WO2010104045A1 - Polymère - Google Patents

Polymère Download PDF

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Publication number
WO2010104045A1
WO2010104045A1 PCT/JP2010/053810 JP2010053810W WO2010104045A1 WO 2010104045 A1 WO2010104045 A1 WO 2010104045A1 JP 2010053810 W JP2010053810 W JP 2010053810W WO 2010104045 A1 WO2010104045 A1 WO 2010104045A1
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group
polymer
formula
optionally substituted
atom
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PCT/JP2010/053810
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English (en)
Japanese (ja)
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敬 佐藤
武継 山本
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住友化学株式会社
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Publication of WO2010104045A1 publication Critical patent/WO2010104045A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F238/00—Copolymers of compounds having one or more carbon-to-carbon triple bonds

Definitions

  • the present invention relates to a polymer.
  • a diphenylacetylene polymer is known as a functional polymer having gas separation ability (see Patent Document 1).
  • an object of the present invention is to provide a polymer excellent in the ability to selectively permeate oxygen and the ability to suppress permeation of carbon dioxide.
  • the polymer of the present invention contains a repeating unit represented by the following formula (1).
  • R 1 represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, tri Represents an alkylsilyl group or a trialkylgermyl group
  • R 2 is represented by the following formula (3), m is an integer of 0 or more and 5 or less, and when there are a plurality of R 2 , they are the same or different from each other. May be.
  • p is an integer of 5 or more and 15 or less.
  • the polymer of the present invention is excellent in the ability to selectively permeate oxygen and the ability to suppress permeation of carbon dioxide, that is, oxygen / carbon dioxide selective permeability, by containing the above-mentioned repeating unit.
  • R 1 is preferably a phenyl group or a substituted phenyl group represented by the following formula (2).
  • R 3 represents an arbitrary monovalent group
  • n is an integer of 0 or more and 5 or less, and when there are a plurality of R 3 , they may be the same or different from each other.
  • R 1 has such a structure, the oxygen / carbon dioxide selective permeability of the polymer is further improved, and the change with time of the polymer can be suppressed.
  • R 3 represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, a trialkylsilyl group, or A trialkylgermyl group is preferred.
  • R 3 has such a structure, the oxygen / carbon dioxide selective permeability of the polymer is further improved, and the change with time of the polymer can be suppressed.
  • R 3 is more preferably a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or a trialkylsilyl group, more preferably a hydrogen atom, a fluorine atom, or a trimethylsilyl group, and a trimethylsilyl group. It is particularly preferred. By making R 3 in this way, the oxygen / carbon dioxide selective permeability of the polymer is further improved, the change of the polymer with time can be suppressed, and further, it is easily dissolved in various organic solvents. Therefore, it is excellent also in film forming property.
  • a polymer excellent in oxygen / carbon dioxide selective permeability can be provided.
  • the polymer of the present invention contains a repeating unit represented by the following formula (1).
  • R 1 represents a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic hydrocarbon group, an optionally substituted aromatic heterocyclic group, tri Represents an alkylsilyl group or a trialkylgermyl group
  • R 2 is represented by the following formula (3)
  • m is an integer of 0 or more and 5 or less, and when there are a plurality of R 2 , they are the same or different from each other. May be.
  • the repeating unit represented by the plurality Included formula (1) in the polymer may be the position of R 1 and the phenyl group are horizontally reversed to each other.
