JP2017009438A - Conductive substrate and method for manufacturing conductive substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a conductive substrate capable of easily forming a conductive portion containing noble metal with high resolution.SOLUTION: A conductive substrate has: a base material; a first conductive portion which is provided on the base material and has conductivity; and a second conductive portion which is provided on the base material so as to come in contact with the first conductive portion and has conductivity. The first conductive portion has: a first conductive layer; and a first catalyst layer which is provided between the first conductive layer and a first surface of the base material and contains a catalyst and a resin composition. The first conductive layer contains at least one of gold, palladium, platinum, rhodium, iridium, ruthenium and osmium.SELECTED DRAWING: Figure 2

Description

  The present invention relates to a conductive substrate that includes at least a base material and a first conductive portion that is provided on the base material and has conductivity. The present invention also relates to a method for manufacturing a conductive substrate.

  In electronic devices and electric devices in various fields, a conductive substrate including a base material and a conductive portion provided on the base material and having conductivity is used. When a conductive substrate is used in an application where corrosion is likely to occur or an application where corrosion should be suppressed, a noble metal such as gold or palladium may be used as a material constituting the conductive portion. For example, when a conductive substrate is used to construct a biosensor for measuring the concentration of glucose in blood, etc., the conductive portion of the conductive substrate comes into contact with an electrolyte solution such as blood to cause an electrochemical reaction. It functions as an electrode for generating. In this case, if the electrode itself is easily oxidized, and the electrode potential is unstable, a factor other than the current value resulting from the electrochemical reaction in the electrolyte appears in the measured current value. It becomes impossible to accurately measure the state of. For this reason, a noble metal that hardly corrodes is preferably used as a material constituting the conductive portion of the conductive substrate.

  On the other hand, precious metals are generally expensive. In addition, a biosensor is usually a consumable that is discarded for each test, and therefore it is required to be low in cost. In consideration of such problems, for example, in Patent Document 1, the conductive substrate may be configured such that the electrode part in contact with the electrolyte contains a noble metal and the wiring part connected to the electrode part does not contain a noble metal. Proposed. According to Patent Document 1, the cost of the conductive substrate can be reduced by making the material constituting the electrode portion and the material constituting the wiring portion different.

JP 2014-206516 A

  In the above-mentioned patent document 1, as an example of a method of forming an electrode part, a method of printing gold nano ink on a substrate by an ink jet printing method is cited. However, the resolution of a pattern formed by an ink jet printing method is generally lower than the resolution of a pattern formed by a high-precision patterning method such as a photolithography method. For this reason, the electroconductive board | substrate produced by the inkjet printing method is unsuitable for the use for which high resolution is calculated | required.

  Moreover, in the above-mentioned Patent Document 1, as another example of the method of forming the electrode portion, a method of forming a gold pattern by electrolytic plating on a nickel pattern formed by vapor deposition is also mentioned. . However, in this case, before the electrolytic plating step is performed, a step of masking a portion corresponding to the wiring portion in the nickel pattern is performed. In addition, a power feeding unit for feeding power to the nickel pattern is also required during the electrolytic plating process. The power feeding unit is removed after the electrolytic plating process. Thus, when forming a gold pattern by an electrolytic plating method, the man-hour of the process before and behind an electrolytic plating process will increase. Also, during the electroplating process, the gold plating solution infiltrates between the mask and the wiring part or base material. As a result, the size and arrangement of the gold pattern deviates from the design, and the amount of gold plating solution used. It is also conceivable that the value will increase more than expected.

  The present invention has been made in consideration of such points, and an object of the present invention is to provide a conductive substrate that can easily form a conductive portion containing a noble metal with high resolution and a method for manufacturing the same.

  The present invention includes a base material, a first conductive portion provided on the base material and having conductivity, and a second conductive portion provided on the base material so as to be in contact with the first conductive portion and having conductivity. And the first conductive part is provided between the first conductive layer, the first conductive layer, and the first surface of the substrate, and includes a catalyst and a resin composition. And the first conductive layer is a conductive substrate including at least one of gold, palladium, platinum, rhodium, iridium, ruthenium, and osmium.

  In the conductive substrate according to the present invention, the first catalyst layer may contain at least one of gold, palladium, platinum, rhodium, iridium, ruthenium or osnium.

  In the conductive substrate according to the present invention, the first conductive portion may be for forming an electrode that is brought into contact with the electrolytic solution to cause an electrochemical reaction.

  In the conductive substrate according to the present invention, the resin composition of the first catalyst layer may have photosensitivity.

  The present invention comprises: a first conductive part forming step for forming a first conductive part on a base material; and a second conductive part forming step for forming a second conductive part on the base material, The conductive portion is in contact with the first conductive portion, and the first conductive portion forming step includes a step of forming a first catalyst layer containing a catalyst and a resin composition on the base material, and a conductive material. Supplying a plating solution containing the base material to form a first conductive layer on the first catalyst layer, wherein the first conductive layer comprises gold, palladium, platinum, rhodium, iridium, It is a manufacturing method of a conductive substrate containing at least either ruthenium or osnium.

  In the method for producing a conductive substrate according to the present invention, the first catalyst layer may contain at least one of gold, palladium, platinum, rhodium, iridium, ruthenium or osnium.

  In the method for manufacturing a conductive substrate according to the present invention, the first conductive portion may be for forming an electrode that is brought into contact with an electrolytic solution to cause an electrochemical reaction.

  In the method for producing a conductive substrate according to the present invention, the resin composition of the first catalyst layer has photosensitivity, and the first catalyst layer forming step includes forming the first catalyst layer on the base material. There may be included a step of irradiating one catalyst layer with light and a step of developing the first catalyst layer irradiated with light.

