JP6149480B2 - Biosensor electrode, biosensor electrode member, and biosensor - Google Patents

Description

  The present invention relates to an electrode for biosensor, an electrode member for biosensor, and a biosensor that prevent corrosion deterioration of an electrode system and has high measurement accuracy.

  Biosensors using electrochemical detection means have been put into practical use as a method for quickly and easily measuring the concentration and the like of a specific component in a biological sample such as blood. A biosensor generally includes an electrode system including a working electrode and a counter electrode as electrodes, and a reaction unit including an enzyme and an electron acceptor (mediator) as basic components. An example of such a biosensor is a glucose sensor that electrochemically quantifies glucose in blood.

  FIG. 9 is a schematic perspective view showing an example of a general biosensor, and FIG. 10 is an exploded perspective view of FIG. As illustrated in FIGS. 9 and 10, a general biosensor 120 includes a working base 111, a counter electrode 112, and a support base 113 on which a wiring portion 115 connected to each pole is disposed. A reaction part 116 including an enzyme and an electron acceptor, and a spacer 121 arranged so that a sample supply path 123 is located on the reaction part 116, and the spacer 121. The cover layer 122 having the air holes 124 is sequentially stacked. For convenience, the working electrode 111 and the counter electrode 112 are omitted in FIG.

Since the biosensor has a sample supply path and an air hole, when a biological sample such as blood (hereinafter sometimes abbreviated as a sample) is in contact with the sample supply path, the sample is brought into the biosensor by capillary action. To produce an enzyme reaction in the reaction section.
For example, in a glucose sensor, an enzyme selectively oxidizes glucose in blood to produce gluconic acid, and simultaneously reduces an electron acceptor to produce a reductant in the reaction part. The reductant is transmitted to the electrode system, and the reductant is oxidized again by applying a certain voltage, and current is generated at that time.
Since the magnitude of the current generated at this time depends on the glucose concentration in the blood, the glucose in the blood can be quantified from the current value measured by the measuring device connected to the biosensor.

Biosensors typified by glucose sensors and the like are required to have high sensitivity and measurement accuracy in order to enable measurement in a short time from a small amount of sample. On the other hand, since biosensors are consumables that are used after being exchanged for each test, they are also required to be low in cost.
In order to obtain a highly sensitive and inexpensive biosensor, a metal material having high conductivity such as silver and nickel has been conventionally used as a material for an electrode system and a wiring part (see Patent Document 1). .
However, as shown in FIG. 9 and FIG. 10, the electrode system having the working electrode and the counter electrode has a reaction part at the upper part thereof and is exposed in the sample supply path. For this reason, the above-mentioned metal material used for the electrode system causes an oxidation-reduction reaction by contact with moisture in the atmosphere and in the sample, hydrogen peroxide generated by an enzymatic reaction in the reaction part, etc. There is a problem that the electrical characteristics of the biosensor deteriorate due to corrosion.

  As an electrode system material, for example, Patent Document 2 reports a biosensor having an electrode system using carbon. Carbon is less likely to corrode than the above-described metal materials and is cheaper than metal materials, so use as an electrode material is being studied. However, since carbon is inferior in conductivity to metal, there is a problem that high sensitivity cannot be obtained in the electrode system and it is difficult to improve electrical characteristics.

JP 2006-023291 A JP 2004-294231 A

  The present invention has been made in view of the above problems, and has as its main object to provide a biosensor electrode, a biosensor electrode member, and a biosensor that prevent corrosion deterioration of the electrode system and has high measurement accuracy. To do.

  In order to solve the above problems, the present invention provides a support base, an electrode system formed on the support base and having a working electrode and a counter electrode, and formed on the support base and connected to the electrode system. A biosensor electrode having at least a wiring part, wherein at least surfaces of the working electrode and the counter electrode contain a noble metal, and the wiring part does not contain a noble metal. An electrode for a sensor is provided.

  According to the present invention, the working electrode and the counter electrode of the electrode system include at least a noble metal having high corrosion resistance on the surface, so that when the electrode is used for a biosensor, moisture is generated in a sample or in a reaction part. Even if it comes into contact with hydrogen peroxide or the like, it becomes difficult to be corroded, and the deterioration of electrical characteristics can be prevented. Further, by making the wiring portion free of noble metal, it is possible to have high conductivity while suppressing cost. For this reason, it can be set as the electrode which can measure the component density | concentration etc. in a sample with high sensitivity and high precision.

  In the said invention, it is preferable that the said noble metal is at least 1 type selected from the group which consists of gold | metal | money, platinum, and palladium. These noble metals have high corrosion resistance against hydrogen peroxide and the like, and are excellent in chemical stability. Also, in the biosensor using the present invention, compatibility with enzymes contained in the reaction part is good. is there.

  The present invention also includes a support substrate, an electrode system formed on the support substrate and having a working electrode and a counter electrode, a wiring portion formed on the support substrate and connected to the electrode system, An electrode member for a biosensor having at least an insulating layer that covers at least the surface of the wiring portion, and a spacer that is formed on the electrode system and the wiring portion and has a sample supply path that overlaps the electrode system in plan view. The biosensor electrode member is characterized in that at least surfaces of the working electrode and the counter electrode contain a noble metal, and the wiring portion does not contain a noble metal.

  According to the present invention, when the working electrode and the counter electrode of the electrode system include a noble metal having high corrosion resistance on at least the surface, when the electrode member is used for a biosensor, the electrode system Even when it comes into contact with hydrogen peroxide or the like generated in the reaction part, it is difficult to be corroded, and it is possible to prevent deterioration of electrical characteristics. In addition, the wiring part does not contain precious metal, but its surface is covered with an insulating layer, so that it does not corrode even when it comes into contact with moisture, hydrogen peroxide, etc., and exhibits high conductivity. Can do. For this reason, it can be set as the electrode member which can measure the component density | concentration etc. in a sample with high sensitivity and high precision.

  The present invention also includes a support substrate, an electrode system formed on the support substrate and having a working electrode and a counter electrode, a wiring portion formed on the support substrate and connected to the electrode system, An insulating layer covering at least the surface of the wiring part; a spacer formed on the electrode system and the wiring part and having a sample supply path overlapping the electrode system in plan view; and exposed from the sample supply path of the spacer. A biosensor having a reaction portion arranged to overlap the electrode system in plan view, and a cover layer arranged to cover at least the sample supply path on the spacer, the working electrode and the Provided is a biosensor characterized in that at least the surface of the counter electrode contains a noble metal, and the wiring part does not contain a noble metal.

  According to the present invention, the working electrode and the counter electrode of the electrode system include a noble metal having high corrosion resistance on at least the surface, so that moisture or reaction parts in the sample can be obtained even if the electrode system is exposed in the sample supply path. Corrosion due to hydrogen peroxide or the like generated in is difficult to occur, and deterioration of electrical characteristics can be prevented. In addition, the wiring part does not contain precious metal, but its surface is covered with an insulating layer, so that it does not corrode even when it comes into contact with moisture, hydrogen peroxide, etc., and exhibits high conductivity. Can do. For this reason, in this invention, it is possible to set it as the biosensor which can measure the component density | concentration etc. in a sample with high sensitivity and high precision.

