ION SELECTIVE ELECTRODE

Abstract: An integral ion selective electrode for the analysis of a potassium ion comprising: (I) a support; (II) an electroconductive metal layer such as a silver metal layer; (III) a layer of a water-insoluble salt of said metal such as a silver chloride layer; (IV) an electrolyte layer which comprises crystalline electrolyte salts of cations including a potassium ion and a sodium ion with the same anions as the anion of the water-­ insoluble salt, said electrolyte layer being substantially free from a binder; and (V) a potassium ion selective layer.

Description: The present invention relates to an ion selective electrode and processes for the preparation of the same. More particularly, the invention relates to an ion selective electrode appropriately employable for the potentiometric determination of a potassium ion, and processes for the preparation of the electrode. Description of prior arts The ion selective electrode is a device for the potentiometric determination of ion concentration in an aqueous sample, and a body fluid such as blood or serum. Its elemental structure is disclosed, for instance, in Japanese Patent Provisional Publication No. 52(1977)-142584 and U.S.P. 4,053,381. In more detail, the ion selective electrode has an integral structure comprising a support, an electroconductive metal layer (e.g., deposited silver metal layer), a layer of a water-insoluble salt of said metal (e.g., a layer of silver chloride), an electrolyte layer which comprises an electrolyte salt of a cation (e.g., potassium ion or sodium ion) with the same anion as the anion of the water-insoluble salt (for instance, potassium chloride or sodium chloride), and an ion selective layer. In practically determining ion concentration by means of an ion selective electrode (i.e., half cell) having the above-described elemental structure, the following procedures are adopted: A couple of ion selective electrodes A & B are connected via a water-retainable bridge. On the ion selective electrodes A & B are spotted a standard liquid (reference liquid) and a liquid sample, respectively, and the potential difference between both electroconductive layers of the ion selective electrodes A & B are measured after lapse of a certain period of time. The measured potential difference is then compared against a calibration curve to determine the concentration of the electrolyte. Alternatively, a couple of ion selective electrodes insulated from each other by a scratched groove disclosed in Japanese Patent Provisional Publication No. 58(1983)-156848 can be used for the measurement in the same manner. The ion selective electrode is composed basically of the above-stated simple structure and can be manufactured in the form of a small sized chip. Accordingly, the ion selective electrode is very advantageously employed for the determination of an electrolyte in a small amount of a liquid sample such as a body liquid. In most cases, a body liquid is available for the determination in a very limited amount. Moreover, the ion selective electrode is employable as a disposable device, because it can be formed in a simple structure and in a small size. It has been noted, however, that a measured value obtained in the use of a small sized ion selective electrode sometimes is not reliable. This arises from fluctuation of electric potential (i.e., potential drift) which often takes place in the measurement procedure. It is thought that the potential drift is reduced by the use of an ion selective electrode in which the thickness of each of the functional layers is increased. However, the increase of the thickness of layers not only results in increase of cost for manufacturing the device, but also results in decrease of the sensitivity. An improvement for obviating the occurrence of the potential drift or other disadvantageous problems has been proposed in Japanese Patent Provisional Publication No. 57(1982)-17852. This improvement comprises preparing a binderless electrolyte layer by vapor deposition of the electrolyte or by a series of procedures of coating an aqueous electrolyte solution containing no binder and then drying the coated layer. This art provides an ion selective electrode which is reduced in occurrence of the potential drift taken place in the conventional ion selective electrode. Nevertheless, more reduction of the possible potential drift is desired for the purpose of enhancing the accuracy of the meaurement in the use of ion selective electrode. It has been noted that the electrolyte layer prepared from an aqueous electrolyte solution containing no binder by a coating-drying procedure comprises a relatively large sized crystalline electrolytes. Therefore, the crystalline elecrolytes are not distributed uniformly in the layer and the resulting electrolyte layer is apt to have a large thickness. The non-uniform electrolyte layer and thick electrolyte layer both serve to decrease the accuracy of measurement. The preparation of an electrolyte layer by vapor deposition of an electrolyte is disadvantageous in an industrially available scale, because the vapor deposition of an electrolyte giving a low vapor pressure is