JP6839125B2 - 生体電極組成物、生体電極、及び生体電極の製造方法 - Google Patents
生体電極組成物、生体電極、及び生体電極の製造方法 Download PDFInfo
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- JP6839125B2 JP6839125B2 JP2018070818A JP2018070818A JP6839125B2 JP 6839125 B2 JP6839125 B2 JP 6839125B2 JP 2018070818 A JP2018070818 A JP 2018070818A JP 2018070818 A JP2018070818 A JP 2018070818A JP 6839125 B2 JP6839125 B2 JP 6839125B2
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- IPENDKRRWFURRE-UHFFFAOYSA-N fluoroimide Chemical compound C1=CC(F)=CC=C1N1C(=O)C(Cl)=C(Cl)C1=O IPENDKRRWFURRE-UHFFFAOYSA-N 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
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- 238000007646 gravure printing Methods 0.000 description 1
- 235000019382 gum benzoic Nutrition 0.000 description 1
- 238000013007 heat curing Methods 0.000 description 1
- WZHKDGJSXCTSCK-UHFFFAOYSA-N hept-3-ene Chemical compound CCCC=CCC WZHKDGJSXCTSCK-UHFFFAOYSA-N 0.000 description 1
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- YUWFEBAXEOLKSG-UHFFFAOYSA-N hexamethylbenzene Chemical compound CC1=C(C)C(C)=C(C)C(C)=C1C YUWFEBAXEOLKSG-UHFFFAOYSA-N 0.000 description 1
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 description 1
- BNRNAKTVFSZAFA-UHFFFAOYSA-N hydrindane Chemical compound C1CCCC2CCCC21 BNRNAKTVFSZAFA-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical class I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- ICIWUVCWSCSTAQ-UHFFFAOYSA-M iodate Chemical compound [O-]I(=O)=O ICIWUVCWSCSTAQ-UHFFFAOYSA-M 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- KXUHSQYYJYAXGZ-UHFFFAOYSA-N isobutylbenzene Chemical compound CC(C)CC1=CC=CC=C1 KXUHSQYYJYAXGZ-UHFFFAOYSA-N 0.000 description 1
- 239000005453 ketone based solvent Substances 0.000 description 1
- 229940087305 limonene Drugs 0.000 description 1
- 235000001510 limonene Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- QUEBYVKXYIKVSO-UHFFFAOYSA-N m-propyltoluene Chemical compound CCCC1=CC=CC(C)=C1 QUEBYVKXYIKVSO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 1
- GHDIHPNJQVDFBL-UHFFFAOYSA-N methoxycyclohexane Chemical compound COC1CCCCC1 GHDIHPNJQVDFBL-UHFFFAOYSA-N 0.000 description 1
- SKTCDJAMAYNROS-UHFFFAOYSA-N methoxycyclopentane Chemical compound COC1CCCC1 SKTCDJAMAYNROS-UHFFFAOYSA-N 0.000 description 1
