, chloride, sulfamate, or other anion compatible with the electroless nickel system. The concentration utilized is typical for electroless nickel plating baths, approximately 0.001 mol/
~0.5 mol/mole.
たいていの無電解ニツケルめつき浴の場合のよ
うに、これらの浴は錯化剤をしばしば含み、そし
てほとんどいかなる型の錯化剤も適当であり、そ
して錯化剤は入手容易性、経済性、および浴によ
り形成される析出物の増大したホウ素含量のそれ
に加えて特定の浴に望む性質に依存して、選択す
ることができる。錯化剤は、一般に、浴可溶性の
カルボン酸および浴可溶性のその誘導体、たとえ
ば、ヒドロキシ置換カルボン酸、アミノ置換カル
ボン酸、およびそれらの浴可溶性誘導体、たとえ
ば、浴可溶性の無水物、塩またはエステルであ
る。他の錯化剤の例は、米国特許第4019910号
（Mallory）に記載されているような、オキシ酸
と多価の酸またはアルコールとの反応により形成
された多価化合物のエステル錯体である。他の錯
体の例は、ピロリン酸およびその誘導体ならびに
有機リン錯化剤たとえばホスホネートである。 As is the case with most electroless nickel plating baths, these baths often contain a complexing agent, and almost any type of complexing agent is suitable, and the complexing agent may be a complexing agent due to availability, economy, and the increased boron content of the precipitate formed by the bath, as well as the properties desired for the particular bath. Complexing agents are generally bath-soluble carboxylic acids and bath-soluble derivatives thereof, such as hydroxy-substituted carboxylic acids, amino-substituted carboxylic acids, and bath-soluble derivatives thereof, such as bath-soluble anhydrides, salts or esters. be. Examples of other complexing agents are ester complexes of polyhydric compounds formed by the reaction of oxyacids with polyhydric acids or alcohols, as described in US Pat. No. 4,019,910 (Mallory). Examples of other complexes are pyrophosphoric acid and its derivatives and organophosphorus complexing agents such as phosphonates.
特定のヒドロキシ置換カルボン酸の錯化剤の例
は、クエン酸、グリコール酸、乳酸およびリンゴ
酸であるが、アミノ置換カルボン酸の酸化剤の例
はβ−アラニン、アミノ錯酸、アミノジ酢酸、お
よびアミノ酸、たとえばα−アラニン、アスパラ
ギン酸、グルタミン酸、グリシン、ロイシン、セ
リン、トリオシン、およびバリンである。オキシ
酸と多価の酸またはアルコールとのエステル錯体
のカテゴリー内に入る錯化剤は、オキシ酸を、１
分子当り少なくとも２価のヒドロキシル基と約４
〜約15個の炭素原子を含有するカルボン酸または
アルコール化合物と反応させることによつて製造
されたエステル錯体を包含する。典型的な適当な
多価化合物の例は、カルボン酸、たとえば、酒石
酸、グルコン酸またはグルコヘプトン酸、および
アルコール、たとえば、マンニトール、２，３−
ブタンジオールおよび１，２，３−プロパントリ
オールである。エステルを形成するとき使用する
オキシ酸は、一般に無機酸、たとえば、ホウ酸、
タングステン酸、モリブデン酸またはクロム酸で
ある。通常、このようなエステル形成錯体は、２
モル以上のオキシ酸と１モルの多価化合物との反
応により形成されたエステル錯体である、ポリエ
ステルの形である。 Examples of complexing agents for certain hydroxy-substituted carboxylic acids are citric acid, glycolic acid, lactic acid and malic acid, while examples of oxidizing agents for amino-substituted carboxylic acids are β-alanine, amino complex acids, aminodiacetic acid, and Amino acids such as alpha-alanine, aspartic acid, glutamic acid, glycine, leucine, serine, triocine, and valine. Complexing agents that fall within the category of ester complexes of oxyacids and polyhydric acids or alcohols
at least divalent hydroxyl groups per molecule and about 4
Includes ester complexes prepared by reaction with carboxylic acid or alcohol compounds containing ~15 carbon atoms. Examples of typical suitable polyhydric compounds are carboxylic acids such as tartaric acid, gluconic acid or glucoheptonic acid, and alcohols such as mannitol, 2,3-
butanediol and 1,2,3-propanetriol. The oxyacid used in forming the ester is generally an inorganic acid, such as boric acid,
Tungstic acid, molybdic acid or chromic acid. Typically, such ester-forming complexes contain 2
It is in the form of polyester, which is an ester complex formed by the reaction of one or more moles of an oxyacid with one mole of a polyhydric compound.
