JP2018043895A - Ruthenium dioxide powder and production method thereof, thick film resistor paste, and thick film resistor - Google Patents
Ruthenium dioxide powder and production method thereof, thick film resistor paste, and thick film resistor Download PDFInfo
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- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 title claims abstract description 449
- 239000000843 powder Substances 0.000 title claims abstract description 150
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 38
- 150000001622 bismuth compounds Chemical class 0.000 claims abstract description 64
- 239000002245 particle Substances 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000011164 primary particle Substances 0.000 claims description 27
- 229940073609 bismuth oxychloride Drugs 0.000 claims description 23
- 239000011521 glass Substances 0.000 claims description 23
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 claims description 23
- 238000000034 method Methods 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 16
- 238000000926 separation method Methods 0.000 claims description 14
- 239000000243 solution Substances 0.000 claims description 12
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- 238000012545 processing Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 239000000203 mixture Substances 0.000 description 48
- 239000002994 raw material Substances 0.000 description 18
- 238000002441 X-ray diffraction Methods 0.000 description 17
- 238000002156 mixing Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical compound [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 9
- 238000004451 qualitative analysis Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- 229910052810 boron oxide Inorganic materials 0.000 description 7
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 7
- 238000011156 evaluation Methods 0.000 description 7
- 239000011812 mixed powder Substances 0.000 description 7
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 7
- 238000005406 washing Methods 0.000 description 7
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 229910052707 ruthenium Inorganic materials 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 4
- 239000001856 Ethyl cellulose Substances 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 4
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 229920001249 ethyl cellulose Polymers 0.000 description 4
- 235000019325 ethyl cellulose Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 150000004665 fatty acids Chemical class 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 235000012239 silicon dioxide Nutrition 0.000 description 4
- 229940116411 terpineol Drugs 0.000 description 4
- 239000011787 zinc oxide Substances 0.000 description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 239000000292 calcium oxide Substances 0.000 description 3
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- KFIKNZBXPKXFTA-UHFFFAOYSA-N dipotassium;dioxido(dioxo)ruthenium Chemical compound [K+].[K+].[O-][Ru]([O-])(=O)=O KFIKNZBXPKXFTA-UHFFFAOYSA-N 0.000 description 3
- -1 for example Chemical compound 0.000 description 3
- 238000004898 kneading Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- XWURZHGKODQZMK-UHFFFAOYSA-N O.[Ru]=O Chemical class O.[Ru]=O XWURZHGKODQZMK-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- VDRDGQXTSLSKKY-UHFFFAOYSA-K ruthenium(3+);trihydroxide Chemical compound [OH-].[OH-].[OH-].[Ru+3] VDRDGQXTSLSKKY-UHFFFAOYSA-K 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 description 1
- VXQBJTKSVGFQOL-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethyl acetate Chemical compound CCCCOCCOCCOC(C)=O VXQBJTKSVGFQOL-UHFFFAOYSA-N 0.000 description 1
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-HUOMCSJISA-N Rosin Natural products O(C/C=C/c1ccccc1)[C@H]1[C@H](O)[C@@H](O)[C@@H](O)[C@@H](CO)O1 KHPCPRHQVVSZAH-HUOMCSJISA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000005407 aluminoborosilicate glass Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 150000001553 barium compounds Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 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
- 239000005388 borosilicate glass Substances 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 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
- 239000011976 maleic acid Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000006072 paste Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003303 ruthenium Chemical class 0.000 description 1
- 150000003304 ruthenium compounds Chemical class 0.000 description 1
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 1
- KHPCPRHQVVSZAH-UHFFFAOYSA-N trans-cinnamyl beta-D-glucopyranoside Natural products OC1C(O)C(O)C(CO)OC1OCC=CC1=CC=CC=C1 KHPCPRHQVVSZAH-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Abstract
Description
本発明は、二酸化ルテニウム粉末とその製造方法、厚膜抵抗体ペースト、及び、厚膜抵抗体に関する。 The present invention relates to a ruthenium dioxide powder and a method for producing the same, a thick film resistor paste, and a thick film resistor.
厚膜抵抗体は、チップ抵抗器、厚膜ハイブリッドＩＣや抵抗ネットワーク等に広く用いられている。厚膜抵抗体は、導電粒子やガラス粉末を、ビヒクルと呼ばれる有機媒体中に分散させた厚膜抵抗体ペーストを基板上に塗布し焼成することにより製造される。厚膜抵抗体中の導電粒子は、厚膜抵抗体の電気的特性を決定する最も重要な役割を有しており、従来、ルテニウム酸鉛などが使用されていた。 Thick film resistors are widely used in chip resistors, thick film hybrid ICs, resistor networks, and the like. The thick film resistor is manufactured by applying a thick film resistor paste, in which conductive particles or glass powder is dispersed in an organic medium called a vehicle, onto a substrate and baking it. The conductive particles in the thick film resistor have the most important role in determining the electrical characteristics of the thick film resistor, and lead ruthenate has been conventionally used.
近年、環境を保護するために電子部品の鉛フリー化が進み、厚膜抵抗体についても、鉛を含まない導電粒子やガラス粉末を用いることが望まれている。鉛フリーの導電粒子として、例えば、酸化ルテニウム粉末が用いられており、その製造方法についても、いくつか報告されている。 In recent years, lead-free electronic components have been developed to protect the environment, and it has been desired to use conductive particles and glass powder that do not contain lead for thick film resistors. As the lead-free conductive particles, for example, ruthenium oxide powder is used, and some production methods thereof have been reported.
例えば、特許文献１には、４価より上の原子価をもつルテニウム塩の水溶液を、還元性を有する水溶性有機物で還元した微粉末状ルテニウム含水酸化物を脱水し、均一粒径の微粉末状の二酸化ルテニウムの製造方法が記載されている。 For example, Patent Document 1 discloses dehydration of fine powdered ruthenium hydroxide obtained by reducing an aqueous solution of a ruthenium salt having a valence higher than tetravalent with a water-soluble organic substance having reducibility to obtain a fine powder having a uniform particle size. A process for the production of a shaped ruthenium dioxide is described.
また、例えば、特許文献２には、ルテニウム化合物とバリウム化合物の混合物を、酸化雰囲気かつ４００℃以上の温度で熱処理してルテニウムとバリウムの板状複合酸化物を合成する工程と、次に、得られた板状複合酸化物に酸化ホウ素もしくはホウ酸を混合した後、５００℃以上の温度で熱処理を行って板状複合酸化物を板状の酸化ルテニウム粉末と酸化ホウ素と酸化バリウムの溶融物中に生成させる工程と、得られた溶融物に溶剤を添加し、酸化ホウ素と酸化バリウムを溶解して板状酸化ルテニウム粉末を回収する工程と、からなる板状酸化ルテニウム粉末の製造方法が記載されている。また、この製造方法により得られる板状酸化ルテニウム粉末は、径が１μｍ〜５μｍの六角板状で、厚みが０．１５μｍ〜０．５μｍであることが記載されている。 For example, Patent Document 2 discloses a step of synthesizing a plate-shaped composite oxide of ruthenium and barium by heat-treating a mixture of a ruthenium compound and a barium compound at an oxidizing atmosphere and a temperature of 400 ° C. or higher, and then obtaining After mixing boron oxide or boric acid with the obtained plate-like composite oxide, heat treatment is performed at a temperature of 500 ° C. or more to convert the plate-like composite oxide into a plate-like ruthenium oxide powder, boron oxide and barium oxide melt. And a step of adding a solvent to the obtained melt, dissolving boron oxide and barium oxide and recovering the plate-like ruthenium oxide powder, and a method for producing the plate-like ruthenium oxide powder is described. ing. Moreover, it is described that the plate-like ruthenium oxide powder obtained by this manufacturing method is a hexagonal plate shape with a diameter of 1 μm to 5 μm and a thickness of 0.15 μm to 0.5 μm.
しかしながら、本発明者の検討によると、特許文献１のように、従来の湿式法で製造された二酸化ルテニウムは、一般的に、粒状（球状を含む）の一次粒子を有するため、厚膜抵抗体の導電粒子として、この粒状の二酸化ルテニウムを用いた場合、導電粒子間の接点が多くなり、電流雑音が問題となることがあった。また、特許文献２に記載される酸化ルテニウムは、板状であるため、導電粒子間で面接触をすることができるが、製造工程が煩雑となり易かった。 However, according to the study of the present inventor, as in Patent Document 1, ruthenium dioxide produced by a conventional wet method generally has primary particles in a granular form (including a spherical shape). When this granular ruthenium dioxide is used as the conductive particles, the number of contacts between the conductive particles increases, and current noise may be a problem. Moreover, since ruthenium oxide described in Patent Document 2 has a plate shape, surface contact can be made between conductive particles, but the manufacturing process tends to be complicated.
本発明は、このような状況に鑑み、従来の粒状の二酸化ルテニウムと比較して、粒子間の接点の数を減少させることができる二酸化ルテニウム粉末と、その簡便な製造方法を提供する。また、本発明は、二酸化ルテニウム粉末を、厚膜抵抗体の導電粒子として用いた場合、従来の粒状の二酸化ルテニウムを用いた場合と比較して、電流雑音を低減させた厚膜抵抗体及び厚膜抵抗体ペーストを提供することを目的とする。 In view of such a situation, the present invention provides a ruthenium dioxide powder capable of reducing the number of contacts between particles as compared with conventional granular ruthenium dioxide, and a simple production method thereof. In addition, the present invention provides a thick film resistor and a thickness in which current noise is reduced when ruthenium dioxide powder is used as the conductive particles of the thick film resistor, compared to the case where conventional granular ruthenium dioxide is used. An object is to provide a film resistor paste.
本発明者は、上述した従来の課題を解決するため鋭意研究を重ねた結果、従来の粒状の二酸化ルテニウムを、ビスマス化合物の存在下で熱処理をすることにより、棒状の形状を有する二酸化ルテニウム粉末を製造できること、棒状の形状を有する二酸化ルテニウム粉末を用いた厚膜抵抗体は、電流雑音が低減されることを見出し、本発明を完成するに至った。 As a result of intensive studies to solve the above-described conventional problems, the present inventor obtained a ruthenium dioxide powder having a rod-like shape by heat-treating conventional granular ruthenium dioxide in the presence of a bismuth compound. It has been found that a thick film resistor using ruthenium dioxide powder having a rod-like shape can be manufactured and current noise is reduced, and the present invention has been completed.
本発明の第１の態様では、ビスマス化合物の存在下、粒状の二酸化ルテニウムを熱処理して、棒状の二酸化ルテニウムを形成すること、を備える、二酸化ルテニウム粉末の製造方法が提供される。 In a first aspect of the present invention, there is provided a method for producing ruthenium dioxide powder, comprising heat-treating granular ruthenium dioxide in the presence of a bismuth compound to form rod-like ruthenium dioxide.