- BDJSOPWXYLFTNW-UHFFFAOYSA-N methyl 3-methoxypropanoate Chemical compound COCCC(=O)OC BDJSOPWXYLFTNW-UHFFFAOYSA-N 0.000 description 1
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 1
- YULMNMJFAZWLLN-UHFFFAOYSA-N methylenecyclohexane Chemical compound C=C1CCCCC1 YULMNMJFAZWLLN-UHFFFAOYSA-N 0.000 description 1
- WPHGSKGZRAQSGP-UHFFFAOYSA-N methylenecyclohexane Natural products C1CCCC2CC21 WPHGSKGZRAQSGP-UHFFFAOYSA-N 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- YNAVUWVOSKDBBP-UHFFFAOYSA-O morpholinium Chemical compound [H+].C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-O 0.000 description 1
- 239000002048 multi walled nanotube Substances 0.000 description 1
- WVFLGSMUPMVNTQ-UHFFFAOYSA-N n-(2-hydroxyethyl)-2-[[1-(2-hydroxyethylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound OCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCO WVFLGSMUPMVNTQ-UHFFFAOYSA-N 0.000 description 1
- SFLRURCEBYIKSS-UHFFFAOYSA-N n-butyl-2-[[1-(butylamino)-2-methyl-1-oxopropan-2-yl]diazenyl]-2-methylpropanamide Chemical compound CCCCNC(=O)C(C)(C)N=NC(C)(C)C(=O)NCCCC SFLRURCEBYIKSS-UHFFFAOYSA-N 0.000 description 1
- 229940094933 n-dodecane Drugs 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- IICQZTQZQSBHBY-UHFFFAOYSA-N non-2-ene Chemical compound CCCCCCC=CC IICQZTQZQSBHBY-UHFFFAOYSA-N 0.000 description 1
- YCBSHDKATAPNIA-UHFFFAOYSA-N non-3-ene Chemical compound CCCCCC=CCC YCBSHDKATAPNIA-UHFFFAOYSA-N 0.000 description 1
- KPADFPAILITQBG-UHFFFAOYSA-N non-4-ene Chemical compound CCCCC=CCCC KPADFPAILITQBG-UHFFFAOYSA-N 0.000 description 1
- JFNLZVQOOSMTJK-KNVOCYPGSA-N norbornene Chemical compound C1[C@@H]2CC[C@H]1C=C2 JFNLZVQOOSMTJK-KNVOCYPGSA-N 0.000 description 1
- IRUCBBFNLDIMIK-UHFFFAOYSA-N oct-4-ene Chemical compound CCCC=CCCC IRUCBBFNLDIMIK-UHFFFAOYSA-N 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- AICOOMRHRUFYCM-ZRRPKQBOSA-N oxazine, 1 Chemical compound C([C@@H]1[C@H](C(C[C@]2(C)[C@@H]([C@H](C)N(C)C)[C@H](O)C[C@]21C)=O)CC1=CC2)C[C@H]1[C@@]1(C)[C@H]2N=C(C(C)C)OC1 AICOOMRHRUFYCM-ZRRPKQBOSA-N 0.000 description 1
- AHHWIHXENZJRFG-UHFFFAOYSA-N oxetane Chemical compound C1COC1 AHHWIHXENZJRFG-UHFFFAOYSA-N 0.000 description 1
