JPS63138255A - Sheet type glass electrode - Google Patents

Abstract

PURPOSE:To obtain a compact electrode which is easy to operate and maintain by using an extremely thin flat plate-shaped ion sensitive glass film having an electrical insulating characteristic as a substrate and supporting the same with a supporting layer having likewise the electrical insulating characteristic at the time of preparing a sheet type glass electrode to be used for measuring pH, etc. CONSTITUTION:The electrode D is formed by depositing metal such as Ag, Cu or IrO2 on the insulating substrate A consisting of PE terephthalate, quartz glass, etc., and the extension part thereof is used as a lead part C. The central part thereof is used as an internal electrode D and is enclosed by a supporting layer F having a hole E. Paste prepd. by mixing an internal liquid prepd. by adding a phosphoric acid buffer soln. to 3.3NKCl supersaturated with AgCl and gelling agent such as agar or gelatin is packed into the hole E. Such electrode is coated with the flat plate-shaped pH sensitive glass film H. The glass electrode for measuring ion is thus easily produced, is miniaturized and is improved in the operability.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention is applicable to ion measurement such as pH and pNa. With regard to glass electrodes, this work was done in particular with the aim of developing a sheet-type glass electrode with a completely new structure, which was previously thought to be impossible.

[Conventional technology]

Conventional electrodes for measuring ions such as pH and pNa are generally called glass electrodes, and as shown in FIG. The formed hemispherical pH, pNa, etc. ion-responsive glass membrane is bonded, and the internal electrode C is inserted into it.
and the interior 1d is enclosed.

[Problem that the invention seeks to solve]

However, in the conventional ion measuring electrode (glass electrode) described above, the ion-responsive glass film must be formed by the blow-up method (balloon method), so the film thickness during processing is limited. Adjustment of fire level, blowing level, etc. for control, or its support pipe a
Preventing the occurrence of micro-cranks when bonding requires considerable skill, and since mass production is difficult, manufacturing costs are not only extremely high, but the overall structure must also be large. However, 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,
With the development of technology to gel the internal liquid,
For example, for electrodes that do not require a glass response membrane, such as salinity measuring electrodes, reference electrodes, or their composite electrodes, the 13th
As illustrated in Figures (a) and (b), it is now possible to make it into a sheet, which reduces the overall structure, reduces manufacturing costs due to ease of manufacture and mass production, and improves operability and maintainability. has been achieved. In the composite electrode for salinity measurement shown in FIGS. 13(a) and 13(b), e is a substrate made of vinyl chloride, etc., and a plurality of (four in this example) 11T! L pole r...
are formed by screen printing or the like, and each base end thereof is formed into a lead part g..., and each tip part is formed into an internal electrode part h... coated with a film of silver chloride. 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 the internal electrode portions h... are present. And j...
are, respectively, the basic internal liquid (e.g. Ag (l supersaturated 3
．． 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 3NKC1, etc., which is made into a paste by heating. The internal electrode portions h are provided by screen printing or the like to be superposed on each of the internal electrode portions h. Further, k, k and m, m are a response membrane made of, for example, an existing material and provided overlying each of the gel-like interiors 1i... and KCj! The liquid junction membrane is made of a porous material impregnated with a liquid junction membrane, and is fixed to the support layer i with an adhesive or the like around the periphery. Furthermore, n is four parts for injection of the test liquid formed on the surface side of the support layer i,
0 is a lid that can be opened and closed for the test liquid injection recess n, one end of which is fixed to the upper surface of the support layer i, and p is an adhesive provided on the upper surface of the support layer i. By tightly and tightly adhering the lid body O to the adhesive layer Np, the recess n for injecting the test liquid can be brought into a sealed state.

In the sheet-type composite electrode for salinity measurement having such a configuration, after opening the lid O and injecting about one drop of the test liquid into the recess n, the lid O is closed and the test liquid is poured. Each response membrane is pressed and spread over the diaphragm m, m, and its lid body 0 is closely fixed to the adhesive layer p. After that, this sheet-type composite electrode for salinity measurement is attached to the The salinity of the test liquid is measured by inserting and connecting the lead part g into a mounting part of a main body (not shown) of a measuring device configured in the shape of a card calculator, for example.

