WO2020031724A1 - ガス検出器 - Google Patents

ガス検出器 Download PDF

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Publication number
WO2020031724A1
WO2020031724A1 PCT/JP2019/029239 JP2019029239W WO2020031724A1 WO 2020031724 A1 WO2020031724 A1 WO 2020031724A1 JP 2019029239 W JP2019029239 W JP 2019029239W WO 2020031724 A1 WO2020031724 A1 WO 2020031724A1
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WO
WIPO (PCT)
Prior art keywords
gas
filter
organic polymer
film
siloxane
Prior art date
Application number
PCT/JP2019/029239
Other languages
English (en)
French (fr)
Inventor
竹内　雅人
純平 古野
健太 福井
井澤　邦之
正和 佐井
三橋　弘和
卓史 谷口
Original Assignee
フィガロ技研株式会社
新コスモス電機株式会社
公立大学法人大阪
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by フィガロ技研株式会社, 新コスモス電機株式会社, 公立大学法人大阪 filed Critical フィガロ技研株式会社
Priority to KR1020217007113A priority Critical patent/KR20210039471A/ko
Priority to CN201980053883.3A priority patent/CN112703394A/zh
Priority to EP19847207.8A priority patent/EP3835772A4/en
Priority to JP2020536458A priority patent/JPWO2020031724A1/ja
Priority to US17/267,060 priority patent/US20210164929A1/en
Publication of WO2020031724A1 publication Critical patent/WO2020031724A1/ja

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    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/28—Electrolytic cell components
    • G01N27/30—Electrodes, e.g. test electrodes; Half-cells
    • G—PHYSICS
    • G01—MEASURING; TESTING
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    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
    • G01N27/403—Cells and electrode assemblies
    • G01N27/406—Cells and probes with solid electrolytes
    • G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
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Definitions

  • the present invention relates to a gas detector such as a gas sensor, and particularly to a filter thereof.
  • Non-Patent Document 1 It is known that an organic polymer permeable membrane such as PTFE (polytetrafluoroethylene) is used as a filter for a gas sensor (Patent Document 1). Further, a gas-selective permeable membrane having high gas permeability and high gas selectivity has been developed (Non-Patent Document 1). In both the PTFE membrane and the gas-selective permeable membrane, gases such as hydrogen and methane having a low molecular weight permeate the membrane quickly, and gases such as toluene having a high molecular weight permeate the membrane only slowly.
  • PTFE polytetrafluoroethylene
  • Gas sensors have a problem that they are easily poisoned by siloxane. Since siloxane has a large molecular weight, the organic polymer breathable membrane is promising as a filter for siloxane. However, the organic polymer-permeable membrane is not suitable for removing ethanol when detecting a gas to be detected such as methane, LPG, and CO because the gas is selected according to the molecular weight.
  • Ethanol is a representative of miscellaneous gases that occur on a daily basis and hinders detection of the detection target gas. Miscellaneous gases include acetone, isopropanol, methanol and the like in addition to ethanol.
  • An object of the present invention is to provide a filter for a gas detector for removing miscellaneous gases such as siloxane and ethanol.
  • the present invention provides a gas detector that introduces an atmosphere into a gas detection unit via a filter.
  • the filter is characterized by comprising an organic polymer filter made of an organic polymer membrane that removes siloxane with air permeability and allows the gas to be detected to pass therethrough, and an inorganic filter that removes alcohol and allows the gas to be detected to pass therethrough.
  • the gas detector is a gas sensor and includes, in addition to the gas detection unit and the filter, a housing that houses the gas detection unit and has the filter attached thereto. Further, the filter may be provided outside the housing of the gas sensor.
  • a gas sensor without a filter may be housed at the base end of a suction pipe or the like, and the filter of the present invention may be provided upstream of the gas flow path to the gas sensor, such as at the tip of the pipe. Even in this case, the operation of the filter is the same.
  • the filter is provided with an organic polymer filter that removes siloxane by air permeability and an inorganic filter that removes alcohol and allows gas to be detected to pass.
  • the organic polymer filter screens the gas according to the molecular weight or the like to prevent the permeation of siloxane.
  • the material of the organic polymer filter include a fluororesin membrane such as a PTFE membrane, and a synthetic resin membrane of a highly permeable organic polymer known as a gas-selective permeable membrane.