  In the present invention, the working electrode and the counter electrode of the electrode system include at least the surface of the noble metal having high corrosion resistance, and the wiring portion does not include the noble metal, thereby preventing corrosion deterioration of the electrode system, Since it has high electroconductivity, there exists an effect that it can be set as the electrode for biosensors which has high measurement accuracy.

It is a schematic plan view which shows an example of the electrode for biosensors of this invention. It is a schematic sectional drawing for demonstrating the aspect of the electrode system in this invention. It is a schematic plan view which shows the example of the arrangement | positioning form of the electrode system and wiring part in this invention. It is a disassembled perspective view which shows an example of the electrode member for biosensors of this invention. It is a schematic perspective view which shows the other example of the spacer in this invention. It is a schematic perspective view which shows an example of the biosensor of this invention. FIG. 7 is an exploded perspective view of FIG. 6. It is a schematic diagram which shows an example of the usage method of the biosensor of this invention. It is a schematic perspective view which shows an example of a common biosensor. FIG. 10 is an exploded perspective view of FIG. 9.

  Hereinafter, the biosensor electrode, biosensor electrode member, and biosensor of the present invention will be described in detail.

A. Biosensor Electrode First, the biosensor electrode of the present invention will be described. The biosensor electrode of the present invention includes a support substrate, an electrode system formed on the support substrate, having a working electrode and a counter electrode, and a wiring formed on the support substrate and connected to the electrode system. An electrode for a biosensor having at least a portion, wherein at least surfaces of the working electrode and the counter electrode contain a noble metal, and the wiring portion does not contain a noble metal.

The biosensor electrode of the present invention will be described with reference to the drawings. FIG. 1 is a schematic plan view showing an example of the biosensor electrode of the present invention. As illustrated in FIG. 1, the biosensor electrode 1 is obtained by forming an electrode system 10 and a wiring portion 15 on a support base 2. In the electrode system 10, a working electrode 11 and a counter electrode 12 are arranged at an interval, and at least the surface of the working electrode 11 and the counter electrode 12 contains a noble metal. Further, the wiring portion 15 does not contain a noble metal, and one end portion is connected to the working electrode 11 or the counter electrode 12 and the other end portion is connected to the terminal portion 16.
In addition, the said electrode system 10 is exposed in the sample supply path of a biosensor provided with the electrode for biosensors of this invention.

  The electrode for a biosensor of the present invention is characterized in that the working electrode and the counter electrode of the electrode system contain a noble metal, and the wiring part does not contain a noble metal. The reason will be described below.

  A biosensor is required to have high conductivity in order to measure a component concentration or the like with high sensitivity and high accuracy for a small amount of sample. In addition, since biosensors are consumables, low cost ones are required. Therefore, in the conventional biosensor electrode, it is preferable to form the electrode system and the wiring portion in a lump using a highly conductive and highly versatile metal material such as silver or nickel.

However, as illustrated in FIGS. 9 and 10, in a general biosensor, the electrode system is provided with a reaction part including an enzyme or the like on the upper part, and is exposed and arranged in the sample supply path. Therefore, there exists a problem that an electrode system corrodes and the electrical property of a biosensor falls.
Specifically, when a biological sample or the like to be measured enters the biosensor from the sample supply channel, glucose in the sample reacts with glucose oxidase contained in the reaction unit, and hydrogen peroxide is generated. Hydrogen corrodes the metal by contact with the electrode system. Further, not only hydrogen peroxide but also moisture originally contained in the sample or outside air is a factor that causes corrosion of the metal by coming into contact with the electrode system.
Since the corroded electrode system has a reduced conductivity, the amount of current flowing to the measuring instrument through the wiring portion is smaller than the amount that should originally flow, and as a result, there is a problem that the accurate component concentration cannot be measured.
In addition, since the degree of corrosion of the electrode system greatly affects the measurement results, it is assumed that the measurement accuracy varies greatly from measurement to measurement depending on the lot variation of the biosensor used and the usage environment of the biosensor. The Therefore, there is a problem that the user of the biosensor cannot accurately monitor his / her blood glucose level and the like.
As an electrode system material, in addition to the above-described metal materials, the use of carbon or the like is also being studied because it is inexpensive. Carbon and the like are said to have better corrosion resistance than the above-mentioned metal materials, but are inferior to metal materials in terms of conductivity. Therefore, in an electrode system using carbon or the like, there is a problem that high sensitivity cannot be obtained and electrical characteristics cannot be improved.
To solve the above problems, in the present invention, a noble metal having high corrosion resistance is used as a metal material of the electrode system, so that it is not easily corroded even when it comes into contact with surrounding moisture or hydrogen peroxide generated during sample measurement. It is possible to maintain high conductivity. That is, the biosensor electrode of the present invention can prevent the deterioration of electrical characteristics and can measure the component concentration and the like in a sample with high sensitivity and high accuracy.

On the other hand, the wiring part connected to the electrode system is a part that is usually not covered in the sample supply path because its surface is usually covered with an insulating layer or the like in the biosensor provided with the biosensor electrode of the present invention. Therefore, the wiring part is not easily corroded even if it comes into contact with moisture or hydrogen peroxide generated during sample measurement. Further, when the wiring part is formed of a noble metal that is the same material as the electrode system as in the prior art, there is a problem that the cost increases.
Therefore, in the present invention, the materials used in the wiring part and the electrode system are different, and the wiring part uses a material having excellent conductivity that does not contain a noble metal, thereby suppressing the overall cost. An electrode for a biosensor capable of highly sensitive measurement was made possible.

  The electrode for a biosensor of the present invention has at least an electrode system, a wiring part, and a support base material. Hereinafter, each part will be described.

1. Electrode System The electrode system in the present invention is formed on the support substrate and has a working electrode and a counter electrode, and at least surfaces of the working electrode and the counter electrode contain a noble metal. .
The working electrode is one electrode for applying a voltage to the reductant electron acceptor. The counter electrode is one electrode for measuring a current that flows due to electrons emitted from the electron acceptor to the working electrode.

Specific examples of the noble metal used in the working electrode and the counter electrode in the present invention include gold (Au), platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), ruthenium (Ru), and osmium. (Os). Since these noble metals have a low ionization tendency and are electrochemically stable, they are not easily corroded by moisture, hydrogen peroxide, etc., and have high conductivity, so that they are used as electrode materials in the present invention. Is preferred.
Among these, the noble metal is preferably at least one selected from the group consisting of gold, platinum and palladium. These precious metals have high corrosion resistance against hydrogen peroxide and are excellent in chemical stability. When used in biosensors, these precious metals have compatibility with enzymes in the reaction zone provided on the electrode system. Because it is good.

  The noble metals contained in the working electrode and the counter electrode may be the same or different. In particular, it is preferable that both electrodes are made of the same noble metal. This is because it is possible to form all at once when forming the electrode system.

  Further, the working electrode and the counter electrode may contain other metals to the extent that they do not affect the corrosion resistance. For example, core-shell nanoparticles having gold as a shell and another metal as a core can be used. The core metal may be a noble metal or a non-noble metal. Examples of the noble metal include the above-described materials and silver. Examples of the non-noble metal include metals exemplified in the section of “2. Wiring section” described later.