difficultly employed, and otherwise the vapor deposition of an electrolyte decomposable at a vaporized temperature requires specific carefulness so that no high vaporization efficiency is expected. SUMMARY OF THE INVENTION The present inventors have proposed a improved process for the preparation of the electrode in Japanese Patent Application No. 59-93774 (the content of which is disclosed in the United States Application No. 732,368 and EP 85 105 706.7. The above process which comprises forming the electrolyte layer by coating an aqueous solution containing the electrolyte salt but containing substantially no binder on the layer of a water-insoluble salt and drying thus coated layer by bringing it in contact with a stream of gas maintained at a temperature of not lower than 40 o C can obviate the occurrence of the potential drift. The process can produce a potassium salt of a smaller crystalline size to improve the stability of the ion selective electrode for the analysis of a potassium ion. However the above potassium salt still tends to have a larger crystalline size than that of a sodium salt which is produced by the same manner. Accordingly, further improvement is desired. The present inventors have studied the ion selective electrode according to the philosophy that the electrolyte layer should be formed by the electrolyte salt of a smaller size in order to obviate the occurrence of the potential drift. They have noted that a mixture made of a potassium salt and a sodium salt used as the electrolyte salt of the electrolyte layer has no adverse influence upon the quality of the ion selective electrolyte such as the analytical accuracy, and at the same time the smaller crystals made of the mixture can be more easily formed than that made of a simple potassium salt. They have also noted that it is possible to much more reduce the occurrence of the potential drift, by utilizing the above phenomenon. Accordingly, a primary object of the present invention is to provide an ion selective electrode which is appropriately employable for the analysis of a potassium ion through potentiometric determination and is reduced in the occurrence of phenomena of bringing about measurement errors such as the potential drift. Another object of the invention is to provide an ion selective electrode for the determination of a potassium ion which is shortened in the response period at the measurement. A further object of the invention is to provide an ion selective electrode appropriately employable for the analysis of a potassium ion in a body liquid. A still further object of the invention is to provide a process appropriately employable for the preparation of an ion selective electrode for the analysis of a potassium ion through potentiometric determination and is reduced in the occurrence of phenomena of bringing about measurement errors such as potential drift. The present invention resides in an integral ion selective electrode for the analysis of a potassium ion comprising: (I) a support; (II) an electroconductive metal layer; (III) a layer of a water-insoluble salt of said metal; (IV) an electrolyte layer being substantially free from a binder; said electrolyte layer comprising the crystalline electrolyte salt of a potassium ion with the same anion as the anion of the water-insoluble salt; and (V) a potassium ion selective layer. the electrolyte layer further comprises the crystalline electrolyte salt of a sodium ion with the same anion as the anion of the water insoluble salt, the crystalline electrolyte salts having a mean size of not more than 50 µm and the salts of a potassium ion is contained in an amount of between 8 - 75 % by weight based on the whole electrolyte salts. The above-described ion selective electrode can be prepared by a process which comprises forming the electrolyte layer by coating an aqueous solution containing a potassium salt and a sodium salt but containing substantially no binder on the layer of a water-insoluble salt and drying thus coated layer by bringing it in contact with a stream of gas maintained at a temperature of not lower than 40 o C. Further, the above-described ion selective electrode can be prepared by a process which comprises forming the electrolyte layer by coating a solution containing a potassium salt and a sodium salt but containing substantially no binder in a mixture of water and an organic solvent on the layer of a water-insoluble salt and drying thus coated layer. BRIEF DESCRIPTION OF THE DRAWINGS Fig. I illustrates an ion selective electrode equipped with a bridge which is employed for the measurement according to the differential method. Fig. 2 shows graphically a variation with time of electric potential observed in the measurement according to the direct method using an ion selective electrode of the invention. DETAILED DESCRIPTION OF THE INVENTION As described hereinbefore, the elemental structure of the ion selective electrode provided by the present invention which comprises a support, an electroconductive metal layer, a layer of a water-insoluble salt of said metal, an electrolyte layer comprising an electrolyte salt of a alkaline metal cation with the same anion as the