  • Fluororesin membranes made of relatively low permeability are made of Teflon AF (Teflon is a registered trademark of EIDupont), Hyflon AD (Hyflon is a registered trademark of Solvay), Cytop (Cytop is a trademark of Asahi Glass) ) And the like.
  • the organic polymer film may be a polysaccharide film such as a cellulose film, a fucoidan film, and a chitosan film.
  • Organic polymer membranes are gas permeable and separate gases by molecular weight or by interaction between the membrane and molecules in addition to molecular weight.
  • the type of the organic polymer film is arbitrary.
  • These membranes remove siloxane having a high molecular weight from the outside air, and allow a gas to be detected such as methane, LPG, and CO, and an alcohol such as ethanol to permeate.
  • a gas such as methane, LPG, and CO
  • an alcohol such as ethanol to permeate.
  • LPG is harder to pass through an organic polymer filter than methane, an organic polymer filter does not hinder detection of LPG because LPG at a high concentration can be detected.
  • the inorganic filter is made of an inorganic adsorbent such as activated carbon, silica gel, zeolite, mesoporous silica and aluminosilicate, or an oxidation catalyst such as a noble metal or a metal oxide.
  • the above-mentioned oxidation catalyst is preferably one in which an oxidation catalyst such as a noble metal catalyst or a metal oxide catalyst is carried on a carrier comprising the above-mentioned inorganic adsorbent, or a precious metal catalyst which is a non-adsorbent polymer fiber (for example, PTFE fiber).
  • An oxide catalyst such as a metal oxide catalyst or a metal oxide catalyst is immobilized, and particularly preferably, a noble metal catalyst is supported on the above-mentioned inorganic adsorbent or polymer fiber.
  • the inorganic adsorbent adsorbs alcohol such as ethanol, methanol and isopropanol, and also adsorbs acetone and the like.
  • the oxidation catalyst oxidizes and removes these miscellaneous gases and causes the inorganic adsorbent to carry the oxidation catalyst, two processes of adsorption and oxidation of miscellaneous gases occur.
  • the form of the inorganic filter is arbitrary.
  • the form may be granular or a sheet made of fibrous activated carbon.
  • many of these inorganic adsorbents also adsorb siloxane except for those having a small pore size such as MS5A (molecular sieve 5A).
  • Either the organic polymer filter or the inorganic filter may be disposed on the outside air side, but it is preferable to treat the atmosphere passing through the organic polymer filter with the inorganic filter. In particular, it is preferable to treat the atmosphere that has passed through the organic polymer filter with an inorganic filter containing an oxidation catalyst. When siloxane is removed upstream of the oxidation catalyst, poisoning of the oxidation catalyst can be prevented in addition to poisoning of the gas detection unit.
  • an organic polymer filter is provided on both the outside (outside air side) and inside (gas detection unit side) of the inorganic filter. With this configuration, the gas detection unit can be sufficiently protected from poisoning.
  • an organic polymer filter When an organic polymer filter and an inorganic filter are integrated, an organic polymer filter may be laminated on a sheet-shaped inorganic filter, and furthermore, an organic polymer film is formed by using the sheet-shaped inorganic filter as a support layer. Is also good. In the latter case, the fibers or particles of the inorganic filter and the organic polymer film are integrated.
  • siloxane is removed from the outside air by the organic polymer film, and alcohol is removed by the inorganic filter. Therefore, the gas detector or gas sensor can detect a gas to be detected such as methane, LPG, CO, etc. without poisoning by siloxane and without false alarm by alcohol.
  • the organic polymer film contains an acidic group or a basic group.
  • the organic polymer membrane is a carboxymethyl cellulose membrane having a carboxyl group, a sulfated cellulose membrane, a fucoidan membrane, a membrane of another acidic polysaccharide, or a chitosan membrane having an amino group.
  • the organic polymer film is considered to exist in the film for a long time because the permeation of siloxane is slow and the heat of dissolution or adsorption of siloxane to the film is large.
  • siloxane accumulates in the film, it is conceivable that the siloxane permeates the film and poisons the gas detector.
  • Patent Document 2 The inventors have confirmed that when a sulfo group is introduced into mesoporous silica, siloxane is polymerized (Patent Document 2).