Furthermore, the working electrode and the counter electrode may contain a conductive organic material to the extent that the conductive performance of the electrode system is not deteriorated. Examples of the conductive organic material include organic conductive substances such as hydrocarbon-based conductive polymers and heteroatom-containing conductive polymers, organic conductive ligands, and the like.
Organic conductive materials include carbon, polypyrrole, polyaniline, polythiophene, polythienylene vinylene, polyazulene, polyisothianaphthene, polyacetylene, polyphenylene, polyphenylene vinylene, polyacene, polyphenylacetylene, polydiacetylene, PEDOT: PSS, or polynaphthalene These organic conductive materials are listed.
Examples of the organic conductive ligand include phthalocyanine, naphthalocyanine, porphyrin and the like.

When the working electrode and the counter electrode include the above-described materials in addition to the noble metal, the content of the noble metal is preferably 25% by mass or more, more preferably 50% by mass or more, with respect to 100% by mass of the total mass of each electrode. It is preferable that When the noble metal content in each electrode is below the above range, corrosion of the working electrode and the counter electrode may occur, or accurate measurement may not be performed due to a decrease in conductivity.
As will be described later, the working electrode and the counter electrode are overcoated on the upper surface of the wiring part in the sample supply path region, and the covering mode covers the entire surface of the wiring part in the sample supply path region. In this case, the total mass of each electrode does not include the mass of the wiring portion in the sample supply path.

The working electrode and the counter electrode only need to have at least a surface containing the above-described noble metal. FIG. 2 is a schematic cross-sectional view for explaining an embodiment of the electrode system in the present invention. 2A to 2C show a cross-sectional view taken along line A1-A2 and a cross-sectional view taken along line B1-B2 in FIG.
As an aspect of the working electrode and the counter electrode, as illustrated in FIG. 2A, a connection aspect in which the electrode system 10 is connected to the wiring portion 15 can be used. In the biosensor provided with the biosensor electrode of this aspect, the connecting portion (17 in FIG. 2A) between the wiring portion and the electrode system is not exposed in the sample supply path.
Further, in the biosensor including the biosensor electrode, when a part of the wiring portion is arranged in the sample supply path, the electrode system 10 is located above the wiring portion 15 as illustrated in FIG. An overcoating aspect formed on the surface may be employed, and as illustrated in FIG. 2C, a covering aspect in which the electrode system 10 covers the entire surface of the wiring portion 15 may be employed. In the case where the electrode system is the embodiment illustrated in FIGS. 2B and 2C, the wiring portion arranged in the sample supply path is covered with the electrode system and is not exposed because the upper surface and the entire surface are not exposed. This is because they are not easily corroded even when in contact with hydrogen peroxide or the like. Especially, as a mode of the working electrode and the counter electrode, a connection mode or a coating mode is preferable because exposure of the wiring part in the sample supply path can be completely prevented.
In the case where the electrode system is the embodiment illustrated in FIG. 2B or 2C, the electrode system does not include a wiring portion arranged in the sample supply path.

  The shape of the working electrode and the counter electrode is not particularly limited, and examples thereof include polygons such as rectangles and squares, comb shapes, and circles.

The thickness of the working electrode and the counter electrode is preferably a thickness capable of exhibiting the original function as an electrode system, for example, preferably within a range of 0.005 μm to 1 μm, for example, 0.01 μm More preferably, it is in the range of 0.20 μm or less.
When the thickness of the working electrode and the counter electrode is less than the above range, the resistance of the electrode system increases and the intended conductivity may not be obtained. On the other hand, if it is larger than the above range, the production cost of the present invention may become too high, which is not preferable. In the biosensor equipped with the biosensor electrode of the present invention, when three-dimensional high processing accuracy is required for forming a sample supply path, etc., the number of processing molds used, processing steps, and time increase dramatically. There is.
The thickness of the working electrode and the counter electrode is a portion indicated by T in FIG. In addition, when the electrode system is the overcoating aspect or the covering aspect illustrated in FIG. 2B or 2C, the thicknesses of the working electrode and the counter electrode are the working electrode or A portion obtained by removing the thickness of the wiring portion from the height to the outermost surface of the counter electrode.

  It is preferable that the working electrode and the counter electrode are arranged with an interval so as not to cause a short circuit. The distance between the working electrode and the counter electrode can be appropriately set according to the size of the biosensor electrode of the present invention.

In addition to the working electrode and the counter electrode, the electrode system may have a reference electrode serving as a reference when determining the potential of the working electrode. Since the reference electrode is located in a region exposed in the sample supply path when used in a biosensor, like the above-described counter electrode and working electrode, it is preferable that the reference electrode includes at least the above-described noble metal on the surface. .
The reference electrode is preferably the same as the noble metal that forms the counter electrode and / or the working electrode.

  Further, in the above electrode system, an electrode (fill detection electrode) for confirming that a sample such as blood is filled in the reagent supply channel, and a hematocrit-compensation electrode (hematocrit-compensation) used when the sample is blood are used. electrode) or the like.

The method for forming the electrode system can be appropriately selected according to the above-described aspect of the electrode system. For example, a film containing the above-mentioned noble metal film is formed on the support substrate and the electrode system is patterned, and a negative pattern of the electrode system is printed on the support substrate with aqueous ink or the like to form a noble metal film on the printed surface. After the film formation, there is a method of forming by removing the unnecessary portion of the water-based ink and the noble metal film on the water-based ink by washing, so-called lift-off. Examples of the noble metal film forming method include known methods such as laminating, metal vapor deposition, sputtering, and ion plating. Examples of the pattern forming method include known methods such as etching and laser ablation.
Moreover, it is also possible to apply a nanometal ink containing the above-mentioned noble metal directly on a supporting substrate, print it in a pattern, and perform processing after performing sintering or the like as necessary. Examples of the printing method include known methods such as an inkjet method using a noble metal paste, a gravure printing method, a screen printing method, and a flexographic printing method.
Further, in the case of the overcoating mode and the covering mode illustrated in FIGS. 2B and 2C, for example, a nanometal ink containing a noble metal is drawn on the wiring portion, and flash wiring annealing is performed to perform the wiring. A method of overcoating the electrode system on the part, a plating method, a transfer method, or the like can also be used.

2. Wiring part The wiring part in this invention is formed on the said support base material, is connected with the said electrode system, and does not contain a noble metal.
Note that the wiring portion is a portion for applying a voltage to an electrically connected electrode system and taking out an electric signal.

  As a material for the wiring portion, a material having high conductivity and not including the noble metal used in the electrode system is preferable. For example, a metal such as copper, iron, cobalt, aluminum, chromium, nickel, titanium, cerium, tantalum, or tin, an alloy containing the above metal such as stainless steel (SUS), a metal compound such as ITO, or the like may be used. it can. Among these, nickel is preferable from the viewpoint of the reliability of the metal wiring. In addition, the said material may be used independently and may use a some material together.

Further, as a material for the wiring portion, carbon, a mixture of a carbon pigment and an organic binder, or the like can be used because it is inexpensive. Examples of the carbon pigment include graphite, amorphous carbon, diamond-like carbon, carbon fiber, carbon black, acetylene black, ketjen black (registered trademark), carbon nanotube, carbon nanohorn, and carbon nanofiber. As the organic binder, acrylic resin, ester resin, vinyl chloride resin, vinyl chloride vinyl acetate copolymer resin, or the like can be used.
In addition, the wiring part may be a single layer made of the above-described material or a laminate.

