JP2021085852A - Electrode for enzyme sensor and enzyme sensor - Google Patents
Electrode for enzyme sensor and enzyme sensor Download PDFInfo
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- JP2021085852A JP2021085852A JP2019217267A JP2019217267A JP2021085852A JP 2021085852 A JP2021085852 A JP 2021085852A JP 2019217267 A JP2019217267 A JP 2019217267A JP 2019217267 A JP2019217267 A JP 2019217267A JP 2021085852 A JP2021085852 A JP 2021085852A
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- conductive layer
- electrode
- graphite
- conductive
- enzyme sensor
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Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
Description
本発明は、酵素センサー用電極及び酵素センサーに関する。 The present invention relates to electrodes for enzyme sensors and enzyme sensors.
血液や汗等の生体試料や食品等に含まれる特定成分を、簡便に計測する酵素センサーが実用化されている。例えば、血液中のグルコースを電気化学的な手段により検出、あるいは定量化する血糖値センサー等が挙げられる。これは血中に含まれるグルコースに対し酵素の基質特異性により選択的に酸化し、メディエーターを介して、あるいは直接電極に電荷が到達して電流が発生、その電流値からグルコース濃度を定量することができる。
実用化されている酵素センサーにおける電極部分は、スパッタやめっき等により金属層が形成されたものが用いられることがある（例えば特許文献１）。しかし、その測定感度は未だ十分とは言い難い状況であり、高価な金属を使用しないことは腐食やコストの観点からも好ましい。
Enzyme sensors that easily measure specific components contained in biological samples such as blood and sweat and foods have been put into practical use. For example, a blood glucose level sensor that detects or quantifies glucose in blood by an electrochemical means can be mentioned. This is to selectively oxidize glucose contained in blood by the substrate specificity of the enzyme, and the electric charge reaches the electrode through the mediator or directly to generate an electric current, and the glucose concentration is quantified from the electric current value. Can be done.
As the electrode portion of the enzyme sensor that has been put into practical use, one in which a metal layer is formed by sputtering, plating, or the like may be used (for example, Patent Document 1). However, the measurement sensitivity is still not sufficient, and it is preferable not to use an expensive metal from the viewpoint of corrosion and cost.
本発明の目的は、感度に優れ、更に腐食への耐性やコストに優れる酵素センサー用電極および酵素センサーを提供することである。 An object of the present invention is to provide an electrode for an enzyme sensor and an enzyme sensor, which are excellent in sensitivity, resistance to corrosion, and cost.
本発明者らは、前記課題を解決すべく検討を重ねた結果、本発明に至った。
すなわち、本発明は、基材上に配置された導電層と、酸化還元酵素とを含有する電極であって、前記導電層が導電性の炭素材料（Ａ）とバインダー（Ｂ）とを含み、炭素材料（Ａ）が少なくとも黒鉛（Ａ−ａ）と黒鉛以外の導電性の炭素材料（Ａ−ｂ）とを含み、前記導電層の表面の６０°光沢が０．５〜１２０である、酵素センサー用電極に関する。
The present inventors have reached the present invention as a result of repeated studies to solve the above problems.
That is, the present invention is an electrode containing a conductive layer arranged on a substrate and an oxidation-reducing enzyme, wherein the conductive layer contains a conductive carbon material (A) and a binder (B). An enzyme in which the carbon material (A) contains at least graphite (Aa) and a conductive carbon material (Ab) other than graphite, and the surface of the conductive layer has a 60 ° gloss of 0.5 to 120. Regarding electrodes for sensors.
また、本発明は、前記導電層の比表面積が５〜８００ｍ２／ｇである前記の酵素センサー用電極に関する。 The present invention also relates to the enzyme sensor electrode having a specific surface area of 5 to 800 m 2 / g of the conductive layer.
また、本発明は、バインダー（Ｂ）が、水溶性樹脂（Ｂ−ａ）および／または水分散樹脂微粒子（Ｂ−ｂ）である前記の酵素センサー用電極に関する。 The present invention also relates to the above-mentioned electrode for an enzyme sensor in which the binder (B) is a water-soluble resin (B-a) and / or water-dispersed resin fine particles (B-b).
また、本発明は、導電層の固形分の合計１００質量％中の炭素材料（Ａ）の含有率が５０〜９０質量％であり、炭素材料（Ａ）に含まれる黒鉛（Ａ−ａ）の含有率（（Ａ−ａ）／（Ａ）×１００）が２５〜９５質量％である前記の酵素センサー用電極に関する。 Further, in the present invention, the content of the carbon material (A) in the total solid content of the conductive layer of 100% by mass is 50 to 90% by mass, and the content of the graphite (Aa) contained in the carbon material (A) is 50 to 90% by mass. The present invention relates to the above-mentioned electrode for an enzyme sensor having a content ((A) / (A) × 100) of 25 to 95% by mass.
また、本発明は、前記の酵素センサー用電極を用いて形成される酵素センサーに関する。 The present invention also relates to an enzyme sensor formed by using the above-mentioned electrode for an enzyme sensor.
本発明によれば、感度に優れ、更に腐食への耐性やコストに優れる酵素センサー用電極および酵素センサーを提供することができる。 According to the present invention, it is possible to provide an electrode for an enzyme sensor and an enzyme sensor which are excellent in sensitivity, resistance to corrosion and cost.
＜酵素センサー用電極＞
本発明の酵素センサー用電極は、少なくとも基材上に配置された導電層と酸化還元酵素からなる。例えば、紙やＰＥＴ（ポリエチレンテレフタラート）フィルム等の基材の少なくとも片側の表面に、導電性の炭素材料（Ａ）とバインダー（Ｂ）と、必要に応じて溶剤とを含有する導電性組成物を塗工、必要に応じてプレス処理等を行って、導電層を形成した後、酸化還元酵素を担持して電極を得ることができる。
<Electrodes for enzyme sensors>
The electrode for an enzyme sensor of the present invention comprises at least a conductive layer arranged on a substrate and an oxidoreductase. For example, a conductive composition containing a conductive carbon material (A), a binder (B), and a solvent, if necessary, on the surface of at least one side of a base material such as paper or PET (polyethylene terephthalate) film. Is applied, and if necessary, a press treatment or the like is performed to form a conductive layer, and then an oxidoreductase is supported to obtain an electrode.
＜導電層＞
（導電性の炭素材料（Ａ））
本発明において、使い捨て性や生体適合性等の観点から、導電性材料として導電性の炭素材料（Ａ）を用いる。導電性の炭素材料（Ａ）としては、導電性に優れた導電層を得られることから、黒鉛（Ａ−ａ）や黒鉛以外の導電性の炭素材料（Ａ−ｂ）とを含有する。
黒鉛（Ａ−ａ）としては、人造黒鉛や天然黒鉛等が挙げられ、黒鉛以外の炭素材料（Ａ−ｂ）としては、カーボンブラック、導電性炭素繊維（カーボンナノチューブ、カーボンナノファイバー、カーボンファイバー）、グラフェン、フラーレン等が挙げられる。これらを単独で、もしくは２種類以上併せて使用することが出来る。
<Conductive layer>
(Conductive carbon material (A))
In the present invention, the conductive carbon material (A) is used as the conductive material from the viewpoint of disposableness, biocompatibility and the like. As the conductive carbon material (A), since a conductive layer having excellent conductivity can be obtained, it contains graphite (Aa) and a conductive carbon material (Ab) other than graphite.
Examples of graphite (Aa) include artificial graphite and natural graphite, and examples of carbon materials (Ab) other than graphite include carbon black and conductive carbon fibers (carbon nanotubes, carbon nanofibers, carbon fibers). , Graphene, fullerene and the like. These can be used alone or in combination of two or more.
導電層に含まれる導電性の炭素材料（Ａ）に含まれる黒鉛（Ａ−ａ）の含有率（（Ａ−ａ）／（Ａ）×１００）は、好ましくは２５〜９５質量％であり、より好ましくは５０〜９０質量％であり、さらに好ましくは６０〜８０質量％である。 The content of graphite (A-a) contained in the conductive carbon material (A) contained in the conductive layer ((A-a) / (A) x 100) is preferably 25 to 95% by mass. It is more preferably 50 to 90% by mass, and even more preferably 60 to 80% by mass.
黒鉛（Ａ−ａ）としては、例えば人造黒鉛や天然黒鉛等を使用することが出来る。人造黒鉛としては、無定形炭素の熱処理により、不規則な配列の微小黒鉛結晶の配向を人工的に行わせたものであり、一般的には石油コークスや石炭系ピッチコークスを主原料として製造される。天然黒鉛としては、球形黒鉛、鱗片状黒鉛、塊状黒鉛、土状黒鉛等を使用することが出来る。また、鱗片状黒鉛を化学処理等した膨張黒鉛（膨張性黒鉛ともいう）や、膨張黒鉛を熱処理して膨張化させた後、微細化やプレスにより得られた膨張化黒鉛等を使用することも出来る。これらの黒鉛の中でも、導電性基材の導電層に用いる場合は、導電性の観点から、天然黒鉛が好ましく、球形黒鉛、鱗片状黒鉛膨張化黒鉛、および薄片化黒鉛等の薄片状黒鉛が好ましい。 As the graphite (Aa), for example, artificial graphite, natural graphite, or the like can be used. Artificial graphite is made by artificially orienting irregularly arranged micrographite crystals by heat treatment of amorphous carbon, and is generally manufactured using petroleum coke or coal-based pitch coke as the main raw material. To. As the natural graphite, spherical graphite, scaly graphite, lump graphite, earth graphite and the like can be used. It is also possible to use expanded graphite (also referred to as expansive graphite) obtained by chemically treating scaly graphite, or expanded graphite obtained by heat-treating expanded graphite to expand it and then refining it or pressing it. You can. Among these graphites, when used for the conductive layer of the conductive base material, natural graphite is preferable from the viewpoint of conductivity, and flaky graphite such as spherical graphite, scaly graphite expanded graphite, and flaky graphite is preferable. ..
