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Humidity-Sensing Component Composition

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Humidity-Sensing Component Composition Patentamt JEuropaischesEuropean Patent Office © Publication number: 0 242 834 Office europeen des brevets A2 © EUROPEAN PATENT APPLICATION © Application number: 87105802.0 © Int.CI.3: G 01 N 27/12 @ Dateoffiling: 21.04.87 © Priority: 24.04.86 JP 93211/86 ©Applicant: MITSUBISHI GAS CHEMICAL COMPANY, INC. 24.04.86 JP 93212/86 5-2,Marunouchi2-chomeChiyoda-Ku 23.12.86 JP 305392/86 Tokyo(JP) © Inventor: Sugio, Akitoshi © Dateof publication of application: 382-155, Besho Ohaza-Sashiougiryo 28.10.87 Bulletin 87/44 Ohmiya-shiSaitama-Ken(JP) © Designated Contracting States: © Inventor: Shimomura.Tadashi FR GB 11 05-21, Higashifukai Nagareyama-shi Chiba-Ken(JP) @ Inventor: Wakabayashi, Hidechika 6-101, Nishlkubocho 15-chome Tokiwadaira Matsudo-shl Chiba-Ken(JP) © Inventor: Kondo,Osamu 25-15-201, Niijyuku 5-chome Katsushika-ku Tokyo(JP) @ Inventor: Ogasawara, Kazuharu 1 1 -1 6, Kanamachi 5-chome Katsushika-ku Tokyo(JP) © Inventor: Nishizawa, Chiharu 17-1,Kanegasaku Matsudo-shl Chiba-Ken(JP) © Representative: Blumbach Weser Bergen Kramer Zwirner Hoffmann Patentanwalte Radeckestrasse43 D-8000Munchen60(DE) Humidity-sensing component composition. © A humidity-sensing component composition includes a metallic oxide and a chalcogen oxyacid salt represented by a general formula AxByOz where A is one of an alkali metal and an alkaline earth metal, B is one of sulphur, selenium, and tellurium, O is oxygen, x is 1 to 2, y 1 to 5, and z 2 to 7. The chalcogen oxyacid salt is blended by an amount of 0.01 to 99.99 mol% in the metallic oxide with the sum of the metallic oxide and the chalcogen oxyacid salt as a reference. The met- allic oxide and the chalcogen oxyacid salt are sintered under an atmosphere of molecular oxygen. Croydon Printing Company Ltd. 0242834 TITLE THE INVENTION 87/8726 EPC HUMIDITY-SENSING COMPONENT COMPOSITION b BAUKUKUUNL) UF THE INVENTION Field of the Invention The present invention relates to a humidity-sensing component composition which detects relative humidity as a 10 change in the value of the electrical resistance. Description of the Prior Art Conventionally, materials known as humidity-sensing component compositions are: 15 (1) Materials using electrolytic quality salts such as lithium chloride; (2) Materials utilizing organic polymer films such as polyamide or polyethylene films; (3) Materials using metallic semiconductors such as 20 selenium or germanium; and (4) Materials utilizing sintered bodies of metallic oxides such as titanium oxide, aluminium oxide, or stannic oxide. Among these, the materials using sintered bodies 25 of metallic oxides have the merit of being more stable chemically and physically than other humidity-sensing component compositions such as organic polymer films, and these can be said to be effective as humidity-sensing component compositions. 30 However, these sintered bodies of metallic oxides usually have the following types of drawbacks: (1) The characteristic resistance value is high, and is not in the practical resistance value range. In regions of low humidity especially, the resistance of the 35 humidity-sensing component composition abruptly becomes - 1 - 5242834 high, so the measurement of humidity in regions of low humidity is difficult. (2) Dependence on temperature in the humidity-sensing characteristics is large, so temperature compensation is 5 necessary. (3) Hysteresis in the humidity-sensing characteristics is investigated when moisture is absorbed and released. (4) Resistance to thermal shock is low, and the LO humidity-sensing characteristics deteriorate. (5) Products of hydration are absorbed on and foul the surface of sintered bodies of metallic oxides so that the humidity-sensing characteristics deteriorate, making periodic heat cleaning necessary. 15 For these reasons, the development of a humidity-sensing component composition with high reliability has been greatly desired. SUMMARY OF THE INVENTION 20 An object of the present invention is to provide, with due consideration to the drawbacks of such conventional materials, a reliable humidity-sensing component composition. 25 Another object of the present invention is to provide a humidity-sensing component composition in which the characteristic resistance value is low and is in the practical resistance value range. Another object of the present invention is to provide 30 a humidity-sensing component composition in which the dependence on temperature in the humidity-sensing characteristics is extremely small so that temperature compensation is unnecessary. Another object of the present invention is to provide in 35 a humidity-sensing component composition which - 2 - 0242834 hysteresis is almost absent in the humidity-sensing component characteristics when moisture is absorbed and released. Another object of the present invention is to provide 5 a humidity-sensing component composition which can withstand thermal shock. Another object of the present invention is to provide a humidity-sensing component composition for which special heat cleaning is unnecessary. 