Therefore, along with the realization of sheets for such salinity measurement electrodes, reference electrodes, and their composite electrodes, pH.

As for glass electrodes for measuring ions such as pNa, it is natural that the overall structure can be made smaller by making them into sheets.

There is a strong demand for lower manufacturing costs and improvements in operability and maintainability.

However, in the conventional glass electrode shown in FIG. 12, the hemispherical ion-responsive glass membrane can be made using the balloon method, which requires considerable skill. In any case, the required film thickness (0
, 1 to 0.3+am), but in order to realize the pending sheet-type glass electrode, it was possible to realize a flat film with a thickness close to the vitrification limit ( Ion-responsive ultra-thin glass membranes such as p)1-responsive glass membranes that require a thickness of 0.1 to 0.3 mm have not yet been realized, as they are currently impossible to manufacture.

That is, conventionally, thin sheet glass with a thickness of at least 1 mIm was manufactured using the vertical pulling method, and thinner temporary glass (
For example, those used for preparations, etc.) were manufactured by further polishing the thinnest possible plate glass obtained by the vertical pulling method. However, in that case, not only is the manufacturing cost extremely high, but also relatively large irregularities and microcracks remain on the glass surface, so that it cannot be used as a glass response membrane for an ion concentration measuring electrode. This is because accurate measurements cannot be made because the sample liquid cannot be adsorbed and desorbed smoothly on the glass surface, which is highly uneven and has microcranks.

In addition, methods for producing ultra-thin flat glass include cutting off part of the circumference of ultra-thin hemispherical glass formed by the balloon method and then reshaping it into flat glass using a hot plate press, or softening pre-formed glass. A preform annulation method in which the glass is stretched by elevating the temperature above that temperature has been known for some time, but in the case of the former glass remolding method, it is difficult to obtain ultrathin flat glass of sufficient size. However, the disadvantage is that microcranks are likely to occur on the glass surface, and the latter preform annulation method requires extremely large-scale equipment and tends to leave distortions in the finished ultra-thin flat glass. There is a drawback.

Moreover, in both of the above methods, the temperature-viscosity curve exhibits a relatively gentle slope, and the temperature range in which the molding operation can be performed is relatively wide.
This method is effective only when the temperature-viscosity curve is relatively steep, such as with special glasses (so-called lithium glass) used as glass response membranes for ion concentration measurement electrodes. When applied to a glass having a composition that exhibits a steep slope and a narrow temperature range in which it can be formed, it is completely impossible to obtain the desired ultra-thin flat glass because crystallization (yi>) of the glass occurs. It was possible.

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 between the two.

The present invention has been made in view of the above-mentioned conventional circumstances, and its purpose is to overcome the above-mentioned problems and to solve the problems of the past by making it more compact, reliable and easy to operate. The objective is to realize a sheet-type glass electrode having 11 points, which is excellent in maintainability, etc., 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 plate having an internal electrode part B and a lead part C is attached to the upper surface of a substrate A made of a material having a conductive property, and is made of a material having a sufficiently high electrical insulation property and corresponds to the internal electrode part B. A support layer F having holes E at locations is formed on the upper surface of the substrate, exposing the lead portion C and its surroundings, and a gel-like internal liquid G is formed in the holes E in the support layer F. Furthermore, a flat ion-responsive glass membrane H manufactured by preheating and high-speed surface heating treatment is applied to a flat ultrathin glass that has been preformed to have a predetermined size. A bonding material 1 having sufficiently high electrical insulation properties is used so that the lower surface is in close contact with the upper surface of the gel-like internal liquid G and the gel-like internal liquid IG is sealed in the hole E, and the supporting material is used around it. It has the feature of being fixed to the top surface of the NF.

[Effect]

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 heated at a high speed during 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 constructed of materials with sufficiently high electrical insulation properties. and fixing the ion-responsive glass membrane H to the support layer F with a bonding material (3) having sufficiently high electrical insulation properties;
By taking this measure, sheet-type glass electrodes with the required high electrical insulation properties can be manufactured much more easily and inexpensively than conventional glass electrodes. Significantly more compact and reliable.