- 125000000466 oxiranyl group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- CFJYNSNXFXLKNS-UHFFFAOYSA-N p-menthane Chemical compound CC(C)C1CCC(C)CC1 CFJYNSNXFXLKNS-UHFFFAOYSA-N 0.000 description 1
- 230000037368 penetrate the skin Effects 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- BEZDDPMMPIDMGJ-UHFFFAOYSA-N pentamethylbenzene Chemical compound CC1=CC(C)=C(C)C(C)=C1C BEZDDPMMPIDMGJ-UHFFFAOYSA-N 0.000 description 1
- WQIQNKQYEUMPBM-UHFFFAOYSA-N pentamethylcyclopentadiene Chemical compound CC1C(C)=C(C)C(C)=C1C WQIQNKQYEUMPBM-UHFFFAOYSA-N 0.000 description 1
- HLTMUYBTNSVOFY-UHFFFAOYSA-N pentylcyclohexane Chemical compound CCCCCC1CCCCC1 HLTMUYBTNSVOFY-UHFFFAOYSA-N 0.000 description 1
- HPQURZRDYMUHJI-UHFFFAOYSA-N pentylcyclopentane Chemical compound CCCCCC1CCCC1 HPQURZRDYMUHJI-UHFFFAOYSA-N 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-O phosphonium Chemical compound [PH4+] XYFCBTPGUUZFHI-UHFFFAOYSA-O 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910001414 potassium ion Inorganic materials 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-O pyridinium Chemical compound C1=CC=[NH+]C=C1 JUJWROOIHBZHMG-UHFFFAOYSA-O 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000005871 repellent Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- ZJMWRROPUADPEA-UHFFFAOYSA-N sec-butylbenzene Chemical compound CCC(C)C1=CC=CC=C1 ZJMWRROPUADPEA-UHFFFAOYSA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 229930006978 terpinene Natural products 0.000 description 1
- 150000003507 terpinene derivatives Chemical class 0.000 description 1
- WMOVHXAZOJBABW-UHFFFAOYSA-N tert-butyl acetate Chemical compound CC(=O)OC(C)(C)C WMOVHXAZOJBABW-UHFFFAOYSA-N 0.000 description 1
- JAELLLITIZHOGQ-UHFFFAOYSA-N tert-butyl propanoate Chemical compound CCC(=O)OC(C)(C)C JAELLLITIZHOGQ-UHFFFAOYSA-N 0.000 description 1
- XTVMZZBLCLWBPM-UHFFFAOYSA-N tert-butylcyclohexane Chemical compound CC(C)(C)C1CCCCC1 XTVMZZBLCLWBPM-UHFFFAOYSA-N 0.000 description 1
- LPSXSORODABQKT-UHFFFAOYSA-N tetrahydrodicyclopentadiene Chemical compound C1C2CCC1C1C2CCC1 LPSXSORODABQKT-UHFFFAOYSA-N 0.000 description 1
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 description 1
- JNRUXZIXAXHXTN-UHFFFAOYSA-N trimethyl(2-methylbut-3-yn-2-yloxy)silane Chemical compound C#CC(C)(C)O[Si](C)(C)C JNRUXZIXAXHXTN-UHFFFAOYSA-N 0.000 description 1
