JPH11132992A - Small-sized oxygen electrode - Google Patents

Abstract

PROBLEM TO BE SOLVED: To reduce the cost of the title electrode and to make the electrode disposable by printing Ag paste on one surface of a rigid substrate to form a counter electrode and an acting electrode having a predetermined shape and printing insulating paste on the intermediate parts of the counter electrode, the acting electrode and a reference electrode excepting the pad parts of the leading end parts and roots of those electrodes to form insulating films. SOLUTION: Ag paste is printed on the single surface of a rigid substrate 12 to simultaneously produce a large number of counter electrodes 1, acting electrodes 2, insulating films 4 and pads 5 or counter electrodes 1, acting electrodes 2, reference electrodes 3, insulating films 4 and pads 5 and this substrate is cut into individual elements 11 to produce oxygen electrodes. Herein, each of the insulating films 4 is formed by printing the insulating paste. Then, the small-sized oxygen electrode is immersed in a sample soln. (sewage of which the oxygen concn. must be measured or the like) 22 to be hermetically closed and the current flowing to the acting electrodes 2 is measured to measure the concn. of oxygen.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a small oxygen electrode. In the medical and environmental fields, there are oxygen electrodes used for measuring, analyzing, and testing oxygen concentrations in dozens of different solutions at the same time. There is a demand for reducing the product value of the oxygen electrode by minimizing its constituent materials and processes.

[0002]

2. Description of the Related Art Conventionally, an oxygen electrode is constituted by providing a working electrode consisting of a negative electrode and a counter electrode consisting of a positive electrode in an electrolyte such as potassium chloride, and dissolved oxygen, water and electrons react on the working electrode. To generate hydroxyl ions, and a current flows between the counter electrode (positive electrode) and working electrode (negative electrode) in proportion to the dissolved oxygen concentration.
The current is measured to estimate the dissolved oxygen concentration.

[0003]

The conventional oxygen electrode described above has a problem in that the constituent material is expensive, the product price is high, and the oxygen electrode cannot be disposable. For this reason, there is a demand for a small-sized oxygen electrode which is disposable and very inexpensive, although high-precision quantitativeness is not required for the use of the oxygen electrode.

[0004] The present invention solves these problems,
An object of the present invention is to reexamine the constituent materials of the oxygen electrode and the like, and to provide a very inexpensive small-sized oxygen electrode realized by a disposable and inexpensive constituent material.

[0005]

FIG. 1, FIG. 6, FIG. 8, FIG.
Means for solving the problem will be described with reference to FIGS. 0, 12, 15, 17, and 19.

FIGS. 1, 6, 8, 10, 12, and 1
5, in FIGS. 17 and 19, the element 11 is an oxygen electrode including a counter electrode 1, a working electrode 2, a reference electrode 3, an insulating film 4, a pad 5, and the like.

The counter electrode 1 is formed by printing Ag paste or A
g is an electrode on which g is deposited, and is for supplying a current to the working electrode 2. The working electrode 2 is an electrode on which an Ag paste is printed or Ag is deposited, and serves to detect the oxygen concentration by measuring a current e flowing between the working electrode 2 and the counter electrode 1.

The reference electrode 3 is an electrode on which an Ag paste is printed or Ag is deposited, and has a surface of Ag / AgCl for flowing a bias current between itself and the counter electrode 1.

Next, the structure will be described sequentially. As shown in FIG. 1, a predetermined shape of a counter electrode 1 and a working electrode 2 or a set of a counter electrode 1, a working electrode 2 and a reference electrode 3 formed by printing an Ag paste on one surface of a hard substrate, and a predetermined shape An insulating film 4 formed by printing an insulating paste on a predetermined intermediate portion excluding a tip portion of the counter electrode 1 and the working electrode 2 or a tip portion of the counter electrode 1, the working electrode 2 and the reference electrode 3 and a portion of the base pad 5; To form a small oxygen electrode.

As shown in FIG. 1, a set of a counter electrode 1 and a working electrode 2 or a pair of a counter electrode 1, a working electrode 2 and a reference electrode 3 having a predetermined shape formed by evaporating Ag on one surface of a hard substrate. And an insulating paste is printed on a predetermined intermediate portion of the counter electrode 1 and the working electrode 2 or the counter electrode 1, the working electrode 2 and the reference electrode 3 excluding the tip portion and the root pad 5 portion. A small oxygen electrode is constituted by the insulating film 4.

As shown in FIG. 6, a counter electrode 1 having a predetermined shape formed by printing an Ag paste on one surface of a hard substrate and an action of a predetermined shape formed by printing an Ag paste on the other surface. A pair of pole 2 or working pole 2 and reference pole 3,
An insulating paste is printed on a counter electrode 1 on one surface formed in a predetermined shape, and on a predetermined intermediate portion excluding the working electrode 2 or the working electrode 2 and the tip of the reference electrode 3 and the base pad 5 on the other surface. The insulating film 4 formed as described above constitutes a small oxygen electrode.

As shown in FIG. 6, a counter electrode 1 of a predetermined shape formed by evaporating Ag on one surface of a hard substrate and a working electrode 2 of a predetermined shape formed by evaporating Ag on the other surface. Alternatively, one set of the working electrode 2 and the reference electrode 3, the counter electrode 1 on one surface formed into a predetermined shape, and the working electrode 2 on the other surface or the tip of the working electrode 2 and the reference electrode 3 and the pad 5 at the base
A small oxygen electrode is constituted by an insulating film 4 formed by printing an insulating paste on a predetermined intermediate portion excluding the portion.

As shown in FIG. 8, a reference electrode 1 and a working electrode 2 having a predetermined shape formed by printing an Ag paste on one surface of a flexible film substrate, or a reference electrode 1 and a working electrode 2 are referred to. One set of poles 3 and a counter electrode 1 formed in a predetermined shape
And a working electrode 2 or a counter electrode 1, a working electrode 2 and an insulating film 4 formed by printing an insulating paste on a predetermined intermediate portion excluding a tip portion of the reference electrode 3 and a portion of the base pad 5. It is composed.

As shown in FIG. 8, a counter electrode 1 and a working electrode 2 or a counter electrode 1, a working electrode 2 and a reference electrode having a predetermined shape formed by evaporating Ag on one surface of a flexible film substrate. 3 and a counter electrode 1 and a working electrode 2 formed in a predetermined shape, or an insulating paste is printed on a predetermined intermediate portion excluding a tip portion of the counter electrode 1 and a working electrode 2 and a reference electrode 3 and a portion of a base pad 5. The insulating film 4 formed as described above constitutes a small oxygen electrode.

As shown in FIG. 10, a counter electrode 1 having a predetermined shape formed by printing an Ag paste on one surface of a flexible film substrate and an Ag paste printed on another surface. A working electrode 2 having a predetermined shape or one set of a working electrode 2 and a reference electrode 3, a counter electrode 1 on one surface formed into a predetermined shape, and a working electrode 2 or a working electrode 2 on another surface or a tip of the reference electrode 3. Insulating film 4 formed by printing an insulating paste on a predetermined intermediate portion excluding a portion and a root pad 5 portion
Thus, a small oxygen electrode is formed.

As shown in FIG. 10, a counter electrode 1 having a predetermined shape formed by evaporating Ag on one surface of a flexible film substrate and a predetermined shape formed by evaporating Ag on the other surface. Working electrode 2 or one set of working electrode 2 and reference electrode 3, counter electrode 1 on one surface formed in a predetermined shape, and working electrode 2 on the other surface or the tip of working electrode 2 and reference electrode 3 and A small oxygen electrode is constituted by the insulating film 4 formed by printing an insulating paste on a predetermined intermediate portion excluding the base pad 5.

As shown in FIG. 12, a counter electrode 1 and a working electrode 2 or a counter electrode 1, a working electrode 2 and a reference electrode 3 each having a predetermined shape formed by printing an Ag paste on one surface of a hard substrate.
And an insulating paste is printed on a predetermined intermediate portion excluding the tip of the counter electrode 1 and the working electrode 2 or the counter electrode 1, the working electrode 2 and the reference electrode 3 and the portion of the base pad 5 formed in a predetermined shape. The small-sized oxygen electrode is constituted by the insulating film 4 formed as described above.

