JP6197503B2 - Biosensor electrode fabric, biosensor electrode and biosensor - Google Patents

Description

  The present invention relates to a biosensor for measuring a specific component in a liquid sample such as blood.

  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 part including a working electrode and a counter electrode, an enzyme, and an electron acceptor as basic components. An example of such a biosensor is a glucose sensor that electrochemically quantifies glucose in blood.

  In the glucose sensor, the enzyme selectively oxidizes glucose in blood to produce gluconic acid, and simultaneously reduces the electron acceptor to produce a reduced form. By applying a constant voltage to the reductant at the electrode portion, the reductant is oxidized again, and current is generated at that time. Since this current depends on the glucose concentration in the blood, glucose in the blood can be quantified.

In addition, a bacterial wall toxin called endotoxin is generally known. In recent years, methods for measuring the concentration of endotoxin using an electrochemical method have been studied. Endotoxin is a toxic substance that constitutes the outer membrane of Gram-negative bacteria such as Escherichia coli and Salmonella. If this endotoxin is mixed in blood or the like even in a very small amount (for example, in the order of ng / mL), it may cause a shock symptom or the like, resulting in the worst death. However, endotoxins are widely present in the air. For this reason, inspections such as the presence of endotoxins in pharmaceuticals such as dialysate are being carried out.
For example, a technique is known in which an electrode is placed in a mixture of an analyte and a reagent, and measurement based on differential pulse voltammetry (DPV) is performed (see Patent Document 1).

  In biosensors, noble metals such as gold, palladium and platinum are generally used as electrode materials from the viewpoint of corrosion resistance. These electrode materials have a property that they are not easily oxidized and reduced even when they come into contact with moisture in the sample or an electron acceptor (mediator). However, there is a problem that noble metals are expensive and cause an increase in cost.

  In addition, as a method for forming an electrode in a biosensor, for example, a method is proposed in which a metal film is formed on the entire surface of a base material by vacuum deposition, sputtering, plating, metal foil adhesion, and the like, and then patterned (for example, a patent). References 2 to 5). However, in such a method, a large amount of metal is used, and unnecessary portions of the metal film are removed, which increases the cost.

  Therefore, it has been attempted to form an electrode by a printing method or the like using an ink containing carbon and a binder resin, or an ink containing metal fine particles and a binder resin. In this case, an electrode exhibiting desired conductivity is used. It is difficult to stably form the electrodes, and the sensitivity of the electrode portions may not be stable, and there is a problem that the performance of individual biosensors tends to vary.

JP 2012-127695 A JP 2007-510902 A JP 2009-505102 A JP 2009-533686 A JP 2009-544039 A

  The present invention has been made in view of the above circumstances, and the biosensor electrode raw material capable of producing an inexpensive biosensor electrode with good corrosion resistance and conductivity of the electrode section, and corrosion resistance of the electrode section. The main object of the present invention is to provide a biosensor electrode having good conductivity and low cost, and a biosensor using the same.

  The present invention is a biosensor electrode raw material used for producing an electrode for a biosensor having a support substrate and an electrode portion, a wiring portion and a terminal portion formed on the support substrate, A long resin base material, a conductive layer formed on the resin base material and containing a conductive material, and a noble metal plating layer which is used to form at least the electrode part and is formed on the conductive layer and contains a noble metal The conductive layer is continuously formed in the longitudinal direction of the resin base material, the noble metal plating layer is formed with a predetermined width in the width direction of the conductive layer, and continuously in the longitudinal direction. Provided is an electrode raw material for a biosensor characterized by being formed.

  According to the present invention, having a noble metal plating layer on the conductive layer, the noble metal plating layer is formed with a predetermined width in the width direction of the conductive layer, and continuously formed in the longitudinal direction, It is possible to obtain a biosensor electrode raw material capable of producing an inexpensive biosensor electrode with good corrosion resistance and conductivity of the electrode portion.

  In the said invention, it is preferable to have the 2nd conductive layer containing the electroconductive material formed adjacent to the said noble metal plating layer on the said conductive layer. This is because by having the second conductive layer, the electrical resistance of the conductive layer and the laminated portion of the second conductive layer can be reduced.

  In the said invention, it is preferable that the said conductive layer is adjacently formed by planar view at the both ends of the width direction of the said noble metal plating layer. This is because it is easy to produce a plurality of biosensor electrodes on a resin substrate.

  The present invention is a biosensor electrode having a support substrate, and an electrode portion, a wiring portion and a terminal portion formed on the support substrate, the support substrate having a resin substrate, The electrode portion has a conductive layer formed on the resin base material and containing a conductive material, and a noble metal plating layer formed on the conductive layer and containing a noble metal. The wiring portion and the terminal portion are made of the resin base. A biosensor electrode comprising the conductive layer formed on a material is provided.

  ADVANTAGE OF THE INVENTION According to this invention, it can be set as the electrode for biosensors with favorable corrosion resistance and electroconductivity of an electrode part because an electrode part has a noble metal plating layer formed on the conductive layer and the conductive layer. In addition, since the wiring portion and the terminal portion have conductive layers, an inexpensive conductive material can be used for the wiring portion and the terminal portion, so that an inexpensive biosensor electrode can be obtained.

  The present invention is formed on a support substrate, an electrode portion formed on the support substrate, a wiring portion and a terminal portion, a reaction portion disposed on the electrode portion, and the support substrate, A biosensor having a spacer for forming a sample supply path for supplying a sample to the electrode part and the reaction part, and a cover disposed on the spacer, wherein the supporting base material has a resin base material, The electrode portion has a conductive layer formed on the resin base material and containing a conductive material, and a noble metal plating layer formed on the conductive layer and containing a noble metal. The wiring portion and the terminal portion are made of the resin base. A biosensor comprising the conductive layer formed on a material is provided.

  According to the present invention, since the electrode portion has the conductive layer and the noble metal plating layer formed on the conductive layer, the biosensor having good corrosion resistance and conductivity of the electrode portion can be obtained. In addition, since the wiring portion and the terminal portion have conductive layers, an inexpensive conductive material can be used for the wiring portion and the terminal portion, so that an inexpensive biosensor can be obtained.

  The raw material for electrode for biosensor of the present invention has an effect that an electrode for biosensor with good corrosion resistance and conductivity of the electrode part can be manufactured at low cost.

It is the schematic plan view and sectional drawing which show an example of the electrode raw material for biosensors of this invention. It is a schematic plan view which shows an example of the electrode for biosensors of this invention. It is a schematic plan view which shows the other example of the electrode for biosensors of this invention. It is the schematic plan view and sectional drawing which show the other example of the electrode raw material for biosensors of this invention. It is a schematic plan view which shows the other example of the electrode for biosensors of this invention. It is the schematic plan view and sectional drawing which show the other example of the electrode raw material for biosensors of this invention. It is a schematic plan view which shows the other example of the electrode for biosensors of this invention. It is a schematic plan view which shows the other example of the electrode raw material for biosensors of this invention. It is a schematic plan view which shows the other example of the electrode raw material for biosensors of this invention. It is a schematic plan view which shows the other example of the electrode for biosensors of this invention. It is a schematic plan view which shows the other example of the electrode raw material for biosensors of this invention. It is a schematic plan view which shows the other example of the electrode for biosensors of this invention. It is the schematic plan view and sectional drawing which show the other example of the electrode raw material for biosensors of this invention. It is a schematic plan view which shows the other example of the electrode for biosensors of this invention. It is process drawing which shows an example of the manufacturing method of the electrode raw material for biosensors of this invention. It is process drawing which shows the other example of the manufacturing method of the electrode raw material for biosensors of this invention. It is process drawing which shows the other example of the manufacturing method of the electrode raw material for biosensors of this invention. It is a schematic plan view which shows the other example of the electrode for biosensors of this invention. It is a disassembled perspective view which shows an example of the biosensor of this invention. It is a disassembled perspective view which shows the other example of the biosensor of this invention. It is a schematic diagram which shows an example of the usage method of the biosensor of this invention.

  Hereinafter, the raw electrode for biosensor, the electrode for biosensor, and the biosensor of the present invention will be described.

A. Biosensor Electrode Fabric The biosensor electrode fabric of the present invention is for producing an electrode for a biosensor having a support substrate and an electrode portion, a wiring portion, and a terminal portion formed on the support substrate. Used to form a long resin base material, a conductive layer formed on the resin base material and containing a conductive material, and at least the electrode part, on the conductive layer And a noble metal plating layer containing a noble metal, wherein the conductive layer is continuously formed in the longitudinal direction of the resin substrate, and the noble metal plating layer is formed with a predetermined width in the width direction of the conductive layer. And formed continuously in the longitudinal direction.

  The biosensor electrode fabric of the present invention is used to produce a biosensor electrode having a support base material, an electrode portion, a wiring portion, and a terminal portion. A plurality of biosensor electrodes are continuously arranged in the longitudinal direction of a long scale resin base material and used for multi-face manufacturing. In the following description, a plurality of biosensor electrodes formed continuously in the longitudinal direction by one in the width direction of the resin base material may be expressed in units of “one row of biosensor electrodes”. .

The raw electrode for biosensor of the present invention will be described with reference to the drawings.
FIG. 1A is a schematic plan view illustrating an example of an electrode raw material for a biosensor of the present invention, and FIG. 1B is a cross-sectional view taken along line AA in FIG. FIG. 2 is a schematic plan view showing an example of a multi-sided biosensor electrode manufactured using the biosensor electrode raw material shown in FIGS. 1 (a) and 1 (b). FIG. 3 is a schematic plan view showing an example of the biosensor electrode in FIG.
As shown in FIGS. 1 (a) and 1 (b), a biosensor electrode fabric 1 of the present invention includes a long resin base 2 and a conductive layer formed on the resin base 2 and containing a conductive material. 3 and a noble metal plating layer 4 formed on the conductive layer 3 and containing a noble metal. In addition, the conductive layer 3 is formed continuously in the longitudinal direction of the resin base material 2, the noble metal plating layer 4 is formed with a predetermined width in the width direction of the conductive layer 3, and is formed continuously in the longitudinal direction. Yes.
1A and 1B is used to manufacture the biosensor electrode 10 shown in FIGS. 2 and 3. Here, the biosensor electrode 10 shown in FIG. 2 and FIG. 3 is formed on the support base 12 and the support base 12 and has an electrode portion 16 having at least a working electrode 13 and a counter electrode 14 (FIGS. 2 and 3). 2 shows an example in which the reference electrode 15 is further provided.), The wiring portion 17 and the terminal portion 18 are provided. Further, in FIG. 2 shows an example in which the electrode 10n ₁ for biosensors in one column are formed. By cutting one row of biosensor electrodes 10n1, _one biosensor electrode 10 shown in FIG. 3 can be manufactured. Further, the noble metal plating layer 4 in FIGS. 1A and 1B is used to form at least the electrode portion 16 in FIGS. Moreover, the conductive layer 3 in FIGS. 1A and 1B is used to form the electrode portion 16, the wiring portion 17 and the terminal portion 18 in FIGS.
As shown in FIGS. 1A and 1B, the biosensor electrode raw fabric 1 of the present invention includes a noble metal plating layer 4 corresponding to at least the electrode portions, wiring portions, and terminals in one row of biosensor electrodes. The conductive layer 3 corresponding to the portion has a pattern adjacent in plan view (hereinafter sometimes referred to as a one-row pattern N1).

