JP5669894B2 - Method for producing corrosion-resistant conductive coating material - Google Patents
Method for producing corrosion-resistant conductive coating material Download PDFInfo
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- JP5669894B2 JP5669894B2 JP2013149281A JP2013149281A JP5669894B2 JP 5669894 B2 JP5669894 B2 JP 5669894B2 JP 2013149281 A JP2013149281 A JP 2013149281A JP 2013149281 A JP2013149281 A JP 2013149281A JP 5669894 B2 JP5669894 B2 JP 5669894B2
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- 238000000576 coating method Methods 0.000 title claims description 79
- 239000011248 coating agent Substances 0.000 title claims description 74
- 239000000463 material Substances 0.000 title claims description 73
- 230000007797 corrosion Effects 0.000 title claims description 70
- 238000005260 corrosion Methods 0.000 title claims description 70
- 238000004519 manufacturing process Methods 0.000 title claims description 15
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 128
- 239000000758 substrate Substances 0.000 claims description 119
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- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052758 niobium Inorganic materials 0.000 claims description 11
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 10
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- BSDOQSMQCZQLDV-UHFFFAOYSA-N butan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] BSDOQSMQCZQLDV-UHFFFAOYSA-N 0.000 description 3
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- ZTILUDNICMILKJ-UHFFFAOYSA-N niobium(v) ethoxide Chemical compound CCO[Nb](OCC)(OCC)(OCC)OCC ZTILUDNICMILKJ-UHFFFAOYSA-N 0.000 description 3
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- 239000012535 impurity Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 238000007733 ion plating Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- QASMZJKUEABJNR-UHFFFAOYSA-N methanolate;tantalum(5+) Chemical compound [Ta+5].[O-]C.[O-]C.[O-]C.[O-]C.[O-]C QASMZJKUEABJNR-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- LZRGWUCHXWALGY-UHFFFAOYSA-N niobium(5+);propan-2-olate Chemical compound [Nb+5].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] LZRGWUCHXWALGY-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- OLGCTTOCPNLTKW-UHFFFAOYSA-J oxolane;tetrachloroniobium Chemical compound C1CCOC1.C1CCOC1.Cl[Nb](Cl)(Cl)Cl OLGCTTOCPNLTKW-UHFFFAOYSA-J 0.000 description 1
- VDJJKYYENYIHFF-UHFFFAOYSA-J oxolane;tetrachlorozirconium Chemical compound C1CCOC1.C1CCOC1.Cl[Zr](Cl)(Cl)Cl VDJJKYYENYIHFF-UHFFFAOYSA-J 0.000 description 1
- NVQGUGFHTHIDRH-UHFFFAOYSA-N oxotitanium(2+) pentane-2,4-dione Chemical compound O=[Ti++].CC(=O)[CH-]C(C)=O.CC(=O)[CH-]C(C)=O NVQGUGFHTHIDRH-UHFFFAOYSA-N 0.000 description 1
- JOUSPCDMLWUHSO-UHFFFAOYSA-N oxovanadium;propan-2-ol Chemical compound [V]=O.CC(C)O.CC(C)O.CC(C)O JOUSPCDMLWUHSO-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- JKDRQYIYVJVOPF-FDGPNNRMSA-L palladium(ii) acetylacetonate Chemical compound [Pd+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O JKDRQYIYVJVOPF-FDGPNNRMSA-L 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 1
- RPESBQCJGHJMTK-UHFFFAOYSA-I pentachlorovanadium Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[V+5] RPESBQCJGHJMTK-UHFFFAOYSA-I 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-M perchlorate Inorganic materials [O-]Cl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-M 0.000 description 1
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 1
- KHIWWQKSHDUIBK-UHFFFAOYSA-N periodic acid Chemical compound OI(=O)(=O)=O KHIWWQKSHDUIBK-UHFFFAOYSA-N 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- KVERJCFPWMYIII-UHFFFAOYSA-J platinum(4+);tetrachloride;hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Cl-].[Cl-].[Pt+4] KVERJCFPWMYIII-UHFFFAOYSA-J 0.000 description 1
- 239000005518 polymer electrolyte Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- ZGSOBQAJAUGRBK-UHFFFAOYSA-N propan-2-olate;zirconium(4+) Chemical compound [Zr+4].CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-] ZGSOBQAJAUGRBK-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001235 sensitizing effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
- 239000004449 solid propellant Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- XPQYLUGYVZNMLC-UHFFFAOYSA-N tantalum(5+);2,2,2-trifluoroethanolate Chemical compound [Ta+5].[O-]CC(F)(F)F.[O-]CC(F)(F)F.[O-]CC(F)(F)F.[O-]CC(F)(F)F.[O-]CC(F)(F)F XPQYLUGYVZNMLC-UHFFFAOYSA-N 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- VUWPOFFYSGYZQR-UHFFFAOYSA-L tert-butylcyclopentane;dichlorotitanium Chemical compound Cl[Ti]Cl.CC(C)(C)[C]1[CH][CH][CH][CH]1.CC(C)(C)[C]1[CH][CH][CH][CH]1 VUWPOFFYSGYZQR-UHFFFAOYSA-L 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 description 1
- TYLYVJBCMQFRCB-UHFFFAOYSA-K trichlororhodium;trihydrate Chemical compound O.O.O.[Cl-].[Cl-].[Cl-].[Rh+3] TYLYVJBCMQFRCB-UHFFFAOYSA-K 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- DUNKXUFBGCUVQW-UHFFFAOYSA-J zirconium tetrachloride Chemical compound Cl[Zr](Cl)(Cl)Cl DUNKXUFBGCUVQW-UHFFFAOYSA-J 0.000 description 1
Images
Description
本発明は、耐食性かつ導電性に優れ、高耐久性である耐食導電被覆材料に関するものであり、より詳しくは、めっき装置や電気化学反応槽の構成部材である陰極への給電用ロールまたは電解槽、あるいは腐食性の電解質を具備した色素増感型太陽電池向けの電極等を用途とする耐食導電被覆材料に関するものである。 TECHNICAL FIELD The present invention relates to a corrosion-resistant conductive coating material that is excellent in corrosion resistance, conductivity, and durability, and more specifically, a roll for supplying power to a cathode or an electrolytic cell that is a constituent member of a plating apparatus or an electrochemical reaction tank. The present invention also relates to a corrosion-resistant conductive coating material that uses an electrode or the like for a dye-sensitized solar cell provided with a corrosive electrolyte.
本発明は例えばめっき装置の給電ロールに使用される新規な材料に関するものである。近年、携帯電話や大画面ディスプレイなどの電子機器は薄型化する傾向にあり、薄型化を支える技術として、高分子フィルム上に金属配線が形成された金属配線付きフィルムが回路基板、電磁波シールド材、タッチパネルなどの用途に多用されている。この金属配線付きフィルムは、例えば特許文献１に記載されているように、フィルムを搬送しながら連続的に電解めっきし、被膜を形成する方法にて製造されている。より詳しくは、銀塩法やスパッタリング法により非常に薄い金属配線が形成された高分子フィルムを、陰極給電ロールに接触させながら、その前後に陽極が配置されためっき液中に該高分子フィルムを搬送させ、陰極−陽極間を通電させることにより金属を電析させて金属配線をさらに形成させる。このようなめっき浴槽を多数配置し、順次搬送させ電析することで、該フィルム上に所望厚みのめっき被膜を得、上記金属配線付きフィルムを製造している。 The present invention relates to a novel material used for, for example, a power supply roll of a plating apparatus. In recent years, electronic devices such as mobile phones and large-screen displays tend to be thinner, and as a technology that supports thinning, films with metal wiring formed on polymer films are used for circuit boards, electromagnetic shielding materials, Widely used for applications such as touch panels. As described in Patent Document 1, for example, this film with metal wiring is manufactured by a method in which a film is formed by continuous electrolytic plating while conveying the film. More specifically, the polymer film in which a very thin metal wiring is formed by a silver salt method or a sputtering method is brought into contact with a cathode feeding roll, and the polymer film is placed in a plating solution in which an anode is arranged before and after the polymer film. The metal is electrodeposited by being conveyed and energized between the cathode and the anode to further form a metal wiring. A large number of such plating baths are arranged, sequentially conveyed and electrodeposited to obtain a plating film having a desired thickness on the film, and the film with metal wiring is manufactured.
本発明はまた、電解槽の構成材料となりうる新規な材料に関するものである。ロケット用固体燃料の原料である過塩素酸塩、半導体製造工程時に使用されるＣＭＰスラリー中の酸化剤として使用される過よう素酸塩などの過ハロゲン酸化合物は、白金族金属電極を陽極、鉄系合金電極を陰極とし、塩素酸ナトリウムを陽極酸化することで得られるが、工業的には鉄系合金製の電解槽を用い、該電解槽自体を陰極としても兼用することで生産性をあげて製造されている。 The present invention also relates to a novel material that can be a constituent material of an electrolytic cell. Perchlorate, which is a raw material for solid fuel for rockets, and perhalogenated compounds such as periodate used as an oxidant in CMP slurry used in the semiconductor manufacturing process, a platinum group metal electrode as an anode, It can be obtained by anodizing sodium chlorate with an iron-based alloy electrode as a cathode, but industrially, an electrolytic cell made of an iron-based alloy is used, and productivity can be increased by using the electrolytic cell itself as a cathode. Have been manufactured.
上述した陰極給電ロールや電解槽に使用される材料は、酸性度が低く、酸化性の高い溶液や高濃度の過ハロゲン酸化合物に晒されるため、高い耐食性を有するものが求められ、かつ電力を抑制して環境負荷を低減するための高い導電性を有するものが求められている。さらに、電解時において電解槽自体を陰極と兼用する場合などは、水素過電圧が低く、水素脆化にも耐えうる材料ではなくてならず、一般的には炭素鋼やステンレスなどが用いられている。 The materials used for the cathode feeding roll and the electrolytic cell described above have low acidity and are exposed to highly oxidative solutions and high-concentration perhalogenate compounds. What has high electroconductivity for suppressing and reducing an environmental load is calculated | required. Furthermore, when the electrolytic cell itself is also used as the cathode during electrolysis, the hydrogen overvoltage must be low and the material must be able to withstand hydrogen embrittlement. Generally, carbon steel or stainless steel is used. .
ところで、このステンレスの防食機構は、ステンレス基体表層に形成される不動態被膜によってステンレス基体を腐食環境から保護するシールド効果によるものである。該不動態被膜は絶縁性の金属酸化物であり、電気的には抵抗成分として働くため、高い導電性を得ることは困難である。 By the way, this stainless steel anticorrosion mechanism is based on the shielding effect of protecting the stainless steel substrate from the corrosive environment by the passive film formed on the surface of the stainless steel substrate. The passive film is an insulating metal oxide and electrically acts as a resistance component, so that it is difficult to obtain high conductivity.
また、ステンレス基体は、非常に強い腐食環境下では、錆の発生や、金属成分の溶出が生じる。ステンレス基体をめっき用電解槽に用いた場合、この錆が表面を覆うことで金属基体内部を保護する機能が発揮するが、その錆がめっき浴中に混入して、電析金属中に不純物として取り込まれ、該電析金属の物性に悪影響を及ぼす。一方、過ハロゲン酸化合物を電解生成する電極あるいは電解槽としてステンレス基体を用いた場合、金属成分の溶出により生成した過ハロゲン酸化合物の純度低下を来たすという問題点があった。 In addition, the stainless steel substrate generates rust and elution of metal components in a very strong corrosive environment. When a stainless steel substrate is used in the electrolytic bath for plating, the rust covers the surface, and the function of protecting the inside of the metal substrate is exerted. However, the rust is mixed in the plating bath and becomes an impurity in the electrodeposited metal. It is taken in and adversely affects the physical properties of the deposited metal. On the other hand, when a stainless steel substrate is used as an electrode or electrolytic cell for electrolytically generating a perhalogenate compound, there is a problem in that the purity of the perhalogenate compound generated by elution of a metal component is lowered.
