TW201321747A - Oxygen sensing agent, method for producing oxygen sensing agent, and oxygen sensing aqueous solution - Google Patents

Abstract

The purpose of the present invention is to provide: an oxygen sensing agent which has high heat resistance, is able to be stored at room temperature, and is able to maintain excellent oxygen sensing ability regardless of the ambient temperature; and a method for producing an oxygen sensing agent. In order to achieve the purpose, the present invention provides an oxygen sensing agent which is obtained by having a carrier support an oxygen sensing aqueous solution and which is characterized in that: the oxygen sensing aqueous solution contains ascorbic acid, a stabilizer that suppresses oxidative decomposition reaction of ascorbic acid, and a redox dye that is reduced by ascorbic acid; and rutin and/or a rutin derivative is used as the stabilizer. The present invention also provides a production method which is suitable for the production of the oxygen sensing agent.

Description

Oxygen detecting agent, manufacturing method thereof, and oxygen detecting aqueous solution

The present invention relates to a method for producing an oxygen detecting agent, an oxygen detecting agent, and an oxygen detecting aqueous solution in which the oxygen content in the atmosphere is changed by a change in color tone.

When foods, pharmaceuticals, etc. are preserved, oxygen in the atmosphere oxidizes foods and pharmaceuticals, and the quality of foods and pharmaceuticals is low. Therefore, in order to prevent the deterioration of the quality during storage, the food, the pharmaceutical, and the like are placed together with the deoxidizer in the packaging container (however, the packaging bag is included), and the package is sealed, and the oxygen in the packaging container is absorbed by a deoxidizing agent or the like. Foods, pharmaceuticals, etc. can be stored in an anaerobic state (for example, an oxygen concentration of 0.1% or less).

In recent years, a deoxidizer and an oxygen detecting agent are collectively enclosed in a packaging container, and the presence or absence of oxygen in the packaging container is detected by an oxygen detecting agent. The oxygen detecting agent is a substance that can be visually recognized by the presence or absence of oxygen in the sealed packaging container by the change in color tone. The user can easily confirm whether the food or the medicine is stored in an anaerobic state based on the color tone exhibited by the oxygen detecting agent.

The oxygen detecting agent is generally composed of a redox dye containing a reducing substance and a color difference between the oxidized state and the reduced state (for example, refer to "Patent Document 1 (Japanese Patent No. 2580157)" and " Patent Document 2 (JP-A-2007-3259)). The reducing substance is for the atmosphere to be absent In the oxygen state, the redox dye is used in a reduced state. The oxygen detecting agent is a structure that detects a color change by oxidizing the redox dye held in a reduced state by oxygen in the atmosphere to detect oxygen in the atmosphere. Therefore, the oxygen detecting agent is required to have a clear color tone change (color change) and rapid discoloration responsiveness accompanying the change in the oxygen content in the atmosphere. Therefore, in the above-mentioned Patent Document 1, the use of the edible red coloring matter which cannot be reduced by the reducing substance makes it possible to make the change in the color tone exhibited by the oxygen detecting agent in the reduced state and the oxidized state more vivid.

However, the conventional oxygen detecting agent has low heat resistance, and when stored at a high temperature (for example, a temperature higher than normal temperature, 35 ° C or the like), the oxygen detecting ability is lowered. When the oxygen content in the atmosphere changes, there is a problem that the color tone change becomes unclear and the color development is lowered.

One of the causes of low oxygen detection ability during high-temperature storage is deterioration of a reducing substance. Reducing saccharides can be used as reducing substances, however, reducing saccharides are browning at high temperatures. In the case of browning of the reducing sugar, the color of the oxygen detecting agent is also browned, so that the change in color tone becomes unclear. Further, when the reducing group of the reducing saccharide is consumed in association with the browning reaction, it is difficult to maintain the redox dye in a reduced state. As a result, in the oxygen detecting agent, a part of the redox dye may have an oxidized structure. In this case, even when oxygen is detected, the change in color tone may become unclear, the color rendering property may be lowered, and the discoloration responsiveness may not be obtained. Therefore, it is known to prevent deterioration of the oxygen detecting ability of the oxygen detecting agent by keeping the oxygen detecting agent at a low temperature (for example, 10 ° C or lower) before shipment to prevent browning of the reducing sugar.