また、用いる黒鉛（Ａ−ａ）の平均粒径は、０．５〜５００μｍが好ましく、特に、２〜１００μｍが好ましい。 The average particle size of the graphite (Aa) used is preferably 0.5 to 500 μm, and particularly preferably 2 to 100 μm.
本発明でいう平均粒径とは、体積粒度分布において、粒子径の細かいものからその粒子の体積割合を積算していったときに、５０％となるところの粒子径（Ｄ５０）であり、一般的な粒度分布計、例えば、動的光散乱方式の粒度分布計（日機装社製「マイクロトラックＵＰＡ」）等で測定される。 The average particle size referred to in the present invention is a particle size (D50) that becomes 50% when the volume ratio of the particles is integrated from the fine particle size distribution in the volume particle size distribution, and is generally used. It is measured with a standard particle size distribution meter, for example, a dynamic light scattering type particle size distribution meter (“Microtrack UPA” manufactured by Nikkiso Co., Ltd.).
市販の黒鉛としては、例えば、薄片状黒鉛として、日本黒鉛工業社製のＣＭＸ、ＵＰ−５、ＵＰ−１０、ＵＰ−２０、ＵＰ−３５Ｎ、ＣＳＳＰ、ＣＳＰＥ、ＣＳＰ、ＣＰ、ＣＢ−１５０、ＣＢ−１００、ＡＣＰ、ＡＣＰ−１０００、ＡＣＢ−５０、ＡＣＢ−１００、ＡＣＢ−１５０、ＳＰ−１０、ＳＰ−２０、Ｊ−ＳＰ、ＳＰ−２７０、ＨＯＰ、ＧＲ−６０、ＬＥＰ、Ｆ＃１、Ｆ＃２、Ｆ＃３、中越黒鉛社製のＣＸ−３０００、ＦＢＦ、ＢＦ、ＣＢＲ、ＳＳＣ−３０００、ＳＳＣ−６００、ＳＳＣ−３、ＳＳＣ、ＣＸ−６００、ＣＰＦ−８、ＣＰＦ−３、ＣＰＢ−６Ｓ、ＣＰＢ、９６Ｅ、９６Ｌ、９６Ｌ−３、９０Ｌ−３、ＣＰＣ、Ｓ−８７、Ｋ−３、ＣＦ−８０、ＣＦ−４８、ＣＦ−３２、ＣＰ−１５０、ＣＰ−１００、ＣＰ、ＨＦ−８０、ＨＦ−４８、ＨＦ−３２、ＳＣ−１２０、ＳＣ−８０、ＳＣ−６０、ＳＣ−３２、伊藤黒鉛工業社製のＥＣ１５００、ＥＣ１０００、ＥＣ５００、ＥＣ３００、ＥＣ１００、ＥＣ５０、西村黒鉛社製の１００９９Ｍ、ＰＢ−９９等が挙げられる。球状天然黒鉛としては、日本黒鉛工業社製のＣＧＣ−２０、ＣＧＣ−５０、ＣＧＢ−２０、ＣＧＢ−５０が挙げられる。土状黒鉛としては、日本黒鉛工業社製の青Ｐ、ＡＰ、ＡＯＰ、Ｐ＃１、中越黒鉛社製のＡＰＲ、Ｓ−３、ＡＰ−６、３００Ｆが挙げられる。人造黒鉛としては、日本黒鉛工業社製のＰＡＧ−６０、ＰＡＧ−８０、ＰＡＧ−１２０、ＰＡＧ−５、ＨＡＧ−１０Ｗ、ＨＡＧ−１５０、中越黒鉛社製のＲＡ−３０００、ＲＡ−１５、ＲＡ−４４、ＧＸ−６００、Ｇ−６Ｓ、Ｇ−３、Ｇ−１５０、Ｇ−１００、Ｇ−４８、Ｇ−３０、Ｇ−５０、ＳＥＣカーボン社製のＳＧＰ−１００、ＳＧＰ−５０、ＳＧＰ−２５、ＳＧＰ−１５、ＳＧＰ−５、ＳＧＰ−１、ＳＧＯ−１００、ＳＧＯ−５０、ＳＧＯ−２５、ＳＧＯ−１５、ＳＧＯ−５、ＳＧＯ−１、ＳＧＸ−１００、ＳＧＸ−５０、ＳＧＸ−２５、ＳＧＸ−１５、ＳＧＸ−５、ＳＧＸ−１が挙げられる。 As commercially available graphite, for example, as flaky graphite, CMX, UP-5, UP-10, UP-20, UP-35N, CSSP, CSPE, CSP, CP, CB-150, CB manufactured by Nippon Graphite Industry Co., Ltd. -100, ACP, ACP-1000, ACB-50, ACB-100, ACB-150, SP-10, SP-20, J-SP, SP-270, HOP, GR-60, LEP, F # 1, F # 2, F # 3, CX-3000, FBF, BF, CBR, SSC-3000, SSC-600, SSC-3, SSC, CX-600, CPF-8, CPF-3, CPB- manufactured by Chuetsu Graphite Co., Ltd. 6S, CPB, 96E, 96L, 96L-3, 90L-3, CPC, S-87, K-3, CF-80, CF-48, CF-32, CP-150, CP-100, CP, HF- 80, HF-48, HF-32, SC-120, SC-80, SC-60, SC-32, EC1500, EC1000, EC500, EC300, EC100, EC50 manufactured by Ito Graphite Industry Co., Ltd. 10099M manufactured by Nishimura Graphite Co., Ltd. , PB-99 and the like. Examples of spherical natural graphite include CGC-20, CGC-50, CGB-20, and CGB-50 manufactured by Nippon Graphite Industry Co., Ltd. Examples of earth-like graphite include blue P, AP, AOP, P # 1 manufactured by Nippon Graphite Industry Co., Ltd., and APR, S-3, AP-6, 300F manufactured by Chuetsu Graphite Co., Ltd. As artificial graphite, PAG-60, PAG-80, PAG-120, PAG-5, HAG-10W, HAG-150 manufactured by Nippon Graphite Industry Co., Ltd., RA-3000, RA-15, RA- of Chuetsu Graphite Co., Ltd. 44, GX-600, G-6S, G-3, G-150, G-100, G-48, G-30, G-50, SGP-100, SGP-50, SGP-25 manufactured by SEC Carbon Co., Ltd. , SGP-15, SGP-5, SGP-1, SGO-100, SGO-50, SGO-25, SGO-15, SGO-5, SGO-1, SGX-100, SGX-50, SGX-25, SGX -15, SGX-5, SGX-1 can be mentioned.
黒鉛以外の導電性の炭素材料（Ａ−ｂ）は特に限定されないが、コストや導電性などの観点から、カーボンブラックや導電性炭素繊維を用いることが好ましい。 The conductive carbon material (Ab) other than graphite is not particularly limited, but it is preferable to use carbon black or conductive carbon fiber from the viewpoint of cost and conductivity.
カーボンブラックとしては、気体もしくは液体の原料を反応炉中で連続的に熱分解し製造するファーネスブラック、特にエチレン重油を原料としたケッチェンブラック、原料ガスを燃焼させて、その炎をチャンネル鋼底面にあて急冷し析出させたチャンネルブラック、ガスを原料とし燃焼と熱分解を周期的に繰り返すことにより得られるサーマルブラック、特にアセチレンガスを原料とするアセチレンブラックなどの各種のものを単独で、もしくは２種類以上併せて使用することができる。また、通常行われている酸化処理されたカーボンブラックや、中空カーボン等も使用できる。
カーボンの酸化処理は、カーボンを空気中で高温処理したり、硝酸や二酸化窒素、オゾン等で二次的に処理したりすることより、例えばフェノール基、キノン基、カルボキシル基、カルボニル基の様な酸素含有極性官能基をカーボン表面に直接導入（共有結合）する処理であり、カーボンの分散性を向上させるために一般的に行われている。
Carbon black includes furnace black, which is produced by continuously pyrolyzing a gas or liquid raw material in a reactor, especially acetylene black, which is made from ethylene heavy oil, and the raw material gas is burned to burn the flame to the bottom of the channel steel. Various types such as channel black that has been rapidly cooled and precipitated, thermal black that is obtained by periodically repeating combustion and thermal decomposition using gas as a raw material, and acetylene black that uses acetylene gas as a raw material, alone or 2 More than one type can be used together. In addition, normally oxidized carbon black, hollow carbon, and the like can also be used.
Oxidation treatment of carbon is performed by treating carbon at a high temperature in air or secondary treatment with nitrate, nitrogen dioxide, ozone, etc., for example, phenol group, quinone group, carboxyl group, carbonyl group, etc. It is a process of directly introducing (covalently bonding) an oxygen-containing polar functional group to the carbon surface, and is generally performed to improve the dispersibility of carbon.