FIG. 4A is a schematic plan view showing another example of the biosensor electrode fabric of the present invention, and FIG. 4B is a cross-sectional view taken along the line AA of FIG. FIG. 5 is a schematic plan view showing an example of a multi-sided biosensor electrode manufactured using the biosensor electrode raw material shown in FIG.
In the present invention, as shown in FIGS. 4A and 4B, it is preferable to have the second conductive layer 5 formed adjacent to the noble metal plating layer 4 on the conductive layer 3 and containing a conductive material. This is because by having the second conductive layer 5, the electrical resistance of the laminated portion of the conductive layer 3 and the second conductive layer 5 can be reduced. In addition, with the above configuration, the electrical resistance in the wiring portion 17 and the terminal portion 18 can be reduced as shown in FIG.

FIG. 6 (a) is a schematic plan view showing another example of an electrode raw material for a biosensor of the present invention, and FIG. 6 (b) is a cross-sectional view taken along line AA of FIG. 6 (a). FIG. 7 is a schematic plan view showing an example of a multi-sided biosensor electrode manufactured using the biosensor electrode raw fabric shown in FIGS. 6 (a) and 6 (b).
In the raw electrode 1 for biosensor of the present invention, the conductive layer 3 is adjacent to the both ends of the noble metal plating layer 4 in the width direction as shown in FIGS. 6 (a) and 6 (b). It is preferable that it is formed. For example, as shown in FIG. 7, two rows of biosensor electrodes 10 n ₁ , 10 n ₂ can be made to face each other on the support base 12 so as to face each other, and a plurality of biosensors can be manufactured. This is because it is easy to manufacture the electrode 10 with multiple faces. In this case, as shown in FIGS. 6A and 6B, the noble metal plating layer 4 and the conductive layer 3 have a width corresponding to the electrode portions of the biosensor electrodes in two rows, The conductive layer 3 is formed in a pattern in plan view having a width corresponding to at least one row of biosensor electrode wiring portions and terminal portions (hereinafter, referred to as a two-row opposing pattern N2 in some cases). Is done.
As shown in FIG. 8, when two rows of biosensor electrodes 10 n ₁ , 10 n ₂ are manufactured on the support base 12 with the electrode parts 16 facing each other and are manufactured in multiple faces, as shown in FIG. 8. In the raw electrode 1 for biosensor of the present invention, the noble metal plating layer 4 and the conductive layer 3 of the one-row pattern N1 are arranged on the resin base material 2 so that the noble metal plating layers 4 face each other. They may be formed with an interval between them.

9 (a) and 9 (b) are schematic plan views showing other examples of the biosensor electrode raw material of the present invention, and FIG. 10 is a biosensor electrode original shown in FIGS. 9 (a) and 9 (b). It is a schematic plan view which shows an example of the electrode for multi-faced biosensors manufactured using anti.
As shown in FIGS. 9 (a) and 9 (b), in the biosensor electrode fabric 1 of the present invention, the noble metal plating layer 4 and the conductive layer 3 of the one-row pattern N1 are repeated in the width direction of the resin substrate 2. In order to manufacture a plurality of rows of biosensor electrodes (in FIG. 10, three rows of biosensor electrodes 10n ₁ , 10n ₂ , 10n ₃ ) in a multi-faceted manner, as shown in FIG. Can be used. In this case, as shown in FIG. 9 (a), the noble metal plating layer 4 and the conductive layer 3 of the one-row pattern N1 may be formed at intervals for each row, as shown in FIG. 9 (b). You may form without providing a space | interval.

11 (a) and 11 (b) are schematic plan views showing other examples of the biosensor electrode original fabric of the present invention, and FIG. 12 is a biosensor electrode original shown in FIGS. 11 (a) and 11 (b). It is a schematic plan view which shows an example of the electrode for multi-faced biosensors manufactured using anti.
As shown in FIGS. 11A and 11B, in the raw electrode 1 for biosensor of the present invention, the noble metal plating layer 4 and the conductive layer 3 of the two-row opposing pattern N2 are arranged in the width direction of the resin base material 2. By repeatedly forming continuously, as shown in FIG. 12, multiple rows of biosensor electrodes (four rows of biosensor electrodes 10n ₁ , 10n ₂ , 10n ₃ , 10n _{4 in} FIG. 12) Can be used to manufacture. In this case, as shown in FIG. 11 (a), the noble metal plating layer 4 and the conductive layer 3 of the two-row facing pattern N2 may be formed at intervals for each row, as shown in FIG. 11 (b). In addition, it may be formed without providing a gap.
In addition, although not shown, in the electrode raw material for a biosensor of the present invention, the noble metal plating layer and the conductive layer of the 1-row pattern and the 2-row facing pattern are repeatedly formed continuously in the width direction of the resin base material. You can also.

According to the present invention, having a noble metal plating layer on the conductive layer, the noble metal plating layer is formed with a predetermined width in the width direction of the conductive layer, and continuously formed in the longitudinal direction, It is possible to obtain a biosensor electrode raw material capable of producing an inexpensive biosensor electrode with good corrosion resistance and conductivity of the electrode portion.
More specifically, the electrode part in which the reaction part is arranged in the biosensor can be a laminate in which a noble metal plating layer is formed on the conductive layer. Therefore, since it can have a noble metal plating layer on the surface of the electrode part, it can have corrosion resistance against hydrogen peroxide generated by the oxidation-reduction reaction of the enzyme and sample in the reaction part, oxygen in the air, moisture, etc. Also, the chemical stability can be improved. Therefore, the corrosion resistance and conductivity of the electrode part can be improved. In addition, the wiring portion and the terminal portion can have a conductive layer formed using an inexpensive conductive material.

In addition, according to the present invention, since the noble metal plating layer can be formed on the conductive layer, it is not necessary to pattern the conductive layer when manufacturing the biosensor electrode raw material. The electrode raw material for biosensors can be manufactured by the method.
Moreover, when the noble metal plating layer is formed thin in order to reduce the manufacturing cost, there is a concern that the electrical resistance becomes high. On the other hand, in the present invention, since the noble metal plating layer can be formed on the conductive layer, even when the noble metal plating layer is thinly formed, the electrical resistance of the portion where the electrode portion is formed can be reduced. . Therefore, the amount of noble metal used can be further reduced, and a low-cost biosensor electrode raw material can be obtained.

Here, in order to reduce the amount of the precious metal used in the biosensor electrode raw material, it is sufficient that the precious metal layer can be continuously formed in the longitudinal direction with a predetermined width in the width direction on the conductive layer. For example, it is considered that the amount of noble metal used can be reduced by a vapor deposition method using a lift-off method or a printing method.
However, there are concerns about the following points when these methods are used.
When the noble metal layer is formed by the evaporation method using the lift-off method, for example, a water-soluble resist layer is formed in a predetermined pattern on the conductive layer, and the noble metal layer is formed on the entire surface of the conductive layer on which the water-soluble resist layer is formed. Is deposited to form a noble metal deposited layer, and then the water-soluble resist layer is dissolved by washing with water to pattern the noble gold deposited layer. Further, the noble metal vapor deposition layer formed on the water-soluble resist layer is recovered and reused. At this time, it is often difficult to recover all of the noble metal deposition layer removed by washing with water. In addition, there is a concern that the manufacturing process of the biosensor electrode raw material becomes complicated and the manufacturing cost increases by including the recovery process of the noble metal vapor deposition layer.
On the other hand, the noble metal plating layer in the present invention can be formed in a predetermined pattern on the conductive layer by electrolytic plating using a plating mask described later, and the noble metal plating layer is formed on the plating mask. Since it is not formed, the amount of noble metal used can be reduced, and the manufacturing process of the biosensor electrode stock can be simplified.
When the printing method is used, as described above, it is difficult to stably form an electrode exhibiting desired conductivity, and there is a concern that the sensitivity of the electrode portion is not stable. In addition, since it has the conductivity necessary to function as an electrode part in the biosensor electrode, it is necessary to increase the thickness of the noble metal printing layer compared to the noble metal plating layer. There is concern that it may be difficult to reduce.

In the present invention, since the noble metal plating layer is formed on the conductive layer, the electrode part, the wiring part, and the terminal part can have a conductive layer integrally formed. Disconnection can be suitably suppressed.
Moreover, the sensitivity of the electrode part in the biosensor electrode manufactured using the biosensor electrode raw material of the present invention can be made stable and favorable.

  Hereinafter, the details of the raw electrode for biosensor of the present invention will be described.

1. Structure of electrode raw material for biosensor The electrode raw material for biosensor of the present invention comprises a long resin base material, a conductive layer formed on the resin base material, and a noble metal plating formed on the conductive layer. The conductive layer is formed continuously in the longitudinal direction of the resin base material, the noble metal plating layer is formed with a predetermined width in the width direction of the conductive layer, and is continuous in the longitudinal direction. Is formed.

In the present invention, as shown in FIGS. 1A, 1B and 9A, one end in the width direction of the noble metal plating layer 4 and one end in the width direction of the conductive layer 3 are formed. It may be formed so as to overlap in plan view, and as shown in FIGS. 6 (a), 6 (b), 9 (b), and 11 (a), 11 (b), the width direction of the noble metal plating layer 4 The conductive layer 3 may be formed adjacent to both ends in plan view. In the present invention, it is more preferable that the conductive layers are formed adjacent to each other in the width direction of the noble metal plating layer in plan view. This is because it is easy to manufacture by manufacturing a plurality of biosensor electrodes on a resin substrate by processing a biosensor electrode raw material by a laser ablation method.
Further, as shown in FIGS. 6A and 6B and FIGS. 11A and 11B, the noble metal plating layer 4 and the conductive layer 3 preferably have a two-row opposed pattern. This is because, when the electrodes are arranged to face each other as shown in FIGS. 7 and 12, it may be easy to perform processing by the laser ablation method.