10 Another object of the present invention is to provide a humidity-sensing component composition which exhibits good humidity-sensing characteristics in regions of low humidity, especially in regions of 40% RH and below. With the above objects in view, the present invention 15 resides in a humidity-sensing component composition including a metallic oxide and a chalcogen oxyacid salt represented by a general formula ABO where A is one of a y <b an alkali metal and an alkaline earth metal, B is one of sulphur, selenium, and tellurium, O is oxygen, x is 1 to 2, 20 y 1 to 5, and z 2 to 7, said chalcogen oxyacid salt being blended by an amount of 0.01 to 99.99 mol% in the metallic oxide with the sum of the metallic oxide and the chalcogen oxyacid salt as a reference, the metallic oxide and the chalcogen oxyacid salt being sintered under an atmosphere 25 of molecular oxygen. BRIEF DESCRIPTION OF THE DRAWINGS The other objects, features, and advantages of the 30 present invention will become more apparent from the following description of the preferred embodiments taken in conjunction with the accompanying drawings, in which: Fig. 1 is a front elevation showing one embodiment of the humidity-sensing component made from the 35 humidity-sensing component composition of the present - 3 - invention. U graphs showing the Fig. 2 to Fig. are characteristics of the humidity-sensing component invention in which: composition of the present 3 show the humidity-sensing i Fig. 2 and Fig. show the relationship characteristics; Fig. 4 and Fig. 5 and the humidity-sensing between temperature the in characteristics; Fig. 6 and Fig. 7 show hysteresis characteristics after the composition the humidity-sensing of high humidity? Fig. 8 and Fig. 0 was held under conditions characteristics before and 9 show the humidity-sensing to a thermal shock after the composition was subjected characteristics test; Fig. 10 shows the humidity-sensing subjected to a water before and after the composition was 11 shows the hysteresis in the 5 resistance test; Fig. the composition was humidity-sensing characteristics after held under conditions of high humidity. EMBODIMENTS hf.TATT.ED DESCRIPTION OF THE PREFERRED 10 according to A humidity-sensing component composition described in detail with the present invention is now reference to the drawings. the metallic oxides used In the present invention, have humidity-sensing characteristics, 25 are materials which which are conventionally known as and, of course, materials humidity-sensing component effective components of a TaO, composition are included. MgO, Ti02, Zr02, Nb205, Mn02, M^O^ FeO, Fe^, CoO, Ta205 Cr203, M0O3, W03, ZnO, In^, Tl^, 30 Co 0 NiO, Ni203, Ni304, Al^, Ga^, PbO, Bi^, and the like are Si02, Ge02, SnO, Sn02, Sb^, of oxides, while ZnFe204, given as examples Mg2Fe204, (above, spinel), 3Al203.2Si02 MgAl204, MgCr203, ZnCr203 examples of compound (Mullite), and the like are given as ZnO, MgO, Zr02, NiO, 35 oxides. Among these, Ti02, Y-Al203, - 4 - 0242834 MgAl202 and the like are particularly desirable. Among the metallic oxides, those refined by thermal decomposition, such as metallic salts, metallic hydroxides, alkoxides, and the like are acceptable. Especially, in providing a 5 humidity-sensing component composition for satisfactory measurement in low humidity regions of 40% RH or less, the use of a combination of metallic oxides such as titanium oxide, and cupric oxide or cuprous oxide is particularly desirable. 10 Chalcogen oxyacid salt is represented by the following general formula (I). ABO (I) x y z * ' 15 wherein A is one of an alkali metal and an alkaline earth metal, B is one of sulphur, selenium, and tellurium, 0 is oxygen, x is 1 to 2, y 1 to 5, and z 2 to 7. Specific examples of sulphur oxyacids are the sulphoxylates sulphites, disulphites , (metabisulphites) , 20 dithionites, disulphates (pyrosulphates) , thiosulphates, and thionates. Specific examples of selenium oxyacids are the selenites and selenates. Specific examples of tellurium oxyacids are the tellurites and tellurates. The ratios of metallic oxides and chalcogen oxyacid 25 salts in the humidity-sensing component composition of the present convention are based on a reference value of the sum of the metallic oxide component and the chalcogen oxyacid salt component. The chalcogen oxyacid salt component will range from 0.01 to 99.99 mol%, with the 30 desirable range being 0.1 to 99.9 mol%, especially less than 50 mol% in consideration of economy and characteristics. After blending each of the components for this humidity-sensing component composition, the sintered body obtained by means of suitable sintering conditions has 35 an extremely improved humidity-sensing characteristic in - 5 - component composition comparison with a humidity-sensing oxide only. prepared from the metallic Particularly when providing a humidity-sensing satisfactory measurement in low component composition for of 40% RH or less, a combination of h humidity regions and cupric oxide or metallic oxides such as titanium oxide, with a of 50 to 98 mol% for cuprous oxide, is used, range for the cupric or cuprous the titanium oxide, 1 to 40% the oxyacid salt oxide, and 1 to 10 mol% for chalcogen desirable.
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