また、粒状の二酸化ルテニウムは、一次粒径が１００ｎｍ以下であることが好ましい。また、熱処理を６００℃以上９００℃以下の温度で行うことが好ましい。また、ビスマス化合物は、酸化ビスマス、塩化ビスマス、及び、オキシ塩化ビスマスから選ばれる少なくとも１種であることが好ましい。また、ビスマス化合物を、粒状の二酸化ルテニウムに対して、モル比で０．１倍以上５倍以下の範囲で、粒状の二酸化ルテニウムと混合した後、熱処理をすることが好ましい。また、棒状の二酸化ルテニウムは、長軸方向に対して垂直な断面の短径が１００ｎｍ以下であり、前記長軸方向の長径と、前記断面における短径との比（長軸方向における長径／断面における短径）が２以上であることが好ましい。 The granular ruthenium dioxide preferably has a primary particle size of 100 nm or less. Moreover, it is preferable to perform heat processing at the temperature of 600 to 900 degreeC. The bismuth compound is preferably at least one selected from bismuth oxide, bismuth chloride, and bismuth oxychloride. Moreover, it is preferable to heat-process after mixing a bismuth compound with granular ruthenium in the range of 0.1 times or more and 5 times or less with respect to granular ruthenium dioxide. Further, the rod-shaped ruthenium dioxide has a minor axis of a section perpendicular to the major axis direction of 100 nm or less, and a ratio of the major axis in the major axis direction to the minor axis in the section (major axis / cross section in the major axis direction). Is preferably 2 or more.
さらに、上記二酸化ルテニウム粉末の製造方法は、棒状の二酸化ルテニウムを形成した後、ビスマス化合物を溶媒に溶解させて得られた溶液中から、棒状の二酸化ルテニウムを固液分離すること、を備えることが好ましい。また、溶媒が酸性水溶液であることが好ましい。 Furthermore, the method for producing the ruthenium dioxide powder may comprise solid-liquid separation of the rod-shaped ruthenium dioxide from a solution obtained by dissolving the bismuth compound in a solvent after forming the rod-shaped ruthenium dioxide. preferable. Moreover, it is preferable that a solvent is acidic aqueous solution.
さらに、上記二酸化ルテニウム粉末の製造方法は、棒状の二酸化ルテニウムを固液分離した後、ビスマス化合物を溶解させた溶液を、濃縮乾燥して、ビスマス化合物を回収することと、回収されたビスマス化合物を含むビスマス化合物の存在下、粒状の二酸化ルテニウムを熱処理して、棒状の二酸化ルテニウムを形成すること、を備えることが好ましい。 Further, in the method for producing the ruthenium dioxide powder, the rod-shaped ruthenium dioxide is subjected to solid-liquid separation, and then the solution in which the bismuth compound is dissolved is concentrated and dried to recover the bismuth compound, and the recovered bismuth compound is recovered. It is preferable to heat-treat granular ruthenium dioxide in the presence of the bismuth compound containing to form rod-shaped ruthenium dioxide.
本発明の第２の態様では、棒状の形状を有し、長軸方向に対して垂直な断面の最小径が１００ｎｍ以下であり、長軸方向における長径と、断面における短径との比（長軸方向における長径／断面における短径）が２以上である、二酸化ルテニウム粉末が提供される。 In the second aspect of the present invention, the minimum diameter of the cross section having a rod shape and perpendicular to the major axis direction is 100 nm or less, and the ratio of the major axis in the major axis direction to the minor axis in the section (long Ruthenium dioxide powder having a major axis in the axial direction / minor axis in the cross section) of 2 or more is provided.
また、上記二酸化ルテニウム粉末は、長軸方向に対して垂直な断面における、長径と短径との比（断面における長径／断面における短径）が２未満である、ことが好ましい。また、厚膜抵抗体の導電粒子として用いられることが好ましい。 The ruthenium dioxide powder preferably has a ratio of major axis to minor axis (major axis in section / minor axis in section) of less than 2 in a section perpendicular to the major axis direction. Further, it is preferably used as conductive particles of a thick film resistor.
本発明の第３の態様では、上記二酸化ルテニウム粉末と、ガラス粉末と、有機ビヒクルとを含む厚膜抵抗体ペーストが提供される。 In a third aspect of the present invention, there is provided a thick film resistor paste containing the ruthenium dioxide powder, glass powder, and organic vehicle.
本発明の第４の態様では、上記二酸化ルテニウム粉末を含む厚膜抵抗体が提供される。 In a fourth aspect of the present invention, a thick film resistor containing the ruthenium dioxide powder is provided.
本発明は、従来の粒状の二酸化ルテニウムと比較して、粒子間の接点の数を減少させることができる二酸化ルテニウム粉末と、その簡便な製造方法を提供する。また、本発明の厚膜抵抗体及び厚膜抵抗体ペーストは、上記二酸化ルテニウム粉末を、厚膜抵抗体の導電粒子として用いており、従来の粒状の二酸化ルテニウムを用いたものと比較して、電流雑音を低減することができる。
The present invention provides a ruthenium dioxide powder capable of reducing the number of contacts between particles as compared with conventional granular ruthenium dioxide, and a simple production method thereof. Moreover, the thick film resistor and the thick film resistor paste of the present invention use the ruthenium dioxide powder as conductive particles of the thick film resistor, compared with the conventional granular ruthenium dioxide, Current noise can be reduced.
以下、図面を参照して、本実施形態の二酸化ルテニウム粉末とその製造方法、それを用いた厚膜抵抗体ペースト、及び、厚膜抵抗体について説明する。なお、図面においては、各構成をわかりやすくするために、一部を強調して、あるいは一部を簡略化して表しており、実際の構造または形状、縮尺等が異なっている場合がある。 Hereinafter, a ruthenium dioxide powder and a manufacturing method thereof, a thick film resistor paste using the same, and a thick film resistor will be described with reference to the drawings. In the drawings, in order to make each configuration easy to understand, some parts are emphasized or some parts are simplified, and actual structures, shapes, scales, and the like may be different.
１．二酸化ルテニウム粉末の製造方法
図１は、本実施形態の二酸化ルテニウム粉末の製造方法の一例を示すフロー図であり、図２〜４は、原料となる粒状の二酸化ルテニウム粉末（図２（Ａ））、及び、得られる棒状の二酸化ルテニウム粉末（図２（Ｂ）、図３〜図４）の一例を示す図である。
1. Method for Producing Ruthenium Dioxide Powder FIG. 1 is a flowchart showing an example of a method for producing ruthenium dioxide powder of the present embodiment, and FIGS. 2 to 4 show granular ruthenium dioxide powder as a raw material (FIG. 2 (A)). And FIG. 3 is a view showing an example of the obtained rod-shaped ruthenium dioxide powder (FIG. 2B, FIGS. 3 to 4).
本実施形態の二酸化ルテニウム粉末の製造方法は、図１に示すように、ビスマス化合物の存在下、粒状の二酸化ルテニウムを熱処理して、棒状の二酸化ルテニウムを形成する工程（ステップＳ１０）を備える。また、棒状の二酸化ルテニウムを形成した後、ビスマス化合物を溶媒に溶解させて得られた溶液中から、棒状の二酸化ルテニウムを固液分離する工程（ステップＳ２０）を備えてもよい。 As shown in FIG. 1, the manufacturing method of the ruthenium dioxide powder of this embodiment includes a step (step S10) of heat-treating granular ruthenium dioxide in the presence of a bismuth compound to form rod-like ruthenium dioxide. Moreover, after forming rod-shaped ruthenium dioxide, you may provide the process (step S20) of carrying out solid-liquid separation of rod-shaped ruthenium dioxide from the solution obtained by melt | dissolving a bismuth compound in a solvent.
また、図１に示すように、棒状の二酸化ルテニウムを固液分離した後、ビスマス化合物を溶解させた溶液を、濃縮乾燥して、ビスマス化合物を回収する工程（ステップＳ３０）、及び、回収されたビスマス化合物を含むビスマス化合物の存在下、粒状の二酸化ルテニウムを熱処理して、棒状の二酸化ルテニウムを形成する工程（ステップＳ３１）を備えてもよい。以下、図１〜図４を参照して、各工程の具体例について説明する。なお、以下の説明は、製造方法の一例であって、製造方法を限定するものではない。 Moreover, as shown in FIG. 1, after solid-liquid-separating rod-shaped ruthenium dioxide, the solution which melt | dissolved the bismuth compound is concentrated and dried, and the process (step S30) which collect | recovers a bismuth compound was collect | recovered You may provide the process (step S31) which heat-processes granular ruthenium dioxide in presence of the bismuth compound containing a bismuth compound, and forms rod-shaped ruthenium dioxide. Hereinafter, specific examples of each process will be described with reference to FIGS. The following description is an example of a manufacturing method and does not limit the manufacturing method.
（１）棒状の二酸化ルテニウム形成工程（ステップＳ１０）
図１に示すように、棒状の二酸化ルテニウムの形成工程（ステップＳ１０）は、粒状の二酸化ルテニウムとビスマス化合物とを混合して第１の混合物を得る混合工程（ステップＳ１１）と、第１の混合物を熱処理して第２の混合物を得る工程（ステップＳ１２）とを含むことができる。以下、各工程について、説明する。
(1) Rod-shaped ruthenium dioxide forming step (step S10)
As shown in FIG. 1, the rod-shaped ruthenium dioxide forming step (step S10) includes a mixing step (step S11) in which granular ruthenium dioxide and a bismuth compound are mixed to obtain a first mixture, and a first mixture. (Step S12) to heat-treat the second mixture to obtain a second mixture. Hereinafter, each process will be described.
（１−１）混合工程（ステップＳ１１）
まず、粒状の二酸化ルテニウムとビスマス化合物とを混合して第１の混合物を得る（ステップＳ１１）。以下、第１の混合物を構成する各材料について、具体的に説明する。
(1-1) Mixing step (Step S11)
First, granular ruthenium dioxide and a bismuth compound are mixed to obtain a first mixture (step S11). Hereinafter, each material which comprises a 1st mixture is demonstrated concretely.
（粒状の二酸化ルテニウム）
原料となる粒状の二酸化ルテニウムは、従来の公知の製造方法で得られた粒状の二酸化ルテニウムを用いることができる。粒状の二酸化ルテニウムは、例えば、公知の湿式合成されたルテニウム酸化物の水和物を、酸化雰囲気中で焙焼して得られた二酸化ルテニウムを使用することができる。ルテニウム酸化物の水和物を合成する合成法には、代表的な方法として、ルテニウム酸カリウム水溶液にエタノールなどのアルコールや有機化合物を加える方法や、塩化ルテニウム水溶液を水酸化カリウムなどのアルカリ性化合物で中和する方法が挙げられる。これらの方法で製造された二酸化ルテニウムは、通常、一次粒子が粒状の形状を有する粉末となる。
(Granular ruthenium dioxide)
Granular ruthenium dioxide obtained by a conventionally known production method can be used as the granular ruthenium dioxide as a raw material. As the granular ruthenium dioxide, for example, ruthenium dioxide obtained by baking a known wet-synthesized hydrate of ruthenium oxide in an oxidizing atmosphere can be used. Typical methods for synthesizing ruthenium oxide hydrates include adding an alcohol or an organic compound such as ethanol to an aqueous potassium ruthenate solution, or an aqueous ruthenium chloride solution with an alkaline compound such as potassium hydroxide. The method of neutralizing is mentioned. Ruthenium dioxide produced by these methods is usually a powder in which primary particles have a granular shape.
