WO2010024076A1 - Controlled-potential electrolysis oxygen sensor - Google Patents

Controlled-potential electrolysis oxygen sensor Download PDF

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Publication number
WO2010024076A1
WO2010024076A1 PCT/JP2009/063346 JP2009063346W WO2010024076A1 WO 2010024076 A1 WO2010024076 A1 WO 2010024076A1 JP 2009063346 W JP2009063346 W JP 2009063346W WO 2010024076 A1 WO2010024076 A1 WO 2010024076A1
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Prior art keywords
oxygen sensor
plate
lid member
constant potential
fixed
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PCT/JP2009/063346
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French (fr)
Japanese (ja)
Inventor
慎治 上杉
祥一 打越
達也 米倉
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理研計器株式会社
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Priority to JP2010526629A priority Critical patent/JP5174914B2/en
Publication of WO2010024076A1 publication Critical patent/WO2010024076A1/en

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    • G—PHYSICS
    • 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
    • G01N27/403—Cells and electrode assemblies
    • G01N27/404—Cells with anode, cathode and cell electrolyte on the same side of a permeable membrane which separates them from the sample fluid, e.g. Clark-type oxygen sensors

Definitions

  • the present invention relates to a constant potential electrolytic oxygen sensor.
  • a water-repellent porous membrane capable of transmitting a test gas is stretched on a window formed in a casing for accommodating an electrolytic solution.
  • a working electrode formed on a surface positioned on the side, and a counter electrode arranged at a certain distance from the working electrode.
  • the potential of the working electrode is reduced by oxygen by a potentiostat. It is configured to detect an electrolysis current flowing between the working electrode and the counter electrode in accordance with the concentration of oxygen gas by being controlled to a constant potential.
  • the test gas is supplied to the working electrode via a pinhole, for example.
  • the thing of the structure of supplying etc. is proposed (for example, refer patent document 1).
  • the entrance value of the pinhole is blocked by water droplets. May decrease to zero, that is, a stable indication value may not be obtained.
  • the present invention has been made based on the above circumstances, and an object thereof is to provide a constant potential electrolytic oxygen sensor in which the influence of the external environment is reduced and a stable indicated value can be obtained with certainty. .
  • the constant potential electrolytic oxygen sensor of the present invention is a constant potential electrolytic oxygen sensor in which at least a working electrode and a counter electrode are provided in a casing forming an electrolyte chamber.
  • a gas permeable membrane body is fixed to the outer surface of a plate-like lid member formed by penetrating a pinhole for introducing a test gas.
  • the gas permeable membrane body is gas impermeable and water repellent. It is characterized by having an outer surface.
  • the constant potential electrolytic oxygen sensor of the present invention is a constant potential electrolytic oxygen sensor in which at least a working electrode and a counter electrode are provided in a casing forming an electrolyte chamber.
  • a working electrode in which an electrode catalyst layer is formed on a gas permeable base film on an inner surface of a plate-like lid member formed by penetrating a pinhole for introducing a test gas through an inner surface side liquid impermeable film.
  • a gas permeable membrane having a gas impermeable and water repellent outer surface is fixed to the outer surface of the plate-like lid member,
  • the inner surface side liquid impervious film is characterized in that a pinhole of the plate-like lid member communicates with a through hole through which the outer surface of the gas permeable base film of the working electrode is exposed.
  • the gas permeable membrane body includes a base film having air permeability and water repellency, and an aluminum foil fixed to the entire outer surface excluding the outer peripheral surface of the base film with an adhesive. It can be set as the structure formed by these.
  • the gas permeable membrane body has an inner surface fixed to the outer surface of the plate-like lid member by an adhesive, and a pinhole of the plate-like lid member communicates therewith. It is preferable that the outer surface of the liquid impervious film on the outer surface side where the through holes are formed is fixed with an adhesive.
  • the inner diameter of the through hole of the inner surface side liquid-impermeable membrane is 0.2 to 5 mm.
  • the inner surface side liquid impervious film is fixed to the plate-like lid member by an adhesive, and the working electrode has an outer surface of the gas permeable base film as an adhesive.
  • the structure fixed to the inner surface side liquid-impermeable film can be obtained.
  • the gas to be detected is configured to flow from the outer peripheral surface of the gas permeable membrane body and be introduced into the pinhole of the plate-like lid member.
  • the air permeability at the introduction part of the test gas is regulated while ensuring the necessary air permeability, so that the responsiveness is not significantly reduced and sufficient durability against the influence of the external environment is obtained. And a stable instruction value (output) can be obtained with certainty.
  • the outer surface of the liquid-impermeable membrane on the outer surface side, in which the inner surface of the gas permeable membrane body is fixed to the outer surface of the plate-like lid member with an adhesive, and the through hole through which the pin hole of the plate-like lid member communicates Since it is possible to obtain high adhesion between the gas permeable membrane body and the plate-like lid member, the above effect can be obtained more reliably.
  • the test gas is introduced from the outer peripheral surface of the gas permeable membrane body and introduced into the pinhole of the plate-like lid member, and the working electrode is specified. Since the structure fixed to the inner surface of the plate-like lid member can provide a sufficient impact resistance, for example, the constant potential electrolytic oxygen sensor is dropped to cause an impact. Even if it is added, it is possible to prevent or reduce the displacement of the working electrode with respect to the plate-like lid member, and it is possible to prevent the invasion of air from other than the pinhole to the working electrode, and stable output. In addition, it is possible to reliably prevent the electrolyte from leaking to the outside.
  • the inner diameter of the through hole of the inner surface side liquid-impermeable membrane is set within a predetermined range, the diffusion of oxygen from the pinhole outlet to the working electrode in the plate-like lid member Therefore, oxygen can be supplied to the entire electrode, and a stable output can be obtained with certainty.
  • the inner surface side liquid-impermeable film is fixed to the plate-like lid member by an adhesive
  • the working electrode is configured such that the outer surface of the gas-permeable base film is fixed to the inner surface-side liquid impermeable film by an adhesive.
  • FIG. 2 is an exploded cross-sectional view of the constant potential electrolytic oxygen sensor shown in FIG. 1. It is an expanded sectional view which shows the outer surface side structure of the plate-shaped cover member in the constant potential electrolytic oxygen sensor shown in FIG..
  • FIG. 1 is a cross-sectional view showing a configuration of an example of a constant potential electrolytic oxygen sensor of the present invention
  • FIG. 2 is an exploded cross sectional view of the constant potential electrolytic oxygen sensor shown in FIG. 1
  • FIG. 3 is a constant cross-sectional view shown in FIG. It is an expanded sectional view which shows the outer surface side structure of the plate-shaped cover member in a potential electrolytic oxygen sensor.
  • the vertical direction in FIG. 1 is defined as “vertical direction”
  • the horizontal direction in FIG. 1 is defined as “left and right direction”.
  • This constant potential electrolysis oxygen sensor 10 includes a sensitive part forming space 12 formed of a substantially cylindrical through-hole extending in the vertical direction formed in one end side part (left end side part in FIG.
  • the casing 11 has a substantially box-shaped casing 11 that has an electrolyte chamber forming space that is formed side by side at the other end portion of the space 12 and that opens to the other end (the right end in FIG. 1).
  • the sensitive portion forming space 12 and the electrolyte chamber forming space are communicated with each other by a communication hole 14 extending in the left-right direction formed at a substantially intermediate position in the portion forming space 12.
  • Reference numeral 15 in FIGS. 1 and 2 is a lead member arrangement space formed on one end surface of the cane 11 and is sealed by being filled with, for example, an adhesive.
  • Reference numeral 23 denotes a circuit board.
  • An opening of the electrolyte chamber forming space in the casing 11 is provided with a closing member 20 having a pressure adjusting function in the electrolyte chamber 13 provided with a gas permeable hydrophobic pressure adjusting film 21 made of, for example, a fluororesin.
  • the closing member 20 is formed with a through hole 22 that allows the internal space in the electrolyte chamber 13 to communicate with the outside through the gas permeable hydrophobic pressure adjusting membrane 21.
  • the inner diameter of the through hole 22 is preferably 0.5 to 9 mm, for example 1 mm, in order to prevent interference with external oxygen.
  • the upper opening of the sensitive part forming space 12 in the casing 11 is formed with, for example, three stepped recesses that form a substantially cylindrical space part that increases in diameter toward the upper surface side.
  • the upper surface side protection plate 25 formed with a fluid flow path composed of a plurality of through holes 25A penetrating in the thickness direction is fitted in a state where the outer peripheral edge portion is disposed on the flat surface of the first stepped portion.
  • an electrolyte solution holding layer 28 made of, for example, filter paper, a working electrode 30, and a pinhole 36 for introducing a test gas are formed through the upper surface side of the upper surface side protection plate 25, for example, from a liquid crystal polymer
  • the upper lid member 16 is screwed and attached via the slip ring 45 in a state where the plate-like lid members (gas supply restriction members) 35 are sequentially accommodated and arranged.
  • reference numeral 37 denotes an O-ring for preventing the electrolytic solution from leaking to the outside
  • reference numeral 17 denotes a dustproof filter fixed to the upper surface side cover member 16 by a double-sided adhesive tape.
  • the working electrode 30 has fine particles such as platinum, gold, ruthenium, and palladium, for example, at a central position on one surface of a gas permeable base film 31 made of, for example, a porous film of fluororesin having air permeability and water repellency, Alternatively, the electrode catalyst layer 32 is formed by firing such a mixture or alloy together with a binder.
  • the working electrode 30 communicates with the inner surface of the plate-like lid member 35 with the pinhole 36 of the plate-like lid member 35, and the gas permeable base of the working electrode 30.