On the other hand, in Patent Document 2, as a reducing substance, It is proposed to use ascorbic acid. Ascorbic acid is different from reducing sugars and does not undergo browning. However, ascorbic acid has lower heat resistance than reducing sugars, and is easily oxidatively decomposed when heated. When it is packaged and stored at a normal temperature for a long period of time, since ascorbic acid gradually oxidizes and decomposes, it is difficult to maintain the redox dye in a reduced state, and the oxygen detecting ability of the aerobic detecting agent deteriorates with time.

Therefore, an object of the present invention is to provide an oxygen detecting agent, a method for producing an oxygen detecting agent, and an oxygen detecting aqueous solution which have high heat resistance, can be stored at room temperature, have excellent color rendering properties, and can maintain superior oxygen detecting ability without being affected by atmospheric temperature. .

[Summary of the Invention]

As a result of earnest research by the inventors of the present invention, the above object is achieved by using the following oxygen detecting agent, a method for producing an oxygen detecting agent, and an oxygen detecting aqueous solution.

The oxygen detecting agent of the present invention is an oxygen detecting agent for supporting an oxygen detecting aqueous solution as a carrier, characterized in that the oxygen detecting aqueous solution contains ascorbic acid, a stabilizer for inhibiting oxidative decomposition reaction of ascorbic acid, and oxidation by reduction of ascorbic acid. The reducing dye is a stimulating agent using rutin and/or a rutin derivative.

In the oxygen detecting agent of the present invention, when the ascorbic acid content in the oxygen detecting aqueous solution is 100 parts by mass, the content of the stabilizer is preferably in the range of 2 parts by mass to 10 parts by mass.

In the oxygen detecting agent of the present invention, when the total mass of the carrier and the oxygen detecting aqueous solution carried by the carrier is 100 mass parts, the blood stasis is contained. The acid 10 mass parts to 30 mass parts, the stabilizers 0.2 mass parts to 3 mass parts, and the redox pigments 0.01 mass parts to 0.1 mass parts are preferable.

Further, in the oxygen detecting agent of the present invention, a dye which cannot be reduced by the reducing sugar is more preferable.

A method for producing an oxygen detecting agent according to the present invention, which is a method for producing an oxygen detecting agent for supporting an oxygen detecting aqueous solution, which comprises a step of dissolving an ascorbic acid stabilizer in a solvent to prepare a stabilization solution. And mixing the stabilization solution with an ascorbic acid solution obtained by dissolving ascorbic acid in a solvent to prepare an ascorbic acid stabilization solution, and the ascorbic acid solution and the redox pigment obtained by dissolving the redox pigment in a solvent The step of mixing the solution to prepare an oxygen detecting aqueous solution, and the step of supporting the oxygen detecting aqueous solution as a carrier, as the stabilizer, use rutin and/or rutin derivative.

The oxygen detecting aqueous solution of the present invention is an oxygen detecting aqueous solution for an oxygen detecting agent, characterized in that the oxygen detecting aqueous solution contains ascorbic acid, a stabilizer for inhibiting oxidative decomposition reaction of ascorbic acid, and a redox pigment reduced by ascorbic acid. The aforementioned stabilizer is rutin and/or rutin derivative.

According to the oxygen detecting agent, the oxygen detecting agent manufacturing method, and the oxygen detecting aqueous solution of the present invention, it contains ascorbic acid, a stabilizer for inhibiting oxidative decomposition reaction of ascorbic acid, and a redox dye which is reduced by ascorbic acid. In the oxygen detecting aqueous solution, ascorbic acid can be stabilized by the stabilizer, and the redox pigment can be maintained in a reduced state in an anaerobic state. State, preventing its change to an oxidized structure. Thereby, the oxygen detecting agent of the present invention has high heat resistance, can be stored at room temperature, and can maintain superior oxygen detecting ability without being affected by the atmospheric temperature. Moreover, since it can be stored at room temperature, the storage cost of the product before shipment can be reduced. In addition, even when it is used in a high-temperature atmosphere such as summer, an oxygen detecting agent which exhibits a clear color tone change depending on a change in oxygen content in the atmosphere and exhibits rapid discoloration responsiveness and excellent color rendering properties.

