JP6352079B2 - Electroless plating solution, plating film, plating product and method for forming plating film - Google Patents
Electroless plating solution, plating film, plating product and method for forming plating film Download PDFInfo
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- JP6352079B2 JP6352079B2 JP2014137885A JP2014137885A JP6352079B2 JP 6352079 B2 JP6352079 B2 JP 6352079B2 JP 2014137885 A JP2014137885 A JP 2014137885A JP 2014137885 A JP2014137885 A JP 2014137885A JP 6352079 B2 JP6352079 B2 JP 6352079B2
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- 238000007747 plating Methods 0.000 title claims description 113
- 238000007772 electroless plating Methods 0.000 title claims description 59
- 238000000034 method Methods 0.000 title claims description 29
- 239000003945 anionic surfactant Substances 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 18
- 150000003856 quaternary ammonium compounds Chemical class 0.000 claims description 17
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 16
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 16
- 125000004432 carbon atom Chemical group C* 0.000 claims description 15
- 239000008139 complexing agent Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 11
- 150000002816 nickel compounds Chemical class 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 5
- PHIQHXFUZVPYII-ZCFIWIBFSA-O (R)-carnitinium Chemical compound C[N+](C)(C)C[C@H](O)CC(O)=O PHIQHXFUZVPYII-ZCFIWIBFSA-O 0.000 claims description 4
- IWSZDQRGNFLMJS-UHFFFAOYSA-N 2-(dibutylamino)ethanol Chemical compound CCCCN(CCO)CCCC IWSZDQRGNFLMJS-UHFFFAOYSA-N 0.000 claims description 4
- MIJDSYMOBYNHOT-UHFFFAOYSA-N 2-(ethylamino)ethanol Chemical compound CCNCCO MIJDSYMOBYNHOT-UHFFFAOYSA-N 0.000 claims description 4
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 4
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 4
- UEEJHVSXFDXPFK-UHFFFAOYSA-N N-dimethylaminoethanol Chemical compound CN(C)CCO UEEJHVSXFDXPFK-UHFFFAOYSA-N 0.000 claims description 4
- AKNUHUCEWALCOI-UHFFFAOYSA-N N-ethyldiethanolamine Chemical compound OCCN(CC)CCO AKNUHUCEWALCOI-UHFFFAOYSA-N 0.000 claims description 4
- OPKOKAMJFNKNAS-UHFFFAOYSA-N N-methylethanolamine Chemical compound CNCCO OPKOKAMJFNKNAS-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 229960004203 carnitine Drugs 0.000 claims description 4
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 claims description 4
- 229960001231 choline Drugs 0.000 claims description 4
- SUHOQUVVVLNYQR-MRVPVSSYSA-N choline alfoscerate Chemical compound C[N+](C)(C)CCOP([O-])(=O)OC[C@H](O)CO SUHOQUVVVLNYQR-MRVPVSSYSA-N 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 4
- 229960004956 glycerylphosphorylcholine Drugs 0.000 claims description 4
- CRVGTESFCCXCTH-UHFFFAOYSA-N methyl diethanolamine Chemical compound OCCN(C)CCO CRVGTESFCCXCTH-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 229960003682 rocuronium bromide Drugs 0.000 claims description 4
- OYTJKRAYGYRUJK-FMCCZJBLSA-M rocuronium bromide Chemical compound [Br-].N1([C@@H]2[C@@H](O)C[C@@H]3CC[C@H]4[C@@H]5C[C@@H]([C@@H]([C@]5(CC[C@@H]4[C@@]3(C)C2)C)OC(=O)C)[N+]2(CC=C)CCCC2)CCOCC1 OYTJKRAYGYRUJK-FMCCZJBLSA-M 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
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- GVNHOISKXMSMPX-UHFFFAOYSA-N 2-[butyl(2-hydroxyethyl)amino]ethanol Chemical compound CCCCN(CCO)CCO GVNHOISKXMSMPX-UHFFFAOYSA-N 0.000 claims description 3
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 52
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- -1 aliphatic sulfonic acid alkali metal salts Chemical class 0.000 description 7
- 150000003863 ammonium salts Chemical class 0.000 description 7
- 238000005259 measurement Methods 0.000 description 7
- 159000000000 sodium salts Chemical class 0.000 description 7
- 230000003746 surface roughness Effects 0.000 description 7
- 159000000001 potassium salts Chemical class 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 5
- 229910052759 nickel Inorganic materials 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 229910052783 alkali metal Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
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- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000007796 conventional method Methods 0.000 description 3
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- 150000002739 metals Chemical class 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- VZCYOOQTPOCHFL-OWOJBTEDSA-N Fumaric acid Chemical compound OC(=O)\C=C\C(O)=O VZCYOOQTPOCHFL-OWOJBTEDSA-N 0.000 description 2
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- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical class OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
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- 238000005238 degreasing Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-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
- QYIGOGBGVKONDY-UHFFFAOYSA-N 1-(2-bromo-5-chlorophenyl)-3-methylpyrazole Chemical compound N1=C(C)C=CN1C1=CC(Cl)=CC=C1Br QYIGOGBGVKONDY-UHFFFAOYSA-N 0.000 description 1
- XXSPKSHUSWQAIZ-UHFFFAOYSA-L 36026-88-7 Chemical compound [Ni+2].[O-]P=O.[O-]P=O XXSPKSHUSWQAIZ-UHFFFAOYSA-L 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-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
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical group OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- QPCDCPDFJACHGM-UHFFFAOYSA-N N,N-bis{2-[bis(carboxymethyl)amino]ethyl}glycine Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(=O)O)CCN(CC(O)=O)CC(O)=O QPCDCPDFJACHGM-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910001096 P alloy Inorganic materials 0.000 description 1
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 1
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 1
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- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000001413 amino acids Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001621 bismuth Chemical class 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
- RJTANRZEWTUVMA-UHFFFAOYSA-N boron;n-methylmethanamine Chemical compound [B].CNC RJTANRZEWTUVMA-UHFFFAOYSA-N 0.000 description 1
- 239000006172 buffering agent Substances 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 150000001991 dicarboxylic acids Chemical class 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- IFQUWYZCAGRUJN-UHFFFAOYSA-N ethylenediaminediacetic acid Chemical compound OC(=O)CNCCNCC(O)=O IFQUWYZCAGRUJN-UHFFFAOYSA-N 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000001530 fumaric acid Substances 0.000 description 1
- 239000000174 gluconic acid Substances 0.000 description 1
- 235000012208 gluconic acid Nutrition 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229940046892 lead acetate Drugs 0.000 description 1
- RLJMLMKIBZAXJO-UHFFFAOYSA-N lead nitrate Chemical compound [O-][N+](=O)O[Pb]O[N+]([O-])=O RLJMLMKIBZAXJO-UHFFFAOYSA-N 0.000 description 1
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 1
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- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000002763 monocarboxylic acids Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
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- 150000002940 palladium Chemical class 0.000 description 1
- 229960003330 pentetic acid Drugs 0.000 description 1
- OFNHPGDEEMZPFG-UHFFFAOYSA-N phosphanylidynenickel Chemical compound [P].[Ni] OFNHPGDEEMZPFG-UHFFFAOYSA-N 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-M phosphinate Chemical compound [O-][PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-M 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 150000003009 phosphonic acids Chemical class 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
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- 150000003464 sulfur compounds Chemical class 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- UVZICZIVKIMRNE-UHFFFAOYSA-N thiodiacetic acid Chemical compound OC(=O)CSCC(O)=O UVZICZIVKIMRNE-UHFFFAOYSA-N 0.000 description 1
Description
本発明は、無電解めっき液、めっき皮膜、めっき品及びめっき皮膜の形成方法に関する。 The present invention relates to an electroless plating solution, a plating film, a plated product, and a method for forming a plating film.