  • the film 31 is fixed by, for example, an adhesive via an inner surface side liquid-impermeable film formed with a through hole through which the outer surface of the film 31 is exposed.
  • the fixing method of the working electrode 30 will be described in detail.
  • the peripheral portion of the outer surface of the gas permeable base film 31 of the working electrode 30 is, for example, a disk having a through hole 33A formed at the central position.
  • the inner surface side double-sided adhesive tape 33 adheres to the inner surface of the plate-like lid member 35, and also adheres to the working electrode 30 on the outer surface side of the upper surface side protection plate 25.
  • the periphery of the gas permeable base film 31 is fixed in a pressed state by a sealing member made of, for example, an O-ring 29 arranged so as to surround the periphery of 28.
  • the through hole in the inner surface side liquid-impermeable film that is, the inner diameter of the through hole 33A formed in the inner surface side double-sided pressure-sensitive adhesive tape 33 is preferably, for example, 0.2 to 5 mm.
  • the test gas introduced from the pinhole 36 can be reliably diffused throughout the working electrode 30, and sufficient impact resistance can be obtained and a stable indicated value can be reliably obtained.
  • the inner diameter of the through hole 33A is too small, sufficient diffusibility of the test gas cannot be obtained, and only part of the working electrode 30 can contribute oxygen gas to the reaction.
  • the size of the inner diameter of the pinhole 36 in the plate-like lid member 35 is practically 1.0 to 200 ⁇ m, for example 80 ⁇ m, when the pinhole has a uniform inner diameter.
  • the thickness of the inner surface side liquid-impermeable film that is, the thickness of the inner surface side double-sided adhesive tape 33 is preferably 0.05 to 0.5 mm, for example.
  • the thickness of the inner surface side double-sided adhesive tape 33 is excessive, the distance until the test gas reaches the electrode becomes long, the current flowing between the working electrode 30 and the counter electrode 53 decreases, or the test Responsiveness to gas may be reduced.
  • the thickness of the inner surface side double-sided pressure-sensitive adhesive tape 33 is too small, sufficient strength and sufficient durability cannot be obtained, and handling becomes difficult.
  • the reference electrode 50 is provided in a state where an electrolyte solution holding layer (not shown) made of, for example, filter paper is interposed at the lower surface side central position of the upper surface side protection plate 25,
  • the electrolytic solution in the electrolytic solution chamber 13 flows into the sensitive part forming space 12 through the communication hole 14, whereby the reference electrode 50 is immersed in the electrolytic solution.
  • the reference electrode 50 is formed on the entire surface of one side of a gas permeable base film made of a fluororesin porous film having air permeability and water repellency, for example, fine particles such as platinum, gold, ruthenium, palladium, or the like.
  • An electrode catalyst layer formed by firing a mixture or alloy of the above together with a binder is formed.
  • the reference electrode 50 can also be comprised with a metal single-piece
  • stepped recesses are formed in the opening on the lower side of the sensitive portion forming space 12 in the casing 11 to form a substantially cylindrical space portion having a larger diameter toward the lower surface.
  • the lower surface side protection plate 55 formed with a fluid flow path composed of a plurality of through holes 55A penetrating in the thickness direction is disposed on the flat surface of the first step, and the lower surface side protection plate 55
  • an electrolytic solution holding layer (not shown) made of filter paper, a counter electrode 53, and a cap member 58 in which a gas discharge through hole 58A for discharging a test gas is formed are sequentially accommodated and arranged.
  • Reference numeral 57 in FIGS. 1 and 2 denotes an O-ring which is pressed by the cap member 58 when the lower surface side lid member 18 is screwed and attached, and the outer peripheral edge of the counter electrode 53 is pressed from the lower surface side. It is fixed.
  • the counter electrode 53 is, for example, fine particles of platinum, gold, ruthenium, palladium, or a mixture thereof at a central position on one surface of a gas permeable base film made of a porous film of a fluororesin having air permeability and water repellency. And an electrode catalyst layer formed by firing together with a binder.
  • the inner diameter of the gas discharge through hole 58A in the cap member 58 is preferably, for example, 0.5 to 0.7 mm in order to prevent interference with external oxygen.
  • the outer surface of the plate-like lid member 35 is formed with a through-hole through which the gas permeable membrane body 40 communicates with the pinhole 36 of the plate-like lid member 35. It is fixed with, for example, an adhesive via a side liquid-impermeable membrane.
  • the gas permeable membrane body 40 has a gas impermeable and water repellent outer surface, and has a base film 41 made of a porous film of, for example, a fluorine resin having air permeability and water repellency, and the base film 41. It is comprised by the aluminum foil 42 fixed to the whole outer surface (upper surface in FIG. 3) except the outer peripheral surface of the film 41 with the adhesive, and as shown in FIG.
  • the peripheral edge in the inner surface of the gas-permeable film body 40 The part is bonded and fixed to the outer surface of the plate-shaped lid member 35 by a disk-shaped outer surface-side double-sided adhesive tape 43 having a through hole 43A formed at the center, for example.
  • the gas permeable membrane body 40 preferably has an air permeability of 0.05 to 0.5 L / day, and the thickness, outer diameter dimension, porosity, and other specific configurations are such that the air permeability is within the above numerical range. Can be set to be within.
  • the through hole in the outer surface side liquid-impermeable film that is, the inner diameter of the through hole 43A formed in the outer surface side double-sided adhesive tape 43 is preferably 0.05 to 5 mm, for example. Thereby, sufficient durability with respect to an external environment can be obtained without significantly reducing gas responsiveness, and a stable indicated value can be obtained with certainty. Further, the thickness of the outer surface side liquid-impermeable film, that is, the thickness of the outer surface side double-sided adhesive tape 43 is preferably 0.5 to 5 mm, for example.
  • the electrolytic solution holding layer 28 interposed between the upper surface side protective plate 25 and the working electrode 30 is impregnated through the hole 25A, and further, the lower surface side protective plate is inserted through the through hole 55A in the lower surface side protective plate 55.
  • a test gas such as air in an ambient atmosphere flows in from the outer peripheral surface of the gas permeable membrane body 40 and is a plate-like lid member.
  • the gas permeable membrane body 40 having a gas impermeable and water repellent outer surface penetrates the pinhole 36 through which the test gas is introduced. It is fixed to the outer surface of the formed plate-like lid member 35, and the test gas flows from the outer peripheral surface of the gas permeable membrane body 40 and is introduced into the pinhole 36 of the plate-like lid member 35.
  • the air permeability of the gas permeable membrane body 40 is regulated while ensuring the air permeability necessary for gas detection, so that the responsiveness is not significantly reduced and the influence of the external environment is sufficient. Durability can be obtained.
  • the gas permeable membrane body 40 is fixed to the outer surface of the plate-like lid member 35 by an outer-surface-side double-sided adhesive tape 43 in which a through hole 43A through which the pin hole 36 of the plate-like lid member 35 communicates is formed. Since the high adhesion between the gas permeable membrane body 40 and the plate-like lid member 35 can be obtained, the above effect can be obtained more reliably.
  • the working electrode 30 is structured to be fixed to the inner surface of the plate-like lid member 35 by the inner surface-side double-sided adhesive tape 33 having the through-hole 33A, it is possible to obtain sufficient impact resistance. For example, even when an impact is applied by dropping the constant potential electrolytic oxygen sensor 10 or the like, the displacement of the working electrode 30 with respect to the plate-like lid member 35 is prevented or reduced, in other words, the plate-like lid. Since the adhesion between the member 35 and the working electrode 30 can be maintained, it is possible to reliably prevent the electrolyte from leaking to the outside and, for example, a gap between the working electrode 30 and the plate-like lid member 35. As a result, it is possible to prevent air from entering the working electrode 30 from other than the pinhole 36, and to obtain a stable output. Can.
  • the working electrode 30 is arranged so that the peripheral edge portion on the inner surface of the gas permeable base film 31 surrounds the periphery of the electrolyte solution holding layer 28 that is in close contact with the working electrode 30 on the outer surface side of the upper surface side protection plate 25.
  • the O-ring 29 By being fixed in a state of being pressed by the O-ring 29, it is possible to reliably obtain the expected structure for improving impact resistance, that is, the above-described effect, that is, the working electrode 30 and the plate-like lid member 35.
  • the effect that a stable output can be obtained by maintaining the adhesion and the effect of preventing the electrolyte from leaking can be obtained more reliably.
  • the working electrode 30 is provided from the outlet of the pinhole 36 in the plate-like lid member 35. Can improve the diffusibility of the test gas up to and supply oxygen gas to the working electrode 30 as a whole, as well as ensuring sufficient impact resistance and ensuring stable output. be able to.
  • a constant potential electrolytic oxygen sensor according to the present invention was fabricated according to the configuration shown in FIGS. 1 to 3, and a durability test against environmental changes was performed by the method described below.
  • the inner diameter of the pinhole in the plate-like lid member is 80 ⁇ m
  • the gas permeable membrane body (40) has a base film (41) made of PTFE and an outer diameter of 80 ⁇ m.
  • the thickness is 6 mm
  • the thickness is 0.1 mm
  • the thickness of the aluminum foil (42) is 0.1 mm
  • the air permeability is 0.15 L / day.
  • the thickness of an outer surface side double-sided adhesive tape (43) is 0.2 mm
  • the internal diameter of a through-hole (43A) is 2 mm.
  • the constant potential electrolytic oxygen sensor according to the present invention can obtain a stable instruction value (output current value) without being affected by environmental changes. It was.