  The present invention includes a base material, and a first conductive portion provided on the base material and having conductivity. The first conductive portion includes a first conductive layer, the first conductive layer, and the base. A first catalyst layer provided between the first surface of the material and containing a catalyst and a resin composition, wherein the first conductive layer is made of gold, palladium, platinum, rhodium, iridium, ruthenium or osnium. It is a conductive substrate containing at least any of the above.

  In the conductive substrate according to the present invention, the first catalyst layer may contain at least one of gold, palladium, platinum, rhodium, iridium, ruthenium or osnium.

  In the conductive substrate according to the present invention, the first conductive portion may be for forming an electrode that is brought into contact with the electrolytic solution to cause an electrochemical reaction.

  In the conductive substrate according to the present invention, the resin composition of the first catalyst layer may have photosensitivity.

  According to the present invention, a conductive part containing a noble metal can be easily formed with high resolution.

FIG. 1 is a plan view showing a conductive substrate according to an embodiment of the present invention. 2 is a cross-sectional view of the conductive substrate of FIG. 1 as viewed from the II-II direction. 3 is a cross-sectional view of the conductive substrate of FIG. 1 as viewed from the III-III direction. FIG. 4 is an exploded perspective view showing a concentration measurement sensor including a conductive substrate according to an embodiment of the present invention. FIG. 5 is a perspective view showing a concentration measurement sensor. 6A to 6D are views showing a process of forming the first conductive layer of the first conductive portion. FIGS. 7A to 7C are views showing a process of forming a stacked body by forming the second conductive layer of the second conductive portion. FIG. 8 is a plan view showing a laminate including a first conductive layer and a second conductive layer. FIG. 9 is a plan view showing a conductive substrate according to a first modification of the embodiment of the present invention. FIG. 10 is a plan view showing a conductive substrate according to a second modification of the embodiment of the present invention. FIG. 11 is a plan view showing a conductive substrate according to a third modification of the embodiment of the present invention. 12 is a cross-sectional view of the conductive substrate of FIG. 11 viewed from the XII-XII direction.

  Hereinafter, embodiments of the present invention will be described with reference to FIGS. In the drawings attached to the present specification, for the sake of illustration and ease of understanding, the scale, the vertical / horizontal dimension ratio, and the like are appropriately changed and exaggerated from those of the actual ones. Further, in this specification, terms such as “substrate”, “base material”, “sheet”, and “film” are not distinguished from each other based only on the difference in names. For example, “substrate” and “base material” are concepts including members that can be called sheets and films. Furthermore, as used in this specification, the shape and geometric conditions and the degree thereof are specified. For example, terms such as “parallel” and “orthogonal”, length and angle values, and the like are bound to a strict meaning. Therefore, it should be interpreted including the extent to which similar functions can be expected.

  First, the conductive substrate 10 according to the present embodiment will be described with reference to FIGS. 1 is a plan view showing the conductive substrate 10, FIG. 2 is a cross-sectional view of the conductive substrate 10 of FIG. 1 as viewed from the II-II direction, and FIG. 3 is a diagram of the conductive substrate 10 of FIG. It is sectional drawing which looked at from the III-III direction. In the present embodiment, the conductive substrate 10 measures the current generated due to the electrochemical reaction of a predetermined component contained in the electrolytic solution, and measures the concentration of the component in the electrolytic solution. An example for constituting a sensor will be described. Hereinafter, of the components in the electrolytic solution, the component whose concentration is to be measured is also referred to as a component to be measured.

As shown in FIG. 1, the conductive substrate 10 is provided on the base 12, the first surface 12 a of the base 12, the first conductive part 14 having conductivity, and the first conductive part 14. And a second conductive portion 18 that is provided on the first surface 12a of the substrate 12 and has conductivity. The base material 12 is configured such that at least the first surface 12a has an insulating property. The first conductive portion 14 includes a pair of working electrodes 15a and a counter electrode 15b disposed between the pair of working electrodes 15a. The working electrode 15a and the counter electrode 15b are electrodes that come into contact with the electrolytic solution when measuring the concentration of the component to be measured in the electrolytic solution. A gap 26 is formed between the working electrode 15a and the counter electrode 15b, whereby the working electrode 15a and the counter electrode 15b are electrically insulated.

  As shown in FIG. 1, the second conductive portion 18 includes a wiring 19 a having one end connected to the pair of working electrodes 15 a and a wiring 19 b having one end connected to the counter electrode 15 b. Further, on the first surface 12a of the substrate 12, a terminal portion 22 having a terminal 23a connected to the other end of the wiring 19a and a terminal 23b connected to the other end of the wiring 19b is further provided. . The terminals 23 a and 23 b are portions to which cables and connectors for applying a voltage to and extracting a current from the concentration measurement sensor 40 (described later) including the conductive substrate 10 are connected. As shown in FIG. 1, there are gaps for ensuring electrical insulation between the working electrode 15a and the wiring 19b, between the counter electrode 15b and the wiring 19a, between the terminal 23a and the terminal 23b, and the like. 26 is formed. In FIG. 1, the boundary line between the wiring 19a of the second conductive portion 18 and the terminal 23a of the terminal portion 22 is drawn for convenience. As will be described later, the wiring 19a and the terminal 23a are connected to the second conductive portion. The layer 36 may be integrally formed. The same applies to the wiring 19b and the terminal 23b.

  As shown in FIG. 1, a floating conductive portion 28 that is insulated from the first conductive portion 14, the second conductive portion 18, and the terminal portion 22 by a gap 26 is further provided on the first surface 12 a of the substrate 12. It may be.

  Hereinafter, the layer configuration of the first conductive portion 14, the second conductive portion 18, and the terminal portion 22 will be described.