The ratio of the width of the noble metal plating layer to the width of the conductive layer is appropriately selected according to the form of the biosensor electrode in the present invention and is not particularly limited.
The ratio of the width of the noble metal plating layer to the width of the conductive layer is, for example, in the range of 10% to 50%, in particular in the range of 10% to 30%, particularly in the range of 10% to 20%. Is preferred.
When the ratio of the width of the noble metal plating layer to the entire width is within the above-described range, the manufacturing cost of the biosensor electrode can be suitably reduced.
The width of the conductive layer described above refers to the distance between both ends in the width direction of the conductive layer formed on the resin substrate. For example, FIG. 1 (a), (b), and FIG. 4 (a), The distance indicated by c1 in (b) and the distance indicated by c2 in FIGS. 6 (a) and 6 (b).
The width of the noble metal plating layer is the distance between both ends in the width direction of the noble metal plating layer formed on the conductive layer, and the width of the noble metal plating layer in one row pattern is shown in FIGS. ), And the width indicated by a1 in FIGS. 4 (a) and 4 (b), and the width of the noble metal plating layer of the two-row opposed pattern is the width indicated by a2 in FIGS. 6 (a) and 6 (b). .

Specific widths of the conductive layer and the noble metal plating layer will be described later.
Further, in the case where at least one of the one-row pattern and the two-row opposed pattern is continuously arranged in a plurality of rows in the width direction of the resin base material, when the interval is provided between the patterns, the width of the interval is not particularly limited. Is preferably in the range of about 1 mm to 20 mm, in particular in the range of 3 mm to 10 mm, particularly in the range of 3 mm to 5 mm.
This is because if the width of the interval is large, unnecessary portions that are not used for the biosensor electrode may increase.
The interval width means an interval distance provided in the width direction between the patterns, for example, a distance indicated by m in FIGS. 8, 9A, and 11A.

  The specific pattern of the noble metal plating layer and the conductive layer in the biosensor electrode raw material of the present invention depends on the arrangement pattern of the multi-faceted biosensor electrode manufactured using the biosensor electrode raw material of the present invention. Can be selected as appropriate. For example, FIG. 1 (a), (b), FIG. 4 (a), (b), FIG. 6 (a), (b), FIG. 8, FIG. 9 (a), (b), and FIG. ) And (b). In the present invention, the conductive layer is preferably a pattern formed continuously in the width direction of the resin base material, and in particular, the conductive layer is a pattern formed on the entire surface of the resin base material. Is preferred. Such patterns include, for example, FIGS. 1A, 1B, 4A, 4B, 6A, 6B, 9B, and 11B. ). This is because a process for patterning the conductive layer is not required when manufacturing the biosensor electrode original fabric, and the biosensor electrode original fabric can be manufactured by a simple manufacturing method.

  Moreover, as shown to Fig.4 (a), (b), the electrode raw material for biosensors of this invention may be the structure which has the 2nd conductive layer 5, and Fig.13 (a), (b) mentioned later ), A structure having an original fabric insulating layer 6 may be employed.

2. Each structure of the biosensor electrode raw material The biosensor electrode raw material of the present invention has a long resin base material, a noble metal plating layer, and a conductive layer.

(1) Noble metal plating layer The noble metal plating layer used for this invention is used in order to form an electrode part at least. For example, when the shape of the electrode part 16 is FIG. 3 and FIGS. 18A and 18C described later, it is used to form the electrode part and a part of the wiring part.
The noble metal plating layer is formed on the conductive layer and contains a noble metal.

  Examples of the noble metal used for the noble metal plating layer include gold, palladium, platinum, and gold-palladium alloy. Gold, palladium, and platinum have good corrosion resistance against hydrogen peroxide, oxygen in the atmosphere, moisture, and the like generated by the redox reaction between the electron acceptor and the sample, and also have good chemical stability. Moreover, it is because compatibility with the enzyme used for the reaction part of a biosensor is good.

Examples of the method for forming the noble metal plating layer include an electrolytic plating method and an electroless plating method.
As a method of forming the noble metal plating layer by an electrolytic plating method, any known method may be used as long as the noble metal plating layer can be formed in a predetermined pattern on the conductive layer with a predetermined thickness. Specifically, a plating mask is formed in a pattern on the conductive layer, and the noble metal plating layer is formed on the conductive layer on which the plating mask is not formed by an electrolytic plating method. Can be formed.
An example of the plating mask is a plating resist layer. Since a known resist can be used for the plating resist layer, description thereof is omitted here. The plating resist layer is usually peeled off after the noble metal plating layer is formed. Moreover, as a plating mask, the precursor layer of the 2nd conductive layer mentioned later can be used.
The noble metal plating layer can be formed by an electroless plating method as long as the noble metal plating layer can be formed on the conductive layer in a predetermined pattern with a predetermined thickness, and can be a known method. . Specifically, a plating resist layer is formed in a pattern on the conductive layer, a catalytic metal for plating is attached on the conductive layer on which the plating resist layer is not formed, and the noble metal plating layer is based on the catalytic metal. The method of growing can be mentioned. As a method for forming the noble metal plating layer by the electroless plating method, more specifically, a method in which palladium is deposited on the conductive layer as a catalyst metal and a palladium plating layer is grown as the noble metal plating layer can be mentioned. Moreover, after depositing palladium on a conductive layer as a catalyst metal, growing a nickel plating layer on the conductive layer to which palladium is adhered, a method of forming a gold plating layer on the nickel plating layer can be mentioned.

The thickness of the noble metal plating layer is not particularly limited as long as it can function as an electrode. For example, the thickness of the noble metal plating layer is within a range of 10 nm to 200 nm, particularly within a range of 30 nm to 100 nm, and particularly within a range of 30 nm to 50 nm. preferable.
This is because if the noble metal plating layer is too thick, it may be difficult to sufficiently reduce the manufacturing cost. In addition, since the biosensor electrode raw material of the present invention is suitably used in a biosensor electrode manufacturing method using a laser ablation method, laser processing is performed when the precious metal plating layer is too thick. This is because it may become difficult to apply. Moreover, it is because it may become difficult to form a favorable noble metal plating layer when the thickness of the noble metal plating layer is too thin.

The width of the noble metal plating layer is appropriately selected according to the arrangement of a plurality of biosensor electrodes manufactured using the biosensor electrode raw material of the present invention. For example, when forming the above-mentioned noble metal plating layer and conductive layer in a single-row pattern, the width of the noble metal plating layer is appropriately selected according to the form of the electrode portion of one biosensor electrode, and is particularly limited. However, it is preferably in the range of 3 mm to 20 mm, especially in the range of 5 mm to 10 mm, particularly in the range of 5 mm to 7 mm.
Further, for example, when forming the above-mentioned two-row opposed pattern noble metal plating layer and conductive layer, the width of the noble metal plating layer is appropriately selected according to the form of two biosensor electrodes, and is particularly limited. However, it is preferably within a range of 7 mm to 50 mm, more preferably within a range of 8 mm to 30 mm, and particularly preferably within a range of 10 mm to 20 mm.
This is because when the width of the noble metal plating layer is too large, the number of noble metal plating layers removed by processing by the laser ablation method increases, and it may be difficult to sufficiently reduce the manufacturing cost. This is because if the width of the noble metal plating layer is too small, it may be difficult to form the electrode portion.

The length of the noble metal plating layer can be appropriately selected according to the length of the resin base material in the longitudinal direction, and is not particularly limited. The length of the noble metal plating layer is, for example, about 10 m to 500 m.
The length of the noble metal plating layer mentioned above refers to the distance between the longitudinal ends of the noble metal plating layer formed in the longitudinal direction on the conductive layer.

(2) Conductive layer The conductive layer in the present invention is formed on a resin substrate and contains a conductive material. The conductive layer is used to form an electrode part, a wiring part, and a terminal part in a biosensor electrode.

  The conductive layer is formed on the resin base material. Moreover, the said conductive layer is continuously formed in the longitudinal direction of the said resin base material. Such a conductive layer may be formed on the entire surface of the resin substrate, or may be formed with a predetermined width in the width direction of the resin substrate, but is formed on the entire surface of the resin substrate. More preferably. This is because a process for patterning the conductive layer is not required when manufacturing the biosensor electrode original fabric, and the biosensor electrode original fabric can be manufactured by a simple manufacturing method.

  As the conductive material used for the conductive layer, a conductive material other than the above-described noble metals is used. As such a conductive material, for example, a metal material such as silver, copper, nickel, aluminum, chromium, or an alloy thereof can be used. In addition, as the conductive material, a conductive resin material containing a binder resin and at least one of metal fine particles composed of the above-described metal material and a carbon material can be used. Examples of the conductive resin material include a metal paste or metal nano ink containing metal fine particles and a binder resin, a carbon ink containing a carbon material and a binder resin, and a metal containing metal fine particles, a carbon material and a binder resin. A carbon ink etc. can be mentioned.

  In particular, the conductive material in the present invention preferably contains nickel. This is because it is easy to form a noble metal plating layer on the conductive layer by electrolytic plating.

  Further, the conductive layer may be a single layer of the above-described conductive material or may be a plurality of layers. When there are a plurality of conductive layers, the upper conductive layer may be formed in a pattern in a region where the noble metal plating layer is formed, for example. In this case, as an example of forming a plurality of conductive layers, for example, a nickel-chromium layer can be formed on a nickel layer.

The method for forming the conductive layer is not particularly limited as long as the conductive layer can be formed on the resin base material.
For example, a method of forming a vapor deposition layer as a conductive layer by a physical vapor deposition method such as a vacuum vapor deposition method or a sputtering method using a metal material can be given. In this case, when the conductive layer is formed on the resin substrate with a predetermined width, the method described in the section of the second conductive layer described later can be used. Moreover, the method of forming a conductive layer can be mentioned by adhere | attaching the metal foil comprised from a metal material on a resin base material. Moreover, the method of forming a metal plating layer as a conductive layer by the plating method using a metal material can be mentioned.
Moreover, the method of forming a conductive resin layer as a conductive layer by the printing methods, such as the gravure printing method using the conductive resin material mentioned above, the flexographic printing method, the screen printing method, the inkjet method, can be mentioned. Moreover, the method of forming a conductive resin layer as a conductive layer can be mentioned by the method of apply | coating a conductive resin material to the whole surface on a resin base material. In addition, about the coating method, it can be made into a general thing.