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 a sheet-type glass electrode for pH measurement will be exemplified and explained here.

The exploded perspective view of FIG. 2 and FIGS. 3 and 4, which show cross sections along the 111-[[1 line and IV-TV line, respectively, show a sheet-type composite electrode for pH measurement according to an embodiment.

In each figure, A represents a material immersed in a solution containing an electrolyte, such as an organic polymer material such as polyethylene, polypropylene, polyethylene terephthalate, acrylic, or polyfluoroethylene, or an inorganic material such as quartz glass or Pyrex glass. The substrate A is made of a material (in this example, a polyethylene terephthalate board) that has sufficiently high electrical insulation properties even when the substrate A is used. A metal selected from alloys or a paste containing the metal, I rQl , SnO.

Semiconductors such as vacuum evaporation methods, physical plating methods such as CVD methods, chemical plating methods such as electrolytic methods, electrolytic methods, silk screen methods, and letterpress methods.

Two pairs of inner and outer electrodes D... are attached and formed by a printing method such as a flat plate method (in this example, the upper surface of the substrate A is grafted and anchored with a silane coupling agent, etc.). , with Ag paste silk screen printing). In addition, the base end portion of all of the electrodes D... located at one end edge of the substrate A is left as it is as a lead part C..., and the outer pair of electrodes,
The other approximately circular tip portion located approximately at the center of the substrate A in D is made of an electrode material such as AgC1: I! I
An internal electrode part B that has been covered (by physical plating method, chemical plating method, chemical plating method, printing method, etc. as described above),
A temperature compensating electrode section T, such as a thermistor, is provided between the pair of inner electrodes formed at B and the other end portion located approximately at the center of the substrate A at D.

Then, on the upper surface of the substrate A, a support layer F is made of a material having sufficiently high electrical insulation properties and has holes E and E at locations corresponding to the electrode portions B and H of both circuit portions. (polyethylene terephthalate layer in this example)
With all the lead parts C... and their surroundings exposed, the top surface of the substrate A is coated with a bonding agent (for example, screen printing) or a bonding agent that can guarantee sufficiently high electrical insulation (for example, IOMΩ or higher). For example, it is formed using a heat fusion means using a polyolefin-based material, silicone resin-based material, etc.). 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 the holes E and E in the support layer F, there is a basic internal liquid (for example, AgCl supersaturated 3.
3NKC1 with @acid 11i fJi solution etc.)
A disc-shaped gel-like internal liquid G is made by adding a gelling agent (e.g., agar, gelatin, glue, alginic acid, various acrylic water-absorbing polymers, etc.) and a gel evaporation inhibitor (e.g., glycerin, ethylene glycol, etc.) to , G are made into a paste form by heating, for example, and then filled by screen printing or the like in such a manner that the upper surface thereof slightly protrudes from the upper surface of the support layer F in a free state, so that the inner electrode portions B, B are filled with the paste. It is placed on top of the .

Furthermore, above the gel-like internal liquid G in one of the holes E and H, a high speed preheating process is performed on the flat glass that has been preformed to have a predetermined size. The outer and lower surfaces of the flat pH-responsive glass membrane produced by surface heating treatment are the gel-like internal liquid G.
A bonding material (for example, a silicone-based or epoxy-based material containing a silane coupling agent, The periphery thereof is fixed to the upper surface of the support layer F using an organic polymer adhesive such as a urethane-based adhesive, 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.

In this example, the total thickness of the p) (measuring sheet-type composite electrode configured as described above is about 0.511 IIa, and as shown in FIG. 5, the pH1ill measurement glass electrode P and the reference electrode R is released to the upper surface side,
The chip-shaped measurement electrode unit U is housed in a synthetic resin casing with one end edge of the substrate A on which the lead portions C are formed protruding outward. be done. The casing constituting the chip-shaped measurement electrode unit U includes an upper frame N forming a recess M for injecting the test liquid, a bottom cover 0 for the upper frame N, and one end edge of the upper frame N. an upper part 1iQ for the test liquid injection recess M attached to the recess M for swinging open and close; A protruding piece (2) for engagement with a measuring device body Z, which will be described later, is continuously provided from the edge of the side where the measuring device is attached.