(First conductive part)
As shown in FIGS. 2 and 3, the first conductive portion 14 such as the working electrode 15 a and the counter electrode 15 b is provided between the first conductive layer 32 and the first conductive layer 32 and the first surface 12 a of the substrate 12. And a first catalyst layer 33 provided on the surface. The first catalyst layer 33 is a layer containing a catalyst for selectively depositing a conductive material constituting the first conductive layer 32 when the first conductive layer 32 is formed by an electroless plating process described later. . Note that “selective” means that the probability that the conductive material is deposited on the portion of the base material 12 where the catalyst is present is higher than the probability that the conductive material is deposited on other portions of the base material 12. I mean.

  A noble metal is used as the conductive material constituting the first conductive layer 32. Specifically, the first conductive layer 32 includes at least one of noble metals such as gold, palladium, platinum, rhodium, iridium, ruthenium, and osnium, and the surface of the first conductive layer 32 is configured by these noble metals. . As a result, the first conductive layer 32 can have high corrosion resistance. Thereby, it is possible to prevent the potential of the first conductive portion 14 from becoming unstable when the first conductive portion 14 is in contact with the electrolytic solution. For this reason, it can suppress that the electric current value resulting from the electrochemical reaction of the to-be-measured component in electrolyte solution fluctuates by the oxidation reaction of 1st electroconductive part 14 itself. The thickness of the first conductive layer 32 is in the range of 0.005 μm to 1 μm, and more preferably in the range of 0.05 μm to 0.30 μm. By setting the thickness of the working electrode 15a and the counter electrode 15b of the first conductive portion 14 to 0.005 μm or more, more preferably 0.01 μm or more, the electrical resistance of the first conductive portion 14 can be sufficiently reduced. Moreover, the manufacturing cost of the 1st electroconductive part 14 can be reduced by making thickness of the working electrode 15a and the counter electrode 15b of the 1st electroconductive part 14 into 1 micrometer or less, More preferably, 0.20 micrometer or less. In the present specification, the numerical range represented by the symbol “to” includes numerical values placed before and after the symbol “to”. For example, the numerical range defined by the expression “0.005 μm to 1 μm” is the same as the numerical range defined by the expression “0.005 μm to 1 μm”.

  In the present embodiment, as will be described later, first, the first catalyst layer 33 including the photosensitive resin composition and the catalyst added to the resin composition is used as the first surface 12a side of the substrate 12. Then, the first catalyst layer 33 is exposed to light to expose the first catalyst layer 33, and then the first catalyst layer 33 is developed, whereby the working electrode 15a of the first conductive portion 14 is developed. The first catalyst layer 33 having a pattern corresponding to the counter electrode 15b is formed. The catalyst contained in the first catalyst layer 33 is appropriately selected according to the conductive material contained in the plating solution for forming the first conductive layer 32. For example, as disclosed in WO2012-141216, iron, cobalt, nickel, copper, palladium, silver, tin, platinum, gold, and alloys thereof can be used as a catalyst. The catalyst of the first catalyst layer 33 exists as fine particles, for example. The thickness of the first catalyst layer 33 is, for example, in the range of 0.001 μm to 10 μm, and more preferably in the range of 0.005 μm to 0.050 μm.

  The photosensitive resin composition is a material that changes physical properties such as solubility based on a reaction induced by light irradiation. Conventionally, ultraviolet rays such as i-line and g-line of a mercury lamp have been widely used as light irradiated to the resin composition. In addition, as a resin composition whose solubility is changed by irradiation with i-line or g-line, for example, a resin composition in which novolak resin is used as a base resin and naphthoquinone diazide is added as a dissolution inhibitor to the base resin is known. ing.

  The resin composition of the first catalyst layer 33 is appropriately selected according to the wavelength of light to be irradiated, the photosensitive type including a positive type or a negative type, and the like. Preferably, the resin composition is selected so that the catalyst can be stably held by adsorption or the like. For example, as the resin composition of the first catalyst layer 33, in addition to the above-described novolak resin, photosensitive polyimide, photosensitive polybenzoxazole, polyhydroxystyrene, naphthoquinonediazide compound, epoxy resin, acrylic resin, dendritic resin Resin materials generally used as a base resin for resist, such as a polymer and an ammonium-terminated hyperbranched polymer, can be used.

  When the first catalyst layer 33 includes a photosensitive resin composition and palladium as a catalyst, as a commercially available member for forming the first catalyst layer 33, for example, electroless plating manufactured by Nissan Chemical Industries, Ltd. Nuclear material MC-001 can be used.

  The first catalyst layer 33 is applied to the resin composition of the first catalyst layer 33 as long as the first catalyst layer 33 can be processed by exposure and development so that the first catalyst layer 33 has a pattern corresponding to the first conductive portion 14. The photosensitivity is not particularly limited. For example, the resin composition of the first catalyst layer 33 may have a so-called negative photosensitivity that is cured by being irradiated with light, or is a so-called positive that is softened by being irradiated with light. The mold may have photosensitivity.

  When the resin composition of the first catalyst layer 33 has negative photosensitivity, as a polymerization initiator added to the resin composition, a photoanionic polymerization initiator, a photocationic polymerization initiator, a photoradical polymerization initiator, etc. A type can be used. Specific examples of the polymerization initiator include bisazide compounds. In addition, when the resin composition of the first catalyst layer 33 has positive photosensitivity, examples of the polymerization initiator added to the resin composition include 1,2-naphthoquinonediazide sulfonic acid ester compounds. Can do. In the following description, a case where the resin composition of the first catalyst layer 33 has negative photosensitivity will be described.