  • the repeating units represented by the formula (1) contained in the polymer may be each independently a cis type or a trans type. The cis type and trans type can be identified by Raman spectroscopic measurement of a polymer film.
  • p is an integer of 5 or more and 15 or less.
  • the polymer of the present invention is excellent in the ability to selectively permeate oxygen and the ability to suppress permeation of carbon dioxide, that is, oxygen / carbon dioxide selective permeability, by containing the above-mentioned repeating unit.
  • the aromatic hydrocarbon group means the remaining atomic group excluding one hydrogen atom bonded to the carbon atom constituting the aromatic ring of the aromatic hydrocarbon
  • the aromatic heterocyclic group refers to the atomic group remaining after removing one hydrogen atom bonded to the carbon atom or heteroatom constituting the aromatic heterocycle of the aromatic heterocyclic compound.
  • an aromatic heterocyclic compound is not only a carbon atom but also an oxygen atom, a sulfur atom, a nitrogen atom, a phosphorus atom, boron as an element constituting a ring among organic compounds having an aromatic cyclic structure.
  • a substance containing a heteroatom such as an atom, silicon atom, selenium atom, tellurium atom or arsenic atom.
  • m in Formula (1) is preferably 1 or more.
  • p in formula (3) is preferably 6 or more and 15 or less, and more preferably 8 or more and 15 or less.
  • Examples of the halogen atom of R 1 in the formula (1) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom and a chlorine atom are preferable.
  • Examples of the optionally substituted alkyl group represented by R 1 in the formula (1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, an isopropyl group, an isobutyl group, a tertiary butyl group, 1- Methylpropyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group, 1-methylpentyl group, 1,1-dimethylpentyl group, 2-methylpentyl group, or hydrogen thereof Those in which a part or all of them are substituted with a halogen atom.
  • substituted alkyl groups include chloromethyl, chloroethyl, chloropropyl, dichloromethyl, dichloroethyl, trichloromethyl, bromomethyl, bromoethyl, bromopropyl, dibromomethyl, dibromoethyl, mono Fluoromethyl group, monofluoroethyl group, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoroisobutyl group, perfluoro-1-methylpropyl group, perfluoropentyl group, perfluoro Butyl group, perfluoroisopentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononanyl group, perfluorodecyl group, perfluoroundecyl group, perfluorododecyl group,
  • Examples of the optionally substituted aromatic hydrocarbon group represented by R 1 in the formula (1) include an unsubstituted aromatic hydrocarbon group, a halogen atom, an alkoxy group, an alkyl group, a trialkylsilyl group, and a trialkylgermyl group. And an aromatic hydrocarbon group substituted with.
  • the aromatic hydrocarbon group includes those having a condensed ring and those having two or more independent benzene rings or condensed rings bonded by a single bond or a divalent organic group.
  • the number of carbon atoms in the aromatic hydrocarbon group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 20.
  • Examples of the aromatic hydrocarbon group include a phenyl group, a C 1 -C 12 alkoxyphenyl group, a C 1 -C 12 alkylphenyl group, a trialkylsilylphenyl group, a trialkylgermylphenyl group, and a 1-naphthyl group.
  • 2-naphthyl group 1-anthryl group, 2-anthryl group, 9-anthryl group, pyrenyl group, perylenyl group, pentafluorophenyl group, etc., among which phenyl group, C 1 -C 12 alkylphenyl group, A trialkylsilylphenyl group is preferred.
  • Examples of the optionally substituted aromatic heterocyclic group represented by R 1 in the formula (1) include a monovalent aromatic substituted with a substituent such as an unsubstituted monovalent aromatic heterocyclic group and an alkyl group. Heterocyclic group is mentioned.
  • the number of carbon atoms of the monovalent aromatic heterocyclic group is usually 4 to 60, preferably 4 to 30, and more preferably about 4 to 20, excluding the number of carbon atoms of the substituent.
  • Examples of the monovalent aromatic heterocyclic group include thienyl group, C 1 to C 12 alkyl thienyl group, pyroyl group, furyl group, pyridyl group, C 1 to C 12 alkyl pyridyl group, pyridazyl group, pyrimidyl group, A pyrazinyl group etc. are mentioned.