  • the polymerization mechanism is thought to be the hydrolysis of the siloxane by the sulfo group.
  • the siloxane molecules adsorbed in the pores of the mesoporous silica can be desorbed into the gas phase by adsorption / desorption equilibrium, but the movement of the siloxane molecules diffused into the organic polymer film should be more restricted. For this reason, siloxane should be able to be fixed and polymerized even with a carboxyl group, a phosphate group, or the like, which is less acidic than a sulfo group. Further, since polymerization of siloxane is considered to be hydrolysis, siloxane should be able to be polymerized by a basic group such as an amino group or a basic hydroxyl group.
  • Nafion (Nafion is a registered trademark of E.I. Dupont) has a skeleton of a fluororesin and a sulfo group and is available in solution. Therefore, it is easy to blend Nafion into the gas-selective permeable membrane.
  • a film of the gas-selective permeable membrane material may be mixed with a Nafion solution to form a film.
  • an organic polymer anion conductor having a basic hydroxyl group can be blended with the gas-selective permeable membrane material.
  • Polysaccharides include those having a carboxyl group such as carboxymethylcellulose, those having a sulfo group such as fucoidan and sulfated cellulose, and those having an amino group such as chitosan.
  • carboxyl group such as carboxymethylcellulose
  • sulfo group such as fucoidan and sulfated cellulose
  • amino group such as chitosan.
  • polysaccharides can be easily formed into a film, and the polysaccharide film has air permeability. Therefore, when these films are used, siloxane can be chemically fixed in the film by polymerization or the like.
  • FIG. 4 is a diagram illustrating a driving pattern of a gas sensor according to the embodiment.
  • FIGS. 1 to 4 show the gas sensor 2 of the embodiment, and FIGS. 5 and 6 show test results.
  • the gas sensor 2 includes, for example, a Si chip 4, and the Si chip 4 is an example of a gas detection unit.
  • the Si chip 4 is housed in a housing 5 made of ceramic or the like, and is fixed in the housing 5 by die bonding or the like.
  • An opening of the housing 5 is covered with a lid 6 made of ceramics, and an atmosphere outside the housing is supplied to the filter 8 from the plurality of openings 7.
  • a film filter 8 is attached to the inner surface of the lid 6 (the surface on the side of the Si chip 4).
  • the filter 8 is composed of two layers, an organic polymer filter 10 and an activated carbon filter 14.
  • the organic polymer filter 10 is arranged on the outside air side of the housing 5, and the activated carbon filter 14 is arranged on the Si chip 4 side.
  • the activated carbon filter 14 is an example of an inorganic filter, and may be an oxidation catalyst filter or the like.
  • the organic polymer filter 10 is arranged on both sides of the inorganic filter.
  • As the inorganic filter different types of filters may be stacked and used.
  • the type of the gas detection unit and the structure of the housing are arbitrary.
  • the pads of the Si chip 4 are connected to terminals 17 provided on the housing 5 via lead wires 16.
  • FIG. 2 shows the structure of the filter 8.
  • the organic polymer filter 10 is formed by laminating a gas-permeable organic polymer film 12 on a porous support film 11, but the support film 11 may not be provided.
  • the support film 11 is a film of a synthetic resin or polysaccharide having continuous pores, and has a thickness of, for example, about 1 ⁇ m to 100 ⁇ m.
  • the gas permeable organic polymer film 12 has a thickness of, for example, about 0.1 ⁇ m to 5 ⁇ m.
  • the activated carbon filter 14 is formed of a fibrous activated carbon sheet having a thickness of about 1 mm in the embodiment, but may be granular activated carbon, silica gel, mesoporous silica, zeolite, aluminosilicate, or the like, and the material and shape are arbitrary.
  • a filter in which an oxidation catalyst such as a noble metal is supported on these adsorbents or a filter in which an oxidation catalyst such as a noble metal is fixed to polymer fibers may be used.
  • the air-permeable organic polymer membrane 12 is a polysaccharide membrane or a gas-selective permeable membrane made of a synthetic polymer.
  • a polysaccharide membrane continuous micropores are likely to occur because long-chain molecules are likely to be regularly arranged.