ホスホネート錯化剤の例は、アミノトリ（メチ
レンホスホン酸）およびその塩、たとえば、アミ
ノトリ（メチレンホスホネート）のペンタナトリ
ウム塩、１−ヒドロキシエチリデン−１，１−ジ
ホスホン酸およびその塩、たとえば、１−ヒドロ
キシエチリデン−１，１−ジホスホン酸のトリナ
トリウム塩、エチレンジアミンテトラ（メチルホ
スホン酸）およびその塩、および１，６−ジアミ
ノヘキサンテトラ（メチルホスホン酸）およびそ
のアルカリ金属およびアルカリ土類金属の塩であ
る。 Examples of phosphonate complexing agents are aminotri(methylenephosphonic acid) and its salts, e.g. pentasodium salt of aminotri(methylenephosphonate), 1-hydroxyethylidene-1,1-diphosphonic acid and its salts, e.g. 1-hydroxy The trisodium salt of ethylidene-1,1-diphosphonic acid, ethylenediaminetetra (methylphosphonic acid) and its salts, and 1,6-diaminohexanetetra (methylphosphonic acid) and its alkali metal and alkaline earth metal salts.
錯化剤の濃度は、もちろん、浴に含める特定の
錯化剤に多少依存する。一般に、浴内の錯化剤
は、少なくとも約0.0005モル／であり、そして
浴の溶解度の制限および経済性を考慮して高くあ
ることができるが、通常約1.5モル／以下であ
る。典型的な範囲は、約0.005〜約１モル／、
ことに錯化剤がカルボン酸であるとき、好ましく
は約0.1〜0.7モル／である。 The concentration of complexing agent will, of course, depend somewhat on the particular complexing agent included in the bath. Generally, the complexing agent in the bath will be at least about 0.0005 mole/ml, and can be higher to account for bath solubility limitations and economics, but usually less than about 1.5 mole/ml. Typical ranges are from about 0.005 to about 1 mole/
Particularly when the complexing agent is a carboxylic acid, it is preferably about 0.1 to 0.7 mol/mol.
これらの浴は、任意に安定剤、たとえば、カル
ボン酸型のもの、イオウイオンの含量を調節する
ためのアンチモン源または鉛源、またはイオウ含
有化合物、たとえば、チオ尿素またはそれとの組
み合わせ、たとえば、チオジグリコール酸を含む
ことができる。イオウ含有化合物を加えるときは
いつでも、過度のイオウは析出物のホウ素含量を
減少するので、イオウ含量を注意して調節しなく
てはならない。いずれのこのようなイオウの添加
も、最大のイオウ濃度が２価のイオウとして約
20ppmであるように、監視すべきである。それ以
外、安定剤を浴へ加えるとき、安定剤は特定の化
合物について典型的な濃度である。 These baths optionally contain stabilizers, e.g. of the carboxylic acid type, antimony or lead sources to adjust the content of sulfur ions, or sulfur-containing compounds, e.g. thiourea or combinations thereof, e.g. Diglycolic acid may be included. Whenever a sulfur-containing compound is added, the sulfur content must be carefully controlled as excessive sulfur will reduce the boron content of the precipitate. Any such sulfur addition will result in a maximum sulfur concentration as divalent sulfur of approximately
20ppm should be monitored. Otherwise, when adding the stabilizer to the bath, the stabilizer will be at a concentration that is typical for the particular compound.
この系中に典型的な浴濃度において含めること
ができる他の組成物の例は、緩衝剤、緩衝系、同
時析出増剤、およびPH調整剤、たとえば、強塩基
である。ポリアロイ析出物は、浴可溶性化合物、
たとえば、多価の酸またはアルコールを、ニツケ
ルおよび他の金属とのポリアロイの一部分として
析出すべき金属のオキシ酸と反応させることによ
つて製造されたエステル錯体である錯化剤、を含
めることによつて達成できる。 Examples of other compositions that can be included in this system at typical bath concentrations are buffers, buffer systems, co-deposition enhancers, and PH modifiers, such as strong bases. Polyalloy precipitates contain bath-soluble compounds,
For example, the inclusion of complexing agents that are ester complexes made by reacting polyhydric acids or alcohols with the oxyacids of the metals to be deposited as part of polyalloys with nickel and other metals. It can be achieved.