従来、電子部品を形成するプリント配線基板や、機械装置等の表面等の様々な分野において、めっき皮膜が形成されている。特に、機械装置のシャフト、軸受け等の摺動部には、耐摩耗性を付与することを目的として、微粒子を含有するめっき液により形成されためっき皮膜が形成される。 Conventionally, plating films have been formed in various fields such as printed wiring boards for forming electronic components and surfaces of mechanical devices. In particular, a plating film formed of a plating solution containing fine particles is formed on sliding parts such as shafts and bearings of mechanical devices for the purpose of imparting wear resistance.
上述のようなめっき液によりめっき皮膜を形成する方法として、ニッケル−リン合金をマトリックスとし、炭化ケイ素粒子を分散した複合メッキにおいて、メッキ後の過熱処理温度を４７０℃〜５３０℃とする複合メッキ方法が提案されている（例えば、特許文献１参照）。当該メッキ方法により形成されためっき皮膜は、皮膜中に炭化ケイ素粒子を含有するので、機械装置の摺動部等に用いた際に耐摩耗性を示す。 As a method for forming a plating film with the plating solution as described above, a composite plating method in which a post-plating overheat treatment temperature is 470 ° C. to 530 ° C. in a composite plating in which a nickel-phosphorus alloy is used as a matrix and silicon carbide particles are dispersed. Has been proposed (see, for example, Patent Document 1). Since the plating film formed by the plating method contains silicon carbide particles in the film, it exhibits wear resistance when used in a sliding portion of a mechanical device.
しかしながら、上述のようなめっき液を用いて機械装置の摺動部等に形成されためっき皮膜は、めっき皮膜自体が耐摩耗性を示すものの、摺動回数が増加するに従ってめっき皮膜表面の摩擦係数が増加して、当該めっき皮膜と摺れる他の部材の表面を摩耗させてしまうという問題がある。 However, the plating film formed on the sliding part of the mechanical device using the plating solution as described above, although the plating film itself exhibits wear resistance, the friction coefficient of the plating film surface as the number of sliding increases. Increases, and there is a problem that the surface of another member that slides on the plating film is worn.
耐摩耗性に優れ、他の部材との摺動回数が増加しても、めっき皮膜の表面の摩擦係数の増加が抑制されており、他の部材の摩耗が抑制されているめっき皮膜を形成することができる無電解めっき液は、未だ開発されていない。 Even if the number of times of sliding with other members increases with excellent wear resistance, the increase in the friction coefficient of the surface of the plating film is suppressed, and a plating film in which the wear of other members is suppressed is formed. An electroless plating solution that can be used has not yet been developed.
本発明は、耐摩耗性に優れ、他の部材との摺動回数が増加しても、めっき皮膜の表面の摩擦係数の増加が抑制されており、他の部材の摩耗が抑制されているめっき皮膜を形成することができる無電解めっき液、上記無電解めっき液により形成されためっき皮膜、上記めっき皮膜を有するめっき品及びめっき皮膜の形成方法を提供することを目的とする。 The present invention has excellent wear resistance, and even if the number of sliding with other members increases, the increase in the friction coefficient of the surface of the plating film is suppressed, and the plating in which the wear of other members is suppressed An object of the present invention is to provide an electroless plating solution capable of forming a film, a plating film formed with the electroless plating solution, a plated product having the plating film, and a method for forming the plating film.
本発明者は上記目的を達成すべく鋭意研究を重ねた結果、水溶性ニッケル化合物、還元剤、錯化剤及び炭化ケイ素粒子を必須成分として含有し、更に、アニオン系界面活性剤、及び炭素数２〜５０のアルカノールアミンを含有する無電解めっき液、当該無電解めっき液により形成されためっき皮膜、及び当該めっき液に被めっき物を接触させてめっき皮膜を形成する工程を有するめっき皮膜の形成方法によれば、上記目的を達成できることを見出し、本発明を完成するに至った。 As a result of intensive studies to achieve the above object, the present inventor contains a water-soluble nickel compound, a reducing agent, a complexing agent and silicon carbide particles as essential components, and further contains an anionic surfactant and carbon number. Formation of an electroless plating solution containing 2 to 50 alkanolamines, a plating film formed by the electroless plating solution, and a step of bringing a plating object into contact with the plating solution to form a plating film According to the method, the inventors have found that the above object can be achieved, and have completed the present invention.
