JPH044545B2 - - Google Patents

Description

[Detailed Description of the Invention] [Field of Industrial Application] The present invention relates to an electrode (glass electrode) for measuring ions such as PH and pNa, and in particular, a sheet type electrode with a completely new configuration that was previously considered impossible. This was done in an attempt to develop a glass electrode.

[Conventional technology]

Conventional electrodes for measuring ions such as PH and pNa are generally called glass electrodes, and as shown in Figure 12, they are attached to the tip of a support tube a made of electrically insulating glass using the balloon method. The formed hemispherical PH, pNa, etc. ion-responsive glass membrane b is bonded, and internal electrodes c and internal liquid d are sealed therein.

[Problem that the invention seeks to solve]

However, in the conventional ion measuring electrode (glass electrode) described above, the ion-responsive glass film b must be formed by the blow-up fire making method (balloon method) as described above, so the film thickness during processing is limited. Adjusting the heat and blowing temperature for control purposes, or preventing the occurrence of micro-cracks when joining them to the support tube a, requires considerable skill, and manufacturing costs are high because mass production is difficult. Not only was this extremely expensive, the overall structure had to be large, and there were many disadvantages in terms of operability and maintainability.

However, recently, as proposed in Japanese Patent Application No. 61-63564 filed by the applicant of the present application, a technology for turning the internal liquid into a gel state has been developed. For items that do not require a glass response membrane, such as a reference electrode or a composite electrode thereof, it is possible to form them into sheets, as illustrated in Figure 13 A and B, making the overall structure smaller, easier to manufacture, and easier to mass-produce. This has led to reductions in manufacturing costs and improvements in operability and maintainability. In addition, the same No. 1
In the composite electrode for salinity measurement shown in Figure 3 A and B, e is a substrate made of vinyl chloride, etc.
A plurality of (four in this example) silver electrodes f...
... is formed by screen printing etc., and each base end thereof is formed into a lead part g...,
Each tip thereof is formed into an internal electrode portion h... coated with a film of silver chloride, and these internal electrode portions h...
A support layer i made of vinyl chloride or the like is formed by screen printing or the like on the substrate e excluding the portion where ... is present. And j... is the basic internal liquid (for example, 3.3NKCl supersaturated with AgCl), respectively.
It is a gel-like internal liquid made by adding a gelling agent (e.g. agar, gelatin, etc.) and a gel evaporation inhibitor (e.g. glycerin, ethylene glycol, etc.) to the liquid, which is made into a paste by heating and then used for screen printing, etc. Each of the internal electrode portions h...is provided in an overlapping manner. Also, k, k and m, m
is a response membrane made of, for example, an organic material and a liquid junction membrane made of a porous body impregnated with KCl, which is placed over the respective gel-like internal liquids i, and around which the above-mentioned It is fixed to the support layer i. Further, n is a test liquid injection recess formed on the surface side of the support layer i, and o is a lid body which can be opened and closed for the test liquid injection recess n, and one end thereof is connected to the test liquid injection recess n. It is fixed to the upper surface of the support layer i, and p is an adhesive layer provided on the upper surface of the support layer i, and the lid body o is attached to the adhesive layer p.
By tightly contacting the test liquid injecting recess n, the test liquid injection recess n can be brought into a sealed state. The sheet-type composite electrode for salinity measurement with such a configuration opens the lid o and injects about one drop of the test liquid into the recess n, and then closes the lid o and pours the test liquid. After pushing and spreading on each response membrane k, k and liaison membrane m, m,
The lid body o is closely fixed to the adhesive layer p, and then this sheet-type composite electrode for salinity measurement is attached to the lead part g... The salinity of the test liquid can be measured by inserting it into the mounting part of the test liquid.

Therefore, along with the realization of sheets for such salinity measurement electrodes, reference electrodes, and their composite electrodes, PH,
Regarding glass electrodes for measuring ions such as pNa, naturally, there is a strong demand for miniaturization of the overall structure by forming the electrode into a sheet, reduction in manufacturing cost, and improvement in operability and maintainability.

