JP5389892B2 - ION SELECTIVE ELECTRODE, ION SELECTIVE ELECTRODE MODULE, AND METHOD FOR PRODUCING ION SELECTIVE ELECTRODE - Google Patents

Description

The present invention relates to an ion-selective electrode, an ion-selective electrode module, and a method for producing an ion-selective electrode used for analyzing ions contained in a liquid, and more particularly, ions contained in human blood, urine, etc. The present invention relates to an ion-selective electrode, an ion-selective electrode module, and a method for manufacturing an ion-selective electrode.

Electrolytes such as sodium ion, potassium ion, and chlorine ion contained in the test sample
By measuring the electromotive force between each electrode of an ion selective electrode module composed of an ion selective electrode selectively responding to each electrolyte and a reference electrode serving as a reference of this electrode, the electrolyte in the test sample is measured. Determine the concentration. The ion selective electrode and the reference electrode are used by being mounted on an automatic analyzer for analyzing components such as biochemical test items and immunological test items contained in a test sample, or a device dedicated to measuring an electrolyte.

In this ion selective electrode, the potential of a sensitive film composed of a component containing a sensitive substance that selectively responds to specific ions contained in the test sample is output to the output pin via the internal electrode. The reference electrode outputs a constant potential generated with respect to the test sample to the output pin via the internal electrode. And the density | concentration of a specific ion can be calculated | required by measuring the electromotive force which is a potential difference between an ion selective electrode and a reference electrode.

By the way, as a manufacturing method of an ion selective electrode capable of miniaturization, a solution containing a sensitive substance that responds to ions to be measured is dissolved in a solvent and repeatedly applied to the electrode body little by little. A method of forming a sensitive film by drying is known (for example, see Patent Document 1).

Japanese Patent Laid-Open No. 11-295261

However, bubbles may be generated in the applied solution, and pores may be formed in the sensitive film by the bubbles after drying. When the pores are formed on the surface of the sensitive membrane in contact with the test sample, when the manufactured ion-selective electrode is examined using a plurality of test samples having different concentrations, for example, the pores of the sensitive membrane are The test sample remains, contaminates the test sample to be measured next, and adversely affects the measurement result. Thereby, there is a problem that the yield of the ion selective electrode is lowered.

The present invention has been made to solve the above-described problems, and an object thereof is to provide an ion-selective electrode, an ion-selective electrode module, and an ion-selective electrode manufacturing method having a high yield.

In order to achieve the above object, an ion selective electrode of the present invention according to claim 1 is a sensor main body having a through hole through which a test sample flows and an opening having an inner surface communicating with a part of the through hole. And a sensitive film that is formed by closing the opening and selectively responds to predetermined ions, and a part of the sensitive film is sandwiched between the sensor body and the side from which the sensitive film is held. And an output element for outputting an electric potential responded by the sensitive film to the outside, and the sensitive film is formed on a part protruding from the inner surface of the output element. The contact surface is held on the inner surface .

An ion selective electrode module of the present invention according to claim 9 is the reference electrode main body having the ion selective electrode according to claims 1 to 8 and a through-hole through which the test sample flows. A liquid junction hole formed in the through hole of the electrode body, an internal liquid accommodated in the reference electrode body so as to be able to flow through the liquid junction hole, and one end portion of the internal liquid are in contact with the internal liquid. A reference electrode having an output element for outputting a substantially constant potential in the liquid junction hole, the sensor body disposed so as to penetrate the through hole of the sensor body and the through hole of the reference electrode body, and the ion-selective electrode module, characterized in that it comprises a support for detachably clamping the reference electrode body.

Furthermore, the manufacturing method of the ion-selective electrode of the present invention according to claim 12, the sensor body having a through hole test sample flows, communicating with a portion of the through hole, an opening having an inner surface, the A pin that fits in the through hole of the sensor is inserted with almost no gap , and a sensitive film made of a sensitive substance that selectively responds to predetermined ions is held in the sensor body and outputs the potential responded by the sensitive film to the outside. The output element is held on the inner surface in contact with the portion of the output element that protrudes from the inner surface, and the output element is partly clamped by the sensor body, and the sensitive film is held from the inner surface to the side where the sensitive film is held. The sensitive film is arranged such that a part different from the part is exposed, and the sensitive film is in contact with an internal electrode formed on a part of the surface that protrudes from the inner surface to the side where the sensitive film is held. Dissolved components containing substances in a solvent Liquid is applied, after the solvent of the applied the solution is vaporized, the manufacturing method of the ion-selective electrode, characterized in that pull the pin from the through hole.

According to the present invention, by providing a mortar-shaped opening communicating with a part of the through-hole in the ion-selective electrode body having a through-hole through which the test sample flows, and forming a sensitive film in the opening, The yield and quality of the ion selective electrode can be improved.