なお、粒状の二酸化ルテニウムの製造方法については、例えば、特許文献１、特許文献２などに開示されており、詳細な条件についてはこれらの文献を参照して条件を適宜、調整することができる。湿式合成して得られた粒状の二酸化ルテニウムは、通常、一次粒子の平均粒径が１０ｎｍ以上３００ｎｍ以下程度となる。なお、原料として、湿式合成されたルテニウム酸化物の水和物（ルテニウム水酸化物）を用いてもよい。この場合、後述する熱処理工程（ステップＳ１２）で、粒状の二酸化ルテニウムに変換された後、棒状の二酸化ルテニウムが形成されてもよい。 In addition, about the manufacturing method of granular ruthenium dioxide, it is disclosed by patent document 1, patent document 2, etc., for example, conditions can be suitably adjusted with reference to these literature about detailed conditions. Granular ruthenium dioxide obtained by wet synthesis usually has an average primary particle size of about 10 nm to 300 nm. Note that wet synthesized ruthenium oxide hydrate (ruthenium hydroxide) may be used as a raw material. In this case, rod-shaped ruthenium dioxide may be formed after being converted into granular ruthenium dioxide in a heat treatment step (step S12) described later.
図２（Ａ）は、後述する実施例１で用いた粒状の二酸化ルテニウム（原料）のＳＥＭ写真である。粒状の二酸化ルテニウムは、図２（Ａ）に示すように、球状、略球状、楕円粒状、略楕円球状などの形状を有する一次粒子を含む。ここで、一次粒子とは、例えば、図２（Ａ）の破線で囲んだ部分に示すように、走査電子顕微鏡（ＳＥＭ）を用いて観察した際に、明確な輪郭を有する最小粒子をいう。粒状の二酸化ルテニウムは、例えば、ＳＥＭを用いて観察される一次粒子の平均粒径が１００ｎｍ以下であり、アスペクト比（一次粒子像の長径／短径）が２未満であることが好ましい。上記形状を有する二酸化ルテニウムを原料として用いた場合、厚膜抵抗体の導電粒子として好適に用いることのできる棒状の二酸化ルテニウムを容易に得ることができる。 FIG. 2A is an SEM photograph of granular ruthenium dioxide (raw material) used in Example 1 described later. As shown in FIG. 2A, granular ruthenium dioxide includes primary particles having a spherical shape, a substantially spherical shape, an elliptical granular shape, a substantially elliptical spherical shape, or the like. Here, the primary particles refer to the smallest particles having a clear outline when observed using a scanning electron microscope (SEM), for example, as shown in a portion surrounded by a broken line in FIG. In the case of granular ruthenium dioxide, for example, the average particle diameter of primary particles observed using SEM is preferably 100 nm or less, and the aspect ratio (major axis / minor axis of the primary particle image) is preferably less than 2. When ruthenium dioxide having the above shape is used as a raw material, rod-shaped ruthenium dioxide that can be suitably used as the conductive particles of the thick film resistor can be easily obtained.
また、粒状の二酸化ルテニウムは、結晶性粉末でもよく、アモルファス状の粉末であってもよい。また、粒状の二酸化ルテニウムは、結晶性粉末及びアモルファス状の粉末の両方を用いてもよい。粒状の二酸化ルテニウムは、容易に製造できるという観点から、アモルファス状の二酸化ルテニウムが好ましい。また、アモルファス状の二酸化ルテニウムを用いた場合、後述する熱処理工程（ステップＳ１２）で、結晶性の二酸化ルテニウムに変換された後、棒状の二酸化ルテニウムが形成されてもよい。 The granular ruthenium dioxide may be a crystalline powder or an amorphous powder. The granular ruthenium dioxide may use both a crystalline powder and an amorphous powder. From the viewpoint that granular ruthenium dioxide can be easily produced, amorphous ruthenium dioxide is preferable. In addition, when amorphous ruthenium dioxide is used, rod-shaped ruthenium dioxide may be formed after conversion to crystalline ruthenium dioxide in a heat treatment step (step S12) described later.
（ビスマス化合物）
ビスマス化合物は、ビスマスを含む化合物であり、熱処理の際に、二酸化ルテニウムと合金化しないものであれば、公知のビスマス化合物を用いることができる。ビスマス化合物は、例えば、塩化ビスマス、オキシ塩化ビスマス、酸化ビスマス、これらの混合物などを用いることができる。中でも、塩化ビスマス及びオキシ塩化ビスマスのうち少なくとも一つを用いることが好ましく、オキシ塩化ビスマスを用いることがより好ましい。
(Bismuth compound)
The bismuth compound is a compound containing bismuth, and a known bismuth compound can be used as long as it is not alloyed with ruthenium dioxide during the heat treatment. As the bismuth compound, for example, bismuth chloride, bismuth oxychloride, bismuth oxide, a mixture thereof, or the like can be used. Among these, it is preferable to use at least one of bismuth chloride and bismuth oxychloride, and it is more preferable to use bismuth oxychloride.
ビスマス化合物は、その形状や製造方法は特に限定されないが、粉末状であることが好ましい。ビスマス化合物は、例えば、市販されている塩化ビスマス粉末やオキシ塩化ビスマス粉末をそのまま用いてもよいし、硫酸ビスマスなど非塩化物系の化合物を塩酸に溶解したものを濃縮乾燥して用いてもよい。 The shape and manufacturing method of the bismuth compound are not particularly limited, but are preferably in powder form. As the bismuth compound, for example, a commercially available bismuth chloride powder or bismuth oxychloride powder may be used as it is, or a non-chloride compound such as bismuth sulfate dissolved in hydrochloric acid may be concentrated and dried. .
（第１の混合物の調製）
第１の混合物は、上記粒状の二酸化ルテニウムと、上記ビスマス化合物とを混合して得られる。粒状の二酸化ルテニウムとビスマス化合物との混合比率は、粒状の二酸化ルテニウムに対するビスマス化合物のモル比が、例えば、０．１倍以上５倍以下であり、０．５倍以上３倍以下が好ましく、０．５倍以上２倍以下がより好ましい。ビスマス化合物の混合比率が大きい場合、棒状の二酸化ルテニウムの合成はできるが、後述する固液分離工程（ステップＳ２０）において、ビスマス化合物と棒状の二酸化ルテニウムとの分離に時間がかかる。よって、生産性を向上させるという観点から、ビスマス化合物の混合比率は上記範囲内で、小さい方が好ましい。
(Preparation of the first mixture)
The first mixture is obtained by mixing the granular ruthenium dioxide and the bismuth compound. The mixing ratio of the granular ruthenium dioxide and the bismuth compound is such that the molar ratio of the bismuth compound to the granular ruthenium dioxide is, for example, 0.1 to 5 times, preferably 0.5 to 3 times, It is more preferably 5 times or more and 2 times or less. When the mixing ratio of the bismuth compound is large, rod-shaped ruthenium dioxide can be synthesized, but it takes time to separate the bismuth compound from the rod-shaped ruthenium dioxide in the solid-liquid separation step (step S20) described later. Therefore, from the viewpoint of improving productivity, the mixing ratio of the bismuth compound is preferably smaller within the above range.
粒状の二酸化ルテニウムとビスマス化合物とを混合する方法は、両者が十分に混合できる方法であれば特に限定されず、公知の混合装置を用いて混合することができる。たとえば、ボールミル、ライカイ機、シェーカーミキサーなどの一般的な混合装置を用いて、混合することができる。 The method for mixing the granular ruthenium dioxide and the bismuth compound is not particularly limited as long as both can be sufficiently mixed, and mixing can be performed using a known mixing device. For example, the mixing can be performed using a general mixing apparatus such as a ball mill, a likai machine, or a shaker mixer.
（１−２）熱処理工程（ステップＳ１２）
次に、第１の混合物を熱処理して、棒状のルテニウムを含む第２の混合物を得る（ステップＳ１２）。第２の混合物は、棒状の二酸化ルテニウムとビスマス化合物とを含む。棒状の二酸化ルテニウムは、ビスマス化合物と分離した状態で成長する。そのメカニズムの詳細は不明であるが、ビスマス化合物の存在下、熱処理することにより、粒状の二酸化ルテニウムから棒状の二酸化ルテニウムを形成することができる。
(1-2) Heat treatment step (step S12)
Next, the first mixture is heat-treated to obtain a second mixture containing rod-like ruthenium (step S12). The second mixture includes rod-shaped ruthenium dioxide and a bismuth compound. Rod-shaped ruthenium dioxide grows in a state separated from the bismuth compound. Although details of the mechanism are unknown, rod-shaped ruthenium dioxide can be formed from granular ruthenium dioxide by heat treatment in the presence of a bismuth compound.
熱処理は、棒状の二酸化ルテニウムが得られる、例えば、酸化性雰囲気下６００℃以上９００℃以下の温度で行うことができる。熱処理温度を上記範囲で調整することにより、得られる棒状の二酸化ルテニウムの長さや太さを容易に制御することができる。熱処理温度が６００℃未満の場合、原料とした粒状の二酸化ルテニウムの形状に変化はなく、棒状の二酸化ルテニウムが得られないことがある。例えば、原料として、アモルファス状の二酸化ルテニウムを使用した場合、熱処理温度が６００℃未満であると、結晶性の二酸化ルテニウムとなるが、一次粒子の形状は、粒状のまま変化しないことがある。一方、熱処理温度が９００℃を超える場合、二酸化ルテニウムとビスマス化合物との合金化が進行し、パイロクロア構造であるルテニウム酸ビスマス（Ｂｉ２Ｒｕ２Ｏ７−δ（０≦δ＜１））が合成されることがある。この場合、二酸化ルテニウムとビスマス化合物との分離ができない。 The heat treatment can be performed at a temperature of 600 ° C. or higher and 900 ° C. or lower in an oxidizing atmosphere to obtain rod-shaped ruthenium dioxide. By adjusting the heat treatment temperature within the above range, the length and thickness of the rod-shaped ruthenium dioxide obtained can be easily controlled. When the heat treatment temperature is lower than 600 ° C., the shape of granular ruthenium dioxide used as a raw material is not changed, and rod-shaped ruthenium dioxide may not be obtained. For example, when amorphous ruthenium dioxide is used as a raw material, if the heat treatment temperature is less than 600 ° C., crystalline ruthenium dioxide is obtained, but the shape of the primary particles may remain in a granular form. On the other hand, when the heat treatment temperature exceeds 900 ° C., alloying of ruthenium dioxide and a bismuth compound proceeds, and bismuth ruthenate (Bi 2 Ru 2 O 7-δ (0 ≦ δ <1)) having a pyrochlore structure is synthesized. May be. In this case, the ruthenium dioxide and bismuth compound cannot be separated.