Fig. 1 is a schematic view showing the change in color tone of the oxygen detecting agent of the present invention.

Hereinafter, an embodiment of the present invention will be described. The oxygen detecting agent of the present invention is a substance which carries an oxygen detecting aqueous solution as a carrier, and changes its color tone depending on the oxygen content in the atmosphere, so that the oxygen content change in the atmosphere can be visually recognized.

1. Oxygen detection aqueous solution

First, an oxygen detection aqueous solution will be described. The oxygen detecting aqueous solution of the present invention is characterized in that it contains ascorbic acid, a stabilizer for inhibiting oxidative decomposition reaction of ascorbic acid, and an aqueous solution of a redox pigment reduced by ascorbic acid, and as a stabilizer, rutin and/or Rutin derivatives.

Ascorbic acid: Ascorbic acid has a left-handed body and a right-handed body. In the present invention, L-ascorbic acid of a left-handed body is mainly used. L-ascorbic acid is widely used as an oxidation inhibitor of food additives, and can be used safely as a component of an oxygen detecting agent enclosed in a packaging container such as a food. Oxygen detection of the amount of ascorbic acid in the aqueous solution, in the oxygen detection aqueous solution, to make redox The total amount of the pigment is maintained in a sufficient amount in the reduced structure. Further, in the present invention, maintaining the reduced state means that the redox dye is maintained in the reduced structure.

Ascorbic acid is easily oxidized by various oxidizing agents. In the present invention, ascorbic acid is used as a reducing agent for maintaining a redox dye in a reduced state by utilizing this property. Ascorbic acid is a relatively stable substance in a dry state, and is gradually colored and decomposed when moisture is absorbed. The oxygen detecting agent can be visually recognized by utilizing a color change accompanying the redox reaction of the redox dye to change the oxygen content in the atmosphere as a change in color tone. When the redox dye reacts with oxygen in the atmosphere, the reaction site must have moderate moisture. Therefore, when ascorbic acid is used as the reducing agent, the ascorbic acid needs to be placed in an environment where water is often present, so even at normal temperature. Ascorbic acid is also unstable and easily oxidatively decomposed. Therefore, although conventional techniques have proposed that ascorbic acid can be used as a reducing agent for a redox dye, it is difficult to use ascorbic acid as a reducing agent in practice.

Stabilizing agent: In the present invention, in view of the above, a stabilizer for inhibiting the oxidative decomposition reaction of ascorbic acid is a rutin and/or a rutin derivative. By adding a stabilizer to the oxygen detecting aqueous solution, the oxidative decomposition of ascorbic acid can be effectively suppressed, and the ascorbic acid can be kept in a stable state in the oxygen detecting aqueous solution. As a result, the redox dye can be maintained in a reduced state in an anaerobic state, and the redox dye can be prevented from changing to an oxidized structure, and ascorbic acid can be used as a reducing agent in practice. Further, by using rutin and/or rutin derivatives, the color development of the oxygen detecting solution can be made more vivid, and an oxygen detecting agent excellent in color rendering property can be obtained.

In this regard, rutin is a kind of citrus flavonoid, and its molecular formula is represented by C ₂₇ H ₃₀ O ₁₆ , which is β-rutose (6-O-α-rhamnopyranosidic-D) in the third oxygen of quercetin. -β-glucose) Glycoside. The rutin derivative may, for example, be α-glucosyl rutin or the like. Rutin is one of the natural extracts widely contained in higher plants and vegetables and fruits, and because it is a kind of polyphenol compound, it can achieve superior effects on oxidation prevention, and can effectively inhibit ascorbic acid in an oxygen detecting aqueous solution. Oxidative decomposition. In addition, since rutin is used as a health food or the like, the composition of the oxygen detecting agent used for storing foods and pharmaceuticals is also very good.