用いるカーボンブラックの比表面積は、値が大きいほど、カーボンブラック粒子どうしの接触点が増えるため、電極の内部抵抗を下げるのに有利となる。具体的には、窒素の吸着量から求められる比表面積（ＢＥＴ）で、好ましくは２０ｍ2／ｇ以上、更に好ましくは５０ｍ2／ｇ以上、また更に好ましくは１００ｍ2／ｇ以上のものを使用することが望ましい。比表面積が２０ｍ2／ｇを下回るカーボンブラックを用いると、十分な導電性を得ることが難しくなる場合がある。
また、用いるカーボンブラックの粒径は、一次粒子径で０．００５〜１μｍが好ましく、特に、０．０１〜０．２μｍが好ましい。ただし、ここでいう一次粒子径とは、電子顕微鏡などで測定された粒子径を平均したものである。
As the specific surface area of the carbon black used increases, the contact points between the carbon black particles increase, which is advantageous in reducing the internal resistance of the electrode. Specifically, the specific surface area (BET) obtained from the amount of nitrogen adsorbed is preferably 20 m 2 / g or more, more preferably 50 m 2 / g or more, and even more preferably 100 m 2 / g or more. Is desirable. If carbon black having a specific surface area of less than 20 m 2 / g is used, it may be difficult to obtain sufficient conductivity.
The particle size of the carbon black used is preferably 0.005 to 1 μm in terms of primary particle size, and particularly preferably 0.01 to 0.2 μm. However, the primary particle size referred to here is an average of the particle sizes measured by an electron microscope or the like.
市販のカーボンブラックとしては、例えば、東海カーボン社製のトーカブラック＃４３００、＃４４００、＃４５００、＃５５００、デグサ社製のプリンテックスＬ、コロンビヤン社製のＲａｖｅｎ７０００、５７５０、５２５０、５０００ＵＬＴＲＡIII、５０００ＵＬＴＲＡ、Ｃｏｎｄｕｃｔｅｘ ＳＣ ＵＬＴＲＡ、Ｃｏｎｄｕｃｔｅｘ ９７５ ＵＬＴＲＡ、ＰＵＥＲＢＬＡＣＫ１００、１１５、２０５、三菱化学社製の＃２３５０、＃２４００Ｂ、＃２６００Ｂ、＃３０５０Ｂ、＃３０３０Ｂ、＃３２３０Ｂ、＃３３５０Ｂ、＃３４００Ｂ、＃５４００Ｂ、キャボット社製のＭＯＮＡＲＣＨ１４００、１３００、９００、ＶｕｌｃａｎＸＣ−７２Ｒ、ＢｌａｃｋＰｅａｒｌｓ２０００、ＴＩＭＣＡＬ社製のＥｎｓａｃｏ２５０Ｇ、Ｅｎｓａｃｏ２６０Ｇ、Ｅｎｓａｃｏ３５０Ｇ、ＳｕｐｅｒＰ−Ｌｉ等のファーネスブラック）、ライオン・スペシャリティ・ケミカルズ社製のＥＣ−２００Ｌ、ＥＣ−３００Ｊ、ＥＣ−６００ＪＤ等のケッチェンブラック、デンカ社製のデンカブラック、デンカブラックＨＳ−１００、ＦＸ−３５等のアセチレンブラックが挙げられるが、これらに限定されるものではなく、２種以上を組み合わせて用いても良い。 Commercially available carbon blacks include, for example, Tokai Carbon's Toka Black # 4300, # 4400, # 4500, # 5500, Degussa's Printex L, Colombian's Raven 7000, 5750, 5250, 5000 ULTRAIII, 5000 ULTRA, etc. Conductex SC ULTRA, Conductex 975 ULTRA, PUERBLACK100, 115, 205, Mitsubishi Chemicals # 2350, # 2400B, # 2600B, # 3050B, # 3030B, # 3230B, # 3350B, # 3400B, # 5400B, Cabot MONARCH1400, 1300, 900, VulcanXC-72R, BlackPearls2000, Ensaco250G, Ensaco260G, Ensaco350G, SuperP-Li, etc. , Etc., Denka Black manufactured by Denka Co., Ltd., Denka Black HS-100, FX-35 and other acetylene blacks, but the present invention is not limited to these, and two or more types may be used in combination. ..
導電性炭素繊維としては石油由来の原料から焼成して得られるものが良いが、植物由来の原料からも焼成して得られるものも用いることが出来る。また、カーボンナノチューブには、グラフェンシートが一層でナノメートル領域の直径を有するチューブを形成する単層カーボンナノチューブと、グラフェンシートが多層である多層カーボンナノチューブがある。そのため、多層カーボンナノチューブの直径は、典型的な単層カーボンナノチューブの０．７−２．０ｎｍに対して、３０ｎｍと大きい値を示す。 As the conductive carbon fiber, those obtained by firing from a raw material derived from petroleum are preferable, but those obtained by firing from a raw material derived from a plant can also be used. Further, the carbon nanotubes include a single-walled carbon nanotube in which a graphene sheet forms a tube having a diameter in a nanometer region, and a multi-walled carbon nanotube in which the graphene sheet is a multi-walled layer. Therefore, the diameter of the multi-walled carbon nanotube shows a large value of 30 nm with respect to 0.7-2.0 nm of a typical single-walled carbon nanotube.
市販の導電性炭素繊維やカーボンナノチューブとしては、昭和電工社製のＶＧＣＦ等の気相法炭素繊維、名城ナノカーボン社製のＥＣ１．０，ＥＣ１．５，ＥＣ２．０，ＥＣ１．５−Ｐ等の単層カーボンナノチューブ、ＣＮａｎｏ社製のＦｌｏＴｕｂｅ９０００、ＦｌｏＴｕｂｅ９１００、ＦｌｏＴｕｂｅ９１１０、ＦｌｏＴｕｂｅ９２００、Ｎａｎｏｃｙｌ社製のＮＣ７０００、Ｋｎａｎｏ社製の１００Ｔ等が挙げられる。 Commercially available conductive carbon fibers and carbon nanotubes include vapor-phase carbon fibers such as VGCF manufactured by Showa Denko Co., Ltd., EC1.0, EC1.5, EC2.0, EC1.5-P manufactured by Meijo Nanocarbon Co., Ltd., etc. Examples thereof include single-walled carbon nanotubes manufactured by CNano, FloTube9100, FloTube9100, FloTube9110, FloTube9200, NC7000 manufactured by Nanocyl, and 100T manufactured by Knano.
（バインダー（Ｂ））
バインダー（Ｂ）の種類は、導電性の炭素材料（Ａ）の分散性や基材への密着性、導電性基材の可とう性および導電性組成物の安定性を付与できるものであれば特に制限されず、樹脂等が挙げられる。
(Binder (B))
The type of the binder (B) is such that it can impart the dispersibility of the conductive carbon material (A), the adhesion to the base material, the flexibility of the conductive base material, and the stability of the conductive composition. The present invention is not particularly limited, and examples thereof include resins.
バインダー（Ｂ）としては、ポリウレタン系樹脂、ポリアミド系樹脂、アクリロニトリル系樹脂、アクリル系樹脂、ブタジエン系樹脂、ポリビニル系樹脂、ポリビニルブチラール系樹脂、ポリオレフィン系樹脂、ポリエステル系樹脂、ポリスチレン系樹脂、ＥＶＡ系樹脂、ポリフッ化ビニリデン系樹脂、ポリテトラフルオロエチレン系樹脂、シリコーン系樹脂、ポリエーテル系樹脂、カルボキシメチルセルロース等のセルロース系樹脂等からなる群から選ばれる１種類以上を含むことができる。ただし、これらの樹脂に限定されるわけではない。バインダー樹脂は１種単独で用いても良く、２種以上併用しても良い。 Examples of the binder (B) include polyurethane resin, polyamide resin, acrylonitrile resin, acrylic resin, butadiene resin, polyvinyl resin, polyvinyl butyral resin, polyolefin resin, polyester resin, polystyrene resin, and EVA resin. It can contain one or more kinds selected from the group consisting of resins, polyvinylidene fluoride-based resins, polytetrafluoroethylene-based resins, silicone-based resins, polyether-based resins, cellulose-based resins such as carboxymethyl cellulose, and the like. However, it is not limited to these resins. The binder resin may be used alone or in combination of two or more.
バインダー樹脂は、バインダー樹脂が基材に適用された後に、硬化（架橋）反応を受ける、硬化性樹脂を用いることもできる。
バインダー樹脂は、水系または非水系溶剤に溶解する溶解性樹脂や分散型樹脂微粒子を用いることもできる。分散型樹脂微粒子は、樹脂微粒子が水系または非水系の分散媒中で溶解せずに、微粒子の状態で存在するもので、その分散体は、一般的にエマルジョンとも呼ばれる。これらは１種単独で用いても良く、２種以上併用しても良い。
As the binder resin, a curable resin that undergoes a curing (crosslinking) reaction after the binder resin is applied to the base material can also be used.
As the binder resin, a soluble resin or dispersed resin fine particles that are soluble in an aqueous or non-aqueous solvent can also be used. Dispersed resin fine particles are those in which the resin fine particles are not dissolved in an aqueous or non-aqueous dispersion medium and exist in the state of fine particles, and the dispersion is also generally called an emulsion. These may be used alone or in combination of two or more.