anion of the water-insoluble salt, said electrolyte layer being substantially free from a binder, and an ion selective layer being as such known. For instance, such embodiment is disclosed in Japanese Patent Provisional Publication No. 57(1982)-17852. The ion selective electrode of the invention can be prepared in the same manner as in the conventional arts except that the electrolyte layer is prepared in a different manner. The constitution of the ion selective electrode and materials used for the preparation can be determined on the basis of the disclosures in Japanese Patent Provisional Publications No. 52(1977)-142584, No. 57(1982)-17852 and No. 58(1983)-211648. For instance, the support can be prepared from a film or sheet of a plastic material such as polyethylene terephthalate. A representative electroconductive metal layer is a silver metal layer formed on a surface of the support by vapor deposition. In the case that the electroconductive metal layer is a silver metal layer, the layer of a water-insoluble salt can be produced by chemical oxidation-chlorination of the surface portion of the silver metal layer to form a silver chloride layer, or by coating a dispersion containing silver chloride and a binder on the surface of the silver metal layer and drying the coated layer. On the layer of a water-insoluble salt is formed an electrolyte layer. The constitution of the electrolyte layer is a characteristic feature of the invention and shall be described hereinafter in detail. The ion selective layer is capable of selecting a specific ion, and shows a high electric resistance and is a substantially electric insulative in a dry state prior to contact with a liquid sample or a reference liquid. The capability of selecting a specific ion includes not only a property of selectively allowing permeation of the specific ion or selectively responding to the specific ion but also a property of selecting a specific ion from other ions or substances with a time differential enough for detecting the specific ion. Moreover, certain materials employable for the formation of the ion selective layer are capable of detecting a potential difference on the ion activity change occurring in the course of ion exchange, whereby showing the same property as the property of selecting a specific ion. This property is also included in the capacity of selecting a specific ion. The ion selective layer ought to be water-insoluble, because a liquid sample and a reference sample both are aqueous liquids. The ion selective layer can be either hydrophilic or hydrophobic, as far as the layer is water-insoluble. However, a hydrophobic ion selective layer is preferred. The ion selective layer can be prepared in the known manner. For instance, a solution of an ion carrier and a hydrophobic organic binder in an ion-carrier solvent is coated on the electrolyte layer and dried to give an ion selective layer. The ion carrier is coated generally in the amount of 0.05 - 10 g/m², and the thickness of the ion selective layer ranges from approx. 3 µm to approx. 125 µm, preferably from approx. 5 µm to approx. 50 µm. Examples of the potassium ion carrier include valinomycin, cyclic polyethers, tetralactones, macrolide actins, enniatin, potassium tetraphenyl borate and their derivatives. Examples of the ion carrier solvent include phthalates, sebacates, aromatic or aliphatic ethers and adipates. Concrete examples of the solvent are described in Japanese Patent Publication No. 58(1983)-4981. For instance, there can be mentioned bromophenyl phenyl ether, 3-methoxyphenyl phenyl ether, 4-methoxyphenyl phenyl ether, dimethyl phthalate, dibutyl phthalate, didodecyl phthalate, dioctylphenyl phosphate, dicresyl phosphate-bis(2-ethylhexyl) phthalate, octyldiphenyl phosphate, tritolyl phosphate, dioctyl adipate and dibutyl sebacate. Moreover, a great number of utilizable solvents are known. The hydrophobic organic binder can be a film-forming natural polymer, its derivative, or a synthetic polymer. Examples of the hydrophobic organic binder include cellulose ester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinylidene chloride, polyacrylonitrile, polyurethane, and polycarbonate of bisphenol A. Details on the ion carrier, ion carrier solvent, hydrophobic organic binder and ion selective layer are given not only in the aforementioned Japanese Patent Publication No. 58(1983)-4981, but also in Japanese Patent Provisional Publication No. 58(1983)-156848, United States Patents No. 4,053,381, No. 4,171,246, and No. 4,214,968, and Research Disclosure No. 16113 (September 1977). Moreover, an ion exchangeable material can be used for the formation of the ion selective layer. In this case, a response on the potential difference originating from change of ion activity caused by the ion exchange is measured. Appropriate ion exchangeable materials and preparation of the ion selective layer using these materials are described in Japanese Patent Publication 52(1977)-47717. The ion selective electrode of the present invention is characterized in that the electrolyte layer comprises both a potassium salt and a sodium salt is substantially free from a binder and comprises crystalline