The figure which shows the structure of the ion selective electrode module which concerns on the Example of this invention. The figure which shows the structure of the multi ion sensor which concerns on the Example of this invention. The figure which expanded a part of multi ion sensor concerning the example of the present invention. The figure which shows the structure of the 1st and 2nd output element of the multi ion sensor which concerns on the Example of this invention. The figure which shows the cross section of the 3rd ion selective electrode which concerns on the Example of this invention. The figure which shows the cross section of the reference electrode which concerns on the Example of this invention. The figure which shows the cross section of the ion selective electrode module which concerns on the Example of this invention. The flowchart which shows the 1st manufacturing process based on the Example of this invention. The figure which shows the one part process of the 1st manufacturing process which concerns on the Example of this invention. The flowchart which shows the manufacturing process of the ion selective electrode module which concerns on the Example of this invention. The figure which shows the general view of the ion selective electrode module which concerns on the Example of this invention.

Embodiments of the ion selective electrode module according to the present invention will be described below with reference to FIGS.

FIG. 1 is a diagram illustrating a configuration of an ion selective electrode module according to an embodiment of the present invention.
This ion selective electrode module 10 includes, for example, sodium ions contained in a test sample,
An ion sensor unit 1 having an ion-selective electrode that selectively responds to specific ions such as potassium ions and chlorine ions, a reference electrode 2 serving as a reference for the ion-selective electrode of the ion sensor unit 1, and ions Support 3 for holding each ion-selective electrode and reference electrode 2 of sensor unit 1
And.

The ion sensor unit 1 is manufactured in a second manufacturing process different from the first manufacturing process, and the multi-ion sensor 4 having the lid 9 including a plurality of ion selective electrodes manufactured in the first manufacturing process. The third ion selective electrode 5 is provided.

Next, the configuration of the multi-ion sensor 4 will be described with reference to FIGS. FIG. 2 is a diagram showing the configuration of the multi-ion sensor 4. 2 (a) is a view of the multi-ion sensor 4 from which the lid 9 shown in FIG. 1 is removed as viewed from the side, and FIG. 2 (b) is a view of FIG. 2 (a).
It is the figure which showed the cross section in line XX of the multi-ion sensor 4 of FIG. FIG. 3 is an enlarged view of a part of the multi-ion sensor 4 shown in FIG. FIG. 4 is a diagram illustrating a partial configuration of the multi-ion sensor 4.

In FIG. 2, the multi-ion sensor 4 includes a first sensor body 6 made of, for example, hard vinyl chloride (PVC), which is a material excellent in electrical insulation, and, for example, sodium turret held by the first sensor body 6. A first ion selective electrode 7 having a first sensitive film 71 that selectively responds to a first ion such as an ion, and a second ion such as a potassium ion held in the first sensor body 6. A second ion-selective electrode 8 having a second sensitive membrane 81 that selectively responds to the first sensor body 6 and a lid 9 detachably disposed on the first sensor body 6.

The first sensor body 6 has a shape in which a protrusion 6a is formed on a part of a cylindrical side surface,
The ion-selective electrode 7 and the second ion-selective electrode 8 are formed of an insulating material so as to be insulated. In addition, the first sensor body 6 includes a first through hole 6d penetrating the vicinity of the center of each of the one surface 6b and the other surface 6c corresponding to the top surface and the bottom surface of the cylindrical portion of the first sensor body 6. And the support 3
In the state where the other surface 6c is in pressure contact with the third ion-selective electrode 5 due to the pinching of the first surface 6b,
The test sample flowing in from the through hole 6d flows out to the third ion selective electrode 5 from the first through hole 6d on the other surface 6c side.

The first opening 6e and the second opening 6e communicate with a part of the first through-hole 6d formed on the cylindrical side surface rotated about 90 ° from the protrusion 6a around the first through-hole 6d. Opening 6
f.

The first opening 6e is located in the vicinity of one surface 6b of the first sensor body 6, and as shown in FIG. 3, the first opening 6e approaches the first through hole 6d from the side surface of the first sensor body 6, A mortar-shaped inclined surface (0 <θ1 <90 °) in which the area of the opening becomes narrow is formed.

The second opening 6f is spaced from the first opening 6e and is located near the other surface 6c of the first sensor body 6, and the first sensor body 6 is the same as the first opening 6e. As the first through hole 6d is approached from the side surface, a mortar-shaped inclined surface whose opening area becomes narrower is formed.

The first ion-selective electrode 7 includes a first sensitive film 71 formed by closing the first opening 6 e of the first sensor body 6, and the first detected by the first sensitive film 71. It is comprised by the 1st output element 72 for outputting the electric potential which responds to ion of this.