なお、熱処理の条件は、原料となる粒状の二酸化ルテニウム及びビスマス化合物の種類や形状、混合割合などに応じて、棒状の二酸化ルテニウムが得られる範囲で適宜調整することができる。例えば、熱処理の雰囲気は、酸化性雰囲気下とすることができ、大気雰囲気で行うことができる。なお、酸化性雰囲気とは、酸素を１０容積％以上を含む気体をいい、例えば、空気を使用することができる。また、熱処理時間は、特に限定されず、所望の形状を有する棒状の二酸化ルテニウムが得られるように適宜調整することができ、例えば、１時間以上４時間以下程度とすることができ、１時間以上３時間未満とすることが好ましい。熱処理時間が上記範囲である場合、容易に棒状の二酸化ルテニウムを得ることができる。 In addition, the conditions of heat processing can be suitably adjusted in the range from which rod-shaped ruthenium dioxide is obtained according to the kind, shape, mixing ratio, etc. of granular ruthenium dioxide and bismuth compound as raw materials. For example, the heat treatment atmosphere can be an oxidizing atmosphere, and can be performed in an air atmosphere. The oxidizing atmosphere refers to a gas containing 10% by volume or more of oxygen, and for example, air can be used. The heat treatment time is not particularly limited, and can be appropriately adjusted so as to obtain rod-shaped ruthenium dioxide having a desired shape. For example, it can be set to about 1 hour or more and 4 hours or less, and can be 1 hour or more. It is preferable to make it less than 3 hours. When the heat treatment time is in the above range, rod-shaped ruthenium dioxide can be easily obtained.
図２（Ｂ）は、後述する実施例１で作製した第２の混合物の粒状のＳＥＭ写真である。第２の混合物は、図２（Ｂ）に示すように、球状のビスマス化合物（図２（Ｂ）の左下の破線部分）と、棒状の形状を有する一次粒子からなる二酸化ルテニウムとを含む。なお、第２の混合物のそれぞれの粉末の組成は、ＥＤＸ定性分析、及び、ＸＲＤ分析により検出することができる。また、粉末の形状はＳＥＭを用いて観察することができる。 FIG. 2B is a granular SEM photograph of the second mixture prepared in Example 1 described later. As shown in FIG. 2B, the second mixture includes a spherical bismuth compound (the lower left broken line portion of FIG. 2B) and ruthenium dioxide composed of primary particles having a rod-like shape. The composition of each powder of the second mixture can be detected by EDX qualitative analysis and XRD analysis. The shape of the powder can be observed using SEM.
ここで棒状の二酸化ルテニウムとは、ＲｕＯ２の組成を有し、かつ、ＳＥＭ観察した場合、その一次粒子の形状が棒状であるものをいう。図３は、棒状の形状を有する一次粒子の一例を示した模式図である。棒状の一次粒子とは、図３に示すように、長軸方向の最大径（長径ｂ）と、長軸方向に対して垂直な断面の最小径（短径ａ）とのアスペクト比（長径ｂ／短径ａ）が２以上の一次粒子をいう。また、短径ａが１００ｎｍ以下である場合、アスペクト比（長径ｂ／短径ａ）がより大きくなり、明確な棒状の形状を有しやすい。なお、一次粒子の形状は、棒状の形状を有するものであれば、図３に示す形状に限定されない。例えば、長軸方向に対して垂直な断面の形状は、正方形や長方形を含む矩形状であってもよく、円状、楕円状、不定形などであってもよい。棒状の二酸化ルテニウムの形状は、上述したように、熱処理温度や熱処理時間を適宜調整することにより、所望の棒状の形状を有する二酸化ルテニウムを得ることができる。また、棒状のルテニウムは、多結晶であってもよい。 Here, the rod-shaped ruthenium dioxide has a composition of RuO 2 and has a rod-shaped primary particle shape when observed with an SEM. FIG. 3 is a schematic view showing an example of primary particles having a rod-like shape. As shown in FIG. 3, the rod-shaped primary particles are the aspect ratio (major axis b) between the maximum diameter (major axis b) in the major axis direction and the minimum diameter (minor axis a) perpendicular to the major axis direction. / Shorter diameter a) refers to primary particles of 2 or more. In addition, when the minor axis a is 100 nm or less, the aspect ratio (major axis b / minor axis a) becomes larger, and a clear rod-like shape is likely to be obtained. Note that the shape of the primary particles is not limited to the shape shown in FIG. 3 as long as it has a rod-like shape. For example, the shape of the cross section perpendicular to the long axis direction may be a rectangle including a square or a rectangle, or may be a circle, an ellipse, an indeterminate shape, or the like. As described above, the shape of the rod-like ruthenium dioxide can be obtained by appropriately adjusting the heat treatment temperature and the heat treatment time, thereby obtaining ruthenium dioxide having a desired rod-like shape. The rod-shaped ruthenium may be polycrystalline.
（２）棒状の二酸化ルテニウムの分離工程（ステップＳ２０）
次いで、図１に示すように、第２の混合物（棒状の二酸化ルテニウム及びビスマス化合物とを含む混合粉末）に含まれるビスマス化合物を溶剤に溶解させた後、得られた溶液中から、棒状の二酸化ルテニウムを固液分離する（ステップＳ２０）。
(2) Separation process of rod-shaped ruthenium dioxide (step S20)
Next, as shown in FIG. 1, after dissolving the bismuth compound contained in the second mixture (mixed powder containing rod-shaped ruthenium dioxide and bismuth compound) in a solvent, rod-shaped dioxide dioxide is obtained from the obtained solution. Ruthenium is solid-liquid separated (step S20).
ビスマス化合物の溶解に用いられる溶剤は、二酸化ルテニウムを溶解せずにビスマス化合物のみを溶解するものであれば、特に限定されず、例えば、無機物化合物の酸（鉱酸）や有機酸などが使用できる。中でも、硝酸や塩酸は、薬品コストや使用後の処理の容易さなどから好適に使用できる。また、硝酸や塩酸などは一般的な濃度の試薬を水で１０〜５０％に希釈したものが作業安全性の点からも使い易い。 The solvent used for dissolving the bismuth compound is not particularly limited as long as it dissolves only the bismuth compound without dissolving ruthenium dioxide. For example, an acid (mineral acid) or an organic acid of an inorganic compound can be used. . Among these, nitric acid and hydrochloric acid can be preferably used from the viewpoint of chemical cost and ease of treatment after use. Nitric acid, hydrochloric acid, etc., which are obtained by diluting a reagent having a general concentration to 10 to 50% with water, are easy to use from the viewpoint of work safety.
ビスマス化合物を溶剤に溶解させる際の条件は、特に限定されず、ビスマス化合物が溶剤に十分溶ければよい。例えば、溶解時の液温は、３０〜６０℃程度とすることができる。溶解時の液温が６０℃を超える場合、安全衛生面で作業性が悪い。また液温が３０℃未満である場合、ビスマス化合物の溶解速度が遅くなり、溶解に時間がかかる。溶解時間は、第２の混合物からビスマス化合物が完全に溶解できればよく、使用する溶剤や洗浄時の液温によって調整することができる。 The conditions for dissolving the bismuth compound in the solvent are not particularly limited as long as the bismuth compound is sufficiently dissolved in the solvent. For example, the liquid temperature at the time of dissolution can be about 30 to 60 ° C. When the liquid temperature at the time of dissolution exceeds 60 ° C., workability is poor in terms of safety and health. On the other hand, when the liquid temperature is lower than 30 ° C., the dissolution rate of the bismuth compound becomes slow and it takes time to dissolve. The dissolution time only needs to be able to completely dissolve the bismuth compound from the second mixture, and can be adjusted by the solvent used and the temperature of the liquid at the time of washing.
溶剤へのビスマス化合物の溶解後、棒状の二酸化ルテニウム粉末を分散させた、ビスマス化合物を溶解して含む溶液が得られる。得られた溶液から、棒状の二酸化ルテニウムを固液分離する。棒状の二酸化ルテニウムを固液分離する方法は特に限定されず、例えば、遠心分離法や真空吸引法、クロスフローろ過法などから選択することが可能である。また、固液分離により得られた棒状の二酸化ルテニウム粉は、純水でリパルプ洗浄し、ビスマス化合物を完全に除去することが好ましい。 After dissolution of the bismuth compound in the solvent, a solution containing the dissolved bismuth compound in which rod-shaped ruthenium dioxide powder is dispersed is obtained. From the resulting solution, rod-shaped ruthenium dioxide is subjected to solid-liquid separation. The method for solid-liquid separation of rod-like ruthenium dioxide is not particularly limited, and can be selected from, for example, a centrifugal separation method, a vacuum suction method, a cross flow filtration method, and the like. Moreover, it is preferable that the rod-shaped ruthenium dioxide powder obtained by solid-liquid separation is repulped with pure water to completely remove the bismuth compound.
固液分離して得られた棒状の二酸化ルテニウム粉末は、電気炉などで乾燥を行う。乾燥温度や時間は、水分が除去できる温度であれば良く、乾燥温度は、例えば、８０℃以上１５０℃以下であると、作業性がよく好ましい。 The rod-shaped ruthenium dioxide powder obtained by solid-liquid separation is dried in an electric furnace or the like. The drying temperature and time may be any temperature at which moisture can be removed, and the drying temperature is preferably 80 ° C. or higher and 150 ° C. or lower for good workability.
（３）ビスマス化合物の回収工程（ステップＳ３０）
また、ビスマス化合物が溶解している洗浄液は、必要に応じて塩酸を添加した後、洗浄液を濃縮乾燥することによって、ビスマス化合物（例えば、塩化ビスマス、オキシ塩化ビスマスまたは、その混合物）が得られる。また、これらのビスマス化合物は回収し、ビスマス化合物の原料として再利用してもよい（ステップＳ３１）。
(3) Step of recovering bismuth compound (Step S30)
The cleaning liquid in which the bismuth compound is dissolved can be obtained by adding hydrochloric acid as necessary and then concentrating and drying the cleaning liquid to obtain a bismuth compound (for example, bismuth chloride, bismuth oxychloride, or a mixture thereof). Further, these bismuth compounds may be recovered and reused as raw materials for the bismuth compounds (step S31).
