JPH03217458A - Electrolytic composition insolubilized by light, pattern forming method using thereof and production of electrode element - Google Patents

Abstract

PURPOSE:To obtain a composition having high sensitivity to be insolubilized with light irradiation and excellent film-forming property and giving an electrode element with forming a stable electrolyte pattern containing a polymeric electrolyte, a crosslinking agent for bisazide-based monomer and a sensitizer. CONSTITUTION:A polymeric electrolyte is mixed with a crosslinking agent for bisazide-based monomer and a sensitizer. Next, a base plate is coated with resultant solution and an electrolyte pattern insoluble in a solvent is formed with locally irradiating light. Otherwise, a base plate is coated with said solution and a part connecting between electrodes is irradiated with light, then an electrolyte pattern insoluble in a solvent is formed, thus said electrolyte of the pattern is solubilized by bringing into contact with an oxidizing atmosphere and an oxygen-permeable membrane is applied on the electrolyte pattern.

Description

[Detailed Description of the Invention] (Summary) Regarding a photoinsolubilizable polymer electrolyte composition and a method for manufacturing an electrode element that can be used in a biosensor, the present invention aims at a polymer electrolyte composition with high susceptibility, and this composition is a polymer electrolyte composition. This solution contains an electrolyte, a bisazide monomer crosslinking agent, and a sensitizer, and this solution is applied to a substrate and partially irradiated with light to make it insolubilized to form a pattern.The electrolyte pattern is also formed in the connection area between electrodes. Next, the electrolytic material is solubilized by contacting with an oxidizing atmosphere, and an oxygen permeable membrane is coated thereon.

[Industrial application field]

The present invention relates to a photoinsolubilizable polymer electrolyte composition, a pattern forming method using the same, and a method for manufacturing an electrode element that can be used in a high-sensor.

Polymer electrolysis is used to manufacture devices with advanced functions, such as high-speed sensors. For example, electrode elements such as oxygen electrodes can be used in conjunction with enzymes that oxidize or reduce only specific substrates or microorganisms that contribute specific substances to indirectly measure local changes in oxygen concentration. , it becomes possible to form a high-speed sensor that selectively measures only a specific substance.

A wide range of substances can be measured by Hyosensor, including sugars such as glucose, sucrose, and galactose, and organic acids such as ascorbic acid (vitamin C), lactic acid, and uric acid. For example, compared to liquid chromatography, it is possible to perform measurements more quickly and easily, so it can be applied to the food, brewing, medical, and clinical testing fields.

Hyosensor measurements are based on electrochemical reactions.
The presence of electrolytes is essential. The present invention relates to a composition that can be used to form an electrolyte layer that can be applied to devices in the above-mentioned fields.

[Conventional technology]

Conventionally, the following method has been used to form an electrolyte layer for producing an electrical conversion element using electrochemical principles.

■Apply photoresist etc. to the substrate, open a window in the area where the electrolyte layer should be formed, then spread the electrolyte solution in a thin layer using spin coating, desoap coating, doctor blade, etc., and apply the photoresist solvent to the unnecessary areas. is removed to form an electrolyte layer in a specific area (lift-off method).

■Apply surface hydrophobic photoresist etc. to the substrate, open a window in the area where the electrolyte layer is to be formed, then daimbu-coat the electrolyte aqueous solution so that the electrolyte solution adheres only to the window area, and then dry. let

■A mask made of a suitable material (stainless steel, etc.) is placed on the substrate, and electrolyte material is deposited on top of it using a vacuum evaporation method.

In all of the above methods, a mask of some kind is brought into contact with the substrate, and an electrolyte layer is formed only in the areas without the mask.

[Problems to be Solved by the Invention] Accordingly, in the above method, it is necessary to apply or bring other materials into contact with the dehyde to be manufactured, which complicates the manufacturing process, and as a result, the quality of the product deteriorates. The yield is low, and it is difficult to miniaturize the electrolyte layer that can be formed, which has been a major obstacle in miniaturizing devices.

In particular, in the case (2) above, the relationship between the photoresist stripping solvent and the dissolution of the electrolyte material is complicated, making it difficult to select an appropriate solvent.

In ■, the relationship between the surface tension and viscosity of the electrolyte solution is complicated, and the viscosity is high like a general polymer electrolyte aqueous solution.
It cannot be applied to materials with low surface tension.

Method (2) is convenient for forming a low molecular weight electrolyte layer, but when it is desired to increase the thickness of the electrolyte layer, the time required for vapor deposition becomes extremely long, making it impractical.