electrolytes having mean size of not more than 50 µm, preferably 0.1 to 40 µm, more preferably 0.2 to 10 µm, in which the crystalline electrolyte is preferably distributed densely and uniformly on the layer of a water-insoluble salt of a metal constituting the electroconductive layer (hereinafter referred to as "water-insoluble salt layer). Preferably, the crystalline electrolytes (electrolyte crystals) are not arranged in piles in the direction vertical to the plane of the ion selective electrode. Accordingly, the mean thickness of the electrolyte layer preferably is almost equal to the mean size of the crystalline electrolytes. In the ion selective electrode of the present invention, the electrolyte layer is formed by arranging uniformly potassium and sodium crystalline electrolytes of a small size without using a binder over the surface of the water-insoluble salt layer. Then the crystalline electrolytes are densely arranged, and a relatively thin electrolyte layer can be formed. An ion selective electrode having such electrolyte layer shows quick response and is prominently reduced in occurrence of the potential drift. Moreover, the ion selective electrode of the invention is almost free from separation of the functoinal layers at the electrolyte layer which is sometimes observed in the use of an ion selective electrode having a binderless electrolyte layer. The reason is thought to reside not only in high density of the electrolyte layer and decrease of the thickness but also in that the small sized electrolyte crystals given in the invention are at least partly engaged physically with the water-insoluble salt layer. Particularly, where the water-insoluble salt layer is a porous silver chloride layer, the engagement between the crystalline electrolyte and the water-insoluble salt layer (i.e., silver chloride layer) is prominently observed. In the case that the electrolyte layer is composed of distributed small-sized crystalline particles, the electrolyte layer is substantially free from poor contact or adhesion between the electrolyte layer and the ion selective layer, which are sometimes observed in the binder-containing electrolyte layer of the conventional ion selective electrode. Generally, the potassium salt content of the whole electrolyte salt ranges from 8 to 75 % by weight. When the potassium salt content exceeds 75 % by weight, the formation of the small-sized crystalline electrolyte tends to be difficult. On the other hand, even when the potassium salt content is less than 8 % by weight, the size of the crystals does not further decrease. According to the study of the present inventors, the potassium and sodium electrolyte salt crystals having the small mean size defined in the invention are not formed by the conventional method which comprises procedures of simply coating an aqueous binderless electrolyte solution on the surface of the water-insoluble salt layer and drying under ambient conditions. It has been discovered that a simple process comprising procedures of coating an aqueous solution containing potassium electrolyte salt such as potassium chloride and sodium electrolyte salt such as sodium chloride on the water-insoluble salt layer and allowing the coated layer to dryness at room temperature gives a crystalline electrolyte of large mean size. The electrolyte layer composed of such large sized crystalline electrolyte is poor in evenness of the distribution of the electrolytes and the thickness of the electrolyte layer. Accordingly, the potential drift is apt to appear more easily and the response time becomes longer because of thus formed thick electrolyte layers. The electrolyte layer of the present invention can be prepared by a process which comprises forming the electrolyte layer by coating an aqueous solution containing both a potassium salt and a sodium salt on the water-insoluble salt layer and drying thus coated layer by bringing it in contact with a stream of gas maintained at a temperature of not lower than 40 o C (preferably 80 - 200 o C), whereby producing a layer of crystalline electrolyte having mean size of not more than 50 µm (preferably 0.1 - 40 µm) over the water-insoluble salt layer. Preferably, the electrolyte layer of the invention is prepared by a process which comprises forming the electrolyte layer by coating a solution containing a potassium salt and a sodium salt in a mixture of water and an organic solvent on the water-insoluble salt layer and drying thus coated layer. There is no specific limitation on the drying conditions, but the coated layer is preferably dried by a stream of gas at a temperature of not lower than 40 o C. More preferably, a temperature of a stream of gas ranges from 50 to 200 o C. The latter process using a mixture of water and an organic solvent is particularly preferred to produce a crystalline electrolyte of a smaller size. Moreover, this process is advantageous in the preparation of the ion selective electrode in a continuous form. In more detail, the ion selective electrode is manufactured industrially by initially producing an ion selective electrode in a continuous form on a continuous plastic sheet and then dividing it to give a