As shown in FIG. 12, a plurality of sets of a counter electrode 1 and a working electrode 2 or a pair of a counter electrode 1, a working electrode 2 and a reference electrode 3 having a predetermined shape formed by evaporating Ag on one surface of a hard substrate. And an insulating paste is printed on a predetermined intermediate portion of the counter electrode 1 and the working electrode 2 or the counter electrode 1, the working electrode 2 and the reference electrode 3 excluding the tip portion and the root pad 5 portion. A small oxygen electrode is constituted by the insulating film 4.

As shown in FIG. 15, a counter electrode 1 having a predetermined shape formed by printing an Ag paste on one surface of a hard substrate and a function of a predetermined shape formed by printing an Ag paste on the other surface. Pole 2 or a plurality of sets of working electrode 2 and reference electrode 3, counter electrode 1 on one surface formed into a predetermined shape, and working electrode 2 or working electrode 2 on the other surface and the tip portion and reference electrode 3 of reference electrode 3 A small oxygen electrode is constituted by the insulating film 4 formed by printing an insulating paste on a predetermined intermediate portion excluding the portion of the pad 5.

As shown in FIG. 15, a counter electrode 1 having a predetermined shape formed by evaporating Ag on one surface of a hard substrate and a working electrode 2 having a predetermined shape formed by evaporating Ag on the other surface. Alternatively, a plurality of pairs of the working electrode 2 and the reference electrode 3, the counter electrode 1 on one surface formed into a predetermined shape, and the working electrode 2 on the other surface or the tip portion of the working electrode 2 and the reference electrode 3 and the pad 5 at the root A small oxygen electrode is constituted by an insulating film 4 formed by printing an insulating paste on a predetermined intermediate portion excluding the portion.

As shown in FIG. 17, reference is made to a counter electrode 1 and a working electrode 2 or a counter electrode 1 and a working electrode 2 each having a predetermined shape formed by printing an Ag paste on one surface of a flexible film substrate. An insulating paste is applied to a plurality of sets of the poles 3 and a predetermined intermediate portion excluding a tip portion of the counter electrode 1 and the working electrode 2 or a tip portion of the counter electrode 1, the working electrode 2 and the reference electrode 3 and a portion of the base pad 5 formed in a predetermined shape. A small oxygen electrode is constituted by the insulating film 4 formed by printing.

Further, as shown in FIG. 17, a counter electrode 1 and a working electrode 2 or a counter electrode 1, a working electrode 2 and a reference electrode having a predetermined shape formed by evaporating Ag on one surface of a flexible film substrate. 3 and a counter electrode 1 and a working electrode 2 formed in a predetermined shape or an insulating paste is printed on a predetermined intermediate portion excluding a tip portion of the counter electrode 1 and a working electrode 2 and a reference electrode 3 and a portion of a base pad 5. The insulating film 4 formed as described above constitutes a small oxygen electrode.

As shown in FIG. 19, a counter electrode 1 having a predetermined shape formed by printing an Ag paste on one surface of a flexible film substrate and an Ag paste printed on another surface. A working electrode 2 having a predetermined shape or a plurality of sets of a working electrode 2 and a reference electrode 3; a counter electrode 1 on one surface formed into a predetermined shape; A small oxygen electrode is constituted by the insulating film 4 formed by printing an insulating paste on a portion and a predetermined intermediate portion excluding the portion of the base pad 5.

As shown in FIG. 19, a counter electrode 1 having a predetermined shape formed by evaporating Ag on one surface of a flexible film substrate and a predetermined shape formed by evaporating Ag on the other surface. Working electrode 2 or a plurality of sets of working electrode 2 and reference electrode 3; counter electrode 1 on one surface formed in a predetermined shape; and working electrode 2 on the other surface or the tip of working electrode 2 and reference electrode 3; A small oxygen electrode is constituted by the insulating film 4 formed by printing an insulating paste on a predetermined intermediate portion excluding the base pad 5.

At this time, the ratio of the area of the counter electrode 1 not covered with the insulating film 4 to the area of the working electrode 2 is set to 1:50 or more. Therefore, it is possible to reexamine the constituent material of the oxygen electrode and the like, and to provide a very inexpensive small-sized oxygen electrode realized by a disposable and necessary and inexpensive constituent material.

[0026]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Next, embodiments and operations of the present invention will be sequentially described in detail with reference to FIGS.

FIG. 1 is a structural explanatory view (part 1, one side) of the present invention. FIG. 1 shows a case where a number of elements 11 each having one set of oxygen electrodes are provided on one surface of a hard substrate 12. FIG.
(A) shows an example of an element 11 composed of a counter electrode 1 and a working electrode 2, and (b) of FIG.
An example of the element 11 composed of

In FIGS. 1A and 1B, an element 11 detects oxygen in a solution. As shown in FIG. 1A, a counter electrode 1, a working electrode 2, and an insulating film are provided. 4 and pad 5, or counter electrode 1, as shown in FIG.
Each of the working electrode 2, the reference electrode 3, the insulating film 4 and the pad 5 is constituted.

The counter electrode 1 is an electrode whose surface is made of Ag (silver), which is manufactured by printing an Ag paste or depositing Ag, and corresponding to the working electrode 2 according to the oxygen concentration in the solution. This is for supplying the generated current (electrons e).

The working electrode 2 is an electrode whose surface is made of Ag (silver), which is manufactured by printing an Ag paste or depositing Ag, and has a counter electrode 1 corresponding to the concentration of oxygen in the solution. Is used to detect the acidity concentration by measuring the current (electrons e) flowing between them.

The reference electrode 3 is made of Ag (silver) and Ag
It is an electrode as Cl (silver chloride) for flowing a bias current between itself and the counter electrode 1. The insulating film 4 insulates other portions except for a predetermined portion of the counter electrode 1, the working electrode 2, the reference electrode 3 and the pad 5.

The pad 5 includes a counter electrode 1, a working electrode 2, and a reference electrode 3.
Is a pad for connecting to an external terminal. FIG. 1C shows a state in which a number of sets of the elements 11 shown in FIG. 1A or 1B are formed on a substrate 12. Here, a V-groove 13 is provided on a hard substrate (for example, a glass epoxy substrate of 1.2 mmt) 12 to make it easy to break.
Are manufactured in large numbers at a time.

As shown in FIG. 1C, a large number of the devices 11 shown in FIGS. 1A and 1B are manufactured on a hard substrate (glass epoxy substrate) 12 at a time. By cutting at each part and further cutting each element 11,
A large number of elements 11 can be manufactured at once from one substrate 12,
It can be manufactured at low cost.

FIG. 1D shows a state in which the device shown in FIG. 1A or 1B is actually immersed in the sample solution 12 and the oxygen concentration in the sample solution 12 is measured. Here, a small amount of a sample solution 22 (a known phosphate buffer, for example, sewage or microorganisms whose oxygen concentration is to be checked) is placed in a sample container 21 and then sealed with liquid paraffin 23. As shown in FIG. 4, it is possible to detect the oxygen concentration by measuring the current flowing through the working electrode 2 (see FIG. 4).

Next, in accordance with the sequence shown in the flow chart of FIG. 2, the manufacturing method of the configuration of FIG. 1 and the procedure of measuring the oxygen concentration using the manufactured small oxygen electrode will be sequentially described in detail. FIG. 2 is a flowchart (part 1) for explaining the operation of the present invention.

In FIG. 2, in step S1, an electrode pattern is printed on a substrate using an Ag paste. This is because the counter electrode 1, the working electrode 2 and the pad 5 of FIG. 1A are formed on the substrate 12 of FIG. 1C, or the counter electrode 1, the working electrode 2, the reference electrode 3 of FIG. The electrode pattern of the pad 5 is printed with an Ag paste. The counter electrode 1, the working electrode 2, the reference electrode 3, and the pad 5 may be printed on one surface of the substrate 12 with an Ag paste as shown in FIGS. The printing is performed on both sides, that is, on one side of the substrate 11, FIG.
May be printed with Ag paste, and the working electrode 2 of FIG. 1A may be printed with Ag paste on the other surface of the substrate 11 (see FIGS. 6A and 6B). ). Similarly,
The counter electrode 1 of FIG. 1B is printed on one surface of the substrate 11 with an Ag paste, and the working electrode 2 and the reference electrode 3 of FIG. 1A are printed on the other surface of the substrate 11 with an Ag paste. (See (c) and (d) of FIG. 6).