２．二酸化ルテニウム粉末
本実施形態の二酸化ルテニウム粉末は、棒状の形状を有し、長軸方向に対して垂直な断面の最小径（短径ａ）が１００ｎｍ以下であり、長軸方向における最大径（長径ｂ）と、断面における最小径（短径ａ）との比（長径ｂ／短径ａ）が２以上である（図３参照）。上記のような形状を有する二酸化ルテニウムを厚膜抵抗体の導電粒子として用いた場合、従来の球状の二酸化ルテニウムを用いた厚膜抵抗体と比較して、電流雑音を低減することができる。これは、厚膜抵抗体に使用する導電粉末の形状を球状ではなく、棒状にすることにより、導電粉末同士の接触点が減り、厚膜抵抗体の電流雑音が低減されると考えられる。なお、長径ｂ／短径ａの上限は、特に限定されないが、例えば、２５以下である。
2. Ruthenium dioxide powder The ruthenium dioxide powder of the present embodiment has a rod-like shape, the minimum diameter (minor axis a) of the cross section perpendicular to the major axis direction is 100 nm or less, and the maximum diameter (major axis) in the major axis direction The ratio (major axis b / minor axis a) between b) and the minimum diameter (minor axis a) in the cross section is 2 or more (see FIG. 3). When ruthenium dioxide having the above shape is used as the conductive particles of the thick film resistor, current noise can be reduced as compared with a thick film resistor using conventional spherical ruthenium dioxide. This is considered to be because the contact point between the conductive powders is reduced by reducing the shape of the conductive powder used for the thick film resistor to a rod shape instead of a spherical shape, and the current noise of the thick film resistor is reduced. The upper limit of major axis b / minor axis a is not particularly limited, but is, for example, 25 or less.
また、本実施形態の二酸化ルテニウム粉末は、長軸方向に対して垂直な断面における、最小径（短径ａ）と、短径ａと垂直な最長径（長径ｃ）との比（長径ｃ／短径ａ）が２未満であることが好ましい（図３参照）。なお、本実施形態の二酸化ルテニウム粉末の形状は、図３に示す形状に限定されない。例えば、二酸化ルテニウム粉末は、長軸方向に対して垂直な断面の形状が、正方形や長方形を含む矩形状であってもよく、円状、楕円状、不定形などであってもよい。 Further, the ruthenium dioxide powder of the present embodiment has a ratio (major axis c / min) of the minimum diameter (minor axis a) and the longest diameter (major axis c) perpendicular to the minor axis a in a cross section perpendicular to the major axis direction. The minor axis a) is preferably less than 2 (see FIG. 3). In addition, the shape of the ruthenium dioxide powder of this embodiment is not limited to the shape shown in FIG. For example, in the ruthenium dioxide powder, the shape of the cross section perpendicular to the major axis direction may be a rectangle including a square or a rectangle, or may be a circle, an ellipse, an indeterminate shape, or the like.
また、本実施形態の二酸化ルテニウム粉末は、例えば、長軸方向における最大径（長径ｂ）が４０ｎｍ以上５００ｎｍ以下であり、断面における最小径（短径ａ）が２０ｎｍ以上１００ｎｍ以下である。 The ruthenium dioxide powder of the present embodiment has, for example, a maximum diameter (major axis b) in the major axis direction of 40 nm or more and 500 nm or less, and a minimum diameter (minor axis a) in the cross section of 20 nm or more and 100 nm or less.
３．厚膜抵抗体ペースト
厚膜抵抗体ペーストは、導電粒子とガラス粉末などの無機成分と、有機ビヒクル等から構成される。上述した本実施形態の二酸化ルテニウム粉末は、棒状の形状を有するため、厚膜抵抗体の導電粒子として用いた場合、粉同士の接点の数を減らして、電流雑音を低減させることができる。以下、厚膜抵抗体ペーストの構成成分について、説明する。
3. Thick Film Resistor Paste The thick film resistor paste is composed of an inorganic component such as conductive particles and glass powder, an organic vehicle, and the like. Since the ruthenium dioxide powder of this embodiment described above has a rod-like shape, when used as conductive particles of a thick film resistor, the number of contact points between the powders can be reduced to reduce current noise. Hereinafter, the components of the thick film resistor paste will be described.
（導電粒子）
厚膜抵抗体ペーストは、上述した棒状の二酸化ルテニウム粉末を含む。また、厚膜抵抗体ペーストは、必要に応じて、棒状の二酸化ルテニウム粉末以外の導電粒子を含んでも良い。導電粒子としては、パイロクロア型やペロブスカイト型の結晶構造を有するルテニウム酸化合物や、銀、パラジウムなどが挙げられる。
(Conductive particles)
The thick film resistor paste contains the rod-shaped ruthenium dioxide powder described above. Further, the thick film resistor paste may contain conductive particles other than the rod-shaped ruthenium dioxide powder as necessary. Examples of the conductive particles include ruthenic acid compounds having a pyrochlore type or perovskite type crystal structure, silver, palladium, and the like.
（ガラス粉末）
ガラス粉末は、鉛を含まないものであれば良く、その組成は特に限定されない。ガラス粉末は、例えば、酸化ケイ素、酸化ホウ素、酸化アルミニウム、酸化亜鉛、アルカリ金属酸化物、アルカリ土類酸化物を混合、溶融して急冷したものを粉砕して用いることができる。また、ガラス粉末の平均粒径は５μｍ以下であることが好ましい。平均粒径が上記範囲である場合、厚膜抵抗体中の導電パスが微細なものとなり、抵抗値のばらつきやノイズの悪化を防ぐことができる。
(Glass powder)
The glass powder is not particularly limited as long as it does not contain lead, and its composition is not particularly limited. As the glass powder, for example, silicon oxide, boron oxide, aluminum oxide, zinc oxide, alkali metal oxide, alkaline earth oxide mixed, melted and rapidly cooled can be used after pulverization. Moreover, it is preferable that the average particle diameter of glass powder is 5 micrometers or less. When the average particle diameter is in the above range, the conductive path in the thick film resistor becomes fine, and variation in resistance value and deterioration of noise can be prevented.
ガラス粉末は、例えば、ホウケイ酸ガラス、アルミノホウケイ酸ガラス、ホウケイ酸アルカリ土類ガラス、ホウケイ酸アルカリガラス、ホウケイ酸亜鉛ガラス、ホウケイ酸ビスマスガラスなどを用いることができる。 As the glass powder, for example, borosilicate glass, alumino borosilicate glass, borosilicate alkaline earth glass, borosilicate alkali glass, borosilicate zinc glass, borosilicate bismuth glass, or the like can be used.
（有機ビヒクル）
厚膜抵抗体ペーストは、溶剤に樹脂成分を溶解した有機ビヒクル中に、上記成分を分散させて調整される。厚膜抵抗体ペーストに用いる樹脂成分としては、エチルセルロース、マレイン酸樹脂、ロジンなどが用いられる。また、溶剤は、ターピネオール、ブチルカルビトール、ブチルカルビトールアセテート等が一般に用いられる。これらの樹脂と溶剤により調合されるビヒクルの配合比は、所望する粘度によって適宜調整して良い。また、厚膜抵抗体ペーストの連続印刷性を考慮すると、沸点が高い溶剤を加えて、乾燥速度を制御することもできる。
(Organic vehicle)
The thick film resistor paste is prepared by dispersing the above components in an organic vehicle in which a resin component is dissolved in a solvent. As the resin component used for the thick film resistor paste, ethyl cellulose, maleic acid resin, rosin and the like are used. As the solvent, terpineol, butyl carbitol, butyl carbitol acetate or the like is generally used. The mixing ratio of the vehicle prepared with these resin and solvent may be appropriately adjusted depending on the desired viscosity. In consideration of the continuous printability of the thick film resistor paste, a solvent having a high boiling point can be added to control the drying rate.
（任意の添加成分）
本実施形態の厚膜抵抗体ペーストは、導電粒子やガラス粉末の他に、面積抵抗値や抵抗温度係数の調整、膨張係数の調整、耐電圧性の向上やその他の改質を目的とし、上記以外のその他の無機成分である微量添加剤を含んでもよい。添加剤としては、二酸化マンガンや酸化銅、二酸化チタン、二酸化ケイ素などが一般に用いられる。
(Optional additive)
The thick film resistor paste of the present embodiment is intended for the purpose of adjusting the area resistance value and the resistance temperature coefficient, adjusting the expansion coefficient, improving the voltage resistance, and other modifications in addition to the conductive particles and the glass powder. A trace additive which is an inorganic component other than the above may be included. As the additive, manganese dioxide, copper oxide, titanium dioxide, silicon dioxide and the like are generally used.
また、本実施形態の厚膜抵抗体ペーストは、分散剤を含んでもよい。二次粒子の形成を抑制するには、例えば、分散剤として脂肪酸を用いることができる。脂肪酸は、飽和、不飽和を問わないが、二酸化ルテニウムを分散させ、再び凝集するのを防ぐ観点から、炭素数１２以上の高級脂肪酸がより好ましい。 Further, the thick film resistor paste of the present embodiment may include a dispersant. In order to suppress the formation of secondary particles, for example, a fatty acid can be used as a dispersant. The fatty acid may be saturated or unsaturated, but higher fatty acids having 12 or more carbon atoms are more preferable from the viewpoint of dispersing ruthenium dioxide and preventing aggregation again.
（厚膜抵抗体ペーストの調製方法）
厚膜抵抗体ペーストを製造する方法は、公知の技術を用いれば良く、たとえば、スリーロールミル、遊星ミル、ビーズミルなどを用いることができる。
(Method for preparing thick film resistor paste)
As a method for producing the thick film resistor paste, a known technique may be used. For example, a three roll mill, a planetary mill, a bead mill or the like can be used.
厚膜抵抗体ペーストでは、導電粒子、ガラス粉末、その他の無機成分などの凝集を解し、有機ビヒクル中に分散することが望ましい。一般的に、粉末の粒径が小さくなると凝集力が強くなり、二次粒子を形成し易くなる。脂肪酸は、無機原料粉末を有機ビヒクル中に分散させる際に加えても良い。あるいは、予め二酸化ルテニウム粉末の表面に付着させた後、有機ビヒクル中に分散させても良い。厚膜抵抗体ペーストに対する有機ビヒクルの割合は特に限定されないが、厚膜抵抗体ペーストの重量に対して３０〜８０％が一般的である。 In the thick film resistor paste, it is desirable to break up aggregation of conductive particles, glass powder, and other inorganic components and disperse them in the organic vehicle. Generally, as the particle size of the powder becomes smaller, the cohesive force becomes stronger and it becomes easier to form secondary particles. The fatty acid may be added when the inorganic raw material powder is dispersed in the organic vehicle. Or after making it adhere to the surface of a ruthenium dioxide powder previously, you may make it disperse | distribute in an organic vehicle. The ratio of the organic vehicle to the thick film resistor paste is not particularly limited, but is generally 30 to 80% with respect to the weight of the thick film resistor paste.