分散型樹脂微粒子の粒子構造は、多層構造、いわゆるコアシェル粒子にすることもできる。例えば、コア部、またはシェル部に缶応期を有する単量体を主に重合させた樹脂を局在化させたり、コアとシェルによってＴｇや組成に差を設けたりすることにより、硬化性、乾燥性、成膜性、バインダーの機械強度を向上させることができる。
樹脂微粒子の平均粒子径は、結着性や粒子の安定性の観点から、１０〜１０００ｎｍであることが好ましく、１０〜３００ｎｍであることが好ましい。なお、本発明における平均粒子径とは、体積平均粒子径のことを表し、動的光散乱法により測定できる。
動的光散乱法による平均粒子径の測定は、以下のようにして行うことができる。樹脂微粒子の固形分に応じて、分散媒と同じ分散液で２００〜１０００倍に希釈しておく。該希釈分散液約５ｍｌを測定装置（日機装社製名黒トラック）のセルに注入し、サンプルに応じた分散媒および樹脂の屈折率条件を入力後、測定を行う。この時得られた体積粒子径分布データ（ヒストグラム）のピークによって測定することができる。
また、グルコースオキシダーゼ（ＧＯｘ）などの酵素は水系溶液に分散したものを担持する場合が多く、グルコースなどの燃料は水系溶剤に溶解されたものとする場合が多いことから、濡れ性や浸透性などの観点から、バインダー（Ｂ）としては、水系溶剤に溶解可能な水溶性樹脂（Ｂ−ａ）や水系の分散媒中で溶解せずに、微粒子の状態で存在する水分散樹脂微粒子（Ｂ−ｂ）を使用することが好ましい。
The particle structure of the dispersed resin fine particles may be a multilayer structure, so-called core-shell particles. For example, by localizing a resin obtained by mainly polymerizing a monomer having a can response period in the core portion or the shell portion, or by providing a difference in Tg and composition between the core and the shell, the curability and drying can be achieved. It is possible to improve the property, film forming property, and mechanical strength of the binder.
The average particle size of the resin fine particles is preferably 10 to 1000 nm, preferably 10 to 300 nm, from the viewpoint of binding properties and particle stability. The average particle size in the present invention represents the volume average particle size and can be measured by a dynamic light scattering method.
The average particle size can be measured by the dynamic light scattering method as follows. Dilute 200 to 1000 times with the same dispersion as the dispersion medium, depending on the solid content of the resin fine particles. Approximately 5 ml of the diluted dispersion is injected into a cell of a measuring device (name black truck manufactured by Nikkiso Co., Ltd.), the refractive index conditions of the dispersion medium and the resin corresponding to the sample are input, and then the measurement is performed. It can be measured by the peak of the volume particle size distribution data (histogram) obtained at this time.
In addition, enzymes such as glucose oxidase (GOx) often carry those dispersed in an aqueous solution, and fuels such as glucose are often dissolved in an aqueous solvent. From the viewpoint of the above, the binder (B) is a water-soluble resin (BA) that is soluble in an aqueous solvent or an aqueous dispersion resin fine particle (B-) that exists in the state of fine particles without being dissolved in an aqueous dispersion medium. b) is preferably used.
水溶性樹脂とはしては、ポリビニル系樹脂やポリウレタン系樹脂、ポリエステル系樹脂、ポリエーテル系樹脂、カルボキシメチルセルロース等のセルロース系樹脂、ホルマリン縮合物、シリコーン系樹脂、及びこれらの複合系樹脂等が挙げられる。更に、これら２種類以上を併用してもよい。 Examples of the water-soluble resin include polyvinyl-based resins, polyurethane-based resins, polyester-based resins, polyether-based resins, cellulose-based resins such as carboxymethyl cellulose, formalin condensates, silicone-based resins, and composite resins thereof. Can be mentioned. Further, these two or more types may be used in combination.
水分散樹脂微粒子としては、（メタ）アクリル系エマルション、ニトリル系エマルション、ウレタン系エマルション、ポリオレフィン系エマルション、フッ素系エマルション（ポリフッ化ビニリデン（ＰＶＤＦ）やポリテトラフルオロエチレン（ＰＴＦＥ）など）、スチレン―ブタジエン系樹脂等が挙げられる。
なお、（メタ）アクリルは、メタクリルまたはアクリルを意味する。
Examples of the water-dispersed resin fine particles include (meth) acrylic emulsion, nitrile emulsion, urethane emulsion, polyolefin emulsion, fluorine emulsion (polyvinylidene fluoride (PVDF), polytetrafluoroethylene (PTFE), etc.), and styrene-butadiene. Examples include system resins.
In addition, (meth) acrylic means methacrylic or acrylic.
導電性組成物のスラリー安定性や塗工性、導電層の耐水性や可とう性等の観点から、水溶性樹脂（Ｂ−ａ）と水分散樹脂微粒子（Ｂ−ｂ）を併用することがさらに好ましい。 From the viewpoints of slurry stability and coatability of the conductive composition, water resistance and flexibility of the conductive layer, etc., the water-soluble resin (BA) and the water-dispersed resin fine particles (B-b) can be used in combination. More preferred.
（溶剤（分散媒））
導電性の炭素材料（Ａ）と、バインダー（Ｂ）とを均一に混合する場合、溶剤を適宜用いることが出来る。そのような溶剤としては、樹脂を溶解できるものや、樹脂微粒子エマルションを安定に分散できるものであれば特に限定されず、水や有機溶剤を挙げることが出来る。
(Solvent (dispersion medium))
When the conductive carbon material (A) and the binder (B) are uniformly mixed, a solvent can be appropriately used. The solvent is not particularly limited as long as it can dissolve the resin or stably disperse the resin fine particle emulsion, and examples thereof include water and an organic solvent.
有機溶剤は、メタノール、エタノール、プロパノール、ブタノール、エチレングリコールメチルエーテル、ジエチレングリコールメチルエーテル等のアルコール類、アセトン、メチルエチルケトン、メチルイソブチルケトン、シクロヘキサノン等のケトン類、テトラヒドロフラン、ジオキサン、エチ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等のエーテル類、ヘキサン、ヘプタン、オクタン等の炭化水素類、ベンゼン、トルエン、キシレン、クメン等の芳香族類、酢酸エチル、酢酸ブチル等のエステル類などの内から導電性組成物の組成に応じ適当なものが使用できる。
また、溶剤は水と有機溶剤または有機溶剤を２種以上用いてもよい。
Organic solvents include alcohols such as methanol, ethanol, propanol, butanol, ethylene glycol methyl ether and diethylene glycol methyl ether, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether and the like. Suitable for the composition of the conductive composition from among ethers, hydrocarbons such as hexane, heptane and octane, aromatics such as benzene, toluene, xylene and cumene, and esters such as ethyl acetate and butyl acetate. Can be used.
Further, as the solvent, water and an organic solvent or two or more kinds of organic solvents may be used.
また、本発明に用いる導電性組成物には、必要に応じて、本発明による効果を妨げない範囲で、紫外線吸収剤、紫外線安定剤、ラジカル補足剤、充填剤、チクソトロピー付与剤、老化防止剤、酸化防止剤、帯電防止剤、難燃剤、熱伝導性改良剤、可塑剤、ダレ防止剤、防汚剤、防腐剤、殺菌剤、消泡剤、レベリング剤、ブロッキング防止剤、硬化剤、増粘剤、顔料分散剤、シランカップリング剤等の各種の添加剤を添加してもよい。 Further, the conductive composition used in the present invention contains, if necessary, an ultraviolet absorber, an ultraviolet stabilizer, a radical catching agent, a filler, a thixotropy-imparting agent, and an antistatic agent as long as the effects of the present invention are not impaired. , Antioxidant, Antistatic, Flame Retardant, Thermal Conductivity Improver, Plasticizer, Anti-Dripping Agent, Antifouling Agent, Preservative, Bactericide, Defoamer, Leveling Agent, Anti-blocking Agent, Hardener, Increase Various additives such as thickeners, pigment dispersants, and silane coupling agents may be added.
（導電性組成物）
導電性組成物は導電性の炭素材料（Ａ）とバインダー（Ｂ）と必要に応じて溶媒（分散媒）を含有し、分散機や混合機などを用いてスラリー化（塗料化、インキ化）したものである。
(Conductive composition)
The conductive composition contains a conductive carbon material (A), a binder (B), and a solvent (dispersion medium) as necessary, and is made into a slurry (paint or ink) using a disperser or a mixer. It was done.
導電性組成物の粘度は、導電性組成物の塗工方式によるが、一般的には、１０ｍＰａ・ｓ以上、３０，０００ｍＰａ・ｓ以下とすることが好ましい。 The viscosity of the conductive composition depends on the coating method of the conductive composition, but is generally preferably 10 mPa · s or more and 30,000 mPa · s or less.
（分散機・混合機）
導電性組成物を得る際に用いられる装置としては、顔料分散等に通常用いられている分散機、混合機が使用できる。
(Disperser / Mixer)
As an apparatus used for obtaining the conductive composition, a disperser or a mixer usually used for pigment dispersion or the like can be used.