  When the conductive layer in the present invention is formed using a conductive resin material, a resistance reduction treatment may be performed. The conductive resin material suitably used in this case and the resistance reduction treatment will be described in the section of “(4) Other configuration (a) Second conductive layer” described later.

In particular, the conductive layer in the present invention is preferably a vapor deposition layer. This is because when the conductive layer is a vapor deposition layer, the thickness of the conductive layer can be reduced, so that patterning by a laser ablation method can be suitably performed.
Moreover, a conductive resin layer can also be suitably used as the conductive layer in the present invention. This is because the conductive layer can be formed by a simple method, so that the productivity of the biosensor electrode raw material of the present invention can be improved.
Further, when a plurality of conductive layers are formed, the upper conductive layer is preferably a metal plating layer. This is because the surface of the conductive layer can be smoothed and the noble metal plating layer can be formed well.

The thickness of the conductive layer is not particularly limited as long as it can function as an electrode. For example, the thickness is preferably in the range of 10 nm to 10 μm, more preferably in the range of 30 nm to 8 μm, and particularly preferably in the range of 30 nm to 3 μm. .
This is because if the thickness of the conductive layer is too thick, it may be difficult to perform patterning when the biosensor electrode in the present invention is processed by the laser ablation method. This is because if it is too thin, it may be difficult to form a good conductive layer.

In addition, the width of the conductive layer is not particularly limited and is appropriately selected according to the pattern of the biosensor electrode manufactured using the biosensor electrode raw fabric. For example, the overall width of the one-row pattern is preferably within a range of 15 mm to 50 mm, more preferably within a range of 20 mm to 40 mm, and particularly preferably within a range of 25 mm to 35 mm.
Further, the overall width of the two-row opposing pattern is preferably within a range of 31 mm to 110 mm, more preferably within a range of 43 mm to 90 mm, and particularly preferably within a range of 53 mm to 80 mm.

In addition, the width of the region in which the noble metal plating layer is not formed in the conductive layer (hereinafter sometimes referred to as a width in plan view of the conductive layer) may be the biosensor electrode raw material of the present invention. It can select suitably according to the arrangement | sequence of the electrode for biosensors manufactured by using, It does not specifically limit. For example, the width in plan view of the conductive layer in the one-row pattern and the two-row opposed pattern described above can be appropriately selected according to the form of the wiring portion and the terminal portion of the biosensor electrode, but is not particularly limited. It is preferably within a range of 12 mm to 30 mm, more preferably within a range of 20 mm to 30 mm, and particularly preferably within a range of 20 mm to 28 mm. If the width of the conductive layer in plan view is too large, the conductive layer that is removed when patterning the wiring portion and the terminal portion increases, which may make it difficult to sufficiently reduce the manufacturing cost. This is because if the width of the conductive layer in plan view is too small, it may be difficult to form the wiring portion and the terminal portion.
The width of the conductive layer in plan view refers to the distance between both ends in the width direction of the region where the noble metal plating layer is not formed in the conductive layer. The widths of the conductive layers in the above-described one-row pattern and two-row opposed pattern in plan view are as shown in FIGS. 1 (a), 1 (b), 4 (a), 4 (b), 13 (a), ( The distance indicated by b1 in b).
In the case where the metal layer and the conductive layer of the two-row opposed pattern are repeatedly arranged in the width direction of the resin base material, when the two conductive layers of the two-row opposed pattern are continuously formed, the width of the conductive layer Is preferably in the range of 24 mm to 60 mm, more preferably in the range of 40 mm to 60 mm, and particularly preferably in the range of 40 mm to 56 mm.
The width of the conductive layer in plan view when the conductive layers having the two-row opposing pattern are continuously formed means a distance indicated by b2 in FIG.

About the length of a conductive layer, it can select suitably according to the length of the longitudinal direction of a resin base material, and it does not specifically limit. Usually, it is formed with a length similar to the length of the noble metal plating layer.
The length of the conductive layer described above refers to the distance between both ends in the longitudinal direction of the conductive layer formed in the longitudinal direction on the resin substrate.

(3) Long resin base material The long resin base material used for this invention supports the noble metal plating layer and conductive layer which were mentioned above.
As the resin substrate, for example, a film of polyethylene terephthalate (PET) resin, vinyl chloride resin, polystyrene (PS) resin, polypropylene (PP) resin, or the like can be suitably used.
The resin base material may or may not have flexibility. Moreover, the support base material may have rigidity and may have elasticity.
Further, the long resin base material may be in the form of a roll or a single wafer, but is preferably in the form of a roll. This is because the electrode part, the wiring part, and the terminal part in the biosensor electrode can be continuously formed by a roll-to-roll method.

  The resin substrate in the present invention may be a single layer or may be a laminate of two or more layers. When two or more resin base materials are laminated, they can be bonded together using an adhesive. The adhesive can be the same as that used for an insulating layer and the like which will be described later, and thus description thereof is omitted here.

The thickness of the resin base material is not particularly limited as long as the above-described noble metal plating layer and conductive layer can be formed. For example, the thickness is preferably in the range of 25 μm to 350 μm, and more preferably in the range of 50 μm to 250 μm. .
If the thickness of the resin substrate is too thin, it may be damaged in the manufacturing process of the biosensor electrode raw material of the present invention, the manufacturing process of the biosensor electrode, etc. This is because if the thickness is too thick, it may be difficult to handle.

(4) Other configurations In addition to the resin base material, the noble metal plating layer and the conductive layer described above, the biosensor electrode raw material of the present invention can be added by appropriately selecting other configurations as necessary. .

(A) Second conductive layer The biosensor electrode raw material of the present invention may have a second conductive layer formed on the conductive layer and containing a conductive material. This is because by having the second conductive layer, the electrical resistance of the conductive layer and the laminated portion of the second conductive layer can be reduced.
The second conductive layer is usually formed on the conductive layer and is not formed on the noble metal plating layer.

The second conductive layer is not particularly limited as long as it is formed on the conductive layer. In the present invention, the second conductive layer 5 is preferably formed adjacent to the noble metal plating layer 4 on the conductive layer 3 as shown in FIGS. 4 (a) and 4 (b). This is because by having the second conductive layer, the electrical resistance of the conductive layer and the laminated portion of the second conductive layer can be reduced. Further, as shown in FIGS. 13A, 13B, and 14, the second conductive layer 5 may be formed on the conductive layer 3 in the region used for the terminal portion 18 in the biosensor electrode 10. . In this case, in a plan view, the noble metal plating layer 4, a raw fabric insulating layer 6 (precursor layer 9) and a second conductive layer 5 are arranged in this order in the width direction of the biosensor electrode raw fabric 1. Is done.
In the present invention, as shown in FIGS. 4A and 4B, the second conductive layer 5 is formed on the entire surface of the conductive layer 3 where the noble metal plating layer 4 is not formed. It is preferable. This is because the biosensor electrode stock can be manufactured by a simpler process.
FIG. 13 (a) is a schematic plan view showing another example of the biosensor electrode raw material of the present invention, and FIG. 13 (b) is a cross-sectional view taken along line AA of FIG. 13 (a). FIG. 14 is a schematic plan view showing an example of a multi-sided biosensor electrode manufactured using the biosensor electrode raw material shown in FIGS. 13 (a) and 13 (b).

About the width | variety of a 2nd conductive layer, it can be made to be the same as that of the width | variety of planar view of the conductive layer mentioned above, for example.
In addition, the thickness of the second conductive layer can be appropriately selected according to the method for forming the second conductive layer. The specific thickness of the second conductive layer can be the same as the thickness of the conductive layer described above, and thus the description thereof is omitted here.

  The second conductive layer is not particularly limited as long as it can be formed on the conductive layer and can exhibit predetermined conductivity. Specifically, examples of the second conductive layer include a vapor deposition layer made of a metal material and a conductive resin layer containing metal fine particles made of a binder resin and a metal material. Hereinafter, each case will be described separately.

(I) When 2nd conductive layer is a vapor deposition layer As a conductive material used for a 2nd conductive layer, the metal material used for the conductive layer mentioned above can be used, for example, nickel, silver, It is preferable to use aluminum.

  Moreover, when the said 2nd conductive layer is a vapor deposition layer, it is preferable that it is a conductive resin layer containing carbon as a conductive layer. This is because the electrical resistance of the laminated portion of the conductive layer and the second conductive layer can be suitably reduced.

  As a method for forming the second conductive layer, for example, a celite processing method can be suitably used. Specifically, on the conductive layer, a water-soluble ink layer is formed in a region where the noble metal plating layer is formed using a water-soluble ink by a printing method or the like, and the entire surface on the conductive layer on which the water-soluble ink layer is formed. After forming a vapor deposition layer using a physical vapor deposition method, a second conductive layer having a predetermined pattern is formed by immersing in water and removing the water-soluble ink layer and the vapor deposition layer on the water-soluble ink layer. can do.

(Ii) When the second conductive layer is a conductive resin layer As the conductive material used for the second conductive layer, a conductive resin material containing metal fine particles composed of a binder resin and a metal material is used. In this case, examples of the metal material used for the metal fine particles include copper, aluminum, and silver.

  In addition, when copper or aluminum is used as the metal material used for the metal fine particles, the second conductive layer is electrically conductive from the one showing the insulating property before and after the resistance reduction treatment by performing the resistance reduction treatment described later. It can be changed to one that shows sex. In this case, since the 2nd conductive layer before a resistance reduction process can be used as a plating mask, it becomes possible to manufacture the electrode raw material for biosensors of this invention by a simpler method.

In this specification, “the second conductive layer before the resistance reduction treatment exhibits insulating properties” means an electrical resistance that is such that the surface of the second conductive layer before the resistance reduction treatment is not plated with a noble metal by an electrolytic plating method. Indicates that
The specific resistance value of the surface of the second conductive layer before the resistance reduction treatment is appropriately determined according to the conditions of the electrolytic plating method, and is, for example, 200 kΩ or more.
The resistance value of the surface of the second conductive layer before the above-described resistance reduction treatment is a value measured using a commercially available stylus resistance measurement device (tester).
In the present specification, the second conductive layer before the resistance reduction treatment may be referred to as a precursor layer.

