JPS6239758A - Measuring instrument for ion activity - Google Patents

Abstract

PURPOSE:To attain available utilization in measuring the activity of one kind or plural kinds of ions by one instrument, by respectively imparting a reference liquid and a liquid to be inspected to the surfaces of the ion selection layers of at least a pair of sheet like ion selection electrodes electrically separated to each other. CONSTITUTION:Sheet like ion selection electrodes 11a-11c equipped with ion selection layers 115, a liquid imparting part for imparting a reference liquid and a liquid to be inspected to the surfaces of respective ion selection layers 115 and a bridge 19 for bringing both liquids to an electrical continuity state are provided to the uppermost part. The liquid imparting part contains a liquid imparting opening part 12, a falling passage 13 for moving the liquids to the parts below the surfaces of the selection layers 115, a horizontal passage 14 for subsequently moving the liquids to the horizontal direction directly under the surfaces of the selection layers 115, liquid rising guide passages 15a-15c (of which the top parts of the side walls have gaps accompanying no generation of a capillary phenomenon to the surfaces of the selection layers) for subsequently raising the liquids and liquid rising aiding guide passages 27a-27c for aiding the rising of the liquids up to the surface positions of the selection layers 115 and securing that the expanse of the liquids reaching the surfaces of the selection layers 115 along the surfaces thereof does not reach the peripheral edges of said layers.

Description

[Detailed Description of the Invention] [Technical Field of the Invention] The present invention relates to aqueous liquids, particularly biological fluids (blood, urine, saliva, etc.).
The present invention relates to an ion activity measurement device used for quantitatively analyzing the activity (or concentration) of a specific ion in a substance using botensiometry.

[Background of the invention] Using an appropriate amount of liquid (tap water, river water, sewage, industrial wastewater, etc.) or biological body fluid (blood such as whole blood, plasma, serum, urine, saliva, etc.), the specific content contained therein is determined. A method for measuring the activity of ions using a sheet-shaped ion activity measurement device is already known.

That is, a reference liquid and a test liquid are sealed on the surface of each ion selective layer of a pair of sheet-like ion selective electrodes that are electrically separated from each other and have an ion selective layer on the top, and then both liquids are separated by a bridge. This method measures the ion activity of the test liquid by measuring the potential difference between each ion selection electrode in a state where they are electrically connected to each other.

An example of such an ion activity measuring device is:

Japanese Patent Application Laid-open No. 52-142588 (US 405338)
1) (US stands for United States patent), Japanese Patent Application Laid-open No. 58-614
Publication No. 8 (US4273839), JP 58-211
Examples include the ion activity measuring instrument described in Publication No. 648 (US 4,437,970) and the like.

These ion activity measuring instruments basically consist of a pair of sheet-shaped ion-selective electrodes arranged with the ion-selective layer facing upward, and a liquid spotting hole (where the standard solution and test solution are applied) placed on top of the ion-selective electrodes. an opening) is provided on each ion-selective layer from above.

A method is used in which ion activity is measured by sealing a reference solution and a test solution through a liquid spotting hole using a pipette or the like and measuring the potential difference generated between the two ion-selective electrodes. Furthermore, as an improved version of the above-mentioned ion activity measurement device, a plurality of ion selection electrode pairs may be incorporated into the ion activity measurement device, and the reference solution and the test solution may be applied once each. There are also known devices that can measure the activities of multiple types of ions.

The method of measuring ion activity using a pair of sheet-like ion-selective electrodes as described in L is a simple and excellent method. However, according to the study of the present inventor, there are various problems in manufacturing the measuring instrument and performing the measuring operation. It turned out that there was a problem.

The first problem is that the ion-selective layer is easily damaged by the tip of the pipette normally used to apply the reference and test solutions. Since the ion-selective layer is not a solid but a jelly-like membrane, it is easily scratched or deformed when the tip of a pipette comes into contact with its surface, which may cause deterioration in the shape of the ion-selective layer. causes measurement errors, and in extreme cases, measurement becomes impossible.

The second problem is that the silver chloride layer of the ion selective electrode easily deteriorates. Most ion-selective electrodes use a silver/silver chloride electrode (half cell) as an internal reference electrode, but in that case, if the ion activity measurement device is left in a bright room, light incident from the liquid spotting hole will The silver chloride layer is altered by
As a result, the electrodes tend to deteriorate.