Furthermore, as a material for the wiring portion, in addition to the above-described materials, other materials that contribute to improvement in conductivity may be included.
Examples of such a material include organic conductive substances and organic conductive ligands described in the above section “1. Electrode system”.

The thickness of the wiring part is not particularly limited and is preferably in the range of 0.005 μm to 40 μm and more preferably in the range of 0.01 μm to 2 μm.
If the thickness of the wiring part is less than the above range, the resistance in the wiring part becomes high, and the intended conductivity may not be obtained. Further, when the size is larger than the above range, in the biosensor provided with the biosensor electrode of the present invention, three-dimensional high processing accuracy is required for forming the sample supply path and the like, and the number of processing molds used, processing steps, and time May increase dramatically.

The wiring part usually has a terminal part for connecting to an external measuring device at the terminal not connected to the electrode system.
The terminal portion is preferably formed from the same material as the wiring portion, and the shape and the like can be appropriately designed according to the measuring instrument.

The method for forming the wiring part is not particularly limited as long as it can be formed in a desired pattern, and a method generally used for forming a wiring can be used.
For example, physical vapor deposition methods such as vacuum vapor deposition, sputtering, ion plating, metal foil etching, and dispersions in which wiring material is dispersed can be used for inkjet, gravure printing, screen printing, flexographic Examples thereof include a method of printing in a pattern using a printing method or the like, and performing processing after firing or the like, if necessary, and a laser ablation method.
Also, a negative pattern of the wiring portion is printed with water-based ink or the like, a metal thin film is formed on the entire surface by vapor deposition, and then the unnecessary portion of the water-based ink and the metal thin film on the water-based ink are washed away to perform so-called lift-off. Thereby, a wiring part can be formed. As the vapor deposition method, the physical vapor deposition method described above can be used.
In addition, even when it has a terminal part at the terminal of a wiring part, a wiring part and a terminal part can be collectively formed using the method mentioned above.

3. Support base material The support base material used for this invention supports an electrode system and a wiring part, and the surface in which an electrode system and a wiring part are formed has insulation.
As the support substrate, for example, a resin substrate, paper, a ceramic substrate, a glass substrate, a semiconductor substrate having at least a surface insulation, a metal substrate, or the like can be used. The support base material may have rigidity or may have elasticity. Among them, it is preferable to have electrical insulation and elasticity, and for example, a film of polyethylene terephthalate (PET) resin, vinyl chloride resin, polystyrene (PS) resin, polypropylene (PP) resin, polycarbonate (PC), or the like is preferably used. Can do.
Note that the support base material may or may not have flexibility. Further, it does not matter whether the supporting substrate is transparent.

  In addition, for the purpose of improving wettability, adhesion, and the like between the support substrate and the conductive material used for the electrode system, the support substrate surface may be treated or modified. Examples thereof include corona treatment, UV treatment, anti-fogging treatment, and modification by coating with a material having a sulfonic acid group or a sulfuric acid group.

The shape, size, thickness, and the like of the support substrate can be appropriately set depending on the shape of the connecting portion of the measuring instrument using the biosensor using the present invention.
Moreover, when manufacturing the biosensor provided with the electrode for biosensors of the present invention in a multi-sided manner, the support substrate may be long or a single wafer. When the supporting substrate is long, the electrode system, the wiring part, and the terminal part can be continuously formed by a roll-to-roll method.

4). Electrode for biosensor The arrangement of the electrode system and the wiring section in the present invention is not particularly limited as long as it is a general form in a biosensor.
FIG. 3 is a schematic plan view showing an example of an arrangement form of the electrode system and the wiring portion in the present invention.
For example, as illustrated in FIGS. 3A and 3B, two wiring parts 15 are formed on the support base 2, and the working electrode 11 and the one terminal of the two wiring parts 15 are respectively provided. The counter electrode 12 may be connected. The working electrode 11 and the counter electrode 12 may be located in the sample supply path in the biosensor equipped with the present invention, and may be arranged in parallel in the longitudinal direction of the biosensor electrode. It may be arranged in parallel in the short direction. In addition, the elongate direction of the electrode for biosensors means the direction connected to a measuring instrument.
When the electrode system has a reference electrode, as illustrated in FIG. 3C, two wiring parts 15 are formed on the support base 2, and the working electrode 11 is provided on one wiring part 15. The counter electrode 12 and the reference electrode 13 may be separately connected to the other wiring portion 15, and as illustrated in FIGS. 3D and 3E, three electrodes are provided on the support base 2. The wiring part 15 may be formed, and the working electrode 11, the counter electrode 12, and the reference electrode 13 may be connected to one terminal of the three wiring parts 15, respectively.
3 (c) to (e), the reference electrode 13 may or may not be located in the sample supply path in the biosensor provided with the present invention. Like the other electrodes, it is exposed in the sample supply path.

B. Next, the electrode member for a biosensor of the present invention will be described. The electrode member for a biosensor of the present invention is formed on a support substrate, an electrode system formed on the support substrate, having a working electrode and a counter electrode, formed on the support substrate, and connected to the electrode system A biosensor having at least a wiring part, an insulating layer covering at least the surface of the wiring part, and a spacer having a sample supply path formed on the electrode system and the wiring part and overlapping the electrode system in plan view An electrode member, wherein at least surfaces of the working electrode and the counter electrode contain a noble metal, and the wiring portion does not contain a noble metal.

The biosensor electrode member of the present invention will be described with reference to the drawings. FIG. 4 is an exploded perspective view showing an example of the electrode member for a biosensor of the present invention. As illustrated in FIG. 4, the biosensor electrode member 20 covers the support base 2, the electrode system 10 and the wiring part 15 formed on the support base 2, and at least the surface of the wiring part 15. It has the insulating layer 21 and the spacer 22 formed on the wiring part 15 covered with the electrode system 10 and the insulating layer 21. In the electrode system 10, the working electrode 11 and the counter electrode 12 are arranged at an interval, and the working electrode 11 and the counter electrode 12 include at least a surface of a noble metal. Further, the wiring portion 15 does not contain a noble metal, and one end portion is connected to the working electrode 11 or the counter electrode 12 and the other end portion is connected to the terminal portion 16.
Further, the spacer 22 has a sample supply path 23 at a position overlapping the electrode system 10 in plan view. That is, the electrode system 10 is exposed in the sample supply path 23.

The biosensor electrode member of the present invention comprises the above-described biosensor electrode. That is, at least the surfaces of the working electrode and the counter electrode of the electrode system contain a noble metal with high corrosion resistance. Therefore, when the electrode member for a biosensor of the present invention is used for a biosensor, even if the electrode system is exposed and arranged in the sample supply path of the spacer, excess water generated in the sample or the reaction part in the biosensor. Even if it comes into contact with hydrogen oxide or the like, it is difficult to be corroded, and the deterioration of electrical characteristics can be prevented.
In addition, the wiring part does not contain precious metal, but its surface is covered with an insulating layer, so that it does not corrode even when it comes into contact with moisture, hydrogen peroxide, etc., and exhibits high conductivity. Can do.
For this reason, the electrode member for biosensors of the present invention can be an electrode member that can measure the component concentration and the like in the sample with high sensitivity and high accuracy by having the above structure.