The reason why the electrical characteristics of the second conductive layer can be changed before and after the low resistance treatment is not necessarily clear, but is estimated as follows. That is, in the metal fine particles using aluminum, an oxide film is usually formed on the surface of the metal fine particles, so that the metal fine particles themselves often exhibit insulating properties. It is conceivable that the oxide film formed on the surface of the metal fine particles can be removed by performing a resistance reduction treatment described later. Moreover, since the binder resin in the second conductive layer can be removed by performing the resistance reduction treatment, it is conceivable that the metal fine particles easily come into contact with each other.
In addition, in the metal fine particles using copper, it is considered that the metal fine particles can be joined to exhibit conductivity by performing a resistance reduction treatment.

  When the second conductive layer is a conductive resin layer, the conductive layer is preferably a vapor deposition layer, and in particular, a vapor deposition layer containing nickel is preferable. This is because the noble metal plating layer can be satisfactorily formed using the second conductive layer as a plating mask.

The average particle diameter of the metal fine particles is not particularly limited as long as the second conductive layer exhibiting predetermined conductivity can be formed. For example, the average particle diameter is within the range of 10 nm to 20 μm, especially within the range of 50 nm to 10 μm, and particularly 100 nm to It is preferable to be in the range of 5 μm. This is because when the average particle size of the metal fine particles is within the above range, desired conductivity can be imparted to the second conductive layer.
In addition, the said average particle diameter is the value calculated | required by observing a metal microparticle with an electron microscope, and arithmetic mean.

The content of the metal fine particles in the second conductive layer is not particularly limited as long as the second conductive layer can exhibit the desired conductivity, but in the range of 40% by mass to 95% by mass, It is preferably in the range of 60% by mass to 90% by mass, particularly in the range of 70% by mass to 85% by mass.
In addition, content of each component in a 2nd conductive layer means the content rate of each component when a 2nd conductive layer is 100 mass%.

  The binder resin may be the same as that used for general metal pastes, and examples thereof include acrylic resins, ester resins, vinyl chloride resins, vinyl acetate resins, and epoxy resins.

  The content of the binder resin in the second conductive layer is not particularly limited as long as the second conductive layer can be formed on the conductive layer, but is preferably in the range of 5% by mass to 50% by mass, It is preferable to be within the range of 10% by mass to 40% by mass, particularly within the range of 15% by mass to 30% by mass. If the content of the binder resin is too small, the adhesion of the second conductive layer is lowered, and if it is too much, the conductivity of the second conductive layer may be lowered. Here, content of the binder resin in said 2nd conductive layer is content of the binder resin in the 2nd conductive layer before the below-mentioned resistance reduction process.

  In addition to the metal fine particles and the binder resin, the second conductive layer contains a conductive pigment, a reaction reagent such as a curing agent and a crosslinking agent, an auxiliary agent and an additive for improving processability, if necessary. Also good.

  As a method for forming the second conductive layer, for example, the printing method described in the section of the conductive layer can be used.

In the method for forming the second conductive layer, the resistance reduction treatment may be performed after the second conductive layer is formed using a printing method or the like. Hereinafter, the resistance reduction process in the present invention will be described.
Here, the resistance reduction treatment is a treatment for reducing the resistance by irradiating the second conductive layer with energy to remove at least one of the oxide film and the binder resin on the surface of the metal fine particles in the second conductive layer. Say. Further, by performing the resistance reduction treatment, the metal fine particles can be melted to form a porous body.
Specifically, when the metal fine particles are made of aluminum, the resistance reduction treatment means a treatment for reducing the resistance by removing at least the oxide film on the surface of the metal fine particles.
When the metal fine particles are made of copper, the resistance reduction treatment refers to a treatment for reducing the resistance by removing the binder resin between the metal fine particles.

The resistance reduction treatment is preferably a treatment in which energy is instantaneously applied to the second conductive layer.
Here, “instantaneously irradiating energy to the second conductive layer” means that the energy irradiation time is in the range of 0.1 to 100 milliseconds. In addition, when performing instantaneous energy irradiation to the 2nd conductive layer in multiple times, the time of one energy irradiation shall be in the said range.

The second conductive layer may be subjected to instantaneous energy irradiation only once or a plurality of times.
In the method of irradiating energy instantaneously, the total energy amount can be adjusted by adjusting the irradiation time or adjusting the irradiation energy. The total energy amount can also be adjusted by performing instantaneous energy irradiation a plurality of times.

As a method for instantaneously irradiating energy to the second conductive layer, the second conductive layer is formed by removing at least one of the oxide film and the binder resin on the surface of the metal fine particles in the second conductive layer by instantaneous energy irradiation. The method is not particularly limited as long as the resistance can be lowered, and examples thereof include flash lamp annealing, laser annealing, plasma treatment, etching treatment, and the like.
Among these, flash lamp annealing or laser annealing is preferable in that the processing time is from sub millisecond to several hundred milliseconds.

  In particular, flash lamp annealing is preferable. In flash lamp annealing, heating with high energy is possible in a very short time, and only the vicinity of the surface of the second conductive layer can be subjected to high heat treatment, while the damage to the resin substrate is suppressed as much as possible in the second conductive layer. It is possible to remove at least one of the oxide film and the binder resin on the surface of the metal fine particles. In addition, the flash lamp can irradiate pulsed light, and can generate only a second conductive layer while reducing the heat load on the resin base material while generating high illuminance and reducing heat load. In addition, the flash lamp can be irradiated with pulsed light that repeatedly irradiates and extinguishes in a short time, which makes it easy to adjust the total amount of energy, such as overheating the second conductive layer and preventing heat generation of the lamp itself Adjustment is easy.

In the flash lamp annealing, for example, a xenon flash lamp can be used as the light source.
The irradiation conditions of the flash lamp are particularly limited as long as it is possible to reduce the resistance of the second conductive layer by removing at least one of the oxide film and the binder resin on the surface of the metal fine particles in the second conductive layer. It is not a thing and it sets suitably.
The irradiation energy of the flash lamp, that is, the pulse energy is such that the resistance of the second conductive layer can be reduced by removing at least one of the oxide film and the binder resin on the surface of the metal fine particles in the second conductive layer. If it is, it will not specifically limit, It adjusts suitably according to the kind of metal particulates and binder resin which are contained in the 2nd conductive layer, the distance of a light source and the 2nd conductive layer, etc., for example, within the limits of 350J-600J can do. If the irradiation energy is small, there are few binder resins to be removed, and sufficient conductivity may not be obtained. If the irradiation energy is too large, not only at least one of the oxide film and the binder resin on the surface of the metal fine particles but also the metal fine particles are removed, and the conductivity may be lowered.

  The irradiation time of the flash lamp, that is, the pulse width can be set, for example, within a range of 0.1 milliseconds to 100 milliseconds. When the irradiation time is short, the binder resin to be removed is small and sufficient conductivity may not be obtained. If the irradiation time is too long, not only at least one of the oxide film and the binder resin on the surface of the metal fine particles but also the metal fine particles are removed, and the conductivity may be lowered.

  The distance between the second conductive layer and the flash lamp is reduced by removing at least one of the oxide film and the binder resin on the surface of the metal fine particles in the second conductive layer by light irradiation from the flash lamp. It is not particularly limited as long as resistance can be achieved, and for example, it can be within a range of 5 mm to 100 mm. When the distance between the second conductive layer and the flash lamp is too short, as will be described later, the flash lamp or the method of irradiating sequentially while moving at least one of the resin base material on which the second conductive layer is formed in a pattern In addition, depending on the moving speed, there may be a portion where the resistance is lowered and a portion where the resistance is not lowered in the second conductive layer. In addition, if the distance between the second conductive layer and the flash lamp is too long, the resistance of the second conductive layer may not be sufficiently reduced.

The atmosphere in the flash lamp annealing can be, for example, an air atmosphere, a nitrogen atmosphere, an argon atmosphere, or the like.
The method of irradiating the second conductive layer with light from the flash lamp is not particularly limited as long as it is a method capable of irradiating the surface of the second conductive layer with a uniform irradiation amount. For example, the second conductive layer A method by batch processing in which the entire surface of the resin substrate formed in a pattern is irradiated simultaneously, and at least one of the flash lamp or the resin substrate in which the second conductive layer is formed in a pattern is moved sequentially. The method by the continuous process to irradiate can be mentioned.

In laser annealing, examples of the laser include a CO ₂ laser and an excimer laser.
The laser irradiation conditions are particularly limited as long as it is possible to reduce the resistance of the second conductive layer by removing at least one of the oxide film and the binder resin on the surface of the metal fine particles in the second conductive layer. It is not a thing and it sets suitably.
The laser irradiation energy, that is, pulse energy, is such that the resistance of the second conductive layer can be reduced by removing at least one of the oxide film and the binder resin on the surface of the metal fine particles in the second conductive layer. There is no particular limitation as long as it is present, and it is appropriately adjusted according to the type of metal fine particles and binder resin contained in the second conductive layer, and can be set within a range of 350J to 600J, for example. If the irradiation energy is small, there are few binder resins to be removed, and sufficient conductivity may not be obtained. If the irradiation energy is too large, not only at least one of the oxide film and the binder resin on the surface of the metal fine particles but also the metal fine particles are removed, and the conductivity may be lowered.
The laser irradiation time, that is, the pulse width can be set in the range of 0.1 milliseconds to 100 milliseconds, for example. When the irradiation time is short, the binder resin to be removed is small and sufficient conductivity may not be obtained. If the irradiation time is too long, not only at least one of the oxide film and the binder resin on the surface of the metal fine particles but also the metal fine particles are removed, and the conductivity may be lowered.
The atmosphere in laser annealing is usually an air atmosphere.

In the plasma treatment, for example, atmospheric pressure plasma, oxygen plasma, plasma in other gas atmosphere, or the like can be used.
The plasma irradiation condition is not particularly limited as long as the binder resin in the second conductive layer can be removed to reduce the resistance of the second conductive layer, and is set as appropriate.

(B) Original Fabric Insulating Layer In the present invention, as shown in FIGS. 13A and 13B, an original fabric insulating layer 6 having insulating properties may be provided on the conductive layer 3. 13A and 13B show an example in which the raw fabric insulating layer 6 is the precursor layer 9. As shown in FIG. 14, the raw fabric insulating layer is usually formed on the conductive layer used as the wiring portion 17 in the biosensor electrode 10 and is not formed on the conductive layer used in the terminal portion 18. is there. In addition, the original fabric insulating layer is usually not formed on the noble metal plating layer.

  Examples of such a raw fabric insulating layer include a precursor layer used for the above-described second conductive layer.