A third problem is that the terminal (probe) for measuring the potential difference generated between the ion selection electrodes is easily contaminated.

A sheet-like ion selective electrode is generally used in the form of an electrode formed on the surface of a plastic sheet support. To measure ion activity using an ion-selective electrode, it is necessary to measure the potential difference between a pair of ion-selective electrodes as described above. For this purpose, an area for electrical connection (for example, an extension of the silver layer) is provided at the end of the conductive site of the ion-selective electrode (the silver layer in the case of a silver/silver chloride electrode). Then, the potential difference is measured by bringing this terminal of a separately prepared potential difference measurement system into contact with that area. In this case, if the arrangement is such that the normal ion selective layer is on the upper side, the surface of the electrical connection area will naturally also be directed upward, and the terminal of the potentiometer will be in contact with the surface of the electrical connection area from above. Placed. Therefore, there is a problem in that the potential difference measurement terminal is likely to be contaminated by the reference liquid or test liquid applied from above.

Fourth, there is a problem that the measurement system of the potentiometric measuring device used in combination with the ion activity measuring device tends to be complicated. In other words, when the normal ion selective layer is arranged on the L side, the surface of the electrical connection area is also directed upward as described above, and the terminal of the potentiometric measuring device contacts the surface of the electrical connection area from above. It is arranged so that For this reason, if wiring of the potential difference measurement system is to be carried out without difficulty, the wiring needs to be carried out upward or towards the sides. -On the other hand, the measuring instrument of the potentiometric measuring device should be placed on the f side of the ion activity measuring instrument in order to avoid contact with the reference liquid and test liquid, and to save space occupied by the device. It will be advantageous. Therefore, the conventional ion active G, which assumes an operation in which the ion selective layer is placed on the upper side and a reference liquid or a test liquid is applied thereto,
When a measuring instrument is used, the measuring system of the potentiometric measuring device used in combination with the measuring instrument tends to become complicated, and the space required by the measuring system increases.

Fifth, with conventional methods, when measuring a large number of test items simultaneously, there are differences in: i) the time and contact area required for the waste liquid or test liquid to contact each electrode surface; this is one of the causes of measurement errors; It was.

[Object of the Invention] An object of the present invention is to provide an ion activity measuring instrument that is advantageously used when measuring the activity of one or more kinds of ions using one instrument.

In particular, it is an object of the present invention to provide an ion activity measuring instrument that can solve all of the above-mentioned problems that tend to occur in hitherto known ion activity measuring instruments.

[Summary of the Invention] The present invention provides at least a pair of sheet-like ion-selective electrodes that are electrically separated from each other and have an ion-selective layer on the top, and a reference liquid and a test liquid are applied to the surface of each ion-selective layer. In an instrument for measuring the ion activity of a test liquid, which has a liquid application part for electrically conducting the two liquids, and a bridge for electrically conducting both liquids, each sheet-shaped ion-selective electrode is arranged so that the ion-selective layer is on the bottom side. The liquid applying section includes an upper liquid applying opening, a descending passageway that moves the liquid to a position below the surface of the ion selective layer, and a horizontal path that moves the liquid horizontally to just below the surface of the ion selective layer. a passageway, a liquid rising guide path which then raises the liquid (however, the top of the side wall of this liquid rising guide path is separated from the surface of the ion selective layer by a gap that does not involve the generation of capillary action); , and is provided at the upper part of the liquid rising guide path to assist the liquid to rise to the surface position of the ion selective layer, and the liquid that reaches the surface of the ion selective layer spreads along the surface to the periphery thereof. The present invention provides an ion activity measuring instrument characterized by including an auxiliary guide path for liquid rise to ensure that the liquid does not reach the maximum level.

In this specification, a gap in which no capillary phenomenon occurs with respect to the surface of the ion-selective layer is defined as a gap in which the liquid moves against its own weight to fill the gap between the ion-selective layer and the top of the side wall of the liquid upward guide path. means a gap larger than the one through which it can be penetrated. The above-mentioned gap varies depending on the surface tension of the liquid, the material of the contacting member, the surface condition, etc., but is generally 50 l or more.

[Effect of the invention J By using the ion activity measuring instrument of the present invention,
The above-mentioned problems that tend to occur in hitherto known ion activity measuring methods and measuring instruments used therein can be solved all at once.