  • the output current value (indicated value) is 10 to 20 minutes after the environmental condition is changed. It was confirmed that it dropped rapidly and eventually became 0, and was greatly affected by environmental changes. The reason for this is considered that dew condensation occurs on the outer surface side of the plate-like lid member, and water droplets generated thereby adhere to the outer surface side opening (entrance) of the pinhole.
  • the gas-impermeable and water-repellent surface (outer surface) of the gas-permeable film body fixed to the outer surface of the plate-like lid member is formed by, for example, depositing aluminum on a base film, or by using a water-repellent gas. It can be formed by applying an impermeable paint to the base film.
  • the constant potential electrolytic oxygen sensor of the present invention is useful in order to prevent the occurrence of an oxygen deficiency accident in, for example, an underground construction site, a mine tunnel, other places where people enter, and work areas.

Abstract

Disclosed is a controlled-potential electrolysis oxygen sensor which can acquire a stable output reliably even if used under a circumstance for frequent dew condensations.  The controlled-potential electrolysis oxygen sensor is constituted such that at least a working electrode and a counter electrode are disposed in a casing forming an electrolyte chamber, and such that the quantity of a gas to be detected is limited by a panel cover member having a pin hole formed to extend therethrough and is fed to the working electrode.  The controlled-potential electrolysis oxygen sensor is constituted such that a gas-permeable film having a gas-impermeable and a water-repellent outer face is fixed on the outer face of the panel cover member.

Description

定電位電解式酸素センサConstant potential electrolytic oxygen sensor
　本発明は、定電位電解式酸素センサに関する。 The present invention relates to a constant potential electrolytic oxygen sensor.
　定電位電解式酸素センサは、例えば、電解液を収容するケーシングに形成された窓に被検ガスの透過が可能な撥水性多孔質膜が張設され、この撥水性多孔質膜の、電解液側に位置される面に形成された作用電極と、この作用電極と一定の距離を離間させて配置された対極とを備えてなり、例えばポテンショスタットにより作用電極の電位が酸素の還元反応が起こる一定の電位に制御されることにより酸素ガスの濃度に対応して作用電極と対極との間に流れる電解電流を検出するよう構成されている。
　このような定電位電解式酸素センサにおいては、検知原理上、作用電極に供給する被検ガスの量を制限することが必要であり、例えば、被検ガスを例えばピンホールを介して作用電極に供給する構造のものなどが提案されている（例えば特許文献１参照）。 In the constant potential electrolytic oxygen sensor, for example, a water-repellent porous membrane capable of transmitting a test gas is stretched on a window formed in a casing for accommodating an electrolytic solution. A working electrode formed on a surface positioned on the side, and a counter electrode arranged at a certain distance from the working electrode. For example, the potential of the working electrode is reduced by oxygen by a potentiostat. It is configured to detect an electrolysis current flowing between the working electrode and the counter electrode in accordance with the concentration of oxygen gas by being controlled to a constant potential.
In such a constant potential electrolytic oxygen sensor, it is necessary to limit the amount of test gas supplied to the working electrode on the detection principle. For example, the test gas is supplied to the working electrode via a pinhole, for example. The thing of the structure of supplying etc. is proposed (for example, refer patent document 1).
特公昭６１－５６７７７号公報Japanese Patent Publication No. 61-56777
　而して、このような構成の定電位電解式酸素センサにおいては、例えば結露が発生しやすい環境下に晒された場合には、ピンホールの入り口が水滴によって塞がれてしまうことにより指示値がゼロに低下してしまうこと、すなわち、安定した指示値を得ることができないことがある。 Thus, in the constant potential electrolytic oxygen sensor having such a configuration, for example, when exposed to an environment where condensation is likely to occur, the entrance value of the pinhole is blocked by water droplets. May decrease to zero, that is, a stable indication value may not be obtained.
　本発明は、以上のような事情に基づいてなされたものであって、外部環境の影響が軽減され、安定した指示値が確実に得られる定電位電解式酸素センサを提供することを目的とする。 The present invention has been made based on the above circumstances, and an object thereof is to provide a constant potential electrolytic oxygen sensor in which the influence of the external environment is reduced and a stable indicated value can be obtained with certainty. .
　本発明の定電位電解式酸素センサは、電解液室を形成するケーシングに、少なくとも作用電極と対極とが設けられてなる定電位電解式酸素センサにおいて、
　被検ガスを導入するピンホールが貫通して形成された板状蓋部材の外面に、ガス透過性膜体が固定されており、当該ガス透過性膜体は、ガス不透過性で、撥水性の外面を有するものであることを特徴とする。 The constant potential electrolytic oxygen sensor of the present invention is a constant potential electrolytic oxygen sensor in which at least a working electrode and a counter electrode are provided in a casing forming an electrolyte chamber.
A gas permeable membrane body is fixed to the outer surface of a plate-like lid member formed by penetrating a pinhole for introducing a test gas. The gas permeable membrane body is gas impermeable and water repellent. It is characterized by having an outer surface.
　本発明の定電位電解式酸素センサは、電解液室を形成するケーシングに、少なくとも作用電極と対極とが設けられてなる定電位電解式酸素センサにおいて、
　被検ガスを導入するピンホールが貫通して形成された板状蓋部材の内面に、内面側液不透過膜を介して、ガス透過性ベースフィルムに電極触媒層が形成されてなる作用電極が固定されていると共に、当該板状蓋部材の外面に、ガス不透過性で、撥水性の外面を有するガス透過性膜体が固定されており、
　前記内面側液不透過膜には、板状蓋部材のピンホールが連通し、作用電極のガス透過性ベースフィルムの外面が露出する貫通孔が形成されていることを特徴とする。 The constant potential electrolytic oxygen sensor of the present invention is a constant potential electrolytic oxygen sensor in which at least a working electrode and a counter electrode are provided in a casing forming an electrolyte chamber.
A working electrode in which an electrode catalyst layer is formed on a gas permeable base film on an inner surface of a plate-like lid member formed by penetrating a pinhole for introducing a test gas through an inner surface side liquid impermeable film. A gas permeable membrane having a gas impermeable and water repellent outer surface is fixed to the outer surface of the plate-like lid member,
The inner surface side liquid impervious film is characterized in that a pinhole of the plate-like lid member communicates with a through hole through which the outer surface of the gas permeable base film of the working electrode is exposed.
　本発明の定電位電解式酸素センサにおいては、ガス透過性膜体は、通気性および撥水性を有するベースフィルムと、このベースフィルムの外周面を除く外面の全面に粘着剤によって固定されたアルミニウム箔とにより形成された構成とすることができる。 In the constant potential electrolytic oxygen sensor of the present invention, the gas permeable membrane body includes a base film having air permeability and water repellency, and an aluminum foil fixed to the entire outer surface excluding the outer peripheral surface of the base film with an adhesive. It can be set as the structure formed by these.
　また、本発明の定電位電解式酸素センサにおいては、ガス透過性膜体は、その内面が、板状蓋部材の外面に粘着剤によって固定された、当該板状蓋部材のピンホールが連通する貫通孔が形成された外面側液不透過膜の外面に粘着剤によって固定された構成とされていることが好ましい。 In the controlled potential electrolytic oxygen sensor of the present invention, the gas permeable membrane body has an inner surface fixed to the outer surface of the plate-like lid member by an adhesive, and a pinhole of the plate-like lid member communicates therewith. It is preferable that the outer surface of the liquid impervious film on the outer surface side where the through holes are formed is fixed with an adhesive.
　さらにまた、本発明の定電位電解式酸素センサにおいては、内面側液不透過膜の貫通孔の内径の大きさが、０．２～５ｍｍである構成とされていることが好ましい。 Furthermore, in the constant potential electrolytic oxygen sensor of the present invention, it is preferable that the inner diameter of the through hole of the inner surface side liquid-impermeable membrane is 0.2 to 5 mm.
　さらにまた、本発明の定電位電解式酸素センサにおいては、内面側液不透過膜が粘着剤により板状蓋部材に固定されており、作用電極は、そのガス透過性ベースフィルムの外面が粘着剤により内面側液不透過膜に固定された構成とすることができる。 Furthermore, in the controlled potential electrolytic oxygen sensor of the present invention, the inner surface side liquid impervious film is fixed to the plate-like lid member by an adhesive, and the working electrode has an outer surface of the gas permeable base film as an adhesive. Thus, the structure fixed to the inner surface side liquid-impermeable film can be obtained.
　本発明の定電位電解式酸素センサによれば、被検ガスがガス透過性膜体の外周面から流入して板状蓋部材のピンホールに導入される構成とされていることにより、ガス検知に必要な通気性は確保しながら、被検ガスの導入部における透気度が規制されるので、応答性を大幅に低下させることなく、しかも、外部環境の影響に対する十分な耐久性を得ることができ、安定した指示値（出力）を確実に得ることができる。 According to the constant potential electrolytic oxygen sensor of the present invention, the gas to be detected is configured to flow from the outer peripheral surface of the gas permeable membrane body and be introduced into the pinhole of the plate-like lid member. The air permeability at the introduction part of the test gas is regulated while ensuring the necessary air permeability, so that the responsiveness is not significantly reduced and sufficient durability against the influence of the external environment is obtained. And a stable instruction value (output) can be obtained with certainty.
　また、ガス透過性膜体の内面が、板状蓋部材の外面に粘着剤によって固定された、当該板状蓋部材のピンホールが連通する貫通孔が形成された外面側液不透過膜の外面に固定された構成とされていることにより、ガス透過性膜体と板状蓋部材との高い密着性を得ることができるので、上記効果を一層確実に得ることができる。 In addition, the outer surface of the liquid-impermeable membrane on the outer surface side, in which the inner surface of the gas permeable membrane body is fixed to the outer surface of the plate-like lid member with an adhesive, and the through hole through which the pin hole of the plate-like lid member communicates Since it is possible to obtain high adhesion between the gas permeable membrane body and the plate-like lid member, the above effect can be obtained more reliably.