The first sensitive film 71 is composed of, for example, a crown ether-based first sensitive substance that selectively responds to the first ions, and PVC that includes the first sensitive substance. As shown in FIG. 3, one surface of the first sensitive film 71 forms a part of the first through hole 6d, and the boundary between the one surface and the inclined surface of the first opening 6e is not uneven. It has a smooth surface. The side surface between the one surface and the other surface is held by the inclined surface of the first opening 6e.

As described above, the first sensitive film 71 formed in the first opening 6e can be observed with the lid 9 not attached to the first sensor body 6.

The first output element 72 is made of, for example, silver. As shown in FIG. 4, one end portion has a ring shape and the other end portion has a rod shape extending from a part of the ring shape. In addition, the ring-shaped inner peripheral portion at the one end is disposed at a position that protrudes outward from the inclined surface of the first opening 6e,
An internal electrode 72a is formed in which silver chloride is formed on the surface of the inner peripheral portion. A first sensitive film 71 is joined to the internal electrode 72a.

Thus, by joining the first sensitive film 71 to the internal electrode 72a, no internal liquid is required, so the first ion selective electrode 7 can be made small.

Further, a part of the other end is disposed outside the protrusion 6a, and constitutes a first output pin 72b connected to, for example, an electrolyte measuring device to which the ion selective electrode module 10 is attached. Then, the potential of the first sensitive film 71 in response to the first ions contained in the test sample or the like flowing into the first through hole 6d of the first sensor body 6 is measured by the electrolyte via the internal electrode 72a. Output to the device.

Further, a portion other than the internal electrode 72 a and the first output pin 72 b is held by the first sensor body 6. In addition, the part currently hold | maintained at the 1st sensor main body 6 is bent so that the 1st output pin 72b can be arrange | positioned perpendicularly | vertically with respect to the 1st through-hole 6d.

The second ion selective electrode 8 is disposed away from the first ion selective electrode 7, and the first ion selective electrode 8
A second sensitive film 81 formed by closing the second opening 6f of the sensor body 6 and a second voltage for outputting a potential in response to the second ion detected by the second sensitive film 81. 2 outputs 8
It is comprised by 2.

The second sensitive film 81 is composed of, for example, a crown ether-based second sensitive substance that selectively responds to the second ions, and PVC that includes the second sensitive substance. Similarly to the first sensitive film 71 shown in FIG. 3, one surface of the second sensitive film 81 forms a part of the first through hole 6d, and the one surface and the inclination of the second opening 6f The boundary of the surface is a smooth surface with no irregularities. The side surface between the one surface and the other surface is held by the inclined surface of the second opening 6f.

In this manner, the second sensitive film 81 formed in the second opening 6f can be observed with the lid 9 not attached to the first sensor body 6.

The second output element 82 is formed in the same manner as the first output element 72, and has one end portion formed in a ring shape and the other end portion formed in a rod shape extending from a part of the ring shape. Further, an inner electrode 82a in which a ring-shaped inner peripheral portion at one end portion is disposed at a position protruding outward from the inclined surface of the second opening 6f, and silver chloride is formed on the surface of the inner peripheral portion is configured. ing. A second sensitive film 81 is joined to the internal electrode 82a.

Thus, the 2nd sensitive film | membrane 81 can be reduced in size by joining the 2nd sensitive film | membrane 81 to the internal electrode 82a.

Further, a part of the other end is disposed outside the protrusion 6a, and constitutes a second output pin 82b connected to the electrolyte measuring device to which the ion selective electrode module 10 is mounted. And
The potential of the second sensitive film 81 in response to the second ions contained in the test sample or the like flowing into the first through hole 6d of the first sensor body 6 is sent to the electrolyte measuring device via the internal electrode 82a. Output. Further, a portion other than the internal electrode 82 a and the second output pin 82 b is held by the first sensor body 6.

The lid 9 has a first ion-selective property in which a liquid, a high-humidity gas, or the like enters the first and second openings 6e and 6f of the first sensor body 6 from the outside of the ion-selective electrode module 10. It is provided to prevent the electrical insulation between the first sensitive film 71 of the electrode 7 and the second sensitive film 81 of the second ion selective electrode 8 from deteriorating.

Thus, using the first sensor body 6, a plurality of first and second ion selective electrodes 7,
By producing 8, a smooth flow path of the sample to be tested constituted by the first through hole 6d can be formed. Moreover, the cost of components can be reduced.

A third opening is further provided in the first sensor body 6, and a fourth ion-selective electrode in which a fourth sensitive film that responds to the fourth ions is formed is provided in the third opening. It may be. Further, when it is not necessary to reduce the size, the internal electrodes 72a and 82a are connected to the first and second sensitive films 7.
1, 81 are disposed above the other surface, the internal electrode disposed above and the first and second sensitive films 71,
An internal solution containing an electrolyte may be enclosed between 81.