厚膜抵抗体ペースト中の導電性粒子は、混合比率が多いと抵抗体の電流雑音が増加することがある。そのため、配合比率は抵抗体に必要な特性に応じて適宜、調整できる。 When the conductive particles in the thick film resistor paste have a large mixing ratio, the current noise of the resistor may increase. Therefore, the blending ratio can be appropriately adjusted according to the characteristics required for the resistor.
また、棒状の二酸化ルテニウム粉末を含む導電粒子とガラス粉末との配合比は、目的とする面積抵抗値によって任意に調整することができる。すなわち、目的とする抵抗値が高い場合は、棒状二酸化ルテニウム粉を少なく配合し、目的とする抵抗値が低い場合は、棒状の二酸化ルテニウム粉を多く配合することができる。ただし、ガラス粉末に比べ導電粒子の割合が多すぎると、出来上がる抵抗膜が脆くなってしまうため、二酸化ルテニウム粉末を含む導電粒子はガラス粉末に比べて等倍以下であることが望ましい。 Moreover, the compounding ratio of the conductive particles containing rod-shaped ruthenium dioxide powder and the glass powder can be arbitrarily adjusted according to the intended sheet resistance value. That is, when the target resistance value is high, less rod-like ruthenium dioxide powder is blended, and when the target resistance value is low, more rod-like ruthenium dioxide powder can be blended. However, if the ratio of the conductive particles is too large compared to the glass powder, the resulting resistive film becomes brittle. Therefore, it is desirable that the conductive particles containing the ruthenium dioxide powder be less than or equal to the glass powder.
また、その他の無機成分の添加剤の割合は、二酸化ルテニウム粉末とガラス粉末の重量の合計に対して０．０５〜２０％が一般的である。 Moreover, the ratio of the additive of other inorganic components is generally 0.05 to 20% with respect to the total weight of the ruthenium dioxide powder and the glass powder.
４．厚膜抵抗体
本実施形態の厚膜抵抗体は、上記の棒状の二酸化ルテニウムを導電粒子として含む。本実施形態の厚膜抵抗体は、上記の厚膜抵抗体ペーストを、基板上で焼成して形成される。なお、二酸化ルテニウムは、焼結しないため、厚膜抵抗体中でもその形状を維持していると考えられる。
4). Thick film resistor The thick film resistor of this embodiment contains the rod-shaped ruthenium dioxide as conductive particles. The thick film resistor of the present embodiment is formed by firing the above thick film resistor paste on a substrate. In addition, since ruthenium dioxide does not sinter, it is thought that the shape is maintained also in a thick film resistor.
以下、実施例を用いて本発明による棒状の二酸化ルテニウム粉の製造方法を説明する。なお、本発明はこれらの実施例によって限定されるものではない。 Hereinafter, the manufacturing method of the rod-shaped ruthenium dioxide powder by this invention is demonstrated using an Example. In addition, this invention is not limited by these Examples.
（実施例１）
（粒状の二酸化ルテニウムの作製）
金属ルテニウム粉末：１００ｇ、水酸化カリウム：８００ｇ、硝酸カリウム：１００ｇを混合し、銀坩堝中において７００℃、３時間溶融し、ルテニウム酸カリウム（Ｋ２ＲｕＯ４）を得た。このルテニウム酸カリウムを純水に溶解した後、エタノール１００ｍｌを加えることで、二酸化ルテニウムを生成した。さらに、生成した二酸化ルテニウムの水洗、乾燥を行い、１ｍｏｌの二酸化ルテニウム粉末を得た。得られた二酸化ルテニウムは、ＳＥＭ観察およびＸＲＤ分析の結果、粒径約５０ｎｍの粒状の一次粒子を有する二酸化ルテニウムであり、アモルファス状であることを確認した。図２（Ａ）に、得られた粒状の二酸化ルテニウム（アモルファス状）のＳＥＭ写真を示す。なお、図２（Ａ）中の破線で囲った部分は、粒状の二酸化ルテニウムの一次粒子の一例を示す。
Example 1
(Production of granular ruthenium dioxide)
Metal ruthenium powder: 100 g, potassium hydroxide: 800 g, potassium nitrate: 100 g were mixed and melted in a silver crucible at 700 ° C. for 3 hours to obtain potassium ruthenate (K 2 RuO 4 ). After dissolving this potassium ruthenate in pure water, 100 ml of ethanol was added to produce ruthenium dioxide. Furthermore, the produced ruthenium dioxide was washed with water and dried to obtain 1 mol of ruthenium dioxide powder. As a result of SEM observation and XRD analysis, the obtained ruthenium dioxide was ruthenium dioxide having primary particles having a particle size of about 50 nm, and was confirmed to be amorphous. FIG. 2A shows an SEM photograph of the obtained granular ruthenium dioxide (amorphous). In addition, the part enclosed with the broken line in FIG. 2 (A) shows an example of the primary particle | grains of granular ruthenium dioxide.
（棒状の二酸化ルテニウムの作製）
次に、得られた粒状の二酸化ルテニウム１ｍｏｌと、オキシ塩化ビスマス（和光純薬工業（株）製）１ｍｏｌを混合して第１の混合物を作製した。第１の混合物をアルミナ坩堝に充填し、空気中８００℃で２時間焙焼して第２の混合物を得た。得られた第２の混合物中の粉末のＳＥＭ観察およびＥＤＸ定性分析、さらにＸＲＤ分析を行った。その結果、第２の混合物は、棒状の二酸化ルテニウム粉末と球状のオキシ塩化ビスマスとの混合粉末であることが確認された。図２（Ｂ）に、得られた第２の混合物のＳＥＭ写真を示す。なお、図２（Ｂ）の左下の破線は、オキシ塩化ビスマスの粉末を示す。
(Production of rod-shaped ruthenium dioxide)
Next, 1 mol of the obtained granular ruthenium dioxide and 1 mol of bismuth oxychloride (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed to prepare a first mixture. The first mixture was filled in an alumina crucible and roasted in air at 800 ° C. for 2 hours to obtain a second mixture. SEM observation, EDX qualitative analysis, and XRD analysis of the powder in the obtained second mixture were performed. As a result, it was confirmed that the second mixture was a mixed powder of rod-shaped ruthenium dioxide powder and spherical bismuth oxychloride. FIG. 2B shows an SEM photograph of the obtained second mixture. In addition, the broken line on the lower left of FIG. 2 (B) shows bismuth oxychloride powder.
（棒状の二酸化ルテニウムの分離）
その後、得られた第２の混合物を４Ｌの純水と１Ｌの硝酸の混合溶液に入れ、５０℃で２時間の撹拌洗浄を行った。沈殿した粉末をろ過、水洗、乾燥した後、得られた粉末のＳＥＭ観察およびＸＲＤ分析した。その結果、得られた粉末は、棒状の二酸化ルテニウムの粉末であることが確認された。図４に得られた棒状の二酸化ルテニウム粉末のＳＥＭ写真を示す。図４に示すように、得られた二酸化ルテニウム粉末は、棒状であり、長軸方向に垂直な断面の形状が正方形を含む矩形状の一次粒子を含む。
(Separation of rod-shaped ruthenium dioxide)
Thereafter, the obtained second mixture was put into a mixed solution of 4 L of pure water and 1 L of nitric acid, followed by stirring and washing at 50 ° C. for 2 hours. The precipitated powder was filtered, washed with water and dried, and then the obtained powder was subjected to SEM observation and XRD analysis. As a result, it was confirmed that the obtained powder was a rod-shaped ruthenium dioxide powder. FIG. 4 shows an SEM photograph of the rod-shaped ruthenium dioxide powder obtained. As shown in FIG. 4, the obtained ruthenium dioxide powder has a rod-like shape and includes primary particles having a rectangular shape including a square shape in a cross section perpendicular to the long axis direction.
（ビスマス化合物の回収）
また、上記洗浄に使用した硝酸水溶液を乾燥した結果、約２３０ｇの白色の粉末を得た。この粉末をＸＲＤ分析した結果、オキシ塩化ビスマスの粉末であることを確認した。
(Recovery of bismuth compounds)
Further, as a result of drying the aqueous nitric acid solution used for the above washing, about 230 g of white powder was obtained. As a result of XRD analysis of this powder, it was confirmed that it was a powder of bismuth oxychloride.
（実施例２）
実施例１と同様の方法で、粒径約５０ｎｍの粒状の一次粒子を有するアモルファス状の二酸化ルテニウム（原料）を作製した。得られた粒状の二酸化ルテニウム１ｍｏｌと、オキシ塩化ビスマス（和光純薬工業（株）製１．５ｍｏｌとを混合して第１の混合物を作製した。第１の混合物をアルミナ坩堝に充填し、空気中８００℃で２時間焙焼して第２の混合物を得た。その後、得られた第２の混合物をＳＥＭ観察およびＥＤＸ定性分析、さらにＸＲＤ分析を行った。その結果、棒状の二酸化ルテニウム粉末と球状オキシ塩化ビスマスの混合粉末であることが確認された。
(Example 2)
Amorphous ruthenium dioxide (raw material) having granular primary particles with a particle size of about 50 nm was produced in the same manner as in Example 1. The obtained granular ruthenium dioxide 1 mol and bismuth oxychloride (1.5 mol manufactured by Wako Pure Chemical Industries, Ltd.) were mixed to prepare a first mixture. The first mixture was filled in an alumina crucible, and air The resulting mixture was roasted at 800 ° C. for 2 hours to obtain a second mixture, which was then subjected to SEM observation, EDX qualitative analysis, and XRD analysis, and as a result, rod-shaped ruthenium dioxide powder. And a mixed powder of spherical bismuth oxychloride.
その後、得られた第２の混合物を４Ｌの純水と１Ｌの硝酸の混合溶液に入れ、５０℃で２時間の撹拌洗浄を行った。沈殿した粉末をろ過、水洗、乾燥した後、ＳＥＭ観察およびＸＲＤ分析した。その結果、得られた粉末は、棒状の二酸化ルテニウム粉末であることを確認した。 Thereafter, the obtained second mixture was put into a mixed solution of 4 L of pure water and 1 L of nitric acid, followed by stirring and washing at 50 ° C. for 2 hours. The precipitated powder was filtered, washed with water and dried, followed by SEM observation and XRD analysis. As a result, it was confirmed that the obtained powder was a rod-like ruthenium dioxide powder.