　本発明の定電位電解式酸素センサによれば、被検ガスがガス透過性膜体の外周面から流入して板状蓋部材のピンホールに導入される構成とされると共に、作用電極が特定の構造により板状蓋部材の内面に固定された構成とされていることにより、さらに、十分な耐衝撃性を得ることができるので、例えば定電位電解式酸素センサを落下させるなどして衝撃が加えられた場合であっても、作用電極の板状蓋部材に対するズレを防止、または、小さくすることができ、作用電極に対するピンホール以外からの空気の侵入を防止することができて安定した出力を確実に得ることができ、しかも、電解液が外部に漏れることを確実に防止することができる。 According to the constant potential electrolytic oxygen sensor of the present invention, the test gas is introduced from the outer peripheral surface of the gas permeable membrane body and introduced into the pinhole of the plate-like lid member, and the working electrode is specified. Since the structure fixed to the inner surface of the plate-like lid member can provide a sufficient impact resistance, for example, the constant potential electrolytic oxygen sensor is dropped to cause an impact. Even if it is added, it is possible to prevent or reduce the displacement of the working electrode with respect to the plate-like lid member, and it is possible to prevent the invasion of air from other than the pinhole to the working electrode, and stable output. In addition, it is possible to reliably prevent the electrolyte from leaking to the outside.
　また、内面側液不透過膜の貫通孔の内径の大きさが所定の範囲内に設定された構成とされていることにより、板状蓋部材におけるピンホールの出口から作用電極までの酸素の拡散性をよくすることができて酸素を電極全体に供給することができて安定した出力を確実に得ることができる。 In addition, since the inner diameter of the through hole of the inner surface side liquid-impermeable membrane is set within a predetermined range, the diffusion of oxygen from the pinhole outlet to the working electrode in the plate-like lid member Therefore, oxygen can be supplied to the entire electrode, and a stable output can be obtained with certainty.
　さらにまた、内面側液不透過膜が粘着剤により板状蓋部材に固定され、さらに、作用電極が、そのガス透過性ベースフィルムの外面が粘着剤により内面側液不透過膜に固定された構成とされていることにより、所期の耐衝撃性向上構造を確実に得ることができ、上記効果を一層確実に得ることができる。 Furthermore, the inner surface side liquid-impermeable film is fixed to the plate-like lid member by an adhesive, and the working electrode is configured such that the outer surface of the gas-permeable base film is fixed to the inner surface-side liquid impermeable film by an adhesive. As a result, the desired impact resistance improving structure can be obtained with certainty, and the above-described effect can be obtained more reliably.
本発明の定電位電解式酸素センサの一例における構成を示す断面図である。It is sectional drawing which shows the structure in an example of the constant potential electrolytic oxygen sensor of this invention. 図１に示す定電位電解式酸素センサの分解断面図である。FIG. 2 is an exploded cross-sectional view of the constant potential electrolytic oxygen sensor shown in FIG. 1. 図１に示す定電位電解式酸素センサにおける板状蓋部材の外面側構造を示す拡大断面図である。It is an expanded sectional view which shows the outer surface side structure of the plate-shaped cover member in the constant potential electrolytic oxygen sensor shown in FIG. 実験例１において作製した本発明に係る定電位電解式酸素センサ、および、比較実験例１および比較実験例２において作製した２つの比較用の定電位電解式酸素センサの各々についての、環境変化に対する耐久性試験の結果を示すグラフである。For each of the constant potential electrolytic oxygen sensor according to the present invention produced in Experimental Example 1 and the two comparative constant potential electrolytic oxygen sensors produced in Comparative Experimental Example 1 and Comparative Experimental Example 2 with respect to environmental changes It is a graph which shows the result of a durability test.
　図１は、本発明の定電位電解式酸素センサの一例における構成を示す断面図、図２は、図１に示す定電位電解式酸素センサの分解断面図、図３は、図１に示す定電位電解式酸素センサにおける板状蓋部材の外面側構造を示す拡大断面図である。以下においては、便宜上、図１における縦方向を「上下方向」、図１における横方向を「左右方向」と定義するが、使用形態等を限定するものではない。
この定電位電解式酸素センサ１０は、一端側部分（図１における左端側部分）に形成された上下方向に伸びる略円柱状の貫通孔よりなる感応部形成用空間１２と、この感応部形成用空間１２の他端側部分に並んで形成された、他端（図１における右端）に開口する電解液室形成用空間とを有する、全体が略箱型形状のケーシング１１を備えており、感応部形成用空間１２における略中間位置に形成された左右方向に伸びる連通孔１４により、感応部形成用空間１２と電解液室形成用空間とが互いに連通されている。図１および図２における符号１５は、ケーング１１における一端面に形成されたリード部材配置空間であって、例えば接着剤が充填されてシールされる。また、符号２３は回路基板である。 1 is a cross-sectional view showing a configuration of an example of a constant potential electrolytic oxygen sensor of the present invention, FIG. 2 is an exploded cross sectional view of the constant potential electrolytic oxygen sensor shown in FIG. 1, and FIG. 3 is a constant cross-sectional view shown in FIG. It is an expanded sectional view which shows the outer surface side structure of the plate-shaped cover member in a potential electrolytic oxygen sensor. In the following, for the sake of convenience, the vertical direction in FIG. 1 is defined as “vertical direction”, and the horizontal direction in FIG. 1 is defined as “left and right direction”.
This constant potential electrolysis oxygen sensor 10 includes a sensitive part forming space 12 formed of a substantially cylindrical through-hole extending in the vertical direction formed in one end side part (left end side part in FIG. 1), and the sensitive part forming part. The casing 11 has a substantially box-shaped casing 11 that has an electrolyte chamber forming space that is formed side by side at the other end portion of the space 12 and that opens to the other end (the right end in FIG. 1). The sensitive portion forming space 12 and the electrolyte chamber forming space are communicated with each other by a communication hole 14 extending in the left-right direction formed at a substantially intermediate position in the portion forming space 12. Reference numeral 15 in FIGS. 1 and 2 is a lead member arrangement space formed on one end surface of the cane 11 and is sealed by being filled with, for example, an adhesive. Reference numeral 23 denotes a circuit board.
　ケーシング１１における電解液室形成用空間の開口部には、例えばフッ素樹脂よりなるガス透過性疎水圧力調整膜２１を備えた、電解液室１３内の圧力調整機能を有する閉塞部材２０が設けられ、これにより、電解液室１３が形成されている。
　閉塞部材２０には、電解液室１３内の内部空間をガス透過性疎水圧力調整膜２１を介して外部に連通させる貫通孔２２が形成されている。この貫通孔２２の内径の大きさは、外部酸素の干渉防止のために、０．５～９ｍｍ、例えば１ｍｍであることが好ましい。 An opening of the electrolyte chamber forming space in the casing 11 is provided with a closing member 20 having a pressure adjusting function in the electrolyte chamber 13 provided with a gas permeable hydrophobic pressure adjusting film 21 made of, for example, a fluororesin. Thereby, the electrolytic solution chamber 13 is formed.
The closing member 20 is formed with a through hole 22 that allows the internal space in the electrolyte chamber 13 to communicate with the outside through the gas permeable hydrophobic pressure adjusting membrane 21. The inner diameter of the through hole 22 is preferably 0.5 to 9 mm, for example 1 mm, in order to prevent interference with external oxygen.
　ケーシング１１における感応部形成用空間１２の上方側開口部には、上面側に向かうに従って大径となる略円柱状空間部を形成する例えば３段の階段状の凹所が形成されており、各々厚み方向に貫通する複数の通孔２５Ａよりなる流体流通路が形成された上面側保護板２５がその外周縁部が１段目の段部の平坦面上に配置された状態で嵌合されて設けられ、さらに、上面側保護板２５の上面側に、例えば濾紙よりなる電解液保持層２８、作用電極３０および被検ガスを導入するピンホール３６が貫通して形成された、例えば液晶ポリマーよりなる板状蓋部材（ガス供給制限部材）３５が順次に収容されて配置された状態で、スリップリング４５を介して上面側蓋部材１６が螺合装着されている。図１および図２における符号３７は、電解液が外部に漏れることを防止するためのＯ－リング、符号１７は、上面側蓋部材１６に両面粘着テープによって固定された防塵フィルターである。 The upper opening of the sensitive part forming space 12 in the casing 11 is formed with, for example, three stepped recesses that form a substantially cylindrical space part that increases in diameter toward the upper surface side. The upper surface side protection plate 25 formed with a fluid flow path composed of a plurality of through holes 25A penetrating in the thickness direction is fitted in a state where the outer peripheral edge portion is disposed on the flat surface of the first stepped portion. Furthermore, an electrolyte solution holding layer 28 made of, for example, filter paper, a working electrode 30, and a pinhole 36 for introducing a test gas are formed through the upper surface side of the upper surface side protection plate 25, for example, from a liquid crystal polymer The upper lid member 16 is screwed and attached via the slip ring 45 in a state where the plate-like lid members (gas supply restriction members) 35 are sequentially accommodated and arranged. 1 and 2, reference numeral 37 denotes an O-ring for preventing the electrolytic solution from leaking to the outside, and reference numeral 17 denotes a dustproof filter fixed to the upper surface side cover member 16 by a double-sided adhesive tape.