例えば、ディスパー、ホモミキサー、若しくはプラネタリーミキサー等のミキサー類；エム・テクニック社製「クレアミックス」、若しくはＰＲＩＭＩＸ社「フィルミックス」等のホモジナイザー類；ペイントコンディショナー（レッドデビル社製）、ボールミル、サンドミル（シンマルエンタープライゼス社製「ダイノミル」等）、アトライター、パールミル（アイリッヒ社製「ＤＣＰミル」等）、若しくはコボールミル等のメディア型分散機；湿式ジェットミル（ジーナス社製「ジーナスＰＹ」、スギノマシン社製「スターバースト」、ナノマイザー社製「ナノマイザー」等）、エム・テクニック社製「クレアＳＳ−５」、若しくは奈良機械社製「ＭＩＣＲＯＳ」等のメディアレス分散機；または、その他ロールミル等が挙げられるが、これらに限定されるものではない。 For example, mixers such as disper, homomixer, or planetary mixer; homogenizers such as "Clearmix" manufactured by M-Technique or "Philmix" manufactured by PRIMIX; paint conditioner (manufactured by Red Devil), ball mill, sand mill. (Symmal Enterprises "Dyno Mill" etc.), Atwriter, Pearl Mill (Eirich "DCP Mill" etc.), or media type disperser such as Coball Mill; Wet Jet Mill (Genus "Genus PY", Sugino) Medialess dispersers such as Machine's "Starburst", Nanomizer's "Nanomizer"), M-Technique's "Claire SS-5", or Nara Machinery's "MICROS"; or other roll mills, etc. However, it is not limited to these.
例えば、メディア型分散機を使用する場合は、アジテーター及びベッセルがセラミック製又は樹脂製の分散機を使用する方法や、金属製アジテーター及びベッセル表面をタングステンカーバイド溶射や樹脂コーティング等の処理をした分散機を用いることが好ましい。そして、メディアとしては、ガラスビーズ、または、ジルコニアビーズ、若しくはアルミナビーズ等のセラミックビーズを用いることが好ましい。分散装置は、１種のみを使用しても良いし、複数種の装置を組み合わせて使用しても良い。 For example, when using a media-type disperser, a method in which the agitator and vessel use a disperser made of ceramic or resin, or a disperser in which the surface of the metal agitator and vessel is treated with tungsten carbide spraying or resin coating. Is preferably used. As the medium, it is preferable to use glass beads, zirconia beads, or ceramic beads such as alumina beads. Only one type of dispersion device may be used, or a plurality of types of devices may be used in combination.
（導電層の形成）
前記した基材に、導電性組成物を塗工、必要に応じてプレス処理等を行って、導電層を形成することができる。
基材上に導電性組成物を塗工する方法としては、特に制限はなく公知の方法を用いることができる。
(Formation of conductive layer)
A conductive layer can be formed by applying a conductive composition to the above-mentioned base material and, if necessary, performing a press treatment or the like.
The method for coating the conductive composition on the base material is not particularly limited, and a known method can be used.
具体的には、ダイコーティング法、ディップコーティング法、ロールコーティング法、ドクターコーティング法、ナイフコーティング法、スプレーコティング法、グラビアコーティング法、スクリーン印刷法または静電塗装法等が挙げる事ができ、乾燥方法としては放置乾燥、送風乾燥機、温風乾燥機、赤外線加熱機、遠赤外線加熱機などが使用できるが、特にこれらに限定されるものではない。 Specific examples include a die coating method, a dip coating method, a roll coating method, a doctor coating method, a knife coating method, a spray coating method, a gravure coating method, a screen printing method, an electrostatic coating method, and the like, and drying. As the method, a neglected drying, a blower dryer, a warm air dryer, an infrared heater, a far infrared heater and the like can be used, but the method is not particularly limited thereto.
また、塗布後に平版プレスやカレンダーロール等による圧延処理を行ってもよく、導電層を軟化させてプレスしやすくするため、加熱しながら行ってもよい。導電層の厚みは、一般的には０．１μｍ以上、１ｍｍ以下であり、好ましくは１μｍ以上、２００μｍ以下である。 Further, after coating, a rolling process such as a planographic press or a calendar roll may be performed, or may be performed while heating in order to soften the conductive layer and facilitate pressing. The thickness of the conductive layer is generally 0.1 μm or more and 1 mm or less, preferably 1 μm or more and 200 μm or less.
（導電層の組成）
本発明に用いる導電層中に含まれる導電性の炭素材料（Ａ）の割合は、導電性や基材への密着性等から、導電層の全固形分に対して５０〜９０質量％が好ましく、６０〜８０質量％がさらに好ましい。導電性の炭素材料（Ａ）以外の成分としては、主にバインダー（Ｂ）となるが、それ以外にも任意の成分を含んでも良い。導電性や密着性などの観点から、導電層中の全固形分に対する導電性の炭素材料（Ａ）とバインダー（Ｂ）の合計の割合は、好ましくは５〜５０質量％であり、より好ましくは１０〜４０質量％である。
(Composition of conductive layer)
The proportion of the conductive carbon material (A) contained in the conductive layer used in the present invention is preferably 50 to 90% by mass with respect to the total solid content of the conductive layer in view of conductivity, adhesion to a base material, and the like. , 60-80% by mass is more preferable. The component other than the conductive carbon material (A) is mainly a binder (B), but any component other than that may be contained. From the viewpoint of conductivity and adhesion, the total ratio of the conductive carbon material (A) and the binder (B) to the total solid content in the conductive layer is preferably 5 to 50% by mass, more preferably 5 to 50% by mass. It is 10 to 40% by mass.
（導電層の光沢）
本発明に用いる導電層の光沢は、０．５〜１２０であり、好ましくは１〜８０であり、さらに好ましくは１．５〜６０である。導電層中の炭素材料の配向状態と光沢には相関があり、光沢が上記範囲において、炭素材料の配向性が高く、再現性と優れた導電性を確保した導電層を得ることができる。なお、導電層の表面の光沢値は、導電層の基材と接していない面を測定して得ることができる。
(Gloss of conductive layer)
The gloss of the conductive layer used in the present invention is 0.5 to 120, preferably 1 to 80, and more preferably 1.5 to 60. There is a correlation between the orientation state of the carbon material in the conductive layer and the gloss, and in the above range of gloss, it is possible to obtain a conductive layer in which the orientation of the carbon material is high and reproducibility and excellent conductivity are ensured. The gloss value of the surface of the conductive layer can be obtained by measuring the surface of the conductive layer that is not in contact with the base material.
（導電層の比表面積）
本発明に用いる導電層の比表面積は、好ましくは５〜８００ｍ２／ｇであり、より好ましくは１０〜５００ｍ２／ｇであり、さらに好ましくは２０〜３００ｍ２／ｇである。
導電層の比表面積が小さいと電極反応に関わる面積が不十分となり、電気化学特性等が十分発揮されない場合がある。一方、比表面積が大きすぎると、基材との密着性が低下するため、導電層の脱離が起こり、導電性が低下する場合がある。
(Specific surface area of conductive layer)
The specific surface area of the conductive layer used in the present invention is preferably 5 to 800 m 2 / g, more preferably 10 to 500 m 2 / g, and further preferably 20 to 300 m 2 / g.
If the specific surface area of the conductive layer is small, the area involved in the electrode reaction may be insufficient, and the electrochemical properties and the like may not be sufficiently exhibited. On the other hand, if the specific surface area is too large, the adhesion to the base material is lowered, so that the conductive layer may be detached and the conductivity may be lowered.
＜酸化還元酵素＞
本発明における酵素としては、反応により電子を授受できる酵素であれば特に制限はなく、検出対象に応じて適宜選択される。
例えば、糖や有機酸などのオキシダーゼやデヒドロゲナーゼなどが利用できる。中でも、人体の血液や尿などの生体試料に含まれるグルコースを検出対象にできるグルコースオキシダーゼやグルコースデヒドロゲナーゼが好ましい場合がある。その他、フルクトースを検出対象にできるフルクトースオキシダーゼやフルクトースデヒドロゲナーゼ、乳酸を検出対象にできる乳酸オキシダーゼや乳酸デヒドロゲナーゼが好ましい場合がある。
用いられる酵素は１種類でも２種類以上であってもよい。また、センシング対象を加水分解等により酸化あるいは還元可能な状態にする酵素等の触媒と、酸化あるいは還元を促進する酵素との組み合わせであってもよい。
<Oxidoreductase>
The enzyme in the present invention is not particularly limited as long as it is an enzyme capable of transferring electrons by reaction, and is appropriately selected depending on the detection target.
For example, oxidases such as sugars and organic acids and dehydrogenases can be used. Among them, glucose oxidase and glucose dehydrogenase, which can detect glucose contained in a biological sample such as human blood or urine, may be preferable. In addition, fructose oxidase or fructose dehydrogenase capable of detecting fructose, or lactate oxidase or lactate dehydrogenase capable of detecting lactic acid may be preferable.
The enzyme used may be one type or two or more types. Further, it may be a combination of a catalyst such as an enzyme that makes the sensing target in a state where it can be oxidized or reduced by hydrolysis or the like, and an enzyme that promotes oxidation or reduction.
＜メディエーター＞
酵素には電極に直接電子を伝達できる直接電子移動型（ＤＥＴ型）酵素と直接電子を伝達できない酵素が存在する。ＤＥＴ型でない酵素の場合には、燃料の酸化によって生じた電子を酵素から電極に伝達する役割を担うメディエーターを併用する必要がある。メディエーターとしては、電極に電子を伝達できる酸化還元物質であれば特に制限はなく、従来公知のものを使用できる。メディエーターの使用方法としては、電極内あるいは電極上に担持させる方法や電解液に溶解させて使用する方法等がある。メディエーターとしては、テトラチアフルバレン、ハイドロキノンや１，４‐ナフトキノン等のキノン類などの非金属化合物、フェロセン、フェリシアン化物、オスミウム錯体、及びこれら化合物を修飾したポリマー等が例示できる。
<Mediator>
Enzymes include direct electron transfer type (DET type) enzymes that can directly transfer electrons to electrodes and enzymes that cannot directly transfer electrons. In the case of a non-DET type enzyme, it is necessary to use a mediator that plays a role of transferring electrons generated by the oxidation of fuel from the enzyme to the electrode. The mediator is not particularly limited as long as it is a redox substance capable of transmitting electrons to the electrode, and conventionally known mediators can be used. As a method of using the mediator, there are a method of supporting it in or on an electrode, a method of dissolving it in an electrolytic solution, and the like. Examples of the mediator include non-metal compounds such as tetrathiafluvalene, hydroquinone and quinones such as 1,4-naphthoquinone, ferrocene, ferricianides, osmium complexes, and polymers modified with these compounds.