従って、めっき装置や電気化学反応槽に用いられる材料において、ステンレス基体では、高い導電性と耐食性との両立という観点から不十分であり、該両特性を兼ね備え、かつ安価で生産性に優れる耐食導電被覆材料が要望されている。 Therefore, in the materials used for the plating apparatus and electrochemical reaction tank, the stainless steel substrate is insufficient from the viewpoint of achieving both high conductivity and corrosion resistance, and has both of these characteristics, and is inexpensive and excellent in productivity. There is a need for coating materials.
さらに、耐食導電被覆材料は以下に示す用途への応用が期待できる。例えば、色素増感太陽電池用電極に求められる性能は、まさしく前記両特性を兼ね備えたものであり、すなわち、チタニア極側で励起された電子を効率よく伝達する良好な導電性や、直射日光下の高温下における耐久性などが重要である。また、一般に色素増感太陽電池の電解質には酸化還元対物質としてヨウ素が混合されているが、該ヨウ素は腐食性が非常に強いため、電極材料には高い耐食性が特に求められる。 Furthermore, the corrosion-resistant conductive coating material can be expected to be applied to the following uses. For example, the performance required for a dye-sensitized solar cell electrode has both of the above characteristics, that is, good conductivity for efficiently transmitting electrons excited on the titania electrode side, and direct sunlight. Durability at high temperatures is important. In general, iodine is mixed as an oxidation-reduction counter substance in an electrolyte of a dye-sensitized solar cell. However, since the iodine is very corrosive, high corrosion resistance is particularly required for an electrode material.
しかしながら、安価な金属基体を用いた色素増感太陽電池用電極材料は若干の事例を除きほとんど提案されていない。例えば非特許文献１に開示されているものは、耐熱性とフレキシブル性を兼備することを主眼としており、ステンレス基体上にケイ素酸化物薄膜を形成し、その上から導電性金属酸化物であるＩＴＯを被覆することで耐食性を持たせているものの、実用的な耐久性不足と材料自身の高電気抵抗により、得られる太陽電池特性が大幅に低下するという問題点がある。そのため、一般的には、ヨウ素により腐食しないＩＴＯ、ＦＴＯなどの導電性金属酸化物により被覆したガラス基体電極が用いられている。又、特に対極側の電極として、酸化還元対の酸化体を還元する触媒作用を有し、かつ耐食性を有するスパッタリング法などの乾式法によって白金を被覆されたガラス電極が用いられている。 However, few electrode materials for dye-sensitized solar cells using inexpensive metal substrates have been proposed except for some cases. For example, what is disclosed in Non-Patent Document 1 is mainly intended to have both heat resistance and flexibility. A silicon oxide thin film is formed on a stainless steel substrate, and a conductive metal oxide is formed thereon. However, there is a problem that the obtained solar cell characteristics are greatly deteriorated due to insufficient practical durability and high electrical resistance of the material itself. Therefore, generally, a glass substrate electrode coated with a conductive metal oxide such as ITO or FTO that does not corrode with iodine is used. In particular, a glass electrode coated with platinum by a dry method such as a sputtering method having a catalytic action for reducing an oxidant of a redox couple and having corrosion resistance is used as the electrode on the counter electrode side.
このような金属酸化物被覆電極の製造には大型の設備が必要であるなどコストが高いという問題点があり、加えて電極の電導度も不足しているため、特に実用的な面積では大幅に性能が低下してしまうという問題点があった。また、乾式法により作製された白金被覆ガラス電極においても、材料コストが高いという問題点があった。さらに、該白金被覆ガラス電極の白金層は非常に薄いために、基体を保護する機能がほとんどなく、ガラスなどの基体しか用いることができず、大型化、軽量化、フレキシブル化が困難であるという問題点が挙げられ、さらに、ＩＴＯ、ＦＴＯなどの導電性金属酸化物は金属基体に比べて抵抗が高いため、発電特性、すなわち取り出せる電流に悪影響を及ぼす。従って、依然としてより安価な製造コストとプロセスで作製でき、かつ良好な導電性と高い耐食性を有する色素増感太陽電池用電極材料が求められている。 The production of such metal oxide-coated electrodes has the problem of high costs, such as the need for large-scale equipment, and in addition, the conductivity of the electrodes is insufficient. There was a problem that the performance deteriorated. In addition, the platinum-coated glass electrode produced by the dry method also has a problem that the material cost is high. Furthermore, since the platinum layer of the platinum-coated glass electrode is very thin, it has almost no function of protecting the substrate, and only a substrate such as glass can be used, and it is difficult to increase the size, weight, and flexibility. In addition, conductive metal oxides such as ITO and FTO have a higher resistance than metal substrates, and thus adversely affect power generation characteristics, that is, current that can be extracted. Accordingly, there is a need for a dye-sensitized solar cell electrode material that can still be produced with a lower manufacturing cost and process, and that has good conductivity and high corrosion resistance.
めっき装置や電気化学反応槽の構成用材料、あるいは色素増感太陽電池用の電極として好適に用いることができ、過ハロゲン酸化合物、ヨウ素、硫酸等に代表される腐食性物質、酸化性物質の存在雰囲気下での使用においても長時間耐えうる、安価で信頼性に優れ、耐食性と導電性に優れた耐食導電被覆材料の製造方法を提供することを目的とする。 It can be suitably used as a component material for plating equipment and electrochemical reaction tanks, or as an electrode for dye-sensitized solar cells. It can be used for corrosive and oxidative substances represented by perhalogenate compounds, iodine, sulfuric acid, etc. An object of the present invention is to provide a method for producing a corrosion-resistant conductive coating material that can withstand a long time even in use in an existing atmosphere, is inexpensive, has excellent reliability, and has excellent corrosion resistance and conductivity.
すなわち、本発明は以下に示すものである。 That is, the present invention is as follows.
（１）第４族及び第５族からなる群から選ばれる少なくとも一つの金属からなる基体上に、
熱分解法によって４族金属の酸化物及び／または５族金属の酸化物層を形成する工程、
次いで、該酸化物層上に、含白金族金属化合物のアルコール溶液からなる塗布液を塗布、乾燥、焼成し、白金族金属含有層及び／またはその酸化物層を形成する工程、
次いで、白金族金属めっき層を前記白金族金属含有層及び／またはその酸化物層上に形成する工程、
を包含する耐食導電被覆材料の製造方法において、
白金族金属層及び／またはその酸化物層を形成する工程における焼成温度が、３５０℃以上６００℃以下であることを特徴とする耐食導電被覆材料の製造方法。
(1) On a substrate made of at least one metal selected from the group consisting of Group 4 and Group 5,
Forming a Group 4 metal oxide and / or a Group 5 metal oxide layer by pyrolysis,
Next, a step of applying a coating solution composed of an alcohol solution of a platinum group metal compound on the oxide layer, drying and baking to form a platinum group metal-containing layer and / or an oxide layer thereof,
Next, a step of forming a platinum group metal plating layer on the platinum group metal-containing layer and / or an oxide layer thereof,
In a method for producing a corrosion-resistant conductive coating material comprising:
A method for producing a corrosion-resistant conductive coating material, wherein a firing temperature in the step of forming a platinum group metal layer and / or an oxide layer thereof is 350 ° C. or higher and 600 ° C. or lower.
（２）前記熱分解法による４族金属の酸化物及び／または５族金属の酸化物層が、
チタン、ジルコニウム、ニオブ、タンタル、バナジウムからなる群から選ばれる少なくとも一つの金属酸化物層であり、かつ、該層の厚さが５０ｎｍ以上７００ｎｍ以下であることを特徴とする請求項１に記載の耐食導電被覆材料の製造方法。
(2) Group 4 metal oxide and / or Group 5 metal oxide layer by the thermal decomposition method,
It is at least one metal oxide layer selected from the group consisting of titanium, zirconium, niobium, tantalum, and vanadium, and the thickness of the layer is not less than 50 nm and not more than 700 nm. A method for producing a corrosion-resistant conductive coating material.
（３）前記白金族金属含有層及び／またはその酸化物層が、
イリジウム、ルテニウム、ロジウム、パラジウム、白金からなる群から選ばれる少なくとも一つの白金族金属又はその酸化物層を含んでなる層であり、かつ、該層の厚さが１０ｎｍ以上３００ｎｍ以下であることを特徴とする請求項１又は２に記載の耐食導電被覆材料の製造方法。
(3) The platinum group metal-containing layer and / or its oxide layer is
It is a layer comprising at least one platinum group metal selected from the group consisting of iridium, ruthenium, rhodium, palladium and platinum or an oxide layer thereof, and the thickness of the layer is 10 nm or more and 300 nm or less. The method for producing a corrosion-resistant conductive coating material according to claim 1 or 2.
（４）前記金属からなる基体が、チタン、ジルコニウム、ニオブ、タンタル、バナジウムからなる群から選ばれる少なくとも一つの金属、またはそれらの金属を主成分とする合金からなる群から選ばれる少なくとも一つであることを特徴とする請求項１〜３のいずれか一つに記載の耐食導電被覆材料の製造方法。 (4) The base made of the metal is at least one selected from the group consisting of titanium, zirconium, niobium, tantalum, and vanadium, or an alloy mainly composed of these metals. It exists, The manufacturing method of the corrosion-resistant electrically conductive coating material as described in any one of Claims 1-3 characterized by the above-mentioned.
本発明によれば、金属基体と白金族金属めっき層との間に、含４族金属化合物溶液及び／又は含５族金属化合物溶液の熱分解によって形成された４族金属の酸化物及び／または５族金属の酸化物層からなる第一の中間層、白金族金属層及び／またはその酸化物層およびそれらの混合層からなる第二の中間層が形成されることにより、金属基体と白金族金属めっき層との密着性と導電性が飛躍的に向上し、導通性と耐食性が著しく改善する。 According to the present invention, a Group 4 metal oxide formed by thermal decomposition of a Group 4 metal compound solution and / or a Group 5 metal compound solution between the metal substrate and the platinum group metal plating layer and / or A metal substrate and a platinum group are formed by forming a first intermediate layer made of a Group 5 metal oxide layer, a platinum group metal layer and / or a second intermediate layer made of the oxide layer and a mixed layer thereof. Adhesion and conductivity with the metal plating layer are dramatically improved, and conductivity and corrosion resistance are remarkably improved.
すなわち、熱処理によって金属基体表層に形成される金属酸化物層と白金族金属層及び／またはその酸化物層は、耐食性と導電性に優れ、白金族金属めっき膜と金属基体の導電経路を長期間にわたり良好に保持、維持することができる。この結果、該白金族金属めっき層が電極表層の耐食性導電膜として有効に作用し、腐食性の強い過ハロゲン酸化合物や強酸などから金属基体を保護し、長期にわたって、めっき装置または電気化学反応槽を構成する材料として機能する。 That is, the metal oxide layer and the platinum group metal layer and / or the oxide layer formed on the surface of the metal substrate by heat treatment are excellent in corrosion resistance and conductivity, and the conductive path between the platinum group metal plating film and the metal substrate is extended for a long time. Can be maintained and maintained well over the entire range. As a result, the platinum group metal plating layer effectively acts as a corrosion-resistant conductive film on the electrode surface layer, protects the metal substrate from highly corrosive perhalogenate compounds, strong acids, etc. It functions as a material that constitutes.