  • the micropores serve as a gas diffusion path, and the size of the micropores determines the size of the molecule that can pass therethrough, and does not allow the passage of hydrogen, methane, LPG, CO, ethanol, and the like without passing through a siloxane having a large molecular size.
  • Synthetic polymer gas-selective permeable membranes generally have high gas permeability, and gas permeability depends on the molecular size, allowing hydrogen, methane, CO, LPG, ethanol, etc. to permeate, but not siloxane.
  • the polymer film 12 can be formed by casting, spin coating, spray coating, roll coating, or the like.
  • the gas-permeable organic polymer film 12 When an acidic group such as a carboxyl group, a sulfo group, a phosphoric acid group, or a basic group such as an amino group or a basic hydroxyl group is introduced into the gas-permeable organic polymer film 12 (hereinafter simply referred to as the polymer film 12), these groups become Bonds with the-(O-Si-O)-moiety of the siloxane molecule.
  • the siloxane concentration in the film increases, the siloxane molecules are polymerized by the hydrolysis of the-(O-Si-O)-moiety, and are completely fixed in the film. For this reason, even if the siloxane is exposed to a high concentration of siloxane for a long time, the siloxane does not pass through the organic polymer filter 10.
  • the preferred polymer membrane 12 is a polysaccharide membrane such as carboxymethylcellulose, sulfated cellulose, fucoidan, and chitosan, and has an acidic group such as a carboxyl group (carboxymethylcellulose), a sulfo group (sulfated cellulose and fucoidan), and an amino group (chitosan).
  • an acidic group or a basic group may be introduced into a gas-selective permeable membrane of a synthetic resin.
  • a proton conductive polymer such as Nafion may be blended with a fluorine resin based gas selective permeable membrane, or a hydroxyl ion conductive polymer may be blended.
  • FIG. 3 shows the Si chip 4, and the Si chip 4 has a micro hot plate 20 provided with electrodes and heaters on the cavity 26.
  • the hot plate 20 is supported by a beam 24, and a film-shaped metal oxide semiconductor 22 is provided on the hot plate 20. 28 is a pad.
  • the gas detection unit is not limited to the Si chip 4, and the gas detection material is not limited to a metal oxide semiconductor.
  • the catalytic combustion catalyst may be used as the gas detection material.
  • the metal oxide semiconductor 22 it may be supported by something other than the hot plate 20.
  • an electrochemical gas sensor in which a detection electrode and a counter electrode are connected to a liquid or solid electrolyte, or a reference electrode is additionally connected thereto may be used.
  • FIG. 4 shows an operation pattern of the gas sensor 2.
  • the gas sensor 2 operates in a cycle P, and is heated to an operating temperature of about 250 ° C. to 450 ° C. (400 ° C. in the embodiment) for a time T1 in each cycle. Detect gas.
  • Figure 5 shows the results of a siloxane endurance test (exposure to 20 ppm D5 for 10 days).
  • the gas sensors used are those shown in FIGS. 1 to 3.
  • a polymer film (carboxymethyl cellulose) and a sheet of activated carbon were used in combination, and in the comparative example, only the sheet of activated carbon was used.
  • the output in 100 ppm of hydrogen was measured and converted to a hydrogen concentration using the initial value of the dependence of the output on the hydrogen concentration.
  • a shift from 100 ppm indicates the degree of poisoning of the gas sensor, and poisoning by siloxane generally increases the output in terms of concentration.
  • the output in 1000 ppm of methane was measured to evaluate the durability to siloxane.
  • FIG. 6 shows a methane concentration equivalent to the output of 200 ppm of ethanol
  • A represents a comparative example without a filter
  • B represents a comparative example having only a polymer membrane (carboxymethylcellulose)
  • C represents a polymer membrane (carboxymethylcellulose) + sheet shape.
  • activated carbon Ethanol cannot be removed by the polymer film alone, but ethanol can be removed by activated carbon.