Step S2 is dried. This is to dry the substrate 11 printed at the Ag pace in S1 so that Ag is exposed on the surface and adheres to the substrate 11. In step S3, the lead portion is printed with an insulating paste. That is, in the case of one side, the insulating film 4 is printed on one side with an insulating paste as shown by oblique lines in FIG. 1 (a) or (b). At this time, counter electrode 1,
The working electrode 2 and the reference electrode 3 are printed with an insulating paste so that the areas of the non-insulated portions of the working electrode 2 and the reference electrode 3 have constant values.
Is not printed with insulating paste to connect to external terminals.

Step S4 is drying. This dries the insulating paste printed in S3. In step S5, the individual elements 11 are cut. Thus, the individual element 11 shown in FIG. 1A or FIG. 1B is cut from the state shown in FIG. 1C.

In step S6, a phosphate buffer, sewage, and microorganisms are placed in the container. S7 is sealed with liquid paraffin. S8
Measures the oxygen concentration. These S6, S7, S8 are:
As shown in FIG. 1 (d) described above, the oxygen concentration of the small oxygen electrode completed in S1 to S5 is to be measured. Sewage and microorganisms are put into the sample solution 21 shown in FIG. 1D, the element 11 is put as shown in the figure, and then sealed with liquid paraffin so as to cover the element. Then, after connection is made as shown in FIG. 3 or FIG. 5 described later, the oxygen concentration can be measured by measuring the current flowing from the counter electrode 1 to the working electrode 2 as shown in FIG. 4, for example.

As described above, one or both sides are printed with Ag paste on the hard substrate 12 to insulate the counter electrode 1, the working electrode 2, the insulating film 4 and the pad 5, or the counter electrode 1, the working electrode 2, and the reference electrode 3 from each other. After a large number of films 4 and pads 5 are manufactured at the same time, they are cut into individual elements 11 to manufacture small oxygen electrodes. Then, as shown in FIG. 1 (d), the manufactured small oxygen electrode is placed in a sample container 21 in which a sample solution (here, sewage, other known phosphate buffer, microorganism, etc. ) 22 is closed and sealed, and the oxygen concentration can be measured by measuring the current flowing through the working electrode 2. The details will be sequentially described below.

FIG. 3 is a diagram illustrating the measurement of the present invention. This shows a connection method when the counter electrode 1, the working electrode 2, and the reference electrode 3 are provided on one surface. As shown in the figure, when the area of the counter electrode 1 and the area of the working electrode 2 are respectively constant, the current i flowing from the counter electrode 1 to the working electrode 2 is O ₂ + 2H ₂ O + e ^{− as} shown in the figure. Since a current e ^{− of the} amount indicated by 4OH ⁻ flows, this is measured and FIG.
And the response characteristic to oxygen and the concentration can be obtained. At this time, the area of the counter electrode 1 and
According to an experiment, a good current can be detected when the ratio to the area of the working electrode 2 is 1:50 or more.

FIG. 4 shows an example of the measurement of the response to oxygen of the present invention. This is because the small oxygen electrode element 11 according to the present invention is placed in a sample container 21 containing a sample solution 22 and sealed with liquid paraffin 23 as shown in FIG. 3 is a measurement example in which the current flowing through the working electrode 2 connected as shown in FIG. Here, a measurement example at 25 ° C. and 1 atm is shown.

FIG. 5 is a diagram illustrating the measurement of the present invention. This is an example in which the counter electrode 1, the working electrode 2 and the reference electrode 3 are provided on one surface, whereas the counter electrode 1 is provided on one surface and the working electrode 2 and the reference electrode are provided on the other surface in FIG. 3 is provided,
The connection method is the same as that of FIG. Assuming that the area of the counter electrode 1 and the area of the working electrode 2 are constant, the current i flowing from the counter electrode 1 to the working electrode 2 is, as in FIG. 3, the amount of O ₂ + 2H ₂ O + e ⁻ → 4OH ⁻ . current e ^- so it flows, to measure this Figure 4
And the response characteristic to oxygen and the concentration can be obtained.

FIG. 6 is a structural explanatory view of the present invention (No. 2, both sides). This is an example in which a counter electrode 1 is provided on one surface and a working electrode 2 or a working electrode 2 and a reference electrode 3 are provided on the other surface.

FIGS. 6A and 6B show examples in which a counter electrode 1 is provided on one surface and a working electrode 2 is provided on the other surface. FIG. 6A shows an example in which a counter electrode is provided on one surface (front) as shown, and FIG. 6B shows an example in which a working electrode 2 is provided on the other surface (back) as shown. Here is an example. An insulating film 4 is provided on one surface (front) and the other surface (back) of the hatched portion to achieve insulation. The pads 5 of the counter electrode 1 and the working electrode 2 are connected to external terminals.

FIGS. 6C and 6D show examples in which a counter electrode 1 is provided on one surface and a working electrode 2 and a reference electrode 3 are provided on the other surface. FIG. 6C shows an example in which the counter electrode 1 is provided on one surface (front) as shown in the figure, and FIG. 6D shows the working electrode 2 as shown on the other surface (back). An example in which the pole 3 is provided is shown. An insulating film 4 is provided on one surface (front) and the other surface (back) of the hatched portion to achieve insulation.
The pads 5 of the counter electrode 1, the working electrode 2, and the reference electrode 3 are connected to the external terminals.

FIG. 6E shows a state in which a V-groove 13 is provided on the substrate 12 to facilitate cutting. Thus, the substrate 12
The V-groove 13 is provided on the upper surface and the counter electrode 1 and the working electrode 2 or the counter electrode 1, the working electrode 2 and the reference electrode 3 having the structure shown in FIGS. 6A, 6B, 6C and 6D at a time. After the insulating film 4 is further formed, each element 11 can be cut and manufactured as shown in FIGS. 6 (a) and 6 (b) or FIGS. 6 (c) and 6 (d). Become.

FIG. 6 (f) shows FIGS. 6 (a) to 6
(E), the element 11 manufactured as described above is inserted into the sample container 21 in the sample container 21 and sealed with the liquid paraffin 23, and then the working electrode 2 is manufactured as described above.
It is possible to measure the oxygen concentration in the sample solution 22 by measuring the current flowing through the sample solution 22.

FIG. 7 is a flowchart (part 2) for explaining the present invention. This is a flowchart in a case where the electrode pattern (electrode pattern of the counter electrode 1, the working electrode 2, and the reference electrode 3) is formed by printing the Ag paste in the flowchart of FIG. 2, whereas Ag is formed by vapor deposition. .

In FIG. 7, in step S11, Ag is deposited on the substrate by using a metal mask as an electrode pattern. this is,
The counter electrode 1, the working electrode 2, and the pad 5 of FIG. 1A or the counter electrode 1, the working electrode 2, the reference electrode 3, and the pad 5 of FIG. 1B are formed on the substrate 12 of FIG. An electrode pattern is formed by vapor deposition using a metal mask. still,
As shown in FIGS. 1A and 1B, Ag may be deposited on one surface of the substrate 12 using a metal mask for the counter electrode 1, the working electrode 2, the reference electrode 3, and the pad 5. (A), (b),
Alternatively, as shown in FIGS. 6C and 6D, printing is performed on both sides separately, that is, Ag is vapor-deposited on one surface of the substrate 11 using the metal mask as the counter electrode 1 of FIG. Ag may be vapor-deposited on the other surface of the substrate 11 using the metal mask for the working electrode 2 of FIG. Similarly, the substrate 11
Ag is vapor-deposited on one surface of the counter electrode 1 of FIG. 6C using a metal mask, and the working electrode 2 and the reference electrode 3 of FIG. Ag may be used for vapor deposition.

In step S12, a lead portion is printed with an insulating paste. This is because, in the case of one side, the one side of FIG.
Alternatively, the insulating film 4 is printed with an insulating paste as shown by oblique lines in FIG. At this time, counter electrode 1, working electrode 2, reference electrode 3
Is printed with an insulating paste so that the area of the non-insulated portion becomes a constant value, and the portion of the pad 5 is not printed with the insulating paste to connect to an external terminal. Also, in the case of both sides, (a), (b) or (c) in FIG.
As shown in (d), the insulating film 4 is printed with an insulating paste.