即ち、本発明は、下記の無電解めっき液、めっき皮膜、めっき品及びめっき皮膜の形成方法に関する。
１．水溶性ニッケル化合物、還元剤、錯化剤及び炭化ケイ素粒子を必須成分として含有する無電解めっき液であって、
第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンから選択される少なくとも１種、並びに、アニオン系界面活性剤を含有する、ことを特徴とする無電解めっき液。
２．前記アニオン系界面活性剤は、ナトリウムスルホネートである、上記項１に記載の無電解めっき液。
３．前記第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンから選択される少なくとも１種は、トリエタノールアミン、モノエタノールアミン、ジエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ−メチルエタノールアミン、Ｎ−エチルエタノールアミン、Ｎ−ｎ−ブチルエタノールアミン、Ｎ−ｔ−ブチルエタノールアミン、Ｎ，Ｎ−ジエチルエタノールアミン、Ｎ，Ｎ−ジブチルエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−エチルジエタノールアミン、Ｎ−ｎ−ブチルジエタノールアミン、Ｎ−ｔ−ブチルジエタノールアミン、Ｎ，Ｎ−ジエチルイソプロパノールアミン、コリン、カルニチン、グリセロホスホコリン、及びロクロニウムブロミドから選択される少なくとも１種である、上記項１又は２に記載の無電解めっき液。
４．前記アニオン系界面活性剤の含有量は０．０１〜１００ｇ／Ｌである、上記項１〜３のいずれかに記載の無電解めっき液。
５．前記第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンの含有量の合計は、０．００１〜５０ｇ／Ｌである、上記項１〜４のいずれかに記載の無電解めっき液。
６．上記項１〜５のいずれかに記載の無電解めっき液を用いて形成されためっき皮膜。
７．上記項６に記載のめっき皮膜を有するめっき品。
８．上記項１〜５のいずれかに記載の無電解めっき液に、被めっき物を接触させてめっき皮膜を形成する工程１を有する、めっき皮膜の形成方法。
９．工程１により形成された無電解めっき皮膜を熱処理する工程２を有する、上記項８に記載のめっき皮膜の形成方法。
１０．前記熱処理の温度は３００〜５００℃である、上記項９に記載のめっき皮膜の形成方法。
That is, the present invention relates to the following electroless plating solution, plating film, plating product, and plating film forming method.
1. An electroless plating solution containing water-soluble nickel compound, reducing agent, complexing agent and silicon carbide particles as essential components,
An electroless plating solution comprising at least one selected from a quaternary ammonium compound and an alkanolamine having 2 to 50 carbon atoms, and an anionic surfactant.
2. The electroless plating solution according to Item 1, wherein the anionic surfactant is sodium sulfonate.
3. At least one selected from the quaternary ammonium compounds and alkanolamines having 2 to 50 carbon atoms is triethanolamine, monoethanolamine, diethanolamine, N, N-dimethylethanolamine, N-methylethanolamine, N- Ethylethanolamine, Nn-butylethanolamine, Nt-butylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn- Item 1 or above, which is at least one selected from butyldiethanolamine, Nt-butyldiethanolamine, N, N-diethylisopropanolamine, choline, carnitine, glycerophosphocholine, and rocuronium bromide. Electroless plating solution according to.
4). The electroless plating solution according to any one of Items 1 to 3, wherein the content of the anionic surfactant is 0.01 to 100 g / L.
5. The electroless plating solution according to any one of Items 1 to 4, wherein the total content of the quaternary ammonium compound and the alkanolamine having 2 to 50 carbon atoms is 0.001 to 50 g / L.
6). A plating film formed using the electroless plating solution according to any one of Items 1 to 5.
7). 7. A plated product having the plating film according to item 6.
8). The formation method of a plating film which has the process 1 which makes a to-be-plated object contact the electroless-plating liquid in any one of said items 1-5, and forms a plating film.
9. Item 9. The method for forming a plating film according to Item 8, which comprises the step 2 of heat-treating the electroless plating film formed in the step 1.
10. The method for forming a plating film according to Item 9, wherein the temperature of the heat treatment is 300 to 500 ° C.
本発明の無電解めっき液は、水溶性ニッケル化合物、還元剤、錯化剤及び炭化ケイ素粒子を必須成分として含有し、且つ、第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンから選択される少なくとも１種、並びに、アニオン系界面活性剤を含有する。本発明の無電解めっき液は、炭化ケイ素粒子を含有するので、当該めっき液を用いて形成されるめっき皮膜が耐摩耗性に優れている。更に、本発明の無電解めっき液は、第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンから選択される少なくとも１種、並びに、アニオン系界面活性剤を含有するので、当該めっき液を用いて形成されためっき皮膜表面の摩擦係数の増加が抑制されており、当該めっき皮膜と摺動する他の部材の摩耗が抑制される。 The electroless plating solution of the present invention contains a water-soluble nickel compound, a reducing agent, a complexing agent and silicon carbide particles as essential components, and is selected from a quaternary ammonium compound and an alkanolamine having 2 to 50 carbon atoms. At least one kind, and an anionic surfactant. Since the electroless plating solution of the present invention contains silicon carbide particles, the plating film formed using the plating solution is excellent in wear resistance. Furthermore, since the electroless plating solution of the present invention contains at least one selected from a quaternary ammonium compound and an alkanolamine having 2 to 50 carbon atoms, and an anionic surfactant, the plating solution is used. An increase in the coefficient of friction on the surface of the plating film formed in this manner is suppressed, and wear of other members that slide with the plating film is suppressed.
また本発明の無電解めっき皮膜の形成方法は、上述の構成を備える無電解めっき液に、被めっき物を接触させる工程を有しており、めっき皮膜表面の摩擦係数の増加が抑制されており、当該めっき皮膜と摺動する他の部材の摩耗が抑制されるめっき皮膜を容易に形成することができる。 The method of forming an electroless plating film of the present invention includes a step of bringing an object to be plated into contact with an electroless plating solution having the above-described configuration, and an increase in the coefficient of friction on the surface of the plating film is suppressed. A plating film in which wear of other members sliding with the plating film is suppressed can be easily formed.
以下、本発明の無電解めっき液、めっき皮膜及びめっき皮膜の形成方法について詳細に説明する。 Hereinafter, the electroless plating solution, the plating film, and the method for forming the plating film of the present invention will be described in detail.
１．無電解めっき液
本発明の無電解めっき液は、水溶性ニッケル化合物、還元剤、錯化剤及び炭化ケイ素粒子を必須成分として含有し、更に、第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンから選択される少なくとも１種、並びに、アニオン系界面活性剤を含有する。
1. Electroless Plating Solution The electroless plating solution of the present invention contains a water-soluble nickel compound, a reducing agent, a complexing agent and silicon carbide particles as essential components, and further includes a quaternary ammonium compound and an alkanol having 2 to 50 carbon atoms. It contains at least one selected from amines and an anionic surfactant.
水溶性ニッケル化合物としては、めっき液に可溶性であって、所定の濃度の水溶液が得られるものであれば特に限定なく使用できる。例えば、硫酸ニッケル、塩化ニッケル、スルファミン酸ニッケル、次亜リン酸ニッケル等を用いることができる。特に、溶解性が良好である点で硫酸ニッケルが好ましい。水溶性ニッケル化合物は、１種単独又は２種以上混合して用いることができる。水溶性ニッケル化合物の濃度は、０．００１〜１ｍｏｌ／Ｌ程度とすることが好ましく、０．０１〜０．３ｍｏｌ／Ｌ程度とすることがより好ましい。 The water-soluble nickel compound can be used without particular limitation as long as it is soluble in the plating solution and can obtain an aqueous solution having a predetermined concentration. For example, nickel sulfate, nickel chloride, nickel sulfamate, nickel hypophosphite, or the like can be used. In particular, nickel sulfate is preferable in terms of good solubility. A water-soluble nickel compound can be used individually by 1 type or in mixture of 2 or more types. The concentration of the water-soluble nickel compound is preferably about 0.001 to 1 mol / L, and more preferably about 0.01 to 0.3 mol / L.