The amount of the stabilizer in the oxygen detecting aqueous solution is preferably such that a sufficient amount of the oxidative decomposition reaction of ascorbic acid in the oxygen detecting aqueous solution can be suppressed. Specifically, when the content of ascorbic acid in the oxygen detecting aqueous solution is 100 parts by mass, the content of the stabilizer in the oxygen detecting aqueous solution is preferably in the range of 2 parts by mass to 10 parts by mass, and 4 parts by mass is preferable. The range of 7 quality parts is better, and the 5 quality parts are best before and after. When the content of the ascorbic acid is less than 2 parts by mass, the content of the stabilizer is too small with respect to the content of ascorbic acid, and the effect of sufficient stabilization cannot be obtained. . In addition, even if the 100 parts of the stabilizer for the ascorbic acid is added in an amount of more than 10 parts by mass, the ascorbic acid oxidative decomposition inhibitory effect which is increased in proportion to the amount of the stabilizer is not increased, and the stabilization is unnecessarily consumed. The agent is not good. In the case of a short-term degree of 2 or 3 days, when the stabilizer (rutine) is added in a mass ratio of 2 mass portions to 10 mass portions, the stabilizer is 10 mass portions. Oxidative decomposition of ascorbic acid when added The suppression effect is higher. However, in the case of a long period of one week or more, the 100 parts by mass of ascorbic acid has a higher oxidative decomposition inhibitory effect of ascorbic acid when added in a mass of 2 parts compared to the case of adding 10 parts by mass. From this, it is understood that the oxidative decomposition inhibitory effect of ascorbic acid is not high in proportion to the amount of the stabilizer, and is estimated to be within the above range, and has a sharp peak of an oxidative decomposition inhibitory effect against ascorbic acid before and after the fifth mass portion. Therefore, the content of the stabilizer is preferably adjusted to be in the range of 2 parts by mass to 10 parts by mass in the range of 2 parts by mass to 10 parts by mass, and preferably 4.5 parts by mass in the range of 4 parts by mass to 7 parts by mass. 5.5 is added within the range of the quality department as the best.

Basic substance: In this case, when rutin is used as a stabilizer, since rutin is slightly soluble in water, rutin is first dissolved in an alkaline aqueous solution to prepare a solution, and then mixed with other components. It is preferred to modulate the oxygen detection aqueous solution. The basic substance used for preparing the alkaline aqueous solution in which the rutin is dissolved may, for example, be sodium hydroxide or calcium hydroxide. On the other hand, in the case of using the above α-glucosyl rutin as a stabilizer, since the ruthenium derivative has high solubility in water, it is suitable to use an alkaline substance when modulating the oxygen detecting aqueous solution. good.

Redox dye: The redox dye used in the present invention is a dye which is reduced by ascorbic acid and which is reversibly changed in an oxidized state and a reduced state. Examples of such a coloring matter include methylene blue, new methylene blue, phenosafranine, Lauth's Violet, and methylene green.

In addition, when a coloring matter which is colorless in a reduced state, such as methylene blue or phenolic saffron, is used as the redox dye, it is easy to use meat for the presence or absence of oxygen. It is judged by the eye that it is preferable to use a pigment which cannot be reduced by ascorbic acid. For example, when a redox dye having a blue color in an oxidized state, such as methylene blue, is used, it is preferable to use a red dye such as a red pigment as a dye which cannot be reduced by ascorbic acid. The red pigment is a pigment that is red regardless of whether there is oxygen in the atmosphere. On the other hand, when a redox redox dye which is red in an oxidized state is used, a dye which cannot be reduced by ascorbic acid is preferably used as a dye which exhibits blue or green regardless of the presence or absence of oxygen in the atmosphere.