In order to overcome the above problems, a method was devised in which photoinsolubility was imparted to a stable synthetic polymer electrolyte with good film-forming properties, and a desired electrolyte layer pattern was directly obtained by light irradiation (Patent Application No. -155207). However, this method uses a divinyl monomer as a crosslinking agent for the polymer electrolyte, so the amount of reaction to the amount of irradiation light, that is, the sensitivity is low, and long-term light irradiation is required. There was a problem of deterioration. There have also been attempts to increase sensitivity by using bisazide-based reagents as crosslinking agents.

However, when a pattern made insolubilized by crosslinking becomes gelled when impregnated with a solvent, its volume expands significantly. In particular, in the case of oxygen electrodes in which a minute pattern is formed between noble metal electrodes and covered with an oxygen-permeable film, over time, the solvent penetrates and gelation of the pattern progresses, causing the formation of the oxygen electrode. This had the disadvantage of significantly reducing functionality.

The present invention provides a stable polymer electrolyte composition that is highly sensitive to insolubilization by light irradiation, has good film-forming properties,
The purpose is to use this to form an electrolyte pattern and to learn a method for manufacturing an electrode element.

[Means for Solving the Problems] The above problems are achieved by applying a photoinsolubilizable electrolyte composition containing a polymer electrolyte, a bisazide monomer crosslinking agent, and a sensitizer, and applying this solution to a substrate to locally apply light. A method of forming an electrolyte pattern that does not dissolve in a solvent by irradiating with This problem can be solved by a method for manufacturing an electrode element that includes a step of coating a film.

[For production]

As polyelectrolytes, it is possible to use acid groups or polymers with activated nitrogen, sulfur, or phosphorus, such as substances with the repeating units shown in the table below.

Polyacrylic acid and its salts CH2-CH COO Polymethacrylic acid and its salts CB. CH2-C- COO Polystyrene sulfonic acid and its salts Partially sulfonated polystyrene SOi Polyethylene sulfonate CH2-CH- S03-Polyvinyl sulfate CH2 CH 0S03 Poly4(2) Salt of vinylpyridine quaternized product P Ionene polymer CH, CH. N-1 Realkylaminomethylboristyrene R2 Aminoacetalized polyvinyl alcohol CH2 CH CH2 CH- NH. Poly4(5) Vininoleimidazole-C}I2-CH Linear polyethyleneimine CHzGHzNH Polyethyleneimine CHzGHzNH CH2 CH2-N- Polydialkyl diallylammonium salt R1 R2 Polyvinylhenzylsulfonium salt R. -SLR2 Polyvinylhenzylphosphonium salt C}l2-Cl As the bisazito monomer, a substance whose azide group is decomposed by light irradiation to liberate nitrogen molecules and activate the remaining nitrogen atoms can be used. Activated nitrogen pulls out hydrogen atoms from the main chain of the polymer electrolyte, which creates unsaturated bonds in the main chain, which causes a crosslinking reaction, and only the light-irradiated portion has low solubility in the solvent. This part forms a pattern.

For example, the following monomers can be used:

4 4' Sulfonic acid, diazidostilbene 2 2′ hmm 2. 6-bis (4-azidohensal) 4 Methylcyclohexanone 0 etc. can be used.

As the sensitizer, commonly used photoreaction initiators such as dyes such as methylene blue, rhodamine, and riboflavin can be used. The light that starts the reaction is 250
It is preferred to use ultraviolet light of ~350 nm, but depending on the type of exacerbating agent, visible light can also be used.

After light irradiation, a polar solvent such as water, alcohol, dimethyl formaldehyde, etc. is used as a solvent to melt and remove the polymer electrolyte in the portions that were not irradiated with light, thereby forming a pattern.

After forming the pattern, oxygen gas, ozone gas, or the like can be used as the oxidizing atmosphere to solubilize the polymer again.

To form an electrolyte layer on a substrate of an electrochemical device, a solution of the composition according to the present invention is uniformly applied to the substrate, dried, and then a pattern of a desired shape is formed by irradiating light onto specific areas. can be formed. This makes it possible to easily form minute patterns, and
Since the patterned electrolyte layer is homogeneous, the final dehyde properties are also uniform.

Furthermore, the sensitivity to light is about 10 times higher than when a divinyl monomer is used as a crosslinking agent. Therefore, deterioration of the polymer electrolyte due to light during patterning can be reduced.

Further, the electrolyte pattern is brought into contact with an oxidizing atmosphere to resolubilize it, and then the oxygen permeable membrane is attached to the wi. Since the pattern is reversed, breakage of the film due to gelation of the pattern can be prevented.

〔Example〕

Implementation Figure 1 shows the procedure for producing an oxygen electrode that forms an electrolyte using the photoinsolubilizable electrolyte composition of the present invention. As a photoinsolubilizable electrolyte composition, 4,4
'-Diazidostilhene-2,2'-sodium disulfonate 1% and Rhodamine B 0. So that it is 1%? A dissolved aqueous solution was used. The manufacturing method will be explained step by step below.