還元剤についても特に限定はなく、無電解めっき液で用いられている公知の還元剤を用いることができる。この様な還元剤としては、次亜リン酸、次亜リン酸塩（ナトリウム塩、カリウム塩、アンモニウム塩）、ジメチルアミンボラン、ヒドラジン等を例示できる。還元剤は１種単独又は２種以上混合して用いることができる。還元剤の濃度は、０．００１〜１ｍｏｌ／Ｌ程度とすることが好ましく、０．００２〜０．５ｍｏｌ／Ｌ程度とすることがより好ましい。 There is no limitation in particular also about a reducing agent, The well-known reducing agent used with the electroless-plating liquid can be used. Examples of such a reducing agent include hypophosphorous acid, hypophosphite (sodium salt, potassium salt, ammonium salt), dimethylamine borane, hydrazine, and the like. A reducing agent can be used individually by 1 type or in mixture of 2 or more types. The concentration of the reducing agent is preferably about 0.001 to 1 mol / L, and more preferably about 0.002 to 0.5 mol / L.
錯化剤についても特に限定はなく、無電解めっき液で用いられている公知の錯化剤を用いることができる。この様な錯化剤としては、酢酸、蟻酸等のモノカルボン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等；マロン酸、コハク酸、アジピン酸、マレイン酸、フマール酸等のジカルボン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等；リンゴ酸、乳酸、グリコール酸、グルコン酸、クエン酸等のヒドロキシカルボン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等；エチレンジアミンジ酢酸、１−ヒドロキシエチリデン−１，１−ジホスホン酸、これらのアンモニウム塩、カリウム塩、ナトリウム塩等、エチレンジアミンテトラ酢酸、ジエチレントリアミンペンタ酢酸等のアミノポリカルボン酸やそれらのナトリウム塩、カリウム塩、アンモニウム塩等を例示できる。更に、ホスホン酸類、アミノ酸類等も錯化剤として用いることができる。これらの錯化剤は１種単独又は２種以上混合して用いることができる。錯化剤の配合量は、０．００１〜２ｍｏｌ／Ｌ程度とすることが好ましく、０．００２〜１ｍｏｌ／Ｌ程度とすることがより好ましい。 The complexing agent is not particularly limited, and a known complexing agent used in an electroless plating solution can be used. Examples of such complexing agents include monocarboxylic acids such as acetic acid and formic acid, ammonium salts, potassium salts and sodium salts thereof; dicarboxylic acids such as malonic acid, succinic acid, adipic acid, maleic acid and fumaric acid, and the like. Ammonium salts, potassium salts, sodium salts, etc .; hydroxycarboxylic acids such as malic acid, lactic acid, glycolic acid, gluconic acid, citric acid, their ammonium salts, potassium salts, sodium salts, etc .; ethylenediaminediacetic acid, 1-hydroxyethylidene Examples include -1,1-diphosphonic acid, ammonium salts, potassium salts and sodium salts thereof, aminopolycarboxylic acids such as ethylenediaminetetraacetic acid and diethylenetriaminepentaacetic acid, and sodium salts, potassium salts and ammonium salts thereof. Furthermore, phosphonic acids and amino acids can also be used as complexing agents. These complexing agents can be used alone or in combination of two or more. The compounding amount of the complexing agent is preferably about 0.001 to 2 mol / L, and more preferably about 0.002 to 1 mol / L.
本発明の無電解めっき液は、炭化ケイ素粒子を含有する。炭化ケイ素粒子の形状は特に限定されず、球状、角錐、立方体形状等のいずれの形状であってもよい。 The electroless plating solution of the present invention contains silicon carbide particles. The shape of the silicon carbide particles is not particularly limited, and may be any shape such as a spherical shape, a pyramid shape, or a cubic shape.
炭化ケイ素粒子の平均粒子径は、０．１〜５．０μｍが好ましく、０．３〜３．０μｍがより好ましい。炭化ケイ素粒子の平均粒子径が大き過ぎると、形成されるめっき皮膜と接する他の部材が摩耗し易くなるおそれがあり、小さ過ぎると、形成されるめっき皮膜の耐摩耗性が低下するおそれがある。 The average particle diameter of the silicon carbide particles is preferably 0.1 to 5.0 μm, and more preferably 0.3 to 3.0 μm. If the average particle diameter of the silicon carbide particles is too large, other members in contact with the formed plating film may be easily worn, and if it is too small, the wear resistance of the formed plating film may be reduced. .
炭化ケイ素粒子の含有量は、０．１〜２００ｇ／Ｌが好ましく、０．５〜１００ｇ／Ｌがより好ましい。炭化ケイ素粒子の含有量が多過ぎると、形成されるめっき皮膜と接する他の部材が摩耗し易くなるおそれがあり、少な過ぎる、形成されるめっき皮膜の耐摩耗性が低下するおそれがある。 The content of silicon carbide particles is preferably from 0.1 to 200 g / L, more preferably from 0.5 to 100 g / L. When the content of the silicon carbide particles is too large, other members in contact with the formed plating film may be easily worn, and when the content is too small, the wear resistance of the formed plating film may be reduced.
本発明の無電解めっき液は、第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンから選択される少なくとも１種を含有する。 The electroless plating solution of the present invention contains at least one selected from a quaternary ammonium compound and an alkanolamine having 2 to 50 carbon atoms.
上記アルカノールアミンの炭素数は、２〜３５であることが好ましい。 The alkanolamine preferably has 2 to 35 carbon atoms.
上記炭素数２〜５０のアルカノールアミンとしては、炭素数２〜５０の第一級〜第三級のアルカノールアミンを用いることができる。 As said C2-C50 alkanolamine, a C2-C50 primary-tertiary alkanolamine can be used.
第一級アルカノールアミンとしては、モノエタノールアミン等が挙げられる。 Examples of the primary alkanolamine include monoethanolamine.