  • Examples of the trialkylsilyl group of R 1 in the formula (1) include trimethylsilyl group, triethylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, pentyldimethylsilyl group, hexyldimethylsilyl group, Heptyldimethylsilyl group, octyldimethylsilyl group, octyldiethylsilyl group, 2-ethylhexyldimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl group, etc. It is done.
  • trialkylgermyl group of R 1 in the formula (1) examples include trimethylgermyl group, triethylgermyl group, tri-isopropylgermyl group, dimethyl-isopropylgermyl group, diethyl-isopropylgermyl group, pentyldimethylgel.
  • Mill group hexyl dimethyl gel mill group, heptyl dimethyl gel mill group, octyl dimethyl gel mill group, octyl diethyl gel mill group, 2-ethylhexyl dimethyl gel mill group, nonyl dimethyl gel mill group, decyl dimethyl gel mill group, 3, 7 -Dimethyloctyl-dimethylgermyl group, dodecyldimethylgermyl group and the like.
  • R 1 is preferably a phenyl group or a substituted phenyl group represented by the following formula (2).
  • R 3 represents an arbitrary monovalent group
  • n is an integer of 0 or more and 5 or less, and when there are a plurality of R 3 , they may be the same or different from each other.
  • R 1 has such a structure, the oxygen / carbon dioxide selective permeability is further improved, and the change with time of the polymer can be suppressed.
  • R 3 in the formula (2) As an arbitrary monovalent group of R 3 in the formula (2), a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aromatic hydrocarbon group, or an optionally substituted group.
  • An aromatic heterocyclic group, a trialkylsilyl group, or a trialkylgermyl group is preferred.
  • R 3 has such a structure, the oxygen / carbon dioxide selective permeability is further improved, and the change with time of the polymer can be suppressed.
  • Examples of the halogen atom of R 3 in the formula (2) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a fluorine atom and a chlorine atom.
  • Examples of the optionally substituted alkyl group represented by R 3 in the formula (2) include methyl group, ethyl group, propyl group, butyl group, pentyl group, hexyl group, isopropyl group, isobutyl group, tertiary butyl group, 1- Methylpropyl group, isopentyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylpropyl group, 1-methylpentyl group, 1,1-dimethylpentyl group, 2-methylpentyl group, or hydrogen thereof Those in which a part or all of them are substituted with a halogen atom.
  • substituted alkyl groups include chloromethyl, chloroethyl, chloropropyl, dichloromethyl, dichloroethyl, trichloromethyl, bromomethyl, bromoethyl, bromopropyl, dibromomethyl, dibromoethyl, mono Fluoromethyl group, monofluoroethyl group, trifluoromethyl group, perfluoroethyl group, perfluoropropyl group, perfluoroisopropyl group, perfluoroisobutyl group, perfluoro-1-methylpropyl group, perfluoropentyl group, perfluoro Butyl group, perfluoroisopentyl group, perfluorohexyl group, perfluoroheptyl group, perfluorooctyl group, perfluorononanyl group, perfluorodecyl group, perfluoroundecyl group, perfluorododecyl group,
  • Examples of the optionally substituted aromatic hydrocarbon group represented by R 3 in the formula (2) include an unsubstituted aromatic hydrocarbon group, a halogen atom, an alkoxy group, an alkyl group, a trialkylsilyl group, and a trialkylgermyl group. And an aromatic hydrocarbon group substituted with.
  • the aromatic hydrocarbon group includes those having a condensed ring and those having two or more independent benzene rings or condensed rings bonded by a single bond or a divalent organic group.
  • the number of carbon atoms in the aromatic hydrocarbon group is usually 6 to 60, preferably 6 to 30, and more preferably 6 to 20.
  • aromatic hydrocarbon group examples include a phenyl group, a C 1 -C 12 alkoxyphenyl group, a C 1 -C 12 alkylphenyl group, a trialkylsilylphenyl group, a trialkylgermylphenyl group, and a 1-naphthyl group.
  • Examples of the optionally substituted aromatic heterocyclic group represented by R 3 in the formula (2) include a monovalent aromatic substituted with a substituent such as an unsubstituted monovalent aromatic heterocyclic group and an alkyl group. Heterocyclic group is mentioned.