（実施例３）
実施例１と同様の方法で、粒径約５０ｎｍの粒状の一次粒子を有するアモルファス状の二酸化ルテニウムを作製した。得られた粒状の二酸化ルテニウム１ｍｏｌと、オキシ塩化ビスマス（和光純薬工業（株）製２．０ｍｏｌを混合して第１の混合物を作製した。第１の混合物をアルミナ坩堝に充填し、空気中８００℃で２時間焙焼して、第２の混合物を得た。その後、得られた第２の混合物をＳＥＭ観察およびＥＤＸ定性分析、さらにＸＲＤ分析を行った。その結果、棒状の二酸化ルテニウム粉末と球状オキシ塩化ビスマスの混合粉末であることが確認された。
(Example 3)
In the same manner as in Example 1, amorphous ruthenium dioxide having primary particles having a particle size of about 50 nm was produced. 1 mol of the obtained ruthenium dioxide and bismuth oxychloride (2.0 mol manufactured by Wako Pure Chemical Industries, Ltd.) were mixed to prepare a first mixture. The first mixture was filled in an alumina crucible, and in the air The mixture was roasted at 800 ° C. for 2 hours to obtain a second mixture, and then the obtained second mixture was subjected to SEM observation, EDX qualitative analysis, and XRD analysis, and as a result, rod-shaped ruthenium dioxide powder And a mixed powder of spherical bismuth oxychloride.
その後、得られた第２の混合物を４Ｌの純水と１Ｌの硝酸の混合溶液に入れ、５０℃で２時間の撹拌洗浄を行った。沈殿した粉末をろ過、水洗、乾燥したのち、ＳＥＭ観察およびＸＲＤ分析した。その結果、得られた粉末は、棒状の二酸化ルテニウム粉末であることを確認した。 Thereafter, the obtained second mixture was put into a mixed solution of 4 L of pure water and 1 L of nitric acid, followed by stirring and washing at 50 ° C. for 2 hours. The precipitated powder was filtered, washed with water, and dried, followed by SEM observation and XRD analysis. As a result, it was confirmed that the obtained powder was a rod-like ruthenium dioxide powder.
（実施例４）
実施例１と同様の方法で、粒径約５０ｎｍの粒状の一次粒子を有するアモルファス状の二酸化ルテニウム（原料）を作製した。得られた粒状の二酸化ルテニウム１ｍｏｌと、オキシ塩化ビスマス（和光純薬工業（株）製０．５ｍｏｌを混合し、アルミナ坩堝に充填し、空気中８００℃で２時間焙焼して、第２の混合物を得た。その後、得られた第２の混合物をＳＥＭ観察およびＥＤＸ定性分析、さらにＸＲＤ分析を行った。その結果、棒状の二酸化ルテニウム粉末と球状オキシ塩化ビスマスの混合粉末であることが確認された。
Example 4
Amorphous ruthenium dioxide (raw material) having granular primary particles with a particle size of about 50 nm was produced in the same manner as in Example 1. The obtained granular ruthenium dioxide 1 mol and bismuth oxychloride (0.5 mol manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, filled in an alumina crucible and roasted at 800 ° C. for 2 hours in the air. Thereafter, SEM observation, EDX qualitative analysis, and XRD analysis were performed on the obtained second mixture, and it was confirmed that it was a mixed powder of rod-shaped ruthenium dioxide powder and spherical bismuth oxychloride. It was done.
その後、得られた第２の混合物を４Ｌの純水と１Ｌの硝酸の混合溶液に入れ、５０℃で２時間の撹拌洗浄を行った。沈殿した粉末をろ過、水洗、乾燥したのち、ＳＥＭ観察およびＸＲＤ分析した。その結果、得られた粉末は、棒状の二酸化ルテニウム粉末であることを確認した。 Thereafter, the obtained second mixture was put into a mixed solution of 4 L of pure water and 1 L of nitric acid, followed by stirring and washing at 50 ° C. for 2 hours. The precipitated powder was filtered, washed with water, and dried, followed by SEM observation and XRD analysis. As a result, it was confirmed that the obtained powder was a rod-like ruthenium dioxide powder.
（実施例５）
実施例１と同様の方法で、粒径約５０ｎｍの粒状の一次粒子を有するアモルファス状の二酸化ルテニウム（原料）を作製した。得られた粒状の二酸化ルテニウム１ｍｏｌと、オキシ塩化ビスマス（和光純薬工業（株）製３．０ｍｏｌを混合し、アルミナ坩堝に充填し、空気中８００℃で２時間焙焼して、第２の混合物を得た。その後、得られた第２の混合物をＳＥＭ観察およびＥＤＸ定性分析、さらにＸＲＤ分析を行った。その結果、棒状の二酸化ルテニウム粉末と球状オキシ塩化ビスマスの混合粉末であることが確認された。
(Example 5)
Amorphous ruthenium dioxide (raw material) having granular primary particles with a particle size of about 50 nm was produced in the same manner as in Example 1. 1 mol of the obtained granular ruthenium dioxide and bismuth oxychloride (3.0 mol manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, filled in an alumina crucible and roasted at 800 ° C. for 2 hours in the air. Thereafter, SEM observation, EDX qualitative analysis, and XRD analysis were performed on the obtained second mixture, and it was confirmed that it was a mixed powder of rod-shaped ruthenium dioxide powder and spherical bismuth oxychloride. It was done.
その後、得られた第２の混合物を４Ｌの純水と１Ｌの硝酸の混合溶液に入れ、５０℃で２時間の撹拌洗浄を行った。沈殿した粉末をろ過、水洗、乾燥したのち、ＳＥＭ観察およびＸＲＤ分析した。その結果、得られた粉末は、棒状の二酸化ルテニウム粉末であることを確認した。 Thereafter, the obtained second mixture was put into a mixed solution of 4 L of pure water and 1 L of nitric acid, followed by stirring and washing at 50 ° C. for 2 hours. The precipitated powder was filtered, washed with water, and dried, followed by SEM observation and XRD analysis. As a result, it was confirmed that the obtained powder was a rod-like ruthenium dioxide powder.
（実施例６）
実施例１と同様の方法で、粒径約５０ｎｍの粒状の一次粒子を有するアモルファス状の二酸化ルテニウム（原料）を作製した。得られた粒状の二酸化ルテニウム１ｍｏｌと、オキシ塩化ビスマス（和光純薬工業（株）製）１ｍｏｌを混合し、アルミナ坩堝に充填し、空気中８００℃で３時間焙焼した。得られた粉末のＳＥＭ観察およびＥＤＸ定性分析、さらにＸＲＤ分析を行った。その結果、短径ａが１００ｎｍ以上であり、長径ｂと短径ａとに差が小さく（長径ｂと短径ａの比：２以上３以下）、球状に近い棒状の二酸化ルテニウムと球状のオキシ塩化ビスマスの混合粉末であることを確認した。
(Example 6)
Amorphous ruthenium dioxide (raw material) having granular primary particles with a particle size of about 50 nm was produced in the same manner as in Example 1. 1 mol of the obtained granular ruthenium dioxide and 1 mol of bismuth oxychloride (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, filled in an alumina crucible, and baked at 800 ° C. for 3 hours in the air. The obtained powder was subjected to SEM observation, EDX qualitative analysis, and XRD analysis. As a result, the minor axis a is 100 nm or more, the difference between the major axis b and the minor axis a is small (ratio of major axis b to minor axis a: 2 or more and 3 or less), rod-like ruthenium dioxide and spherical oxy It was confirmed to be a mixed powder of bismuth chloride.
（比較例１）
実施例１と同様の方法で、粒径約５０ｎｍの粒状の一次粒子を有するアモルファス状の二酸化ルテニウム（原料）を作製した。得られ二酸化ルテニウムをアルミナ坩堝に充填し、空気中７００℃で２時間焙焼した。得られた粉末のＳＥＭ観察およびＥＤＸ定性分析、さらにＸＲＤ分析を行った。その結果、粒径約８０ｎｍの球状二酸化ルテニウムであることを確認した。
(Comparative Example 1)
Amorphous ruthenium dioxide (raw material) having granular primary particles with a particle size of about 50 nm was produced in the same manner as in Example 1. The obtained ruthenium dioxide was filled in an alumina crucible and roasted at 700 ° C. for 2 hours in air. The obtained powder was subjected to SEM observation, EDX qualitative analysis, and XRD analysis. As a result, it was confirmed to be spherical ruthenium dioxide having a particle size of about 80 nm.
（比較例２）
実施例１と同様の方法で、粒径約５０ｎｍの粒状の一次粒子を有するアモルファス状の二酸化ルテニウム（原料）を作製した。得られたアモルファス状二酸化ルテニウム１ｍｏｌと、オキシ塩化ビスマス（和光純薬工業（株）製）１ｍｏｌを混合し、アルミナ坩堝に充填し、空気中５００℃で５時間焙焼した。得られた粉末のＳＥＭ観察の結果、２種類の大きさの異なる球状粉の混合物であることを確認した。ＥＤＸ定性分析およびＸＲＤ分析の結果、小粒径が結晶性の二酸化ルテニウム粉であり、それより粒径の大きな球状粉がオキシ塩化ビスマスであることを確認した。
(Comparative Example 2)
Amorphous ruthenium dioxide (raw material) having granular primary particles with a particle size of about 50 nm was produced in the same manner as in Example 1. 1 mol of the obtained amorphous ruthenium dioxide and 1 mol of bismuth oxychloride (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, filled in an alumina crucible, and baked at 500 ° C. in air for 5 hours. As a result of SEM observation of the obtained powder, it was confirmed that it was a mixture of two kinds of spherical powders having different sizes. As a result of EDX qualitative analysis and XRD analysis, it was confirmed that the small particle diameter was crystalline ruthenium dioxide powder, and the spherical powder having a larger particle diameter was bismuth oxychloride.
（比較例３）
実施例１と同様の方法で、粒径約５０ｎｍの粒状の一次粒子を有するアモルファス状の二酸化ルテニウム（原料）を作製した。得られたアモルファス状二酸化ルテニウム１ｍｏｌと、オキシ塩化ビスマス（和光純薬工業（株）製）１ｍｏｌを混合し、アルミナ坩堝に充填し、空気中１０００℃で２時間焙焼した。得られた粉をＳＥＭ観察した結果、球状粉が得られた。ＸＲＤ分析を行った結果、単体のＢｉ２Ｒｕ２Ｏ７粉末であることが確認された。
(Comparative Example 3)
Amorphous ruthenium dioxide (raw material) having granular primary particles with a particle size of about 50 nm was produced in the same manner as in Example 1. 1 mol of the obtained amorphous ruthenium dioxide and 1 mol of bismuth oxychloride (manufactured by Wako Pure Chemical Industries, Ltd.) were mixed, filled in an alumina crucible, and baked at 1000 ° C. in air for 2 hours. As a result of SEM observation of the obtained powder, a spherical powder was obtained. As a result of XRD analysis, it was confirmed that the powder was a single Bi 2 Ru 2 O 7 powder.