In step S13, drying is performed. This dries the insulating paste printed in S12. S14 is the individual element 1
Cut into 1 As a result, the individual element 11 shown in FIG. 1A or FIG. 1B is cut from the state shown in FIG. 1C, or the state shown in FIG. ,
Alternatively, the individual elements 11 shown in FIGS. 6C and 6D are cut. Then, the process proceeds to S6 of FIG.

As described above, the counter electrode 1, the working electrode 2, the insulating film 4 and the pad 5, or the counter electrode 1, the working electrode 2 and the reference electrode 3 are formed on one or both surfaces of the hard substrate 12 by Ag vapor deposition using a metal mask. And a large number of insulating films 4 and pads 5 are manufactured at the same time, and then cut into individual elements 11 to manufacture a small oxygen electrode. Then, this manufactured small-sized oxygen electrode is connected to FIG.
Alternatively, as shown in FIG. 6 (f), a sample solution (here, sewage, other known phosphate buffer, microorganisms) 22 for which the oxygen concentration is to be measured is put in a sample container 21 and sealed. The oxygen concentration can be measured by measuring the current flowing through the working electrode 2.

FIG. 8 is a structural explanatory view of the present invention (No. 3, one side). FIG. 8 shows one side of flexible film 14 on one side.
A large number of elements 11 each having a pair of oxygen electrodes are provided. FIG. 8A shows an example of an element 11 composed of a counter electrode 1 and a working electrode 2, and FIG. 8B shows an example of an element 11 composed of a counter electrode 1, a working electrode 2 and a reference electrode 3. Is shown.

In FIGS. 8A and 8B, the element 11 detects oxygen in the solution. As shown in FIG. 8A, the counter electrode 1, the working electrode 2, and the insulating film are used. 4 and pad 5, or counter electrode 1, as shown in FIG.
Each of the working electrode 2, the reference electrode 3, the insulating film 4 and the pad 5 is constituted. Here, the counter electrode 1, the working electrode 2, the reference electrode 3, the insulating film 4, and the pad 5 are the same as those in FIG.

FIG. 8C shows a state in which a large number of sets of the element 11 shown in FIG. 8A or 8B are formed on a flexible film 14. Here, a state in which a large number of elements 11 are manufactured on a flexible film substrate (for example, a PET (polyethylene phthalate) film 14 of 0.2 mmt) is shown.

The element 11 shown in FIG. 8A or FIG. 8B is replaced with a flexible film 1 as shown in FIG.
4, a large number of devices 11 can be manufactured at once from one flexible film 14, and can be manufactured at low cost.

FIG. 8D shows a state in which the element 11 of FIG. 8A or 8B is actually immersed in the sample solution 12 and the oxygen concentration in the sample solution 12 is measured.
Here, a very small amount of a sample solution 22 (known phosphate buffer, known oxygen
(Microorganism), and then sealed with liquid paraffin 23 and connected as shown in FIG. 3 or FIG.
It is possible to detect the oxygen concentration by measuring the current flowing through the device (see FIG. 4).

Next, in accordance with the order shown in the flow chart of FIG. 9, the manufacturing method of the configuration of FIG. 8 and the procedure of measuring the oxygen concentration using the manufactured small oxygen electrode will be sequentially described in detail. FIG. 9 is a flowchart (part 3) for explaining the operation of the present invention.

In FIG. 9, S21 is a film (PE
T) Print the electrode pattern on the top with Ag paste. This is because the counter electrode 1, the working electrode 2 and the pad 5 shown in FIG. 8A are formed on the film 14 shown in FIG.
The electrode patterns of the counter electrode 1, the working electrode 2, the reference electrode 3 and the pad 5 are printed with an Ag paste. In addition, (a) of FIG.
(B), the counter electrode 1 on one side of the film 14 as shown in FIG.
The working electrode 2, the reference electrode 3, and the pad 5 may be printed with an Ag paste.
On one surface of the first electrode 1, a counter electrode 1 shown in FIG.
It is printed with a paste, and is printed on the other surface of the substrate 11 in FIG.
(B) may be printed with an Ag paste. Similarly, on one surface of the substrate 11, FIG.
The counter electrode 1 of (c) of FIG.
The working electrode 2 and the reference electrode 3 shown in FIG. 10D described later may be printed with Ag paste on another surface.

Step S22 is to dry. This is A in S21
g The film 14 printed at a pace is dried, and the surface is coated with Ag.
Is exposed and fixed to the film 14. S23
Print the lead portion with an insulating paste. That is, in the case of one side, the insulating film 4 is printed on one side with an insulating paste as shown by oblique lines in FIG. 8A or 8B. At this time, printing is performed with an insulating paste so that the areas of the non-insulated portions of the counter electrode 1, the working electrode 2, and the reference electrode 3 have a constant value, and the pads 5 are not printed with the insulating paste to connect to the external terminals. . In the case of both sides, the insulating film 4 is printed on both sides with an insulating paste as shown by oblique lines in FIGS. At this time, printing is performed with an insulating paste so that the areas of the non-insulated portions of the counter electrode 1, the working electrode 2, and the reference electrode 3 have a constant value, and the pads 5 are not printed with the insulating paste to connect to the external terminals. .

In step S24, drying is performed. This dries the insulating paste printed in S23. S25 is the individual element 1
Cut into 1 As a result, the individual element 11 shown in FIG. 8A or FIG. 8B is cut from the state shown in FIG. 8C.

In step S26, a phosphate buffer, sewage, and microorganisms are placed in the container. S27 seals with liquid paraffin.
In step S28, the oxygen concentration is measured. These S26 and S2
7 and S28, as shown in FIG.
The oxygen concentration of the small oxygen electrode completed in 21 to S25 is to be measured. Here, as for the sewage, the phosphate buffer, the sewage and the microorganisms are known as shown in FIG.
(D), the device 11 is placed as shown in the figure, and then sealed with liquid paraffin 23 so as to cover the device. Then, after the connection as shown in FIG. 3 or FIG. 5 described above, the oxygen concentration can be measured by measuring the current flowing through the working electrode 2 as shown in FIG. 4 described above, for example.

As described above, one side or both sides are printed on a flexible film (PET film) 14 with Ag paste to form the counter electrode 1, the working electrode 2, the insulating film 4, and the pad 5, or the counter electrode 1, the working electrode 2 After a large number of reference electrodes 3, insulating films 4, and pads 5 are manufactured at the same time, they are cut into individual elements 11 to manufacture small oxygen electrodes. Then, as shown in FIG. 8 (d), the manufactured small oxygen electrode is placed in a sample container 21 in a sample solution (to be measured for oxygen concentration, here sewage, other known phosphate buffer, microorganisms). ) 22 is closed and sealed, and the oxygen concentration can be measured by measuring the current flowing through the working electrode 2.

FIG. 10 is a structural explanatory view of the present invention (No. 4,
Both sides). This is an example in which a counter electrode 1 is provided on one surface and a working electrode 2 or a working electrode 2 and a reference electrode 3 are provided on the other surface.

FIGS. 10A and 10B show examples in which a counter electrode 1 is provided on one surface and a working electrode 2 is provided on the other surface.
FIG. 10 (a) shows the counter electrode 1 as shown in FIG.
10B shows an example in which the working electrode 2 is provided on the other surface (back side) as shown in FIG. An insulating film 4 is provided on one surface (front) and the other surface (back) of the hatched portion to achieve insulation. The pads 5 of the counter electrode 1 and the working electrode 2 are connected to external terminals.

FIGS. 10C and 10D show examples in which a counter electrode 1 is provided on one surface and a working electrode 2 and a reference electrode 3 are provided on the other surface. FIG. 10C shows an example in which the counter electrode 1 is provided on one surface (front) as shown in the figure, and FIG. 10D shows the working electrode 2 as shown on the other surface (back). An example in which the pole 3 is provided is shown. An insulating film 4 is provided on one surface (front) and the other surface (back) of the hatched portion to achieve insulation.
The pads 5 of the counter electrode 1, the working electrode 2, and the reference electrode 3 are connected to the external terminals.

FIG. 10E shows a state in which the film is provided on a film (PET film) 14. As described above, a number of elements 11 are formed on the film 14 and the counter electrode 1 and the working electrode 2 or the counter electrode 1 having the structure shown in FIG. 10A, FIG. 10B, FIG. Working electrode 2 and reference electrode 3,
Further, after each of the insulating films 4 is formed, it is possible to cut the devices 11 and manufacture them as shown in FIGS. 10A and 10B or FIGS. 10C and 10D. .