The chip-shaped measuring electrode unit (U) which incorporates the sheet-type composite electrode for pH measurement with such a configuration opens the upper lid Q,
By injecting one or several drops of the test liquid into the test liquid injection recess M, the glass electrode P for pH measurement and the comparison electrode R located at the bottom are sufficiently exposed to the test liquid. After that, the top lid Q is closed, and then the chip-shaped measurement electrode unit U is inserted into the attachment part Y of the measuring instrument main body Z configured in the form of a card calculator, as illustrated in FIG. , the lead portion C... and the engaging protrusion (2) are inserted and connected, and the ptr of the test liquid is measured.

Next, we will discuss the specifics of the novel manufacturing method for ion-responsive glass membranes such as the pH-responsive glass membrane H (in this example, length x width x thickness -10mm x 8aa+X O, laa+) or pNa-responsive glass membrane. Let me explain the steps in detail.

First, predetermined components and amounts of powder raw materials are mixed, melted and solidified in a platinum crucible, etc., and then annealed to form a glass having a predetermined composition (for example, p
Manufacture large glass ingots of H glass. As a result, in this example, length x width x thickness = 328 + nm
A large glass ingot measuring 93 mm x 23 m+s was obtained.

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

Next, the above-mentioned large glass ingot is cut into an appropriate size 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 small glass blocks. As a result, in this example, length x width x thickness = 45m + mX 4
Fourteen glass blocks measuring 5 mm x 23 mm were obtained.

Subsequently, each glass block is sliced using the same mechanical cutting means to obtain a target thickness of 0,
1 ffim) as thick as possible (0.2m+a)
A first glass sheet is manufactured. As a result, in this example, length x width x thickness = 45au+X 45m5x O, 2m
A large number of m first glass sheets were obtained.

Therefore, each of the first glass sheets still has the target thickness.
Thickness greater than (0, 1 mm) (0, 2n+m)
At the same time, relatively large irregularities caused by the mechanical cutting remain on its surface, so that it is still in an opaque (ground glass-like) state and is not in a completed state that can be used as the pH-responsive glass MH. No.

Therefore, each of the first glass sheets is treated with, for example, 5% NH,
By immersing it in an F aqueous solution or the like and etching it by a predetermined thickness (0.05 mm in this example) from the surface (both front and back sides), the target thickness is 0, 1 as.
) and whose surface irregularities have been reduced to some extent. 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, vertical ×
A second glass sheet with width×thickness=45ms+×45mm×O, 1ms was obtained.

Note that when cutting to the final target thickness by the mechanical cutting means, the first glass sheet having the target thickness can be directly obtained, so the process of manufacturing the second glass sheet by etching is not necessarily necessary. Not necessary.

Next, each of the second glass sheets is cut into chips having a predetermined size by a mechanical cutting means (such as dicing using a scriber).

As a result, in this example, with the desired size and thickness, Length x Width x Thickness = l Os+wX 8mmX O, 1m
A chip-shaped second glass sheet of s 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 of the chip-shaped second glass sheets obtained as described above needs to be transparent and have a sufficiently smooth surface by eliminating any remaining unevenness on its surface. Surface treatment is performed by novel heat treatment means.

In other words, the chip-like structure is designed to effectively prevent glass cracking and melting and condensation caused by sudden 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 used high-speed surface heat treatment to preheat the material and then solidify it.

As a result, it has a sufficient size, no microcracks, no distortion, no crystallization (devitrification), and has a sufficiently smooth and transparent surface, which could not be achieved using any conventional method. satisfies the strict condition that p
It has become possible to easily and inexpensively produce ultrathin flat glass that can be used as an H-responsive glass membrane regardless of its composition.

By the way, various methods can be considered as specific implementation means for the high-speed surface heat treatment on preheating, but according to the prototype experiments to date, the following three methods are the most suitable.