さらに、色素増感型太陽電池用電極においても、強い酸化性および腐食性を示すヨウ素に対して、金属基体表層に形成される金属酸化物層と白金族金属層及び／またはその酸化物層は金属基体を保護し、金属基体が持つ高い導電体特性により、良好な発電特性を発揮する。 Further, in the dye-sensitized solar cell electrode, the metal oxide layer and the platinum group metal layer and / or the oxide layer thereof formed on the surface of the metal substrate with respect to iodine exhibiting strong oxidizing and corrosive properties It protects the metal substrate and exhibits good power generation characteristics due to the high conductor properties of the metal substrate.
本発明の耐食導電被覆材料において、使用する基体は金属基体であり、特に強酸性および強酸化性の使用環境における耐食性の観点から周期律表第４族金属及び第５族金属からなる群から選ばれる少なくとも一つの金属およびそれを主成分とする合金であることが好ましく、具体的にはチタン、ジルコニウム、ニオブ、タンタル、バナジウムおよびそれを主成分とする合金からなる群から選ばれる少なくとも一つの金属基体であるが、その中でも耐食性が優れ、かつ導電性が高い酸化物を形成し易いチタン、ニオブ、タンタルおよびそれを主成分とする合金が最も好ましい。また、この基体とその基体表層に形成する白金族金属めっき層との密着性を強化するため、事前に該基体表面を、ブラストやエッチング処理等を行い、表面積拡大、表面粗化を行ったものを使用することが好ましい。 In the corrosion-resistant conductive coating material of the present invention, the substrate to be used is a metal substrate, and particularly selected from the group consisting of Group 4 metals and Group 5 metals in the periodic table from the viewpoint of corrosion resistance in a strongly acidic and strong oxidizing environment. And at least one metal selected from the group consisting of titanium, zirconium, niobium, tantalum, vanadium and alloys based on it. Among these, titanium, niobium, tantalum and alloys containing them as their main components are most preferred because they are excellent in corrosion resistance and easily form oxides with high conductivity. In addition, in order to enhance the adhesion between the substrate and the platinum group metal plating layer formed on the surface of the substrate, the surface of the substrate has been subjected to blasting, etching, etc. in advance to increase the surface area and roughen the surface. Is preferably used.
ブラストやエッチング処理後、表面の選択エッチングを行い清浄化及び活性化を行うことができる。この清浄化および活性化の手法としては酸洗浄が挙げられ、代表的なものは、硫酸、塩酸及びフッ酸などの液に前記金属基体を浸漬し表面の一部を溶解することにより活性化を行うことができる。 After blasting or etching treatment, the surface can be selectively etched to be cleaned and activated. This cleaning and activation method includes acid cleaning, and typical ones are activated by immersing the metal substrate in a solution such as sulfuric acid, hydrochloric acid and hydrofluoric acid to dissolve a part of the surface. It can be carried out.
次いで、活性化した金属基体表面に、第一中間層である４族金属の酸化物及び／または５族金属の酸化物層を形成する。 Next, a Group 4 metal oxide and / or Group 5 metal oxide layer, which is a first intermediate layer, is formed on the surface of the activated metal substrate.
この第一中間層の形成方法は、４族及び／または５族金属化合物と水酸基を有する有機溶媒からなる塗布液を塗布、乾燥、焼成する熱分解法によって形成することができる。 The first intermediate layer can be formed by a thermal decomposition method in which a coating solution composed of a group 4 and / or group 5 metal compound and an organic solvent having a hydroxyl group is applied, dried, and fired.
ところで、４族及び／または５族金属化合物と水酸基を有する有機溶媒とからなる塗布液を塗布、乾燥、焼成する方法として、他にゾルゲル法による方法も考えられるが、該ゾルゲル法にて形成された酸化物層を第一中間層に適用した場合は、導電性が劣化するので不適である。なぜなら、ゾルゲル法にて作製された酸化物層は、金属−酸素結合のネットワークがより完全であるために、導電性の高い酸化物層を形成できないためである。 By the way, as a method of applying, drying, and baking a coating solution composed of a group 4 and / or group 5 metal compound and an organic solvent having a hydroxyl group, a method based on a sol-gel method is also conceivable. When the oxide layer is applied to the first intermediate layer, it is not suitable because the conductivity deteriorates. This is because an oxide layer manufactured by a sol-gel method cannot form a highly conductive oxide layer because the network of metal-oxygen bonds is more complete.
熱分解法によって第一中間層である４族金属の酸化物及び／または５族金属の酸化物層を形成する場合には、塗布液を塗布した金属基体を５０〜１００℃で１０分程度乾燥させた後、３５０℃以上６００℃以下、耐食性と導電性の観点から、より好ましくは４２５〜５２５℃の範囲で熱処理を行う熱分解法により第一中間層である４族金属の酸化物及び／または５族金属の酸化物層を形成する。 When forming a Group 4 metal oxide and / or Group 5 metal oxide layer as the first intermediate layer by pyrolysis, the metal substrate coated with the coating solution is dried at 50 to 100 ° C. for about 10 minutes. Then, from the viewpoint of corrosion resistance and conductivity at 350 ° C. or more and 600 ° C. or less, more preferably, the oxide of the Group 4 metal as the first intermediate layer by a thermal decomposition method in which heat treatment is performed in the range of 425 to 525 ° C. and / or Alternatively, a Group 5 metal oxide layer is formed.
塗布液に用いる第４族及び／または５族金属化合物としては金属アルコキシド、塩化物、酢酸塩、有機金属化合物があり、具体的な例としてはチタニウム（ＩＶ）エトキシド、チタニウム‐ｉｓｏ‐プロポキシド、チタニウム‐ｎ‐ブトキシド、チタニウム（ＩＶ）−ｔ‐ブトキシド、四塩化チタン、チタニウム（ＩＶ）オキシアセチルアセトナート、ビス（ｔｅｒｔ‐ブチルシクロペンタジエニル）チタニウムジクロリド、ジルコニウム（ＩＶ）エトキシド、ジルコニウムテトラ‐ｎ‐ブトキシド、ジルコニウム（ＩＶ）−ｔ‐ブトキシド、ジルコニウム−ｉｓｏ‐プロポキシド、塩化ジルコニウム（ＩＶ）、テトラクロロビス（テトラヒドロフラン）ジルコニウム、ビス（インデニル）ジルコニウムジクロリド、ビス（シクロペンタジエニル）ジルコニウムクロリドヒドリド、ビス（ｎ‐ブチルシクロペンタジエニル）ジルコニウムジクロリド、ビス（２‐メチルインデニル）ジルコニウムジクロリド、ビス（メチルシクロペンタジエニル）ジルコニウムジクロリド、ペンタメチルシクロペンタジエニルジルコニウムトリクロリド、バナジウム（Ｖ）−トリイソプロポキシド−オキシド、バナジウム（Ｖ）−ｔ‐トリプロポキシド、バナジウム（Ｖ）−ｎ‐トリブドキシド、酸化バナジウムアセチルアセトナート、塩化バナジウム、ビス（シクロペンタジエニル）バナジウムジクロリド、ジクロロエトキシオキソバナジウム（Ｖ）、シクロペンタジエニルバナジウムテトラカルボニル、ペンタイソプロポキシニオブ、ペンタエトキシニオブ、ペンタエトキシニオブ（Ｖ）、ペンタエトキシニオブ（Ｖ）、塩化ニオブ（Ｖ）、シクロペンタジエニルニオブ（Ｖ）−テトラクロリド、２−エチルヘキサン酸ニオブ（Ｖ）、テトラクロロビス（テトラヒドロフラン）ニオブ（ＩＶ）、テトラキス（２，２，６，６−テトラメチル−３，５−ヘプタンジオナト）ニオブ（ＩＶ）、タンタル（Ｖ）エトキシド、タンタル（Ｖ）メトキシド、タンタル（Ｖ）−２，２，２−トリフルオロエトキシド、タンタル（Ｖ）ブドキシド、タンタルテトラエトキシジメチルアミノエトキシド、五塩化タンタル、四塩化ペンタメチルシクロペンタジエニルタンタル、トリス（ジエチルアミド）−ｔ−ブチルイミドタンタル、ペンタキス（ジメチルアミノ）タンタル（Ｖ）、ペンタメチルシクロペンタジエニルタンタルテトラクロリド、２，４−ペンタンジオン酸タンタル（Ｖ）テトラエトキシド、テトラエトキシアセチルアセトナトタンタル（Ｖ）などが挙げられるが、塗布液の保存安定性や経済的観点から、好ましくはアルコキシドまたは塩化物である第４族及び／または５族金属化合物を用いるのが良い。 Examples of Group 4 and / or Group 5 metal compounds used in the coating solution include metal alkoxides, chlorides, acetates, and organometallic compounds. Specific examples include titanium (IV) ethoxide, titanium-iso-propoxide, Titanium-n-butoxide, titanium (IV) -t-butoxide, titanium tetrachloride, titanium (IV) oxyacetylacetonate, bis (tert-butylcyclopentadienyl) titanium dichloride, zirconium (IV) ethoxide, zirconium tetra- n-butoxide, zirconium (IV) -t-butoxide, zirconium-iso-propoxide, zirconium (IV) chloride, tetrachlorobis (tetrahydrofuran) zirconium, bis (indenyl) zirconium dichloride, bis (cyclopentadiene) L) Zirconium chloride hydride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (2-methylindenyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, pentamethylcyclopentadienyl zirconium trichloride , Vanadium (V) -triisopropoxide-oxide, vanadium (V) -t-tripropoxide, vanadium (V) -n-triboxide, vanadium oxide acetylacetonate, vanadium chloride, bis (cyclopentadienyl) vanadium Dichloride, dichloroethoxyoxovanadium (V), cyclopentadienyl vanadium tetracarbonyl, pentaisopropoxyniobium, pentaethoxyniobium, pentaethoxyniobium (V), pen Ethoxy niobium (V), niobium chloride (V), cyclopentadienyl niobium (V) -tetrachloride, niobium 2-ethylhexanoate (V), tetrachlorobis (tetrahydrofuran) niobium (IV), tetrakis (2,2 , 6,6-tetramethyl-3,5-heptanedionato) niobium (IV), tantalum (V) ethoxide, tantalum (V) methoxide, tantalum (V) -2,2,2-trifluoroethoxide, tantalum (V ) Butoxide, tantalum tetraethoxydimethylaminoethoxide, tantalum pentachloride, pentamethylcyclopentadienyl tantalum tetrachloride, tris (diethylamide) -t-butylimidotantalum, pentakis (dimethylamino) tantalum (V), pentamethylcyclopenta Dienyl tantalum tetrachloride, 2,4-pe Examples thereof include tantalum tantionate (V) tetraethoxide and tetraethoxyacetylacetonato tantalum (V). From the storage stability and economical viewpoint of the coating solution, the alkoxide or chloride is preferably used. Alternatively, a Group 5 metal compound is preferably used.
また、塗布液に用いる水酸基を有する有機溶媒としては具体的にはメタノール、エタノール、プロピルアルコール、イソプロピルアルコール、ブタノール、ペンタノール、ヘキサノール、シクロヘキサノールが挙げられ、好ましくはプロピルアルコール、イソプロピルアルコール、ブタノール、ペンタノールが挙げられる。 Specific examples of the organic solvent having a hydroxyl group used in the coating solution include methanol, ethanol, propyl alcohol, isopropyl alcohol, butanol, pentanol, hexanol, and cyclohexanol, preferably propyl alcohol, isopropyl alcohol, butanol, Examples include pentanol.