Next, the configuration of the third ion selective electrode 5 of the ion sensor unit 1 will be described with reference to FIG. FIG. 5 is a view showing a cross section of the third ion selective electrode 5. The third ion-selective electrode 5 is composed of, for example, a second sensor main body 51 made of PVC having excellent electrical insulation, and third ions such as chlorine ions held by the second sensor main body 51. A third sensitive film 52 that selectively responds and a third output element 53 for outputting a potential that responds to the third ions detected by the third sensitive film 52.

The second sensor body 51 has a shape in which a protrusion 51a is formed on a part of a cylindrical side surface,
There is provided a second through hole 51d penetrating the vicinity of the center of each of the one surface 51b and the other surface 51c corresponding to the top and bottom surfaces of the cylindrical portion. Then, the second surface on the one surface 51b side in a state where the one surface 51b is pressed against the other surface 6c of the first sensor body 6 in the multi-ion sensor 4 and the other surface 51c is pressed against the reference electrode 2 by the support 3 being held. The test sample flowing in from the through hole 51d flows out to the reference electrode 2 from the second through hole 51d on the other surface 61c side.

One surface on the one surface 51b side of the protrusion 51a is the same size as the other surface of the protrusion 6a on the other surface 6c side of the first sensor body 6, and the one surface 51b is the same size as the other surface 6c. The hole 51 d has the same size as the cross section of the first through hole 6 d of the first sensor body 6. When sandwiched by the support 3, the one surface 51b of the second sensor body 51 and the one surface of the protrusion 51a coincide with the other surface 6c of the first sensor body 6 and the other surface of the protrusion 6a. The one surface 51b is in pressure contact with the other surface 6c so that the through-hole 51d matches the first through-hole 6d. The other side 51
c is in pressure contact with the reference electrode 2.

The 3rd sensitive film | membrane 52 is comprised by the 3rd sensitive substance etc. which respond selectively to a 3rd ion, and when the 3rd ion is a chlorine ion, it pressure-molds the mixture containing silver chloride, for example. Is formed. The pressure-formed mixture has a cylindrical shape, and a hole penetrating the vicinity of the center of the cylindrical shape forms a part of the second through hole 51d, and the second sensor body 5 is formed on a surface other than the cylindrical hole.
1 is held.

One end surface of the third output element 53 is connected to the side surface of the third sensitive film 52. The other end portion forms a third output pin 53b that can be connected to the electrolyte measuring device on the outside of the protrusion 51a, and when held by the support 3, the second ion selective electrode in the multi-ion sensor 4 is formed. 8 second
Are arranged in parallel with the output pin 82b. Further, the portion other than the one end surface and the third output pin 53 b is held by the second sensor body 51. And the 3rd sensitive film | membrane 52 responded to the 3rd ion contained in the test sample etc. which flowed into the 2nd through-hole 51d of the 2nd sensor main body 51. FIG.
Is output to the electrolyte measuring device. The third output pin 53b is connected to the second through hole 51d.
It is arranged perpendicular to.

Next, the configuration of the reference electrode 2 will be described with reference to FIG. FIG. 6 is a view showing a cross section of the reference electrode 2. The reference electrode 2 includes a reference electrode body 21 made of, for example, PVC excellent in electrical insulation, a liquid junction hole 22 held in the reference electrode body 21, and a test sample via the liquid junction hole 22. The internal liquid 23 accommodated in the reference electrode body 21 so as to be able to circulate, and the internal liquid 2
4 and a fourth output 24 for outputting a potential with respect to the test sample detected by the liquid junction hole 22.

The reference electrode main body 21 has a shape in which a protrusion 21a is formed on a part of a cylindrical side surface, and a third penetration that penetrates the vicinity of the center of each of the one surface 21b and the other surface 21c that correspond to the top and bottom surfaces of the columnar portion. 21 d of holes and the recessed part formed in the outer periphery of the 3rd through-hole 21d in the said column shape are provided. Then, the second surface of the second sensor main body 51 is in a state in which the one surface 21b is in pressure contact with the other surface 51c of the second sensor main body 51 of the third ion selective electrode 5 by holding the support 3.
The test sample flowing from the third through hole 21d on the one surface 21b side from the through hole 51d of the other surface 21
It discharges to the outside from the third through hole 21d on the c side.

One surface on the one surface 21b side of the protrusion 21a is a protrusion 51a on the other surface 51c side of the second sensor body 51.
The other surface is the same size as the other surface, and the one surface 21b is the same size as the other surface 51c.
The through hole 21 d has the same size as the cross section of the second through hole 51 d of the second sensor body 51. And when nipped by the support body 3, one surface 21b and one surface of the protrusion 21a are the other surface 51c.
The one surface 21b is in pressure contact with the other surface 51c so as to coincide with the other surface of the projection 51a and so that the third through hole 21d coincides with the second through hole 51d.