- NWMVPLQDJXJDEW-UHFFFAOYSA-N trimethyl(3-methylpent-1-yn-3-yloxy)silane Chemical compound CCC(C)(C#C)O[Si](C)(C)C NWMVPLQDJXJDEW-UHFFFAOYSA-N 0.000 description 1
- JABYJIQOLGWMQW-UHFFFAOYSA-N undec-4-ene Chemical compound CCCCCCC=CCCC JABYJIQOLGWMQW-UHFFFAOYSA-N 0.000 description 1
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 1
- 229920003169 water-soluble polymer Polymers 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
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- A61B5/25—Bioelectric electrodes therefor
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
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- A61L31/14—Materials characterised by their function or physical properties, e.g. injectable or lubricating compositions, shape-memory materials, surface modified materials
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- C—CHEMISTRY; METALLURGY
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- A61L31/00—Materials for other surgical articles, e.g. stents, stent-grafts, shunts, surgical drapes, guide wires, materials for adhesion prevention, occluding devices, surgical gloves, tissue fixation devices
- A61L31/04—Macromolecular materials
- A61L31/041—Mixtures of macromolecular compounds
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- H—ELECTRICITY
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/06—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances
- H01B1/12—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of other non-metallic substances organic substances
- H01B1/122—Ionic conductors
Landscapes
- Health & Medical Sciences (AREA)
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- Chemical & Material Sciences (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- General Health & Medical Sciences (AREA)
- Heart & Thoracic Surgery (AREA)
- Surgery (AREA)
- Animal Behavior & Ethology (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
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- Pathology (AREA)
- Physics & Mathematics (AREA)
- Biomedical Technology (AREA)
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- Molecular Biology (AREA)
- Nanotechnology (AREA)