第一中間層である４族金属の酸化物及び／または５族金属の酸化物層の上記溶液−熱分解法による形成は、より耐食性を向上させる効果があるが、金属酸化物は抵抗成分としても機能するため、導電性を特に重視する場合には本工程は省いても良い。なぜなら、次工程の第二中間層の形成時に、基体金属の最表に極薄い金属酸化物層である第一中間層も形成され、この酸化物層のみでも充分に耐食性を発揮することができる。 The formation of the Group 4 metal oxide and / or Group 5 metal oxide layer, which is the first intermediate layer, by the above-described solution-pyrolysis method is more effective in improving corrosion resistance, but the metal oxide is used as a resistance component. Therefore, this step may be omitted when the conductivity is particularly important. This is because the first intermediate layer, which is an extremely thin metal oxide layer, is also formed on the outermost surface of the base metal during the formation of the second intermediate layer in the next step, and even this oxide layer alone can sufficiently exhibit corrosion resistance. .
第一中間層である４族金属の酸化物及び／または５族金属の酸化物層の厚みは、５０ｎｍ未満では耐食性が充分に発揮することができず、７００ｎｍ超では抵抗が高くなって導電特性が悪化するため、５０ｎｍ以上７００ｎｍ以下が好ましい。 If the thickness of the Group 4 metal oxide and / or Group 5 metal oxide layer, which is the first intermediate layer, is less than 50 nm, the corrosion resistance cannot be sufficiently exerted, and if it exceeds 700 nm, the resistance is increased and the conductive properties are increased. Is worse, 50 nm or more and 700 nm or less are preferable.
次いで、第一中間層の上層に第二中間層である白金族金属層及び／またはその酸化物層を形成する。該白金族金属層及び／またはその酸化物層は熱分解法やゾルゲル法などの方法で形成するのが好ましい。 Next, a platinum group metal layer and / or an oxide layer thereof as a second intermediate layer is formed on the first intermediate layer. The platinum group metal layer and / or its oxide layer is preferably formed by a method such as a thermal decomposition method or a sol-gel method.
前記白金族金属層及び／またはその酸化物層の成分としては、イリジウム、ルテニウム、ロジウム、パラジウム、白金からなる群から選ばれる少なくとも一つを含んだものであることが好ましく、各金属の有機金属化合物または金属塩化物を、水酸基を有する有機溶媒、例えばエタノール、プロピルアルコール、シクロヘキサノールなどの溶媒に溶解させて塗布液を調製する。 The component of the platinum group metal layer and / or its oxide layer preferably contains at least one selected from the group consisting of iridium, ruthenium, rhodium, palladium, and platinum. A compound or metal chloride is dissolved in an organic solvent having a hydroxyl group, for example, a solvent such as ethanol, propyl alcohol, or cyclohexanol to prepare a coating solution.
さらに、耐食性が特に求められる場合、前記塗布液にチタン、ジルコニウム、タンタル、ニオブ、バナジウム、錫の有機金属化合物または塩化物をさらに添加することにより得られる白金族金属層及び／またはその酸化物層の耐食性を向上することができる。添加する割合として、前記塗布液中に、タンタル、バナジウム、ニオブでは２０〜４８モル％、チタン、ジルコニウム、錫では５〜２０モル％となるように調製することが好ましい。 Furthermore, when corrosion resistance is particularly required, a platinum group metal layer and / or an oxide layer thereof obtained by further adding an organometallic compound or chloride of titanium, zirconium, tantalum, niobium, vanadium, tin to the coating solution. Corrosion resistance can be improved. As a ratio to be added, it is preferable that the coating liquid is prepared so as to be 20 to 48 mol% for tantalum, vanadium and niobium, and 5 to 20 mol% for titanium, zirconium and tin.
中間層を形成するための塗布方法として特に限定されず従来公知のものを使用することができ、例えば、スプレー塗布法、噴霧法、カーテンフローコート法、ドクターブレード法、ディップ塗布法、刷毛塗法、スピンコート法などを用いることができる。 The coating method for forming the intermediate layer is not particularly limited and conventionally known methods can be used. For example, spray coating method, spraying method, curtain flow coating method, doctor blade method, dip coating method, brush coating method A spin coating method or the like can be used.
塗布液を塗布した金属基体を５０〜１００℃で１０分程度乾燥させた後、３５０℃以上、より好ましくは３８０〜６００℃の範囲で焼成を行う熱分解法により白金族金属層及び／またはその酸化物層を形成する。 After the metal substrate coated with the coating solution is dried at 50 to 100 ° C. for about 10 minutes, the platinum group metal layer and / or its layer is formed by a pyrolysis method in which baking is performed at 350 ° C. or more, more preferably 380 to 600 ° C. An oxide layer is formed.
上記焼成工程では、金属基体の最表に形成させた極薄い絶縁性の金属酸化物中へ、熱処理によって形成される白金族金属層及び／またはその酸化物結晶粒子が熱拡散によって浸透する。すなわち、４族金属の酸化物及び／または５族金属の酸化物層中に白金族金属層及び／またはその酸化物粒子が分散した混合層が形成され、該白金族金属層及び／またはその酸化物粒子を介することで、絶縁性の金属酸化物層に導電経路が形成される。この結果、金属基体と白金族金属層及び／またはその酸化物との良好な導電性が保持できるようになる。 In the firing step, the platinum group metal layer formed by heat treatment and / or oxide crystal particles thereof penetrates into the ultrathin insulating metal oxide formed on the outermost surface of the metal substrate. That is, a mixed layer in which a platinum group metal layer and / or oxide particles thereof are dispersed in a group 4 metal oxide and / or a group 5 metal oxide layer is formed, and the platinum group metal layer and / or its oxidation is formed. A conductive path is formed in the insulating metal oxide layer by passing the object particles. As a result, good conductivity between the metal substrate and the platinum group metal layer and / or its oxide can be maintained.
白金族金属層及び／またはその酸化物層、該金属酸化物層中に白金族金属層及び／またはその酸化物粒子が分散した混合層は、金属基体を保護する機能を持つ。しかし、塗布から熱分解の工程を複数回繰り返すと、該白金族金属層の厚みは増すが、基体金属表層の酸化物層も同時に成長するため、耐食性導電被覆材料の導電特性に悪影響を及ぼしてしまう。さらに、熱分解法による白金族金属層及び／またはその酸化物層は厚くなると多数のクラックを生じやすく、金属基材との密着性が急激に低下するため、この上層に設ける白金族金属めっき被膜の形成が困難になる。逆に、薄すぎると基体金属への保護機能が低下してしまうため、導電性と保護機能が高く発現できるように厚みは１０ｎｍ〜３００ｎｍの範囲が好ましいが、経済的観点から５０ｎｍ〜１５０ｎｍの範囲がより好ましい。 The platinum group metal layer and / or oxide layer thereof, and the mixed layer in which the platinum group metal layer and / or oxide particles thereof are dispersed in the metal oxide layer have a function of protecting the metal substrate. However, if the process from coating to thermal decomposition is repeated a plurality of times, the thickness of the platinum group metal layer increases, but the oxide layer of the base metal surface layer also grows at the same time, which adversely affects the conductive properties of the corrosion-resistant conductive coating material. End up. Furthermore, since the platinum group metal layer and / or its oxide layer by the pyrolysis method are thick, many cracks are likely to occur, and the adhesion to the metal base material is drastically lowered. It becomes difficult to form. On the other hand, if the thickness is too thin, the protective function for the base metal is lowered. Therefore, the thickness is preferably in the range of 10 nm to 300 nm so that the electrical conductivity and the protective function can be expressed highly, but from the economical viewpoint, the range of 50 nm to 150 nm. Is more preferable.
次いで第二中間層の上層に白金族金属めっき層を形成する。
第二中間層として１０ｎｍ〜３００ｎｍ厚みの白金族金属層及び／またはその酸化物層を設けただけでは、基体金属の酸化物層が主であるために、導電性が悪く、基体金属を腐食環境下から完全に保護することが難しいため、めっき法によりイリジウム、白金、金のいずれかの被膜を形成させる必要があるが、耐食性と導電性の観点から本発明においては白金が最も適している。
Next, a platinum group metal plating layer is formed on the second intermediate layer.
The provision of a platinum group metal layer having a thickness of 10 nm to 300 nm and / or an oxide layer thereof as the second intermediate layer is mainly an oxide layer of the base metal, so that the conductivity is poor and the base metal is corrosive environment. Since it is difficult to completely protect from the bottom, it is necessary to form a film of iridium, platinum, or gold by a plating method, but platinum is most suitable in the present invention from the viewpoint of corrosion resistance and conductivity.
白金族金属めっき被膜の形成法には、スパッタリング法、イオンプレーティング法、電気めっき法、無電解めっき法などがあるが、複雑な装置を必要とせず、複雑な形状にも均一に形成が可能な電気めっき法または無電解めっき法が好適である。 There are sputtering methods, ion plating methods, electroplating methods, electroless plating methods, etc. as methods for forming platinum group metal plating films, but they do not require complicated equipment and can be uniformly formed even in complex shapes. An electroplating method or an electroless plating method is preferable.
形成する白金族金属めっき層の厚みは、０．２μｍ以上８μｍ以下が適当であるが、経済的観点から、１μｍ以上５μｍ以下がより好ましく、２μｍ以上４μｍ以下が最も好ましい。 The thickness of the platinum group metal plating layer to be formed is suitably 0.2 μm or more and 8 μm or less, but from the economical viewpoint, it is more preferably 1 μm or more and 5 μm or less, and most preferably 2 μm or more and 4 μm or less.
金属基体上に、白金に代表されるめっき層が施された従来の材料と本発明の中間層を有する耐食導電被覆材料の違いについて説明する。
チタン、ジルコニウム、ニオブ、タンタル、バナジウムなどの金属基体には表層に自然酸化被膜層が形成されている。該酸化被膜層を除去せずに、金属めっき層を形成した場合、金属めっき層と金属酸化物層間との密着性が悪いために、通常は基体の活性化処理直後に、または置換めっきにより基体金属酸化物層を除去した後に、めっきを行う。
A difference between a conventional material in which a plating layer typified by platinum is formed on a metal substrate and a corrosion-resistant conductive coating material having an intermediate layer of the present invention will be described.
A natural oxide film layer is formed on the surface of a metal substrate such as titanium, zirconium, niobium, tantalum, or vanadium. When the metal plating layer is formed without removing the oxide film layer, the adhesion between the metal plating layer and the metal oxide layer is poor, and therefore the substrate is usually immediately after the substrate activation treatment or by displacement plating. After removing the metal oxide layer, plating is performed.
白金めっきに限らず、金属めっき膜には必ず欠陥（ピンホール、クラックなど）が存在する。そのため、金属基体の活性化処理直後に白金めっきされた材料を腐食環境下に置いた場合、この欠陥に腐食液が入り込み、局部電池が形成されることになる。白金は最も貴な電極電位を持つ金属であるため、耐食性に優れるチタン、ジルコニウム、ニオブ、タンタル、バナジウムなどでも例外ではなく、局部電池が形成されてしまう。 Not only platinum plating but also metal plating films always have defects (pinholes, cracks, etc.). Therefore, when a platinum-plated material is placed in a corrosive environment immediately after the activation process of the metal substrate, a corrosive liquid enters this defect, and a local battery is formed. Since platinum is a metal having the most noble electrode potential, titanium, zirconium, niobium, tantalum, vanadium, etc., which have excellent corrosion resistance, are no exception, and a local battery is formed.
その結果、金属基体の溶解が始まり時間の経過とともに白金めっき層の剥離が起こるため、強酸性のめっき液に接する電解槽や給電用端子、色素増感型太陽電池用の電極など、特に耐食性が強く求められる環境での使用は困難である。欠陥を低減する方法として白金めっき層を厚くする方法もあるが、白金は高価な貴金属であり経済的ではない。 As a result, since the dissolution of the metal substrate starts and the platinum plating layer peels off over time, it has particularly high corrosion resistance such as an electrolytic cell in contact with a strongly acidic plating solution, a power supply terminal, and an electrode for a dye-sensitized solar cell. It is difficult to use in highly demanding environments. As a method of reducing defects, there is a method of increasing the thickness of the platinum plating layer, but platinum is an expensive noble metal and is not economical.