  As a method for forming an insulating layer for a raw fabric, for example, the precursor layer described above is formed in a predetermined pattern on a conductive layer, a noble metal plating layer is formed by an electrolytic plating method, and then the precursor layer is partially formed. By performing the resistance reduction treatment, there may be mentioned a method in which the portion not subjected to the resistance reduction treatment is formed as the original fabric insulating layer, and the portion subjected to the resistance reduction treatment is formed as the second conductive layer described above.

(C) Anchor layer In this invention, you may have an anchor layer formed between a resin base material, a noble metal plating layer, and a conductive layer. By having an anchor layer, the adhesiveness of a resin base material, a noble metal plating layer, and a conductive layer can be mentioned.
Examples of the material used for the anchor layer include two-component cured urethane resin, thermosetting urethane resin, melamine resin, cellulose ester resin, chlorine-containing rubber resin, chlorine-containing vinyl resin, acrylic resin, and epoxy. And an adhesive containing a vinyl resin and a vinyl copolymer resin.

3. Method for Producing Biosensor Electrode Fabric The method for producing the biosensor electrode fabric of the present invention is not particularly limited as long as the biosensor electrode fabric having the above-described configuration can be produced. For example, the following manufacturing method can be used.
FIGS. 15A to 15D are process diagrams showing an example of a method for manufacturing an electrode raw material for a biosensor of the present invention. As shown in FIG. 15A, the conductive layer 3 is formed on the long resin base material 2. Next, as shown in FIG. 15B, a plating resist layer 7 is formed on the conductive layer 3 in a pattern. Next, as shown in FIG. 15C, a noble metal plating layer 4 is formed on the exposed portion on the conductive layer 3 on which the plating resist layer 7 is formed by an electrolytic plating method. Next, the plating resist layer 7 is peeled off, whereby the biosensor electrode substrate 1 shown in FIG.

  16 (a) to 16 (c) are process diagrams showing another example of the method for producing an electrode raw material for a biosensor of the present invention. In the present invention, after the conductive layer 3 and the noble metal plating layer 4 are formed on the resin base material 2 in the steps described with reference to FIGS. 15A to 15D, FIGS. The second conductive layer 5 may be formed by the process shown. Specifically, as shown in FIG. 16A, after forming the water-soluble ink layer 8 by a printing method using a water-soluble resist in the region where the noble metal plating layer 4 is formed, FIG. As shown in FIG. 2, the vapor deposition layer 5 is formed on the entire surface of the noble metal plating layer 4 and the conductive layer 3 on which the water-soluble ink layer 8 is formed by using a physical vapor deposition method. Next, the water-soluble ink layer and the vapor-deposited layer on the water-soluble ink layer are removed by immersing in water, and the second conductive layer 5 is patterned on the conductive layer 3 as shown in FIG. Form. The second conductive layer 5 can be formed by the above process.

  17 (a) to 17 (e) are process diagrams showing another example of the method for producing the electrode raw material for a biosensor of the present invention. As shown in FIG. 17A, the conductive layer 3 is formed on the long resin base material 2. Next, as shown in FIG. 17B, a precursor layer 9 containing metal fine particles and a binder resin in a pattern is formed on the conductive layer 3 by a printing method. Next, as shown in FIG. 17C, a noble metal plating layer 4 is formed on the exposed portion on the conductive layer 3 on which the precursor layer 9 is formed by an electrolytic plating method. Next, as shown in FIG. 17D, the precursor layer 9 is subjected to a resistance reduction process such as a flash lamp annealing process for irradiating the flash lamp L, so that as shown in FIG. A raw electrode 1 for a biosensor having two conductive layers 5 is manufactured. In addition, in 18 (d) and (e), although the example which forms the 2nd conductive layer 5 by giving a resistance reduction process to the whole surface of the precursor layer 9, although not shown in figure, a part of precursor layer is shown. The second conductive layer may be formed by subjecting to a resistance reduction treatment.

4). Applications The raw electrode for biosensor of the present invention is used for producing an electrode for biosensor. Moreover, it can use suitably in order to pattern a noble metal plating layer and a conductive layer by a laser ablation method, and to manufacture an electrode part, a wiring part, and a terminal part.

B. Biosensor electrode The biosensor electrode of the present invention comprises a support base material, and an electrode part, a wiring part and a terminal part formed on the support base material, wherein the support base material is a resin. A wiring layer and a terminal, the electrode portion having a conductive layer formed on the resin base material and including a conductive material, and a noble metal plating layer formed on the conductive layer and including a noble metal. A part has the said conductive layer formed on the said resin base material, It is characterized by the above-mentioned.

The biosensor electrode of the present invention will be described with reference to the drawings.
2, FIG. 3, FIG. 5, FIG. 7, FIG. 10, FIG. 12, and FIG. 14 are schematic plan views showing examples of the biosensor electrode of the present invention. The details of each drawing are the same as the contents described in the above-mentioned section “A. Raw electrode for biosensor”, and thus the description thereof is omitted here.
As shown in FIG. 3, the biosensor electrode 10 of the present invention may be one in which an electrode portion 16, a wiring portion 17, and a terminal portion 18 are individually formed on a support base 12. As shown in FIGS. 5, 7, 10, 12, and 14, the electrode portion 16, the wiring portion 17, and the terminal portion 18 may be formed on the support base 12 in a multifaceted manner. .

ADVANTAGE OF THE INVENTION According to this invention, it can be set as the electrode for biosensors with favorable corrosion resistance and electroconductivity of an electrode part because an electrode part has a noble metal plating layer formed on the conductive layer and the conductive layer. In addition, since the wiring portion and the terminal portion have conductive layers, an inexpensive conductive material can be used for the wiring portion and the terminal portion, so that an inexpensive biosensor electrode can be obtained.
Hereinafter, the details of the biosensor electrode of the present invention will be described.

1. Electrode part, wiring part and terminal part The electrode for a biosensor of the present invention is usually one in which an electrode part, a wiring part and a terminal part are formed on a supporting substrate. In the present invention, the electrode part has a conductive layer formed on the resin base material and containing a conductive material, and a noble metal plating layer formed on the conductive layer and containing a noble metal, and the wiring part and the terminal part. However, it has the said conductive layer formed on the said resin base material. The conductive layers of the electrode part, the wiring part and the terminal part are usually formed integrally.

  The electrode part has at least a working electrode and a counter electrode, and may further have a reference electrode. 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 flowing by electrons emitted from the electron acceptor to the working electrode. The reference electrode is an electrode serving as a reference when determining the potential of the working electrode. A wiring part is electrically connected to the working electrode, the counter electrode, and the reference electrode, and a terminal part, which will be described later, is usually electrically connected to the wiring part. Can be taken out.

  As a form of an electrode part, a wiring part, and a terminal part, if it is a form of the general electrode part in a biosensor, it will not specifically limit. For example, as shown in FIG. 18A, two wiring portions 17 and terminal portions 18 are formed on the support base 12, the working electrode 13 is connected to one wiring portion 17, and the other wiring portion 17. As shown in FIG. 3, two wiring portions 17 and terminal portions 18 are formed on the support base 2, and the working electrode 13 is connected to one wiring portion 17. The counter electrode 14 and the reference electrode 15 may be separately connected to the other wiring part 17, and as illustrated in FIGS. 18B and 18C, the three wiring parts 17 are provided on the support base 2. Further, the working electrode 13, the counter electrode 14, and the reference electrode 15 may be connected to the three wiring parts 17, respectively.

  The wiring part has a conductive layer. Moreover, the wiring part usually has a noble metal plating layer. Further, the noble metal plating layer and the conductive layer in the wiring portion are formed so that the end portion of the noble metal plating layer and the end portion of the conductive layer are in contact with each other. “The end portion of the noble metal plating layer and the end portion of the conductive layer are in contact with each other” can be the same as the content described in the above-mentioned section “A. Raw electrode for biosensor”. Description is omitted.

  Moreover, the terminal part has a conductive layer like the wiring part. Further, the terminal part is usually formed continuously with the wiring part.

  Since the noble metal plating layer used for the electrode part, the conductive layer used for the wiring part and the terminal part can be the same as the contents described in the above-mentioned section “A. Description of is omitted.

As a ratio of the width of the region in which the noble metal plating layer is formed with respect to the entire length of the electrode portion, the wiring portion and the terminal portion of the present invention (hereinafter sometimes referred to as a noble metal plating layer forming region). As long as at least the electrode part can have a noble metal plating layer, it is not particularly limited, and is appropriately selected depending on the form of the electrode part, the wiring part and the terminal part.
Specifically, the ratio of the width of the noble metal plating layer formation region to the total length of the electrode part, the wiring part and the terminal part is in the range of 8% to 25%, particularly in the range of 8% to 20%. It is preferable to be within.
This is because when the ratio of the width of the noble metal plating layer forming region is within the above-described range, the cost of the biosensor electrode can be suitably reduced.
In the present invention, the total length of the electrode part, the wiring part, and the terminal part refers to the distance from the end of the electrode part to the end of the terminal part, for example, the distance indicated by d in FIG. Further, the width of the noble metal plating layer forming region refers to the distance at which the noble metal plating layer is formed in the length direction of the electrode portion, the wiring portion, and the terminal portion, and refers to the distance indicated by e in FIG.

The conductivity of the electrode part, the wiring part, and the terminal part is not particularly limited as long as desired measurement can be performed, and can be appropriately selected according to the application of the biosensor electrode.
Specifically, it is preferable that the resistance values of the electrode part, the wiring part, and the terminal part are 1000Ω or less, particularly 50Ω to 300Ω.
The resistance value can be measured by a stylus-type resistance value measuring device (tester) that is generally commercially available.

  The method for forming the electrode part, the wiring part, and the terminal part is not particularly limited as long as it can form the noble metal plating layer and the conductive layer in a desired pattern. For example, the above-mentioned “A. Biosensor A method of patterning a noble metal plating layer and a conductive layer by a laser ablation method using the electrode raw material for a biosensor described in the section of “Electrode material for electrode” can be suitably used.

The laser ablation method can be a known method.
As the laser, for example, various lasers such as a solid-state laser (such as a neodymium yag laser and a titanium sapphire laser), a copper vapor laser, a diode laser, a carbon dioxide gas laser, and an excimer laser can be used. The power output of the laser can usually be about 10W to 100W.
As an apparatus used for the laser ablation method, a general apparatus can be used, for example, a microlaser system available from LPKF Laser Electronic GmbH (Garbsen, Germany) and Exitech (Oxford, UK). Examples include available laser micromachining systems.
The details of the laser ablation method can be the same as those described in, for example, Japanese Translation of PCT International Publication No. 2009-505102, and a description thereof is omitted here.