FIG. 1(A), FIG. 1(G): An electrode pattern was formed on the glass substrate 1 by subsotering of platinum and vacuum evaporation of silver.

A plan view of the pattern is shown in FIG. 1(G).

The platinum cathode electrode 2 and the silver anode electrode 3 were each formed through the following steps. A glass substrate was placed on one electrode of a parallel plate type sputtering device, a platinum plate was placed on the other electrode side, a high frequency power of 13 Ml{z was applied between both electrodes, and argon gas was introduced. 5 X
A cathode electrode 2 of a platinum layer with a thickness of 1000 mm was formed on the glass substrate 1 by platinum sputtering using a plasma at 10-' Torr through a hole in a stainless steel mask placed on the glass electrode. Next, this glass substrate 1 is placed in a vacuum evaporation apparatus, and silver is vacuum-deposited onto the glass substrate 1 through the holes of a stainless steel mask placed on the glass substrate, thereby forming an anode electrode of a silver layer in a predetermined pattern. 3 was formed.

FIG. 1(B), FIG. 1(C): Next, the photo-insolubilizable electrolyte composition was applied by spin coating and dried to produce a 50 μm thick film.

Figure 1 (D), Figure 1 (E), Figure 1 (H): A photomask for irradiating the anode and cathode parts with light is placed on this substrate, and the light from a 500k high-pressure mercury lamp is applied. By irradiating it for 10 seconds and then immersing it in ethanol and developing it, it was possible to form an insolubilized polymer electrolyte layer only in the irradiated area.

A plan view of the pattern is shown in FIG. 1(H).

The substrate was placed in a quartz container under an oxygen stream saturated with water vapor, and ultraviolet rays were irradiated from the outside for 10 minutes through a quartz window. As a result, the electrolyte in the pattern has a low molecular weight, becomes soluble in water, and does not gel.

Figure 1 (F): As an oxygen permeable film material, OMR-83 (Tokyo Ohka ■), a Suga type resist, was applied to the surface of this substrate using the Dinop coat method, dried at 80°C for 20 minutes, and then exposed to ultraviolet rays. The film was irradiated for 60 seconds and then reheated at 120° C. for 20 minutes to form an oxygen permeable film 5. The thickness of the formed oxygen permeable membrane was about 20 μm.

The yield of the completed oxygen electrode was 99% or more. In addition, the oxygen electrode was immersed in water saturated with air, and the anode-cathode voltage was 0. When the response characteristics were examined at 8V, the output fluctuation was within ±3%. Further, the oxygen permeable membrane was not damaged during use.

. During use, about half of the devices failed due to damage to the oxygen permeable membrane due to swelling of the electrolyte pattern.

[Effects of the Invention] The present invention makes it possible to form an electrolyte layer, which plays the most important role, by light irradiation when producing an electrochemical measurement element, especially an oxygen electrode, thereby improving the yield and characteristics of the element. It is possible to improve the homogeneity of the elements and increase the response speed of the element.

Furthermore, since the sensitivity of insolubilizing the electrolyte by light irradiation has been significantly improved compared to the conventional method, photodeterioration of the polymer electrolyte is reduced and reliability is improved. Furthermore, during use as an electrode element, the polymer electrolyte will not swell and damage the oxygen permeable membrane.

[Brief explanation of drawings]

FIG. 1 is a sectional view and a plan view showing the manufacturing process of an oxygen electrode using the photoinsolubilizable polymer electrolyte of the present invention. In the figure, 1 is a glass substrate, 2 is a platinum cathode, 3 is a silver anode, 4 is a photo-insolubilizable electrolyte, 5 is a photomask, and 6 is an oxygen permeable membrane.

Claims (3)

[Claims] 1. A photoinsolubilizable electrolyte composition comprising a polymer electrolyte, a bisazide monomer crosslinking agent, and a sensitizer. 2. A pattern forming method comprising applying a solution of the photo-insolubilizable electrolyte composition according to claim 1 to a substrate and locally irradiating it with light to form an electrolyte pattern that does not dissolve in a solvent. 3. A solution of the photo-insolubilizable electrolyte composition according to claim 1 is applied to a substrate, irradiation with light is applied to the connecting portion between the electrodes to form an electrolyte pattern that does not dissolve in a solvent, and then the substrate is brought into contact with an oxidizing atmosphere. A method for manufacturing an electrode element, comprising the steps of: solubilizing the electrolyte in the pattern; and coating the electrolyte with an oxygen permeable membrane.