一方、本発明による耐食導電被覆材料では、白金族金属めっき層に欠陥があっても、熱処理工程で形成された金属基体表面の極薄い絶縁性の金属酸化物層により金属基体が腐食環境から保護されているため、局部電池の形成が抑制される。さらに、均一に分散している白金族金属層及び／またはその酸化物層の電極電位は白金金属と同等かそれ以上のため、白金族金属層及び／またはその酸化物層が侵されることもなく、高い耐食性能を長時間にわたり発揮する。 On the other hand, in the corrosion-resistant conductive coating material according to the present invention, even if the platinum group metal plating layer has a defect, the metal substrate is protected from the corrosive environment by the extremely thin insulating metal oxide layer formed on the surface of the metal substrate formed by the heat treatment process. Therefore, the formation of the local battery is suppressed. Furthermore, since the electrode potential of the uniformly dispersed platinum group metal layer and / or oxide layer thereof is equal to or higher than that of platinum metal, the platinum group metal layer and / or oxide layer thereof is not affected. High corrosion resistance performance is demonstrated for a long time.
さらに、基体表層の金属酸化物層中には、白金族金属層及び／またはその酸化物粒子が分散した混合層があり、該白金族金属層及び／またはその酸化物粒子を介することで、絶縁性の金属酸化物層に導電経路が形成されているため、金属基体と白金族金属層及び／またはその酸化物との良好な導電性が長時間にわたり保持できる。 Further, in the metal oxide layer on the surface of the substrate, there is a mixed layer in which a platinum group metal layer and / or oxide particles thereof are dispersed, and insulation is achieved through the platinum group metal layer and / or oxide particles thereof. Since the conductive path is formed in the conductive metal oxide layer, good conductivity between the metal substrate and the platinum group metal layer and / or its oxide can be maintained for a long time.
また、あらかじめ基体にプレス加工等の曲げ加工、切削加工、エッチング加工等の機械加工後に、白金族金属層及び／またはその酸化物層からなる中間層を、次いで、その上層に白金族金属めっき層の形成を行うことによって、複雑な形状の基体形成時にも白金族金属めっき層を損傷することなく、該白金族金属めっき膜の効果を確実に得ることができる。例えば、白金族金属めっき層の形成に関し、上記のように加工後の基体を陰極として電気めっきを行えば、加工によって基体表面が凹凸状態にあっても、均一に白金族金属めっき層を形成することが可能となり、安定した性能を得ることができる。 In addition, an intermediate layer made of a platinum group metal layer and / or an oxide layer thereof is formed on the base body in advance after bending such as press working, cutting, etching, etc., and then a platinum group metal plating layer is formed thereon. Thus, the effect of the platinum group metal plating film can be surely obtained without damaging the platinum group metal plating layer even when forming a substrate having a complicated shape. For example, regarding the formation of a platinum group metal plating layer, if electroplating is performed using the processed substrate as a cathode as described above, the platinum group metal plating layer is uniformly formed even if the substrate surface is uneven due to processing. And stable performance can be obtained.
以下、本発明を実施例に基づいて詳細に説明するが、本発明は実施例によりなんら限定されるものではない。なお、本実施例中ｗｔ％とあるのは質量％を指す。 EXAMPLES Hereinafter, although this invention is demonstrated in detail based on an Example, this invention is not limited at all by the Example. In this example, wt% refers to mass%.
（実施例１）
金属基体としてＴｉ基体（ＪＩＳ２種）を用いた。Ｔｉ基体は大きさが２０×３０ｍｍ、厚さが０．５ｍｍの圧延材である。該基体に、蓚酸１０ｗｔ％水溶液中で８時間エッチングを行うことにより、梨地仕上げを行った。次に、有機溶媒による脱脂処理後、０．１Ｎフッ酸中に３０秒間浸漬させて酸化被膜除去を行い、Ｔｉ基体表面処理工程を終了した。
Example 1
A Ti substrate (JIS type 2) was used as the metal substrate. The Ti substrate is a rolled material having a size of 20 × 30 mm and a thickness of 0.5 mm. The satin finish was performed by etching the substrate for 8 hours in a 10 wt% oxalic acid aqueous solution. Next, after the degreasing treatment with an organic solvent, the oxide film was removed by immersion in 0.1N hydrofluoric acid for 30 seconds, and the Ti substrate surface treatment step was completed.
ジルコニウムテトラ‐ｎ‐ブトキシド３．８３ｇ、ブタノール９５ｍｌ、アセチルアセトン５ｍｌを混ぜて、窒素雰囲気下で８時間攪拌、濃縮後、エタノールで希釈し濃度が０．００５Ｍに調製することで中間層用塗布液を準備した。表面処理工程を終了したＴｉ基体上にデッィプ法により塗布後、４００℃で１時間の熱処理を行うことで、厚み２３０ｎｍのＺｒＯ２層を形成した。 Zirconium tetra-n-butoxide (3.83 g), butanol (95 ml), and acetylacetone (5 ml) were mixed, stirred for 8 hours in a nitrogen atmosphere, concentrated, diluted with ethanol to a concentration of 0.005M, and the intermediate layer coating solution was prepared. Got ready. A ZrO 2 layer having a thickness of 230 nm was formed by applying a heat treatment at 400 ° C. for 1 hour after applying the surface treatment process on the Ti substrate by the dip method.
三塩化イリジウム三水和物２．４７ｇ、タンタル（Ｖ）エトキシド１．２２ｇ、イソプロパノール９８ｍｌ、シクロヘキサノール２ｍｌを混ぜて、窒素雰囲気下で８時間攪拌することで中間層用塗布液を調整した。ＺｒＯ２層を形成したＴｉ基体上にデッィプ法により塗布後、５００℃で１時間の熱処理を行うことで、厚み１１０ｎｍのＩｒＯ２−Ｔａ２Ｏ５層および導電経路が形成されたＺｒＯ２／ＴｉＯ２層を形成後、該基体を陰極として電気めっき法によって厚さ３μｍの白金めっき膜を形成した耐食導電被覆材料を合計１０枚作製した。 An intermediate layer coating solution was prepared by mixing 2.47 g of iridium trichloride trihydrate, 1.22 g of tantalum (V) ethoxide, 98 ml of isopropanol, and 2 ml of cyclohexanol, and stirring for 8 hours in a nitrogen atmosphere. After coating the De'ipu method on Ti substrate forming the ZrO 2 layer, by performing a heat treatment for 1 hour at 500 ° C., ZrO 2 / TiO of IrO 2 -Ta 2 O 5 layer and the conductive paths of thickness 110nm was formed After the formation of the two layers, a total of 10 corrosion-resistant conductive coating materials having a platinum plating film having a thickness of 3 μm formed by electroplating using the substrate as a cathode were produced.
（比較参考例１）
金属基体としてＴｉ基体（ＪＩＳ２種）を用いた。Ｔｉ基体は大きさが２０×３０ｍｍ、厚さが０．５ｍｍの圧延材である。該基体に、ジルコンショットを用いたショットブラスト加工により、梨地仕上げを行った。次に、有機溶媒による脱脂処理後、３Ｎ塩酸中に３０秒間浸漬させて酸化被膜除去を行い、Ｔｉ基体表面処理工程を終了した。
( Comparative Reference Example 1 )
A Ti substrate (JIS type 2) was used as the metal substrate. The Ti substrate is a rolled material having a size of 20 × 30 mm and a thickness of 0.5 mm. The substrate was finished with a satin finish by shot blasting using a zircon shot. Next, after degreasing treatment with an organic solvent, the oxide substrate was removed by immersion in 3N hydrochloric acid for 30 seconds to complete the Ti substrate surface treatment step.
三塩化イリジウム三水和物３．５２ｇ、エタノール９８ｍｌ、シクロヘキサノール２ｍｌを混ぜて、窒素雰囲気下で８時間攪拌することで中間層用塗布液を調整した。表面処理工程を終了したＴｉ基体上に刷毛塗法により塗布後、４９０℃で１時間の熱処理を行うことで、厚み５０ｎｍのＩｒＯ２層および導電経路が形成されたＴｉＯ２層（約１００ｎｍ）を形成後、該基体を陰極として電気めっき法によって厚さ３μｍの白金めっき膜を形成した耐食導電被覆材料を合計１０枚作製した。 An intermediate layer coating solution was prepared by mixing 3.52 g of iridium trichloride trihydrate, 98 ml of ethanol, and 2 ml of cyclohexanol, and stirring for 8 hours in a nitrogen atmosphere. After applying the surface treatment process to the Ti substrate by the brush coating method, heat treatment is performed at 490 ° C. for 1 hour to form an IrO 2 layer having a thickness of 50 nm and a TiO 2 layer (about 100 nm) in which a conductive path is formed. After the formation, a total of 10 corrosion-resistant conductive coating materials were produced, in which a platinum plating film having a thickness of 3 μm was formed by electroplating using the substrate as a cathode.
（比較参考例２）
金属基体としてＮｂ基体を用いた。Ｎｂ基体は大きさが２０×３０ｍｍ、厚さが０．２ｍｍの圧延材である。該基体に、ジルコンショットを用いたショットブラスト加工により、梨地仕上げを行った。次に、有機溶媒による脱脂処理後、６Ｎフッ酸中に１分間浸漬させて酸化被膜除去を行い、Ｎｂ基体表面処理工程を終了した。
( Comparative Reference Example 2 )
An Nb substrate was used as the metal substrate. The Nb substrate is a rolled material having a size of 20 × 30 mm and a thickness of 0.2 mm. The substrate was finished with a satin finish by shot blasting using a zircon shot. Next, after degreasing treatment with an organic solvent, the oxide film was removed by immersion in 6N hydrofluoric acid for 1 minute, and the Nb substrate surface treatment step was completed.
表面処理工程を終了したＮｂ基体を空気中、４００℃で１時間の熱処理を行うことで、厚み２２５ｎｍのＮｂＯ２層を形成した。 A NbO 2 layer having a thickness of 225 nm was formed by heat-treating the Nb substrate after the surface treatment step in air at 400 ° C. for 1 hour.
三塩化ルテニウム三水和物２．０９ｇ、ニオブ（Ｖ）エトキシド０．６４ｇ、エタノール９０ｍｌ、アセチルアセトン１０ｍｌを混ぜて、窒素雰囲気下で８時間攪拌することで中間層用塗布液を調整した。表面処理工程を終了したＮｂ基体上にデッィプ法により塗布後、５００℃で１時間の熱処理を行うことで、厚み７５ｎｍのＲｕＯ２層および導電経路が形成されたＮｂＯ２層を形成後、該基体を陰極として電気めっき法によって厚さ３μｍの白金めっき膜を形成した耐食導電被覆材料を合計１０枚作製した。 An intermediate layer coating solution was prepared by mixing 2.09 g of ruthenium trichloride trihydrate, 0.64 g of niobium (V) ethoxide, 90 ml of ethanol, and 10 ml of acetylacetone and stirring for 8 hours in a nitrogen atmosphere. After applying the surface treatment process on the Nb substrate by the dip method, heat treatment is performed at 500 ° C. for 1 hour to form a 75 nm-thick RuO 2 layer and an NbO 2 layer in which a conductive path is formed. A total of 10 corrosion-resistant conductive coating materials having a platinum plating film having a thickness of 3 μm formed thereon by electroplating using as a cathode.