However, in the conventional glass electrode shown in FIG. 12, the hemispherical ion-responsive glass membrane b can be heated using the balloon method, which requires considerable skill.
In any case, it was possible to create a film with the required film thickness (0.1 to 0.3 mm), but it was necessary to make it into a flat glass electrode, which is absolutely necessary if the sheet-type glass electrode is to be realized. Ion-responsive ultra-thin glass membranes, such as PH-responsive glass membranes, which require a film thickness close to the limit (0.1 to 0.3 mm), are currently impossible to manufacture and have not yet been realized.

That is, in the past, thin glass sheets with a thickness of at least 1 mm were manufactured by the vertical pulling method, and thinner glass sheets (for example, those used for preparations) were produced using the vertical pulling method as much as possible. It was manufactured by further polishing thin plate glass. However, in that case, not only would the manufacturing cost be extremely high, but
Since relatively large irregularities and microcracks remain on the glass surface, it cannot be used as a glass response membrane for ion concentration measurement electrodes. This is because the glass surface, which has large irregularities and microcracks, does not allow for smooth adsorption and desorption of the subject's armpit, making accurate measurements impossible.

In addition, methods for manufacturing ultra-thin flat glass include cutting off a portion of ultra-thin hemispherical glass formed by the balloon method and then reshaping it into flat glass using a hot plate press, and softening pre-formed glass. A preform annulation method in which glass is stretched by elevating the temperature above that temperature has been known for some time, but in the case of the former glass reshaping method, it is difficult to obtain ultrathin flat glass of sufficient size. However, it has the disadvantage that microcracks are likely to occur on the glass surface, and the latter preform annealing method requires extremely large-scale equipment and causes distortion in the finished ultra-thin flat glass. It has the disadvantage that it tends to remain. Moreover, in both of the above methods, ordinary glass (such as so-called sodium glass) whose temperature-viscosity curve exhibits a relatively gentle slope and whose composition allows a relatively wide temperature range for molding operation is used. This method is effective only in cases where the temperature-viscosity curve exhibits a relatively steep slope, such as with special glass (so-called lithium glass) used as a glass response membrane for ion concentration measurement electrodes. When applied to a composition having a narrow temperature range in which the molding operation can be performed, crystallization (devitrification) of the glass occurs, making it completely impossible to obtain the desired ultra-thin flat glass.

In order to realize a sheet-type glass electrode with sufficient reliability, in addition to the problem of realizing the flat ion-responsive glass membrane mentioned above, it is also necessary to There is also the problem of having to ensure a high degree of electrical insulation.

The present invention has been made in view of the above-mentioned conventional circumstances, and its purpose is to overcome the above-mentioned problems, thereby achieving extremely compact size, reliability, and operability, which have been problems in the past. The object of the present invention is to realize a sheet-type glass electrode that has advantages such as excellent maintainability and can be easily and inexpensively manufactured.

[Means for solving problems]

In order to achieve the above object, the sheet-type glass electrode according to the present invention has a sufficiently high electrical insulation as shown in the basic configuration diagram in Fig. 1 (however, the thickness is larger than the actual one). An electrode D having an internal electrode portion B and a lead portion C is adhered to the upper surface of a substrate A made of a material having a conductive property, and an electrode D made of a material having a sufficiently high electrical insulation property and corresponding to the internal electrode portion B. A support layer F having holes E at locations is formed on the upper surface of the substrate A in a state where the lead portion C and its surroundings are exposed, and a gel-like internal liquid G is formed in the holes E in the support layer F. A flat ion-responsive glass membrane H produced by charging the glass and subjecting the flat ultra-thin glass pre-formed to a predetermined size to high-speed surface heating treatment under preheating. Bringing the lower surface into close contact with the upper surface of the gel-like internal armpit G and sealing the gel-like internal liquid G into the hole E,
It is characterized in that it is fixed to the upper surface of the support layer F around it using a bonding material having sufficiently high electrical insulation.

[Effects] The effects achieved due to this characteristic configuration are as follows.