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Abstract

ガスセンサのハウジング内にガス検出部が収容され、ハウジングに取り付けられたフィルタを介して、ハウジング外の雰囲気をガス検出部へ導入する。フィルタは、通気性でシロキサンを除去する有機高分子フィルタ、及びアルコールを除去し検出対象ガスを透過させる無機フィルタを備えている。

Description

ガス検出器
　この発明はガスセンサ等のガス検出器に関し、特にそのフィルタに関する。
　PTFE（ポリテトラフルオロエチレン）等の有機高分子通気性膜を、ガスセンサのフィルタとすることが知られている（特許文献１）。また高いガス透過性と高いガス選択性とを有する気体選択性透過膜が開発されている（非特許文献１）。PTFE膜の場合も気体選択性透過膜の場合も、分子量の小さな水素、メタン等のガスは速やかに膜を透過し、分子量の大きなトルエン等のガスはゆっくりとしか膜を透過しない。
　ガスセンサには、シロキサンにより被毒されやすいとの問題がある。シロキサンは分子量が大きいので、有機高分子通気性膜はシロキサンのフィルタとして有望である。しかしながら有機高分子通気性膜は分子量によりガスを選別するので、メタン、LPG、CO等の検出対象ガスを検出する際に、エタノールを除去することに適していない。なおエタノールは日常的に発生する雑ガスの代表で、検出対象ガスの検出を妨げる。雑ガスとしては、エタノール以外にアセトン、イソプロパノール、メタノール等がある。
特開2008-128687A WO2017-138190A
Energy-efficient polymeric gas separation membranes for a sustainable future: A review; Davide F. Sanders, et al. Polymer 54(2013)4719-4761
　この発明の課題は、シロキサン、及びエタノール等の雑ガスを除去するガス検出器用のフィルタを提供することにある。
　この発明は、フィルタを介して雰囲気をガス検出部へ導入するガス検出器において、
　フィルタは、通気性でシロキサンを除去し、検出対象ガスを透過させる有機高分子膜から成る有機高分子フィルタ、及びアルコールを除去し検出対象ガスを透過させる無機フィルタ、を備えていることを特徴とする。好ましくは、ガス検出器はガスセンサであり、ガス検出部とフィルタに加えて、ガス検出部を収容しかつフィルタが取り付けられているハウジングを備えている。またフィルタはガスセンサのハウジングの外部に設けても良い。例えば、フィルタのないガスセンサを吸引パイプの基端などに収容し、パイプの先端など、ガスセンサへのガス流路の上流側に、この発明のフィルタを設けても良い。このようにしてもフィルタの作用は同一である。
　この発明では、フィルタに、通気性でシロキサンを除去する有機高分子フィルタと、アルコールを除去し検出対象ガスを透過させる無機フィルタを設ける。有機高分子フィルタは分子量などによりガスを選別し、シロキサンの透過を阻止する。有機高分子フィルタの材料には、PTFE膜等のフッ素樹脂膜、気体選択性透過膜として知られる高通気性の有機高分子の合成樹脂膜などがある。フッ素樹脂膜には、PTFEのように比較的通気性の低いものから、Teflon AF(TeflonはE.I.Dupontの登録商標)，Hyflon AD(HyflonはSolvayの登録商標)，Cytop(Cytopは旭ガラスの商標)等のように高通気性の気体選択性透過膜などがある。また有機高分子膜は、セルロース膜、フコイダン膜、キトサン膜などの多糖類の膜でも良い。有機高分子膜は通気性があり、分子量により、あるいは分子量に加えて膜と分子との相互作用により、ガスを選別する。そして有機高分子膜の種類は任意である。これらの膜は、分子量の大きなシロキサンを外気から除去し、メタン、LPG、CO等の検出対象ガス、及びエタノール等のアルコールを透過させる。なおLPGはメタンに比べ有機高分子フィルタを通り難いが、高濃度のLPGを検出すればよいので、有機高分子フィルタはLPGの検出を妨げない。