That is, by using the ion activity measurement device of the present invention, physical deterioration due to contact with the pipette tip of the ion selective layer of the ion selective electrode, and chemical deterioration of the electrode portion of the ion selective electrode due to exposure to light can be effectively prevented. It can be avoided.

Further, in the ion activity measuring instrument of the present invention, since the surface of the electrical connection region is disposed facing downward, wiring for potential difference measurement downward to the liquid supply system above can be easily realized. Therefore, contamination of the potential difference measuring terminals is prevented, and the measurement system of the potential difference measuring device can be simplified.

Furthermore, in the ion activity measurement device of the present invention, the top of the side wall of the liquid rising guide path is separated from the surface of the ion selective layer by a gap that does not cause capillary action, and Since the area where the top of the guide path and the ion selective layer face each other is small, if oily substances are used as plasticizers in the ion selective layer, these substances will come into contact with the top of the side wall and flow out. There is no fear that the distribution will become uneven. Further, since the spaces on the liquid rising guide paths adjacent to each other with the gap in between are in an open state at least in relation to each other, there are few bubbles generated in the rising liquid or on the liquid surface. Therefore, the ion activity measuring method and measuring instrument of the present invention also have the effect that measurement errors due to the generation of bubbles are unlikely to occur.

Furthermore, in the ion activity measurement device of the present invention, a liquid rising auxiliary guide path is provided at the upper part of the liquid rising guide path for assisting the liquid to rise to the surface position of the ion selective layer.
The contact time of the reference liquid or test liquid to each electrode surface is made uniform. Therefore.

There are almost no measurement errors caused by differences in contact time.

Furthermore, the liquid rising auxiliary guide path is used to ensure that the liquid that reaches the surface of the ion-selective layer does not spread along the surface to the periphery of the ion-selective layer. The contact area to the selective layer is also very well homogenized. Therefore, measurement errors due to differences in contact area hardly occur.

The ion activity measuring device of the present invention also has the advantage that the sheet-like ion selection electrode and the device frame are unlikely to be distorted during manufacturing and assembly of the device. As a result, an ion activity measuring instrument capable of measuring ion activity with high accuracy is obtained.

[Detailed Description of the Invention] The ion activity measuring instrument of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a perspective view showing an example of the ion activity measuring instrument of the present invention. FIG. 1A is an elevational sectional view taken along the line II of the ion activity measuring device shown in FIG. 1, and FIG. 1B is a bottom view of the ion activity measuring device shown in FIG. FIG. 1C is an enlarged view of the circled portion X of the elevational cross-sectional view shown in FIG. FIG. 1E is a diagram schematically showing the state of ions when the conditions such as the wettability of the ion selective layer, the surface tension of the liquid, and the elapsed time after applying the liquid are different from the example of FIG. 1D. FIG. 1F is a diagram schematically showing the state of liquid adhesion to the surface of the ion selective layer of the selective electrode, and FIG. 1F is a perspective view of the liquid rising auxiliary guide path used in the above six examples.

FIG. 2 is a diagram showing each constituent member separated in order to explain in detail each member constituting the ion activity measuring instrument shown in FIG. 1.

The ion activity measurement device of the embodiment shown in these figures includes three pairs of sheet-like ion selective electrodes (one pair of ion selective electrodes has an ion selective layer on the top).

Consists of a combination of an ion selection electrode for a reference solution and an ion selection electrode for a test solution that are electrically separated from each other)11
a, llb, and llc are arranged so that the ion selective layer is on the lower side. In this arrangement, the sheet-like ion-selective electrode is mounted on a support made of, for example, a plastic sheet, with a metallic silver vapor deposited layer 1, as shown in FIG. 1C.
12, a silver chloride layer 113, an electrolyte layer 114, and an ion selective layer 115 are laminated, and the sheet-like ion selective electrode thus configured is placed in an inverted state in a measuring instrument. There is.