That is, according to the present invention, as will become clearer from the description of the examples to be described later, a flat plate-like ultrathin glass preformed to have a predetermined size is subjected to a high-speed surface treatment under preheating. In addition to using an ultra-thin, flat, ion-responsive glass membrane H that was made possible for the first time through a completely new method of heat treatment, both the substrate A and the support layer F are made of materials that have sufficiently high electrical insulation properties. and the ion-responsive glass membrane H for the supporting layer F.
By taking measures to fix the material using a bonding material with sufficiently high electrical insulation properties,
It has become possible to manufacture sheet-type glass electrodes with the required high electrical insulation properties much more easily and at a lower cost than conventional glass electrodes, which has led to significant downsizing and reliability of glass electrodes for ion measurement. , the intended purpose of improving operability, maintainability, etc. has been fully achieved.

〔Example〕

Hereinafter, specific examples of the sheet-type glass electrode according to the present invention will be described based on the drawings (FIGS. 2 to 11). Note that here, explanation will be given using a sheet-type glass electrode for PH measurement as an example.

The exploded perspective view of FIG. 2, and FIGS. 3 and 4 showing the - line cross section and the - line cross section show a sheet-type composite electrode for PH measurement according to an embodiment.

In each figure, A is an organic polymer material such as polyethylene, polypropylene, polyethylene terephthalate, acrylic, polyethylene fluoride, or an inorganic material such as quartz glass or Pyrex glass, immersed in a solution containing an electrolyte. The substrate A is made of a material (polyethylene terephthalate board in this example) that has sufficiently high electrical insulation properties even when A metal selected from such alloys, a paste containing the metal, or a semiconductor such as IrO ₂ or SnO ₂ is plated using a physical plating method such as a vacuum evaporation method or a CVD method, or a chemical plating method such as an electrolytic method or an electroless method. Two pairs of inner and outer electrodes D... are attached and formed by a printing method such as a plating method, a silk screen method, a letterpress method, or a planar method (in this example, a grafting process is performed on the upper surface of the substrate A, and a silane coupling agent is applied to the upper surface of the substrate A. etc., and then silk screen printing with Ag paste). The proximal end portion of all of these electrodes D, which is located at one end edge of the substrate A, remains as it is, and serves as a lead portion C... The other approximately circular tip portion located in the section is formed into an internal electrode section B, which is coated with an electrode material such as AgCl (by physical plating method, chemical plating method, printing method, etc. as described above). A temperature-compensating electrode portion T, such as a thermistor, is provided between the other tip portion of the inner pair of electrodes D, D located approximately at the center of the substrate A.

Then, on the upper surface of the substrate A, there is provided a support layer F (made of a material having sufficiently high electrical insulation properties) and having holes E, E at locations corresponding to the internal electrode portions B, B. In this example, the polyethylene terephthalate layer) covers all the lead portions C...
...and its periphery is exposed on the upper surface of the substrate A by, for example, screen printing, or
It is formed using a heat-sealing method using a bonding agent (eg, polyolefin, silicone resin, etc.) that can guarantee sufficiently high electrical insulation (eg, 10 MΩ or more). Incidentally, the upper surface of this support layer F is also subjected to a grafting process and an anchoring process using a silane coupling agent or the like.

In addition, in both holes E and E of the support layer F, a basic internal solution (for example, 3.3 NKCl supersaturated with AgCl with a phosphate buffer added) and a gelling agent (for example, agar, gelatin, Disc-shaped gel-like internal liquids G and G, which are made by adding glue (glue, alginic acid, various acrylic absorbent polymers, etc.) and gel evaporation inhibitors (e.g. glycerin, ethylene glycol, etc.), can be turned into a paste by heating, for example. Then, using a screen printing method or the like, it is filled in such a manner that its upper surface slightly protrudes from the upper surface of the support layer F in a free state, and is provided on the internal electrode portions B, B in an overlapping manner.