FIG. 10F shows an element 11 manufactured as described above with reference to FIGS. 10A to 10E.
Is inserted into the sample solution 22 in the sample container 21 and sealed with the liquid paraffin 23. Then, as described above, the current flowing through the working electrode 2 is measured to measure the oxygen concentration in the sample solution 22. It is possible to do.

FIG. 11 is a flowchart (part 4) for explaining the present invention. This is because the flowchart in FIG.
7 is a flowchart in a case where an electrode pattern (electrode pattern of a counter electrode 1, a working electrode 2, and a reference electrode 3) is formed by printing g paste and Ag is formed by vapor deposition.

In FIG. 11, S31 is a film (P
Ag is vapor-deposited on the ET film 14 using a metal mask as an electrode pattern. This is because the counter electrode 1, the working electrode 2, and the pad 5 of FIG. 8A are formed on the film 14 of FIG. 8C, or the counter electrode 1, the working electrode 2, the reference electrode 3 of FIG. The electrode pattern of the pad 5 is formed by vapor deposition using a metal mask. In addition, (a) of FIG.
(B), the counter electrode 1 on one side of the film 14 as shown in FIG.
Ag may be deposited on the working electrode 2, the reference electrode 3, and the pad 5 using a metal mask, but as shown in FIGS. 10 (a) and 10 (b) or FIGS. 10 (c) and 10 (d), In other words, Ag is vapor-deposited on one surface of the film 14 using the metal mask on the counter electrode 1 of FIG. 10A, and the working electrode of FIG. Ag may be vapor-deposited using a metal mask. Similarly,
Ag was deposited on one surface of the film 14 using the metal mask as the counter electrode 1 in FIG. 10C, and the working electrode 2 and the reference electrode 3 in FIG. Ag may be deposited using a mask.

In step S32, the lead portion is printed with an insulating paste. This is because, in the case of one side, the one side of FIG.
Alternatively, the insulating film 4 is printed with an insulating paste as shown by oblique lines in FIG. At this time, counter electrode 1, working electrode 2, reference electrode 3
Is printed with an insulating paste so that the area of the non-insulated portion becomes a constant value, and the portion of the pad 5 is not printed with the insulating paste to connect to an external terminal. In the case of both sides, (a), (b) or (c) in FIG.
As shown in (d), the insulating film 4 is printed with an insulating paste.

In step S33, drying is performed. This dries the insulating paste printed in S32. S34 is the individual element 1
Cut into 1 As a result, the individual element 11 shown in FIG. 8A or FIG. 8B is cut from the state shown in FIG. 8C, or the state shown in FIG.
(B) or cutting into individual elements 11 of (c) and (d) of FIG. Then, the process proceeds to S26 of FIG.

As described above, the counter electrode 1, the working electrode 2, the insulating film 4, and the pad 5, or the counter electrode 1, the working electrode 2, and the reference electrode are formed on one or both sides by Ag vapor deposition using a metal mask on the flexible film 14. After manufacturing a large number of the insulating films 4, the insulating films 4 and the pads 5 at the same time, the device is cut into individual elements 11 to manufacture a small oxygen electrode. Then, as shown in FIG. 8 (d) or FIG. 10 (f), the manufactured small oxygen electrode is placed in a sample container 21 in which a sample solution (oxygen concentration is to be measured; Phosphate buffer, microorganism) 22
And sealing is performed, and the current flowing through the working electrode 2 is measured to measure the oxygen concentration.

FIG. 12 is a structural explanatory view of the present invention (No. 5,
(One side). FIG. 12 shows a configuration in which a number of elements 11 each having a plurality of sets of oxygen electrodes are provided on one surface of a hard substrate 12. FIG. 12A shows an example of the external shape of an element 11 having a plurality of sets of oxygen electrodes on a substrate 12. Here, V-grooves are provided so that the element 11 having a plurality of sets of oxygen electrodes can be easily cut.

FIG. 12B shows an example of the element 11 composed of a plurality of pairs of the counter electrode 1 and the working electrode 2. (C) of FIG. 12 illustrates a detailed configuration example of one element 11 of (b) of FIG. Here, an example is shown in which 12 sets of oxygen electrodes (oxygen electrodes including a counter electrode 1 and a working electrode 2) are provided on a hard substrate (for example, a glass epoxy substrate of 1.2 mmt).
As shown, a lead wire 9 and a pad 5 are provided for each oxygen electrode.

FIG. 12D shows a state in which the insulating film 4 is formed from the top of FIG. 12C. (E) of FIG.
FIG. 12D shows a state in which the element 11 of FIG. 12D is actually immersed in the sample solution 22 and the oxygen concentration in the sample solution 22 is measured. Here, a small amount of the sample solution 22 is placed in the sample container 21.
(Known phosphate buffer, sewage, microorganisms to be examined for oxygen concentration) individually or as a whole, and then sealed with liquid paraffin 23, as shown in FIG. 3 or FIG. It is possible to detect the oxygen concentration by measuring the current flowing through the working electrode 2 after the connection (see FIG. 4).

FIG. 13 shows an example of measuring the response to oxygen of the present invention. This means that n sets of oxygen electrodes (an oxygen electrode composed of a counter electrode 1 and a working electrode 2) constituting the element 11 of the small oxygen electrode according to the present invention as shown in FIG.
After each sample was placed in a sample container 21 containing a sample solution 22 and sealed with liquid paraffin 23, the current flowing through the working electrode 2 was measured by connecting as shown in FIG.
It is a measurement example when time is set on the horizontal axis. Here, 25
It is an example of measurement at ° C and 1 atm.

Next, in accordance with the sequence shown in the flow chart of FIG. 14, the manufacturing method of the configuration of FIG. 12 and the procedure of measuring the oxygen concentration using the manufactured small oxygen electrode will be sequentially described in detail.

FIG. 14 is a flowchart (part 5) for explaining the operation of the present invention. In FIG. 14, in S41, an electrode pattern group is printed on a substrate by using an Ag paste. this is,
The electrode pattern of the counter electrode 1, the working electrode 2 and the pad 5 of FIG. 12C, or the electrode pattern of the counter electrode 1, the working electrode 2, the reference electrode 3 and the pad 5 of FIG. 12C is shown on the substrate 12 of FIG. Printing is performed as shown in FIG. FIG.
2 (c), the counter electrode 1 is placed on one side of the substrate 12 as shown in FIG.
The working electrode 2 and the pad 5 may be printed with an Ag paste. Alternatively, the working electrode 2 and the pad 5 may be printed separately on both sides, that is, the counter electrode 1 of FIG. The working electrode 2 shown in FIG. 15C may be printed on the other surface of the substrate 11 with an Ag paste. Similarly, the counter electrode 1 is printed on one surface of the substrate 11 with Ag paste, and the working electrode 2 and the reference electrode 3 are printed on the other surface of the substrate 11 with Ag.
You may make it print with a paste.

In step S42, drying is performed. This is A in S41
The substrate 11 printed at the g pace is dried so that Ag is exposed on the surface and adheres to the substrate 11. In step S43, the lead portion is printed with an insulating paste. In this case, in the case of one side, the insulating film 4 is printed on one side with an insulating paste as shown by oblique lines in FIG. At this time, printing is performed with the insulating paste so that the areas of the non-insulated portions of the counter electrode 1 and the working electrode 2 have a constant value, and the pad 5 is not printed with the insulating paste to connect to the external terminals. In the case of double-sided printing, an insulating film 4 shown in FIGS.

In step S44, drying is performed. This dries the insulating paste printed in S43. S45 cuts into electrode pattern groups (individual elements 11). As a result, FIG.
(D), the individual elements 11 are cut.

In step S46, a phosphate buffer, sewage, and microorganisms are placed in the container. S47 seals with liquid paraffin.
In step S48, the oxygen concentration is measured. These S46 and S4
7, S48, as shown in (e) of FIG.
Regarding the small oxygen electrode completed in S41 to S45,
Try to measure the oxygen concentration, here for sewage,
As is well known, the phosphate buffer, the wastewater, and the microorganisms are individually or entirely put in the sample solution 21 of FIG. 12E, and the element 11 is put as shown in the figure, and then covered with liquid paraffin. To seal. Then, after the connection as shown in FIG. 3 or FIG. 5 described above, the oxygen concentration can be measured by measuring the current flowing through the working electrode 2 as shown in FIG. 13, for example.