（比較参考例３）
金属基体としてＮｂ基体を用いた。Ｎｂ基体は大きさが２０×３０ｍｍ、厚さが０．２ｍｍの圧延材である。該基体に、ジルコンショットを用いたショットブラスト加工により、梨地仕上げを行った。次に、有機溶媒による脱脂処理後、６Ｎフッ酸中に１分間浸漬させて酸化被膜除去を行い、Ｎｂ基体表面処理工程を終了した。
( Comparative Reference Example 3 )
An Nb substrate was used as the metal substrate. The Nb substrate is a rolled material having a size of 20 × 30 mm and a thickness of 0.2 mm. The substrate was finished with a satin finish by shot blasting using a zircon shot. Next, after degreasing treatment with an organic solvent, the oxide film was removed by immersion in 6N hydrofluoric acid for 1 minute, and the Nb substrate surface treatment step was completed.
三塩化ルテニウム三水和物２．６１ｇ、エタノール９８ｍｌ、シクロヘキサノール２ｍｌを混ぜて、窒素雰囲気下で８時間攪拌することで中間層用塗布液を調整した。表面処理工程を終了したＮｂ基体に刷毛塗法により塗布後、４７５℃で１時間の熱処理を行うことで、厚み５０ｎｍのＲｕＯ２層および導電経路が形成されたＮｂＯ２層（約１２０ｎｍ）を形成後、該基体を陰極として電気めっき法によって厚さ３μｍの白金めっき膜を形成した耐食導電被覆材料を合計１０枚作製した。 The intermediate layer coating solution was prepared by mixing 2.61 g of ruthenium trichloride trihydrate, 98 ml of ethanol, and 2 ml of cyclohexanol, and stirring for 8 hours in a nitrogen atmosphere. After applying the surface treatment process to the Nb substrate by brush coating, heat treatment is performed at 475 ° C. for 1 hour to form a RuO 2 layer having a thickness of 50 nm and an NbO 2 layer (about 120 nm) in which a conductive path is formed. Thereafter, a total of 10 corrosion-resistant conductive coating materials having a platinum plating film having a thickness of 3 μm formed by electroplating using the substrate as a cathode were produced.
（実施例２）
金属基体としてＺｒ基体を用いた。Ｚｒ基体は大きさが２０×３０ｍｍ、厚さが０．２ｍｍの圧延材である。該基体に、ジルコンショットを用いたショットブラスト加工により、梨地仕上げを行った。次に、有機溶媒による脱脂処理後、６Ｎフッ酸中に１分間浸漬させて酸化被膜除去を行い、Ｚｒ基体表面処理工程を終了した。
( Example 2 )
A Zr substrate was used as the metal substrate. The Zr substrate is a rolled material having a size of 20 × 30 mm and a thickness of 0.2 mm. The substrate was finished with a satin finish by shot blasting using a zircon shot. Next, after degreasing treatment with an organic solvent, the oxide film was removed by immersion in 6N hydrofluoric acid for 1 minute, and the Zr substrate surface treatment step was completed.
チタニウムテトラ‐ｎ‐ブトキシド３．４０ｇ、ブタノール９５ｍｌ、アセチルアセトン５ｍｌを混ぜて、窒素雰囲気下で８時間攪拌、濃縮後、ブタノールで希釈し濃度が０．００５Ｍに調製することで中間層用塗布液を準備した。表面処理工程を終了したＺｒ基体上にデッィプ法により塗布後、４００℃で１時間の熱処理を行うことで、厚み３１０ｎｍのＴｉＯ２層を形成した。 Mix titanium tetra-n-butoxide (3.40 g), butanol (95 ml), and acetylacetone (5 ml), stir in a nitrogen atmosphere for 8 hours, concentrate, and then dilute with butanol to adjust the concentration to 0.005M. Got ready. A TiO 2 layer having a thickness of 310 nm was formed by applying a heat treatment at 400 ° C. for 1 hour after applying the surface treatment process on the Zr substrate by the dip method.
三塩化ロジウム三水和物２．１１ｇ、ジルコニウムテトラ‐ｎ‐ブトキシド０．７７ｇ、エタノール５０ｍｌ、ブタノール４５ｍｌ、シクロヘキサノール２ｍｌ、アセチルアセトン３ｍｌを混ぜて、窒素雰囲気下で８時間攪拌することで中間層用塗布液を調整した。ＴｉＯ２層を形成したＺｒ基体上に刷毛塗法により塗布後、５００℃で１時間の熱処理を行うことで、厚み１５０ｎｍのＲｈ２Ｏ３−ＺｒＯ２層および導電経路が形成されたＴｉＯ２／ＺｒＯ２層を形成後、還元剤にヒドラジンを用いた無電解めっき法によって厚さ２μｍの白金めっき膜を形成した耐食導電被覆材料を合計１０枚作製した。 Rhodium trichloride trihydrate (2.11 g), zirconium tetra-n-butoxide (0.77 g), ethanol (50 ml), butanol (45 ml), cyclohexanol (2 ml), and acetylacetone (3 ml) are mixed and stirred for 8 hours in a nitrogen atmosphere for an intermediate layer. The coating solution was adjusted. After applying the brush coating method on the Zr substrate on which the TiO 2 layer is formed, a heat treatment is performed at 500 ° C. for 1 hour, so that the Rh 2 O 3 —ZrO 2 layer having a thickness of 150 nm and the conductive path formed in TiO 2 / After the formation of the ZrO 2 layer, a total of 10 corrosion-resistant conductive coating materials having a platinum plating film having a thickness of 2 μm formed by an electroless plating method using hydrazine as a reducing agent.
（比較参考例４）
金属基体としてＴａ基体を用いた。Ｔａ基体は大きさが２０×３０ｍｍ、厚さが０．２ｍｍの圧延材である。該基体に、炭化珪素を用いたショットブラスト加工により、梨地仕上げを行った。次に、有機溶媒による脱脂処理後、６Ｎフッ酸中に１分間浸漬させて酸化被膜除去を行い、Ｔａ基体表面処理工程を終了した。
( Comparative Reference Example 4 )
A Ta substrate was used as the metal substrate. The Ta substrate is a rolled material having a size of 20 × 30 mm and a thickness of 0.2 mm. The base was finished by shot blasting using silicon carbide. Next, after degreasing treatment with an organic solvent, the oxide film was removed by immersion in 6N hydrofluoric acid for 1 minute, and the Ta substrate surface treatment step was completed.
表面処理工程を終了したＴａ基体を空気中、５２５℃で１時間の熱処理を行うことで、厚み１１５ｎｍのＴａ２Ｏ５層を形成した。 The Ta substrate having finished the surface treatment process was heat-treated in air at 525 ° C. for 1 hour to form a Ta 2 O 5 layer having a thickness of 115 nm.
パラジウム（ＩＩ）アセチルアセトナート１．３７ｇ、塩化白金（ＩＶ）酸六水和物２．３３ｇ、無水四塩化すず０．２６ｇ、トルエン４５ｍｌ、ブタノール４５ｍｌ、エタノール５ｍｌ、純水５ｍｌを混ぜて、窒素雰囲気下で８時間攪拌することで中間層用塗布液を調整した。Ｔａ２Ｏ５層を形成したＴａ基体上にデッィプ法により塗布後、５００℃で１時間の熱処理を行うことで、厚み１３０ｎｍのPｄ−Ｐｔ−ＳｎＯ２層および導電経路が形成されたＴａ２Ｏ２層を形成後、還元剤にヒドラジンを用いた無電解めっき法によって厚さ２μｍの白金めっき膜を形成した耐食導電被覆材料を合計１０枚作製した。 Palladium (II) acetylacetonate 1.37 g, platinum (IV) chloride hexahydrate 2.33 g, anhydrous tin tetrachloride 0.26 g, toluene 45 ml, butanol 45 ml, ethanol 5 ml, pure water 5 ml were mixed and mixed with nitrogen. The intermediate layer coating solution was prepared by stirring for 8 hours under an atmosphere. After coating the De'ipu method on Ta substrate to form a Ta 2 O 5 layer, by performing a heat treatment for 1 hour at 500 ° C., Ta 2 the Pd-Pt-SnO 2 layer and the conductive path in the thickness 130nm was formed O After the formation of the two layers, a total of 10 corrosion-resistant conductive coating materials having a platinum plating film with a thickness of 2 μm formed by electroless plating using hydrazine as a reducing agent.
（実施例３）
金属基体としてＶ基体を用いた。Ｖ基体は大きさが２０×３０ｍｍ、厚さが０．２ｍｍの圧延材である。該基体に、炭化珪素を用いたショットブラスト加工により、梨地仕上げを行った。次に、有機溶媒による脱脂処理後、６Ｎフッ酸中に１分間浸漬させて酸化被膜除去を行い、Ｖ基体表面処理工程を終了した。
( Example 3 )
A V substrate was used as the metal substrate. The V substrate is a rolled material having a size of 20 × 30 mm and a thickness of 0.2 mm. The base was finished by shot blasting using silicon carbide. Next, after degreasing treatment with an organic solvent, the oxide substrate was removed by immersion in 6N hydrofluoric acid for 1 minute to complete the V substrate surface treatment step.
タンタル（Ｖ）‐ｎ‐ブトキシド５．４７ｇ、ブタノール９７ｍｌ、アセチルアセトン３ｍｌを混ぜて、窒素雰囲気下で８時間攪拌することで中間層用塗布液を調整した。表面処理工程を終了したＶ基体上にデッィプ法により塗布後、５２０℃で１時間の熱処理を行うことで、厚み４００ｎｍのＴａ２Ｏ５層を形成した。 The intermediate layer coating solution was prepared by mixing 5.47 g of tantalum (V) -n-butoxide, 97 ml of butanol, and 3 ml of acetylacetone and stirring for 8 hours under a nitrogen atmosphere. A Ta 2 O 5 layer having a thickness of 400 nm was formed by applying a heat treatment at 520 ° C. for 1 hour after coating on the V substrate after the surface treatment step by the dip method.
塩化白金酸六水和物５．１８ｇ、ブタノール１００ｍｌを混ぜて、窒素雰囲気下で８時間攪拌することで中間層用塗布液を調整した。Ｔａ２Ｏ５層を形成したＶ基体上に刷毛塗法により塗布後、５００℃で１時間の熱処理を行うことで、厚み１５０ｎｍのＰｔ層および導電経路が形成されたＴａ２Ｏ５／Ｖ２Ｏ５層を形成後、還元剤にヒドラジンを用いた無電解めっき法によって厚さ２μｍの白金めっき膜を形成した耐食導電被覆材料を合計１０枚作製した。 The intermediate layer coating solution was prepared by mixing 5.18 g of chloroplatinic acid hexahydrate and 100 ml of butanol and stirring for 8 hours under a nitrogen atmosphere. After coating the Ta 2 O 5 layer brushing method on the V base formed, and in the heat treatment of 1 hour at 500 ° C., Ta Pt layer and a conductive path in the thickness 150nm was formed 2 O 5 / V 2 After forming the O 5 layer, a total of 10 corrosion-resistant conductive coating materials having a platinum plating film having a thickness of 2 μm were prepared by an electroless plating method using hydrazine as a reducing agent.
（比較例１）
実施例１において、中間層をストライクめっき法にてＣｒ層を形成した以外は、同様に実施して白金めっき膜を形成し、被覆材料を合計１０枚作製した。
(Comparative Example 1)
In Example 1, except that the Cr layer was formed by the strike plating method, a platinum plating film was formed in the same manner, and a total of 10 coating materials were produced.
（比較例２）
比較参考例１において、中間層を形成しなかった以外は、同様に実施して白金めっき膜を形成し、被覆材料を合計１０枚作製した。
(Comparative Example 2)
In Comparative Reference Example 1 , a platinum plating film was formed in the same manner except that the intermediate layer was not formed, and a total of 10 coating materials were produced.