Furthermore, above the gel-on-the-gel internal liquid G in one of the holes E, E, a plate-like ultra-thin glass pre-formed to have a predetermined size is heated at high speed. Flat PH-responsive glass membrane H manufactured by surface heating treatment
However, a bonding material (for example, a silane cup) having a sufficiently high electrical insulation property is used so that its lower surface is in close contact with the upper surface of the gel-like internal liquid G and the gel-like internal liquid G is sealed in the hole E. It is fixed to the upper surface of the support layer F at its periphery using an organic polymer adhesive such as a silicone-based, epoxy-based, or urethane-based adhesive containing a ring agent, etc., thereby forming a glass electrode P for PH measurement.

Furthermore, above the gel-like internal liquid G in the other hole E, there is a juncture membrane J made of an inorganic sintered porous material or an organic polymer porous material impregnated with KCl, the lower surface of which is in the gel-like state. The reference electrode R is formed by being in close contact with the upper surface of the internal liquid G and being joined to the upper surface of the support layer F at its periphery.

The sheet-type composite electrode for PH measurement configured as described above has a total thickness of about 0.5 mm in this example, and as shown in FIG. 5, the glass electrode P for PH measurement and the reference electrode R is released to the upper surface side, and one end edge of the substrate A on which the lead portion C... is formed is made to protrude outward,
A chip-shaped measurement electrode unit U is housed in a casing K made of synthetic resin. A casing K constituting the chip-shaped measurement electrode unit U is an upper frame member N forming a recess M for injecting the test liquid.
, a bottom lid O for the upper frame N, and an upper lid Q for the test liquid injection recess M attached to one end edge of the upper frame N so as to be able to swing open and close.
Furthermore, the lead portion C in the casing K (in this example, the portion of the upper frame N)
...A projecting piece V for engagement with a measuring instrument main body Z, which will be described later, is continuously provided from the protruding edge.

The chip-shaped measurement electrode unit U incorporating the sheet-type composite electrode for PH measurement with such a configuration is provided with the above-mentioned upper lid Q.
By injecting one or several drops of the test liquid into the recess M for test liquid injection, the glass electrode P for PH measurement and the reference electrode R located at the bottom of the recess M are sufficiently tested. After contacting the liquid with the liquid, the upper lid Q is closed, and then the chip-shaped measuring electrode unit U is inserted into the measuring instrument main body Z configured in the form of a card calculator, as illustrated in FIG. To the adhesive part Y,
The PH of the test liquid is measured by inserting and connecting the lead portion C... and the engagement protrusion V.

Next, the PH-responsive glass film H (in this example, vertical
We will now explain in detail the specific steps of a novel manufacturing method for ion-responsive glass membranes such as pNa-responsive glass membranes (width x thickness = 10mm x 8mm x 0.1mm) or pNa-responsive glass membranes.

First, after mixing predetermined ingredients and amounts of powder raw materials and melting and solidifying them in a platinum crucible, etc.,
By performing an annealing treatment, a large glass ingot of glass having a predetermined composition (for example, PH glass) is manufactured. As a result, in this example, a large glass ingot with length x width x thickness = 328 mm x 93 mm x 23 mm was obtained.

Producing large-sized glass ingots in this manner not only allows considerable cost reduction, but also has the advantage of ensuring quality stability and composition uniformity.

Next, the large glass ingot is cut into a suitable cutting method using a mechanical cutting method (for example, there are known methods that can be carried out relatively easily, such as a wire cutting method, an inner peripheral cutting method, an outer peripheral cutting method, etc.). Divide into sized glass blocks. As a result, in this example, 14 glass blocks with length x width x thickness = 45 mm x mm x 23 mm were obtained.

Subsequently, by slicing each of the above-mentioned glass blocks using the same mechanical cutting means, a first glass sheet having a thickness (0.2 mm) as close as possible to the target thickness (0.1 mm) is manufactured. As a result, in this example, a large number of first glass sheets having length x width x thickness = 45 mm x 45 mm x 0.2 mm were obtained.

Therefore, each of the first glass sheets still has a thickness (0.2 mm) larger than the target thickness (0.1 mm), and relatively large unevenness caused by the mechanical cutting remains on its surface. Therefore, it is in an opaque (ground glass-like) state and is not yet in a completed state that can be used as the PH-responsive glass film H.