  By the way, when the parallel light traveling along the direction orthogonal to the normal direction of the first catalyst layer 33 is irradiated to the first catalyst layer 33 through the opening of the mask, the light in the first catalyst layer 33 is light. The dimension of the region that reacts to is usually larger than the dimension of the opening of the mask due to light diffraction. Therefore, when the resin composition of the first catalyst layer 33 has negative photosensitivity, the size of the region cured by light irradiation is larger than the size of the opening of the mask. As a result, the dimensions such as the width of the first conductive portion 14 are also larger than the dimensions of the opening of the mask. For this reason, when the first conductive portion 14 including the working electrode 15a and the counter electrode 15b having a small width, for example, a width of about several μm is to be formed, the size of the opening of the mask is set to the light caused by light diffraction. It will be set in consideration of the spread of. In consideration of this point, when the first conductive portion 14 including the working electrode 15a and the counter electrode 15b having a small width, for example, a width of about several μm is to be formed, the resin composition of the first catalyst layer 33 is positive. It is considered preferable to have the photosensitivity of the mold.

  Preferably, a noble metal is used as the catalyst contained in the first catalyst layer 33 as in the first conductive layer 32. Specifically, the first catalyst layer 33 includes at least one of noble metals such as gold, palladium, platinum, rhodium, iridium, ruthenium or osnium as a catalyst. In this case, the stability of the potential of not only the first conductive layer 32 but also the first catalyst layer 33 can be improved. For this reason, even if the electrolytic solution contacts not only the first conductive layer 32 but also the first catalyst layer 33, the current value caused by the electrochemical reaction of the component to be measured in the electrolytic solution is further suppressed. can do.

(Second conductive part)
As shown in FIGS. 2 and 3, the second conductive portion 18 such as the wiring 19 a and the wiring 19 b has a second conductive layer 36. The second conductive portion 18 is for transmitting the current value resulting from the electrochemical reaction of the component to be measured in the electrolytic solution from the first conductive portion 14 to the outside of the conductive substrate 10. The possibility that the second conductive portion 18 is in contact with the electrolytic solution is low, and therefore the corrosion resistance required for the second conductive portion 18 is lower than the corrosion resistance required for the first conductive portion 14. . Therefore, the material constituting the second conductive layer 36 of the second conductive portion 18 only needs to have sufficient conductivity, and does not need to have high corrosion resistance. As a material constituting the second conductive layer 36, copper, silver, aluminum, conductive carbon, or the like can be used. The thickness of the second conductive layer 36 is in the range of 0.005 μm to 40 μm, and more preferably in the range of 0.01 μm to 2 μm.

  As long as the working electrode 15a of the first conductive portion 14 and the wiring 19a of the second conductive portion 18 can be electrically connected, for example, the first conductive layer 32, the first catalyst layer 33, and the second conductive layer 36 are used. The positional relationship with is not particularly limited. For example, as shown in FIGS. 2 and 3, the second conductive layer 36 may be configured to cover a part of the surface of the first conductive layer 32. Or although not shown in figure, the 1st catalyst layer 33 and the 1st conductive layer 32 may be comprised so that a part of surface of the 2nd conductive layer 36 may be covered.

  As shown in FIG. 3, the terminal portion 22 and the floating conductive portion 28 may have a second conductive layer 36 similarly to the second conductive portion 18.

(Base material)
As long as the 1st electroconductive part 14 and the 2nd electroconductive part 18 can be supported, the material which comprises the base material 12 is not specifically limited. For example, a flexible material may be used as the material constituting the substrate 12, or a hard material may be used. In other words, the conductive substrate 10 may be configured as a so-called flexible substrate having flexibility, or may be configured as a so-called rigid substrate having high rigidity. When the electroconductive board | substrate 10 is comprised as a rigid board | substrate, as a material which comprises the base material 12, well-known materials, such as glass epoxy, can be mentioned.

  When the conductive substrate 10 has flexibility, examples of the material constituting the base material 12 include resin materials such as polyester resin, epoxy resin, and polyimide resin. Moreover, you may use the glass shape | molded thinly to such an extent that it has flexibility as a material which comprises the base material 12. FIG. The thickness of the base material 12 is set within a range of 10 μm to 300 μm, for example.

  In this specification, “flexible” means that the conductive substrate 10 is folded when the conductive substrate 10 is wound into a roll shape having a diameter of 30 cm in an environment of room temperature, for example, 25 ° C. It means no degree of flexibility. A “fold” is a deformation that appears in the conductive substrate 10 in a direction that intersects the direction in which the conductive substrate 10 is wound, and that the conductive substrate 10 is wound in the opposite direction so as to restore the deformation. This means that the deformation does not return to the original level.

  By the way, the surface of the substrate 12 such as the first surface 12a generally has a concave portion or a convex portion. That is, a predetermined roughness exists on the surface of the substrate 12. As will be described later, when the first conductive layer 32 is formed by plating, the surface of the first conductive layer 32 may also reflect the roughness of the first surface 12a of the substrate 12. On the other hand, the degree of progress of the electrochemical reaction in the first conductive part 14 in contact with the electrolytic solution is proportional to the area of the surface of the first conductive part 14, that is, the area of the surface of the first conductive layer 32. Accordingly, when the surface of the first conductive layer 32 has a concave portion or a convex portion, and the area of the surface of the first conductive layer 32 increases by the amount of the concave portion or the convex portion, the electrochemical reaction in the first conductive portion 14 proceeds. The degree also increases. That is, the value of the current flowing through the first conductive portion 14 is not only the concentration of the component to be measured in the electrolyte solution in contact with the first conductive portion 14 but also the surface of the first conductive layer 32 constituting the first conductive portion 14. Depends on the roughness of the. Therefore, in order to calculate the concentration of the component to be measured more accurately, the substrate 12 having a small roughness of the first surface 12a is employed, thereby reducing the roughness of the surface of the first conductive layer 32. preferable. For example, it is preferable to use the substrate 12 having an arithmetic average roughness Ra on the first surface 12a of 100 nm or less. In addition, the evaluation method of arithmetic average roughness Ra is prescribed | regulated by JISB0606-2001, for example.