For example, when these pigments are used together with the above methylene blue, the oxygen detecting aqueous solution can change the color tone as follows due to the presence or absence of oxygen in the atmosphere gas. First, in the anaerobic state, methylene blue is rendered colorless (reduced methylene blue) by the reducing sugar remaining in a reduced state. At this time, the oxygen detecting aqueous solution is red by the above red pigment. On the other hand, in the aerobic state, methylene blue is oxidized to appear blue. At this time, the oxygen detecting aqueous solution is purple to blue. When the redox dye which is colorless in the reduced state is used, the dye which cannot be reduced by the reducing saccharide is added to the oxygen detecting aqueous solution, and the change in the color tone of the oxygen detecting agent accompanying the change in the oxygen content is more distinct. And the presence or absence of oxygen can be easily determined with the naked eye.

2. Oxygen detector

Next, the oxygen detecting agent of the present invention will be described. The oxygen detecting agent is a substance which carries the above oxygen detecting aqueous solution as a carrier.

Carrier: In the present invention, the material constituting the carrier is not particularly limited, and it is preferably an absorbent body which can impregnate the liquid oxygen detecting aqueous solution. As a material constituting such a carrier, for example, an organic polymer material, an alkaline earth metal, cerium oxide or the like can be used. In the present invention, as the material constituting the carrier, in consideration of the absorbability and stability of the oxygen detecting aqueous solution, the organic polymer material is particularly used. The material is suitable. As the organic polymer material, an ion exchange resin or a cellulose material is particularly preferable. Here, the ion exchange resin means an insoluble porous synthetic resin having an acidic group or a basic group which can be ion-exchanged. Further, as the cellulose material, bleached kraft paper is preferred. When the carrier is composed of bleached kraft paper, the oxygen detecting agent formed by the oxygen detecting aqueous solution can be maintained in a good state. In addition, the bleached kraft paper is a bleached paper, and the color of the dye contained in the oxygen detecting aqueous solution such as a redox dye is sharp. Thereby, the change in the color tone of the oxygen detecting agent in color can be made clear with the change in the oxygen content in the atmosphere.

Further, in the present invention, the shape of the carrier is not particularly limited. Depending on the material constituting the carrier, it may have various shapes such as a sheet shape, a tablet shape, and a powder shape. In particular, it is preferable that the type having a sufficient surface area as compared with the volume is suitable and the use property is superior. From this point of view, in the present invention, the shape of the carrier is preferably in the form of a sheet. The carrier has a sufficient surface area as compared with the volume, so that the contact area between the atmosphere gas and the oxygen detecting aqueous solution can be increased, and the oxygen detecting agent can exhibit sufficient oxygen detecting ability in the case of miniaturization.

The thickness of the carrier is preferably 200 μm or more, preferably 200 μm to 500 μm. If the thickness of the carrier is thinner than 200 μm, the oxygen detecting ability of the oxygen detecting agent is lowered because the amount of impregnation of the oxygen detecting aqueous solution is small. Further, in the case where the thickness of the carrier exceeds 500 μm, the sheet-shaped carrier may be damaged by the packaging when it is packaged by the packaging material.

Moisture content: In the oxygen detecting agent of the present invention, after the aqueous solution is carried by the carrier, the aqueous component is dried to a predetermined amount. The moisture content of the oxygen detecting agent is not particularly limited and may be appropriately changed depending on the conditions of use. However, it is the amount of water that the carrier can carry, and the redox pigment. The concentration is such that the amount of water in which the redox reaction can proceed smoothly is suitable. In other words, the concentration of the redox dye in the oxygen-detecting aqueous solution carried by the carrier is adjusted to a concentration at which the redox reaction of the redox dye can proceed smoothly in the presence of other components adjusted to a predetermined amount. It is good. By allowing the redox reaction to proceed smoothly, rapid discoloration responsiveness and vivid color tone can be ensured, and when the oxygen content in the atmosphere changes, it can be immediately detected.

As such a moisture content, for example, the mass portion of the alkaline substance is preferably from 450 to 1050 parts by mass, and preferably from 550 parts to 950 parts by mass. When the water content is from 450 parts by mass to 1050 parts by mass, as described above, the redox reaction of the redox dye can be smoothly carried out in the presence of water and other components which can be carried by the carrier. In particular, when the water content is from 550 mass parts to 950 mass parts, the oxygen concentration detection solution of the appropriate concentration can be carried in a good state for the oxidation reaction of the redox dye, so that the oxygen can be detected quickly. Discoloration responsiveness and vivid tonal changes.