　作用電極３０は、通気性と撥水性を備えた例えばフッ素系樹脂の多孔質膜などよりなるガス透過性ベースフィルム３１の一面上における中央位置に、例えば白金、金、ルテニウム、パラジウムなどの微粒子、または、これらの混合物や合金などがバインダーと共に焼成されてなる電極触媒層３２が形成されて構成されている。 The working electrode 30 has fine particles such as platinum, gold, ruthenium, and palladium, for example, at a central position on one surface of a gas permeable base film 31 made of, for example, a porous film of fluororesin having air permeability and water repellency, Alternatively, the electrode catalyst layer 32 is formed by firing such a mixture or alloy together with a binder.
　而して、上記定電位電解式酸素センサ１０においては、作用電極３０が、板状蓋部材３５の内面に、板状蓋部材３５のピンホール３６が連通し、作用電極３０のガス透過性ベースフィルム３１の外面が露出する貫通孔が形成された内面側液不透過膜を介して例えば粘着剤により固定されている。
　作用電極３０の固定方法について具体的に説明すると、図３に示すように、作用電極３０のガス透過性ベースフィルム３１の外面における周縁部が例えば中央位置に貫通孔３３Ａが形成された円板状の内面側両面粘着テープ３３（内面側液不透過膜）により板状蓋部材３５の内面に接着されると共に、上面側保護板２５の外面側において、作用電極３０に密着される電解液保持層２８の周囲を囲むよう配置された例えばＯ－リング２９よりなるシール部材によって、ガス透過性ベースフィルム３１の内面における周縁部が押圧された状態で、固定されている。 Thus, in the above-described constant potential electrolysis oxygen sensor 10, the working electrode 30 communicates with the inner surface of the plate-like lid member 35 with the pinhole 36 of the plate-like lid member 35, and the gas permeable base of the working electrode 30. The film 31 is fixed by, for example, an adhesive via an inner surface side liquid-impermeable film formed with a through hole through which the outer surface of the film 31 is exposed.
The fixing method of the working electrode 30 will be described in detail. As shown in FIG. 3, the peripheral portion of the outer surface of the gas permeable base film 31 of the working electrode 30 is, for example, a disk having a through hole 33A formed at the central position. The inner surface side double-sided adhesive tape 33 (inner surface side liquid impervious film) adheres to the inner surface of the plate-like lid member 35, and also adheres to the working electrode 30 on the outer surface side of the upper surface side protection plate 25. The periphery of the gas permeable base film 31 is fixed in a pressed state by a sealing member made of, for example, an O-ring 29 arranged so as to surround the periphery of 28.
　内面側液不透過膜における貫通孔、すなわち内面側両面粘着テープ３３に形成された貫通孔３３Ａの内径の大きさは、例えば０．２～５ｍｍであることが好ましい。これにより、ピンホール３６より導入された被検ガスを作用電極３０全体に対して確実に拡散させることができると共に、十分な耐衝撃性が得られて安定した指示値を確実に得ることができる。一方、貫通孔３３Ａの内径の大きさが過小である場合には、被検ガスの十分な拡散性が得られず、酸素ガスを作用電極３０の一部分しか反応に寄与させることができなくなるため、安定した指示値を得ることが困難になり、また、貫通孔３３Ａの内径の大きさが過大である場合には、十分な耐衝撃性を得ることができず、安定した指示値を得ることが困難になると共に、応答性が悪くなったり、起動特性が悪くなったりしやすい。
　ここに、板状蓋部材３５におけるピンホール３６の内径の大きさは、ピンホールが均一な内径を有するものである場合において、実用上、１．０～２００μｍであり、例えば８０μｍである。 The through hole in the inner surface side liquid-impermeable film, that is, the inner diameter of the through hole 33A formed in the inner surface side double-sided pressure-sensitive adhesive tape 33 is preferably, for example, 0.2 to 5 mm. As a result, the test gas introduced from the pinhole 36 can be reliably diffused throughout the working electrode 30, and sufficient impact resistance can be obtained and a stable indicated value can be reliably obtained. . On the other hand, if the inner diameter of the through hole 33A is too small, sufficient diffusibility of the test gas cannot be obtained, and only part of the working electrode 30 can contribute oxygen gas to the reaction. It becomes difficult to obtain a stable indicated value, and when the inner diameter of the through hole 33A is excessive, sufficient impact resistance cannot be obtained, and a stable indicated value can be obtained. It becomes difficult, and the responsiveness tends to deteriorate and the start-up characteristic tends to deteriorate.
Here, the size of the inner diameter of the pinhole 36 in the plate-like lid member 35 is practically 1.0 to 200 μm, for example 80 μm, when the pinhole has a uniform inner diameter.
　また、内面側液不透過膜の厚み、すなわち内面側両面粘着テープ３３の厚みは、例えば０．０５～０．５ｍｍであることが好ましい。内面側両面粘着テープ３３の厚みが過大である場合には、被検ガスが電極に到達するまでの距離が長くなり、作用電極３０と対極５３との間に流れる電流が低下したり、被検ガスに対する応答性が低下したりする。一方、内面側両面粘着テープ３３の厚みが過小である場合には、十分な強度や十分な耐久性が得られなくなると共に、取り扱いが困難となるため、作業性が低下する。 Further, the thickness of the inner surface side liquid-impermeable film, that is, the thickness of the inner surface side double-sided adhesive tape 33 is preferably 0.05 to 0.5 mm, for example. When the thickness of the inner surface side double-sided adhesive tape 33 is excessive, the distance until the test gas reaches the electrode becomes long, the current flowing between the working electrode 30 and the counter electrode 53 decreases, or the test Responsiveness to gas may be reduced. On the other hand, when the thickness of the inner surface side double-sided pressure-sensitive adhesive tape 33 is too small, sufficient strength and sufficient durability cannot be obtained, and handling becomes difficult.
　この定電位電解式酸素センサ１０においては、参照電極５０が上面側保護板２５の下面側中央位置において例えば濾紙よりなる電解液保持層（図示せず）が介在された状態で設けられており、電解液室１３内の電解液が連通孔１４を介して感応部形成用空間１２に流入されることにより参照電極５０が電解液中に浸漬された状態とされる。
　参照電極５０は、通気性と撥水性を備えたフッ素系樹脂の多孔質膜などよりなるガス透過性ベースフィルムの一面上における全面に、例えば白金、金、ルテニウム、パラジウムなどの微粒子、または、これらの混合物や合金などがバインダーと共に焼成されてなる電極触媒層が形成されて構成されている。なお、参照電極５０は、金属単体により構成することもできる。 In the constant potential electrolytic oxygen sensor 10, the reference electrode 50 is provided in a state where an electrolyte solution holding layer (not shown) made of, for example, filter paper is interposed at the lower surface side central position of the upper surface side protection plate 25, The electrolytic solution in the electrolytic solution chamber 13 flows into the sensitive part forming space 12 through the communication hole 14, whereby the reference electrode 50 is immersed in the electrolytic solution.
The reference electrode 50 is formed on the entire surface of one side of a gas permeable base film made of a fluororesin porous film having air permeability and water repellency, for example, fine particles such as platinum, gold, ruthenium, palladium, or the like. An electrode catalyst layer formed by firing a mixture or alloy of the above together with a binder is formed. In addition, the reference electrode 50 can also be comprised with a metal single-piece | unit.
　ケーシング１１における感応部形成用空間１２の下方側開口部には、下面側に向かうに従って大径となる略円柱状空間部を形成する例えば３段の階段状の凹所が形成されており、各々厚み方向に貫通する複数の通孔５５Ａよりなる流体流通路が形成された下面側保護板５５がその外周縁部が１段目の段部の平坦面上に配置されると共に、この下面側保護板５５の下面側に、例えば濾紙よりなる電解液保持層（図示せず）、対極５３および被検ガスを排出するガス排出用貫通孔５８Ａが形成されたキャップ部材５８が順次に収容されて配置された状態において、スリップリング５９を介して下面側蓋部材１８が螺合装着されている。図１および図２における符号５７はＯ－リングであって、下面側蓋部材１８が螺合装着されることによりキャップ部材５８によって押圧されて対極５３の外周縁部をその下面側から押圧状態で固定している。 For example, three stepped recesses are formed in the opening on the lower side of the sensitive portion forming space 12 in the casing 11 to form a substantially cylindrical space portion having a larger diameter toward the lower surface. The lower surface side protection plate 55 formed with a fluid flow path composed of a plurality of through holes 55A penetrating in the thickness direction is disposed on the flat surface of the first step, and the lower surface side protection plate 55 On the lower surface side of the plate 55, for example, an electrolytic solution holding layer (not shown) made of filter paper, a counter electrode 53, and a cap member 58 in which a gas discharge through hole 58A for discharging a test gas is formed are sequentially accommodated and arranged. In this state, the lower surface side cover member 18 is screwed and attached via the slip ring 59. Reference numeral 57 in FIGS. 1 and 2 denotes an O-ring which is pressed by the cap member 58 when the lower surface side lid member 18 is screwed and attached, and the outer peripheral edge of the counter electrode 53 is pressed from the lower surface side. It is fixed.
　対極５３は、通気性と撥水性を備えたフッ素系樹脂の多孔質膜などよりなるガス透過性ベースフィルムの一面上における中央位置に、例えば白金、金、ルテニウム、パラジウムなどの微粒子またはこれらの混合物や合金などがバインダーと共に焼成されてなる電極触媒層が形成されて構成されている。 The counter electrode 53 is, for example, fine particles of platinum, gold, ruthenium, palladium, or a mixture thereof at a central position on one surface of a gas permeable base film made of a porous film of a fluororesin having air permeability and water repellency. And an electrode catalyst layer formed by firing together with a binder.