As described above, one side or both sides are printed on the hard substrate 12 with Ag paste to insulate the counter electrode 1, the working electrode 2, the insulating film 4, and the pad 5, or the counter electrode 1, the working electrode 2, and the reference electrode 3 from each other. Element 11 having a plurality of sets of film 4 and pad 5
Are manufactured at the same time, and then cut into individual elements 11 to manufacture a small oxygen electrode. Then, as shown in FIG. 12 (e), the manufactured small oxygen electrode is placed in a sample container 21 in a sample solution (to be measured for oxygen concentration, here, sewage, other known phosphate buffer, microorganisms). ) 22 can be individually or wholly put in one and sealed, and the current flowing through the working electrode 2 can be measured to measure the oxygen concentration.

FIG. 15 is a structural explanatory view of the present invention (No. 6,
Both sides). FIG. 15 shows a configuration in which a large number of elements 11 having a plurality of sets of oxygen electrodes are provided on both surfaces of a hard substrate 12. FIG. 15A shows an example of the external shape of an element 11 having a plurality of sets of oxygen electrodes on a substrate 12. Here, V
The groove is provided so that the element 11 having a plurality of sets of oxygen electrodes can be easily cut.

FIG. 15B shows a state in which a plurality of pairs of counter electrodes 1 are formed on one surface (front) of the substrate 12. FIG.
FIG. 5C shows a state in which a plurality of sets of working electrodes 1 are formed on the other surface (back surface) of the substrate 12.

FIG. 15D shows a plurality of sets of the counter electrode 1, the lead wire 9, and the pad 5 on one surface (table) of FIG.
Is formed and cut out. (E) of FIG.
FIG. 15D shows a state in which the insulating film 4 is formed as shown by hatching on the lead wire 9 of a plurality of sets of the counter electrode 1 on one surface (table) of FIG.

FIG. 15F shows a plurality of sets of the working electrode 2, the lead wire 9, and the pad 5 on the other surface (back surface) of FIG.
Is formed and cut out. (G) of FIG.
FIG. 15F shows a state in which the insulating film 4 is formed on the other surface (back surface) of the lead wire 9 of the plurality of working electrodes 2 as indicated by oblique lines.

FIG. 15 (h) is a diagram corresponding to FIG. 15 (e),
The element 11 formed as shown in FIG.
2 shows a state when the oxygen concentration in the sample solution 22 is measured by immersion in the sample solution 22. Here, a small amount of a sample solution 22 (a known phosphate buffer solution, for example, sewage or microorganisms whose oxygen concentration is to be checked) is individually or entirely placed in a sample container 21 and then sealed with liquid paraffin 23. As shown in FIG. 3 or FIG. 5 described above, it is possible to detect the oxygen concentration by measuring the current flowing through the working electrode 2 by connecting.
FIG. 6 shows an explanatory flowchart (part 6) of the present invention.
This is a flowchart in the case where the electrode pattern (electrode pattern of the counter electrode 1, the working electrode 2, and the reference electrode 3) is formed by printing an Ag paste in the flowchart of FIG. 14, whereas Ag is formed by vapor deposition. .

In FIG. 16, in step S51, Ag is deposited on the substrate by using a metal mask as an electrode pattern. In this method, the electrode patterns of the counter electrode 1, the working electrode 2, and the pad 5 are formed on the substrate 12 of FIG. 12A by vapor deposition using a metal mask. As shown in FIG. 12B, Ag may be deposited on one surface of the substrate 12 using a metal mask for the counter electrode 1, the working electrode 2, and the pad 5, but FIGS. 15B and 15C ) To print on both sides as shown in
Ag is vapor-deposited on one surface of the substrate 11 using the metal mask as the counter electrode 1 of FIG.
Ag may be deposited on the working electrode 2 of (c) of FIG. 5 using a metal mask. Similarly, on one surface of the substrate 11, Ag was vapor-deposited on the counter electrode 1 using a metal mask.
Ag may be vapor-deposited on the other surface of the working electrode 2 and the reference electrode 3 using a metal mask.

In step S52, a lead portion is printed with an insulating paste. In this case, in the case of one side, the insulating film 4 is printed on one side with an insulating paste as shown by oblique lines in FIG. At this time, printing is performed with the insulating paste so that the areas of the non-insulated portions of the counter electrode 1 and the working electrode 2 have a constant value, and the pad 5 is not printed with the insulating paste to connect to the external terminals. In the case of both sides, as shown in FIGS. 15E and 15G, the insulating film 4 is printed with an insulating paste.

In step S53, drying is performed. This dries the insulating paste printed in S52. S54 cuts into electrode pattern groups (individual elements 11). Thus, the individual elements 11 are cut. Then, the process proceeds to S46 of FIG.

As described above, a plurality of sets of the counter electrode 1, the working electrode 2, the insulating film 4, and the pad 5, or the plurality of sets of the counter electrode 1 are formed on one or both sides of the hard substrate 12 by Ag vapor deposition using a metal mask. After a large number of the electrodes 2, the reference electrodes 3, the insulating films 4, and the pads 5 are simultaneously manufactured, a small oxygen electrode is manufactured by cutting the individual elements 11. Then, as shown in FIG. 12 (e) or FIG. 15 (h), the manufactured small oxygen electrode is placed in a sample container 21 in which a sample solution (oxygen concentration is to be measured; (A phosphate buffer solution, a microorganism) 22 is sealed, and the oxygen concentration can be measured by measuring the current flowing through the working electrode 2.

FIG. 17 is a structural explanatory view of the present invention (No. 7,
(One side). FIG. 17 shows an element 1 having a plurality of sets of oxygen electrodes on one side of a flexible film (PET film) 14.
1 is provided in large numbers.

FIG. 17A shows an example of the appearance of an element 11 having a plurality of sets of oxygen electrodes on a film 14. FIG.
(B) shows one of the elements 11 having a plurality of oxygen electrodes from the film 14 in (a) of FIG. Here, the element 1 includes a plurality of pairs of counter electrodes 1, working electrodes 2, lead wires 9, and pads 5.

FIG. 17C shows a state in which the insulating film 4 is formed on the lead wire 9 of the element 11 composed of a plurality of sets shown in FIG. 17B. (D) of FIG.
(C) shows a state when the element 11 is actually immersed in the sample solution 22 and the oxygen concentration in the sample solution 22 is measured. Here, a small amount of a sample solution 22 (a known phosphate buffer solution, for example, sewage or microorganisms for which an oxygen concentration is to be checked) is individually or individually placed in a sample container 21 and then sealed with liquid paraffin 23. As shown in FIG. 3 or FIG. 5, the oxygen concentration can be detected by measuring the current flowing through the working electrode 2 as described above.

FIG. 18 is a flow chart (7) for explaining the operation of the present invention. In FIG. 18, in S61, an electrode pattern group is printed on a film (PET film) 14 using an Ag paste. In this method, the electrode patterns of the counter electrode 1, the working electrode 2, the lead wire 9, and the pad 5 are printed on the film 14 of FIG. It should be noted that printing is performed on both sides separately, that is, on one side of the film 14, FIG.
The counter electrode 1 of FIG. 9A may be printed with an Ag paste, and the working electrode 2 of FIG. 19B may be printed on the other surface of the film 14 with an Ag paste. Similarly, film 14
The counter electrode 1 may be printed on one surface of the film 14 with an Ag paste, and the working electrode 2 and the reference electrode 3 may be printed on the other surface of the film 14 with an Ag paste.

In step S62, drying is performed. This is A in S61
g The film 14 printed at a pace is dried, and the surface is coated with Ag.
Is exposed and fixed to the substrate 11. S63,
Print the leads with insulating paste. In this case, in the case of one side, the insulating film 4 is printed on one side with an insulating paste as shown by oblique lines in FIG. At this time, printing is performed with an insulating paste so that the areas of the non-insulated portions of the counter electrode 1 and the working electrode 2 have a constant value, and the pad 5 is not printed with the insulating paste to connect to external terminals. In the case of both sides, (d) and (f) of FIG.
Are printed, respectively.

In step S64, drying is performed. This dries the insulating paste printed in S63. S65 cuts into electrode pattern groups (individual elements 11). As a result, FIG.
(C), the individual elements 11 are cut.