In the oxygen detecting agent produced as described above, when the total mass is 100 mass parts, 10 parts by mass of ascorbic acid to 30 parts by mass, 0.2 parts by mass of the stabilizer, 3 parts by mass, and 0.01 part by mass of the redox pigment are included. The range of 0.1 mass parts is suitable. In addition, when the mass of the entire material is 100 parts by mass, the range of 0.5 mass parts to 3.0 mass parts of the basic substance is preferable. The oxygen detecting agent can cause the redox reaction of the redox dye to proceed smoothly in the presence of ascorbic acid and a stabilizer in the presence of the ascorbic acid, the stabilizer, and the redox dye as the solid components in the above range. Rapid discoloration responsiveness and sharp tonal changes are obtained during oxygen detection. However, the quality of the above "all" means the quality of the "carrier" and the bearer carried by the carrier. The total mass of the total mass of the "oxygen detecting aqueous solution" does not include a packaging material and a deoxidizing agent which are coated with a carrier such as a transparent film described later.

Packaging material: The oxygen detecting agent of the present invention is preferably formed by coating at least a surface portion of the carrier carried by the oxygen detecting aqueous solution with a transparent film (packaging material). By coating the surface of the carrier with a transparent film, even if it contacts a stored substance such as a food, the oxygen detecting aqueous solution does not come into contact with the food or the like, and is therefore hygienic.

As the transparent film used herein, any substance may be used as long as it has a certain strength, and for example, polyethylene, polypropylene, polyvinyl chloride, polystyrene, cellulose acetate, cellophane or the like may be used. film.

Further, the oxygen detecting agent of the present invention may be configured by sealing and enclosing a carrier carried by the oxygen detecting aqueous solution in a flat oxygen detecting agent bag formed of a transparent film. In this way, by sealing and sealing the carrier carried by the oxygen detecting aqueous solution in a flat oxygen detecting bag made of a transparent film, it is possible to prevent the components of the preserved substance such as food from damaging the oxygen detecting function. In other words, when the carrier carried by the oxygen detecting aqueous solution is exposed or partially exposed to the outside, if moisture, oil, alcohol, or the like is present in the food or the like, the substance enters the carrier from the exposed portion, and the color of the oxygen detecting aqueous solution is discolored. And damage the oxygen detection function. Such a problem does not occur because the carrier for carrying the oxygen detecting aqueous solution is sealed and sealed in a flat oxygen detecting bag composed of a transparent film to constitute an oxygen detecting agent.

The transparent film used herein must have oxygen permeability and impermeability to liquids such as water, oil, and alcohol. As such a transparent film, a film made of polyethylene, polypropylene, polyester, polyamide or the like can be used, and a film composed of polyester or polyamide having a small oxygen permeation amount can be opened to be less susceptible to moisture. , It is suitable for use with extremely small pinholes such as alcohol and oil. More specifically, low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) are used as the polyethylene, and non-oriented polypropylene (OPP) or biaxially oriented polypropylene (CPP) is preferably used as the polypropylene. These synthetic resin films can be used not only as a single layer film but also as a laminated film in which different materials are laminated. Examples of the laminated film include non-oriented polypropylene/biaxially oriented polypropylene, non-oriented polypropylene/low density polyethylene, polyethylene terephthalate (PET)/low density polyethylene, and polyparaphenylene. Bilayer film of ethylene dicarboxylate/biaxially oriented polypropylene, and low density polyethylene/non-oriented polypropylene/low density polyethylene, low density polyethylene/biaxially oriented polypropylene/low density polyethylene, double Three or more films of axially oriented polypropylene/non-oriented polypropylene/low density polyethylene.