　キャップ部材５８におけるガス排出用貫通孔５８Ａの内径の大きさは、外部酸素の干渉防止のために、例えば０．５～０．７ｍｍであることが好ましい。 The inner diameter of the gas discharge through hole 58A in the cap member 58 is preferably, for example, 0.5 to 0.7 mm in order to prevent interference with external oxygen.
　而して、この定電位電解式酸素センサ１０においては、板状蓋部材３５の外面に、ガス透過性膜体４０が板状蓋部材３５のピンホール３６が連通する貫通孔が形成された外面側液不透過膜を介して例えば粘着剤により固定されている。
　ガス透過性膜体４０は、ガス不透過性で、かつ撥水性の外面を有するものであって、通気性および撥水性を有する例えばフッ素系樹脂の多孔質膜よりなるベースフィルム４１と、このベースフィルム４１の外周面を除く外面（図３における上面）の全面に粘着剤によって固定されたアルミニウム箔４２とにより構成されており、図３に示すように、ガス透過性膜体４０の内面における周縁部が例えば中央に貫通孔４３Ａが形成された円板状の外面側両面粘着テープ４３により板状蓋部材３５の外面に接着されて固定されている。 Thus, in the constant potential electrolytic oxygen sensor 10, the outer surface of the plate-like lid member 35 is formed with a through-hole through which the gas permeable membrane body 40 communicates with the pinhole 36 of the plate-like lid member 35. It is fixed with, for example, an adhesive via a side liquid-impermeable membrane.
The gas permeable membrane body 40 has a gas impermeable and water repellent outer surface, and has a base film 41 made of a porous film of, for example, a fluorine resin having air permeability and water repellency, and the base film 41. It is comprised by the aluminum foil 42 fixed to the whole outer surface (upper surface in FIG. 3) except the outer peripheral surface of the film 41 with the adhesive, and as shown in FIG. 3, the peripheral edge in the inner surface of the gas-permeable film body 40 The part is bonded and fixed to the outer surface of the plate-shaped lid member 35 by a disk-shaped outer surface-side double-sided adhesive tape 43 having a through hole 43A formed at the center, for example.
　ガス透過性膜体４０は、空気透過率が０．０５～０．５Ｌ／ｄａｙであるものが好ましく、厚み、外径寸法、空隙率およびその他の具体的構成は、空気透過率が前記数値範囲内となるよう設定することができる。 The gas permeable membrane body 40 preferably has an air permeability of 0.05 to 0.5 L / day, and the thickness, outer diameter dimension, porosity, and other specific configurations are such that the air permeability is within the above numerical range. Can be set to be within.
　外面側液不透過膜における貫通孔、すなわち外面側両面粘着テープ４３に形成された貫通孔４３Ａの内径の大きさは、例えば０．０５～５ｍｍであることが好ましい。これにより、ガス応答性を大幅に低下させることなく、外部環境に対する十分な耐久性を得ることができ、安定した指示値を確実に得ることができる。
　また、外面側液不透過膜の厚み、すなわち外面側両面粘着テープ４３の厚みは、例えば０．５～５ｍｍであることが好ましい。 The through hole in the outer surface side liquid-impermeable film, that is, the inner diameter of the through hole 43A formed in the outer surface side double-sided adhesive tape 43 is preferably 0.05 to 5 mm, for example. Thereby, sufficient durability with respect to an external environment can be obtained without significantly reducing gas responsiveness, and a stable indicated value can be obtained with certainty.
Further, the thickness of the outer surface side liquid-impermeable film, that is, the thickness of the outer surface side double-sided adhesive tape 43 is preferably 0.5 to 5 mm, for example.
　上記定電位電解式酸素センサ１０は、電解液室１３に収容された、例えば硫酸水溶液よりなる電解液が連通孔１４を介して感応部形成用空間１２に流入して上面側保護板２５における通孔２５Ａを介して上面側保護板２５と作用電極３０との間に介在される電解液保持層２８に含浸されると共に、更に、下面側保護板５５における通孔５５Ａを介して下面側保護板５５と対極５３との間に介在される電解液保持層に含浸された状態において、例えば環境雰囲気の空気などの被検ガスがガス透過性膜体４０の外周面から流入して板状蓋部材３５のピンホール３６に導入され、当該ピンホール３６によって透過量が制限された状態で通常拡散（クヌーセン拡散領域およびクヌーセン拡散と通常拡散とが起こる拡散領域外）により作用電極３０に供給されると共に、作用電極３０と対極５３との間に一定の電位差が生じるよう、参照電極５０の電位状態を基準として、作用電極３０に所定の電圧が印加され、作用電極３０および対極５３の両電極間に生ずる電流値が測定されることにより被検ガス中の酸素ガスの濃度が検出される。 In the constant potential electrolytic oxygen sensor 10, an electrolytic solution made of, for example, a sulfuric acid aqueous solution contained in the electrolytic solution chamber 13 flows into the sensitive portion forming space 12 through the communication hole 14 and passes through the upper surface protection plate 25. The electrolytic solution holding layer 28 interposed between the upper surface side protective plate 25 and the working electrode 30 is impregnated through the hole 25A, and further, the lower surface side protective plate is inserted through the through hole 55A in the lower surface side protective plate 55. In a state where the electrolytic solution holding layer interposed between 55 and the counter electrode 53 is impregnated, a test gas such as air in an ambient atmosphere flows in from the outer peripheral surface of the gas permeable membrane body 40 and is a plate-like lid member. 35 is introduced into the 35 pinholes 36, and the diffusion amount is limited by the pinholes 36, and normal diffusion (outside of the Knudsen diffusion region and the diffusion region where Knudsen diffusion and normal diffusion occur) is applied to the working electrode 30. A predetermined voltage is applied to the working electrode 30 based on the potential state of the reference electrode 50 so that a constant potential difference is generated between the working electrode 30 and the counter electrode 53. The concentration of oxygen gas in the test gas is detected by measuring the current value generated between both electrodes.
　而して、上記構成の定電位電解式酸素センサ１０によれば、ガス不透過性で、撥水性の外面を有するガス透過性膜体４０が被検ガスを導入するピンホール３６が貫通して形成された板状蓋部材３５の外面に固定されており、被検ガスがガス透過性膜体４０の外周面から流入して板状蓋部材３５のピンホール３６に導入される構成とされていることにより、ガス検知に必要な通気性は確保しながら、ガス透過性膜体４０の透気度が規制されるので、応答性を大幅に低下させることなく、しかも、外部環境の影響に対する十分な耐久性を得ることができる。例えば結露が発生しやすい環境下で使用される場合であっても、板状蓋部材３５の外面側における結露の発生によってピンホール３６の外面側開口が塞がれることを確実に防止することができ、従って、安定した指示値を確実に得ることができる。　　　 Thus, according to the potentiostatic oxygen sensor 10 having the above-described configuration, the gas permeable membrane body 40 having a gas impermeable and water repellent outer surface penetrates the pinhole 36 through which the test gas is introduced. It is fixed to the outer surface of the formed plate-like lid member 35, and the test gas flows from the outer peripheral surface of the gas permeable membrane body 40 and is introduced into the pinhole 36 of the plate-like lid member 35. As a result, the air permeability of the gas permeable membrane body 40 is regulated while ensuring the air permeability necessary for gas detection, so that the responsiveness is not significantly reduced and the influence of the external environment is sufficient. Durability can be obtained. For example, even when used in an environment where condensation is likely to occur, it is possible to reliably prevent the outer surface side opening of the pinhole 36 from being blocked by the occurrence of condensation on the outer surface side of the plate-like lid member 35. Therefore, a stable indication value can be obtained with certainty. *
　また、ガス透過性膜体４０が、板状蓋部材３５の外面に、当該板状蓋部材３５のピンホール３６が連通する貫通孔４３Ａが形成された外面側両面粘着テープ４３によって固定された構成とされていることにより、ガス透過性膜体４０と板状蓋部材３５との高い密着性を得ることができるので、上記効果を一層確実に得ることができる。 Further, the gas permeable membrane body 40 is fixed to the outer surface of the plate-like lid member 35 by an outer-surface-side double-sided adhesive tape 43 in which a through hole 43A through which the pin hole 36 of the plate-like lid member 35 communicates is formed. Since the high adhesion between the gas permeable membrane body 40 and the plate-like lid member 35 can be obtained, the above effect can be obtained more reliably.
　さらにまた、作用電極３０が貫通孔３３Ａを有する内面側両面粘着テープ３３によって板状蓋部材３５の内面に固定された構造とされていることにより、十分な耐衝撃性を得ることができるので、例えば定電位電解式酸素センサ１０を落下させるなどして衝撃が加えられた場合であっても、作用電極３０の板状蓋部材３５に対するズレを防止または小さくすること、換言すれば、板状蓋部材３５と作用電極３０との密着性を維持することができるので、電解液が外部に漏れることを確実に防止することができると共に、例えば作用電極３０と板状蓋部材３５との間に隙間が形成されるなどして作用電極３０に対するピンホール３６以外からの空気の侵入を防止することができて安定した出力を確実に得ることができるという、効果を得ることができる。 Furthermore, since the working electrode 30 is structured to be fixed to the inner surface of the plate-like lid member 35 by the inner surface-side double-sided adhesive tape 33 having the through-hole 33A, it is possible to obtain sufficient impact resistance. For example, even when an impact is applied by dropping the constant potential electrolytic oxygen sensor 10 or the like, the displacement of the working electrode 30 with respect to the plate-like lid member 35 is prevented or reduced, in other words, the plate-like lid. Since the adhesion between the member 35 and the working electrode 30 can be maintained, it is possible to reliably prevent the electrolyte from leaking to the outside and, for example, a gap between the working electrode 30 and the plate-like lid member 35. As a result, it is possible to prevent air from entering the working electrode 30 from other than the pinhole 36, and to obtain a stable output. Can.