2. Support base material The support base material used for this invention is used in order to support the above-mentioned electrode part, wiring part, and terminal part. The supporting base material has a resin base material.

  About the resin base material used for a support base material, since it can be made to be the same as that of the content demonstrated in the above-mentioned item of "A. Electrode raw material for biosensors", description here is abbreviate | omitted.

3. Other Configurations The electrode for a biosensor of the present invention is not particularly limited as long as it has the above-described support base, electrode portion, wiring portion, and terminal portion, and other configurations are appropriately selected as necessary. Can be added.

(1) Anchor layer In this invention, the anchor layer may be formed between the support base material, the electrode part, the wiring part, and the terminal part. The anchor layer can be the same as the content described in the above-mentioned section “A. Biosensor Electrode Material”, and thus the description thereof is omitted here.

(2) Insulating layer In the present invention, an insulating layer is formed on the support base on which the electrode part, the wiring part and the terminal part are formed so that the electrode part and the terminal part are exposed and the wiring part is covered. May be. The details of the insulating layer will be described in the section “C. Biosensor” described later, and therefore the description thereof is omitted here.

(3) Spacer In the present invention, a spacer for forming a sample supply path may be formed on the insulating layer. Since the spacer is described in the section “C. Biosensor” described later, the description thereof is omitted here.

4). Application The biosensor electrode of the present invention can be used in the biosensor described in the section “C. Biosensor” described later.

5. Method for Producing Biosensor Electrode The biosensor electrode of the present invention comprises a noble metal plating layer and a conductive layer by a laser ablation method using the biosensor electrode raw material described in “A. Biosensor electrode raw material” described above. It is preferable to manufacture by patterning.

C. Biosensor The biosensor of the present invention includes a support substrate, an electrode portion, a wiring portion and a terminal portion formed on the support substrate, a reaction portion disposed on the electrode portion, and the support substrate. And a spacer that forms a sample supply path for supplying a sample to the electrode unit and the reaction unit, and a cover disposed on the spacer, wherein the support substrate is a resin substrate. The electrode portion has a conductive layer formed on the resin substrate and containing a conductive material, and a noble metal plating layer formed on the conductive layer and containing a noble metal, and the wiring portion and the terminal portion are And having the conductive layer formed on the resin base material.

The biosensor of the present invention will be described with reference to the drawings.
FIG. 19 is an exploded perspective view showing an example of the biosensor of the present invention. As shown in FIG. 19, the biosensor 20 is disposed on the support base 12, the electrode part 16, the wiring part 17 and the terminal part 18 formed on the support base 12, and the working electrode 13 of the electrode part 16. The reaction part 21 formed, the insulating part 22 formed so as to expose the electrode part 16 and the terminal part 18 so as to cover the wiring part 17, and the insulating layer 22 formed on the insulating layer 22, and the sample is applied to the electrode part 16 and the reaction part 21. It has a spacer 24 that forms a sample supply path 23 to be supplied, and a cover 25 that is disposed on the spacer 24 so as to cover the sample supply path 23. The electrode part 16 has a working electrode 13, a counter electrode 14 and a reference electrode 15, and a reaction part 21 is formed on the working electrode 13.
The cover 25 has an air hole 26 that penetrates the cover 25.
The spacer 24 is arranged so as to form, for example, a sample supply path 23 communicating with the air hole 26 of the cover 25 so that the reaction portion 21 and the counter electrode 14 on the working electrode 13 are exposed.
In this biosensor 20, the sample supply path 23 and the air hole 26 are formed, so that the sample to be measured is obtained from the reaction section 21 and the counter electrode 14 on the working electrode 13 by utilizing the capillary phenomenon from the sample supply path 23. The target component of the sample can be measured by passing through the upper part.

FIG. 20 is an exploded perspective view showing another example of the biosensor of the present invention. As illustrated in FIG. 20, in the biosensor 20, the electrode portion 16, the wiring portion 17, and the terminal portion 18 are formed on the support base 12, the electrode portion 16 and the terminal portion 18 are exposed, and the wiring portion 17 is formed. An insulating layer 22 is further formed so as to be covered, and a spacer 24 for forming the sample supply path 23 and the air vent channel 27 is disposed on the insulating layer 22, and the sample supply path 23 and the air vent flow are disposed on the spacer 24. A cover 25 is disposed so as to cover the path 27. The electrode part 16 has a working electrode 13, a counter electrode 14 and a reference electrode 15, and a reaction part 21 is formed on the working electrode 13.
The spacer 24 is disposed so as to form, for example, a sample supply path 23 and an air vent path 27 communicating with the sample supply path 23 so that the reaction portion 21 and the counter electrode 14 on the working electrode 13 are exposed. The sample supply path 23 and the air vent channel 27 together form a T-shaped channel.
In the biosensor 20, the sample supply path 23 and the air vent path 27 are formed, so that the sample to be measured is taken from the sample supply path 23 using the capillary phenomenon, and the reaction portion 21 and the counter electrode on the working electrode 13 are measured. The target component of the sample can be measured by passing the upper part of 14.

  According to the present invention, since the electrode portion has the conductive layer and the noble metal plating layer formed on the conductive layer, the biosensor having good corrosion resistance and conductivity of the electrode portion can be obtained. In addition, since the wiring portion and the terminal portion have conductive layers, an inexpensive conductive material can be used for the wiring portion and the terminal portion, so that an inexpensive biosensor can be obtained.

  Hereinafter, details of the biosensor of the present invention will be described. The supporting substrate, electrode part, wiring part, and terminal part in the biosensor of the present invention can be the same as the contents described in the above-mentioned section “B. Electrode for biosensor”. Is omitted. In the present invention, an electrode formed by patterning a noble metal plating layer and a conductive layer by a laser ablation method using the biosensor electrode raw material described in the above section "A. Biosensor electrode raw material" It is preferable that they are a part, a wiring part, and a terminal part.

1. Reaction part The reaction part in this invention is arrange | positioned at the upper part of an electrode part.
In the present invention, the reaction part contains a biological substance, and accompanies the change movement of the substrate-specific substance
Convert chemical potential, thermal or optical changes into electrical signals.

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.

Moreover, when measuring an endotoxin density | concentration, the blood cell component (Limulus Ambozyte Lysate; LAL) of a horseshoe crab can be used for a reaction part. For example, the reaction part may include a factor C, a factor B, a coagulase precursor, and a peptide containing a dye bound thereto. Specifically, examples of the substance containing factor C, factor B and a coagulase precursor include horseshoe crab, amebocyte lysate (a horseshoe crab blood cell extract). Moreover, as the peptide to which the dye is bonded, an oligopeptide having a dye bonded to one end and a peptide protecting group bonded to the other end can be used. Examples of the oligopeptide include X-A-Y (wherein X is a protecting group, Y is a dye, and A is an oligopeptide). Examples of the protecting group X include peptide protecting groups such as t-butoxycarbonyl group (BoC) and benzoyl group. Examples of the dye Y include pNA (p-nitroaniline) and MCA (7-methoxy). Coumarin-4-acetic acid), DNA (2,4-dinitroaniline), Dansyl dye and the like. Oligopeptides should have 2 to 10 amino acids, preferably 2 to 5, more preferably 3 to 4, and examples of tripeptides include Leu-Gly-Arg and Thr-Gly-Arg. it can.
In this case, a sample containing endotoxin is brought into contact with a reaction part containing a peptide to which a factor C, a factor B, a coagulase precursor, and a dye are bound, and the active factor C is converted from the factor C and the active factor B is converted from the factor B. The factor causes a cascade reaction in which active clotting enzymes are generated one after another from the clotting enzyme precursor and a release reaction of the dye from the peptide by the active clotting enzyme, and is applied to the sample and reaction part after the release reaction. Applying differential pulse voltammetry, endotoxins can be quantified based on the measured current value.
The active clotting enzyme generated by the cascade reaction releases the dye from the peptide to which the dye is bound in the sample and the reaction part. For example, when the peptide to which the dye is bound is Boc-Leu-Gly-Arg-pNA, the dye is pNA.
In addition, about the measuring method of such an endotoxin density | concentration, Unexamined-Japanese-Patent No. 2012-127695 can be referred, for example.

  Biosensors are widely used in reaction systems involving enzymes such as cholesterol sensors, alcohol sensors, scroll sensors, lactate sensors, and fructose sensors as well as glucose sensors and endotoxin sensors by changing the enzyme in the reaction part. be able to. As the enzyme 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 used as appropriate.

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 electron acceptor can obtain a reaction amount in accordance with the amount of enzyme (titer / unit), but it may be a small excess of the optimum mass 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 reaction part may contain a hydrophilic polymer or a surfactant. When a hydrophilic polymer is contained, the blood becomes a gel and the response current value is slightly reduced, but the influence on the sensor response of red blood cells and other proteins can be reduced. When a surfactant is contained, the sample can be easily guided to the reaction part even if the sample has a high viscosity.
As the hydrophilic polymer, carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, ethyl cellulose, methyl cellulose, polyvinyl pyrrolidone, polyvinyl alcohol, polyvinyl acetic acid, polyvinyl butyral, or a mixture thereof can be used.
Examples of the surfactant used in the reaction part include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, and polyethylene glycols.

The reaction part can be formed by applying a solution containing an enzyme and an electron acceptor on the working electrode of the electrode part and then drying to remove the solvent component.
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.

  The reaction part may be formed at the upper part of the working electrode. For example, the reaction part may be formed on the working electrode, the reaction part is formed between the spacer and the cover, and is opposed to the working electrode through a space. You may arrange so that.

2. Insulating layer In the present invention, an insulating layer may be formed on the supporting base so that the electrode part and the terminal part are exposed and the wiring part is covered. Since the insulating layer is formed so as to cover the wiring portion, corrosion of the wiring portion can be effectively prevented and a short circuit can be prevented.

As a material for the insulating layer, 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 insulating layer can be formed at a low cost. When an adhesive is used, the insulating layer can be formed with high accuracy.
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 insulating layer can 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 part and the reaction part, and the thickness of a wiring part.

As the formation position of the insulating layer, the insulating layer may be formed so as to cover the wiring portion and not the electrode portion and the terminal 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. Moreover, when using a double-sided tape as an adhesive agent, after patterning a double-sided tape by stamping etc., the method of sticking a double-sided tape on a support base material is mentioned.

3. Spacer The spacer in the present invention is formed on a supporting substrate and forms a sample supply path for supplying a sample to the electrode part and the reaction part. When the insulating layer is formed on the support base material, the spacer is formed on the edge layer.