本発明による方法を実施するとき、高いホウ素
含量を有するニツケル−ホウ素同時析出物は、ジ
ルコニルイオンおよび／またはバナジルイオンの
源を含む、適度のPHおよび適度の温度を有するホ
ウ素還元無電解ニツケル浴から析出することによ
つて、形成される。操作PHは13より小、典型的に
は４〜10であり、そして適度の条件下で進行さ
せ、同時になお高いホウ素の析出物を形成すると
いう、この方法の能力の最大の利点を得るために
は、好ましくは浴のPHは約５〜７に維持し、その
間温度は90℃以下、典型的には約60〜約70℃に維
持される。この方法により、浴中のニツケル源か
らのニツケルは還元剤からのホウ素と同時に析出
し、この同時析出物は、析出物の合計重量に基づ
いて、２重量％を超えるホウ素を含む。 When carrying out the process according to the invention, a nickel-boron co-precipitate with a high boron content is obtained from a boron-reduced electroless nickel bath with a moderate PH and a moderate temperature, containing a source of zirconyl ions and/or vanadyl ions. It is formed by precipitation. The operating PH is less than 13, typically between 4 and 10, and is carried out under moderate conditions to take full advantage of the method's ability to still form high boron precipitates. The pH of the bath is preferably maintained between about 5 and 7, while the temperature is maintained below 90°C, typically between about 60 and about 70°C. By this method, nickel from the nickel source in the bath is co-precipitated with boron from the reducing agent, and this co-precipitate contains more than 2% by weight boron, based on the total weight of the precipitate.
この方法は、浴可溶性ニツケル源、浴可溶性ボ
ラン還元剤、浴へ加えたときバナジルイオンおよ
び／またはジルコニルイオンを遊離するホウ素析
出増進剤を、好ましくは無電解浴錯化剤と組み合
わせて、含む無電解析出浴を調整することからな
る。浴の調製は、任意に、１種もしくは２以上の
安定剤、イオウイオン含量調節剤、緩衝剤、緩衝
剤系、ポリアロイ析出源、同時析出増進剤などを
添加することを含むことができる。典型的には、
浴のPHを所望の適度なPH範囲内に調整することが
必要であり、これは通常強塩基、たとえば、水酸
化物を加え、あるいはPHが高過ぎるとき、強酸、
たとえば、硫酸または他の鉱酸を加えることによ
つて、行う。 The process comprises an electroless bath-soluble nickel source, a bath-soluble borane reducing agent, a boron precipitation enhancer that liberates vanadyl ions and/or zirconyl ions when added to the bath, preferably in combination with an electroless bath complexing agent. It consists of adjusting the analysis bath. Preparation of the bath can optionally include adding one or more stabilizers, sulfur ion content regulators, buffers, buffer systems, polyalloy precipitation sources, co-precipitation enhancers, and the like. Typically,
It is necessary to adjust the PH of the bath to within the desired moderate PH range, and this is usually done by adding a strong base, e.g. hydroxide, or, if the PH is too high, by adding a strong acid,
For example, by adding sulfuric acid or other mineral acids.
浸漬すべき支持体は、このように調製した浴へ
浸漬する。この浴によつて形成されるニツケル−
ホウ素同時析出物の重さまたは厚さは、もちろ
ん、めつき速度および支持体の浴内の浸漬時間と
ともに変化する。この方法によるめつき速度は約
0.2〜約0.5ミル（約0.0051〜約0.0127mm）／時で
あり、そして典型的な槽の負荷は約0.25〜1.0平
方フイート／浴ガロン（約0.006〜0.025m2／浴
）である。 The support to be immersed is immersed in the bath thus prepared. Nickel formed by this bath
The weight or thickness of the boron co-deposit will, of course, vary with the plating rate and the immersion time of the support in the bath. The plating speed using this method is approx.
0.2 to about 0.5 mils/hour, and typical bath loadings are about 0.25 to 1.0 square feet/bath gallon (about 0.006 to 0.025 m<2> /bath).
本発明に従つて製造される製品は、金属および
非金属の両者の支持体を含み、前記支持体は少な
くとも約２重量％のホウ素含量を有する無電解ニ
ツケル−ホウ素同時析出物の保護被膜でめつきさ
れており、前記析出物は本発明に従う浴によつて
形成されている。これらの製品は、析出物の重量
に基づいて、５重量％程度に高くあるいはそれよ
り高いホウ素含量を有することができる。通常、
析出物の残部はニツケルであろう。このような同
時析出物は、800〜1000VHN50程度の増大した硬
度を示す。 Articles made in accordance with the present invention include both metallic and non-metallic supports, said supports being covered with a protective coating of an electroless nickel-boron co-deposit having a boron content of at least about 2% by weight. and the precipitate is formed by the bath according to the invention. These products can have boron contents as high as 5% by weight or higher, based on the weight of the precipitate. usually,
The remainder of the precipitate will be nickel. Such co-precipitates exhibit increased hardness of the order of 800-1000 VHN 50 .