　また、作用電極３０が、そのガス透過性ベースフィルム３１の内面における周縁部が上面側保護板２５の外面側において、作用電極３０に密着される電解液保持層２８の周囲を囲むよう配置されたＯ－リング２９によって押圧された状態で、固定されていることにより、所期の耐衝撃性向上構造を確実に得ることができ、上記効果、すなわち、作用電極３０と板状蓋部材３５との密着性が維持されることによる安定した出力が得られるという効果および電解液の液漏れ防止効果を一層確実に得ることができる。 Further, the working electrode 30 is arranged so that the peripheral edge portion on the inner surface of the gas permeable base film 31 surrounds the periphery of the electrolyte solution holding layer 28 that is in close contact with the working electrode 30 on the outer surface side of the upper surface side protection plate 25. By being fixed in a state of being pressed by the O-ring 29, it is possible to reliably obtain the expected structure for improving impact resistance, that is, the above-described effect, that is, the working electrode 30 and the plate-like lid member 35. The effect that a stable output can be obtained by maintaining the adhesion and the effect of preventing the electrolyte from leaking can be obtained more reliably.
　また、内面側両面粘着テープ３３の貫通孔３３Ａの内径の大きさが０．２～５ｍｍに設定された構成とされていることにより、板状蓋部材３５におけるピンホール３６の出口から作用電極３０までの被検ガスの拡散性をよくすることができて酸素ガスを作用電極３０全体に供給することができると共に、十分な耐衝撃性を確実に得ることができて安定した出力を確実に得ることができる。 In addition, since the inner diameter of the through hole 33A of the inner surface side double-sided adhesive tape 33 is set to 0.2 to 5 mm, the working electrode 30 is provided from the outlet of the pinhole 36 in the plate-like lid member 35. Can improve the diffusibility of the test gas up to and supply oxygen gas to the working electrode 30 as a whole, as well as ensuring sufficient impact resistance and ensuring stable output. be able to.
　以下、本発明の効果を確認するために行った実験例を示す。 Hereinafter, experimental examples performed to confirm the effects of the present invention will be shown.
＜実験例１＞
　図１～図３に示す構成に従って、本発明に係る定電位電解式酸素センサを作製し、以下に示す方法による環境変化に対する耐久性試験を行った。この定電位電解式酸素センサにおいては、板状蓋部材におけるピンホールの内径の大きさが８０μｍであり、ガス透過性膜体（４０）は、ベースフィルム（４１）の材質がＰＴＦＥ、外径が６ｍｍ、厚みが０．１ｍｍであり、アルミニウム箔（４２）の厚みが０．１ｍｍであって、空気透過率が０．１５Ｌ／ｄａｙであるものである。また、外面側両面粘着テープ（４３）の厚みが０．２ｍｍ、貫通孔（４３Ａ）の内径の大きさが２ｍｍである。
〔試験方法〕
　上記定電位電解式酸素センサを温度が－１０℃の環境中に３時間以上放置した後、温度４０℃、相対湿度９８％ＲＨの環境（結露しやすい環境）中において当該定電位電解式酸素センサによるガス検知を行うことにより環境変化に対する指示変動（出力電流の変動）の状態を調べた。結果を図４においてグラフ（ｅ）で示す。図４に示すグラフは、環境条件を変化させる３０分前の時点からガス検知（計測）を開始したことを示すものである。　　　 <Experimental example 1>
A constant potential electrolytic oxygen sensor according to the present invention was fabricated according to the configuration shown in FIGS. 1 to 3, and a durability test against environmental changes was performed by the method described below. In this constant potential electrolytic oxygen sensor, the inner diameter of the pinhole in the plate-like lid member is 80 μm, and the gas permeable membrane body (40) has a base film (41) made of PTFE and an outer diameter of 80 μm. The thickness is 6 mm, the thickness is 0.1 mm, the thickness of the aluminum foil (42) is 0.1 mm, and the air permeability is 0.15 L / day. Moreover, the thickness of an outer surface side double-sided adhesive tape (43) is 0.2 mm, and the internal diameter of a through-hole (43A) is 2 mm.
〔Test method〕
After the constant potential electrolytic oxygen sensor is left in an environment at a temperature of −10 ° C. for 3 hours or more, the constant potential electrolytic oxygen sensor is used in an environment having a temperature of 40 ° C. and a relative humidity of 98% RH (an environment in which condensation is likely to occur). The state of indication fluctuation (change in output current) with respect to environmental changes was examined by performing gas detection using the above. The results are shown by a graph (e) in FIG. The graph shown in FIG. 4 shows that gas detection (measurement) is started from a point 30 minutes before the environmental condition is changed.
　図４に示す結果から明らかなように、本発明に係る定電位電解式酸素センサによれば、環境変化に対する影響を受けることなく、安定した指示値（出力電流値）を得ることができることが確認された。 As is clear from the results shown in FIG. 4, it is confirmed that the constant potential electrolytic oxygen sensor according to the present invention can obtain a stable instruction value (output current value) without being affected by environmental changes. It was.
＜比較実験例１＞
　実験例１において作製した定電位電解式酸素センサにおいて、板状蓋部材の外面にガス透過性膜体を設けなかったことの他は実験例１において作製したものと同様の構成を有する比較用の定電位電解式酸素センサを作製し、実験例１と同様にして、環境変化に対する耐久性試験を行った。結果を図４においてグラフ（ｆ）で示す。 <Comparative Experimental Example 1>
In the controlled potential electrolytic oxygen sensor produced in Experimental Example 1, a comparative example having the same configuration as that produced in Experimental Example 1 except that the gas permeable membrane was not provided on the outer surface of the plate-like lid member. A constant potential electrolytic oxygen sensor was produced, and a durability test against environmental changes was performed in the same manner as in Experimental Example 1. The results are shown by a graph (f) in FIG.
　図４に示す結果から明らかなように、この比較用の定電位電解式酸素センサにおいては、環境条件が変更されてから１０～２０分間の時間が経過したときに出力電流値（指示値）が急激に低下し、最終的には０となり、環境変化に対する影響を大きく受けることが確認された。この理由は、板状蓋部材の外面側において結露が発生しこれにより生じた水滴がピンホールの外面側開口（入り口）に付着したためであると考えられる。 As is apparent from the results shown in FIG. 4, in this comparative potentiostatic oxygen sensor, the output current value (indicated value) is 10 to 20 minutes after the environmental condition is changed. It was confirmed that it dropped rapidly and eventually became 0, and was greatly affected by environmental changes. The reason for this is considered that dew condensation occurs on the outer surface side of the plate-like lid member, and water droplets generated thereby adhere to the outer surface side opening (entrance) of the pinhole.
＜比較実験例２＞
　実験例１において作製した定電位電解式酸素センサにおいて、ガス透過性膜体の代わりに、アルミニウム箔が設けられていないベースフィルムのみを設けたことの他は実験例１において作製したものと同様の構成を有する比較用の定電位電解式酸素センサを作製し、実験例１と同様にして、環境変化に対する耐久性試験を行った。結果を図４においてグラフ（ｇ）で示す。 <Comparative Experiment Example 2>
The constant potential electrolytic oxygen sensor produced in Experimental Example 1 is the same as that produced in Experimental Example 1 except that only a base film without an aluminum foil is provided instead of the gas permeable membrane. A comparative potentiostatic oxygen sensor having a configuration was prepared, and a durability test against environmental changes was performed in the same manner as in Experimental Example 1. A result is shown with a graph (g) in FIG.
　図４に示す結果から明らかなように、この比較用の定電位電解式酸素センサにおいても、比較実験例１で作製したものと同様に、環境条件が変更されてから１０～２０分間の時間が経過したときに出力電流値（指示値）が急激に低下して最終的には０となり、環境変化に対する影響を大きく受けることが確認された。この理由は、板状蓋部材の外面側において結露が発生しこれにより生じた水滴がピンホールの外面側開口（入り口）に付着したためであると考えられる。 As is apparent from the results shown in FIG. 4, in this comparative potentiostatic electrolytic oxygen sensor, as in the case of Comparative Experimental Example 1, the time of 10 to 20 minutes after the environmental conditions were changed When it passed, the output current value (indicated value) suddenly decreased and finally became 0, and it was confirmed that the output current value (instruction value) was greatly affected by environmental changes. The reason for this is considered that dew condensation occurs on the outer surface side of the plate-like lid member, and water droplets generated thereby adhere to the outer surface side opening (entrance) of the pinhole.
　以上、本発明の実施形態について説明したが、本発明は上記の実施形態に限定されるものではない。
　例えば、板状蓋部材の外面に固定されるガス透過性膜体におけるガス不透過性で撥水性を有する表面（外面）は、例えば、アルミニウムをベースフィルムに蒸着することにより、あるいは、撥水性ガス不透過性の塗料をベースフィルムに塗布することにより、形成することができる。 As mentioned above, although embodiment of this invention was described, this invention is not limited to said embodiment.
For example, the gas-impermeable and water-repellent surface (outer surface) of the gas-permeable film body fixed to the outer surface of the plate-like lid member is formed by, for example, depositing aluminum on a base film, or by using a water-repellent gas. It can be formed by applying an impermeable paint to the base film.
　本発明の定電位電解式酸素センサは、例えば地下の工事現場や坑道、その他の人が立ち入る場所や作業領域などにおける酸欠事故の発生を未然に防止するために、有用なものである。 The constant potential electrolytic oxygen sensor of the present invention is useful in order to prevent the occurrence of an oxygen deficiency accident in, for example, an underground construction site, a mine tunnel, other places where people enter, and work areas.