　無機フィルタは、活性炭、シリカゲル、ゼオライト、メソポーラスシリカ、アルミノシリケートなどの無機吸着剤、あるいは貴金属、金属酸化物などの酸化触媒などから成る。上記の酸化触媒は好ましくは、上記の無機吸着剤から成る担体に貴金属触媒、金属酸化物触媒などの酸化触媒を担持したものや、吸着剤ではない高分子の繊維（例えばＰＴＦＥ繊維）に貴金属触媒や金属酸化物触媒などの酸化触媒を固定化したものであり、特に好ましくは上記の無機吸着剤または高分子の繊維に貴金属触媒を担持したものである。無機吸着剤は、エタノール、メタノール、イソプロパノール等のアルコールを吸着し、他にアセトン等も吸着する。酸化触媒はこれらの雑ガスを酸化させて除去し、無機吸着剤に酸化触媒を担持させると、雑ガスの吸着と酸化の２つのプロセスが生じる。無機フィルタの形態は任意で、例えば活性炭の場合、粒状でも、繊維状活性炭から成るシート状でも良い。これらの無機吸着剤の多くは、MS5A（モレキュラーシーブ5A）などの細孔径が小さなものを除き、シロキサンも吸着する。　
　有機高分子フィルタと無機フィルタは、どちらが外気側に配置されてもかまわないが、有機高分子フィルタを透過した雰囲気を、無機フィルタで処理することが好ましい。特に、有機高分子フィルタを透過した雰囲気を、酸化触媒を含む無機フィルタで処理することが好ましい。酸化触媒よりも上流側でシロキサンを除去すると、ガス検出部の被毒の他に、酸化触媒の被毒も防止できる。最も好ましくは、無機フィルタの外側（外気側）と内側（ガス検出部側）の双方に、有機高分子フィルタを設ける。このようにすると、ガス検出部を被毒から充分に保護できる。　
　有機高分子フィルタと無機フィルタを一体にする場合、シート状の無機フィルタに有機高分子フィルタを積層しても良く、さらにはシート状の無機フィルタを支持層として有機高分子膜を成膜しても良い。後者の場合、無機フィルタの繊維あるいは粒子と有機高分子膜は一体化する。
　この発明では、有機高分子膜によりシロキサンを外気から除去し、無機フィルタによりアルコールを除去する。このためガス検出器あるいはガスセンサは、シロキサンによる被毒無しに、かつアルコールによる誤報無しに、メタン、LPG、CO等の検出対象ガスを検出できる。
　好ましくは、有機高分子膜は酸性基あるいは塩基性基を含有している。特に好ましくは、有機高分子膜は、カルボキシル基を有するカルボキシメチルセルロースの膜、硫酸化セルロースの膜、フコイダンの膜、その他の酸性多糖類の膜、あるいはアミノ基を有するキトサンの膜である。
　有機高分子膜は、シロキサンの透過が遅く、さらにシロキサンの膜への溶解熱あるいは吸着熱が大きいため、膜内に長期間存在すると考えられる。しかしながら、シロキサンが膜内に蓄積すると、シロキサンが膜を透過し、ガス検出部を被毒することが考えられる。
　発明者らは、メソポーラスシリカにスルホ基を導入すると、シロキサンが重合することを確認した（特許文献２）。重合機構は、スルホ基によるシロキサンの加水分解と考えられる。メソポーラスシリカの細孔内に吸着したシロキサン分子は、吸脱着平衡により気相に脱離できるが、有機高分子膜中に拡散したシロキサン分子は移動がより制限されるはずである。このためスルホ基に比べ酸性が弱いカルボキシル基、リン酸基などでも、シロキサンを固定し、重合させることができるはずである。またシロキサンの重合は加水分解と考えられるので、アミノ基、塩基性水酸基等の塩基性基でも、シロキサンを重合できるはずである。
　Nafion（NafionはE.I.Dupontの登録商標）はフッ素樹脂の骨格とスルホ基とを有し、溶液で入手できる。このため気体選択性透過膜にNafionをブレンドすることは容易で、例えば気体選択性透過膜材料の溶液にNafion溶液を混合して成膜すればよい。また塩基性水酸基を持つ有機高分子アニオンイオン導電体を気体選択性透過膜材料にブレンドすることもできる。
　多糖類には、カルボキシメチルセルロースのようにカルボキシル基を持つもの、フコイダン、硫酸化セルロースのようにスルホ基を持つもの、キトサンのようにアミノ基を持つものがある。また多糖類は一般に成膜が容易で、かつ多糖類の膜は通気性がある。そこでこれらの膜を用いると、シロキサンを重合等により膜内に化学的に固定できる。