The liquid junction hole 22 is made of, for example, a tubular porous material, and the inner surface of the porous material forms a part of the third through hole 21 a of the reference electrode main body 21. In addition, one end and the other end of the porous body are held by the reference electrode main body 21.

The internal liquid 23 contains high-concentration potassium chloride and the like, and is accommodated in a recess in the reference electrode body 21 so as to be able to flow through the liquid junction hole 22 with respect to the test sample flowing into the third through hole 21a. Has been.

One end of the fourth output element 24 is disposed in the recess of the reference electrode main body 21, and forms an internal electrode 24 a made of, for example, silver / silver chloride, and is in contact with the internal liquid 23. In addition, the other end portion is formed with a fourth output pin 24b that can be connected to the electrolyte measuring device on the outside of the protrusion 21a of the reference electrode main body 21. The electrode 5 is arranged in parallel to the third output pin 53b. Further, portions other than the internal electrode 24 a and the fourth output pin 24 b are held by the reference electrode body 21. Then, a constant potential of the liquid junction hole 22 that responds to the test sample flowing into the third through hole 21d of the reference electrode main body 21 is output to the electrolyte measuring device. The fourth
The output pin 24b is arranged to be perpendicular to the third through hole 21d.

Next, the structure of the support body 3 is demonstrated with reference to FIG.1 and FIG.7.
FIG. 7 shows a cross section of the ion-selective electrode module 10 in which the multi-ion sensor 4, the third ion-selective electrode 5, and the reference electrode 2 of the ion sensor unit 1 are held by the support 3. FIG.

The support body 3 refers to the first and second support bodies 31 and 32 in which the respective electrodes are integrated, the multi-ion sensor 4 and the third ion selective electrode 5, and the third ion selective electrode 5. And packings 33 and 34 disposed between the electrodes 2.

The first support 31 has a cylindrical shape, and a bent portion 31a in which the edge of the cylindrical one end is bent substantially perpendicularly toward the central direction of the cylindrical, and the other end of the cylindrical Second formed on the outer surface
A threaded surface 31b that is threadedly engaged with the support 32, a projection 6a of the first sensor body 6 in the multi-ion sensor 4 formed on a part of the cylindrical side surface, and a third ion-selective electrode 5. The protrusion 51a of the second sensor body 51 and the protrusion 2 of the reference electrode body 21 in the reference electrode 2
And a notch 31c engaged with 1a.

The second support 32 has a cylindrical shape shorter than that of the first support 31, and a bent portion 32a in which an edge of one end of the cylindrical shape is bent substantially perpendicularly toward the center direction, and the cylinder. And a threaded surface 32b that is threadedly engaged with the threaded surface 31b of the first support 31 formed on the inner surface of the other end of the shape.

The packing 33 includes the other surface 6 c of the first sensor body 6 and one surface 51 of the second sensor body 51.
It arrange | positions at the outer periphery of the 1st and 2nd through-holes 6d and 51d between b. Also packing 34
Are arranged on the outer periphery of the second and third through holes 51d, 21d between the other surface 51c of the second sensor body 51 and the one surface 21b of the reference electrode body 21. And the 1st and 2nd support body 31,
When sandwiched by 32, the test sample flowing into the second through hole 51d from the first through hole 6d and the test sample flowing into the third through hole 21d from the second through hole 51d are externally provided. Can be prevented from leaking.

And from the opening part of the other end part of the 1st support body 31, the multi ion sensor 4 and the packing 3
3, the third ion-selective electrode 5, the packing 34, and the reference electrode 2 are connected to each projection 6 of each electrode.
The first support 3 so that a, 51a and 21a engage with the notch 31c of the first support 31.
After being accommodated in 1, the second support 32 is screwed to hold each electrode from the directions of arrows L1 and L2 shown in FIG.

The first support 31 may be lengthened, and the multi-ion sensor provided with the fourth ion selective electrode, the third ion selective electrode 5, and the reference electrode 2 may be integrated. Also,
Similarly to the third ion selective electrode 5, a fifth ion selective electrode that responds to one ion may be integrated.

Hereinafter, the manufacturing process of the ion selective electrode module 10 will be described with reference to FIGS. FIG. 8 is a flowchart showing a first manufacturing process for manufacturing the multi-ion sensor 4. FIG. 9 is a diagram showing a part of the first manufacturing process. FIG. 10 is a flowchart showing a process of manufacturing the ion selective electrode module 10 using the multi-ion sensor 4 manufactured in FIG. FIG. 11 is a diagram showing an overview of the ion selective electrode module 10.

In FIG. 8, the first manufacturing process S22 includes steps S1 to S10. First, in a state where the first and second output elements 72 and 82 are arranged at predetermined positions of the mold, for example, PVC is poured into the mold and injection molding is performed, whereby the first and second output elements The first sensor body 6 holding 72 and 82 is produced (step S1).