Therefore, each of the first glass sheets is
%NH ₄ F aqueous solution, etc., and further coat the surface (both front and back sides) to a specified thickness (0.05 mm in this example).
By performing the etching process, a second glass sheet having the target thickness (0.1 mm) and having surface irregularities reduced to some extent is manufactured. Although this etching process makes it possible to obtain a second glass sheet that is thinner and has surface irregularities reduced to some extent, it is still in a translucent state and not in a completed state. As a result, in this example, a second glass sheet having dimensions of length x width x thickness = 45 mm x 45 mm x 0.1 mm was obtained.

In addition, when cutting to the final target thickness by the mechanical cutting means, the first thickness of the target thickness is
Since the glass sheet can be obtained directly, this etching process for manufacturing the second glass sheet is not necessarily required.

Next, each of the second glass sheets is cut into chips having a predetermined size by mechanical cutting means (such as dicing using a scriber). As a result, in this example, a chip-shaped second glass sheet having the desired size and thickness of length x width x thickness = 10 mm x 8 mm x 0.1 mm was obtained.

Note that this chip-shaped second glass sheet is thoroughly cleaned, for example, by ultrasonic cleaning or the like, in order to remove wax, fluorine, etc.

Now, each chip-shaped second glass sheet obtained as described above needs to be transparent and have a sufficiently smooth surface by eliminating any remaining unevenness on its surface, so it is necessary to make it transparent and have a sufficiently smooth surface. Surface treatment is performed by a novel heat treatment means.

In other words, the chip-like structure is designed to effectively prevent glass cracking and melting and condensation caused by rapid temperature changes or extremely uneven temperature distribution, which have traditionally been very difficult problems during glass heat treatment. 2. The entire glass sheet is heated in advance to just before the melting temperature, and in the preheated state on the verge of melting, a predetermined amount of thermal energy is further applied to the surface in a short period of time to melt only the surface. The team applied high-speed surface heat treatment under preheating to allow the material to dry and then solidify.

As a result, it has a sufficient size, does not cause microcracks, distortion, or crystallization (devitrification), and has a sufficiently smooth surface, which could not be achieved using any conventional method. It has now become possible to easily and inexpensively produce ultrathin flat glass that satisfies the strict condition of being transparent and can be used satisfactorily as a PH-responsive glass membrane H, regardless of its composition.

By the way, various methods can be considered as specific implementation means for the above-mentioned high-speed surface heat treatment under preheating, but according to the prototype tests to date, the following three methods have been found to be the most suitable.

One of them (first method) is a preheating laser heat irradiation method, as shown in Figure 7.
XY table 1, heater block 2 placed on the XY table 1, and heater block 2
a temperature controller 3 for the XY table 1, a laser irradiation device 4 capable of irradiating, for example, a CO ₂ laser R (several W to about 10 W is sufficient) to a fixed point on the XY table 1, the XY table 1, and the temperature controller. 3. Constructing a system consisting of a controller 5 for controlling the laser irradiation device 4, etc., respectively,
Then, the second chip-shaped product obtained as described above was used.
After placing the glass sheet S on the heater block 2, first, the temperature regulator 3 for the heater block 2 is controlled by the controller 5 to heat the entire chip-shaped second glass sheet S in advance to just before the melting temperature. The temperature is raised (in this example, it is about 600°C below the softening point), and then, in the preheated state on the verge of melting, the XY table 1 and the laser irradiation device 4 are controlled by the controller 5, and the heater block 2 is heated. A CO ₂ laser R is scanned at a predetermined speed (in this example, about several cm/sec) over a required location or the entire surface of the chip-shaped second glass sheet S.
By applying a predetermined amount of thermal energy in a short period of time by irradiating the surface with the metal, high-speed surface heat treatment is performed under preheating, in which only the surface is melted and then solidified. Generally, when light is irradiated onto glass, heat absorption occurs first at the interface (surface), so as mentioned above, the chip-shaped second
By simply irradiating the CO ₂ laser R from one side of the glass sheet S, both the front and back sides can be treated at the same time. Further, this preheating laser heat irradiation method is particularly suitable when it is sufficient to precisely vitrify only a part (required part) of the surface of the chip-shaped second glass sheet S.