　１０　定電位電解式酸素センサ
　１１　ケーシング
　１２　感応部形成用空間
　１３　電解液室
　１４　連通孔
　１５　リード部材配置空間
　１６　上面側蓋部材
　１７　防塵フィルター
　１８　下面側蓋部材
　２０　閉塞部材
　２１　ガス透過性疎水圧力調整膜
　２２　貫通孔
　２３　回路基板
　２５　上面側保護板
　２５Ａ　通孔
　２８　電解液保持層
　２９　Ｏ－リング
　３０　作用電極
　３１　ガス透過性ベースフィルム
　３２　電極触媒層
　３３　内面側両面粘着テープ
　３３Ａ　貫通孔
　３５　板状蓋部材
　３６　ピンホール
　３７　Ｏ－リング
　４０　ガス透過性膜体
　４１　ベースフィルム
　４２　アルミニウム箔
　４３　外面側両面粘着テープ
　４３Ａ　貫通孔
　４５　スリップリング
　５０　参照電極
　５３　対極
　５５　下面側保護板
　５５Ａ　通孔
　５７　Ｏ－リング
　５８　キャップ部材
　５８Ａ　ガス排出用貫通孔
　５９　スリップリング DESCRIPTION OF SYMBOLS 10 Constant potential electrolytic oxygen sensor 11 Casing 12 Sensing part formation space 13 Electrolyte chamber 14 Communication hole 15 Lead member arrangement space 16 Upper surface side cover member 17 Dust-proof filter 18 Lower surface side cover member 20 Closure member 21 Gas-permeable hydrophobic pressure adjustment Membrane 22 Through hole 23 Circuit board 25 Upper surface side protection plate 25A Through hole 28 Electrolyte holding layer 29 O-ring 30 Working electrode 31 Gas permeable base film 32 Electrode catalyst layer 33 Inner surface side double-sided adhesive tape 33A Through hole 35 Plate-shaped lid Member 36 Pinhole 37 O-ring 40 Gas permeable membrane body 41 Base film 42 Aluminum foil 43 Double-sided adhesive tape on outer surface 43A Through hole 45 Slip ring 50 Reference electrode 53 Counter electrode 55 Lower surface side protective plate 55A Through hole 57 O-ring 58 Cap member 58A Gas exhaust through hole 59 Lip ring

Claims (11)

  1. 　電解液室を形成するケーシングに、少なくとも作用電極と対極とが設けられてなる定電位電解式酸素センサにおいて、
    　被検ガスを導入するピンホールが貫通して形成された板状蓋部材の外面に、ガス透過性膜体が固定されており、当該ガス透過性膜体は、ガス不透過性で、撥水性の外面を有するものであることを特徴とする定電位電解式酸素センサ。     In a constant potential electrolytic oxygen sensor in which at least a working electrode and a counter electrode are provided in a casing forming an electrolyte chamber,
    A gas permeable membrane body is fixed to the outer surface of a plate-like lid member formed by penetrating a pinhole for introducing a test gas. The gas permeable membrane body is gas impermeable and water repellent. A constant potential electrolytic oxygen sensor characterized by having an outer surface.
  2. 　ガス透過性膜体は、通気性および撥水性を有するベースフィルムと、このベースフィルムの外周面を除く外面の全面に粘着剤によって固定されたアルミニウム箔とにより形成されていることを特徴とする請求項１に記載の定電位電解式酸素センサ。 The gas permeable membrane body is formed of a base film having air permeability and water repellency, and an aluminum foil fixed to the entire outer surface excluding the outer peripheral surface of the base film with an adhesive. Item 2. The constant potential electrolytic oxygen sensor according to Item 1.
  3. 　ガス透過性膜体は、その内面が、板状蓋部材の外面に粘着剤によって固定された、当該板状蓋部材のピンホールが連通する貫通孔が形成された外面側液不透過膜の外面に粘着剤によって固定されていることを特徴とする請求項１または請求項２に記載の定電位電解式酸素センサ。 The gas permeable membrane body has an inner surface fixed to the outer surface of the plate-like lid member with an adhesive, and has an outer surface on the outer surface side liquid-impermeable membrane in which a through hole is formed to communicate with the pinhole of the plate-like lid member. The constant potential electrolytic oxygen sensor according to claim 1 or 2, wherein the oxygen sensor is fixed to the substrate by an adhesive.
  4. 　電解液室を形成するケーシングに、少なくとも作用電極と対極とが設けられてなる定電位電解式酸素センサにおいて、
    　被検ガスを導入するピンホールが貫通して形成された板状蓋部材の内面に、内面側液不透過膜を介して、ガス透過性ベースフィルムに電極触媒層が形成されてなる作用電極が固定されていると共に、当該板状蓋部材の外面に、ガス不透過性で、撥水性の外面を有するガス透過性膜体が固定されており、
    　前記内面側液不透過膜には、板状蓋部材のピンホールが連通し、作用電極のガス透過性ベースフィルムの外面が露出する貫通孔が形成されていることを特徴とする定電位電解式酸素センサ。     In a constant potential electrolytic oxygen sensor in which at least a working electrode and a counter electrode are provided in a casing forming an electrolyte chamber,
    A working electrode in which an electrode catalyst layer is formed on a gas permeable base film on an inner surface of a plate-like lid member formed by penetrating a pinhole for introducing a test gas through an inner surface side liquid impermeable film. A gas permeable membrane having a gas impermeable and water repellent outer surface is fixed to the outer surface of the plate-like lid member,
    The inner surface side liquid-impermeable film has a through hole through which a pinhole of a plate-like lid member communicates and an outer surface of a gas permeable base film of a working electrode is exposed. Oxygen sensor.
  5. 　内面側液不透過膜の貫通孔の内径の大きさが、０．２～５ｍｍであることを特徴とする請求項４に記載の定電位電解式酸素センサ。 The constant potential electrolytic oxygen sensor according to claim 4, wherein the inner diameter of the through hole of the inner surface side liquid-impermeable membrane is 0.2 to 5 mm.
  6. 　内面側液不透過膜が粘着剤により板状蓋部材に固定されており、作用電極は、そのガス透過性ベースフィルムの外面が粘着剤により内面側液不透過膜に固定されていることを特徴とする請求項４または請求項５に記載の定電位電解式酸素センサ。 The inner surface side liquid impervious film is fixed to the plate-like lid member by an adhesive, and the working electrode has an outer surface of the gas permeable base film fixed to the inner surface side liquid impermeable film by an adhesive. The constant potential electrolytic oxygen sensor according to claim 4 or 5.
  7. 　ガス透過性膜体は、通気性および撥水性を有するベースフィルムと、このベースフィルムの外周面を除く外面の全面に粘着剤によって固定されたアルミニウム箔とにより形成されていることを特徴とする請求項４または請求項５に記載の定電位電解式酸素センサ。 The gas permeable membrane body is formed of a base film having air permeability and water repellency, and an aluminum foil fixed to the entire outer surface excluding the outer peripheral surface of the base film with an adhesive. The constant potential electrolytic oxygen sensor according to claim 4 or 5.
  8. 　ガス透過性膜体は、通気性および撥水性を有するベースフィルムと、このベースフィルムの外周面を除く外面の全面に粘着剤によって固定されたアルミニウム箔とにより形成されていることを特徴とする請求項６に記載の定電位電解式酸素センサ。 The gas permeable membrane body is formed of a base film having air permeability and water repellency, and an aluminum foil fixed to the entire outer surface excluding the outer peripheral surface of the base film with an adhesive. Item 7. The constant potential electrolytic oxygen sensor according to Item 6.
  9. 　ガス透過性膜体は、その内面が、板状蓋部材の外面に粘着剤によって固定された、当該板状蓋部材のピンホールが連通する貫通孔が形成された外面側液不透過膜の外面に粘着剤によって固定されていることを特徴とする請求項４、請求項５および請求項８のいずれかに記載の定電位電解式酸素センサ。 The gas permeable membrane body has an inner surface that is fixed to the outer surface of the plate-like lid member by an adhesive, and an outer surface of the outer surface side liquid-impermeable membrane in which a through-hole that communicates with the pinhole of the plate-like lid member is formed. The constant potential electrolytic oxygen sensor according to any one of claims 4, 5, and 8, wherein the oxygen sensor is fixed to an adhesive.
  10. 　ガス透過性膜体は、その内面が、板状蓋部材の外面に粘着剤によって固定された、当該板状蓋部材のピンホールが連通する貫通孔が形成された外面側液不透過膜の外面に粘着剤によって固定されていることを特徴とする請求項６に記載の定電位電解式酸素センサ。 The gas permeable membrane body has an inner surface that is fixed to the outer surface of the plate-like lid member by an adhesive, and an outer surface of the outer surface side liquid-impermeable membrane in which a through-hole that communicates with the pinhole of the plate-like lid member is formed. The constant potential electrolytic oxygen sensor according to claim 6, wherein the oxygen sensor is fixed to the substrate with an adhesive.
  11. 　ガス透過性膜体は、その内面が、板状蓋部材の外面に粘着剤によって固定された、当該板状蓋部材のピンホールが連通する貫通孔が形成された外面側液不透過膜の外面に粘着剤によって固定されていることを特徴とする請求項７に記載の定電位電解式酸素センサ。 The gas permeable membrane body has an inner surface fixed to the outer surface of the plate-like lid member with an adhesive, and has an outer surface on the outer surface side liquid-impermeable membrane in which a through hole is formed to communicate with the pinhole of the plate-like lid member. The constant potential electrolytic oxygen sensor according to claim 7, wherein the oxygen sensor is fixed to the substrate with an adhesive.
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