第二級アルカノールアミンとしては、ジエタノールアミン、Ｎ−メチルエタノールアミン、Ｎ−エチルエタノールアミン、Ｎ−ｎ−ブチルエタノールアミン、Ｎ−ｔ−ブチルエタノールアミン等が挙げられる。 Examples of the secondary alkanolamine include diethanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nt-butylethanolamine and the like.
第三級アルカノールアミンとしては、トリエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ，Ｎ−ジエチルエタノールアミン、Ｎ，Ｎ−ジブチルエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−エチルジエタノールアミン、Ｎ−ｎ−ブチルジエタノールアミン、Ｎ−ｔ−ブチルジエタノールアミン、Ｎ，Ｎ−ジエチルイソプロパノールアミン等が挙げられる。 The tertiary alkanolamines include triethanolamine, N, N-dimethylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn- Examples include butyldiethanolamine, Nt-butyldiethanolamine, N, N-diethylisopropanolamine and the like.
第四級アンモニウム化合物としては、コリン、カルニチン、グリセロホスホコリン、ロクロニウムブロミド等が挙げられる。 Examples of the quaternary ammonium compound include choline, carnitine, glycerophosphocholine, rocuronium bromide and the like.
上記第四級アンモニウム化合物、及び炭素数２〜５０のアルカノールアミンは、単独で用いてもよいし、２種以上を混合して用いてもよい。これらの中でも、トリエタノールアミン、モノエタノールアミン、ジエタノールアミン、Ｎ，Ｎ−ジメチルエタノールアミン、Ｎ−メチルエタノールアミン、Ｎ−エチルエタノールアミン、Ｎ−ｎ−ブチルエタノールアミン、Ｎ−ｔ−ブチルエタノールアミン、Ｎ，Ｎ−ジエチルエタノールアミン、Ｎ，Ｎ−-ジブチルエタノールアミン、Ｎ−メチルジエタノールアミン、Ｎ−エチルジエタノールアミン、Ｎ−ｎ−ブチルジエタノールアミン、Ｎ−ｔ−ブチルジエタノールアミン、Ｎ，Ｎ−ジエチルイソプロパノールアミン、コリン、カルニチン、グリセロホスホコリン、ロクロニウムブロミド等を用いることが好ましい。 The said quaternary ammonium compound and C2-C50 alkanolamine may be used independently, and 2 or more types may be mixed and used for it. Among these, triethanolamine, monoethanolamine, diethanolamine, N, N-dimethylethanolamine, N-methylethanolamine, N-ethylethanolamine, Nn-butylethanolamine, Nt-butylethanolamine, N, N-diethylethanolamine, N, N-dibutylethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, Nn-butyldiethanolamine, Nt-butyldiethanolamine, N, N-diethylisopropanolamine, choline Carnitine, glycerophosphocholine, rocuronium bromide and the like are preferably used.
上記第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンの含有量の合計は特に限定されないが、本発明の無電解めっき液の量を１Ｌとして、０．００１〜５０ｇ／Ｌが好ましく、０．０１〜１０ｇ／Ｌがより好ましい。上記第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンの含有量の合計が少な過ぎると形成されるめっき皮膜の耐摩耗性が低下するおそれがあり、多過ぎるとめっき皮膜の析出速度が低下し、析出反応が生じ難くなるおそれがある。 Although the sum total of content of the said quaternary ammonium compound and C2-C50 alkanolamine is not specifically limited, 0.001-50 g / L is preferable when the quantity of the electroless-plating liquid of this invention is 1L, 0 0.01 to 10 g / L is more preferable. If the total content of the quaternary ammonium compound and the alkanolamine having 2 to 50 carbon atoms is too small, the wear resistance of the formed plating film may be lowered, and if too much, the deposition rate of the plating film is lowered. In addition, the precipitation reaction may be difficult to occur.
アニオン系界面活性剤としては特に限定されず、従来公知のものを用いることができる。上記アニオン系界面活性剤としては、例えば、芳香族又は脂肪族スルホン酸アルカリ金属塩、芳香族又は脂肪族カルボン酸アルカリ金属塩等が挙げられる。 It does not specifically limit as an anionic surfactant, A conventionally well-known thing can be used. Examples of the anionic surfactant include aromatic or aliphatic sulfonic acid alkali metal salts, aromatic or aliphatic carboxylic acid alkali metal salts, and the like.
芳香族又は脂肪族スルホン酸アルカリ金属塩としては、芳香族又は脂肪族ナトリウム塩（ナトリウムスルホネート）が挙げられる。 Aromatic or aliphatic sulfonic acid alkali metal salts include aromatic or aliphatic sodium salts (sodium sulfonate).
芳香族又は脂肪族カルボン酸アルカリ金属塩としては、芳香族又は脂肪族カリウム塩、芳香族又は脂肪族ナトリウム塩が挙げられ、中でも、ラウリン酸カリウム、オレイン酸ナトリウム等を用いることができる。 Aromatic or aliphatic carboxylic acid alkali metal salts include aromatic or aliphatic potassium salts, aromatic or aliphatic sodium salts, among which potassium laurate, sodium oleate and the like can be used.
上記アニオン系界面活性剤としては、ナトリウムスルホネートを用いることが好ましい。 As the anionic surfactant, sodium sulfonate is preferably used.
上記アニオン系界面活性剤は、単独で用いてもよいし、２種以上を混合して用いてもよい。 The said anionic surfactant may be used independently and may be used in mixture of 2 or more types.
アニオン系界面活性剤の含有量は特に限定されないが、０．０１〜１００ｇ／Ｌが好ましく、０．１〜１０ｇ／Ｌがより好ましい。アニオン系界面活性剤の含有量が少な過ぎると形成されるめっき皮膜の耐摩耗性が低下するおそれがあり、多過ぎるとめっき皮膜の析出速度が低下し、析出反応が生じ難くなるおそれがある。 Although content of an anionic surfactant is not specifically limited, 0.01-100 g / L is preferable and 0.1-10 g / L is more preferable. If the content of the anionic surfactant is too small, the wear resistance of the formed plating film may be reduced. If the content is too large, the deposition rate of the plating film may be reduced, and the precipitation reaction may be difficult to occur.
本発明の無電解めっき液には、その他必要に応じて、通常用いられている各種の添加剤を配合することができる。例えば、安定剤として、硝酸鉛、酢酸鉛等の鉛塩；硝酸ビスマス、酢酸ビスマス等のビスマス塩；チオジグリコール酸等の硫黄化合物等を１種単独又は２種以上混合して添加することができる。安定剤の添加量は、特に限定的ではないが、例えば、０．０１〜１００ｍｇ／Ｌ程度とすることができる。 In the electroless plating solution of the present invention, various commonly used additives can be blended as necessary. For example, as a stabilizer, lead salts such as lead nitrate and lead acetate; bismuth salts such as bismuth nitrate and bismuth acetate; sulfur compounds such as thiodiglycolic acid may be added singly or in combination of two or more. it can. Although the addition amount of a stabilizer is not specifically limited, For example, it can be set as about 0.01-100 mg / L.