- Materials Engineering (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Radiology & Medical Imaging (AREA)
- Dermatology (AREA)
- Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Cell Electrode Carriers And Collectors (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Description
(A)イオン性材料、及び
(B)前記(A)成分以外の樹脂
を含有する生体電極組成物であって、
前記(A)成分が、フルオロスルホン酸、フルオロスルホンイミド、及びフルオロスルホンアミドのうちのいずれかの銀塩の構造を有する繰り返し単位aと、珪素を有する繰り返し単位bの両方を有するものである生体電極組成物を提供する。
(A)イオン性材料、及び
(B)前記(A)成分以外の樹脂
を含有する生体電極組成物であって、
前記(A)成分が、フルオロスルホン酸、フルオロスルホンイミド、及びフルオロスルホンアミドのうちのいずれかの銀塩の構造を有する繰り返し単位aと、珪素を有する繰り返し単位bの両方を有するものである生体電極組成物である。
本発明の生体電極組成物は、(A)イオン性材料及び(B)(A)成分以外の樹脂を含有するものである。以下、各成分について、更に詳細に説明する。
本発明の生体電極組成物に(A)イオン性材料として配合されるポリマー型の塩の有する、フルオロスルホン酸、フルオロスルホンイミド、フルオロスルホンアミドのうちのいずれかの銀塩の構造を有する繰り返し単位aが下記一般式(1)−1〜(1)−4で示される構造をいずれか1つ以上有するものであることが好ましい。
本発明の生体電極組成物の(A)成分としては、下記一般式(2)で示される繰り返し単位a1〜a7から選ばれる1種以上を含むものであることが好ましい。
本発明の生体電極組成物の(A)成分は、上記の繰り返し単位aに加えて、珪素を有する繰り返し単位bを有する。
本発明の生体電極組成物の(A)成分には、上記の繰り返し単位a、bに加えて、下記一般式(4)記載のアルキル基を有する繰り返し単位cを共重合することが出来る。
本発明の生体電極組成物に配合される(B)成分は、上記の(A)イオン性材料(塩)と相溶して塩の溶出を防ぎ、カーボン等の導電性向上剤を保持し、粘着性を発現させるための成分である。なお、(B)成分は、上述の(A)成分以外の樹脂であればよく、熱硬化性樹脂及び光硬化性樹脂のいずれか、又はこれらの両方であることが好ましく、特には、シリコーン系、アクリル系、及びウレタン系の樹脂から選ばれる1種以上であることが好ましい。
また、本発明の生体電極組成物には、生体に対する粘着性を付与するために、粘着性付与剤を添加してもよい。このような粘着性付与剤としては、例えば、シリコーンレジンや非架橋性のシロキサン、非架橋性のポリ(メタ)アクリレート、非架橋性のポリエーテル等を挙げることができる。
また、本発明の生体電極組成物には、有機溶剤を添加することができる。有機溶剤としては、具体的には、トルエン、キシレン、クメン、1,2,3−トリメチルベンゼン、1,2,4−トリメチルベンゼン、1,3,5−トリメチルベンゼン、スチレン、αメチルスチレン、ブチルベンゼン、sec−ブチルベンゼン、イソブチルベンゼン、シメン、ジエチルベンゼン、2−エチル−p−キシレン、2−プロピルトルエン、3−プロピルトルエン、4−プロピルトルエン、1,2,3,5−テトラメチルトルエン、1,2,4,5−テトラメチルトルエン、テトラヒドロナフタレン、4−フェニル−1−ブテン、tert−アミルベンゼン、アミルベンゼン、2−tert−ブチルトルエン、3−tert−ブチルトルエン、4−tert−ブチルトルエン、5−イソプロピル−m−キシレン、3−メチルエチルベンゼン、tert−ブチル−3−エチルベンゼン、4−tert−ブチル−o−キシレン、5−tert−ブチル−m−キシレン、tert−ブチル−p−キシレン、1,2−ジイソプロピルベンゼン、1,3−ジイソプロピルベンゼン、1,4−ジイソプロピルベンゼン、ジプロピルベンゼン、3,9−ドデカジイン、ペンタメチルベンゼン、ヘキサメチルベンゼン、ヘキシルベンゼン、1,3,5−トリエチルベンゼン等の芳香族系炭化水素系溶剤、n−ヘプタン、イソヘプタン、3−メチルヘキサン、2,3−ジメチルペンタン、3−エチルペンタン、1,6−ヘプタジエン、5−メチル−1−ヘキシン、ノルボルナン、ノルボルネン、ジシクロペンタジエン、1−メチル−1,4−シクロヘキサジエン、1−ヘプチン、2−ヘプチン、シクロヘプタン、シクロヘプテン、1,3−ジメチルシクロペンタン、エチルシクロペンタン、メチルシクロヘキサン、1−メチル−1−シクロヘキセン、3−メチル−1−シクロヘキセン、メチレンシクロヘキサン、4−メチル−1−シクロヘキセン、2−メチル−1−ヘキセン、2−メチル−2−ヘキセン、1−ヘプテン、2−ヘプテン、3−ヘプテン、n−オクタン、2,2−ジメチルヘキサン、2,3−ジメチルヘキサン、