（比較例３）
比較参考例２において、中間層をストライクめっき法にてＮｉ層を形成した以外は、同様に実施して白金めっき膜を形成し、被覆材料を合計１０枚作製した。
(Comparative Example 3)
In Comparative Reference Example 2 , a platinum plating film was formed in the same manner except that the Ni layer was formed by strike plating, and a total of 10 coating materials were produced.
（比較例４）
比較参考例３において、中間層を形成しなかった以外は、同様に実施して白金めっき膜を形成し、被覆材料を合計１０枚作製した。
(Comparative Example 4)
In Comparative Reference Example 3 , a platinum plating film was formed in the same manner except that the intermediate layer was not formed, and a total of 10 coating materials were produced.
（比較例５）
実施例２において、中間層を形成しなかった以外は、同様に実施して無電解白金めっき膜を形成し、被覆材料を合計１０枚作製した。
(Comparative Example 5)
In Example 2 , an electroless platinum plating film was formed in the same manner except that the intermediate layer was not formed, and a total of 10 coating materials were produced.
（比較例６）
比較参考例４において、中間層をストライクめっき法にてＮｉ層を形成した以外は、同様に実施して無電解白金めっき膜を形成し、被覆材料を合計１０枚作製した。
(Comparative Example 6)
In Comparative Reference Example 4 , an electroless platinum plating film was formed in the same manner except that the Ni layer was formed by the strike plating method, and a total of 10 coating materials were produced.
（比較例７）
実施例３において、第一中間層として置換めっきにてＺｎめっきを、続いて第二中間層としてストライクめっき法にてＣｕ層を形成した以外は、同様に実施して無電解白金めっき膜を形成し、被覆材料を合計１０枚作製した。
(Comparative Example 7)
In Example 3 , an electroless platinum plating film was formed in the same manner except that Zn plating was performed by displacement plating as the first intermediate layer, and subsequently the Cu layer was formed by strike plating as the second intermediate layer. Thus, a total of 10 coating materials were produced.
（各材料の用途評価）
１：給電用端子・ロールなどめっき装置構成用材料としての評価
このようにして作製した本発明にかかる耐食導電被覆材料と比較例に対して、硫酸銅めっき浴環境に近い模擬液である６０℃に保持された、塩酸を５０ｐｐｍ含む硫酸水溶液（２５０ｇ／Ｌ）を用いて浸漬試験を９０日間実施し、金属基体から模擬液中に溶出された金属イオン濃度をシーケンシャル形高周波プラズマ発光分析装置によって測定し、耐食性を比較した結果（５回実施した平均値）を表１に示す。また、電気的特性を図るために、初期表面抵抗と浸漬試験実施後の比較を行った結果を表２に示す。
(Evaluation of usage of each material)
1: Evaluation as a material for plating apparatus construction such as power supply terminals and rolls In contrast to the corrosion-resistant conductive coating material according to the present invention thus prepared and the comparative example, 60 ° C. is a simulated solution close to a copper sulfate plating bath environment. The immersion test was conducted for 90 days using an aqueous sulfuric acid solution (250 g / L) containing 50 ppm of hydrochloric acid, and the concentration of metal ions eluted from the metal substrate into the simulated solution was measured using a sequential high-frequency plasma emission spectrometer. Table 1 shows the results of comparison of corrosion resistance (average value carried out 5 times). Table 2 shows the result of comparison between the initial surface resistance and the immersion test in order to achieve electrical characteristics.
２：色素増感太陽電池用電極としての評価
次に、作製した本発明にかかる耐食導電被覆材料と比較例で作製した材料に対して、太陽電池作動環境に近い模擬液である５０℃に保持された４ｗｔ％Ｉ２およびヨウ化物塩含有アセトニトリル溶液を用いて浸漬試験を３０日間実施し、金属基体から模擬液中に溶出された金属イオン濃度をシーケンシャル形高周波プラズマ発光分析装置によって測定し、耐食性を比較した結果を表３に示す。また集電特性を図るために、初期表面抵抗と浸漬試験実施後表面処理抵抗の比較を行った結果を表４に示す。
2: Evaluation as an electrode for a dye-sensitized solar cell Next, the prepared corrosion-resistant conductive coating material according to the present invention and the material prepared in the comparative example are maintained at 50 ° C., which is a simulated liquid close to the operating environment of the solar cell. The 4 wt% I 2 and iodide salt-containing acetonitrile solution was subjected to an immersion test for 30 days, and the concentration of metal ions eluted from the metal substrate into the simulated solution was measured with a sequential type high-frequency plasma emission spectrometer, and the corrosion resistance Table 3 shows the result of comparison. Table 4 shows the results of comparison between the initial surface resistance and the surface treatment resistance after the immersion test in order to improve the current collection characteristics.
さらに、実施例１および比較例１において作製した被覆材料を対極電極として用いて色素増感太陽電池セルを作製した。さらに、実施例１および比較例１に対して、太陽電池作動環境に近い模擬液である５０℃に保持された４ｗｔ％Ｉ２およびヨウ化物塩含有アセトニトリル溶液を用いて浸漬試験を３０日間実施後、同様にセルを作製し、浸漬試験前後における太陽電池特性の変化について評価した結果について表５に示す。 Furthermore, the dye-sensitized solar cell was produced using the coating material produced in Example 1 and Comparative Example 1 as a counter electrode. Furthermore, after the immersion test was conducted for 30 days with respect to Example 1 and Comparative Example 1, using a 4 wt% I 2 and iodide salt-containing acetonitrile solution maintained at 50 ° C., which is a simulated liquid close to the solar cell operating environment. Table 5 shows the results of evaluation of changes in solar cell characteristics before and after the immersion test in the same manner.
すなわち、透明導電膜付きの透明基体としてＦＴＯガラス（日本板ガラス製２５ｍｍ×５０ｍｍ）を用い、その表面に二酸化チタンペースト（昭和電工製）をバーコーターで塗布し、乾燥後４５０℃で３０分焼成してそのまま室温となるまで放置し、１０μｍの厚さの多孔質酸化チタン半導体電極を形成した。 That is, FTO glass (25 mm x 50 mm made by Nippon Sheet Glass) was used as a transparent substrate with a transparent conductive film, and a titanium dioxide paste (made by Showa Denko) was applied to the surface with a bar coater, dried and baked at 450 ° C. for 30 minutes. The porous titanium oxide semiconductor electrode having a thickness of 10 μm was formed as it was until the temperature reached room temperature.
続いて色素吸着工程に移った。増感色素として、一般にＮ３ｄｙｅと呼ばれるビス（４，４’−ジカルボキシ−２，２’−ビピリジン）ジイソチオシアネートルテニウム錯体を使用し、色素濃度０．５ｍｍｏｌ／Ｌとなるよう調製したエタノール溶液中に、一旦１５０℃まで加熱した前記多孔質酸化チタン半導体電極を浸漬し、遮光下１晩静置した。その後エタノールにて余分な色素を洗浄してから風乾することで太陽電池の半導体電極を作製した。さらに、得られた半導体電極の酸化チタン投影面積が２５ｍｍ2になるよう、半導体層を研削した。 Then, it moved to the dye adsorption process. In an ethanol solution prepared using a bis (4,4′-dicarboxy-2,2′-bipyridine) diisothiocyanate ruthenium complex generally called N3dye as a sensitizing dye and having a dye concentration of 0.5 mmol / L The porous titanium oxide semiconductor electrode once heated to 150 ° C. was immersed and allowed to stand overnight under light shielding. Thereafter, excess pigment was washed with ethanol and then air-dried to produce a semiconductor electrode of a solar cell. Furthermore, the semiconductor layer was ground so that the projected area of titanium oxide of the obtained semiconductor electrode was 25 mm 2 .
前記のように作製した半導体電極と、実施例１もしくは比較例１において作製した電極を対極として該半導体電極に対向するよう設置し、電解質を毛管現象にて両電極間に含浸させた。電解質としては、溶媒をメトキシアセトニル、還元剤としてヨウ化リチウム、酸化剤としてヨウ素、添加剤としてｔ−ブチルピリジン、１，２−ジメチル−３−プロピルイミダゾリウムアイオダイドを含む溶液を用いた。 The semiconductor electrode produced as described above and the electrode produced in Example 1 or Comparative Example 1 were installed as a counter electrode so as to face the semiconductor electrode, and an electrolyte was impregnated between both electrodes by capillary action. As the electrolyte, a solution containing methoxyacetonyl as a solvent, lithium iodide as a reducing agent, iodine as an oxidizing agent, t-butylpyridine as an additive, and 1,2-dimethyl-3-propylimidazolium iodide was used.
上記の太陽電池セルについて、５ｍｍ角の窓をつけた光照射面積規定用マスクを装着させた上で、光量１００ｍＷ／ｃｍ2の擬似太陽光を照射して開放電圧（以下、「Ｖｏｃ」と略記する。）、短絡電流密度（以下、「Ｊｓｃ」と略記する。）、形状因子（以下、「ＦＦ」と略記する。）、および光電変換効率を評価した。 About the above-mentioned solar battery cell, a mask for light irradiation area regulation with a 5 mm square window is attached, and then a simulated sunlight with a light amount of 100 mW / cm 2 is irradiated to open voltage (hereinafter abbreviated as “Voc”). ), Short circuit current density (hereinafter abbreviated as “Jsc”), form factor (hereinafter abbreviated as “FF”), and photoelectric conversion efficiency.
「Ｖｏｃ」、「Ｊｓｃ」、「ＦＦ」及び光電変換効率の各測定値については、より大きい値が太陽電池セルの性能として好ましいことを表す。 About each measured value of "Voc", "Jsc", "FF", and a photoelectric conversion efficiency, it represents that a larger value is preferable as a performance of a photovoltaic cell.
３：電気化学反応槽：固体高分子型燃料電池用セパレータとしての評価
さらに、プレス加工にてガス流路を形成したＴｉ基体を用いて、比較参考例１および比較例２に記載の方法に従って基体を処理後、白金めっきの代わりに、２μｍ厚みの金めっき膜を形成しセパレータを製造した。両極に触媒を担持した固体電解質膜、ガス拡散電極、前述のセパレータを用いて単電池を組み立て、燃料として高純度水素ガスおよび空気を用いて発電を行い、Ｉ−Ｖ特性を調べた。続いて、１０００時間の連続発電試験を実行した後に同様にＩ−Ｖ特性を調べた結果を図１に示した。
3: Electrochemical reaction tank: Evaluation as a separator for a polymer electrolyte fuel cell Further, a substrate according to the method described in Comparative Reference Example 1 and Comparative Example 2 using a Ti substrate having a gas flow path formed by pressing. After the treatment, a 2 μm-thick gold plating film was formed instead of platinum plating to produce a separator. A cell was assembled using a solid electrolyte membrane carrying a catalyst on both electrodes, a gas diffusion electrode, and the separator described above, and power generation was performed using high-purity hydrogen gas and air as fuel, and IV characteristics were examined. Subsequently, the results of examining the IV characteristics in the same manner after the continuous power generation test for 1000 hours is shown in FIG.