実施例のガスセンサの断面図 実施例での積層膜の断面図 実施例でのチップの平面図 実施例でのガスセンサの駆動パターンを示す図 シロキサン（D5×20ppm）に対する実施例と比較例の耐久性を示す図 実施例と比較例との、エタノール200ppmへの感度をメタンに換算して示す図
　以下に本発明を実施するための最適実施例を示す。
　図１～図４に実施例のガスセンサ２を示し、図５、図６に試験結果を示す。ガスセンサ２は例えばSiチップ４を備え、Siチップ４はガス検出部の例である。Siチップ４はセラミック等のハウジング５に収容され、ダイボンド等によりハウジング５内に固定されている。ハウジング５の開口部をセラミックスのリッド６が覆い、複数の開口７からハウジング外の雰囲気をフィルタ８へ供給する。リッド６の内面（Siチップ４側の面）に膜状のフィルタ８が取り付けられている。フィルタ８は、有機高分子フィルタ１０と活性炭フィルタ１４の２層から成り、有機高分子フィルタ１０がハウジング５の外気側に、活性炭フィルタ１４がSiチップ４側に配置されている。活性炭フィルタ１４は無機フィルタの例で、酸化触媒フィルタ等でも良く、好ましくは、無機フィルタの両側に有機高分子フィルタ１０を配置する。また無機フィルタは種類の異なるフィルタを積層して用いてもよい。なおガス検出部の種類とハウジングの構造は任意である。またSiチップ４のパッドはリード線１６を介して、ハウジング５に設けた端子１７に接続されている。
　図２にフィルタ８の構造を示す。有機高分子フィルタ１０は多孔質の支持膜１１上に通気性有機高分子膜１２を積層したものであるが、支持膜１１はなくても良い。支持膜１１は連続気孔を有する合成樹脂あるいは多糖類の膜で、膜厚は例えば1μm～100μm程度である。通気性有機高分子膜１２は例えば膜厚が0.1μm～5μm程度である。活性炭フィルタ１４は、実施例では厚さ1mm程度の繊維状活性炭のシートから成るが、粒状活性炭でも良く、またシリカゲル、メソポーラスシリカ、ゼオライト、アルミノシリケートなどでも良く、材質と形状は任意である。また、活性炭フィルタ１４の代わりに、これらの吸着剤に貴金属などの酸化触媒を担持したフィルタや高分子の繊維に貴金属などの酸化触媒を固定したフィルタを用いても良い。
　通気性有機高分子膜１２は、多糖類の膜あるいは合成高分子から成る気体選択性透過膜である。多糖類の膜では、長鎖状の分子が規則的に配列されやすいので、連続したマイクロポアが生じやすい。そしてこのマイクロポアがガスの拡散経路となり、マイクロポアのサイズが透過し得る分子のサイズを定め、分子サイズの大きなシロキサンを透過させず、水素、メタン、LPG、CO、エタノール等を透過させる。合成高分子の気体選択性透過膜は一般に高通気性で、ガスの透過性は分子サイズに依存し、水素、メタン、CO、LPG、エタノール等を透過させるが、シロキサンは透過させない。また高分子膜１２は、キャスティング、スピンコーティング、スプレーコーティング、ロールコーティング等により成膜できる。
　通気性有機高分子膜１２（以下単に高分子膜１２）にカルボキシル基、スルホ基、リン酸基等の酸性基、あるいはアミノ基、塩基性水酸基などの塩基性基を導入すると、これらの基はシロキサン分子の-（O-Si-O）-の部分と結合する。膜中のシロキサン濃度が増すと、シロキサン分子は-（O-Si-O）-の部分が加水分解されて重合し、膜中に完全に固定される。このため、高濃度のシロキサン長期間暴露されても、シロキサンは有機高分子フィルタ１０を透過しない。
　好ましい高分子膜１２は、カルボキシルメチルセルロース、硫酸化セルロース、フコイダン、キトサン等の多糖類膜で、カルボキシル基（カルボキシメチルセルロース）、スルホ基（硫酸化セルロース及びフコイダン）、アミノ基（キトサン）等の酸性基あるいは塩基性基を備えている。多糖類の膜以外に、合成樹脂の気体選択性透過膜に、酸性基あるいは塩基性基を導入しても良い。例えばフッ素樹脂系の気体選択性透過膜にNafion等のプロトン導電性高分子をブレンドし、あるいは水酸イオン導電性高分子をブレンドしても良い。