As is clear from FIG. 1A, the liquid applying section for applying the reference liquid and the test liquid to the surface of the ion selective layer of the ion selective electrode has an upper liquid applying opening 12, a liquid applying part for applying the reference liquid and the test liquid to the surface of the ion selective layer of the ion selective electrode, and an upper liquid applying opening 12 for applying the liquid to the ion selective layer surface. a descending passage 13 for moving to a position below the surface;
A horizontal passage 14 for moving the liquid horizontally directly below the surface of the ion-selective layer, and a liquid rising guide path 15a, 1 for moving the liquid from a position directly below each ion-selective electrode.
5b, tSC. Liquid rising guide path 15
a, 15b, and 15c, the tops of the side walls are separated from the surface of the ion-selective layer by gaps that do not cause capillarity to the surface of the ion-selective layer. That is, as shown in FIGS. 1A and 1C, a large opening 25 is provided above the liquid upward guide path. Further, in the space provided by the opening 25, there are provided upper portions of the liquid rising guide paths 15a, 15b, 15cc7).

Liquid rising auxiliary guide paths 27a, 27b, and 27c are provided. This space and the installation of the liquid rising auxiliary guide path create a horizontal passage 1 as schematically shown in FIG. 1D.
The liquid rising after passing through 4 is guided by the liquid rising auxiliary guide path and comes into contact with the ion selection electrode surface. Also, the wettability of the ion selective layer, the surface tension of the liquid, and the time after applying the liquid! 6 of the transition whistles reach the space where the top of the auxiliary guideway and the ion selective layer face each other, or as schematically shown in Figure 1E. As shown, it expands into the space provided by the opening 25. Therefore, the space and the liquid rising auxiliary guide path can prevent the liquid from spreading in the horizontal direction on the surface of the ion selective layer due to capillary action.

The spaces on the adjacent liquid rising guide paths are open at least in relation to each other through a gap that does not cause capillarity to the surface of the ion selective layer. Further, the gap above the top of the side wall of the liquid rising guide path may communicate with the outside of the measuring instrument via a space other than the liquid rising guide path. Embodiments in which they are in communication are also included in the present invention.

The horizontal passage 14 has a liquid transfer member (referred to as porous in this specification) having continuous fine gaps that can cause capillary action (a wire band, cotton gauze, or a non-porous material having continuous gaps).
Filling with i+j T:) l 6 is preferable for smooth liquid transfer, and filling the porous member for liquid delivery is particularly advantageous when the reference liquid and test liquid are small.

The three pairs of ion selection electrodes 11a, llb, llc are housed in an L frame 18 made of plastic and are normally in a fixed state. This upper frame 18 is provided with a liquid application opening 12, and the two liquid application openings (a reference liquid application opening and a test liquid application opening) are traversed. A bridge (for example, a yarn bridge such as polyethylene terephthalate fiber heating yarn (spun yarn)) 19 is provided for electrically conducting the liquids (reference liquid and test liquid) applied to each liquid application opening. It is being

Although not shown in the figure, a small protrusion area is provided around the liquid opening 12 to prevent the liquid to be dispensed from overflowing to the outside of the opening and to easily and reliably apply the liquid. It can be used as a guide.

A sheet-shaped first intermediate member (spacer) 26 is provided at the bottom of the upper frame 18 . A part of the descending passage 13 for the drop-supplied liquid and an upper space 25 of the liquid ascending guide passage are formed in the first intermediate member 26 in the shape of an opening.

Furthermore, a sheet-like water-impermeable second intermediate member (for example, a plastic mask) is disposed below the first intermediate member 26.
20 are provided. Descending passage 13 for drop-supplied liquid
, part of the liquid ascending guide paths 15a, 15b, 15c (although not shown, the r liquid and the ascending auxiliary guide paths 27a, 27
b and 27c) are formed in the shape of openings in the sheet-like water-impermeable second intermediate member 20.

The water-impermeable second intermediate member includes a liquid rise auxiliary guide path 27.
a, 27b, and 27c are provided.

An example of the shape of each liquid rising auxiliary guide path 27 is the ring shape shown in the perspective view in FIG. There are no particular restrictions. There is no particular restriction on the size of the liquid E rising auxiliary guide path as long as the height is 25 cm or more in the northern space, and the distance between the liquid E rising auxiliary guide path and the ion selective layer is set to a gap that causes capillary phenomenon. It may be a gap with or without a gap. It is preferable that the diameter of the space (indicated as the inner diameter in FIG. 1F) of the space in the center of the liquid rising auxiliary guide path that guides the rise of the liquid is approximately the same as or smaller than the diameter of the liquid rising guide path. If the inner diameter of the liquid rising auxiliary guide path is the same as the diameter of the liquid rising auxiliary guide path, the liquid rising auxiliary guide path is integrally molded with the water-impermeable second intermediate member as described later. The inner surfaces of the guide path and the liquid rising guide path can also be formed as a continuous curved surface. Further, the outer diameter of the liquid rising auxiliary guide path is preferably set to a size such that the liquid rising auxiliary guide path is located inside the end portion of the ion selective layer.