In step S66, a phosphate buffer, sewage, and microorganisms are placed in the container. In step S67, the container is sealed with liquid paraffin.
In step S68, the oxygen concentration is measured. These S66, S6
7, S68 is performed as shown in FIG.
For the small oxygen electrode completed in S61 to S65,
Try to measure the oxygen concentration, here for sewage,
As is known, the phosphate buffer, the wastewater and the microorganisms are individually or entirely put into the sample solution 21 shown in FIG. 17D, and the element 11 is put as shown in the figure, and then covered with liquid paraffin. To seal. Then, after the connection as shown in FIG. 3 or FIG. 5 described above, the oxygen concentration can be measured by measuring the current flowing through the working electrode 2.

As described above, the flexible film 14
g printed on one or both sides with paste, counter electrode 1, working electrode 2, insulating film 4 and pad 5, or counter electrode 1 and working electrode 2
After manufacturing a large number of devices 11 each including a plurality of sets including the reference electrode 3, the insulating film 4, and the pad 5, the device 11 is cut into individual devices 11 to manufacture a small oxygen electrode. Then, the manufactured small oxygen electrode is connected to the sample container 2 as shown in FIG.
A sample solution (to be measured for oxygen concentration, here, sewage, other known phosphate buffer, microorganisms) 22 is placed individually or as a whole in one and sealed.
It is possible to measure the oxygen concentration by measuring the current flowing through the device.

FIG. 19 is a structural explanatory view of the present invention (No. 8,
Both sides). FIG. 19 shows a configuration in which a number of elements 11 having a plurality of sets of oxygen electrodes are provided on both sides of a flexible film 14.

FIG. 19A shows a state in which an element 11 composed of a plurality of pairs of counter electrodes 1, lead wires 9 and pads 5 is formed on one surface (table) of a film 14. FIG. 19B shows a state in which the element 11 including a plurality of sets of the working electrode 2, the lead wire 9, and the pad 5 is formed on the other surface (back surface) of the film 14.

FIG. 19C shows a state in which a plurality of sets of the counter electrode 1, the lead wire 9, and one pad 5 are taken out on one surface (table) of the film 14 of FIG. 19A. FIG.
(D) of FIG. 9 shows a state in which the insulating film 4 is formed on the portion of the lead wire 9 in (c) of FIG.

FIG. 19 (e) shows a state in which a plurality of sets of the working electrode 2, the lead wire 9 and one pad 5 are taken out on one surface (table) of the film 14 of FIG. 19 (b). FIG. 19F shows a state in which the insulating film 4 is formed on the portion of the lead wire 9 in FIG. 19E.

FIG. 19 (g) is the same as FIG. 19 (d),
The element 11 formed as shown in FIG.
2 shows a state when the oxygen concentration in the sample solution 22 is measured by immersion in the sample solution 22. Here, a small amount of a sample solution 22 (a known phosphate buffer solution, for example, sewage or microorganisms whose oxygen concentration is to be checked) is individually or entirely placed in a sample container 21 and then sealed with liquid paraffin 23. As shown in FIG. 3 or FIG. 5, the oxygen concentration can be detected by measuring the current flowing through the working electrode 2 as described above.

FIG. 20 is a flow chart (8) for explaining the present invention. This is a flowchart in a case where the electrode pattern (electrode pattern of the counter electrode 1, the working electrode 2, and the reference electrode 3) is formed by printing the Ag paste in the flowchart of FIG. .

In FIG. 20, S71 is a film (P
Ag is vapor-deposited on the ET film 14 using a metal mask as an electrode pattern. In this method, the electrode patterns of the counter electrode 1, the working electrode 2, the lead wire 9 and the pad 5 are formed on the film 14 of FIG. 17A by vapor deposition using a metal mask. As shown in FIG. 17A, the counter electrode 1, the working electrode 2, and the pad 5 may be deposited on one surface of the film 14 with Ag using a metal mask.
(B) As shown in FIG.
19A is vapor-deposited on one surface of the substrate 11 with a metal mask using a metal mask, and the working electrode 2, lead wire 9 and pad 5 of FIG. Ag may be deposited using a metal mask.

In step S72, the lead portion is printed with an insulating paste. In this case, in the case of one side, the insulating film 4 is printed on one side with an insulating paste as shown by oblique lines in FIG. At this time, printing is performed with the insulating paste so that the areas of the non-insulated portions of the counter electrode 1 and the working electrode 2 have a constant value, and the pad 5 is not printed with the insulating paste to connect to the external terminals. In the case of both sides, as shown in FIGS. 19D and 19F, the insulating film 4 is printed with an insulating paste.

Step S73 is to dry. This dries the insulating paste printed in S72. S74 cuts into electrode pattern groups (individual elements 11). Thus, the individual elements 11 are cut. Then, the process proceeds to S66 in FIG.

As described above, a plurality of sets of the counter electrode 1, the working electrode 2, the insulating film 4, and the pad 5, or the plurality of sets of the counter electrodes 1 are formed on one or both sides of the flexible film 14 by Ag vapor deposition using a metal mask. After a large number of working electrodes 2, reference electrodes 3, insulating films 4, and pads 5 are manufactured at the same time, they are cut into individual elements 11 to manufacture a small oxygen electrode. Then, the manufactured small oxygen electrode is connected to FIG. 17 (d) or FIG. 19 (g).
As shown in (2), a sample solution (sewage, other known phosphate buffer, microorganisms here) to be subjected to measurement of oxygen concentration 22 is put in a sample container 21 and sealed. By measuring, it becomes possible to measure the oxygen concentration.

FIG. 21 is an explanatory view of an electrode pattern group according to the present invention. FIG. 21A shows a state in which twelve sets of oxygen electrodes are connected. Here, the counter electrode 1 constituting the 12 sets of oxygen electrodes is commonly connected and grounded, and the working electrode 2 is connected to a measuring device (not shown) so that 12 sets of the working electrodes 2 can be drawn out and the current flowing individually can be measured.

FIG. 21B shows a state in which the insulating film 4 is formed on the oblique line portion of the lead wire. The pad 5 is connected to each external terminal. FIG. 22 shows a production example of the present invention. This is because the film (PET film) 14 is wound rightward from the left roll around which the film 14 is wound, and the electrode pattern (counter electrode 1, working electrode 2, reference electrode 3, etc.) is formed in the first printing portion. And dried in the first drying oven. Next, the insulating paste is printed in the printing part, dried in the last drying oven, the finished product is wound up on the right roll, and the electrode pattern and the insulating film 4 are formed on the film 14 in a flow operation. It becomes possible.

[0114]

As described above, according to the present invention,
After forming the counter electrode 1, the working electrode 2, and the reference electrode 3 on a hard substrate or a flexible film on one side or both sides by Ag paste or vapor deposition, the lead wires are printed and insulated by an insulating paste to insulate the individual elements. Since a structure capable of mass-producing a small oxygen electrode by cutting into 11 is adopted, the oxygen electrode can be manufactured using a simple structure, which is easy to mass-produce, and using an inexpensive material. Thus, it has become possible to realize an inexpensive and small disposable small oxygen electrode.

[Brief description of the drawings]

FIG. 1 is a structural explanatory view of the present invention (No. 1, one side).

FIG. 2 is a flowchart (part 1) for explaining the operation of the present invention.

FIG. 3 is an explanatory diagram of measurement according to the present invention.

FIG. 4 is an example of measurement of responsiveness to oxygen according to the present invention.

FIG. 5 is an explanatory diagram of measurement according to the present invention.

FIG. 6 is a structural explanatory view of the present invention (No. 2, both sides).

FIG. 7 is a flowchart (part 2) for explaining the operation of the present invention.

FIG. 8 is a structural explanatory view (part 3, one side) of the present invention.

FIG. 9 is a flowchart (part 3) for explaining the operation of the present invention.

FIG. 10 is a structural explanatory view (No. 4, both sides) of the present invention.

FIG. 11 is a flowchart (part 4) for explaining the operation of the present invention.
It is.

FIG. 12 is a structural explanatory view of the present invention (No. 5, one side).

FIG. 13 is a measurement example of the responsiveness to oxygen of the present invention.

FIG. 14 is a flowchart (part 5) for explaining the operation of the present invention;
It is.

FIG. 15 is a structural explanatory view (No. 6, both sides) of the present invention.