For example, tetrahydrofuran (THF), which is a solvent for the first sensitive material, PVC, etc.
Is added to prepare a first dissolved solution. Further, a second solution obtained by adding tetrahydrofuran (THF) to the second sensitive substance, PVC, or the like, is prepared (step S2).

After the adjustment of the first and second dissolving solutions, as shown in FIG. 9A, the first and second output elements 72 are provided.
, 82 is inserted into the first through hole 6d of the first sensor body 6 fitted with a metal pin such as stainless steel that fits almost without any gap. Then, the first opening 6e of the first sensor body 6 is arranged in such a manner that the first and second output pins 72b and 82b are horizontally oriented and the inclined surface is directed upward so that the area of the opening is widened. A predetermined amount of the first dissolving solution is applied so as to be blocked.

By the first application, the first solution forms a substantially uniform liquid layer on the metal pin and over the inclined surface of the first opening 6e. After a predetermined time of application, as shown in FIG. 8B, THF is vaporized from the applied first solution to form a first film thinner than the first liquid layer (step S3). At this time, the side surface of the first film is held by being welded with THF to the inclined surface of the first opening 6e.

By applying the h-th application (h = 2), the first solution forms a substantially uniform h-th liquid layer on the (h-1) film and the inclined surface of the first opening 6e. To do. After a predetermined time of application, THF is vaporized from the applied first solution, and an h-th film thinner than the h-th liquid layer is superimposed on the (h-1) film (step S4). .

When h is i (Yes in step S5), the first sensitive film 71 made of the first to i-th films is formed in the first opening 6e. If h is less than i (No in step S5), a film thinner than the first sensitive film 71 is formed in the first opening 6e and is not joined to the internal electrode 72a, or Since there is a problem that the film strength is insufficient or the service life of the sensitive film is short, the process returns to step S4. Note that the side of the first sensitive film 71 is held by being welded with THF on the inclined surface of the first opening 6e.

Here, when the inclination angle of the inclined surface of the first opening 6e is 90 ° or more, for example, when THF is vaporized in the applied first solution and bubbles are generated, the bubbles are inclined. It remains in the first dissolved solution because it is prevented from rising due to adhesion. The remaining bubbles form pores when the film is formed. When pores are formed on, for example, one surface of the first sensitive film 71 shown in FIG. 3, the test sample remains in the pores, the remaining test sample contaminates the next test sample, and the next test sample is contaminated. There is a problem that the measurement accuracy of the test sample is lowered.

Further, when a large pore is formed in the vicinity of one surface of the first sensitive film 71, the film layer on the one surface responding to the first ions is thinned, so that the performance that passes the inspection at the time of manufacture is obtained. However, there is a problem that the service life after that is shortened. Furthermore, if the total volume of the pores formed in the membrane is large, there is a problem that the membrane resistance increases, the noise of the detection signal in the measuring instrument increases, and the measurement accuracy deteriorates.

In this way, the metal pin is inserted into the first through hole 6d, and the first solution is applied to the first opening 6e in which the inclined surface is arranged in the direction in which the area of the opening becomes wider upward. As a result, the first through-hole 6d in which the boundary between the one surface of the first sensitive film 71 and the first opening 6e has no irregularities is provided.
The surface can be formed. In addition, since bubbles generated in the applied first solution rise and are released into the atmosphere, the formation of pores in the first sensitive film 71 can be prevented.

As a result, it is possible to prevent contamination between test samples flowing into the first through-hole 6d, increase in membrane resistance, and decrease in service life, and improve the yield and quality of the first ion selective electrode 7. it can.

By the first application of the second solution, the second solution is applied to the metal pin and the second opening 6.
A substantially uniform first liquid layer is formed over the inclined surface f. After a predetermined time of application, THF is vaporized from the applied second solution to form a first film thinner than the first liquid layer (step S).
6).

By the m-th application (m = 2), the second solution forms a substantially uniform m-th liquid layer on the (m-1) film and the inclined surface of the second opening 6f. To do. After a predetermined time of application, THF is vaporized from the applied second solution, and an mth film thinner than the mth liquid layer is superimposed on the (m-1) th film (step S7). .

When m is n (Yes in step S8), the second sensitive film 81 made of the first to nth films is formed in the second opening 6f. If m is less than n (No in step S8), a film thinner than the second sensitive film 81 is formed in the second opening 6f and is not joined to the internal electrode 82a, or Since there is a problem that the film strength is insufficient or the service life of the sensitive film is short, the process returns to step S7.

In this manner, the metal pin is inserted into the first through hole 6d, and the second solution is applied to the second opening 6f in which the inclined surface is arranged in the direction in which the area of the opening becomes wider upward. As a result, the first through-hole 6d in which the boundary between the one surface of the second sensitive film 81 and the second opening 6f is smooth without any irregularities.
The surface can be formed. In addition, since bubbles generated in the applied second solution rise and are released into the atmosphere, the formation of pores in the second sensitive film 81 can be prevented.