The other method (second method) is a preheating lamp heat irradiation method, and as shown in FIG. 8, a fixed base 6 made of a heat insulating material and a heat-resistant , a working board 7 made of a material with excellent thermal conductivity and heat dissipation, and preferably black in color (e.g. carbon plate), and a lamp light (e.g. halogen lamp light) L on the working board 7.
A lamp light irradiation device 8 that can collect light, adjust the light emission output, light concentration, irradiation time, etc., and obtain sufficient light emission output (achieves a maximum temperature of several hundred degrees Celsius in the light collection part). , a controller 9 for controlling the lamp light irradiation device 8, and a chip-shaped second glass sheet S obtained as described above is placed on the working board 7. Then, the lamp light irradiation device 8 is controlled by the controller 5,
First, the chip-shaped second glass sheet S is irradiated with lamp light L while gradually increasing the light emitting output while condensing the light to the same size or slightly larger than the chip-shaped second glass sheet S. The entire glass sheet S is heated slowly in advance to just before the melting temperature (in this example, it was about 600°C, which is below the softening point), and then continued in the preheated state on the verge of melting to achieve a relatively high light emitting output. (In this example
By applying a predetermined amount of thermal energy by irradiating the entire surface of the chip-shaped second glass sheet S with lamp light L (approximately 1200°C) for a very short period of time (in this example, for a few seconds), High-speed surface heat treatment is performed under preheating to melt only the surface with good uniformity and then solidify it. In this case as well, by simply irradiating the limp light L from one side of the chip-shaped second glass sheet S, both the front and back sides can be treated at the same time. In addition, this preheating lamp heat irradiation method is particularly suitable for precision vitrification of the entire surface of the chip-shaped second glass sheet S. By performing scanning irradiation in this state, similar to the preheating lamp heat irradiation method described above, precision vitrification of only a part (required location) of the chip-shaped second glass sheet S can be achieved relatively easily. It is also possible to realize this with less energy consumption.

Still another method (third method) is a so-called belt moving furnace method, as shown in FIG.
A rotary belt 11 that moves in one direction at a set speed in the furnace 10, and a plurality of heaters 12 (in this example, three pairs of upper and lower pairs) each of which can be individually set in temperature and provided along the belt movement direction of the furnace 10. . . . and a rotating belt 11 and a heater 12 . . . and a controller 13 for controlling the electric heating furnace system. As shown in Fig. 10, two upper and lower substrates with excellent thermal conductivity (for example, boron nitride, non-oxide ceramic plates such as boron nitride, carbon plates, carbon graphite plates, alumina plates, etc.) are used. In this example, an extremely thin spacer (in this example, an alumina plate with a thickness of 0.635 mm) 15,
Working block 16 sandwiched through 15
The state of these working blocks 16...
are continuously placed on the rotating belt 11,
It is passed through the furnace 10 from the inlet 10A to the outlet 10B at a predetermined time (speed). In addition,
The relationship between the moving distance D and the temperature T in the furnace 10 is determined by the speed control of the belt 11 by the controller 13 and the individual temperature control for each heater 11, for example, as schematically shown in FIG. Can be set arbitrarily. That is, the chip-shaped second glass sheets S held between the working blocks 16 introduced from the inlet 10A of the furnace 10 are heated in their entirety during the preheating period up to point A in FIG. is gradually heated to just before the melting temperature (in this example, the temperature is approximately below the softening point).
The temperature was 600℃. 700℃ for pNa glass responsive membrane
In the preheated state on the verge of melting, a predetermined amount of thermal energy is then applied during an extremely short surface melting period (about 10 seconds in this example) until reaching point B in Figure 11. By being
A high-speed surface heat treatment is performed under preheating in which only the surfaces (front and back surfaces) are melted with good uniformity as a whole, and then solidified at point C (cooling point) in FIG. 11. In addition, in FIG. 9, 10a is the inlet air curtain air (or
_N2 gas) jetter, 10b is the air (or _N2 gas) jetter for the exit air curtain, 10C is the air (or _N2 gas) jetter for the firing ring and cooling gas, 10D is the firing ring and cooling gas discharge pipe. It is.