次の実施例により、本発明をさらに説明する。 The following examples further illustrate the invention.
実施例
0.3モル／の乳酸、0.08モル／のクエン酸、
0.04モル／のジメチルアミノボラン、0.01モ
ル／の塩化ジルコニルハ水和物、0.01モル／
のニツケル、およびPH0.6を維持するために十分
な水酸化アンモニウムを含む無電解浴を調製し
た。この浴を65℃に加熱し、その中に支持体を浸
漬し、その時4.1重量％のホウ素と95.5重量％の
ニツケルとの析出物が形成した。Example 0.3 mol/lactic acid, 0.08 mol/citric acid,
0.04 mol/dimethylaminoborane, 0.01 mol/zirconyl chloride hahydrate, 0.01 mol/
of nickel, and sufficient ammonium hydroxide to maintain a pH of 0.6. This bath was heated to 65° C. and the support was immersed therein, when a precipitate of 4.1% by weight boron and 95.5% by weight nickel formed.
実施例
次の成分を水性浴へ加えることによつて、他の
無電解ニツケル浴を調製した：0.3モル／の乳
酸、0.08モル／の乳酸、0.08モル／のクエン
酸、0.04モル／のジメチルアミンボラン、
0.001モル／の硫酸バナジル、0.01モル／の
ニツケル、および浴のPHを70℃において6.0とす
るための濃度の水酸化アンモニウム。3.6重量％
のホウ素と96.4重量％のニツケルを含有する析出
組成物が、形成した。EXAMPLE Another electroless nickel bath was prepared by adding the following ingredients to an aqueous bath: 0.3 mol/lactic acid, 0.08 mol/lactic acid, 0.08 mol/citric acid, 0.04 mol/dimethylamine. Boran,
0.001 mole/vanadyl sulfate, 0.01 mole/nickel, and ammonium hydroxide in a concentration to bring the pH of the bath to 6.0 at 70°C. 3.6% by weight
A precipitated composition containing 96.4% by weight of boron and 96.4% by weight of nickel was formed.
Claims (1)
ニルイオン、バナジルイオン、およびそれらの組
み合わせから成る群より選ばれたイオン源であ
る、ことを特徴とする、ホウ素の百分率が比較的
高いニツケルホウ素析出物を形成するための無電
解ニツケル浴。 ２ 前記ホウ素析出増進化合物はジルコニル塩ま
たはバナジル塩である特許請求の範囲第１項記載
の無電解浴。 ３ 前記ホウ素析出増進化合物は、塩化ジルコニ
ル、硫酸バナジル、メタバナジン酸ナトリウム、
およびそれらの組み合わせから成る群より選ばれ
る特許請求の範囲第１項記載の無電解浴。 ４ 前記ホウ素析出増進化合物は、合計の浴体積
に基づいて、少なくとも約0.0005モル／の濃度
で浴内に含まれる特許請求の範囲第１項記載の無
電解浴。 ５ 前記還元剤はアミンボランまたは環式アミン
ボランである特許請求の範囲第１項記載の無電解
浴。 ６ 前記ボラン還元剤は、合計の浴体積に基づい
て、少なくとも約0.001モル／の濃度で浴内に
含まれる特許請求の範囲第１項記載の無電解浴。 ７ 前記浴は、合計の浴体積に基づいて、少なく
とも約0.0005モル／の濃度で錯化剤をさらに含
む特許請求の範囲第１項記載の無電解浴。 ８ 錯化剤をさらに含み、前記錯化剤はカルボン
酸またはその浴可溶性誘導体である特許請求の範
囲第１項記載の無電解浴。 ９ 錯化剤をさらに含み、前記錯化剤はヒドロキ
シ置換カルボン酸である特許請求の範囲第１項記
載の無電解浴。 １０ 錯化剤をさらに含み、前記錯化剤は、オキ
シ酸と多価の酸もしくはアルコールとのエステル
錯体である特許請求の範囲第１項記載の無電解
浴。 １１ 錯化剤をさらに含み、前記錯化剤は有機リ
ン酸の錯化剤である特許請求の範囲第１項記載の
無電解浴。 １２ 前記浴は安定剤をさらに含む特許請求の範
囲第１項記載の無電解浴。 １３ 前記浴は緩衝剤をさらに含む特許請求の範
囲第１項記載の無電解浴。 １４ 前記浴は同時析出増進剤をさらに含む特許
請求の範囲第１項記載の無電解浴。 １５ 前記浴は90℃以下の温度である特許請求の
範囲第１項記載の無電解浴。 １６ 前記浴は13より小さいPHである特許請求の
範囲第１項記載の無電解浴。 １７ 前記浴は約５〜約７のPHである特許請求の
範囲第１項記載の無電解浴。 １８ 支持体を無電解ニツケル浴中へ浸漬し、そ
してその上にニツケル−ホウ素析出物を析出する
ことからなり、前記浴は、 浴可溶性ニツケル源、 浴可溶性ボラン還元剤、および 浴可溶性ホウ素析出増進化合物、 からなり、前記ホウ素析出増進化合物は、ジルコ
ニルイオン、バナジルイオン、およびそれらの組
み合わせから成る群より選ばれたイオン源である
ことを特徴とする、ニツケル−ホウ素無電解析出
のホウ素含量を増加する方法。 １９ 前記浴を90℃以下の温度に維持する特許請
求の範囲第１８項記載の方法。 ２０ 前記浴を13より小さいPHに維持する特許請
求の範囲第１８項記載の方法。 ２１ 前記浴は約４〜約10のPHに維持する特許請
求の範囲第１８項記載の方法。 ２２ 前記浴は約５〜約７のPHに維持する特許請
求の範囲第１８項記載の方法。 ２３ 前記浴は浴可溶性錯化剤をさらに含む特許
請求の範囲第１８項記載の方法。 ２４ 前記析出工程は、析出物の合計重量に基づ
いて、少なくとも約２重量％のホウ素を含む析出
物を形成する特許請求の範囲第１８項記載の方
法。[Scope of Claims] 1. An electroless nickel bath comprises: a bath-soluble nickel source, a bath-soluble borane reducing agent, and a bath-soluble boron precipitation enhancement compound, wherein the boron precipitation enhancement compound includes zirconyl ions, vanadyl ions, and the like. An electroless nickel bath for forming a nickel-boron deposit having a relatively high percentage of boron, characterized in that the ion source is selected from the group consisting of a combination of 2. The electroless bath according to claim 1, wherein the boron precipitation enhancing compound is a zirconyl salt or a vanadyl salt. 3 The boron precipitation enhancing compound includes zirconyl chloride, vanadyl sulfate, sodium metavanadate,