  • the number of carbon atoms of the monovalent aromatic heterocyclic group is usually 4 to 60, preferably 4 to 30, and more preferably about 4 to 20, excluding the number of carbon atoms of the substituent. .
  • Examples of the monovalent aromatic heterocyclic group include thienyl group, C 1 to C 12 alkyl thienyl group, pyroyl group, furyl group, pyridyl group, C 1 to C 12 alkyl pyridyl group, pyridazyl group, pyrimidyl group, A pyrazinyl group etc. are mentioned.
  • trialkylsilyl group represented by R 3 in the formula (2) include trimethylsilyl group, triethylsilyl group, tri-isopropylsilyl group, dimethyl-isopropylsilyl group, diethyl-isopropylsilyl group, pentyldimethylsilyl group, hexyl.
  • Dimethylsilyl group Dimethylsilyl group, heptyldimethylsilyl group, octyldimethylsilyl group, octyldiethylsilyl group, 2-ethylhexyldimethylsilyl group, nonyldimethylsilyl group, decyldimethylsilyl group, 3,7-dimethyloctyl-dimethylsilyl group, dodecyldimethylsilyl group A trimethylsilyl group, a triethylsilyl group, a tri-isopropylsilyl group, a dimethyl-isopropylsilyl group, a diethyl-isopropylsilyl group, and more preferably a trimethylsilyl group.
  • Examples include a ryl group and a triethylsilyl group.
  • trialkylgermyl group represented by R 3 in the formula (2) include trimethylgermyl group, triethylgermyl group, tri-isopropylgermyl group, dimethyl-isopropylgermyl group, and diethyl-isopropylgermyl group.
  • Pentyldimethylgermyl group hexyldimethylgermyl group, heptyldimethylgermyl group, octyldimethylgermyl group, octyldiethylgermyl group, 2-ethylhexyldimethylgermyl group, nonyldimethylgermyl group, decyldimethylgermyl group 3,7-dimethyloctyl-dimethylgermyl group, dodecyldimethylgermyl group, etc., preferably trimethylgermyl group, triethylgermyl group, tri-isopropylgermyl group, dimethyl-isopropylgermyl group, Diethyl-isopropylgermi Group, more preferably a trimethylgermyl group and a triethylgermyl group.
  • R 3 is a hydrogen atom, a halogen atom, an optionally substituted alkyl group, or a trialkylsilyl. It is preferably a group, more preferably a hydrogen atom, a fluorine atom or a trimethylsilyl group, and even more preferably a trimethylsilyl group.
  • the polymer of the present invention may contain a repeating unit other than the repeating unit represented by the formula (1).
  • the content of the represented repeating unit is preferably 1% by weight or more, more preferably 10% by weight or more and 100% by weight or less, and more preferably 50% by weight or more and 100% by weight or less, based on all repeating units More preferably.
  • the content of the repeating unit represented by the formula (1) is preferably 20% by weight or more and 60% by weight or less with respect to all the repeating units.
  • the weight average molecular weight (M w ) of the polymer is preferably 1 ⁇ 10 3 or more and 5 ⁇ 10 7 or less, and preferably 1 ⁇ 10 4 or more and 2 ⁇ 10 7 or less. More preferably, it is 1 ⁇ 10 5 or more and 1 ⁇ 10 7 or less.
  • the number average molecular weight (M n ) of the polymer is preferably 1 ⁇ 10 3 or more and 2 ⁇ 10 7 or less, and preferably 1 ⁇ 10 4 or more and 1 ⁇ 10 7 or less. More preferably, it is 1 ⁇ 10 5 or more and 5 ⁇ 10 6 or less.
  • the dispersion ratio (M w / M n ) representing the degree of molecular weight distribution of the polymer is preferably 1.0 or more and 10.0 or less, and more preferably 1.1 or more and 8.0 or less. Preferably, it is 1.1 or more and 5.0 or less.
  • the weight average molecular weight (M w ), number average molecular weight (M n ) and dispersion ratio (M w / M n ) of the polymer are determined in terms of polystyrene by chromatography using tetrahydrofuran as a solvent. As the column, “GPC KF-807L” of Shodex KF-800 series may be used.
  • the 5% weight loss temperature (T d5 ) of the polymer is preferably 380 ° C. or more and 550 ° C. or less, more preferably 390 ° C. or more and 500 ° C. or less, and 400 More preferably, it is at least 490 ° C.