Hereinafter, each structure in the electrode member for biosensors of this invention is demonstrated.
The support base, the electrode system, and the wiring portion are the same as those described in the above section “A. Electrode for biosensor”, and thus the description thereof is omitted here.

1. Spacer The spacer used in the present invention is formed on the electrode system and the wiring part, and has a sample supply path that overlaps the electrode system in plan view.
Specifically, in the biosensor including the biosensor electrode member of the present invention, the spacer is provided with a gap between the support base and the cover layer, and a flow path for supplying a sample to the biosensor from the outside. It is to be provided.

The material of the spacer is not particularly limited as long as it can form a spacer having a predetermined thickness. For example, a photocurable resin, a thermosetting resin, an adhesive, or the like can be used. In the case of using a photocurable resin or a thermosetting resin, the spacer can be formed at low cost. When an adhesive is used, the spacer can be formed with high accuracy. Moreover, a resin base material can also be used as a spacer, for example, a polyethylene terephthalate (PET) resin, a vinyl chloride resin, a polystyrene (PS) resin, a polypropylene (PP) resin, a polyester resin etc. can be used.
Examples of adhesives include, for example, acrylic adhesives, ester adhesives, vinyl adhesives, silicone adhesives, etc. as synthetic adhesives, starch glues such as glue, natural rubber, and sap as natural adhesives. A polymer or the like can be used. A hot melt adhesive can also be used. Moreover, you may use a double-sided tape as an adhesive agent.

  The thickness of the spacer is preferably in the range of 15 μm or more and 500 μm or less because it is the height of the sample supply path. When the thickness of the spacer is less than the above range, there is a possibility that the sample supply due to the capillary phenomenon is not stabilized. Further, when the thickness is larger than the above range, in the biosensor including the biosensor electrode member of the present invention, there is a possibility that the sample does not flow uniformly in the reaction part and the sample does not flow in a part of the reaction part. .

At least one sample supply path is formed in the spacer. The sample supply path is a portion that is provided through the spacer in the horizontal direction and guides the sample supplied from the outside to the working electrode.
The width of the sample supply path is preferably in the range of 0.5 mm to 5 mm. If the width of the sample supply path is less than the above range, the sample may not be stably supplied to the flow path due to capillary action, or the sensitivity may be low because the area of the electrode system cannot be increased. Also, if the width is larger than the above range, when the biosensor is manufactured with multiple impositions, the spacer may collapse into an arch shape when the individual biosensors are cut, and the volume in the sample supply path may easily change. There is. The width of the sample supply path may be uniform throughout, or may be wider toward the outer edge.
The shape of the sample supply path is not particularly limited as long as the electrode system can be exposed in a desired area.

Further, as illustrated in FIG. 5, an air vent channel 25 may be formed in the spacer separately from the sample supply channel 23 according to the shape of the electrode system and the wiring part. This is because sample supply by capillary action can be promoted.
The air vent channel is arranged to communicate with the sample supply channel. Usually, in the region where the sample supply channel is arranged, the air vent channel is arranged in a region (wiring unit side) behind the electrode system and the reaction unit.
The shape of the air vent channel is not particularly limited as long as sample supply by capillary action can be promoted. For example, the sample feed channel and the air vent channel are combined to form a T-shaped channel. Can do. With such a configuration, when a sample is supplied from the outside, an air vent channel through which air in the sample supply channel escapes functions. The width of the air vent channel can be set within a range of 0.3 mm to 10 mm, for example.

As a method for forming the spacer, any method can be used as long as the spacer can be formed in a predetermined pattern, and the method is appropriately selected according to the material of the spacer. For example, when using a photocurable resin composition, printing methods, such as a gravure printing method and a screen printing method, can be mentioned. Moreover, when using a double-sided tape as an adhesive agent, the method of sticking a double-sided tape after forming a sample supply path etc. by punching etc. in a double-sided tape is mentioned. Moreover, when using a resin base material as a spacer, after forming a sample supply path etc. in the resin base material by punching etc., the method of sticking a spacer through an contact bonding layer is mentioned.
The adhesive used for the adhesive layer can be the same as the adhesive used for the spacer, and the thickness thereof is preferably in the range of 3 μm or more and 50 μm or less. It is preferable that the combined thickness or more, for example, about 20 μm.
In addition, the surface of the wiring part here shall be covered with the insulating layer mentioned later.

2. Insulating layer The insulating layer in the present invention covers at least the surface of the wiring part.
Specifically, the insulating layer covers the surface of the wiring portion, thereby preventing corrosion of the wiring portion and preventing a short circuit.

As a material for the insulating layer, a photo-curing resin, a thermosetting resin, or the like generally used as a material for the insulating layer can be used. For example, acrylic resin, phenol resin, fluorine resin, epoxy resin, cardo resin, vinyl resin, imide resin, novolac resin, polyparaxylene, and the like can be given. In addition, the insulating layer can be formed with high accuracy using an adhesive. Note that the adhesive is the same as the adhesive used for the spacer, and thus the description thereof is omitted here. Furthermore, inorganic materials such as SiO ₂ , SiN _x , and Al ₂ O ₃ can be used as the material for the insulating layer.

  The film thickness of the insulating layer may be a film thickness that can insulate the wiring portion, and may be in the range of 3 μm to 50 μm, for example. Especially, it is preferable that the thickness of an insulating layer is thicker than the thickness which combined the electrode system and the reaction part, and the thickness of a wiring part.

The insulating layer is formed at least on the surface of the wiring part, but it is not necessary to cover the electrode system and the terminal part. For example, the insulating layer is formed on the support substrate including the surface of the wiring part excluding the electrode system and the terminal part. May be.
In the present invention, when the electrode system is in the connection mode illustrated in FIG. 2A, the wiring part and the wiring part of the connecting part of the electrode system must not be covered with an insulating layer. In addition, in the case of the overcoating mode and the covering mode illustrated in FIGS. 2B and 2C, the wiring portion covered under or on the electrode system must not be covered with an insulating layer. This is because if these portions are covered with an insulating layer, they are insulated between the electrode system and the wiring portion.

As a method for forming the insulating layer, any method can be used as long as it can form the insulating layer in a predetermined pattern, and the method is appropriately selected according to the material of the insulating layer. For example, when using a photocurable resin composition, printing methods, such as a gravure printing method and a screen printing method, are mentioned, for example. At this time, a photo-curing resin or a thermosetting resin may be applied in a pattern and then cured, and after applying the photo-curing resin or thermosetting resin to the entire surface, energy is applied only to the portion to be cured. In addition, it may be cured.
In the case where a double-sided tape is used as the adhesive, a method of applying the double-sided tape after patterning the double-sided tape by punching or the like can be mentioned. Further, when an inorganic material is used as the material for the insulating layer, a CVD method or the like can be used.

3. Biosensor electrode member The electrode member for biosensor of the present invention is characterized in that a spacer sample supply path is disposed so as to overlap the above electrode system in plan view, and the electrode system is exposed in the sample supply path It is what. In the sample supply path, the wiring part and the connection part between the wiring part and the electrode system are not exposed.
The electrode system may be completely exposed in the sample supply path, or a part of the working electrode and the counter electrode may be exposed. However, the saturation of the redox reaction at the counter electrode is sufficient in measuring the current value. Since it is preferable that an area that can be suppressed is exposed, the entire electrode system is usually exposed.