and a combination thereof. 4. The electroless bath of claim 1, wherein the boron precipitation enhancing compound is included in the bath at a concentration of at least about 0.0005 mole/based on total bath volume. 5. The electroless bath according to claim 1, wherein the reducing agent is an amine borane or a cyclic amine borane. 6. The electroless bath of claim 1, wherein the borane reducing agent is included in the bath at a concentration of at least about 0.001 mole/mole/based on total bath volume. 7. The electroless bath of claim 1, wherein the bath further comprises a complexing agent at a concentration of at least about 0.0005 mole/based on total bath volume. 8. The electroless bath according to claim 1, further comprising a complexing agent, wherein the complexing agent is a carboxylic acid or a bath-soluble derivative thereof. 9. The electroless bath according to claim 1, further comprising a complexing agent, the complexing agent being a hydroxy-substituted carboxylic acid. 10. The electroless bath according to claim 1, further comprising a complexing agent, wherein the complexing agent is an ester complex of an oxyacid and a polyhydric acid or alcohol. 11. The electroless bath according to claim 1, further comprising a complexing agent, wherein the complexing agent is an organic phosphoric acid complexing agent. 12. The electroless bath of claim 1, wherein the bath further comprises a stabilizer. 13. The electroless bath according to claim 1, wherein the bath further comprises a buffer. 14. The electroless bath of claim 1, wherein the bath further comprises a co-deposition enhancer. 15. The electroless bath according to claim 1, wherein the bath has a temperature of 90°C or less. 16. The electroless bath of claim 1, wherein said bath has a pH of less than 13. 17. The electroless bath of claim 1, wherein said bath has a pH of about 5 to about 7. 18 consisting of immersing the support in an electroless nickel bath and depositing a nickel-boron deposit thereon, the bath comprising: a bath-soluble nickel source, a bath-soluble borane reducing agent, and a bath-soluble boron precipitation enhancer. increasing the boron content of nickel-boron electroless deposition, wherein the boron precipitation enhancing compound is an ion source selected from the group consisting of zirconyl ions, vanadyl ions, and combinations thereof. how to. 19. The method of claim 18, wherein the bath is maintained at a temperature of 90°C or less. 20. The method of claim 18, wherein the bath is maintained at a pH of less than 13. 21. The method of claim 18, wherein said bath is maintained at a pH of about 4 to about 10. 22. The method of claim 18, wherein the bath is maintained at a pH of about 5 to about 7. 23. The method of claim 18, wherein the bath further comprises a bath-soluble complexing agent. 24. The method of claim 18, wherein the precipitation step forms a precipitate containing at least about 2% by weight boron, based on the total weight of the precipitate.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US29552381A | 1981-08-24 | 1981-08-24 | |