  • the 5% weight loss temperature of the polymer refers to a value measured by thermogravimetry (a differential heat / thermogravimetry apparatus, manufactured by Shimadzu Corporation, model: DTG-60 / 60H). The temperature elevation rate during measurement is 10 ° C./min, and the temperature is elevated in a nitrogen atmosphere.
  • the polymer of this invention since the said polymer has high oxygen / carbon dioxide selective permeability, it can expand
  • the polymer of the present invention has high oxygen permeability and is suitable for the following uses. (1) A refining device for producing air or oxygen obtained by removing carbon dioxide from air. (2) An air intake mechanism for an air cell or a fuel cell that takes in oxygen in the air to generate electric power.
  • the film thickness is not particularly limited, but from the viewpoint of suppressing the transmission of carbon dioxide and water vapor and ensuring oxygen permeability, it is preferably 0.1 ⁇ m or more and 100 ⁇ m or less. Preferably they are 0.1 micrometer or more and 50 micrometers or less.
  • the above-mentioned polymer is, for example, a method of polymerizing a monomer represented by the following formula (A) or a polymer obtained by polymerizing a monomer represented by the following formula (B), if necessary. It can be manufactured by a method of adding 2 or the like.
  • Polymerization of the monomers represented by the formulas (A) and (B) is performed, for example, by a method of reacting at 40 to 100 ° C. for 2 to 24 hours in the presence of a transition metal catalyst.
  • R 2 is, for example, a mixed solvent of (perfluoroalkyl) phenyliodonium trifluoromethanesulfonate with chloroform / acetonitrile. It is carried out by a method of immersing in
  • Tetra-n-butyltin (215 ⁇ L, 6.55 ⁇ 10 ⁇ 2 mmol) was added to a solution of tantalum pentachloride (143 mg, 0.399 mmol) in toluene (17.1 mL) under a nitrogen atmosphere, and the mixture was stirred at 80 ° C. for 10 minutes. did.
  • Separately prepared toluene solution (4.27 mL) of 4-trimethylsilyldiphenylacetylene (1.07 g, 4.27 mmol) was added to the above toluene solution and stirred at 80 ° C. for 3 hours to obtain product A.
  • the desired polymer was precipitated.
  • the precipitate was collected by filtration and dried under reduced pressure overnight to obtain a reddish brown polymer in a yield of 67.8% (0.725 g).
  • the obtained polymer was soluble in common organic solvents such as toluene, chloroform, and tetrahydrofuran (hereinafter sometimes referred to as “THF”).
  • THF tetrahydrofuran
  • M w 11.3 ⁇ 10 6
  • M n 5.89 ⁇ 10 6
  • Mw / Mn 1.92
  • T d5 399 ° C.
  • a toluene solution was prepared for the obtained polymer (1.0 wt%), cast into a glass petri dish, and the solvent was slowly evaporated at room temperature. After the solvent was evaporated and dried, the film was peeled off to obtain a self-supporting polymer film (polymer film of Example 1). The thickness of the polymer film determined by a micrometer was 69 ⁇ m.
  • the main reaction formula of Example 1 is shown below.
  • Example 2 Under a nitrogen atmosphere, tetra-n-butyltin (115 ⁇ L, 0.349 mmol) was added to a solution of tantalum pentachloride (62.5 mg, 0.175 mmol) in toluene (5 mL), and the mixture was stirred at 80 ° C. for 10 minutes. A separately prepared toluene solution (3.27 mL) of 4-trimethylsilylphenyl-2,5-difluorophenylacetylene (500 mg, 1.75 mmol) was added to the above toluene solution, and the mixture was stirred at 80 ° C. for 3 hours. Got.
  • the precipitate was collected by filtration and dried under reduced pressure overnight to obtain a reddish brown polymer in a yield of 75.6% (0.378 g).
  • the obtained polymer was soluble in common organic solvents such as toluene, chloroform and THF.
  • the 1 H NMR spectrum of the obtained polymer showed a very broad peak. In addition, it was difficult to observe 13 C NMR.
  • M w 2.6 ⁇ 10 6
  • M n 4.64 ⁇ 10 5
  • M w / M n 5.6
  • T d5 369 ° C.
  • a toluene solution was prepared for the obtained polymer (1.0 wt%), cast into a glass petri dish, and the solvent was slowly evaporated at room temperature. After the solvent was evaporated and dried, the film was peeled off to obtain a self-supporting polymer film.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Separation Using Semi-Permeable Membranes (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