multiple of ion selective electrodes. The use of a mixture of water and an organic solvent (which is miscible with water) is effective not only to shorten the period required for the formation of the electrolyte layer but also to facilitate the preparation of the electrolyte layer comprising crystalline electrolytes densely distributed over the water-insoluble salt layer. The mixture of water and an organic solvent is preferably in the range of 2:8 to 8:2. Examples of the organic solvent include lower aliphatic alcohols such as methanol, ethanol, propanol and isopropanol, aliphatic ketones such as acetone, methyl ethyl ketone and diethyl ketone, ethers such as diethyl ether and tetrahydrofuran, and esters of lower aliphatic acids with lower aliphatic alcohols such as ethyl acetate and butyl acetate. The organic solvent can be employed singly and in combination. There is no specific limitation on the concentration of the aqueous electrolyte solution (which may contain an organic solvent) employed for the preparation of the electrolyte layer. Generally, the concentration of the electrolyte in the solution ranges from approx. 0.5 to approx. 20 % by weight, preferably approx. 0.5 to approx. 15 % by weight, more preferably approx. 0.5 to approx. 10 % by weight. An electrolyte solution of a higher concentration within the above-defined range is preferably employed for enhancing the efficiency in the industrial manufacturing of the electrode. The anion which is a counter ion to the potassium ion and the sodium ion, both consisting in the electrolyte salt of the electrolyte layer of the invention ought to be identical to the anion of the water-insoluble salt. Accordingly, the anion is selected in consideration of the whole constitutional conditions of the ion selective electrode. Generally, the electroconductive layer is made of a silver metal, and the water-insoluble salt is composed of silver chloride. For this reason, the mixture of potassium chloride and sodium chloride is generally employed as the electrolyte. Nevertheless, if the anion of the water-insoluble salt is an anion other than the chloride ion, such as a bromide ion, iodide ion, sulfonium ion or carboxylic ion, the anion of the electrolyte salt is selected to be consistent with the above-selected anion. The present invention is further described by the following examples. Example 1 On a polyethylene terephthalate film (thickness: 188 µm, 30 mm x 100 mm) was formed a silver metal layer of approx. 800 nm thick by vapor deposition under vacuum. The deposited silver metal layer is covered at both sides by means of a liquid resist of the polymer composition described in Japanese Patent Provisional Publication No. 58(1983)-102146. The center portion of the deposited silver metal layer was removed by cutting with a bit to form an insulating area of a U shape. The exposed portion of the deposited silver metal layer was processed in a processing solution containing hydrochloric acid and potassium dichromate (aqueous solution containing hydrochloric acid 36 mmol./ℓ and potassium dichromate 16 mmol./ℓ) for approx. 60 sec. After the processing was complete, the composite element was washed with water and dried to give a filmy silver-silver chloride electrode (i.e., a composite of the support, electrocondutive silver metal layer, and a silver chloride layer). On the silver-silver chloride electrode film was coated an aqueous organic solution (acetone 2.5 g. + ethanol 20 g. + water 20 g.) containing potassium chloride and sodium chloride set forth in Table 1. Then the coated layer was dried by applying thereto an air stream (1.5 m/sec.) of 80 o C for 3 min. The weight of the electrolyte layer was approx. 2.3 g/m² upon dryness. Microscopic observation indicated that the dried electrolyte layer was composed of a great number of potassium chloride and sodium chloride fine crystals having a mean size described in Table 1 which were densely distributed over the silver chloride layer. On thus formed electrolyte layer was then coated a potassium ion selective layer (thickness 25 µm) of the below-described composition was formed in the conventional manner. Thus, Ion Selective Electrode I for the analysis of potassium ion was prepared. Evaluation of Ion Selective Electrode A liquid receiver of a plastic film provided with a couple of liquid receiving openings was fixed onto the surface of the ion selective electrode under adhesion. The two liquid receiving openings are connected to each other with a polyester spun thread bridge. Thus, an electrode device for the analysis of potassium ion was prepared. The electrode device for the potassium ion analysis is schematically illustrated in Fig. 1. In Fig. 1, 11 indicates the polyethylene terephthalate film (support), each of 12a and 12b indicates the deposited silver metal layer (the deposited silver metal layer is devided by the scratched groove to expose the surface of the support, whereby giving two separated areas), each of 13a and 13b indicates the silver chloride layer, 14 indicates the electrolyte layer, 15 indicates the ion selective layer, 16 indicates the liquid receiver, each of 17a and 17b indicates the liquid receiving opening, and 18 indicates the bridge. In one liquid receiving opening 17a was spotted a potassium ion-containing reference solution (Calibrate 2), and in another liquid receiving opening 17b was spotted a liquid sample (Calibrate 1, 2 or 3 was employed). In the measurement according to a differential method, the within-run precision was measured in the conventional manner. The results are set forth in Table 2. The CV value which indicates the dispersion in measurement is desired to be within approx. 