| US295523 | 1981-08-24 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS5842766A JPS5842766A (en) | 1983-03-12 |
| JPH0153352B2 true JPH0153352B2 (en) | 1989-11-14 |
Family
ID=23138067
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14675182A Granted JPS5842766A (en) | 1981-08-24 | 1982-08-24 | Adjustment of boron content in non-electrolytic nickel-boron deposit |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0073583B1 (en) |
| JP (1) | JPS5842766A (en) |
| CA (1) | CA1176404A (en) |
| DE (1) | DE3269823D1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4503131A (en) * | 1982-01-18 | 1985-03-05 | Richardson Chemical Company | Electrical contact materials |
| JPH01222064A (en) * | 1988-03-02 | 1989-09-05 | Hitachi Ltd | Chemical nickel plating solution and method for using same |
| JP2002226974A (en) * | 2000-11-28 | 2002-08-14 | Ebara Corp | ELECTROLESS Ni-B PLATING SOLUTION, ELECTRONIC DEVICE, AND MANUFACTURING METHOD THEREOF |
| US6645567B2 (en) | 2001-12-19 | 2003-11-11 | Intel Corporation | Electroless plating bath composition and method of using |
| JP5344416B2 (en) * | 2006-03-09 | 2013-11-20 | 奥野製薬工業株式会社 | Bending resistance improver for self-catalyzed electroless nickel plating solution and self-catalyzed electroless nickel plating solution |
| JP2013028866A (en) * | 2006-03-09 | 2013-02-07 | Okuno Chemical Industries Co Ltd | Electroless nickel plating liquid |
| CN111118480B (en) * | 2020-01-14 | 2022-02-11 | 常州大学 | Chemical plating solution for low-temperature chemical plating of Ni-B binary alloy layer and chemical plating method |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1198167B (en) * | 1958-11-26 | 1965-08-05 | Du Pont | Aqueous bath for the chemical deposition of coatings made of nickel-boron or cobalt-boron alloys |
| US4139660A (en) * | 1963-07-16 | 1979-02-13 | Bernhard Joos | Method for increasing solid surface tension |
| GB1360592A (en) * | 1973-02-14 | 1974-07-17 | Rca Corp | Electroless cobalt plating bath |
| US4019910A (en) * | 1974-05-24 | 1977-04-26 | The Richardson Chemical Company | Electroless nickel polyalloy plating baths |
| US4151311A (en) * | 1976-01-22 | 1979-04-24 | Nathan Feldstein | Post colloid addition of catalytic promoters to non noble metal principal catalytic compounds in electroless plating catalysts |
| IT1070268B (en) * | 1976-10-19 | 1985-03-29 | Alfachimici Spa | COMPOSITION FOR THE ANELECTRIC DEPOSITION OF NICKEL-BASED ALLOYS |
| US4259376A (en) * | 1977-09-16 | 1981-03-31 | Nathan Feldstein | Catalytic promoters in electroless plating catalysts applied as an emulsion |
| GB2066857A (en) * | 1980-01-07 | 1981-07-15 | Vmei Lenin Nis | >Method for the production of an abrasive surface |
-
1982
- 1982-07-14 CA CA000407217A patent/CA1176404A/en not_active Expired
- 1982-08-10 EP EP19820304210 patent/EP0073583B1/en not_active Expired
- 1982-08-10 DE DE8282304210T patent/DE3269823D1/en not_active Expired
- 1982-08-24 JP JP14675182A patent/JPS5842766A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS5842766A (en) | 1983-03-12 |
| DE3269823D1 (en) | 1986-04-17 |
| CA1176404A (en) | 1984-10-23 |
| EP0073583B1 (en) | 1986-03-12 |
| EP0073583A1 (en) | 1983-03-09 |
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