　図３はSiチップ４を示し、Siチップ４は電極とヒータを備えるマイクロホットプレート２０をキャビティ２６上に備えている。ホットプレート２０はビーム２４により支持され、ホットプレート２０上に膜状の金属酸化物半導体２２が設けられている。２８はパッドである。
　ガス検出部はSiチップ４に限らず、ガスの検出材料は金属酸化物半導体に限らない。例えば接触燃焼触媒をガス検出材料としても良く、その場合、膜状の接触燃焼触媒をホットプレート２０上に設けるか、図示しないヒータコイルに接触燃焼触媒を支持させるかは任意である。また金属酸化物半導体２２の場合も、ホットプレート２０以外のものに支持させても良い。さらにガス検出部として、液体あるいは固体の電解質に、検出極と対極、あるいはこれらに加えて参照極を接続した電気化学ガスセンサを用いても良い。
　図４はガスセンサ２の動作パターンを示す。ガスセンサ２は周期Pで動作し、１周期毎に時間T1の間、250℃～450℃程度（実施例では400℃）の動作温度へ加熱され、加熱時の金属酸化物半導体の抵抗値から、ガスを検出する。
　図５は、シロキサンへの耐久試験（20ppmのD5中に10日間暴露）への結果を示す。用いたガスセンサは図１～図３のもので、実線の実施例では高分子膜（カルボキシメチルセルロース）とシート状活性炭を併用し、比較例ではシート状活性炭のみを用いた。水素100ppm中での出力を測定し、水素濃度への出力の依存性の初期値を用いて、水素濃度に換算した。100ppmからのシフトはガスセンサの被毒の程度を表し、シロキサンによる被毒では一般に濃度換算の出力が増加する。同様にメタン1000ppm中での出力を測定し、シロキサンへの耐久性を評価した。有機高分子フィルタ１０を設けることにより、シロキサンの影響を小さくできる。なおこのことから明らかなように、活性炭フィルタ１４に代えて酸化触媒フィルタを用いる場合、有機高分子フィルタ１０により酸化触媒フィルタの被毒も防止できる。
　図６は、エタノール200ppmの出力と等しくなるメタン濃度を示し、Aはフィルタ無しの比較例、Bは高分子膜（カルボキシメチルセルロース）のみの比較例、Cは高分子膜（カルボキシメチルセルロース）＋シート状活性炭の実施例である。高分子膜のみではエタノールを除去できないが、活性炭によりエタノールを除去できている。
２　　　ガスセンサ
４　　　Siチップ（ガス検出部）
５　　　ハウジング
６　　　リッド
７　　　開口
８　　　フィルタ
１０　　有機高分子フィルタ
１１　　支持膜
１２　　通気性有機高分子膜
１４　　活性炭フィルタ（無機フィルタ）
１６　　リード線
１７　　端子
２０　　マイクロホットプレート
２２　　金属酸化物半導体
２４　　ビーム
２６　　キャビティ
２８　　パッド　　　

Claims (6)

  1. 　フィルタを介して雰囲気をガス検出部へ導入するガス検出器において、
    　前記フィルタは、
    　　通気性でシロキサンを除去し、検出対象ガスを透過させる有機高分子膜から成る有機高分子フィルタ、及び
    　　アルコールを除去し検出対象ガスを透過させる無機フィルタ、を備えていることを特徴とする、ガス検出器。
  2. 　前記ガス検出器はガスセンサであり、
    　前記ガス検出部と前記フィルタに加えて、前記ガス検出部を収容しかつ前記フィルタが取り付けられているハウジングを備えていることを特徴とする、請求項１のガス検出器。
  3. 　前記ハウジング内での位置関係で、前記有機高分子フィルタが外気側に、前記無機フィルタがガス検出部側に配置されていることを特徴とする、請求項２のガス検出器。
  4. 　前記無機フィルタが酸化触媒を含有することを特徴とする、請求項１～３のいずれかのガス検出器。
  5. 　前記有機高分子膜は酸性基あるいは塩基性基を含有していることを特徴とする、請求項１～４のいずれかのガス検出器。
  6. 　前記有機高分子膜は、カルボキシル基を有するカルボキシメチルセルロースの膜、硫酸化セルロースの膜、フコイダンの膜、あるいはアミノ基を有するキトサンの膜であることを特徴とする、請求項５のガス検出器。
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