The liquid rising auxiliary guide path can be provided by bonding with an adhesive or the like above the opening of the liquid rising guide path of the water-impermeable second intermediate member. Further, when manufacturing the water-impermeable second intermediate member, it is also possible to integrally mold the liquid rising auxiliary guide path with the water-impermeable second intermediate member.

Note that the first intermediate member 26 and the water-impermeable second intermediate member 20 provided with the liquid rising auxiliary guide path are as follows.

It is preferable that it is bonded to the lower surface of the upper frame 18 using an adhesive (pressure-sensitive adhesive, heat-sensitive adhesive, etc.), heat fusion, or a physical adhesive.

A lower frame 21 made of plastic is disposed below the water-impermeable sheet-like second intermediate member 20 .

The horizontal passage 14 is formed in the lower frame 21 as a recess. This horizontal passage 14 is filled (accommodated) with a liquid transfer porous member 16 as desired.The liquid transfer porous member 16 may be fixed to the horizontal passage 14.

Ion selection electrodes 11a and 11a are provided on both sides of the lower frame 21.
lb, llc electrical connection areas 22a, 22b,
A notch 23 is provided to expose the portion 22c downward (see FIG. 1B). The notches 23 may be formed individually to suit each of the plurality of pairs of ion-selective electrodes, and the electrical connection areas of all the ion-selective electrodes can be formed in a pair of notches provided on both sides of the instrument. It may also be made to expose more. The drawing shows an example of the latter.

The lower frame body 21 is provided on the lower surface of the water-impermeable second intermediate member 20.
It is desirable that they be joined by an adhesive (pressure sensitive adhesive, heat sensitive Wc adhesive, etc.), heat fusion, or a physical engagement material.

Note that as long as it is possible to fill the ion selective electrode and, if desired, fill the porous member for liquid transfer, the upper frame,
Of course, all or part of the first intermediate member (spacer), the water-impermeable first intermediate member provided with the liquid elevating guide path, and the lower frame may be integrally molded. Furthermore, it is not necessary to integrate the upper frame, the first intermediate member, the water-impermeable second intermediate member, and the lower frame, and the upper frame, the first intermediate member, and the water-impermeable Both the second intermediate member and the lower frame can be constructed from a plurality of members.

The upper frame, the first intermediate member, the water-impermeable second intermediate member, and the lower frame can be manufactured from any desired shape-retaining material, but the quality, such as moldability and impact strength, etc. In view of this, it is preferable to form it from a plastic material. For example, known methods such as a method of placing a plastic material in a desired mold and molding it, a drawing method using a sheet-shaped plastic material, etc. can be used.

That is, as illustrated in FIGS. 1 and 2, the sheet-like ion selective electrode includes an upper frame body having openings at positions corresponding to the respective liquid application openings, and an upper frame body having openings at positions corresponding to the openings for applying liquid. Each of the openings has an opening at a position corresponding to the opening on the top surface of the rising guide path, and the latter opening is made larger than the opening on the top surface of the liquid rising guide path so as to prevent the latter opening from coming into contact with the rising liquid. one intermediate member, having an opening at a position corresponding to the descending passage and the liquid ascending guide passage;
The container is provided with a water-impermeable second intermediate member in which a liquid rise auxiliary guide channel is placed above the opening of the latter, and a lower frame 7 with a recess forming a horizontal passage, with a bridge in the upper part. An ion activity measuring instrument fixed to the upper frame body across the opening of the frame body can be used particularly effectively for carrying out ion activity measurements.

FIG. 3 shows another embodiment of the ion activity measuring instrument of the present invention,
Similar to FIG. 2 above, this is a diagram showing each constituent member separately so as to explain each member constituting the ion activity measuring instrument in detail.

Also in the ion activity measurement device of the embodiment shown in this figure,
Three pairs of sheet-like ion selective electrodes 31a, 31b, and 31c each having an ion selective layer on the top are arranged so that the ion selective layer is on the lower side.

The three pairs of ion selection electrodes 31a, 31b, and 31c are housed in an upper frame 38 made of plastic and are normally in a fixed state. This upper frame 38 is provided with a liquid application opening 32 .