Concentration Measurement Sensor Next, an example in which the concentration measurement sensor 40 that measures the concentration of the component to be measured in the electrolytic solution using the above-described conductive substrate 10 will be described. FIG. 4 is an exploded perspective view showing the concentration measurement sensor 40 provided with the conductive substrate 10, and FIG. 5 is a perspective view showing the concentration measurement sensor 40.

  As shown in FIG. 4, the concentration measurement sensor 40 includes a conductive substrate 10 having a first conductive portion 14, a second conductive portion 18, and a terminal portion 22 provided on the first surface 12 a side of the substrate 12, and a conductive material. Spacer 42 disposed on the first surface 12a side of the base 12 of the conductive substrate 10. A sample supply path 43 is formed in the spacer 42 so as to overlap the first conductive portion 14 of the conductive substrate 10. The sample supply path 43 is configured to expose the first conductive portion 14 of the conductive substrate 10 overlapped with the spacer 42 to the outside. For example, the sample supply path 43 is configured as an opening or a notch. The sample supply path 43 functions to guide an electrolytic solution such as blood supplied to the concentration measurement sensor 40 to the first conductive portion 14 by capillary action. The width of the sample supply path 43 is, for example, in the range of 0.5 mm to 5 mm.

  As shown in FIG. 4, a cover 46 may be disposed on the spacer 42 so as to sandwich the spacer 42 with the conductive substrate 10. An air hole 47 is formed in the cover 46 so as to overlap the sample supply path 43 of the spacer 42. Further, the reaction unit 44 may be arranged between the cover 46 and the spacer 42 so as to overlap the first conductive unit 14 of the conductive substrate 10 exposed from the sample supply path 43 of the spacer 42. The reaction unit 44 includes a material for promoting an electrochemical reaction of a component to be measured in the electrolytic solution. For example, when the concentration measurement sensor 40 is for measuring the concentration of glucose in blood, the reaction unit 44 includes glucose oxidase that decomposes glucose to generate glucolactone and hydrogen peroxide.

  As a material constituting the spacer 42 and the cover 46, the same material as that constituting the base 12 is used. For example, the spacer 42 and the cover 46 are made of an insulating resin material. The spacer 42 has a thickness in the range of 15 μm to 500 μm, for example. The cover 46 has a thickness in the range of 50 μm to 100 μm, for example.

  Although not shown, an insulating layer that covers the second conductive portion 18 may be disposed between the conductive substrate 10 and the spacer 42. Further, a further base material for supporting the conductive substrate 10 may be provided on the second surface 12 b side of the base material 12 of the conductive substrate 10.

Method for Measuring Concentration of Component to be Measured A method for measuring the concentration of the component to be measured in the electrolytic solution, here, the concentration of glucose using the concentration measuring sensor 40 thus configured will be described.

  When the user supplies an electrolyte such as blood to the sample supply path 43 of the concentration measurement sensor 40, the electrolyte is drawn into the concentration measurement sensor 40 due to the capillary phenomenon of the sample supply path 43. When the electrolytic solution reaches the reaction part 44, a current flows through the first conductive part 14 as described below.

  The reaction unit 44 contains potassium ferricyanide as an electron acceptor in addition to the glucose oxidase described above. In this case, the reaction unit 44 specifically reacts with glucose in the blood, and emits gluconic acid and electrons. This electron turns potassium ferricyanide into potassium ferrocyanide. Potassium ferrocyanide becomes potassium ferricyanide again when a voltage is applied to the blood from the outside via the terminal portion 22, the second conductive portion 18, and the first conductive portion 14. At this time, a current proportional to the concentration of glucose in the blood is generated. The concentration of glucose in the blood can be calculated by taking out and measuring this current flowing through the first conductive portion 14 through the second conductive portion 18 and the terminal portion 22 to the outside. Details of the electrochemical reaction that occurs in the reaction unit 44 and the first conductive unit 14 are described in, for example, Japanese Patent Application Laid-Open No. 2014-163838, and thus the description thereof is omitted here.

  The electrolyte supplied to the concentration measurement sensor 40 is not limited to blood. In addition, a current value caused by an electrochemical reaction of a component to be measured by supplying an electrolyte derived from a living body such as sweat or urine, an electrolyte derived from the environment, an electrolyte derived from food, or the like to the concentration measurement sensor 40 May be measured.

  In the above-described concentration measurement sensor 40, the example in which the conductive substrate 10 is used for calculating the concentration of the component to be measured by measuring the current flowing through the electrochemical reaction is shown. However, the conductive substrate 10 is used to cause an electrochemical reaction in the electrolytic solution in contact with the first conductive portion 14, thereby transdermally injecting a predetermined component in the electrolytic solution into a human body or the like. May be. That is, the conductive substrate 10 may be used to perform so-called ion foresis.

Method for Manufacturing Conductive Substrate Next, an example of a method for manufacturing the conductive substrate 10 will be described.

  First, the base material 12 is prepared. At this time, the elongate base material 12 may be prepared, or the base material 12 which has the same external shape as the electroconductive board | substrate 10 may be prepared. That is, the method of manufacturing the conductive substrate 10 may be performed by a so-called roll-to-roll method in which the long base 12 is conveyed while being transported along the longitudinal direction of the base 12, or You may implement by what is called a sheet-fed system.