4 %, and the slope value is desired to be near 59 mV/decade which is standard value. In the above-described measurements, the sample Nos. 2, 3 and 4 showed no value deviating from the expected value (±50 mV) even in fifty times-repeated runs, while the sample Nos. 5, 6 and 7 showed values deviating from the expected value (±50 mV) in a ratio of 1 time (sample Nos. 5 and 6) or 2 times (sample No. 7) per fifty times-repeated runs. Example 2 The procedures for sample Nos. 2, 3 and 4 in Example 1 were repeated except that the potassium ion selective layer did not contain the potassium tetrakis-p-chlorophenyl borate to prepare ion selective electrodes for the analysis of potassium ion. The above-described evaluation was performed on the ion selective electrodes. The results are almost the same as those given on the ion selective electrodes of sample Nos. 2, 3 and 4 in Example 1. Example 3 A filmy silver-silver chloride electrode (reference electrode) and the ion selective electrode for the potassium ion analysis prepared in Example 1 (sample No. 2, 3 or 4) were cut off along the scratched groove and connected to each other by means of a combination of a liquid receiver and a bridge in the same manner as illustrated in Fig. 1. On the reference electrode was spotted a reference liquid (Calibrate 2), while on the ion selective electrode was spotted a liquid sample (Calibrate 1, 2 or 3). The variation with time of the potential was measured according to the known direct method. The results are illustrated in Fig. 2. As is clear from Fig. 2, the potential reached a stable value within a very short time. Example 4 In the same manner as in Example 3, the reference electrode and the ion selective electrode for the potassium ion analysis (sample No. 2, 3 or 4) were cut off along the scratched groove and connected to each other by means of a combination of a liquid receiver and a bridge in the same manner as illustrared in Fig. 1. The measurements of the method as in Example 3 were repeated using a liquid sample containing potassium chloride 2.8 meq/ℓ and sodium chloride 99 meq/ℓ, and a reference liquid containing potassium chloride 2.8 meq/ℓ and sodium chloride 179 meq/ℓ. The measured potential difference gave 0.3 - 2.0 mV values. The values showed that influence from sodium ion in the measurement of potassium ion gave approx. 0.05 - 0.2 meq/ℓ. Thus it was confirmed that existence of a considerable amount of sodium ion formed no obstacle to the practical measurement for potassium ion. Example 5 The procedures in Example 1 were repeated except that the electrolyte salt solution was 42.5 g. of water containing 1.11 g. of KCℓ and 1.39 g. of NaCℓ to prepare an ion selective electrode for the analysis of potassium ion. In one opening 17a was spotted a potassium ion-containing reference solution (Calibrate 2), and in another opening 17b was spotted a liquid sample (Calibrate 1, 2 or 3 was employed). In the measurement according to a differential method using Calibrate 1, 2 or 3, the measured within-run precision of the ion selective electrode was similar to the result of Sample No. 4 in Example 1.

Claims: An integral ion selective electrode for analysis of a potassium ion comprising: a support (11); an electroconductive metal layer (12a, 12b); a layer of a water-insoluble salt of the metal (13a, 13b); an electrolyte layer (14) being substantially free from a binder; said electrolyte layer (14) comprising the crystalline electrolyte salt of a potassium ion with the same anion as the anion of the water-insoluble salt, and a potassium ion selective layer (15), characterised in which the electrolyte layer further comprises the crystalline electrolyte salt of a sodium ion with the same anion as the anion of the water insoluble salt, the crystalline electrolyte salts have a mean size of not more than 50 µm and in which the salt of a potassium ion is contained in an amount of between 8 - 75 % by weight based on the whole electrolyte salts, The integral ion selective electrode as defined in claim 1, wherein the mean size of the crystalline electrolyte salt ranges from 0.1 to 40 µm. The integral ion selective electrode as defined in claim 1, wherein the mean size of the crystalline electrolyte salt ranges from 0.2 to 10 µm. The integral ion selective electrode as defined in claim 1, wherein the electroconductive metal layer (12a, 12b) is made of silver, said layer of a water-insoluble salt (13a, 13b) is a layer of silver chloride and said electrolyte salts consist of potassium chloride and sodium chloride.

Inventors: NIRASAWA, MITSUHARU, SESHIMOTO, OSAMU
Applicants: FUJI PHOTO FILM CO., LTD.
Application year: 1985
Main classification: G01N27
IPC codes: G01N27