Abstract

L'invention concerne un polymère comprenant des unités de répétition représenté par la formule (1).[Dans la formule (1), R1 représente un atome d'hydrogène, un atome halogène, un aryle éventuellement substitué, un groupe aromatique hydrocarboné éventuellement substitué, un groupe aromatique hétérocyclique éventuellement substitué, un trialkylsilyle ou un trialkylgermyle; R2 est représenté par la formule (3) (dans laquelle m est un nombre entier compris entre 0 et 5 et lorsqu'il existe deux R2 ou plus, ces R2 peuvent être identiques ou différents). Dans la formule (3), p est un nombre entier compris entre 5 et 15.]
PCT/JP2010/053810 2009-03-09 2010-03-08 Polymère WO2010104045A1 (fr)

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JP2009-055644 2009-03-09

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JPWO2020189675A1 (fr) * 2019-03-19 2020-09-24

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KR101601994B1 (ko) 2008-04-15 2016-03-17 에자이 알앤드디 매니지먼트 가부시키가이샤 3-페닐피라졸로[5,1-ｂ]티아졸 화합물

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JPH0259031A (ja) * 1988-08-25 1990-02-28 Sanyo Chem Ind Ltd 気体分離膜
JPH07278236A (ja) * 1994-04-15 1995-10-24 Sagami Chem Res Center 一置換アセチレンと二置換アセチレンとの共重合体の製造方法
JP2006265511A (ja) * 2005-02-25 2006-10-05 Kyoto Univ ハロゲン含有ポリ（ジフェニルアセチレン）誘導体およびハロゲン含有ジフェニルアセチレン化合物

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JPS60166309A (ja) * 1984-02-09 1985-08-29 Agency Of Ind Science & Technol フツ素またはトリフルオロメチル基を有するポリフエニルアセチレン類
JPH0259031A (ja) * 1988-08-25 1990-02-28 Sanyo Chem Ind Ltd 気体分離膜
JPH07278236A (ja) * 1994-04-15 1995-10-24 Sagami Chem Res Center 一置換アセチレンと二置換アセチレンとの共重合体の製造方法
JP2006265511A (ja) * 2005-02-25 2006-10-05 Kyoto Univ ハロゲン含有ポリ（ジフェニルアセチレン）誘導体およびハロゲン含有ジフェニルアセチレン化合物

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SEKI, HIROYUKI ET AL.: "Polymerization of [o-n-(perfluorohexyl)phenyl]acetylene and polymer properties", JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY, vol. 33, no. 11, 1995, pages 1907 - 1912 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020189675A1 (fr) * 2019-03-19 2020-09-24
WO2020189675A1 (fr) * 2019-03-19 2020-09-24 フィガロ技研株式会社 Capteur de gaz
JP7107494B2 (ja) 2019-03-19 2022-07-27 フィガロ技研株式会社 ガス検出器

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