その表１の結果によれば、本発明にかかる各耐食導電被覆材料は、浸漬試験９０日後においてもほとんど変化することなく基体が保護され、給電用端子・ロールなどめっき装置構成用材料用途に必要な耐食特性に優れていることが認められた。これに対し、同様に浸漬試験を行った比較例２、４、５では金属基体上に直接Ｐｔめっき層を形成したために、密着性が非常に悪く、いずれの試験片もＰｔめっき層が剥離し、基体が大きく腐食されているのが確認された。比較例１、３、６、７では、Ｐｔめっき層のピンホールから腐食液がしみ込み、初期には中間層とＰｔめっき層間で局部電池が形成することで基体が保護されていたが、最終的には中間層が消失した部位から基体の腐食が開始されることが確認できた。 According to the results in Table 1, each of the corrosion-resistant conductive coating materials according to the present invention is protected for the substrate with almost no change even after 90 days of the immersion test, and is necessary for the use of a plating apparatus constituting material such as a power supply terminal or roll. Excellent corrosion resistance. On the other hand, in Comparative Examples 2, 4, and 5 in which the immersion test was performed in the same manner, the Pt plating layer was formed directly on the metal substrate, so the adhesion was very poor, and the Pt plating layer was peeled off in any test piece. It was confirmed that the substrate was greatly corroded. In Comparative Examples 1, 3, 6, and 7, the corrosive liquid soaked from the pinhole of the Pt plating layer, and the base was protected by forming a local battery between the intermediate layer and the Pt plating layer in the initial stage. Specifically, it was confirmed that the corrosion of the substrate started from the site where the intermediate layer disappeared.
その表２の結果によれば、本発明にかかる各耐食導電被覆材料は、浸漬試験９０日後においてもほとんど変化することなく基体の導電特性を維持し、給電用端子・ロールなどめっき装置構成用材料用途に必要な導電特性に優れていることが認められた。これに対し、同様に浸漬試験を行った比較例２、４、５では金属基体上に直接Ｐｔめっき層を形成したために、密着性が非常に悪く、いずれの試験片もＰｔめっき層が剥離し基体の腐食が進行しているために、導電特性を測定することができなかった。比較例１、３、６、７では、Ｐｔめっき層のピンホールから腐食液がしみ込み、初期には中間層とＰｔめっき層間で局部電池が形成することで基体が保護されていたが、基体表面には酸化被膜が形成されて、浸漬日数が経過すると、耐食導電被覆材自身の抵抗が高くなる傾向になることが確認できた。 According to the results of Table 2, each of the corrosion-resistant conductive coating materials according to the present invention maintains the conductive characteristics of the substrate with almost no change even after 90 days of immersion test, and is a material for plating apparatus construction such as power supply terminals and rolls. It was found that the conductive properties required for the application were excellent. On the other hand, in Comparative Examples 2, 4, and 5 in which the immersion test was performed in the same manner, the Pt plating layer was formed directly on the metal substrate, so the adhesion was very poor, and the Pt plating layer was peeled off in any test piece. Since the corrosion of the substrate has progressed, the conductive properties could not be measured. In Comparative Examples 1, 3, 6, and 7, the corrosion solution soaked from the pinhole of the Pt plating layer, and the substrate was protected by forming a local battery between the intermediate layer and the Pt plating layer at the beginning. It has been confirmed that an oxide film is formed on the surface, and that the resistance of the corrosion-resistant conductive coating itself tends to increase when the number of immersion days elapses.
その表３の結果によれば、本発明にかかる各耐食導電被覆材料は、浸漬試験３０日後においてもほとんど変化することなく基材を保護し、色素増感太陽電池用電極に必要な耐食特性に優れていることが認められた。これに対し、同様に浸漬試験を行った比較例２、４、５では金属基体上に直接Ｐｔめっき層を形成したために、密着性が非常に悪く、いずれの試験片もＰｔめっき層の剥離し、基体が大きく腐食されているのが確認された。比較例１、３、６、７では、Ｐｔめっき層のピンホールから腐食液がしみ込み、初期には中間層とＰｔめっき層間で局部電池が形成することで基体が保護されていたが、最終的には中間層が消失した部位から基体の腐食が開始されることが確認できた。 According to the results of Table 3, each corrosion-resistant conductive coating material according to the present invention protects the base material with almost no change even after 30 days of immersion test, and has the corrosion resistance characteristics required for the dye-sensitized solar cell electrode. It was found to be excellent. On the other hand, in Comparative Examples 2, 4, and 5 in which the immersion test was conducted in the same manner, the Pt plating layer was formed directly on the metal substrate, so the adhesion was very poor, and any of the test pieces peeled off the Pt plating layer. It was confirmed that the substrate was greatly corroded. In Comparative Examples 1, 3, 6, and 7, the corrosive liquid soaked from the pinhole of the Pt plating layer, and the base was protected by forming a local battery between the intermediate layer and the Pt plating layer in the initial stage. Specifically, it was confirmed that the corrosion of the substrate started from the site where the intermediate layer disappeared.
その表４の結果によれば、本発明にかかる各耐食導電被覆材料は、浸漬試験３０日後においてもほとんど変化することなく基体の導電特性を維持し、色素増感太陽電池用電極に必要な導電特性に優れていることが認められた。これに対し、同様に浸漬試験を行った比較例２、４、５では金属基体上に直接Ｐｔめっき層を形成したために、密着性が非常に悪く、いずれの試験片もＰｔめっき層が剥離し基体の腐食が進行しているために、導電特性を測定することができなかった。比較例１、３、６、７では、Ｐｔめっき層のピンホールから腐食液がしみ込み、初期には中間層とＰｔめっき層間で局部電池が形成することで基体が保護されていたが、基体表面には酸化被膜が形成されて、浸漬日数が経過すると、耐食導電被覆材自身の抵抗が高くなる傾向になることが確認できた。 According to the results of Table 4, each corrosion-resistant conductive coating material according to the present invention maintains the conductive properties of the substrate with almost no change even after 30 days of immersion test, and the necessary conductivity for the dye-sensitized solar cell electrode. It was recognized that the characteristics were excellent. On the other hand, in Comparative Examples 2, 4, and 5 in which the immersion test was performed in the same manner, the Pt plating layer was formed directly on the metal substrate, so the adhesion was very poor, and the Pt plating layer was peeled off in any test piece. Since the corrosion of the substrate has progressed, the conductive properties could not be measured. In Comparative Examples 1, 3, 6, and 7, the corrosion solution soaked from the pinhole of the Pt plating layer, and the substrate was protected by forming a local battery between the intermediate layer and the Pt plating layer at the beginning. It has been confirmed that an oxide film is formed on the surface, and that the resistance of the corrosion-resistant conductive coating itself tends to increase when the number of immersion days elapses.
表５の結果によれば、本発明における耐食導電被覆材料は、浸漬試験後３０日においても良好な太陽電池特性を維持できていることが認められた。これに対し、同様に浸漬試験を行なった比較例１では、浸漬時間の経過とともに金属基体からがＰｔめっき層の一部が剥離し、中間層であるＣｒ層および金属基体の溶解が始まるとともに、電解液との接触により短絡して発電が不可能になることが確認できた。 According to the result of Table 5, it was recognized that the corrosion-resistant conductive coating material in the present invention can maintain good solar cell characteristics even 30 days after the immersion test. On the other hand, in Comparative Example 1 in which the immersion test was performed in the same manner, a part of the Pt plating layer was peeled off from the metal substrate with the lapse of the immersion time, and the dissolution of the Cr layer as the intermediate layer and the metal substrate started. It was confirmed that power generation was impossible due to a short circuit due to contact with the electrolyte.
図１によれば、初期には比較参考例１（金めっき）および比較例２（金めっき）のＩ−Ｖ特性曲線は良好な発電特性を示した。しかし、１０００時間の連続発電試験を実施後のＩ−Ｖ特性曲線を比較すると、比較参考例１においては性能の劣化がほとんど見られず、耐食導電被覆材料が良好な集電性能を維持され、優れた発電特性を確認した。それに対して比較例２では、耐食導電被覆材料のＴｉ基体が腐食して抵抗が高くなったうえに、溶解した金属イオンがプロトン伝導性電解質膜に悪影響を与えた結果、Ｉ−Ｖ特性の低下が見られ、耐食導電被覆材料として劣ることが確認された。 According to FIG. 1, the IV characteristic curves of Comparative Reference Example 1 (gold plating) and Comparative Example 2 (gold plating) initially showed good power generation characteristics. However, when comparing the IV characteristic curves after the 1000 hour continuous power generation test, in Comparative Reference Example 1 , almost no deterioration in performance was observed, and the corrosion-resistant conductive coating material maintained good current collection performance, Excellent power generation characteristics were confirmed. On the other hand, in Comparative Example 2, the Ti base of the corrosion-resistant conductive coating material was corroded to increase resistance, and the dissolved metal ions adversely affected the proton conductive electrolyte membrane, resulting in a decrease in IV characteristics. It was confirmed that it was inferior as a corrosion-resistant conductive coating material.
本発明の耐食導電被覆材料は、めっき装置や電気化学反応槽の構成用部材、例えば給電用の端子、ロール、電解槽そして色素増感太陽電池用電極を主たる用途とするが、固体高分子形燃料電池セパレータへも好適に使用できる。 The corrosion-resistant conductive coating material of the present invention is mainly used for components for plating apparatuses and electrochemical reaction tanks, such as power supply terminals, rolls, electrolytic cells, and dye-sensitized solar cell electrodes. It can also be suitably used for a fuel cell separator.
Claims (4)
熱分解法によって４族金属の酸化物及び／または５族金属の酸化物層を形成する工程、
次いで、該酸化物層上に、含白金族金属化合物を含有するアルコール溶液からなる塗布液を塗布、乾燥、焼成し、白金族金属含有層またはその酸化物層を形成する工程、
次いで、白金族金属めっき層を前記白金族金属含有層またはその酸化物層上に形成する工程を包含する耐食導電被覆材料の製造方法において、
白金族金属含有層またはその酸化物層を形成する工程における焼成温度が、３５０℃以上６００℃以下であることを特徴とする耐食導電被覆材料の製造方法。 On a substrate made of at least one metal selected from the group consisting of Group 4 and Group 5,
Forming a Group 4 metal oxide and / or a Group 5 metal oxide layer by pyrolysis,
Next, on the oxide layer, a step of applying a coating solution composed of an alcohol solution containing a platinum group metal compound, drying and baking to form a platinum group metal containing layer or an oxide layer thereof,
Next, in the method for producing a corrosion-resistant conductive coating material including the step of forming a platinum group metal plating layer on the platinum group metal-containing layer or the oxide layer thereof,
A method for producing a corrosion-resistant conductive coating material, wherein a firing temperature in the step of forming a platinum group metal- containing layer or an oxide layer thereof is 350 ° C. or higher and 600 ° C. or lower.
チタン、ジルコニウム、ニオブ、タンタル、バナジウムからなる群から選ばれる少なくとも一つの金属酸化物層であり、かつ、該層の厚さが５０ｎｍ以上７００ｎｍ以下であることを特徴とする請求項１に記載の耐食導電被覆材料の製造方法。 Group 4 metal oxide and / or Group 5 metal oxide layer by the thermal decomposition method,
It is at least one metal oxide layer selected from the group consisting of titanium, zirconium, niobium, tantalum, and vanadium, and the thickness of the layer is not less than 50 nm and not more than 700 nm. A method for producing a corrosion-resistant conductive coating material.
イリジウム、ルテニウム、ロジウム、パラジウム、白金からなる群から選ばれる少なくとも一つの白金族金属又はその酸化物を含んでなる層であり、かつ、該層の厚さが１０ｎｍ以上３００ｎｍ以下であることを特徴とする請求項１又は２に記載の耐食導電被覆材料の製造方法。 The platinum group metal-containing layer or its oxide layer is
It is a layer comprising at least one platinum group metal selected from the group consisting of iridium, ruthenium, rhodium, palladium and platinum or an oxide thereof, and the thickness of the layer is 10 nm or more and 300 nm or less. A method for producing a corrosion-resistant conductive coating material according to claim 1 or 2.
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