(First conductive part forming step)
Next, the 1st electroconductive part formation process which forms the 1st electroconductive part 14 on the 1st surface 12a of the base material 12 is implemented. For example, first, as shown in FIG. 6A, a first catalyst layer 33 containing a catalyst and a resin composition is formed on the first surface 12 a of the substrate 12. Next, a catalyst layer irradiation step of irradiating the first catalyst layer 33 with light is performed so that the first catalyst layer 33 remains on the first surface 12a of the substrate 12 in a pattern corresponding to the first conductive portion 14. For example, as shown in FIG. 6B, first, a mask 70 including an opening 71 and a shielding part 72 is disposed in the vicinity of the first catalyst layer 33. The opening 71 is formed in a pattern corresponding to the first conductive portion 14. Next, the first catalyst layer 33 is irradiated with light through the mask 70. Accordingly, the first catalyst layer 33 can be cured by irradiating the first catalyst layer 33 with light in a pattern corresponding to the opening 71. Next, the first catalyst layer 33 irradiated with light is developed. For example, by supplying a developer such as an alkaline aqueous solution to the first catalyst layer 33, a portion of the first catalyst layer 33 that is not irradiated with light is dissolved in the developer. In this way, as shown in FIG. 6C, the first catalyst layer 33 containing the catalyst and the resin composition is formed on the first surface 12 a of the substrate 12 in a pattern corresponding to the first conductive portion 14. The first catalyst layer forming step is completed.

  Thereafter, a plating solution containing a conductive material having a noble metal such as gold, palladium, platinum, rhodium, iridium, ruthenium or osnium is supplied to the substrate 12. That is, an electroless plating process is performed. Thereby, as shown in FIG. 6D, the first conductive layer 32 can be formed on the first catalyst layer 33. That is, the first conductive layer 32 having a pattern corresponding to the first catalyst layer 33 can be formed on the first surface 12 a side of the substrate 12.

  As the plating solution, a solution containing ions of a conductive material such as gold, palladium, platinum, rhodium, iridium, ruthenium or osnium is used. The plating solution may appropriately contain a complexing agent, a reducing agent, a pH adjusting agent, a pH buffering agent, a reaction accelerator, a stabilizer, a surfactant, and the like as disclosed in WO2012-141216. . For example, when the plating solution contains palladium as a conductive material, as a commercially available plating solution, Parasigma EL manufactured by Matsuda Sangyo Co., Ltd., Neoparabright Pd plating solution manufactured by Nihon Kojun Chemical Co., Ltd., or the like can be used.

  In order to improve the adhesion of the first catalyst layer 33 to the base material 12, after the first catalyst layer 33 is formed on the first surface 12a of the base material 12, or after the development of the first catalyst layer 33, A heat treatment step for heating the first catalyst layer 33 may be performed. Further, in order to increase the density of the catalyst on the surface of the first catalyst layer 33, for example, as disclosed in WO2012-141216, after the first catalyst layer 33 is developed, the first catalyst layer 33 is activated. Also good.

(Second conductive part forming step)
Next, a second conductive part forming step is performed in which the second conductive part 18 is formed on the first surface 12 a of the base material 12 so as to be in contact with the first conductive part 14. For example, first, as shown in FIG. 7A, the first conductive portion 14 is partially covered with a resist layer 35. For example, in the present embodiment, a portion of the first conductive portion 14 that can come into contact with the electrolytic solution when the conductive substrate 10 is incorporated in the concentration measurement sensor 40 is covered with the resist layer 35. As a method for forming the resist layer 35, for example, a photolithography method can be employed.

  Next, as shown in FIG. 7B, the second conductive layer 36 is formed on the first surface 12 a side of the substrate 12. A method for forming the second conductive layer 36 is not particularly limited, and a vacuum film formation method such as an evaporation method or a sputtering method, a plating method, a printing method, or the like can be appropriately employed.

  Thereafter, as shown in FIG. 7C, the resist layer 35 is removed. Thereby, the second conductive layer 36 formed on the resist layer 35 is also removed at the same time. In this way, the first conductive portion 14 provided on the first surface 12a of the base 12 and the second conductive portion provided on the first surface 12a of the base 12 so as to be in contact with the first conductive portion 14. 18 can be obtained. FIG. 8 is a plan view showing the stacked body 30. FIG. 7C is a cross-sectional view of the stacked body 30 of FIG. 8 viewed from the VII-VII direction.

  7A to 7C, the second conductive layer 36 is formed in a state where the first conductive portion 14 is partially covered with the resist layer 35, and then the second conductive layer on the resist layer 35 is formed. An example in which the layer 36 is removed together with the resist layer 35 is shown. However, the present invention is not limited to this, and the second conductive layer 36 may be formed on the first surface 12 a of the substrate 12 without providing the resist layer 35. In this case, as the direction in which the second conductive layer 36 is formed, the second conductive layer 36 may be selectively formed on an arbitrary portion of the first surface 12a of the substrate 12, such as an ink jet printing method or a screen printing method. Possible methods can be employed.

(Processing process of laminate)
Next, the first conductive portion 14 and the second conductive portion 18 are processed so that the first conductive portion 14, the second conductive portion 18, and the boundary between the first conductive portion 14 and the second conductive portion 18 are A gap 26 is formed. Accordingly, the first conductive portion 14 having the working electrode 15a and the counter electrode 15b, the second conductive portion 18 having the wiring 19a and the wiring 19b connected to the working electrode 15a and the counter electrode 15b, and the wiring 19a and the wiring 19b, respectively. And the terminal part 22 having the terminal 23a and the terminal 23b respectively connected to the conductive substrate 10 can be obtained.