One of them (the first method) is a so-called preheating laser heat irradiation method, and as shown in FIG.
And on that XY table! ! a heater block 2 placed therein, a temperature regulator 3 for the heater block 2,
A laser irradiation device 4 capable of irradiating, for example, a Cot laser R (several watts to IOW is sufficient) to a fixed point on the XY table l, the XY table l, a temperature controller 3. A system comprising a controller 5 for controlling the laser irradiation device 4 and the like, and
Chip-shaped second glass sheet S obtained as described above
is placed on the heater block 2, and first, the temperature controller 3 for the heater block 2 is controlled by the controller 5, and the chip-shaped second glass sheet S is placed on the heater block 2.
The temperature of the entire body is raised in advance to just before the melting temperature (in this example, it was about 600°C below the softening point), and after that, the XY table 1 and the laser irradiation device 4 are controlled by the controller in the preheated state just before melting. 5, the CO2 laser R is scanned at a predetermined speed (approximately several cm/sec in this example) over a required location or the entire surface of the chip-shaped second glass sheet S on the heater block 2. By applying a predetermined amount of thermal energy (j+u) in a short period of time by irradiation (scanning), only the surface is melted and then solidified, which is a high-speed surface heat treatment for preheating. Note that when -C is irradiated with light to the glass, heat absorption occurs first at the interface (surface), so the CO□ laser R is irradiated from one side of the chip-shaped second glass sheet S as described above. By simply doing this, you can process both the front and back sides 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 location) 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 (e.g. carbon plate) 7 made of a material with excellent thermal conductivity and heat dissipation and preferably black in color, and capable of condensing lamp light (e.g. halogen lamp light) L onto the working board 7. , its luminous output,! I luminosity,
A lamp light irradiation device 8 that can adjust the irradiation time etc. and obtain sufficient light emission output (can achieve a maximum temperature of several thousand degrees Celsius in the condensing part), and a controller 9 for controlling the lamp light irradiation device if8. Configure a system consisting of
Then, the chip-shaped second glass sheet S obtained as described above is placed on the working board 7! ! 2, the lamp light irradiation device 8 is controlled by the controller 5, and the light is focused on the chip-shaped second glass sheet S to the same size or slightly thicker than that. In this state, lamp light is irradiated while gradually increasing the light emission output, and the entire chip-shaped second glass sheet S is slowly raised in advance to just before the melting temperature (in this example, it was about 600 ° C. below the softening point). , and then in the preheated state on the verge of melting, a relatively high light emitting output (
By irradiating the entire surface of the chip-shaped second glass sheet S with lamp light (approximately 1200°C in this example) for a very short time (about several seconds in this example) and applying a predetermined amount of thermal energy. , only the surface has good overall uniformity (
The material is preheated and subjected to high-speed surface heat treatment, which involves melting it and then solidifying it. In addition, also in this case, the chip-shaped second
By simply irradiating lamp light from one side of the 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 narrowing down the light concentration during surface treatment after preheating, or by performing scanning irradiation in that state,
Similar to the preheating lamp heat irradiation method described above, the chip-shaped second
It is also possible to realize precision vitrification of only a part (required part) of the surface of the glass sheet S with a relatively small amount of labor and energy consumption.