2,4−ジメチルヘキサン、2,5−ジメチルヘキサン、3,3−ジメチルヘキサン、3,4−ジメチルヘキサン、3−エチル−2−メチルペンタン、3−エチル−3−メチルペンタン、2−メチルヘプタン、3−メチルヘプタン、4−メチルヘプタン、2,2,3−トリメチルペンタン、2,2,4−トリメチルペンタン、シクロオクタン、シクロオクテン、1,2−ジメチルシクロヘキサン、1,3−ジメチルシクロヘキサン、1,4−ジメチルシクロヘキサン、エチルシクロヘキサン、ビニルシクロヘキサン、イソプロピルシクロペンタン、2,2−ジメチル−3−ヘキセン、2,4−ジメチル−1−ヘキセン、2,5−ジメチル−1−ヘキセン、2,5−ジメチル−2−ヘキセン、3,3−ジメチル−1−ヘキセン、3,4−ジメチル−1−ヘキセン、4,4−ジメチル−1−ヘキセン、2−エチル−1−ヘキセン、2−メチル−1−ヘプテン、1−オクテン、2−オクテン、3−オクテン、4−オクテン、1,7−オクタジエン、1−オクチン、2−オクチン、3−オクチン、4−オクチン、n−ノナン、2,3−ジメチルヘプタン、2,4−ジメチルヘプタン、2,5−ジメチルヘプタン、3,3−ジメチルヘプタン、3,4−ジメチルヘプタン、3,5−ジメチルヘプタン、4−エチルヘプタン、2−メチルオクタン、3−メチルオクタン、4−メチルオクタン、2,2,4,4−テトラメチルペンタン、2,2,4−トリメチルヘキサン、2,2,5−トリメチルヘキサン、2,2−ジメチル−3−ヘプテン、2,3−ジメチル−3−ヘプテン、2,4−ジメチル−1−ヘプテン、2,6−ジメチル−1−ヘプテン、2,6−ジメチル−3−ヘプテン、3,5−ジメチル−3−ヘプテン、2,4,4−トリメチル−1−ヘキセン、3,5,5−トリメチル−1−ヘキセン、1−エチル−2−メチルシクロヘキサン、1−エチル−3−メチルシクロヘキサン、1−エチル−4−メチルシクロヘキサン、プロピルシクロヘキサン、イソプロピルシクロヘキサン、1,1,3−トリメチルシクロヘキサン、1,1,4−トリメチルシクロヘキサン、1,2,3−トリメチルシクロヘキサン、1,2,4−トリメチルシクロヘキサン、1,3,5−トリメチルシクロヘキサン、アリルシクロヘキサン、ヒドリンダン、1,8−ノナジエン、1−ノニン、2−ノニン、3−ノニン、4−ノニン、1−ノネン、2−ノネン、3−ノネン、4―ノネン、n−デカン、3,3−ジメチルオクタン、3,5−ジメチルオクタン、4,4−ジメチルオクタン、3−エチル−3−メチルヘプタン、2−メチルノナン、3−メチルノナン、4−メチルノナン、tert−ブチルシクロヘキサン、ブチルシクロヘキサン、イソブチルシクロヘキサン、4−イソプロピル−1−メチルシクロヘキサン、ペンチルシクロペンタン、1,1,3,5−テトラメチルシクロヘキサン、シクロドデカン、1−デセン、2−デセン、3−デセン、4−デセン、5−デセン、1,9−デカジエン、デカヒドロナフタレン、1−デシン、2−デシン、3−デシン、4−デシン、5−デシン、1,5,9−デカトリエン、2,6−ジメチル−2,4,6−オクタトリエン、リモネン、ミルセン、1,2,3,4,5−ペンタメチルシクロペンタジエン、α−フェランドレン、ピネン、テルピネン、テトラヒドロジシクロペンタジエン、5,6−ジヒドロジシクロペンタジエン、1,4−デカジイン、1,5−デカジイン、1,9−デカジイン、2,8−デカジイン、4,6−デカジイン、n−ウンデカン、アミルシクロヘキサン、1−ウンデセン、1,10−ウンデカジエン、1−ウンデシン、3−ウンデシン、5−ウンデシン、トリシクロ[6.2.1.02,7]ウンデカ−4−エン、n−ドデカン、2−メチルウンデカン、3−メチルウンデカン、4−メチルウンデカン、5−メチルウンデカン、2,2,4,6,6−ペンタメチルヘプタン、1,3−ジメチルアダマンタン、1−エチルアダマンタン、1,5,9−シクロドデカトリエン、1,2,4−トリビニルシクロヘキサン、イソパラフィン等の脂肪族炭化水素系溶剤、シクロヘキサノン、シクロペンタノン、2−オクタノン、2−ノナノン、2−ヘプタノン、3−ヘプタノン、4−ヘプタノン、2−ヘキサノン、3−ヘキサノン、ジイソブチルケトン、メチルシクロヘキサノン、メチルn−ペンチルケトン等のケトン系溶剤、3−メトキシブタノール、3−メチル−3−メトキシブタノール、1−メトキシ−2−プロパノール、1−エトキシ−2−プロパノール等のアルコール系溶剤、プロピレングリコールモノメチルエーテル、エチレングリコールモノメチルエーテル、プロピレングリコールモノエチルエーテル、エチレングリコールモノエチルエーテル、プロピレングリコールジメチルエーテル、ジエチレングリコールジメチルエーテル、ジイソプロピルエーテル、ジイソブチルエーテル、ジイソペンチルエーテル、ジ−n−ペンチルエーテル、メチルシクロペンチルエーテル、メチルシクロヘキシルエーテル、ジ−n−ブチルエーテル、ジ−secブチルエーテル、ジ−sec−ペンチルエーテル、ジ−tert−アミルエーテル、ジ−n−ヘキシルエーテル、アニソール等のエーテル系溶剤、プロピレングリコールモノメチルエーテルアセテート、プロピレングリコールモノエチルエーテルアセテート、乳酸エチル、ピルビン酸エチル、酢酸ブチル、3−メトキシプロピオン酸メチル、3−エトキシプロピオン酸エチル、酢酸tert−ブチル、プロピオン酸tert−ブチル、プロピレングリコールモノtert−ブチルエーテルアセテート等のエステル系溶剤、γ−ブチロラクトン等のラクトン系溶剤などを挙げることができる。