The electrode member for a biosensor of the present invention may have a reaction part containing an enzyme and an electron acceptor at least above the working electrode of the electrode system exposed from the sample supply path. The size of the reaction part is not limited as long as it can cover at least the working electrode exposed from the sample supply path, and the working electrode and counter electrode exposed from the sample supply path can be completely covered. Size is preferred. Moreover, the magnitude | size which covers the whole inside of the frame of a sample supply path may be sufficient. Furthermore, the reaction part may be formed on a wiring part whose surface is covered with an insulating layer beyond the frame of the sample supply path.
Since the reaction part will be described in detail in the section “C. Biosensor” described later, description thereof is omitted here.

C. Biosensor Next, the biosensor of the present invention will be described. The biosensor of the present invention includes a support substrate, an electrode system formed on the support substrate and having a working electrode and a counter electrode, and a wiring portion formed on the support substrate and connected to the electrode system. An insulating layer covering at least the surface of the wiring part; a spacer formed on the electrode system and the wiring part and having a sample supply path overlapping the electrode system in plan view; and exposed from the sample supply path of the spacer A biosensor having a reaction portion arranged to overlap with the electrode system formed in plan view, and a cover layer arranged to cover at least the sample supply path on the spacer, the working electrode and At least the surface of the counter electrode contains a noble metal, and the wiring portion does not contain a noble metal.

The biosensor of the present invention will be described with reference to the drawings. FIG. 6 is a schematic perspective view showing an example of the biosensor of the present invention, and FIG. 7 is an exploded perspective view of FIG. In FIG. 6, illustration of the wiring portion and the insulating layer is omitted.
As illustrated in FIGS. 6 and 7, in the biosensor 30, the electrode system 10, the wiring part 15, and the terminal part 16 are formed on the support base 2, and the upper part of the electrode system 10 and the wiring part 15. The spacers 22 arranged in the above and the cover layer 32 arranged so as to cover the spacers 22 are sequentially laminated and fixed.
The electrode system 10 has a working electrode 11 and a counter electrode 12, and the surface of the wiring portion 15 connected to the electrode system 10 is covered with an insulating layer 21. The spacer 22 has a sample supply path 23, the electrode system 10 is exposed in the sample supply path 23, and the reaction unit 31 is arranged so as to overlap the electrode system 10 and the sample supply path 23 in plan view. ing. Further, an air hole 24 is formed on the cover layer 32 so as to overlap the sample supply path 23 in plan view.
The biosensor 30 includes the sample supply path 23 and the air holes 24, so that the sample supplied from the sample supply path 23 using the capillary phenomenon causes an enzyme reaction with the reaction unit 31, and the working electrode 11 and the counter electrode. As a result, the target component can be measured.

The biosensor of the present invention has the above-described electrode member for biosensor. That is, at least the surfaces of the working electrode and the counter electrode of the electrode system contain a noble metal with high corrosion resistance. Therefore, even when the electrode system comes into contact with moisture in the sample or the like, hydrogen peroxide generated in the reaction part, etc., it is difficult to be corroded, and deterioration of electrical characteristics can be prevented. In addition, the wiring part does not contain precious metal, but its surface is covered with an insulating layer, so that it does not corrode even when it comes into contact with moisture, hydrogen peroxide, etc., and exhibits high conductivity. Can do.
For this reason, in this invention, it is possible to set it as the biosensor which can measure the component density | concentration etc. in a sample with high sensitivity and high precision.

Hereinafter, each configuration in the biosensor of the present invention will be described.
The support substrate, electrode system, wiring portion, insulating layer and spacer in the present invention are the same as those described in the above sections “A. Biosensor electrode” and “B. Biosensor electrode member”. Therefore, the description here is omitted.

1. Reaction part The reaction part in this invention is arrange | positioned so that it may overlap with the electrode system exposed from the said sample supply path of the said spacer by planar view.
Specifically, the reaction part is a part that contains a biological substance and converts a chemical potential, heat, or an optical change accompanying an change movement of a substrate-specific substance into an electrical signal.

  Here, the reaction section is “arranged so as to overlap the electrode system exposed from the sample supply path of the spacer in plan view” means that the reaction section is formed in the frame of the sample supply path, As illustrated in FIG. 7, it may be disposed between the cover layer 32 and the sample supply path 23 in the spacer 22, and is opposed to the electrode system 10 through a space. It may be arranged so as to.

The reaction part includes, for example, an enzyme and an electron acceptor as a biological substance. When measuring the glucose concentration, glucose oxidase (GOD) or glucose dehydrogenase (GDH) can be used as the enzyme. Glucose oxidase and glucose dehydrogenase preferably have high purity, and the species of origin is not particularly limited as long as it has an activity in the range described below. For example, glucose oxidase includes GLO-201 manufactured by Toyobo Co., Ltd. Can be used.
As the electron acceptor, potassium ferricyanide, a ferrocene derivative, a quinone derivative, an osmuum derivative, or the like can be used.

The biosensor of the present invention is widely used not only for glucose sensors but also for reaction systems involving enzymes such as cholesterol sensors, alcohol sensors, scroll sensors, lactic acid sensors, and fructose sensors by changing the enzyme in the reaction part. be able to. As enzymes used for each biosensor, those suitable for the reaction system such as cholesterol esterase, cholesterol oxidase, alcohol oxidase, lactate oxidase, fructose dehydrogenase, xanthine oxidase, amino acid oxidase and the like can be appropriately used.
Furthermore, the biosensor of the present invention constitutes an outer membrane of gram-negative bacteria such as Escherichia coli and Salmonella by using a reaction part containing a peptide to which a factor C, a factor B, a coagulation enzyme precursor, and a dye are bound. An endotoxin sensor that measures the concentration of endotoxin, which is a toxic substance, can also be used.

The enzyme and electron acceptor are used after appropriately diluted with a solvent. Examples of the solvent include water, alcohol, and a water-alcohol mixed solvent. In addition, the enzyme and the electron acceptor may be uniformly dispersed in a linear or cyclic hydrocarbon poor solvent.
The enzyme and the electron acceptor are preferably in the range of 0.3 unit to 10 unit and the range of 0.5 μg to 200 μg, respectively, per test specimen. The reaction part enzyme and the electron acceptor can obtain a reaction amount in accordance with the enzyme amount (titer / unit), but it may be a small excess of the optimum weight part that ensures the performance of the reaction part.

  Moreover, since the detection part proportional to the area can be obtained, it is preferable to set the reaction part as wide as possible.

The method for forming the reaction part is not particularly limited as long as the reaction part can be arranged at a desired position. For example, it can be formed by applying a solution containing an enzyme and an electron acceptor on the electrode system exposed in the sample supply path and then drying to remove the solvent component. In addition, a solution containing an enzyme and a solution containing a potential receptor may be applied individually. In this case, the enzyme is applied on at least the working electrode of the electrode system.
As a method for applying a solution containing an enzyme and an electron acceptor, for example, a dispenser method can be used.
When forming the reaction part, the enzyme loses its activity when left at a temperature of 40 ° C. or higher for a long time. Therefore, it is preferable to dry the solvent at 40 ° C. or lower and quickly return to room temperature after drying.

2. Cover Layer The cover layer in the present invention is disposed so as to cover at least the sample supply path on the spacer.
Specifically, the cover layer functions as a lid material in the biosensor of the present invention.