  As described above, in the conductive substrate 10 according to the present embodiment, noble metal is used in the first conductive portion 14 that is in contact with the electrolytic solution, and noble metal such as nickel and copper is used in the second conductive portion 18 and the terminal portion 22. A cheaper material is used. For this reason, compared with the case where a noble metal is used for all the electroconductive parts of the electroconductive board | substrate 10, the manufacturing cost of the electroconductive board | substrate 10 can be reduced.

  In the present embodiment, the first conductive layer 32 containing a noble metal is formed on the first catalyst layer 33 containing a catalyst and a resin composition by electroless plating. The first catalyst layer 33 is configured to have photosensitivity, and therefore, the pattern of the first catalyst layer 33 can be accurately determined using a photolithography method. Therefore, the pattern of the first conductive layer 32 formed on the first catalyst layer 33 can be determined with higher accuracy than when a printing method such as an inkjet method is used. For this reason, the electroconductive board | substrate 10 which can be utilized in the use for which high resolution is calculated | required can be provided. Moreover, since the 1st conductive layer 32 can be selectively deposited on the 1st catalyst layer 33, it can suppress that the 1st conductive layer 32 precipitates in an unnecessary location, Thereby, The amount of plating solution containing noble metal can be reduced. Also in this respect, according to the present embodiment, the manufacturing cost of the conductive substrate 10 can be reduced.

  Note that various modifications can be made to the above-described embodiment. Hereinafter, modified examples will be described with reference to the drawings as necessary. In the following description and the drawings used in the following description, the same reference numerals as those used for the corresponding parts in the above embodiment are used for the parts that can be configured in the same manner as in the above embodiment. A duplicate description is omitted. In addition, when it is clear that the operational effects obtained in the above-described embodiment can be obtained in the modified example, the description thereof may be omitted.

(First modification)
In the above-described embodiment, the example in which the wiring 19a and the wiring 19b of the second conductive portion 18 are in contact with the working electrode 15a and the counter electrode 15b of the first conductive portion 14 has been described. However, as long as the wiring 19a and the wiring 19b of the second conductive portion 18 are electrically connected to the working electrode 15a and the counter electrode 15b of the first conductive portion 14, other electrodes and wirings are interposed therebetween, respectively. It may be. For example, as shown in FIG. 9, the first conductive portion 14 is disposed along the outer edge of the base material 12 and is disposed along the outer edge of the base material 12 and the intermediate electrode 15 c connected to the pair of working electrodes 15 a. And an intermediate electrode 15d connected to the counter electrode 15b. One end of the wiring 19a of the second conductive portion 18 is connected to the intermediate electrode 15c, and one end of the wiring 19b is connected to the intermediate electrode 15d. Therefore, the wiring 19a and the wiring 19b are electrically connected to the working electrode 15a and the counter electrode 15b via the intermediate electrode 15c and the intermediate electrode 15d, respectively. Similarly to the working electrode 15a and the counter electrode 15b, the intermediate electrode 15c and the intermediate electrode 15d are a first conductive layer 32, and a first electrode provided between the first conductive layer 32 and the first surface 12a of the substrate 12. And a catalyst layer 33.

(Second modification)
In the above-described embodiment, the example in which the first conductive portion 14 of the conductive substrate 10 is for forming an electrode that is brought into contact with the electrolytic solution to cause an electrochemical reaction has been described. There is no limit. For example, the conductive substrate 10 may be used in applications in which an electrochemical reaction does not occur in a liquid that is in contact with the first conductive portion 14 of the conductive substrate 10 such as a PH sensor. Further, the first conductive portion 14 of the conductive substrate 10 may function as a mounting electrode on which an electronic component or an optical component is mounted, or a connection electrode to which a connector is connected. In this case, in the first conductive layer 32 constituting the surface of the first conductive portion 14, the use of the above-described noble metal such as palladium suppresses occurrence of problems such as electromigration in the first conductive portion 14. be able to. Thereby, the reliability of the mounting electrode and the connection electrode constituted by the first conductive portion 14 can be improved.

  FIG. 10 is a plan view showing the conductive substrate 10 in which the first conductive portion 14 is configured to function as a mounting electrode. In the example illustrated in FIG. 10, the first conductive portion 14 of the conductive substrate 10 includes mounting electrodes 16 a to 16 d on which four terminals of electronic components (not shown) are mounted. The second conductive portion 18 includes wirings 20a to 20d to which the corresponding mounting electrodes 16a to 16d of the first conductive portion 14 are connected. The terminal portion 22 has terminals 24a to 24d to which the corresponding wirings 20a to 20d of the second conductive portion 18 are respectively connected.

  In the example shown in FIG. 10, a noble metal is used in the first conductive portion 14 that contacts the terminal of the electronic component, and an inexpensive material such as nickel or copper is used in the second conductive portion 18 or the terminal portion 22. Used. For this reason, the manufacturing cost of the conductive substrate 10 can be reduced. The first conductive portion 14 is produced by forming the first conductive layer 32 containing a noble metal on the first catalyst layer 33 containing a catalyst and a resin composition by electroless plating. For this reason, each mounting electrode 16a-16d of the 1st electroconductive part 14 can be precisely formed with high resolution. Moreover, the usage-amount of the plating solution containing a noble metal can also be reduced.