本発明の生体電極組成物には、導電性を更に高めるために、導電性向上剤として、カーボン材料を添加することができる。カーボン材料としては、カーボンブラック、カーボンナノチューブ、炭素繊維等を挙げることができる。カーボンナノチューブは単層、多層のいずれであってもよく、表面が有機基で修飾されていても構わない。カーボン材料の添加量は、樹脂100質量部に対して1〜50質量部の範囲とすることが好ましい。
また、本発明の生体電極組成物には、カーボン材料以外の導電性向上剤を添加することもできる。具体的には、樹脂を金、銀、白金等の貴金属でコートした粒子や繊維、ナノワイヤー、あるいは、金、銀、白金等のナノ粒子、インジウムスズの酸化物(ITO)、インジウム亜鉛酸化物(IZO)、スズ酸化物、亜鉛酸化物等の金属酸化物の粒子などを挙げることができる。
また、本発明では、導電性基材と該導電性基材上に形成された生体接触層とを有する生体電極であって、前記生体接触層が、上述の本発明の生体電極組成物の硬化物である生体電極を提供する。
本発明の生体電極は、導電性基材を有するものである。この導電性基材は、通常、センサーデバイス等と電気的に接続されており、生体から生体接触層を介して取り出した電気信号をセンサーデバイス等まで伝導させる。
本発明の生体電極は、導電性基材上に形成された生体接触層を有するものである。この生体接触層は、生体電極を使用する際に、実際に生体と接触する部分であり、導電性及び粘着性を有する。生体接触層は、上述の本発明の生体電極組成物の硬化物であり、即ち、上述の(A)イオン性材料(塩)及び(B)樹脂、更には必要に応じてカーボン材料等の添加剤を含有する粘着性の樹脂層である。
また、本発明では、導電性基材と該導電性基材上に形成された生体接触層とを有する生体電極の製造方法であって、前記導電性基材上に、上述の本発明の生体電極組成物を塗布し、硬化させることで前記生体接触層を形成する生体電極の製造方法を提供する。
Mw=36,400
Mw/Mn=2.11
Mw=21,700
Mw/Mn=1.91
Mw=46,700
Mw/Mn=1.84
Mw=29,600
Mw/Mn=1.88
Mw=78,100
Mw/Mn=4.1
Mw=25,100
Mw/Mn=1.86
Mw=56,300
Mw/Mn=2.10
Mw=43,300
Mw/Mn=1.98
Mw=67,800
Mw/Mn=2.05
Mw=78,300
Mw/Mn=2.11
Mw=116,000、Mw/Mn=2.20
Mw=44,900
Mw/Mn=2.59
Mw=57,900
Mw/Mn=1.89
(シロキサン化合物1)
30%トルエン溶液での粘度が27,000mPa・sであり、アルケニル基含有量が0.007モル/100gであり、分子鎖末端がSiMe2Vi基で封鎖されたビニル基含有ポリジメチルシロキサンをシロキサン化合物1とした。
(シロキサン化合物2)
Me3SiO0.5単位及びSiO2単位からなるMQレジンのポリシロキサン(Me3SiO0.5単位/SiO2単位=0.8)の60%トルエン溶液をシロキサン化合物2とした。
(シロキサン化合物3)
30%トルエン溶液での粘度が42,000mPa・sであり、アルケニル基含有量が0.007モル/100gであり、分子鎖末端がOHで封鎖されたビニル基含有ポリジメチルシロキサン40質量部、Me3SiO0.5単位及びSiO2単位からなるMQレジンのポリシロキサン(Me3SiO0.5単位/SiO2単位=0.8)の60%トルエン溶液100質量部、及びトルエン26.7質量部からなる溶液を乾留させながら4時間加熱後、冷却して、MQレジンにポリジメチルシロキサンを結合させたものをシロキサン化合物3とした。
(シロキサン化合物4)
メチルハイドロジェンシリコーンオイルとして、信越化学工業製 KF−99を用いた。
アクリルポリマー1
Mw=108,000
Mw/Mn=2.32
PGMEA:プロピレングリコール−1−モノメチルエーテル−2−アセテート
PGME:プロピレングリコール−1−モノメチルエーテル
PGEE:プロピレングリコール−1−モノエチルエーテル
ラジカル発生剤:和光純薬工業社製 V−601
白金触媒:信越化学工業製 CAT−PL−50T
カーボンブラック:デンカ社製 デンカブラックHS−100
多層カーボンナノチューブ:Sigma−Aldrich社製 直径110〜170nm、長さ5〜9μmのもの
金コート粒子:積水化学社製 ミクロパールAU(直径100μm)
銀コート粒子:三菱マテリアル社製 銀コート粉(直径30μm)
ITO粒子:三菱マテリアル社製 ITO粉(直径0.03μm)
表1及び表2に記載の組成で、イオン性材料(塩)、樹脂、有機溶剤、及び添加剤(ラジカル発生剤、白金触媒、導電性向上剤)をブレンドし、生体電極組成物溶液(生体電極組成物溶液1〜14、比較生体電極組成物溶液1〜8)を調製した。