In the example of FIG. 3, three pairs of ion selection electrodes are distributed into one pair and two pairs on the left and right sides of the liquid application opening 32.

With such a configuration, the distance between the housing and the opening at the foot of the opening can be reduced from 1 to 3.
This is advantageous when a highly viscous liquid is used as a sample because it is closer than the measuring instrument shown in FIG. 2.

A plastic bridge support member 52 having two openings 51 at positions corresponding to the liquid application openings 32 is placed at the bottom of the upper frame 38 . A bridge 39 is provided across the openings of the two openings 51 to electrically conduct the liquids (reference liquid and test liquid) applied to each part of the liquid application opening. It is equipped.

A sheet-shaped first intermediate member (spacer) 46 is provided below the bridge support member 52 . A part of the downward passage 33 for the drop-supplied liquid and upper spaces 45a and 45b of the liquid upward guide passage are formed in the first intermediate member 46 in the shape of openings.

Furthermore, a sheet-like water-impermeable second intermediate member (for example, a plastic mask) is disposed below the first intermediate member 26.
A descending passage 33 for the liquid supplied at the zero point where 40 is provided.
Parts of the liquid rise guide paths 35a, 35b, 35C (l, not shown) are liquid rise auxiliary guide paths 47a, 47.
b and 47c) are formed in the shape of openings in the sheet-like water-impermeable second intermediate member 40. The water-impermeable second intermediate member is further provided with liquid rise auxiliary guide paths 47a, 47b, and 47c. The shapes, etc. of the liquid rising auxiliary guide paths 47a, 47b, 470 are the same as those shown in the above-mentioned FIG. 1 to small IF diagram. Also, liquid rise auxiliary guide paths 47a, 47b
, 47c, Liquid and Kogyo nai-ro 35a, 35b, 35c,
The relationship with the northern spaces 45a and 45b is also the same as that in the embodiments shown in FIGS. 1 to 1F above.

Note that the first intermediate member 46 and the water-impermeable second intermediate member 40 provided with the liquid rising auxiliary guide path are coated with an adhesive (pressure-sensitive adhesive, heat-sensitive adhesive, It is preferable that they be joined by a bonding agent, etc.), heat fusion, or a physical engagement material.

A lower frame 41 made of plastic is disposed below the sheet-like water-impermeable intermediate member 40 .

The horizontal passage 34 is formed in the lower frame 41 as a recess. Then, this horizontal passage 34 is filled with a liquid transfer porous member 36 if desired. Note that the liquid transfer porous member 36 may be fixed to the horizontal passage 34.

Ion selection electrodes 31a, 3 are provided on both sides of the lower frame 41.
A notch 43 is provided to expose the electrical connection area of each of 1b and 31c downward (see FIG. 1B).

The lower frame body 41 is on the lower surface of the water-impermeable second intermediate member 40,
It is preferable that they be joined by an adhesive (pressure-sensitive adhesive, heat-sensitive adhesive, etc.), heat fusion, or a physical engagement material.

All or part of the one-part frame, the bridge support member, the water-impermeable intermediate member, and the lower frame, as long as it is possible to accommodate the ion-selective electrode and fill the porous member for liquid transfer, if desired. Of course, they may be integrally molded. Further, as in the above example, each member may be composed of a plurality of members, and each member may be formed of any material.

That is, in the ion activity measuring instrument composed of the members shown in FIG. 3, the upper frame 18 shown in FIG. 2 has a different arrangement of the liquid application openings, and a one-part frame body 3 having an opening at a position corresponding to the part;
8 and a bridge support member 52 having an opening at a position corresponding to the opening described above.

The measuring instrument shown in FIG. 3 has an embodiment in which the upper frame body and the bridge support member are divided as described above, and each member has a simple form, so that it has the advantage of being easy to manufacture.

In addition, in the measuring instrument shown in Figure 3, the thread bridge is not fixed to the upper frame but is fixed to an independent bridge supporting plate (bridge support member). No distortion occurs in the upper frame during the fusion operation. There is also the advantage that the accuracy of assembly during the manufacturing of the shouting equipment is improved, and as a result, it is easier to obtain highly accurate ion activity measurements.