By the way, like the preheating lamp heat irradiation method, the belt moving furnace method is particularly suitable for precision vitrification of the entire surface of the chip-shaped second glass sheet S, and is extremely suitable for mass production. suitable. However, as shown in Figures 7 and 8 above,
Even in the preheating laser heat irradiation method and the preheating lamp heat irradiation method shown in the figure, a handling device etc. for automatically converting the chip-shaped second glass sheet S or the heater block 2 or working board 7 that supports it may be attached. It is possible to build a mass production system.

In addition, if it is not necessary to manufacture the second glass sheet by the etching process, the first glass sheet after slicing by mechanical cutting is diced into chips, and the chip-shaped first glass sheet is As with the chip-shaped second glass sheet S, it may be subjected to the high-speed surface heat treatment under preheating.

〔Effect of the invention〕

As is clear from the detailed description above, the present invention is a completely novel method in which a flat plate-like ultrathin glass preformed to have a predetermined size is subjected to high-speed surface heating treatment under preheating. In addition to using an ultra-thin flat plate-shaped ion-responsive glass membrane, which was made possible for the first time by using this method, the substrate and supporting layer are both made of materials with sufficiently high electrical insulation, and the supporting layer is By fixing the ion-responsive glass membrane to the layer using a bonding material with sufficiently high electrical insulation, a sheet-shaped glass electrode with the required high electrical insulation can be formed using conventional glass. It is now much easier and cheaper to manufacture than conventional electrodes, and has fully achieved the intended purpose of significantly downsizing glass electrodes for ion measurement and improving reliability, operability, maintainability, etc. This has led to excellent results.

[Brief explanation of drawings]

FIG. 1 shows a partially sectional external perspective view (view corresponding to claims) showing the basic structure of a sheet-type glass electrode according to the present invention. In addition, FIGS. 2 to 6 are for explaining the structure of a sheet-type composite electrode for PH measurement as a specific example of the sheet-type glass electrode according to the present invention, and FIG. 2 is an exploded perspective view. Figure 3 shows a cross-sectional view taken along the - line in Figure 2, Figure 4 shows a cross-sectional view taken along the - line in Figure 2, and Figure 5 shows the sheet-type composite electrode for PH measurement housed in the casing. Fig. 6 shows a perspective view of the unit as it is connected to the main body of the measuring instrument, and Figs. Figure 7 is a schematic system configuration diagram of the first method, and Figure 8 is a diagram of the second method.
FIG. 9 is a schematic system configuration diagram of the third method, FIG. 10 is a side view of its main parts, and FIG. 11 is a graph showing an example of its control characteristics. and Figures 12 and 13.
The drawings are for explaining the technical background of the present invention and the problems of the prior art. , b respectively show a longitudinal cross-sectional view and an external perspective view of a sheet-type composite electrode for salinity measurement. A... Highly electrically insulating substrate, B... Internal electrode part,
C... Lead part, D... Electrode, E... Hole, F...
Highly electrically insulating support layer, G...Gel-like internal liquid, H...
... Flat ion-responsive glass membrane, I... Highly electrically insulating bonding material.

Claims (1)

[Claims] 1. An electrode having an internal electrode part and a lead part is attached to the upper surface of a substrate made of a material having sufficiently high electrical insulation properties, and an electrode made of a material having sufficiently high electrical insulation properties and corresponding to the internal electrode part. forming a support layer having holes at locations exposed on the upper surface of the substrate with the lead portion and its surroundings exposed; and filling the holes in the support layer with a gel-like internal liquid; A flat ion-responsive glass membrane is fabricated by subjecting a flat ultrathin glass preformed to a predetermined size to high-speed surface heating treatment under preheating. A bonding material having sufficiently high electrical insulation properties is used to tightly contact the upper surface of the support layer and seal the gel-like internal liquid in the holes, and the support layer is fixed to the upper surface of the supporting layer around the bonding material. Characteristic sheet type glass electrode.