The oxygen detecting agent of the present invention can be used as an oxygen detecting agent monomer, or can be integrated with a deoxidizing agent and used as a composite deoxidizing agent. In the oxygen detecting agent using the sheet-shaped carrier, by integrating with the deoxidizing agent, it is not necessary to separately enclose the deoxidizing agent and the oxygen detecting agent when the packaging container for food or the like (including the packaging bag) is sealed. The deoxidizer and the oxygen detecting agent can be enclosed at the same time, which solves the complexity in use. Moreover, it is possible to prevent any of the two from being leaked.

The oxygen detecting agent of the present invention and the deoxidizing agent used for the integration are not particularly limited, and those having good functions as a deoxidizing agent may be an organic deoxidizing agent or an iron powder inorganic deoxidizing agent.

As a method of integrating the oxygen detecting agent and the deoxidizing agent, for example, it is considered to enclose the deoxidizing agent in a desired position in the deoxidizer bag, and the oxygen detecting agent is adhered by an appropriate adhesive means. The adhesive means is not particularly limited, and a double-sided adhesive, an adhesive, a paste, or the like can be suitably used.

3. Method for producing oxygen detecting agent

Next, a method of producing the oxygen detecting agent of the present invention will be described. The oxygen detecting agent is produced by modulating the above oxygen detecting aqueous solution and carrying the oxygen detecting aqueous solution.

(1) Modulation method of oxygen detecting aqueous solution

First, a description will be given of a preparation example of an oxygen detecting aqueous solution. When the oxygen detecting aqueous solution is prepared, first, a stabilization solution (A) containing the above stabilizer at a predetermined concentration, an ascorbic acid solution (B) containing ascorbic acid at a predetermined concentration, and, if necessary, added are prepared. An aqueous solution (C) of a dye which cannot be reduced by ascorbic acid is contained at a predetermined concentration, and an aqueous solution (D) containing a redox dye at a predetermined concentration is contained. Then, the oxygen detecting aqueous solution was prepared by sequentially mixing these solutions (A) to (D).

Next, the stabilization solution (A) is mixed with the ascorbic acid solution (B) to prepare an ascorbic acid stabilization solution (E). In the ascorbic acid stabilization solution (E), an aqueous solution (C) containing a pigment which cannot be reduced by reducing sugars is mixed (F) as needed. Then, the oxygen detecting aqueous solution (G) of the present invention is prepared by mixing the thus prepared aqueous solution ((E) or (F)) with the redox dye aqueous solution (D). However, the mixing amount of each of the solutions (A) to (D) is prepared so that the content of each component in the oxygen detecting agent is within the above-described preferable range.

When the oxygen detecting aqueous solution (G) is prepared as described above, the stabilization solution (A) is preferably prepared as described later. First, it is preferable to use "water" as the solvent for the stabilization solution (A), and "water" for the other solutions (B) to (D), so that the affinity of each solution is good. Here, when using rutin as a stabilizer, as described above, since rutin is slightly soluble in water, it is directly in water. Dissolution is difficult. In such a case, rutin is dissolved in an alkaline aqueous solution to become a stabilization solution. Further, when a rutin derivative having high solubility in water is used as a stabilizer, it may of course be directly dissolved in water.

As the alkaline aqueous solution, an aqueous sodium hydroxide solution or an aqueous calcium hydroxide solution can be used. It is preferred to use the aqueous sodium hydroxide solution or the aqueous calcium hydroxide solution in an amount of 0.2% by mass to 0.8% by mass based on the concentration of the aqueous alkaline solution. When the concentration of the alkaline aqueous solution is less than 0.2% by mass, it is difficult to dissolve rutin at normal temperature (20 ° C ± 15 ° C (JIS Z 8703)) or lower. On the other hand, although the concentration of the alkaline aqueous solution exceeds 0.8% by mass, there is no particular problem, but when the alkaline component is infiltrated into the side of the food or the like of the preserved product by the packaging material, there is a case where bitterness or the like affects the taste. .