FIG. 4 shows another embodiment of the ion activity measuring instrument of the present invention,
Similar to FIGS. 2 and 3 above, this is a diagram showing each constituent member in separate layers so as to explain in detail each member constituting the ion activity measuring instrument.

In the example shown in FIG. 4, the upper frame 48 and the bridge support member 61 are provided independently, similar to the example shown in FIG.

In the example of FIG. 4, the bridge support member 61 has a large opening 62, and in addition to its function as a bridge support member, the first intermediate member (spacer) 26 shown in FIGS. provides a space 62 corresponding to the space 25 provided by.

Therefore, as an intermediate member, the opening 5 corresponding to the descending passage
3 and openings 57a, 57b corresponding to the liquid rising guide path,
Only a water-impermeable intermediate member 50 having 57c is provided.

That is, the ion activity measuring device constructed from the respective members shown in FIG. There are openings at a position corresponding to the top surface of the liquid rising guide path and a position corresponding to the side opening of the liquid rising guide path. The bridge support member also has a large opening, and has openings at positions corresponding to the descending passage and the liquid rising guide passage, and the liquid rising auxiliary guide passage is placed above the latter opening. This shows an embodiment in which the container includes a permeable intermediate member and a lower frame body having a recessed portion forming a water vertical passage, and the bridge is fixed to the support member so as to cross the opening of the bridge support member. ing.

Although various typical embodiments of the measuring instrument of the present invention shown in the accompanying drawings have been shown so far, it goes without saying that the ion activity measuring instrument of the present invention is not limited to these embodiments. For example, a preferred embodiment of the ion activity measuring instrument of the present invention is an ion activity measuring instrument in which the characteristic configurations shown in each embodiment are mutually combined.

In the measuring instrument of the present invention, the bridge and the liquid transfer member can be appropriately selected from (porous) materials having continuous fine gaps that can cause capillary action. In addition to heating thread, porous materials for bridges include membrane filters, fM paper, filter paper laminated with a single layer of hydrophobic organic polymer on both sides as described in JP-A No. 55-20499, and porous materials for liquid transfer members. In addition to wire-colored belt cloth and nonwoven cotton gauze fabric, various types of heated thread-like woven fabrics, heated thread-like knitted fabrics, membrane filters, filter papers, and the like can be used.

[Brief explanation of drawings]

FIG. 1 is a perspective view showing an example of the ion activity measuring instrument of the present invention. FIG. 1A is a three-dimensional cross-sectional view of the ion activity measuring device shown in FIG. 1 taken along line I-I, and FIG. 1B is a bottom view of the ion activity measuring device shown in FIG. 1C is an enlarged view of the circled part In the diagram shown, the first
Figure E differs from the example in Figure 1D in terms of wettability of the ion selective layer,
When the conditions such as the surface tension of the liquid and the elapsed time after applying the liquid are different. FIG. 1F is a diagram schematically showing the state of liquid adhesion to the surface of the ion selective layer, and FIG. 1F is a perspective view of the liquid rising auxiliary guide path used on each side. FIG. 2 is a diagram showing each constituent member separated in order to explain in detail each member constituting the ion activity measuring instrument shown in FIG. 1. FIG. 3 shows another embodiment of the ion activity measuring instrument of the present invention,
Similar to FIG. 2, this is a diagram showing each constituent member separately so as to explain in detail each member constituting the ion activity measuring instrument. FIG. 4 is a diagram illustrating still another embodiment of the ion activity measuring instrument of the present invention, with each component separated, similar to FIGS. 2 and 3 above. ++a +lk +lr・i+soi supper J9Tit
Burmese 31a, 31b, 31C: Ion selective electrode 111 Niblast sheet support 112: Metallic silver vapor deposited layer 113: Silver chloride layer 114: Electrolyte layer 115: Ion selective layer 12.32: Liquid application opening 13.33 :Liquid descending passage 14.34:Liquid above water passage 15a, 15b, 15c:Liquid rising guide path 25:Space on liquid rising guide path 35a, 35b, 35C:f Above-body external guide path 45a, 45
b: Spaces 55a, 55b, 55C on the liquid rising guide path:
Liquid rising guide path 62: Space on the liquid rising guide path 16.36: Porous member for liquid transfer 18.38.48:): Part frame 19.39 Nib bridge 52 Nib bridge support member 26.46: First intermediate member ( Spacer) 61 Bridge support member (spacer) 27: Liquid and rising auxiliary guide path 27a, 27b, 27c: Liquid rising auxiliary guide path 47a,
47b, 47c: liquid rise auxiliary guide path 57a, 57b,
57c; Liquid rising auxiliary guide path 20.40: Water-impermeable second intermediate member (mask) 50: Water-impermeable intermediate member (mask) 21.41: Lower frame 22a, 22b, 22c: Ion selective electrode Electrical connection area 23.43: Notch portion Patent applicant: Fuji Photo Film Co., Ltd. Agent
Person Patent Attorney Yasushi Yanagawa Figure 1C Figure 1D Figure 1E Figure 1F