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. A resin base material can also be used as the spacer.
Note that the adhesive is the same as the adhesive used for the insulating layer, and a description thereof will be omitted here.

  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. If the spacer is too thin, sample supply due to capillary action may not be stable. If the spacer is too thick, the sample may not flow uniformly to the reaction part, and the sample may not flow to a part of the reaction part.

The spacer forms a sample supply path. The sample supply channel is a channel provided through the spacer in the horizontal direction, and guides a sample supplied from the outside to the electrode unit and the reaction unit.
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 too narrow, stable sample supply due to capillary action may be difficult, or the area of the reaction part may be reduced and sensitivity may be reduced. Moreover, if the width of the sample supply path is too wide, when the biosensor is manufactured with multiple impositions, when the individual biosensors are cut, the spacer may collapse into an arch shape 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 from the back of the sample supply path toward the inlet.

Further, an air vent channel may be formed by the spacer. The 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 deeper than the electrode unit 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, after forming a sample supply path etc. by punching etc. in a double-sided tape, the method of sticking a double-sided tape on a support base material 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 on a support base material 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.

4). Cover The cover used in the present invention is disposed on the spacer so as to cover the sample supply path.

As the cover, for example, a resin substrate, a ceramic substrate, a glass substrate, a semiconductor substrate, a metal substrate, or the like can be used. As a resin base material, films, such as a polyethylene terephthalate (PET) resin, a vinyl chloride resin, a polystyrene (PS) resin, a polypropylene (PP) resin, a polyester resin, can be used suitably, for example.
The cover may or may not have flexibility. Moreover, the cover may have rigidity and may have elasticity.
In addition, when the biosensor is manufactured with multiple faces, the cover may be a roll or a single sheet.

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

  The shape of the cover is appropriately selected according to the arrangement of the electrode part, the wiring part, and the terminal part in the biosensor. For example, the cover may have a notch so that the terminal part is exposed. .

The cover may have an air hole that penetrates the cover. Sample supply by capillary action can be promoted in the biosensor.
In the biosensor of the present invention, the air hole is disposed so as to communicate with the sample supply path. Usually, in the region where the sample supply path is arranged, air holes are arranged in a region deeper than the electrode unit and the reaction unit.
The diameter of the air hole can be set within a range of 0.3 mm to 1 mm, for example.
Examples of the shape of the air hole include a circle, an ellipse, and a polygon.
Examples of the air hole forming method include laser processing, punching processing, and the like.

  The cover arrangement method is appropriately selected according to the configuration of the biosensor. For example, when a double-sided tape is used for the spacer or the insulating layer, the support base material on which the electrode portion, the wiring portion, and the terminal portion are formed and the cover can be bonded via the spacer or the insulating layer. Moreover, when forming a spacer using a photocurable resin or a thermosetting resin on a support base material, the support base material in which the spacer was formed and a cover can be bonded through an adhesive layer. .

5. FIG. 21A and FIG. 21B are schematic views showing a state in which the biosensor of the present invention is connected to the measurement apparatus, FIG. 21A is an overall view, and FIG. It is a figure explaining the inside of the measuring apparatus in the broken-line part of 21 (a).
As illustrated in FIGS. 21A and 21B, the measurement device 60 is a known measurement device that connects the biosensor 20 and detects an object to be detected included in the sample. . The measurement device 60 includes, for example, a connection electrode 63 for receiving an electrical signal generated by the biosensor 20, a calculation unit (not shown), a power source (not shown), a display unit 61, and an operation unit 62. When the biosensor 20 is attached to the attachment portion of the measurement device 60, the two terminal portions 18 of the biosensor 20 are connected to the connection electrodes 63 of the measurement device 60, respectively. With this connection, an electrical signal generated by the biosensor 20 is transmitted to the measuring device 60.

  As a measurement method, for example, a measurer attaches the biosensor 20 to the measurement device 60, introduces a sample from the tip of the biosensor 20 into a 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 unit of the biosensor 10. Then, the signal is transmitted from the terminal portion 18 via the electrode portion and the wiring portion 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 20 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.

  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 exhibits the same function and effect. Are included in the technical scope.

  Hereinafter, the present invention will be specifically described using examples and comparative examples.

[Example 1]
<Preparation of electrode stock for biosensor>
A conductive layer was formed by depositing nickel with a thickness of 50 nm on the entire surface of a PET resin substrate having a width of 35 mm, a length of 100 m, and a thickness of 250 μm. Next, a plating resist layer having a width of 29 mm, a length of 100 m, and a thickness of 10 μm was printed and formed by screen printing.
Next, a gold plating with a thickness of 50 nm was applied to the portion without the plating resist layer (width 6 mm, length 100 m) by electrolytic plating to form a noble metal plating layer. Finally, the plating resist layer was peeled off to obtain a biosensor electrode raw material having the configuration shown in FIGS. The overall width (distance indicated by c1 in FIG. 1 (a)) of the obtained biosensor electrode is 35 mm, and the width of the noble metal plating layer (distance indicated by a1 in FIG. 1 (a)) is 6 mm. there were.

<Production of electrodes for biosensors>
The obtained noble metal plating layer and conductive layer of the electrode raw material for biosensor were patterned using a laser ablation method. Further, as shown in FIG. 3, the biosensor electrode has a working electrode 13, a counter electrode 14, a reference electrode 15, and a part of the wiring part 17 having a noble metal plating layer in Example 1. And patterned. The biosensor electrode was obtained by the above procedure. The total length of the electrode part, wiring part and terminal part (distance indicated by d in FIG. 3) was 25 mm, and the width of the noble metal plating layer formation region (distance indicated by e in FIG. 3) was 5 mm. It was.

[Example 2]
A conductive layer was formed on the entire surface of a PET resin substrate having a width of 70 mm, a length of 100 m, and a thickness of 250 μm with a coater coated with carbon ink with a thickness of 5 μm. Next, a water-soluble ink layer having a width of 12.5 mm, a length of 100 m, and a thickness of 3 μm was printed at the center by gravure printing. Next, silver was vapor-deposited on the entire surface, and the water-soluble ink layer was washed with water to form a silver layer at a location other than the central portion. Next, a plating resist layer having a width of 26.25 mm was formed on each part other than the width of 12.5 mm (both the width of the center) by screen printing. Next, gold plating with a thickness of 50 nm was applied to the portion without the plating resist layer (width 12.5 mm, length 100 m) by electrolytic plating to form a noble metal plating layer. Finally, the plating resist layer was peeled off to obtain a biosensor electrode fabric having the configuration shown in FIG. The total width (distance indicated by c2 in FIG. 6A) of the obtained biosensor electrode was 70 mm, and the width of the noble metal plating layer (distance indicated by a2 in FIG. 6A) was 12. It was 5 mm.
Moreover, the biosensor electrode was obtained by the same method as in Example 1 using the biosensor electrode raw material described above.

[Comparative example]
By applying gold plating with a thickness of 50 nm on the entire surface of the same PET resin substrate as in Example 1 to form a noble metal plating layer, an electrode raw material for a biosensor was obtained.
In addition, a biosensor electrode was obtained in the same manner as in Example 1.

[Evaluation]
(Ratio of precious metal plating layer width)
The ratio of the width of the noble metal plating layer to the overall width of the electrode raw material (raw material) for biosensors of Examples 1 and 2 and the comparative example, and the electrode portion, wiring portion, and terminal of the electrode (electrode) for biosensor Table 1 shows the ratio of the width of the noble metal plating layer formation region (the width of the noble metal plating layer)) to the overall length of the portion.
In Examples 1-2, the usage-amount of the noble metal plating layer was able to be reduced.

(Resistance value)
The resistance value from the terminal part of the obtained biosensor electrode to the working electrode (one side electrode) was measured. The results are shown in Table 1. The resistance values in Table 1 are values measured using resistance values with a MAS830L high-precision digital multi-tester.
As shown in Examples 1 and 2, it was confirmed that the biosensor electrode having the noble metal plating layer and the conductive layer exhibited conductivity that can actually function as the biosensor electrode.

DESCRIPTION OF SYMBOLS 1 ... Raw material electrode for biosensors 2 ... Long resin base material 3 ... Conductive layer 4 ... Precious metal plating layer 5 ... Second conductive layer 10 ... Electrode for biosensor 13 ... Working electrode 14 ... Counter electrode 15 ... Reference electrode 16 ... Electrode unit 17 ... Wiring unit 18 ... Terminal unit 21 ... Reaction unit 24 ... Spacer 23 ... Sample supply path 25 ... Cover 20 ... Biosensor 60 ... Measuring device

Claims (4)

A biosensor electrode raw material used for producing a biosensor electrode having a support base material and an electrode portion, a wiring portion and a terminal portion formed on the support base material,
A long resin substrate;
A conductive layer formed on the resin substrate and containing a conductive material;
A noble metal plating layer which is used to form at least the electrode portion and is formed on the conductive layer and contains a noble metal;
The conductive layer is continuously formed in the longitudinal direction of the resin base material,
The noble metal plating layer is formed with a predetermined width in the width direction of the conductive layer, continuously formed in the longitudinal direction ,
An electrode raw material for a biosensor , comprising a second conductive layer formed on the conductive layer adjacent to the noble metal plating layer and containing a conductive material .   2. The biosensor electrode raw material according to claim 1, wherein the conductive layer is formed adjacent to each other in a plan view at both ends in the width direction of the noble metal plating layer. A biosensor electrode having a support substrate and an electrode portion, a wiring portion and a terminal portion formed on the support substrate,
The support substrate has a resin substrate;
The electrode portion has a conductive layer formed on the resin substrate and containing a conductive material and a noble metal plating layer formed on the conductive layer and containing a noble metal,
The wiring portion and the terminal portion, have a the conductive layer formed on the resin substrate,
Electrode biosensor, which comprises have a second conductive layer containing the precious metal plating layer is formed adjacent the conductive material on the conductive layer. A support substrate;
An electrode part, a wiring part and a terminal part formed on the support substrate;
A reaction part disposed on the electrode part;
A spacer that is formed on the support substrate and forms a sample supply path for supplying a sample to the electrode part and the reaction part;
A biosensor having a cover disposed on the spacer,
The support substrate has a resin substrate;
The electrode portion has a conductive layer formed on the resin substrate and containing a conductive material and a noble metal plating layer formed on the conductive layer and containing a noble metal,
The wiring portion and the terminal portion, have a the conductive layer formed on the resin substrate,
Biosensor characterized in that it have a second conductive layer containing the precious metal plating layer is formed adjacent the conductive material on the conductive layer.