(Third Modification)
In the above-described embodiment, the example in which the conductive substrate 10 includes the first conductive portion 14 including the noble metal and the second conductive portion 18 not including the noble metal has been described. However, the present invention is not limited to this, and as shown in FIG. 11, the working electrode 15a, the counter electrode 15b, the wiring 19a, the wiring 19b, the terminal 23a, the terminal 23b, etc. are all formed by the first conductive portion 14 containing a noble metal. It may be configured. 12 is a cross-sectional view of the conductive substrate 10 of FIG. 11 as viewed from the XII-XII direction. Also in this modified example, as in the case of the above-described embodiment, the first conductive portion 14 is provided between the first conductive layer 32 and the first conductive layer 32 and the first surface 12a of the substrate 12. And a first catalyst layer 33 provided. Therefore, the working electrode 15a, the counter electrode 15b, the wiring 19a, the wiring 19b, the terminal 23a, and the terminal 23b can be precisely formed with high resolution. Moreover, compared with the case where the 1st conductive layer 32 is formed into a film over the whole region of the base material 12, the usage-amount of the plating solution containing a noble metal can also be reduced.

(Other variations)
In the above-described embodiment and each modification, an example in which the first catalyst layer 33 formed on the substrate 12 is irradiated with light and thereby the first catalyst layer 33 is patterned is shown. However, the present invention is not limited to this, and the first catalyst layer 33 may be patterned by irradiating the first catalyst layer 33 formed on the substrate 12 with an electron beam. That is, the above-described catalyst layer irradiation step may be a step of irradiating the first catalyst layer 33 with an electron beam so that the first catalyst layer 33 remains in a pattern corresponding to the first conductive portion 14. In this case, the first catalyst layer 33 may not contain a polymerization initiator. As a resin composition of the 1st catalyst layer 33, a well-known electron beam curable resin composition which is disclosed by Unexamined-Japanese-Patent No. 2014-051013 can be used, for example. Moreover, as an electron beam, the kind of electron beam generally utilized in order to harden an electron beam curable resin composition as disclosed by Unexamined-Japanese-Patent No. 2014-051013 can be used, for example.

  Further, in the above-described embodiment and each modification, examples in which the first catalyst layer 33 is configured to have photosensitivity have been shown. For example, the example which the 1st catalyst layer 33 hardens | cures by irradiating light was shown. However, the present invention is not limited to this, and the first catalyst layer 33 may be configured to be cured by applying heat.

  In addition, although some modified examples with respect to the above-described embodiment have been described, naturally, a plurality of modified examples can be applied in combination as appropriate.

DESCRIPTION OF SYMBOLS 10 Conductive substrate 12 Base material 14 1st electroconductive part 15a Working electrode 15b Counter electrode 15c Intermediate electrode 15d Intermediate electrode 16a-16d Mounting electrode 18 2nd electroconductive part 19a Wiring 19b Wiring 20a-20d Wiring 22 Terminal part 23a Terminal 23b Terminal 24a to 24d Terminal 26 Gap 28 Floating conductive part 30 Laminate 32 First conductive layer 33 First catalyst layer 35 Resist layer 36 Second conductive layer 40 Concentration measuring sensor 42 Spacer 43 Sample supply path 44 Reaction part 46 Cover 47 Air hole

Claims (12)

A substrate;
A first conductive portion provided on the base material and having conductivity;
A second conductive part provided on the base material so as to be in contact with the first conductive part, and having conductivity,
The first conductive portion includes a first conductive layer, and a first catalyst layer provided between the first conductive layer and the base material and including a catalyst and a resin composition,
The first conductive layer is a conductive substrate including at least one of gold, palladium, platinum, rhodium, iridium, ruthenium or osnium.   2. The conductive substrate according to claim 1, wherein the first catalyst layer includes at least one of gold, palladium, platinum, rhodium, iridium, ruthenium, and osnium.   3. The conductive substrate according to claim 1, wherein the first conductive portion is for forming an electrode that is brought into contact with an electrolytic solution to cause an electrochemical reaction. 4.   4. The conductive substrate according to claim 1, wherein the resin composition of the first catalyst layer has photosensitivity. 5. A first conductive part forming step of forming a first conductive part on the substrate;
A second conductive part forming step of forming a second conductive part on the substrate,
The second conductive part is in contact with the first conductive part,
The first conductive part forming step includes:
A first catalyst layer forming step of forming a first catalyst layer containing a catalyst and a resin composition on the substrate;
Supplying a plating solution containing a conductive material to the substrate to form a first conductive layer on the first catalyst layer, and
The first conductive layer includes at least one of gold, palladium, platinum, rhodium, iridium, ruthenium, and osnium.   The method for manufacturing a conductive substrate according to claim 5, wherein the first catalyst layer includes at least one of gold, palladium, platinum, rhodium, iridium, ruthenium, and osnium.   The method of manufacturing a conductive substrate according to claim 5 or 6, wherein the first conductive portion is for forming an electrode that is brought into contact with an electrolytic solution to cause an electrochemical reaction. The resin composition of the first catalyst layer has photosensitivity,
The first catalyst layer forming step includes a step of irradiating the first catalyst layer formed on the substrate with light and a step of developing the first catalyst layer irradiated with the light. The manufacturing method of the electroconductive board | substrate as described in any one of Claims 5 thru | or 7. A substrate;
A first conductive portion provided on the base material and having conductivity,
The first conductive portion includes a first conductive layer, and a first catalyst layer provided between the first conductive layer and the base material and including a catalyst and a resin composition,
The first conductive layer is a conductive substrate including at least one of gold, palladium, platinum, rhodium, iridium, ruthenium or osnium.   The conductive substrate according to claim 9, wherein the first catalyst layer includes at least one of gold, palladium, platinum, rhodium, iridium, ruthenium, and osnium.   The conductive substrate according to claim 9 or 10, wherein the first conductive portion is for forming an electrode that is brought into contact with an electrolytic solution to cause an electrochemical reaction.   The conductive substrate according to claim 9, wherein the resin composition of the first catalyst layer has photosensitivity.

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