For the cover layer, for example, a resin substrate, a ceramic substrate, a glass substrate, a semiconductor substrate, a metal substrate, or the like can be used. The cover layer may have rigidity or may have elasticity. Among them, it is preferable to have electrical insulating properties and elasticity. For example, films such as polyethylene terephthalate (PET) resin, vinyl chloride resin, polystyrene (PS) resin, polypropylene (PP) resin, and polyester resin can be suitably used.
Moreover, the cover layer may or may not have flexibility.

The cover layer may be transparent or opaque, but is preferably transparent. In the case of the transparent cover layer, the introduction of the sample can be visually observed when the biosensor is used.
In the case of a transparent cover layer, the transmittance in the visible light region (visible light transmittance) is preferably 80% or more. Here, the visible light transmittance can be measured by JIS K7361-1 (a test method for the total light transmittance of a plastic-transparent material).

Further, when the air vent channel is not provided in the spacer, the air hole 24 is provided on the surface of the cover layer 32 as illustrated in FIG. When the sample enters from the sample supply path, it is degassed from the air hole, so that the sample supply by capillary action can be promoted.
The size of the air hole is not particularly limited as long as the biosensor of the present invention is capable of causing capillary action, and is described in the above-mentioned section “B. Electrosensor member for biosensor 2. Spacer”. The contents are the same as those described above. Examples of the shape of the air hole include a circle, an ellipse, and a polygon.

The positions of the air holes in the cover layer are arranged so as to communicate with the sample supply path of the spacer. Usually, in the region where the sample supply path is disposed, air holes are disposed in a region (wiring portion side) behind the electrode system and the reaction unit.
In addition, as a formation method of an air hole, punching etc. are mentioned, for example.

Moreover, the cover layer may have a hydrophilic layer on the surface on the spacer side in addition to the air holes described above. This is because by having the hydrophilic layer, the sample can be quickly and easily guided to the electrode system and the reaction part.
Further, a water-repellent region may be provided around the air hole. This is because the sample can be prevented from flowing out of the air hole.

The shape of the cover layer is appropriately selected according to the support base material on which the electrode system and the wiring portion are formed. For example, the cover layer may have a cutout portion so that the terminal portion is exposed.
In addition, when the biosensor is manufactured with multiple faces, the cover layer may be long or a single wafer.

  The cover layer may be disposed at any position on the spacer so as to cover at least the sample supply path. The cover layer may be provided in a region other than the terminal portion, and the cover layer is provided on the entire surface of the support substrate. May be.

  The arrangement method of the cover layer is appropriately selected according to the configuration of the cover layer. For example, when a double-sided tape is used for the spacer, the support substrate on which the electrode system, the wiring portion, and the terminal portion are formed and the cover layer can be pasted via the spacer. For example, when using a photocurable resin for a spacer, a cover layer and a spacer or a support base material can be stuck through an adhesive layer. About the contact bonding layer used for bonding of a cover layer, it can be set as the material of the contact bonding layer demonstrated in the term of "B. Electrode member for biosensors."

3. Biosensor Examples of the sample measured using the biosensor of the present invention include biological samples such as blood, saliva and urine, environmental inspection and food inspection products, and waste liquid. Many of these samples contain a considerable amount of moisture, and the resistivity is not significantly different. For example, the resistivity of the sample is preferably in the range of 1 Ωcm to 1 kΩcm. Specifically, the blood resistivity is 100 Ωcm to 160 Ωcm. (There are fluctuation factors such as hematocrit and individual differences.) The resistivity of the sample is a value measured by an electrode type or electromagnetic conductivity meter (electrical conductivity meter).

The biosensor of the present invention is used by being connected to a measuring device. FIGS. 8A and 8B are schematic views showing a state in which the biosensor of the present invention is connected to a measuring apparatus, FIG. 8A is an overall view, and FIG. It is a figure explaining the inside of the measuring apparatus in the broken-line part of a).
As illustrated in FIGS. 8A and 8B, the measurement device 60 is a known measurement device that connects the biosensor 30 and detects an object to be detected included in the sample. . The measuring device 60 includes, for example, a connection electrode 63 for receiving an electrical signal generated by the biosensor 30, a calculation unit (not shown), a power source (not shown), a display unit 61, and an operation unit 62. When the biosensor 30 is attached to the attachment portion of the measurement device 60, the two terminal portions 16 of the biosensor 30 are connected to the connection electrodes 63 of the measurement device 60, respectively. With this connection, the electrical signal generated by the biosensor 30 is transmitted to the measuring device 60.

  As a measurement method, for example, the measurer attaches the biosensor 30 to the measurement device 60, introduces a sample from the tip of the biosensor 30 to the sample supply path provided in the spacer, operates the operation unit 62, and performs measurement. To start. When the sample introduced into the sample supply path includes an object to be detected, the object to be detected reacts with a biological substance disposed in the reaction unit, and an electric signal is detected by the electrode system of the biosensor 30. It reaches the terminal portion 16 via the electrode system and the wiring portion, and is transmitted to the measuring device 60 via the connection electrode 63 of the measuring device 60. The measuring device 60 converts the electrical signal received from the biosensor 30 into a measured value by the calculation unit. The obtained measurement value is displayed on the display unit 61, and the measurer can visually recognize the measurement result.

4). Biosensor Manufacturing Method A general method can be used as the biosensor manufacturing method of the present invention. About the manufacturing method of each member in the biosensor of this invention, it is the same as that of the content demonstrated by each item mentioned above.

  In the present invention, the biosensor may be manufactured in multiple faces. In this case, the support base material on which the electrode system and the wiring portion are formed, the spacer, and the cover layer are bonded together in this order, and then cut to obtain individual biosensors.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has any configuration that has substantially the same configuration as the technical idea described in the claims of the present invention and that exhibits the same effects. Are included in the technical scope.

Hereinafter, the present invention will be specifically described with reference to examples.
In the following description, when the electrode system formed in the example or the like is of the above-described topcoat mode or coating mode, the sample supply path when the biosensor electrode of the example or the like is used for the biosensor. A wiring portion located in the region, that is, a wiring portion that is overcoated or covered with an electrode system is referred to as an “electrode system pattern portion”, and is distinguished from a wiring portion outside the region.

[Example 1]
By preparing a polyester sheet (manufactured by SKC) having a thickness of 300 μm as a supporting substrate and screen printing a conductive carbon ink (product name: CH-8, manufactured by Jujo Chemical Co., Ltd.) on one side of the sheet, Electrode system pattern portions, wiring portions, and terminal portions corresponding to the working electrode and counter electrode patterns were formed.
Next, gold nano ink (product name: NPG-J manufactured by Harima Kasei Co., Ltd.) is inkjet printed on the upper surface of the electrode system pattern portion, and then the printed matter is subjected to flash lamp annealing treatment with a pulsed xenon lamp. Then, an electrode system (overcoat mode) made of gold nano-ink was formed on the upper surface of the electrode system pattern part to obtain a biosensor electrode.