また、ｐＨ緩衝剤として、ホウ酸、リン酸、亜リン酸、炭酸、それらのナトリウム塩、カリウム塩、アンモニウム塩等を配合することができる。緩衝剤の配合量は特に限定的ではないが、例えば０．１〜２００ｇ／Ｌ程度とすることができる。 Further, boric acid, phosphoric acid, phosphorous acid, carbonic acid, sodium salts, potassium salts, ammonium salts and the like thereof can be blended as pH buffering agents. Although the compounding quantity of a buffering agent is not specifically limited, For example, it can be about 0.1-200 g / L.
本発明の無電解めっき液のｐＨは、通常、２〜１２程度とすればよく、３〜１０程度とすることが好ましく、４〜８程度とすることがより好ましい。ｐＨ調整には、硫酸、リン酸等の無機酸および水酸化ナトリウム、アンモニア水等を使用することができる。 The pH of the electroless plating solution of the present invention is usually about 2 to 12, preferably about 3 to 10, and more preferably about 4 to 8. For pH adjustment, inorganic acids such as sulfuric acid and phosphoric acid, sodium hydroxide, aqueous ammonia and the like can be used.
２．めっき皮膜
本発明は、また、上記無電解めっき液を用いて形成されためっき皮膜でもある。上記めっき皮膜の厚みは、０．１〜１０００μｍ程度が好ましく、０．５〜１００μｍ程度がより好ましく、１〜５０μｍ程度が更に好ましい。
2. Plating film The present invention is also a plating film formed using the electroless plating solution. The thickness of the plating film is preferably about 0.1 to 1000 μm, more preferably about 0.5 to 100 μm, and still more preferably about 1 to 50 μm.
めっき皮膜の摩擦係数は、後述するめっき皮膜の形成方法での熱処理温度が３００℃の場合、０．６６０〜０．６９５程度であり、熱処理温度が３５０℃の場合、０．６６０〜０．６８５程度であり、熱処理温度が４００℃の場合、０．６２０〜０．６４５程度であり、５００℃の場合、０．７２０〜０．７５０程度である。 The friction coefficient of the plating film is about 0.660 to 0.695 when the heat treatment temperature in the plating film forming method described later is 300 ° C., and 0.660 to 0.685 when the heat treatment temperature is 350 ° C. When the heat treatment temperature is 400 ° C., it is about 0.620 to 0.645, and when it is 500 ° C., it is about 0.720 to 0.750.
なお、本明細書において、めっき皮膜の表面の摩擦係数は、荷重変動型摩擦摩耗試験システム（新東科学株式会社製 製品名：トライボギアＨＨＳ−２０００）を用いて、加減重往復測定の測定方法により、測定子φ１０ｍｍＳＵＳボール、１００〜５００ｇｆ、往復回数５０回、移動距離１５ｍｍ、移動速度５ｍｍ／ｓｅｃ、サンプルレート５０Ｈｚの測定条件により測定される値である。 In addition, in this specification, the friction coefficient of the surface of the plating film is determined by the measurement method of the reciprocating weight measurement using a load fluctuation type frictional wear test system (product name: Tribogear HHS-2000, manufactured by Shinto Kagaku Co., Ltd.). , Measuring point φ10 mm SUS ball, 100 to 500 gf, 50 reciprocations, moving distance 15 mm, moving speed 5 mm / sec, sample rate 50 Hz.
めっき皮膜の表面平均粗さ（Ｒａ）は、後述するめっき皮膜の形成方法での熱処理温度が３００℃の場合、０．０８６０〜０．０８９５μｍ程度であり、熱処理温度が３５０℃の場合、０．０８５０〜０．０８８５μｍ程度であり、熱処理温度が４００℃の場合、０．０８３０〜０．０８５５μｍ程度であり、５００℃の場合、０．１０５０〜０．１２００μｍ程度である。 The surface average roughness (Ra) of the plating film is about 0.0860 to 0.0895 μm when the heat treatment temperature in the plating film formation method described later is 300 ° C., and is 0. When the heat treatment temperature is 400 ° C., it is about 0.0830 to 0.0855 μm, and when it is 500 ° C., it is about 0.1050 to 0.1200 μm.
なお、本明細書において、めっき皮膜の表面平均粗さは、表面粗さ計（株式会社東京精密製 製品名：サーフコム１４００Ａ−１２）を用いて、測定長さ４．０ｍｍ、測定速度０．３ｍｍ／ｓ、移動・戻り速度０．３ｍｍ／ｓの測定条件により測定される値である。 In this specification, the surface roughness of the plating film is measured using a surface roughness meter (product name: Surfcom 1400A-12, manufactured by Tokyo Seimitsu Co., Ltd.), measuring length 4.0 mm, measuring speed 0.3 mm. This is a value measured under the measurement conditions of / s and moving / returning speed of 0.3 mm / s.
３．めっき皮膜の形成方法
本発明は、また、水溶性ニッケル化合物、還元剤、錯化剤及び炭化ケイ素粒子を必須成分として含有し、更に、第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンから選択される少なくとも１種、並びに、アニオン系界面活性剤を含有する無電解めっき液に、被めっき物を接触させてめっき皮膜を形成する工程１を有するめっき皮膜の形成方法でもある。
3. The present invention also includes a water-soluble nickel compound, a reducing agent, a complexing agent and silicon carbide particles as essential components, and further from a quaternary ammonium compound and an alkanolamine having 2 to 50 carbon atoms. It is also a method for forming a plating film having Step 1 of forming a plating film by bringing an object to be plated into contact with an electroless plating solution containing at least one selected type and an anionic surfactant.
（工程１）
工程１は、上記無電解めっき液に被めっき物を接触させてめっき皮膜を形成する工程である。上記無電解めっき液としては、上述のものを用いることができる。上記無電解めっき液を用いてめっき皮膜の形成を行うには、常法に従って、該無電解めっき液を被めっき物に接触させればよい。通常は、該無電解めっき液中に被めっき物を浸漬することによって、効率よくめっき皮膜を形成することができる。
(Process 1)
Step 1 is a step of forming a plating film by bringing an object to be plated into contact with the electroless plating solution. As the electroless plating solution, those described above can be used. In order to form a plating film using the electroless plating solution, the electroless plating solution may be brought into contact with an object to be plated according to a conventional method. Usually, a plating film can be efficiently formed by immersing an object to be plated in the electroless plating solution.