＜イオン伝導体＞
本発明におけるイオン伝導体として電極の間でイオンの伝導を行うものを用いてもよい。イオン伝導体の形態はイオン伝導性を有するものであれば特に限定されるものではない。イオン伝導体としては、液体に溶ける電解質や固体のポリマー電解質などを使用しても良い。
<Ion conductor>
As the ion conductor in the present invention, a conductor that conducts ions between electrodes may be used. The form of the ionic conductor is not particularly limited as long as it has ionic conductivity. As the ionic conductor, a liquid-soluble electrolyte, a solid polymer electrolyte, or the like may be used.
＜基材＞
基材の性質は特に制限されず、天然材料であっても合成材料であっても良い。天然材料としては紙、不織布、布等が挙げられる。合成材料としては、ＰＥＴ（ポリエチレンテレフタレート）、ＰＥＮ（ポリエチレンナフタレート）、ポリイミド、ポリ塩化ビニル、ポリアミド、ナイロン、ＯＰＰ（延伸ポリプロピレン）、ＣＰＰ（未延伸ポリプロピレン）などの樹脂基材が挙げられる。更に、カーボンペーパーやカーボンクロス等の導電性基材も例として挙げられる。基材の厚みは特に制限されず、酵素センサーの形状等に合わせて選択できる。
<Base material>
The properties of the base material are not particularly limited, and may be a natural material or a synthetic material. Examples of natural materials include paper, non-woven fabric, and cloth. Examples of the synthetic material include resin substrates such as PET (polyethylene terephthalate), PEN (polyethylene naphthalate), polyimide, polyvinyl chloride, polyamide, nylon, OPP (stretched polypropylene), and CPP (unstretched polypropylene). Further, a conductive base material such as carbon paper or carbon cloth can be mentioned as an example. The thickness of the base material is not particularly limited and can be selected according to the shape of the enzyme sensor and the like.
＜酵素センサー・酵素センサー用電極＞
酵素センサーは、少なくとも作用極及び対極、あるいは作用極、対極及び参照極で構成される。また、必要に応じて血液などの試料を電極へ導入するスペーサーやカバー等を設けてもよい。
酵素センサーに用いる複数の電極は、異なる基材上に導電層をそれぞれ形成することで作製する場合や、同一の基材上にそれぞれの電極について導電層を形成する場合や、同一の基材上に導電層を設置した後に非導電部位を形成することで電極を作製してもよい。また予め、基材に金属スパッタなどで金属層を形成した上に、各電極の導電層を形成して電極を作製してもよい。参照極を設置する場合は、例えば導電層の上部へ更に銀や塩化銀などを積層することによって作製される。各電極のリード部は、金属スパッタなどで金属層を形成する方法、導電層を延長して用いる方法、延長した導電層の上部や下部に金属スパッタなどで金属層を更に形成する方法等、が例示できる。
酸化還元酵素やメディエーターを設置する方法としては、これらの電極上部、あるいは作用極の上部及び／または内部に、酸化還元酵素や必要に応じてメディエーターを含ませる方法や、酸化還元酵素や必要に応じてメディエーターを加えた混合物層を形成させる方法、予め前記組成物中に分散させて塗工・印刷の後、乾燥して電極中に設置する方法、等が挙げられる。酸化還元酵素やメディエーターを含む混合物層を形成する場合、親水性化合物および／または親水性樹脂を混合してもよい。
<Enzyme sensor / Electrode for enzyme sensor>
The enzyme sensor is composed of at least the working electrode and the counter electrode, or the working electrode, the counter electrode and the reference electrode. Further, if necessary, a spacer, a cover, or the like for introducing a sample such as blood into the electrode may be provided.
A plurality of electrodes used for an enzyme sensor may be produced by forming conductive layers on different base materials, or when forming a conductive layer for each electrode on the same base material, or on the same base material. An electrode may be produced by forming a non-conductive portion after installing the conductive layer on the surface. Further, the electrode may be produced by forming a metal layer on the base material by metal sputtering or the like in advance and then forming a conductive layer of each electrode. When the reference electrode is installed, it is produced by, for example, further laminating silver, silver chloride, or the like on the upper part of the conductive layer. For the lead portion of each electrode, a method of forming a metal layer by metal sputtering or the like, a method of extending the conductive layer and using it, a method of further forming a metal layer by metal sputtering or the like on the upper or lower part of the extended conductive layer, etc. It can be exemplified.
As a method of installing the oxidoreductase or the mediator, a method of incorporating the oxidoreductase or the mediator as needed in the upper part of these electrodes or the upper part and / or the inside of the working electrode, the oxidoreductase or as necessary Examples thereof include a method of forming a mixture layer to which a mediator is added, a method of dispersing the mixture in the composition in advance, coating and printing, and then drying and placing the mixture in the electrode. When forming a mixture layer containing an oxidoreductase or a mediator, a hydrophilic compound and / or a hydrophilic resin may be mixed.
酵素センサーは、前記の通り血液等の生体試料や食品等に含まれる特定成分を、酵素の基質特異性により選択的に酸化あるいは還元し、その電流値等から定性あるいは定量するものである。酵素センサーの用途としては、例えば、各種有機物を対象とした有機物センサー、血液や汗、尿、便、涙、唾液、呼気などの生体試料中の有機物や体液を対象とした生体センサー、水分を対象にした水分センサー、果物や食品中の糖等を対象にした食品用センサー、ＩｏＴセンサー、大気や河川、土壌など環境中の有機物を対象にした環境センサー、動物や昆虫、植物を対象にした動植物センサー等が挙げられる。生体センサーとしては、例えば、血液中の糖をセンシングする血糖値センサーや、尿中の糖をセンシングする尿糖値センサー、汗中の乳酸値をセンシングする疲労度センサーや熱中症センサー、汗や尿中の水分をセンシングする発汗センサーや排尿センサー等が挙げられる。また、生体向けのウェアラブルセンサーとしての用途として例えば、おむつ内にセンサーを仕込んだ排尿センサーや尿糖値センサー、経皮貼付型の発汗、熱中症センサーなどが挙げられる。 As described above, the enzyme sensor selectively oxidizes or reduces a specific component contained in a biological sample such as blood or food, depending on the substrate specificity of the enzyme, and qualitatively or quantifies it from the current value or the like. Applications of enzyme sensors include, for example, organic matter sensors for various organic substances, biological sensors for organic substances and body fluids in biological samples such as blood, sweat, urine, stool, tears, saliva, and exhaled breath, and water. Moisture sensor, food sensor for fruits and sugar in food, IoT sensor, environmental sensor for organic matter in the environment such as air, rivers and soil, animals and plants for animals, insects and plants Examples include sensors. Examples of biological sensors include a blood glucose level sensor that senses sugar in blood, a urine sugar level sensor that senses sugar in urine, a fatigue sensor and heat stroke sensor that senses lactic acid level in sweat, and sweat and urine. Examples include a sweating sensor and a urine sensor that sense the moisture inside. Further, as an application as a wearable sensor for a living body, for example, a urination sensor or a urine sugar level sensor in which a sensor is installed in a diaper, a percutaneous sticking type sweating sensor, a heat stroke sensor and the like can be mentioned.
以下に、実施例により本発明をさらに具体的に説明するが、以下の実施例は本発明の権利範囲を何ら制限するものではない。 Hereinafter, the present invention will be described in more detail with reference to Examples, but the following Examples do not limit the scope of rights of the present invention at all.
＜導電性組成物の作製＞
（製造例１：導電性組成物（１）の作成）
イオン交換水５００質量部に水溶性樹脂（Ｂ−１：ＣＭＣダイセル＃１２４０（ダイセル化学工業社製））５質量部を撹拌しながら添加して溶解させた。その後、黒鉛（Ａ−１：球状化黒鉛 ＣＧＢ−５０（日本黒鉛社製））７２質量部と黒鉛以外の炭素材料（Ａ−４：ライオナイト ＥＣ−２００Ｌ（ライオン社製））８質量部を添加した。次いで、サンドミルにて分散を行った。
次に水分散性樹脂微粒子（Ｂ−４：アクリル樹脂水分散液 Ｗ−１６８（トーヨーケム社製 固形分５０質量％））３０質量部を添加、混合し、表１に示す導電性組成物（１）を得た。
<Preparation of conductive composition>
(Production Example 1: Preparation of Conductive Composition (1))
5 parts by mass of a water-soluble resin (B-1: CMC Daicel # 1240 (manufactured by Daicel Chemical Industries, Ltd.)) was added to 500 parts by mass of ion-exchanged water with stirring to dissolve it. After that, 72 parts by mass of graphite (A-1: spheroidized graphite CGB-50 (manufactured by Nippon Graphite Co., Ltd.)) and 8 parts by mass of carbon material other than graphite (A-4: Lionite EC-200L (manufactured by Lion Co., Ltd.)) were added. Added. Then, dispersion was performed with a sand mill.