FIG. 16 is a flowchart (part 6) for explaining the operation of the present invention.
It is.

FIG. 17 is a structural explanatory view (No. 7, one side) of the present invention.

FIG. 18 is a flowchart for explaining the operation of the present invention (part 7).
It is.

FIG. 19 is a structural explanatory view (No. 8, both sides) of the present invention.

FIG. 20 is a flowchart (part 8) for explaining the operation of the present invention;
It is.

FIG. 21 is an explanatory diagram of an electrode pattern group according to the present invention.

FIG. 22 is a production example of the present invention.

[Explanation of symbols]

 1: counter electrode 2: working electrode 3: reference electrode 4: insulating film 5: pad 9: lead wire 11: element 12: substrate 13: V-groove 14: film (PET film) 21: container (sample container) 22: sample solution 23: Liquid paraffin

Claims (17)

[Claims] 1. A counter electrode having a predetermined shape and a working electrode formed by printing an Ag paste on one surface of a hard substrate, or a set of a counter electrode, a working electrode and a reference electrode, and a counter electrode formed in the predetermined shape. A small oxygen electrode comprising: an insulating film formed by printing an insulating paste on a predetermined intermediate portion excluding a tip portion of a working electrode, a working electrode, and a reference electrode, and a pad portion at the base of the working electrode and the reference electrode. 2. A predetermined shape of a counter electrode and a working electrode or a set of a counter electrode, a working electrode and a reference electrode formed by evaporating Ag on one surface of a hard substrate, and a counter electrode and a working electrode formed in the predetermined shape. Alternatively, a small oxygen electrode comprising an insulating film formed by printing an insulating paste on a predetermined intermediate portion excluding a tip portion of a counter electrode, a working electrode, a reference electrode and a pad portion at a root. 3. A working electrode having a predetermined shape formed by printing Ag paste on one surface of a hard substrate and a working electrode or a working electrode having a predetermined shape formed by printing Ag paste on another surface, and a reference electrode. An insulating paste is printed on one set and a counter electrode on one surface formed in the predetermined shape, and a predetermined intermediate portion excluding the working electrode on the other surface or the tip portion of the working electrode and the reference electrode and the pad portion at the base. A small oxygen electrode characterized by comprising an insulating film formed by the above method. 4. A working electrode having a predetermined shape formed by evaporating Ag on one surface of a hard substrate and a working electrode having a predetermined shape formed by evaporating Ag on another surface, or a set of a working electrode and a reference electrode. And forming an insulating paste on a counter electrode of one surface formed in the predetermined shape, and a predetermined intermediate portion excluding the working electrode or the working electrode and the tip portion of the working electrode and the reference electrode and the pad portion at the base of the other surface. A small oxygen electrode comprising: an insulating film; 5. A predetermined shape of a counter electrode and a working electrode or a set of a counter electrode, a working electrode and a reference electrode formed by printing an Ag paste on one surface of a flexible film substrate; Characterized by comprising an insulating film formed by printing an insulating paste on a counter electrode and a working electrode, or a predetermined intermediate portion excluding a tip portion of a counter electrode, a working electrode and a reference electrode and a root pad portion. electrode. 6. A predetermined shape of a counter electrode and a working electrode or a set of a counter electrode, a working electrode and a reference electrode formed by evaporating Ag on one surface of a flexible film substrate; A small oxygen electrode comprising an insulating film formed by printing an insulating paste on a predetermined intermediate portion excluding a tip portion of a counter electrode and a working electrode or a tip portion of a counter electrode, a working electrode, and a reference electrode and a base pad portion. . 7. A working electrode or working electrode having a predetermined shape formed by printing an Ag paste on one surface of a flexible film substrate and printing an Ag paste on another surface. And a set of a reference electrode, and a counter electrode on one surface formed in the above-mentioned predetermined shape, and a working electrode on the other surface or a predetermined intermediate portion excluding the tip portion of the working electrode and the reference electrode and the base pad portion. A small oxygen electrode comprising: an insulating film formed by printing a paste. 8. A counter electrode of a predetermined shape formed by evaporating Ag on one surface of a flexible film substrate and Ag on another surface.
And a set of a working electrode or a working electrode and a reference electrode formed in a predetermined shape, a counter electrode on one surface formed in the predetermined shape, and a working electrode or a working electrode on the other surface or a tip of the reference electrode. A small oxygen electrode, comprising: an insulating film formed by printing an insulating paste on a predetermined intermediate portion excluding a portion and a root pad portion. 9. A counter electrode and a working electrode of a predetermined shape formed by printing an Ag paste on one surface of a hard substrate, or a plurality of pairs of a counter electrode, a working electrode and a reference electrode, and a function of the counter electrode formed in the predetermined shape. A small oxygen electrode comprising: an insulating film formed by printing an insulating paste on a predetermined intermediate portion excluding a tip portion of a working electrode, a working electrode, and a reference electrode, and a pad portion at the base of the working electrode and the reference electrode. 10. A counter electrode and a working electrode of a predetermined shape formed by evaporating Ag on one surface of a hard substrate, or a plurality of pairs of a counter electrode, a working electrode and a reference electrode, and a counter electrode and a working electrode formed in the predetermined shape. Alternatively, a small oxygen electrode comprising an insulating film formed by printing an insulating paste on a predetermined intermediate portion excluding a tip portion of a counter electrode, a working electrode, a reference electrode and a pad portion at a root. 11. A counter electrode having a predetermined shape formed by printing an Ag paste on one surface of a hard substrate and a working electrode having a predetermined shape formed by printing an Ag paste on another surface, or a working electrode and a reference electrode. A plurality of sets, and an insulating paste is printed on a counter electrode on one surface formed in the above-mentioned predetermined shape, and on a predetermined intermediate portion excluding the working electrode on the other surface or the tip portion of the working electrode and the reference electrode and the pad portion at the base. A small oxygen electrode characterized by comprising an insulating film formed by the above method. 12. A counter electrode having a predetermined shape formed by evaporating Ag on one surface of a hard substrate and a working electrode having a predetermined shape formed by evaporating Ag on another surface, or a plurality of sets of working electrodes and reference electrodes. And forming an insulating paste on a counter electrode of one surface formed in the predetermined shape, and a predetermined intermediate portion excluding the working electrode or the working electrode and the tip portion of the working electrode and the reference electrode and the pad portion at the base of the other surface. A small oxygen electrode characterized by comprising an insulating film formed as described above. 13. A predetermined shape formed by printing an Ag paste on one surface of a flexible film substrate, and a plurality of sets of a counter electrode, a working electrode, and a reference electrode, a working electrode, and a reference electrode; Characterized by comprising an insulating film formed by printing an insulating paste on a counter electrode and a working electrode, or a predetermined intermediate portion excluding a tip portion of a counter electrode, a working electrode and a reference electrode and a root pad portion. electrode. 14. A predetermined shape of a counter electrode and a working electrode or a plurality of sets of a counter electrode, a working electrode and a reference electrode formed by evaporating Ag on one surface of a flexible film substrate; A small oxygen electrode comprising an insulating film formed by printing an insulating paste on a counter electrode and a working electrode or a predetermined intermediate portion excluding a tip portion of a counter electrode, a working electrode and a reference electrode, and a root pad portion; . 15. A working electrode or working electrode having a predetermined shape formed by printing an Ag paste on one surface of a flexible film substrate and printing an Ag paste on another surface. And a plurality of pairs of reference electrodes, and a counter electrode on one surface formed into the above-mentioned predetermined shape, and a working electrode on the other surface or a predetermined intermediate portion excluding the tip portion of the working electrode and the reference electrode and the pad portion at the base. A small oxygen electrode comprising: an insulating film formed by printing a paste. 16. A counter electrode having a predetermined shape formed by evaporating Ag on one surface of a flexible film substrate and A on another surface.
g of a working electrode of a predetermined shape formed by vapor deposition or a plurality of sets of a working electrode and a reference electrode; a counter electrode of one surface formed in the predetermined shape; and a working electrode of another surface or a tip of a working electrode and a reference electrode. And an insulating film formed by printing an insulating paste on a predetermined intermediate portion excluding a base portion and a pad portion at the base. 17. A small-sized device according to claim 1, wherein a ratio of an area of said counter electrode not covered with said insulating film to an area of said working electrode is 1:50 or more. Oxygen electrode.