Still another method (third method) is a so-called belt moving furnace method, and as shown in FIG. A plurality of heaters 12 (in this example, three pairs of upper and lower pairs) are provided along the belt movement direction and whose temperature can be set individually.
・And those rotating helmets) 11 and heaters 12...
A controller 13 for controlling the electric heating furnace system is constructed, and a plurality of chip-shaped second glass sheets S obtained as described above are
As shown in the figure, two substrates (upper and lower) with excellent thermal conductivity (for example, non-oxide ceramic plates such as boron nitride and silicon nitride, carbon plates, carbon graphite plates, alumina plates, etc.; in this example, vertical x horizontal ×Thickness = 50m+x 50m
mX 0. 635II1m alumina plate) 14.14
A very thin spacer (in this example, a thickness of 0.6
The working blocks 16 are held between 35111 m of alumina plates) 15° 15, and the working blocks 16 are placed continuously on the rotating bell) 11, and the inside of the furnace 10 is heated. It is made to pass from the population 10A to the exit 10B at a predetermined time (speed). The relationship between the movement path HD 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, as shown schematically in FIG. 11, for example. It can be set as desired. That is, the inlet 10A of the furnace IO
During the amount of preheating up to point A in FIG. 11, the chip-shaped second glass sheets S sandwiched between the working blocks 16 introduced from (In this example, the temperature was raised to approximately 600°C, which is below the softening point. In the case of a pNa glass responsive membrane, the temperature was raised to approximately 600°C, which is below the softening point.)
0°C), and in the preheated state on the verge of melting, a predetermined amount of heat is applied during an extremely short surface melting period (about 10 seconds in this example) until reaching point B in Figure 11. By applying energy, only the surfaces (both the front and back sides) are melted with good uniformity as a whole, and then the 11th
A high-speed surface heat treatment is performed to preheat the material to reach the 0 point (cooling point) in the figure and solidify it. In FIG. 9, 10a is an inlet air curtain air (or Nt gas) injector, 10b is an outlet air curtain air (or Nt gas) injector, and IOC is a firing/cooling gas air (or N2) injector. 100 is a firing and cooling gas discharge pipe.

Incidentally, 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, even in the preheating laser heat irradiation method and the preheating lamp heat irradiation method shown in FIGS. 7 and 8, the chip-shaped second glass sheet S or the heating block 2 or working board 7 that supports it is automatically replaced. It is possible to construct a mass production system by adding handling equipment and the like.

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, the glass sheet may be subjected to high-speed surface heat treatment after the 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 after preheating. In addition to using an ultra-thin, flat, ion-responsive glass membrane that 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 with a bonding material that has sufficiently high electrical insulation properties, the ion-responsive glass membrane can be made to have a high electrical insulation property, making it possible to create a net-type glass electrode that has the required high electrical insulation properties compared to conventional glass electrodes. This technology has the advantage of being able to be manufactured very easily and inexpensively, thereby fully achieving the intended purpose of significantly downsizing glass electrodes for ion measurement and improving reliability, operability, maintainability, etc. The effects of this approach have come to fruition.

[Brief explanation of the drawing]

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. Further, FIGS. 2 to 6 show specific examples of sheet-type glass electrodes according to the present invention.
Figure 2 is an exploded perspective view, Figure 3 is a cross-sectional view taken along line 11 in Figure 2, and Figure 4 is a cross-sectional view taken along line IV--IV in Figure 2. The figure also shows the fifth
The figure shows a perspective view of the unit in which the p Figures 7 to 11 are for explaining the manufacturing procedure of the flat ion-responsive glass membrane, which is the main component. 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. 12 and 13 are for explaining the technical background of the present invention and the problems of the prior art, and FIG. 12 shows a partially sectional side view of a glass electrode for ion measurement according to the conventional configuration. , FIGS. 13(a) and 13(b) respectively show a vertical 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 11,
!・・・・・・High electrical insulation bonding material. Figure 1 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, ■.
・・・・・・High electrical insulation bonding material. Figure 7 Figure 8 Figure 11 Figure 12

Claims (1)

[Claims] An electrode having an internal electrode portion and a lead portion is attached to the upper surface of a substrate made of a material having sufficiently high electrical insulation, and an electrode made of a material having sufficiently high electrical insulation and corresponding to the internal electrode portion. a support layer having holes at certain locations, with the lead portion and its surroundings exposed;
The pores formed on the upper surface of the substrate and in the support layer are filled with a gel-like internal liquid, and the flat ultrathin glass, which has been preformed to have a predetermined size, is heated under preheating. A flat plate-like ion-responsive glass membrane produced by high-speed surface heating treatment was heated sufficiently to bring its lower surface into close contact with the upper surface of the gel-like internal liquid and to seal the gel-like internal liquid into the holes. A sheet-type glass electrode, characterized in that the periphery of the sheet-type glass electrode is fixed to the upper surface of the support layer using a bonding material having high electrical insulation properties.