Next, 30 parts by mass of water-dispersible resin fine particles (B-4: acrylic resin water dispersion W-168 (solid content 50% by mass manufactured by Toyochem Co., Ltd.)) was added and mixed, and the conductive composition (1) shown in Table 1 was added and mixed. ) Was obtained.
表１に示す組成比や材料を変更した以外は、導電性組成物（１）（製造例１）と同様の方法により、それぞれ導電性組成物（２）〜（７）、（９）〜（１１）を得た。 The conductive compositions (2) to (7) and (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9) to (9), respectively 11) was obtained.
（製造例２：導電性組成物（８）の作製）
イオン交換水５００質量部に水溶性樹脂（Ｂ−１ＣＭＣダイセル＃１２４０（ダイセル化学工業社製））５質量部を撹拌しながら添加して溶解させた。その後、黒鉛（Ａ−１：球状化黒鉛 ＣＧＢ−５０（日本黒鉛社製））６４質量部と黒鉛以外の炭素材料（Ａ−４：ライオナイト ＥＣ−２００Ｌ（ライオン社製））１６質量部を添加した。次いで、製造例１から分散方法を変更しディスパーにて分散を行った。
次に水分散性樹脂微粒子（Ｂ−４：アクリル樹脂水分散液 Ｗ−１６８（トーヨーケム社製 固形分５０質量％））３０質量部を添加、混合し、表１に示す導電性組成物（８）を得た。
(Production Example 2: Preparation of Conductive Composition (8))
5 parts by mass of a water-soluble resin (B-1CMC Daicel # 1240 (manufactured by Daicel Chemical Industries, Ltd.)) was added to 500 parts by mass of ion-exchanged water with stirring to dissolve it. After that, 64 parts by mass of graphite (A-1: spheroidized graphite CGB-50 (manufactured by Nippon Graphite Co., Ltd.)) and 16 parts by mass of carbon material other than graphite (A-4: Lionite EC-200L (manufactured by Lion Co., Ltd.)) were added. Added. Next, the dispersion method was changed from Production Example 1 and dispersion was performed with a disperser.
Next, 30 parts by mass of water-dispersible resin fine particles (B-4: acrylic resin water dispersion W-168 (solid content 50% by mass manufactured by Toyochem Co., Ltd.)) was added and mixed, and the conductive composition (8) shown in Table 1 was added and mixed. ) Was obtained.
導電性組成物の製造例で使用した材料、および導電性の炭素材料（Ａ）の分散方法を以下に示す。
（導電性の炭素材料（Ａ））
黒鉛（Ａ−ａ）
・Ａ−１：球状化黒鉛 ＣＧＢ−５０（日本黒鉛社製）
・Ａ−２：鱗片化黒鉛 ＣＢ−１５０（日本黒鉛社製）
・Ａ−３：薄片化黒鉛 ＵＰ−２０（日本黒鉛社製）
黒鉛以外の炭素材料（Ａ−ｂ）
・Ａ−４：ライオナイト ＥＣ−２００Ｌ（ライオン・スペシャリティ・ケミカルズ社製）
・Ａ−５：ケッチェンブラック ＥＣ−３００Ｊ（ライオン・スペシャリティ・ケミカルズ社製）
（バインダー（Ｂ））
水溶性樹脂（Ｂ−ａ）
・Ｂ−１：ＣＭＣダイセル＃１２４０（ダイセル化学工業社製）
・Ｂ−２：クラレポバールＰＶＡ２３５（クラレ社製）
非水溶性樹脂
・Ｂ−３：ＫＦポリマー＃９１００（クレハ社製）
水分散樹脂微粒子（Ｂ−ｂ）
・Ｂ−４：アクリル樹脂水分散液 Ｗ−１６８（トーヨーケム社製 固形分５０質量％）
導電性の炭素材料（Ａ）の分散方法
・Ｄ−１：サンドミル
・Ｄ−２：ディスパー
The material used in the production example of the conductive composition and the method of dispersing the conductive carbon material (A) are shown below.
(Conductive carbon material (A))
Graphite (A-a)
-A-1: Spheroidized graphite CGB-50 (manufactured by Nippon Graphite Co., Ltd.)
-A-2: Scaled graphite CB-150 (manufactured by Nippon Graphite Co., Ltd.)
-A-3: Thinned graphite UP-20 (manufactured by Nippon Graphite Co., Ltd.)
Carbon material other than graphite (Ab)
・ A-4: Lionite EC-200L (manufactured by Lion Specialty Chemicals)
・ A-5: Ketjen Black EC-300J (manufactured by Lion Specialty Chemicals)
(Binder (B))
Water-soluble resin (BA)
-B-1: CMC Daicel # 1240 (manufactured by Daicel Chemical Industries, Ltd.)
・ B-2: Kuraray Poval PVA235 (manufactured by Kuraray)
Water-insoluble resin B-3: KF polymer # 9100 (manufactured by Kureha Corporation)
Water-dispersed resin fine particles (Bb)
B-4: Acrylic resin aqueous dispersion W-168 (solid content 50% by mass manufactured by Toyochem Co., Ltd.)
Dispersion method of conductive carbon material (A) ・ D-1: Sand mill ・ D-2: Disper
＜酵素センサー用電極の作製＞
［実施例１］
（酵素センサー用電極（1）の作製）
<Manufacturing electrodes for enzyme sensors>
[Example 1]
(Preparation of electrode (1) for enzyme sensor)
・導電層の作製
非導電性基材として厚さ１００μｍのＰＥＴ基材（ルミラー（東レ社製））上に、導電性組成物（１）をドクターブレードを用いて塗布した後、加熱乾燥して導電層（１）を得た。
-Preparation of conductive layer The conductive composition (1) was applied to a PET base material (Lumirror (manufactured by Toray Industries, Inc.)) having a thickness of 100 μm as a non-conductive base material using a doctor blade, and then heat-dried. A conductive layer (1) was obtained.
・酵素センサー用電極の作製
前記、導電層（１）を１０×３０ｍｍに切り出した後、下部５×５ｍｍ以外をテープでマスキング処理を行った。マスキング処理を行っていない５×５ｍｍの導電層に、メディエーターであるフェロセンのメタノール溶液と、酸化還元酵素であるグルコースオキシダーゼ水溶液をそれぞれ滴下・自然乾燥させてメディエーターと酵素を担持し、酵素センサー用電極（１）を得た。
-Preparation of Electrode for Enzyme Sensor After cutting out the conductive layer (1) to 10 × 30 mm, masking treatment was performed on the lower portion other than 5 × 5 mm with tape. A methanol solution of ferrocene, which is a mediator, and an aqueous solution of glucose oxidase, which is an oxidoreductase, are added dropwise and air-dried to a 5 x 5 mm conductive layer that has not been masked to support the mediator and enzyme. (1) was obtained.
［実施例２、実施例４〜５、実施例７〜９、実施例１１、比較例１〜３］
（酵素センサー用電極（２）、（４）〜（５）、（７）〜（９）、（１１）〜（１４）の作製）
[Example 2, Examples 4 to 5, Examples 7 to 9, Example 11, Comparative Examples 1 to 3]
(Preparation of electrodes (2), (4) to (5), (7) to (9), (11) to (14) for enzyme sensors)
・導電層の作製
表２に示す導電性組成物に変更した以外は、実施例１の導電層の作製方法と同様の方法により、導電層（２）、（４）〜（５）、（７）〜（９）、（１１）〜（１４）を得た。
-Preparation of conductive layer Conductive layers (2), (4) to (5), (7) by the same method as the method for producing a conductive layer of Example 1 except that the composition was changed to the conductive composition shown in Table 2. )-(9) and (11)-(14) were obtained.
・酵素センサー用電極の作製
上記で作成した導電層を用い、表２に示す導電層に変更した以外は実施例１の酵素センサー用電極の作製方法と同様の方法により、酵素センサー用電極（２）、（４）〜（５）、（７）〜（９）、（１１）〜（１４）を得た。
-Making the electrode for the enzyme sensor Using the conductive layer prepared above, the electrode for the enzyme sensor (2) was obtained by the same method as the method for manufacturing the electrode for the enzyme sensor in Example 1 except that the conductive layer was changed to the conductive layer shown in Table 2. ), (4) to (5), (7) to (9), and (11) to (14) were obtained.
［実施例３］
（酵素センサー用電極（３）の作成）
[Example 3]
(Creation of electrode (3) for enzyme sensor)
・導電層の作製
非導電性基材として厚さ１００μｍのＰＥＴ基材（ルミラー（東レ社製））上に、導電性組成物（２）をドクターブレードを用いて塗布した後、加熱乾燥を行った。その後、ロールプレスを行って、導電層（３）を得た。
-Preparation of conductive layer The conductive composition (2) is applied to a PET base material (Lumirror (manufactured by Toray Industries, Inc.)) having a thickness of 100 μm as a non-conductive base material using a doctor blade, and then heat-dried. It was. Then, a roll press was performed to obtain a conductive layer (3).