無電解めっき液の液温は、通常、２５℃以上程度とすればよく、４０〜１００℃程度とすることが好ましい。また必要に応じて、めっき液の撹拌や被めっき物の揺動を行うことができる。 The liquid temperature of the electroless plating solution is usually about 25 ° C. or higher, and preferably about 40 to 100 ° C. If necessary, the plating solution can be stirred and the object to be plated can be swung.
被めっき物の材質については特に限定はない。例えば、鉄、コバルト、ニッケル、パラジウム等の金属やこれらの合金等は無電解めっきの還元析出に対して触媒性を有するので、常法に従って前処理を行った後、直接めっき皮膜を形成することができる。銅等の触媒性のない金属や、ガラス、セラミックス等については、常法に従ってパラジウム核などの金属触媒核を付着させた後に、めっき処理を行えばよい。 There is no particular limitation on the material of the object to be plated. For example, metals such as iron, cobalt, nickel, and palladium, and alloys thereof have catalytic properties for reduction deposition of electroless plating, so a direct plating film should be formed after pretreatment according to a conventional method. Can do. For non-catalytic metals such as copper, glass, ceramics, etc., a metal catalyst nucleus such as a palladium nucleus is attached according to a conventional method, and then a plating treatment may be performed.
（工程２）
本発明のめっき皮膜の形成方法は、更に、工程１により形成された無電解めっき皮膜を熱処理する工程２を有していてもよい。
(Process 2)
The plating film forming method of the present invention may further include a step 2 of heat-treating the electroless plating film formed in the step 1.
工程１により形成された無電解めっき皮膜を熱処理する方法としては特に限定されず、従来公知の方法により熱処理することができる。上記無電解めっき皮膜を熱処理する方法としては、例えば、被めっき物に形成されためっき皮膜を被めっき物と共に加熱炉内で加熱する方法が挙げられる。 The method for heat-treating the electroless plating film formed in step 1 is not particularly limited, and can be heat-treated by a conventionally known method. As a method of heat-treating the electroless plating film, for example, a method of heating a plating film formed on the object to be plated together with the object to be plated in a heating furnace may be mentioned.
上記熱処理の温度は特に限定されないが、１００〜８００℃が好ましく、３００〜５００℃がより好ましい。熱処理の温度が低過ぎるとめっき皮膜の耐摩耗性が十分でないおそれがあり、高過ぎると、めっき皮膜表面の摩擦係数が高くなり、めっき皮膜と接触する他の部材の摩耗を十分に抑制できないおそれがある。 Although the temperature of the said heat processing is not specifically limited, 100-800 degreeC is preferable and 300-500 degreeC is more preferable. If the temperature of the heat treatment is too low, the wear resistance of the plating film may not be sufficient, and if it is too high, the friction coefficient of the plating film surface will be high, and the wear of other members in contact with the plating film may not be sufficiently suppressed. There is.
上記熱処理の加熱時間としては特に限定されないが、１０〜１８０分が好ましく、３０〜１２０分がより好ましい。加熱時間が短過ぎるとめっき皮膜の耐摩耗性が十分でないおそれがあり、長過ぎるとめっき皮膜表面の摩擦係数が高くなり、めっき皮膜と接触する他の部材の摩耗を十分に抑制できないおそれがある。 Although it does not specifically limit as a heat time of the said heat processing, 10 to 180 minutes are preferable and 30 to 120 minutes are more preferable. If the heating time is too short, the wear resistance of the plating film may not be sufficient, and if it is too long, the friction coefficient of the plating film surface becomes high, and there is a possibility that the wear of other members in contact with the plating film cannot be sufficiently suppressed. .
４．めっき品
本発明は、また、上記めっき皮膜を有するめっき品でもある。めっき品としては、本発明のめっき皮膜を有していれば特に限定されず、被めっき物の表面にめっき皮膜が形成されていればよい。
4). Plating product The present invention is also a plating product having the plating film. The plating product is not particularly limited as long as it has the plating film of the present invention, and it is sufficient that the plating film is formed on the surface of the object to be plated.
上記被めっき物の材質としては特に限定されないが、例えば、鉄、コバルト、ニッケル、パラジウム、銅等の金属やこれらの合金、又は、ガラス、セラミックス等が挙げられる。 Although it does not specifically limit as a material of the said to-be-plated thing, For example, metals, such as iron, cobalt, nickel, palladium, copper, these alloys, glass, ceramics, etc. are mentioned.
本発明のめっき品は、特に、機械装置の摺動部等の、他の部材と摺動する部材であると、本発明のめっき品と摺動する他の部材の摩耗を抑制することができる。 When the plated product of the present invention is a member that slides with other members, such as a sliding portion of a mechanical device, wear of the other members that slide with the plated product of the present invention can be suppressed. .
本発明の無電解めっき液は、炭化ケイ素粒子を含有するので、当該めっき液を用いて形成されるめっき皮膜が耐摩耗性に優れている。更に、本発明の無電解めっき液は、第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンから選択される少なくとも１種、並びに、アニオン系界面活性剤を含有するので、当該めっき液を用いて形成されためっき皮膜表面の摩擦係数の増加が抑制されており、当該めっき皮膜と摺動する他の部材の摩耗が抑制されている。 Since the electroless plating solution of the present invention contains silicon carbide particles, the plating film formed using the plating solution is excellent in wear resistance. Furthermore, since the electroless plating solution of the present invention contains at least one selected from a quaternary ammonium compound and an alkanolamine having 2 to 50 carbon atoms, and an anionic surfactant, the plating solution is used. The increase in the coefficient of friction on the surface of the plating film formed in this manner is suppressed, and the wear of other members sliding with the plating film is suppressed.
また本発明の無電解めっき皮膜の形成方法は、上述の構成を備える無電解めっき液に、被めっき物を接触させる工程を有しており、めっき皮膜表面の摩擦係数の増加が抑制されており、当該めっき皮膜と摺動する他の部材の摩耗が抑制されるめっき皮膜を容易に形成することができる。 The method of forming an electroless plating film of the present invention includes a step of bringing an object to be plated into contact with an electroless plating solution having the above-described configuration, and an increase in the coefficient of friction on the surface of the plating film is suppressed. A plating film in which wear of other members sliding with the plating film is suppressed can be easily formed.