［厚膜抵抗体の作製と評価］
以下、実施例７〜９及び比較例４〜６は、実施例１又は比較例１で製造した二酸化ルテニウム粉末を使用して厚膜抵抗体を作製し、その抵抗値と電流雑音を評価した。表２に、それぞの実施例及び比較例の厚膜抵抗体ペーストの組成と厚膜抵抗体作製時の膜厚を示す。また、図５に測定した抵抗値と電流雑音の結果をまとめて示す。
（実施例７）
実施例１で得られた棒状の二酸化ルテニウム粉末３重量％、鉛フリーガラス粉末（二酸化ケイ素：３５重量％、酸化ほう素：２０重量％、酸化アルミニウム：５重量％、酸化カルシウム：５重量％、酸化バリウム：２０重量％、酸化亜鉛：１５重量％）５７重量％及び、有機ビヒクル（エチルセルロースをターピネオールに溶解したもの）４０重量％を３本ロールミルによって混練し、評価用の厚膜抵抗体ペーストを作製した。
[Production and evaluation of thick film resistors]
Hereinafter, in Examples 7 to 9 and Comparative Examples 4 to 6, a thick film resistor was produced using the ruthenium dioxide powder produced in Example 1 or Comparative Example 1, and the resistance value and current noise were evaluated. Table 2 shows the compositions of the thick film resistor pastes of the respective examples and comparative examples and the film thicknesses when the thick film resistors were produced. FIG. 5 collectively shows the measured resistance values and current noise results.
(Example 7)
3% by weight of rod-shaped ruthenium dioxide powder obtained in Example 1, lead-free glass powder (silicon dioxide: 35% by weight, boron oxide: 20% by weight, aluminum oxide: 5% by weight, calcium oxide: 5% by weight, Thick film resistor paste for evaluation was prepared by kneading 57% by weight of barium oxide: 20% by weight, zinc oxide: 15% by weight) and 40% by weight of organic vehicle (ethyl cellulose dissolved in terpineol) by a three-roll mill. Produced.
得られた厚膜抵抗体ペーストを、事前に銀ペーストを用いて電極を形成したアルミナ基板上に、サイズ１×１ｍｍ、厚さ７μｍの抵抗体パターンで印刷した。これを乾燥（２５０℃×１５分）した後、ピーク温度８５０℃、ピーク時間９分のベルト焼成炉によって焼成し、厚膜抵抗体を形成した。得られた厚膜抵抗体の抵抗値と電流雑音とを測定した。抵抗値は４端子法による測定を行った。また電流雑音は、（株）ノイズ研究所製の電流雑音測定器「ＲＣＮ−２０１１」によって測定を行った。 The obtained thick film resistor paste was printed in a resistor pattern having a size of 1 × 1 mm and a thickness of 7 μm on an alumina substrate on which an electrode was previously formed using a silver paste. This was dried (250 ° C. × 15 minutes) and then fired in a belt firing furnace having a peak temperature of 850 ° C. and a peak time of 9 minutes to form a thick film resistor. The resistance value and current noise of the obtained thick film resistor were measured. The resistance value was measured by a four-terminal method. The current noise was measured with a current noise measuring device “RCN-2011” manufactured by Noise Research Laboratory.
（実施例８）
実施例１で得られた棒状の二酸化ルテニウム粉末６重量％、鉛フリーガラス粉末（二酸化ケイ素：３５重量％、酸化ほう素：２０重量％、酸化アルミニウム：５重量％、酸化カルシウム：５重量％、酸化バリウム：２０重量％、酸化亜鉛：１５重量％）５４重量％と、有機ビヒクル（エチルセルロースをターピネオールに溶解したもの）４０重量％を３本ロールミルによって混練し、評価用の厚膜抵抗体ペーストを作製した。得られた厚膜抵抗体ペーストの特性を実施例６と同様に測定した。
(Example 8)
6% by weight of rod-shaped ruthenium dioxide powder obtained in Example 1, lead-free glass powder (silicon dioxide: 35% by weight, boron oxide: 20% by weight, aluminum oxide: 5% by weight, calcium oxide: 5% by weight, Thick film resistor paste for evaluation was prepared by kneading 54% by weight of barium oxide: 20% by weight, zinc oxide: 15% by weight) and 40% by weight of organic vehicle (ethyl cellulose dissolved in terpineol) by a three roll mill. Produced. The characteristics of the obtained thick film resistor paste were measured in the same manner as in Example 6.
（実施例９）
実施例１で得られた棒状の二酸化ルテニウム粉末９重量％、鉛フリーガラス粉末（二酸化ケイ素：３５重量％、酸化ほう素：２０重量％、酸化アルミニウム：５重量％、酸化カルシウム：５重量％、酸化バリウム：２０重量％、酸化亜鉛：１５重量％）５１重量％と、有機ビヒクル（エチルセルロースをターピネオールに溶解したもの）４０重量％を３本ロールミルによって混練し、評価用の厚膜抵抗体ペーストを作製した。得られた厚膜抵抗体ペーストの特性を実施例６と同様に測定した。
Example 9
9% by weight of rod-shaped ruthenium dioxide powder obtained in Example 1, lead-free glass powder (silicon dioxide: 35% by weight, boron oxide: 20% by weight, aluminum oxide: 5% by weight, calcium oxide: 5% by weight, Thick film resistor paste for evaluation was prepared by kneading 51% by weight of barium oxide: 20% by weight, zinc oxide: 15% by weight) and 40% by weight of organic vehicle (ethyl cellulose dissolved in terpineol) by a three-roll mill. Produced. The characteristics of the obtained thick film resistor paste were measured in the same manner as in Example 6.
（比較例４〜６）
比較例１で作製した球状の二酸化ルテニウム粉末を用いた以外は、実施例７〜９と同様の方法で厚膜抵抗体を作製し、それぞれ比較例４〜６の評価用の厚膜抵抗体ペーストとした。得られた厚膜抵抗体ペーストの特性を、実施例６と同様に測定した。
(Comparative Examples 4-6)
Except for using the spherical ruthenium dioxide powder produced in Comparative Example 1, thick film resistors were produced in the same manner as in Examples 7 to 9, and thick film resistor pastes for evaluation in Comparative Examples 4 to 6, respectively. It was. The characteristics of the obtained thick film resistor paste were measured in the same manner as in Example 6.
（評価）
実施例１〜実施例６では、棒状の二酸化ルテニウム粉末が得られた。また、実施例５は、棒状の二酸化ルテニウムを製造できたが、固液分離工程において分離しきれないビスマス化合物が多く残留した。また、実施例６では、長軸方向の長径ｂと、長軸方向に垂直な断面の短径ａとのアスペクト比が、他の実施例と比較して小さくなった。
(Evaluation)
In Examples 1 to 6, rod-shaped ruthenium dioxide powder was obtained. In Example 5, rod-like ruthenium dioxide could be produced, but many bismuth compounds that could not be separated in the solid-liquid separation process remained. In Example 6, the aspect ratio between the major axis b in the major axis direction and the minor axis a in the cross section perpendicular to the major axis direction was smaller than in the other examples.
実施例７〜８及び比較例４〜６は、実施例１で製造した棒状の二酸化ルテニウム粉末と比較例１で製造した球状の二酸化ルテニウム粉末（従来法）とを使用して厚膜抵抗体を作製し、作製した厚膜抵抗体の抵抗値と電流雑音を評価した。その結果、球状の二酸化ルテニウム（比較例１）を用いた厚膜抵抗体では、抵抗値１００ｋΩ／□で電流雑音が０ｄＢ以上となるところ、棒状の二酸化ルテニウム粉末（実施例１）を用いた抵抗ペーストの場合、抵抗値１ＭΩ／□まで電流雑音がマイナス値となることがわかった。このことから、棒状の二酸化ルテニウム粉末を使用した厚膜抵抗体は、従来の球状の二酸化ルテニウムを使用した厚膜抵抗体よりも電流雑音を低下させる効果があることが示された。 In Examples 7 to 8 and Comparative Examples 4 to 6, a thick film resistor was formed using the rod-like ruthenium dioxide powder produced in Example 1 and the spherical ruthenium dioxide powder produced in Comparative Example 1 (conventional method). The resistance value and current noise of the manufactured thick film resistor were evaluated. As a result, in the thick film resistor using the spherical ruthenium dioxide (Comparative Example 1), the resistance using the rod-shaped ruthenium dioxide powder (Example 1) when the resistance value is 100 kΩ / □ and the current noise is 0 dB or more. In the case of the paste, it was found that the current noise becomes a negative value up to a resistance value of 1 MΩ / □. From this, it was shown that the thick film resistor using the rod-shaped ruthenium dioxide powder has the effect of lowering current noise than the thick film resistor using the conventional spherical ruthenium dioxide.
１０…棒状の二酸化ルテニウム
ａ…長軸方向と垂直な断面における短径
ｂ…長軸方向の最大径（長径）
ｃ…長軸方向と垂直な断面における短径に垂直な最長径（長径）
DESCRIPTION OF SYMBOLS 10 ... Rod-shaped ruthenium dioxide a ... Short diameter in a cross section perpendicular | vertical to a major axis direction b ... The largest diameter (major axis) of a major axis direction
c: Longest diameter (major axis) perpendicular to the minor axis in the cross section perpendicular to the major axis direction
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| JPS4825320B1 (en) * | 1967-12-20 | 1973-07-27 | ||
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| JP2007302497A (en) * | 2006-05-10 | 2007-11-22 | Sumitomo Metal Mining Co Ltd | Ruthenium oxide powder and its production method |
| WO2012176696A1 (en) * | 2011-06-21 | 2012-12-27 | 住友金属鉱山株式会社 | Ruthenium oxide powder, composition for thick film resistor elements using same, and thick film resistor element |
| JP2013053030A (en) * | 2011-09-02 | 2013-03-21 | Sumitomo Metal Mining Co Ltd | Plate-like ruthenium oxide powder, method for producing the same, and thick film resistor composition using the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS4825320B1 (en) * | 1967-12-20 | 1973-07-27 | ||
| JPS5997524A (en) * | 1982-11-01 | 1984-06-05 | イ−・アイ・デユポン・ド・ネモア−ス・アンド・コンパニ− | Manufacture of pyrochlores containing high surface area bismuth |
| JPS6124101A (en) * | 1984-07-13 | 1986-02-01 | 住友金属鉱山株式会社 | Thick film conductive paste |
| JP2007302497A (en) * | 2006-05-10 | 2007-11-22 | Sumitomo Metal Mining Co Ltd | Ruthenium oxide powder and its production method |
| WO2012176696A1 (en) * | 2011-06-21 | 2012-12-27 | 住友金属鉱山株式会社 | Ruthenium oxide powder, composition for thick film resistor elements using same, and thick film resistor element |
| JP2013053030A (en) * | 2011-09-02 | 2013-03-21 | Sumitomo Metal Mining Co Ltd | Plate-like ruthenium oxide powder, method for producing the same, and thick film resistor composition using the same |
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