・酵素センサー用電極の作製
前記、導電層（３）を１０×３０ｍｍに切り出した後、下部５×５ｍｍ以外をテープでマスキング処理を行った。マスキング処理を行っていない５×５ｍｍの導電層に、メディエーターであるフェロセンのメタノール溶液と、酸化還元酵素であるグルコースオキシダーゼ水溶液をそれぞれ滴下・自然乾燥させてメディエーターと酵素を担持し、酵素センサー用電極（３）を得た。
-Preparation of Electrode for Enzyme Sensor After cutting out the conductive layer (3) to 10 × 30 mm, masking treatment was performed on the lower portion other than 5 × 5 mm with tape. A methanol solution of ferrocene, which is a mediator, and an aqueous solution of glucose oxidase, which is an oxidoreductase, are added dropwise and air-dried to a 5 x 5 mm conductive layer that has not been masked to support the mediator and enzyme. (3) was obtained.
［実施例６、１０］
（酵素センサー用電極（６）、（１０）の作製）
[Examples 6 and 10]
(Preparation of electrodes (6) and (10) for enzyme sensors)
・導電層の作製
表２に示す導電性組成物に変更した以外は、実施例３の導電層の作製方法と同様の方法により、導電層（６）、（１０）を得た。
-Preparation of conductive layer Conductive layers (6) and (10) were obtained by the same method as the method for producing a conductive layer in Example 3 except that the composition was changed to the conductive composition shown in Table 2.
・酵素センサー用電極の作製
上記で作成した導電層を用い、表２に示す導電層に変更した以外は実施例３の酵素センサー用電極の作製方法と同様の方法により、酵素センサー用電極（６）、（１０）を得た。
-Making the electrode for the enzyme sensor Using the conductive layer prepared above, the electrode for the enzyme sensor (6) was obtained by the same method as the method for manufacturing the electrode for the enzyme sensor in Example 3 except that the conductive layer was changed to the conductive layer shown in Table 2. ), (10) were obtained.
［導電層および酵素センサー用電極の評価］
下記のとおり、導電層および酵素センサー用電極の評価を行った。得られた評価結果を表２に示す。
[Evaluation of conductive layers and electrodes for enzyme sensors]
The conductive layer and the electrode for the enzyme sensor were evaluated as follows. The obtained evaluation results are shown in Table 2.
（導電層の比表面積）
導電層の比表面積は、窒素吸着量測定（日本ベル社製 ＢＥＬＳＯＲＰ−ｍｉｎｉ）で評価した。具体的には、非導電性基材上に作製した導電層を剥がして得られた粉体を測定容器に入れ、１５０℃で加熱処理を行い、吸着水を取り除いた。その後、窒素吸着測定装置にて液体窒素下（７７Ｋ）で窒素吸着量を測定し、ＢＥＴプロットにて比表面積を算出した。評価結果を表２に示す。
(Specific surface area of conductive layer)
The specific surface area of the conductive layer was evaluated by measuring the amount of nitrogen adsorbed (BELSORP-mini manufactured by Nippon Bell Co., Ltd.). Specifically, the powder obtained by peeling off the conductive layer produced on the non-conductive substrate was placed in a measuring container and heat-treated at 150 ° C. to remove adsorbed water. Then, the amount of nitrogen adsorbed was measured under liquid nitrogen (77K) with a nitrogen adsorption measuring device, and the specific surface area was calculated by BET plot. The evaluation results are shown in Table 2.
（導電層の光沢）
導電層の光沢は、ｍｉｃｒｏ−ＴＲＩ−Ｇｌｏｓｓ（ＢＹＫ Ａｄｄｉｔｉｖｅｓ＆Ｉｎｓｔｒｕｍｅｎｔｓ社製）で評価した。具体的には、非導電性基材上に作製した導電層の面にｍｉｃｒｏ−ＴＲＩ−Ｇｌｏｓｓを接触させ、３か所の６０°光沢を測定し、その平均値を光沢値とした。評価結果を表２に示す。
(Gloss of conductive layer)
The gloss of the conductive layer was evaluated by micro-TRI-Gloss (manufactured by BYK Adaptives & Instruments). Specifically, micro-TRI-Gloss was brought into contact with the surface of the conductive layer prepared on the non-conductive base material, and 60 ° gloss was measured at three places, and the average value was taken as the gloss value. The evaluation results are shown in Table 2.
＜電気化学評価＞
（リニアスイープボルタメトリー（ＬＳＶ）測定）
前記で作製した酵素センサー用電極を作用極、対極を白金コイル電極、参照電極をＡｇ／ＡｇＣｌ電極、電解液として０．１Ｍリン酸緩衝液（ｐＨ７．０）を入れ、反応基質（センシング対象物）としてＤ−グルコースを２０ｍＭとなるように添加し、−０．２Ｖ（ｖｓＡｇ／ＡｇＣｌ）から＋０．５Ｖ（ｖｓＡｇ／ＡｇＣｌ）の範囲でＬＳＶ測定を行なった。ＬＳＶ測定で得られた電流曲線から、電流密度の最大値（ｍＡ／ｃｍ２）を、下記の基準を指標として評価した。評価結果を表２に示す。酵素センサー用電極の電流密度の最大値が大きい程、センシング対象物質を検出しやすいため感度が高いと言える。
<Electrochemical evaluation>
(Linear sweep voltammetry (LSV) measurement)
The electrode for the enzyme sensor prepared above is the working electrode, the counter electrode is the platinum coil electrode, the reference electrode is the Ag / AgCl electrode, and 0.1 M phosphate buffer (pH 7.0) is added as the electrolytic solution, and the reaction substrate (sensing object). ), D-glucose was added so as to be 20 mM, and LSV measurement was performed in the range of −0.2 V (vsAg / AgCl) to +0.5 V (vsAg / AgCl). From the current curve obtained by the LSV measurement, the maximum value (mA / cm2) of the current density was evaluated using the following criteria as an index. The evaluation results are shown in Table 2. It can be said that the larger the maximum value of the current density of the electrode for the enzyme sensor, the higher the sensitivity because it is easier to detect the substance to be sensed.
〇：「比較例１の電流密度の最大値に対する、実施例または比較例の同最大値の百分率が１４０％以上」
△：「比較例１の電流密度の最大値に対する、実施例または比較例の同最大値の百分率が１０５％以上、１４０％未満」
×；「比較例１の電流密度の最大値に対する実施例または比較例の同最大値の百分率が１０５％未満」
〇: "The percentage of the maximum value of the current density of Comparative Example 1 is 140% or more of the maximum value of the example or the comparative example."
Δ: “The percentage of the maximum value of the current density of Comparative Example 1 to the maximum value of the same maximum value of Example or Comparative Example is 105% or more and less than 140%”.
X; "The percentage of the maximum value of the current density of Comparative Example 1 to the maximum value of the example or the comparative example is less than 105%"
表２に示すように、本発明の導電層では、炭素材料の配向状態の改良や、比表面積を最適化することで、酵素センサー用電極で検出できる電流値が大きく向上することが確認された。導電層の比表面積の最適化で酸化還元酵素の担持効率が向上し、センシング対象の酸化が効果的に行えたと考える。また、導電層中の炭素材料の配向状態（光沢値）を制御することで、センシング対象の酸化によって取り出された電子がスムーズに移動するためと考える。したがって、腐食への耐性とコストに優れる炭素材料を用いた本発明の酵素センサー用電極および酵素センサーは、良好な感度が得られる。
一方、比較例１では、炭素材料の配向状態が不十分でなく、比較例３では、黒鉛（Ａ−ａ）を含まず、導電性が不十分でないため、センシング対象の酸化によって取り出された電子がスムーズに起こらず、電気化学特性が低下したと想定している。更に、比較例１では、酸化還元酵素の担持が不十分であったため、電気化学特性が低下したと想定している。
As shown in Table 2, it was confirmed that in the conductive layer of the present invention, the current value that can be detected by the electrode for the enzyme sensor is greatly improved by improving the orientation state of the carbon material and optimizing the specific surface area. .. It is considered that the optimization of the specific surface area of the conductive layer improved the carrying efficiency of the oxidoreductase and effectively oxidized the object to be sensed. It is also considered that by controlling the orientation state (gloss value) of the carbon material in the conductive layer, the electrons taken out by the oxidation of the sensing target move smoothly. Therefore, the electrode for the enzyme sensor and the enzyme sensor of the present invention using a carbon material having excellent resistance to corrosion and cost can obtain good sensitivity.
On the other hand, in Comparative Example 1, the orientation state of the carbon material is not insufficient, and in Comparative Example 3, graphite (Aa) is not contained and the conductivity is not insufficient, so that the electrons taken out by the oxidation of the sensing target are taken out. Does not occur smoothly, and it is assumed that the electrochemical characteristics have deteriorated. Further, in Comparative Example 1, it is assumed that the electrochemical properties are deteriorated because the support of the oxidoreductase is insufficient.
Claims (5)
前記導電層が導電性の炭素材料（Ａ）とバインダー（Ｂ）とを含み、炭素材料（Ａ）が黒鉛（Ａ−ａ）と黒鉛以外の導電性の炭素材料（Ａ−ｂ）とを含み、
前記導電層の表面の６０°光沢が０．５〜１２０である、
酵素センサー用電極。 An electrode containing a conductive layer and an oxidoreductase, which is arranged on a base material.
The conductive layer contains a conductive carbon material (A) and a binder (B), and the carbon material (A) contains graphite (Aa) and a conductive carbon material (Ab) other than graphite. ,
The surface of the conductive layer has a 60 ° gloss of 0.5 to 120.
Electrode for enzyme sensor.
An enzyme sensor formed by using the electrode for an enzyme sensor according to any one of claims 1 to 4.
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