[Example 2]
A 25 μm thick polyester roll (manufactured by Toray Industries, Inc.) is prepared as a supporting substrate, and water-based ink (product name: MCA2055 manufactured by DIC Graphics) is gravure-printed on one side of the roll to thereby form wiring parts and terminals. A water-based ink layer having a negative pattern of part was formed.
Next, a part of the roll was cut off, a nickel vapor deposition layer was formed on the entire surface, and then washed with water to lift off the aqueous ink layer other than the negative pattern of the wiring part and the terminal part together with the nickel vapor deposition layer. Thereby, the wiring part and terminal part which consist of nickel vapor deposition were formed.
The working electrode and the counter electrode pattern were inkjet printed with gold nano ink (product name: NPG-J, manufactured by Harima Kasei Co., Ltd.) at predetermined positions on the surface of the polyester sheet on which the wiring portion and terminal portion were printed, and then pulsed xenon By performing flash lamp annealing treatment on the printed pattern with a lamp, an electrode system (connection mode) having a working electrode and a counter electrode connected to the end of the wiring part was formed, and an electrode for a biosensor was obtained. The electrical resistivity of the electrode system was 6.3 × 10 ⁻⁶ Ωcm.

[Example 3]
The electrode system of the connection mode in the same manner as in Example 2 except that a polyester film (product name: E5100 manufactured by Toyobo Co., Ltd.) having a corona treatment on the surface and having an A4 size and a thickness of 38 μm was used as the support substrate. An electrode for a biosensor having The electrical resistivity of the electrode system was 8.0 × 10 ⁻⁶ Ωcm.

[Example 4]
A bio having a connected electrode system in the same manner as in Example 2 except that an A4 size, 100 μm thick anti-fogging polyester film (product name: MSX6993 manufactured by 3M Healthcare) was used as a supporting substrate. A sensor electrode was obtained. The electrical resistivity of the electrode system was 4.8 × 10 ⁻⁶ Ωcm.

[Example 5]
In the same manner as in Example 2, an electrode system pattern portion, a wiring portion, and a terminal portion corresponding to a working electrode and counter electrode pattern made of nickel vapor deposition were formed on one side of a polyester roll as a supporting substrate.
Next, a gold nano ink is drawn on the upper surface of the electrode system pattern portion, and thereafter, a flash lamp annealing process is performed using a pulsed xenon lamp. ) To obtain a biosensor electrode.

[Example 6]
In the same manner as in Example 2, a water-based ink layer having a negative pattern of a power feeding portion, an electrode system pattern portion, a wiring portion, and a terminal portion by gravure printing water-based ink on one side of a polyester roll as a support substrate. Was deposited.
Next, the surface of the roll having the water-based ink layer was subjected to nickel vapor deposition with a roll-to-roll, and then the film was washed with water to lift off the water-based ink layer together with the nickel vapor-deposited layer. Thereby, the electrode system pattern part which consists of nickel vapor deposition, the pattern of the electric power feeding part, the wiring part, and the terminal part were formed on the said roll.
Next, after the wiring part and the terminal part are masked with a masking film, gold plating is performed with a roll-to-roll, and an electrode system (covering mode) made of gold plating is formed on all surfaces of the electrode system pattern part. The electrode surface for the biosensor was obtained by forming a power supply unit in which the pattern surface of the power supply unit was all plated with gold.
In addition, the said electric power feeding part is provided for the plating manufacturing method. When a biosensor is manufactured using the biosensor electrode, the power feeding unit is removed in the cutting process and is not included in the biosensor that is the final product.

[Example 7]
In the same manner as in Example 2, a water-based ink layer having a negative pattern of an electrode system pattern portion, a wiring portion, and a terminal portion is formed on one surface of a polyester roll as a support substrate by gravure printing. did.
A part of the roll having the water-based ink layer was cut off, aluminum was vapor-deposited on the entire surface, and then lifted off by washing with water to form an electrode system pattern portion, wiring portion, and terminal portion made of aluminum vapor deposition.
Next, insulating ink (product name: S-114 manufactured by Suntype Co., Ltd.) so as to cover the wiring part.
An insulating layer was formed by screen printing. At this time, it is assumed that no insulating layer is formed on the electrode system pattern portion.
Next, the gold nano-ink is superimposed on the upper surface of the electrode system pattern portion, and then printed and drawn. Thereafter, the electrode system pattern portion is made of gold nano-ink on the upper surface of the electrode system pattern portion by performing a flash lamp annealing treatment using a pulsed xenon lamp. (Overcoat mode) was formed to obtain a biosensor electrode.

[Comparative Example 1]
After forming the insulating layer so as to cover the wiring part, the same as in Example 7 except that the gold nano-ink printing and the flash lamp annealing treatment were not performed on the upper surface of the electrode system pattern part. An electrode was obtained. In the obtained biosensor electrode, the electrode pattern portion is directly used as an electrode system.

[Evaluation]
When Examples 1 to 7 and Comparative Example 1 were allowed to stand at room temperature in the atmosphere for 1 month, the electrode system of Comparative Example 1 was oxidized (corrosion) in the atmosphere and the formation of an oxide film was observed. No oxidation was observed in any of the electrode systems of Examples 1 to 7, and corrosion degradation could be prevented.

DESCRIPTION OF SYMBOLS 1 ... Biosensor electrode 2 ... Support base material 10 ... Electrode system 11 ... Working electrode 12 ... Counter electrode 15 ... Wiring part 20 ... Biosensor electrode member 21 ... Insulating layer 22 ... Spacer 23 ... Sample supply path 24 ... Air hole 30 … Biosensor 31… Reaction part 32… Cover layer

Claims (4)

A support substrate;
An electrode system formed on the support substrate and having a working electrode and a counter electrode;
A biosensor electrode having at least a wiring portion formed on the support substrate and connected to the electrode system,
The working electrode and the counter electrode is comprised of only a noble metal film containing a noble metal,
All SANYO that the wiring part does not contain a noble metal,
The biosensor electrode, wherein the working electrode and the counter electrode are respectively connected to the wiring portion by a connecting portion having the noble metal film on the wiring portion .   The biosensor electrode according to claim 1, wherein the noble metal is at least one selected from the group consisting of gold, platinum, and palladium. A support substrate;
An electrode system formed on the support substrate and having a working electrode and a counter electrode;
A wiring portion formed on the support substrate and connected to the electrode system;
An insulating layer covering at least the surface of the wiring part;
A biosensor electrode member having at least a spacer having a sample supply path formed on the electrode system and the wiring portion and overlapping the electrode system in plan view,
The working electrode and the counter electrode is comprised of only a noble metal film containing a noble metal,
All SANYO that the wiring part does not contain a noble metal,
The biosensor electrode member, wherein the working electrode and the counter electrode are respectively connected to the wiring portion by a connecting portion having the noble metal film on the wiring portion . A support substrate;
An electrode system formed on the support substrate and having a working electrode and a counter electrode;
A wiring portion formed on the support substrate and connected to the electrode system;
An insulating layer covering at least the surface of the wiring part;
A spacer having a sample supply path formed on the electrode system and the wiring portion and overlapping the electrode system in plan view;
A reaction section arranged to overlap the electrode system exposed from the sample supply path of the spacer in plan view;
A biosensor having a cover layer arranged to cover at least the sample supply path on the spacer,
The working electrode and the counter electrode is comprised of only a noble metal film containing a noble metal,
All SANYO that the wiring part does not contain a noble metal,
The biosensor, wherein the working electrode and the counter electrode are respectively connected to the wiring portion by a connecting portion having the noble metal film on the wiring portion .

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