以下に実施例及び比較例を示して本発明を具体的に説明する。但し、本発明は実施例に限定されない。 The present invention will be specifically described below with reference to examples and comparative examples. However, the present invention is not limited to the examples.
（無電解めっき液の調製）
表１に示す配合により、実施例１〜１９及び比較例１〜３の無電解めっき液を調製した。
(Preparation of electroless plating solution)
Electroless plating solutions of Examples 1 to 19 and Comparative Examples 1 to 3 were prepared according to the formulation shown in Table 1.
得られた各実施例及び比較例の無電解めっき液を用いて、下記の方法によりめっき皮膜の形成を行った。 A plating film was formed by the following method using the obtained electroless plating solutions of the examples and comparative examples.
表１に示す化合物を含有する各無電解ニッケルめっき液を用いて、軟鋼板（ＪＩＳ−ＳＰＣＣ ＳＢ）５×５ｃｍを被めっき物として、ｐＨ４．５、浴温９０℃の無電解ニッケルめっき液中に被めっき物を浸漬することによって厚さ３０μｍの無電解ニッケルめっき皮膜を形成した。 In each of the electroless nickel plating solutions containing the compounds shown in Table 1, a mild steel plate (JIS-SPCC SB) 5 × 5 cm is to be plated, and in an electroless nickel plating solution having a pH of 4.5 and a bath temperature of 90 ° C. An electroless nickel plating film having a thickness of 30 μm was formed by immersing the object to be plated in the substrate.
前処理工程および使用薬品は以下の通りである。
（１）浸漬脱脂（商標名：エースクリーン８０１ 奥野製薬工業（株）製）
（２）電解脱脂（商標名：トップクリーナーＥ 奥野製薬工業（株）製）
（３）酸活性（商標名：トップサン 奥野製薬工業（株）製）
得られためっき皮膜に対し、加熱炉を用いて３００℃、３５０℃、４００℃、５００℃の各温度で、６０分間熱処理を行った。
The pretreatment process and chemicals used are as follows.
(1) Immersion degreasing (trade name: A-screen 801 manufactured by Okuno Pharmaceutical Co., Ltd.)
(2) Electrolytic degreasing (trade name: Top Cleaner E, Okuno Pharmaceutical Co., Ltd.)
(3) Acid activity (trade name: Top Sun, manufactured by Okuno Pharmaceutical Co., Ltd.)
The obtained plating film was heat-treated at 300 ° C., 350 ° C., 400 ° C., and 500 ° C. for 60 minutes using a heating furnace.
得られた各試料について、下記の方法によりめっき皮膜の摩擦係数、及び表面粗さを測定した。 About each obtained sample, the friction coefficient and surface roughness of the plating film were measured with the following method.
（摩擦係数）
めっき皮膜の表面について、荷重変動型摩擦摩耗試験システム（新東科学株式会社製 製品名：トライボギアＨＨＳ−２０００）を用いて、加減重往復測定の測定方法により、測定子φ１０ｍｍＳＵＳボール、１００〜５００ｇｆ、往復回数５０回、移動距離１５ｍｍ、移動速度５ｍｍ／ｓｅｃ、サンプルレート５０Ｈｚの測定条件により、摩擦係数を測定した。１００〜５００ｇｆの各荷重の、往復回数５０回目の摩擦係数の平均値を算出し、摩擦係数の測定値とした。
(Coefficient of friction)
About the surface of the plating film, using a load fluctuation type frictional wear test system (product name: Tribogear HHS-2000, manufactured by Shinto Kagaku Co., Ltd.), a measuring element φ10 mmSUS ball, 100 to 500 gf, The friction coefficient was measured under the measurement conditions of 50 reciprocations, moving distance 15 mm, moving speed 5 mm / sec, and sample rate 50 Hz. The average value of the friction coefficient at the 50th reciprocation for each load of 100 to 500 gf was calculated and used as the measured value of the friction coefficient.
（表面粗さ）
めっき皮膜の表面について、表面粗さ計（株式会社東京精密製 製品名：サーフコム１４００Ａ−１２）を用いて、測定長さ４．０ｍｍ、測定速度０．３ｍｍ／ｓ、移動・戻り速度０．３ｍｍ／ｓの測定条件により、表面粗さを測定した。測定を３回行い、平均値を算出して表面粗さの測定値とした。
(Surface roughness)
About the surface of the plating film, using a surface roughness meter (product name: Surfcom 1400A-12, manufactured by Tokyo Seimitsu Co., Ltd.), measurement length 4.0 mm, measurement speed 0.3 mm / s, movement / return speed 0.3 mm The surface roughness was measured under the measurement conditions of / s. Measurement was performed three times, and an average value was calculated as a measured value of surface roughness.
結果を表２に示す。 The results are shown in Table 2.
表２から明らかなように、第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンから選択される少なくとも１種、並びに、アニオン系界面活性剤を含有するとの構成を備える実施例１〜１９は、往復回数５０回目の摩擦係数が低くなっており、耐摩耗性に優れ、他の部材との摺動回数が増加しても、めっき皮膜の表面の摩擦係数の増加が抑制されていることが分かる。このことから、めっき皮膜と摺動する他の部材の摩耗が抑制されているめっき皮膜が形成されていることが分かった。 As is clear from Table 2, Examples 1 to 19 having a constitution containing at least one selected from a quaternary ammonium compound and an alkanolamine having 2 to 50 carbon atoms and an anionic surfactant are as follows: The friction coefficient at the 50th reciprocation is low, it has excellent wear resistance, and even if the number of sliding with other members increases, the increase in the friction coefficient on the surface of the plating film is suppressed. I understand. From this, it was found that a plating film in which wear of other members sliding with the plating film was suppressed was formed.
これに対し、上述の構成を有していない比較例１〜３は、往復回数５０回目の摩擦係数高くなっており、他の部材との摺動回数が増加した場合に、他の部材の摩耗が抑制されていないことが分かった。 On the other hand, Comparative Examples 1 to 3 that do not have the above-described configuration have a high coefficient of friction at the 50th reciprocation, and wear of other members increases when the number of sliding with other members increases. Was found not to be suppressed.
Claims (8)
第四級アンモニウム化合物及び炭素数２〜５０のアルカノールアミンから選択される少なくとも１種、並びに、アニオン系界面活性剤を含有する、ことを特徴とする無電解めっき液。 An electroless plating solution containing water-soluble nickel compound, reducing agent, complexing agent and silicon carbide particles as essential components,
An electroless plating solution comprising at least one selected from a quaternary ammonium compound and an alkanolamine having 2 to 50 carbon atoms, and an anionic surfactant.
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