As a result, contamination between test samples flowing into the first through-hole 6d, increase in membrane resistance, and reduction in service life can be prevented, and the yield and quality of the second ion selective electrode 8 can be improved. it can.

After “Yes” in steps S5 and S8, the metal pin is removed from the first sensor body 6. Then, the first and second sensitive films 71 and 81 are connected to the first and second openings 6 of the first sensor body 6.
Inspection is performed by observing from e and 6f (step S8).

Thus, the first and second sensitive films 71 and 81 can be observed from the first openings 6e and 6f, and the inspection can be performed at the stage where the multi-ion sensor 4 is manufactured.

And when the 1st and 2nd sensitive films | membranes 71 and 81 do not contain a pore (step S9)
Yes), the first sensor body 6 on which the first and second sensitive films 71 and 81 are formed is passed, and the lid 9 is attached to the passed first sensor body 6 (step S10). The first
When the sensitive film 71 or the second sensitive film 81 includes pores (No in step S9)
The first sensor body 6 having the first and second sensitive films 71 and 81 is rejected, and the process returns to step S2.

FIG. 10 is a flowchart showing a manufacturing process of the ion selective electrode module 10. Production of the ion selective electrode module 10 is started (step S21).

The first manufacturing process S22 is executed to manufacture the multi-ion sensor 4. Further, the second manufacturing process is executed. In the second manufacturing process, after forming the third sensitive film 52, the third output element 53 is connected to the formed third sensitive film 52. Next, in a state where the third sensitive film 52 connected to the third output element 53 is disposed at a predetermined position of the mold, for example, PVC is poured into the mold and injection molding is performed. Through this process, the third ion-selective electrode 5 including the second sensor main body 51 holding the third sensitive film 52 and the third output element 53 is manufactured (step S23).
).

In the manufacturing process of the reference electrode 2, the fourth output element 24 is disposed at a predetermined position of the mold,
PVC is poured into the mold, and a reference electrode body excluding a part of the reference electrode body 21 including, for example, the one surface 21 b is manufactured so that the liquid junction hole 22 can be arranged in the reference electrode body 21. Next, after disposing the liquid junction hole 22 in the reference electrode main body, the internal liquid 23 is accommodated in the recess in the reference electrode main body excluding the part, and the part is welded. 22, internal liquid 2
3 and the reference electrode 2 including the reference electrode main body 21 holding the fourth output element 24 is produced (
Step S24).

After steps S22, S23, S24, using the support 3, the multi-ion sensor 4,
The third ion selective electrode 5 and the reference electrode 2 are integrated (step S25).

The integrated multi ion sensor 4, third ion selective electrode 5, and reference electrode 2 are comprehensively inspected. If any of the multi-ion sensor 4, the third ion-selective electrode 5, or the reference electrode 2 fails (No in step S26), the process returns to step S25. If the multi-ion sensor 4, the third ion-selective electrode 5, and the reference electrode 2 have passed (Yes in step S26), the production of the ion-selective electrode module 10 shown in FIG. The process ends (step S27).

In this way, by using the support 3 to which the multi-ion sensor 4, the third in-selective electrode 5, and the reference electrode 2 are detachable, the unit that is defective in the comprehensive inspection can be easily replaced with a good one. can do.

Further, by using the ion selective electrode module 10, it is possible to save the trouble of individually mounting the ion selective electrode and the reference electrode on the electrolyte measuring device. In addition, it is possible to prevent a measurement accuracy defect due to a positional shift such as a flow path or packing between the electrodes when mounting.

According to the embodiment of the present invention described above, the metal pin is inserted into the first through hole 6d of the first sensor body 6, and the inclined surface is arranged in the direction in which the area of the opening becomes wider upward. 1 and 2
By applying the first and second dissolving solutions to the openings 6e and 6f, the boundary between one surface of the first and second sensitive films 71 and 81 and the first and second openings 6e and 6f is uneven. Smooth first without
The surface of the through-hole 6d can be formed. Moreover, it is possible to prevent pores from being formed in the first and second sensitive films 71 and 81.

As a result, it is possible to prevent contamination between test samples flowing into the first through-hole 6d, increase in membrane resistance, and decrease in service life, and improve the yield and quality of the first ion selective electrode 7. it can.

Further, the first and second ion selective electrodes 7 and 8 can be inspected at the stage where the first and second sensitive films 71 and 81 are formed in the first and second openings 6e and 6f. it can. Thereby, it is possible to reduce the labor of the manufacturing process from the production of the multi-ion sensor 4 when the first and second sensitive films 71 and 81 are defective to the comprehensive inspection.