直径3cm、厚さ0.2mmのアルミニウム製の円板の上にアプリケーターを用いて生体電極組成物溶液を塗布し、室温で6時間風乾した後、オーブンを用いて窒素雰囲気下120℃で30分間ベークして硬化させて、1つの生体電極組成物溶液につき生体電極を4枚作製した。このようにして得られた生体電極は、図3(a)、(b)に示されるように、一方の面には生体接触層3を有し、他方の面には導電性基材としてアルミニウム製の円板8を有するものであった。次に、図3(b)に示されるように、生体接触層で覆われていない側のアルミニウム製の円板8の表面に銅配線9を粘着テープで貼り付けて引き出し電極とし、これをインピーダンス測定装置に接続した。図4に示されるように、人の腕の肌と生体接触層側が接触するように生体電極1’を2枚貼り付けて、その間隔を15cmとした。ソーラトロン社製の交流インピーダンス測定装置SI1260を用い、周波数を変えながら初期インピーダンスを測定した。次に、残りの2枚の生体電極を純水中に1時間浸積し、水を乾燥させた後、上記と同様の方法で肌上のインピーダンスを測定した。周波数1,000Hzにおけるインピーダンスを表3に示す。
生体電極組成物溶液を、アプリケーターを用いて厚さ100μmのPEN(ポリエチレンナフタレート)基板上に塗布し、室温で6時間風乾後、オーブンを用いて窒素雰囲気下120℃で30分間ベークして硬化させて、粘着フィルムを作製した。この粘着フィルムから25mm幅のテープを切り取り、これをステンレス版(SUS304)に圧着させ、室温で20時間放置した後、引っ張り試験機を用い角度180度、300mm/分の速度で粘着フィルムから作製したテープをステンレス版から引きはがすのに要する力(N/25mm)を測定した。結果を表3に示す。
上記の導電性評価試験で作製した生体電極において、生体接触層の厚さをマイクロメーターを用いて測定した。結果を表3に示す。
4…イオン性ポリマー(イオン性材料)、 5…カーボン材料、
6…樹脂((A)成分以外の樹脂)、 7…生体、 8…アルミニウム製の円板、
9…銅配線。
Claims (12)
- (A)イオン性材料、及び
(B)前記(A)成分以外の樹脂
を含有する生体電極組成物であって、
前記(A)成分が、フルオロスルホン酸、フルオロスルホンイミド、及びフルオロスルホンアミドのうちのいずれかの銀塩の構造を有する繰り返し単位aと、珪素を有する繰り返し単位bの両方を有するものであることを特徴とする生体電極組成物。 - 前記繰り返し単位aが、下記一般式(1)−1〜(1)−4で示される構造をいずれか1つ以上有するものであることを特徴とする請求項1に記載の生体電極組成物。
- 前記(A)成分が、繰り返し単位aとして、下記一般式(2)で示される繰り返し単位a1〜a7から選ばれる1種以上を、前記繰り返し単位bとして、下記一般式(3)で示される繰り返し単位b1を含むものであることを特徴とする請求項1又は請求項2に記載の生体電極組成物。
- 前記(A)成分が、前記繰り返し単位a、bに加えて、下記一般式(4)で示される繰り返し単位cを有するものであることを特徴とする請求項1から請求項3のいずれか一項に記載の生体電極組成物。
- 前記(B)成分が、RxSiO(4−x)/2単位(Rは炭素数1〜10の置換又は非置換の一価炭化水素基、xは2.5〜3.5の範囲である。)及びSiO2単位を有するシリコーン樹脂、アルケニル基を有するジオルガノシロキサン、並びにSiH基を有するオルガノハイドロジェンポリシロキサンを含有するものであることを特徴とする請求項1から請求項4のいずれか一項に記載の生体電極組成物。
- 前記生体電極組成物が、更に有機溶剤を含有するものであることを特徴とする請求項1から請求項5のいずれか一項に記載の生体電極組成物。
- 前記生体電極組成物が、更にカーボン材料を含有するものであることを特徴とする請求項1から請求項6のいずれか一項に記載の生体電極組成物。
- 前記カーボン材料が、カーボンブラック及びカーボンナノチューブのいずれか又は両方であることを特徴とする請求項7に記載の生体電極組成物。
- 導電性基材と該導電性基材上に形成された生体接触層とを有する生体電極であって、
前記生体接触層が、請求項1から請求項8のいずれか一項に記載の生体電極組成物の硬化物であることを特徴とする生体電極。 - 前記導電性基材が、金、銀、塩化銀、白金、アルミニウム、マグネシウム、スズ、タングステン、鉄、銅、ニッケル、ステンレス、クロム、チタン、及び炭素から選ばれる1種以上を含むものであることを特徴とする請求項9に記載の生体電極。
- 導電性基材と該導電性基材上に形成された生体接触層とを有する生体電極の製造方法であって、
前記導電性基材上に、請求項1から請求項8のいずれか一項に記載の生体電極組成物を塗布し、硬化させることで前記生体接触層を形成することを特徴とする生体電極の製造方法。 - 前記導電性基材として、金、銀、塩化銀、白金、アルミニウム、マグネシウム、スズ、タングステン、鉄、銅、ニッケル、ステンレス、クロム、チタン、及び炭素から選ばれる1種以上を含むものを用いることを特徴とする請求項11に記載の生体電極の製造方法。
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