Claims (1)

[Claims] 1. At least a pair of sheet-like ion-selective electrodes having an ion-selective layer on the top, which are electrically separated from each other, and a reference liquid and a test liquid are applied to the surface of each ion-selective layer. In an instrument for measuring the ion activity of a test liquid, which has a liquid supplying part for the test and a bridge for electrically conducting both liquids, each sheet-shaped ion-selective electrode is arranged so that the ion-selective layer is on the lower side. , and the liquid applying section includes an upper liquid applying opening, a descending passage that moves the liquid to a position below the surface of the ion selective layer, and a horizontal passage that moves the liquid horizontally immediately below the surface of the ion selective layer. a liquid rise guide path for subsequently raising the liquid (provided that the top of the side wall of this liquid rise guide path is separated from the surface of the ion selective layer by a gap that does not involve the generation of capillary action); Provided at the upper part of the liquid rising guide path, it assists the liquid to rise to the surface position of the ion selective layer, and the liquid that reaches the surface of the ion selective layer spreads along the surface to reach its periphery. An ion activity measuring instrument characterized by comprising a liquid rising auxiliary guide path to ensure that liquid rise does not occur. 2. The ion activity measuring instrument according to claim 1, wherein the horizontal passage is filled with a porous member for liquid transfer. 3. The space above the top of the side wall of the liquid rising guide path communicates with the outside of the measuring instrument through a space other than the liquid rising guide path. Ion activity measuring instrument. 4. The space above the top of the side wall of the liquid rising guide path communicates with the outside of the measuring instrument through a space other than the liquid rising guide path. Ion activity measuring instrument. 5. Sheet-like ion selective electrodes are arranged in an upper frame body having openings at positions corresponding to the respective liquid application openings, at positions corresponding to the openings, and at positions corresponding to the upper surface openings of the liquid raising guide path. a first intermediate member having an opening, the latter opening being larger than the top opening of the liquid ascending guide so as not to come into contact with the rising liquid; a descending passage and a liquid rising guide; a second water-impermeable intermediate member having an opening at a position corresponding to the second opening, on which a liquid rise auxiliary guideway rests; and a lower frame having a recess forming a horizontal passage. Claims 1 to 4, characterized in that the bridge is fixed to the upper frame so as to cross the opening of the upper frame. The ion activity measurement device described. 6. An upper frame body in which the sheet-like ion selective electrode has an opening at a position corresponding to each liquid application opening, a bridge support member having an opening at a position corresponding to the opening, and a bridge support member corresponding to the opening. The latter opening is larger than the upper opening of the liquid rising guide so as to prevent it from coming into contact with the rising liquid. a water-impermeable first intermediate member having an opening at a position corresponding to the descending passage and the liquid ascending guide passage, with the liquid ascending auxiliary guiding passage disposed above the latter opening; A container comprising two intermediate members and a lower frame having a recessed portion forming a horizontal passageway, wherein the bridge is fixed to the support member so as to cross the opening of the bridge support member. An ion activity measuring instrument according to any one of claims 1 to 4. 7. Sheet-like ion selective electrodes are arranged in an upper frame body having openings at positions corresponding to the respective liquid application openings, at positions corresponding to the openings, and at positions corresponding to the upper surface openings of the liquid ascending guide path, respectively. a bridge support member having an opening, the latter opening being larger than the upper opening of the liquid ascending guideway so as not to come into contact with the rising liquid; Consisting of a water-impermeable intermediate member having an opening in a corresponding position, on which the liquid rise auxiliary guideway rests, and a lower frame having a recess forming a horizontal passage. The ion according to any one of claims 1 to 4, wherein the ion is provided in a container, and the bridge is fixed to the support member so as to cross the opening of the bridge support member. Activity measurement device.