Further, by making the multi-ion sensor 4, the third in-selective electrode 5, and the reference electrode 2 detachable using the support 3, the unit that is defective in the comprehensive inspection of the ion-selective electrode module 10 can be used. The ion-selective electrode module 10 can be replaced with a better one.
It is possible to reduce the cost and time of parts required for the manufacture of the present invention.

Furthermore, the use of the ion selective electrode module 10 can save the trouble of individually mounting the ion selective electrode and the reference electrode on the electrolyte measuring device. In addition, it is possible to prevent a measurement accuracy defect due to a positional shift such as a flow path or packing between the electrodes when mounting.

DESCRIPTION OF SYMBOLS 1 Ion sensor part 2 Reference electrode 3 Support body 4 Multi ion sensor 5 3rd ion selective electrode 6 1st sensor main body 6a, 21a, 51a, protrusion 6b, 21b, 51b One surface 6c, 21c, 51c The other surface 6d 1st 1 through-hole 7 1st ion-selective electrode 8 2nd ion-selective electrode 9 lid 10 ion-selective electrode module 21 reference electrode body 21d 3rd through-hole 31 1st support body 31a, 32a Bending part 31b 32b Threaded surface 31c Notch 32 Second support 33, 34 Packing 51 Second sensor body 51d Second through hole

Claims (12)

A sensor body having an opening having an inner surface communicating with a part of the through hole through which the test sample flows and a part of the through hole;
A sensitive membrane formed by closing the opening and selectively responding to predetermined ions;
A part of the sensor is sandwiched between the sensor body and a part different from the part is arranged on the side where the sensitive film is held from the inner surface. The output of
With
The ion-selective electrode, wherein the sensitive film is held on the inner surface in contact with a portion protruding from the inner surface of the output element.   2. The ion selection according to claim 1, wherein one end portion of the output element has a ring shape, and an inner peripheral portion of the ring shape is arranged to protrude from the inner surface to a side where the sensitive film is held. Sex electrode.   The ion selective electrode according to claim 1, wherein the opening has an inclined surface in which an area of the opening becomes narrower as the through hole is approached. The opening includes at least a first opening and a second opening that is spaced from the first opening,
A first sensitive film selectively responding to first ions formed by closing the first opening, and the sensor main body for outputting a potential responded by the first sensitive film to the outside A first output element held in the
A second sensitive film that selectively responds to second ions formed by closing the second opening, and a sensor body that outputs a potential responded by the second sensitive film to the outside. The ion-selective electrode according to claim 1, further comprising: a second output element.   2. The output element according to claim 1, wherein one end portion of the output element is joined to the sensitive film at the inclined surface, and the other end portion is an output pin connectable to an external device protruding outward from the sensor body. 4. The ion selective electrode according to 3.   4. The ion selective electrode according to claim 1, wherein one surface of the sensitive membrane forms a part of the surface of the through hole. 5.   The ion-selective electrode according to claim 6, further comprising a lid that is detachably attached to the sensor body so as to cover the other surface of the sensitive membrane. The ion selective electrode according to claim 1, further comprising an internal electrode formed on a part of a surface of the output element that protrudes from the inner surface to a side where the sensitive film is held. An ion selective electrode according to claim 1 to 8,
A reference electrode body having a through-hole through which the test sample flows, a liquid junction hole formed in the through-hole of the reference electrode body, and inside the reference electrode body so as to be able to flow to the test sample through the liquid junction hole And a reference electrode having an output element for outputting a substantially constant potential in the liquid junction hole by contacting one end of the internal liquid and the internal liquid,
A support body that detachably holds the sensor body and the reference electrode body, which are disposed so as to penetrate the through hole of the sensor body and the through hole of the reference electrode body;
An ion-selective electrode module comprising:   A packing for preventing leakage of the test sample from between the sensor main body and the reference electrode main body is disposed on the outer periphery of the through hole between the sensor main body and the reference electrode main body. The ion selective electrode module according to claim 9. The support includes first and second supports having surfaces that are screwed together,
The sensor body and the reference electrode body are clamped by screwing the second support body into the first support body containing the sensor body and the reference electrode body. Item 10. The ion selective electrode module according to Item 9. A through hole test sample flows, communicating with a portion of the through hole, an opening having an inner surface, in the through hole of the sensor body having, inserted substantially without clearance fit pins,
A sensitive film made of a sensitive substance that selectively responds to a predetermined ion is in contact with a portion of the output element that is held by the sensor body and outputs the potential responded by the sensitive film to the outside. The output element is held by the inner surface, and a part of the output element is sandwiched by the sensor body, and the output element is arranged such that a part different from the part protrudes from the inner surface to the side where the sensitive film is held. Apply a solution in which a component containing the sensitive substance is dissolved in a solvent so that the sensitive film comes into contact with an internal electrode formed on a part of the surface that is on the side where the sensitive film is held. A method for producing an ion-selective electrode, wherein the pin is removed from the through hole after the solvent of the dissolved solution is vaporized .

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