Further, the stabilizer concentration in the stability solution is preferably from 0.2% by mass to 1% by mass. When the stabilizer concentration is less than 0.2% by mass, the oxidative decomposition of ascorbic acid cannot be suppressed by a small amount of addition, and the amount of the necessary stabilization solution is increased in order to obtain a sufficient stabilization effect of ascorbic acid. As a result, when the stabilizer is dissolved in an alkaline aqueous solution, the amount of the alkaline component in the stabilized aqueous solution exceeds the above range, which is not preferable. On the other hand, when the concentration of the stabilizer in the stabilization solution exceeds 1%, if the amount of ascorbic acid in the aqueous solution is detected by oxygen, the stabilization effect of the stabilizer against ascorbic acid may exceed the peak value, and the solution may be stabilized. On the contrary, the amount of addition of ascorbic acid is low.

(2) Manufacture of oxygen detecting agent

The oxygen detecting aqueous solution prepared as described above is carried by a carrier, and is appropriately dried by making the amount of water within the above range, thereby obtaining an oxygen detecting agent of the present invention. Also, when drying, although it is naturally dry, it is improved by From the viewpoint of productivity, it is also possible to carry out heat drying or vacuum drying.

Hereinafter, the examples and comparative examples are shown to specifically describe the present invention. However, the invention is not limited to the following examples.

[Example 1] 1. Oxygen detection of aqueous solution modulation

The oxygen detecting aqueous solution of the examples was prepared in the following manner.

First, 95.5 g of water (distilled water) and 0.5 g of sodium hydroxide were mixed to prepare a 0.5% by mass aqueous sodium hydroxide solution (alkaline aqueous solution). 100 g of this 0.5% by mass aqueous sodium hydroxide solution was mixed with 0.25 g of rutin to prepare a stability solution having a rutin concentration of 0.2% by mass. Further, as the rutin, rutin trihydrate manufactured by Tokyo Chemical Industry Co., Ltd. was used.

Further, together with the tranquilizing solution, an aqueous solution of ascorbic acid having a concentration of 2% by mass, an aqueous solution of edible red pigment of 0.4% by mass, and an aqueous solution of methylene blue of 0.8% by mass were prepared.

When the respective solutions were prepared in the above manner, first, 10 g of the stabilization solution and 50 g of a 2% by mass aqueous solution of ascorbic acid were mixed to prepare an ascorbic acid stabilization solution. Next, 10 g of a 0.4% by mass aqueous solution of edible red pigment was mixed with the ascorbic acid stabilization solution, and finally 10 g of a 0.8% by mass aqueous solution of methylene blue was mixed as the oxygen detection aqueous solution of Example 1.

2. Manufacture of oxygen detector

Next, the oxygen detecting aqueous solution prepared by the above procedure was impregnated with a filter paper having a width of 15 mm and a length of 50 mm, and dried at 35 ° C for 3 hours to prepare an oxygen detecting agent. At this time, the oxygen detecting agent A is blue. Moreover, the oxygen detecting agent A thus produced is detected by oxygen in the whole mass (the quality of the filter paper and the impregnation of the filter paper after drying) When the mass of the aqueous solution G is 100 mass parts, it is 0.03 mass parts of rutin, 1.25 mass parts of ascorbic acid, 0.63 mass parts of sodium hydroxide, 0.05 mass part of edible red pigment, and methylene blue 0.10 of redox pigment. It is composed of the quality department.

[Example 2]

In Example 2, in addition to the preparation of the stabilization solution, 0.50 g of rutin was added to 100 g of a 5% by mass aqueous sodium hydroxide solution to prepare a stability solution having a rutin concentration of 0.5% by mass. In the same manner as in Example 1, an oxygen detecting aqueous solution was prepared in the same manner to produce an oxygen detecting agent.

[Example 3]

In Example 3, in addition to the preparation of the stabilization solution, 0.75 g of rutin was added to 100 g of a 5% by mass aqueous sodium hydroxide solution to prepare a stabilization solution having a rutin concentration of 0.7% by mass. In the same manner as in Example 1, an oxygen detecting aqueous solution was prepared in the same manner to produce an oxygen detecting agent.

[Example 4]

In Example 4, in addition to the preparation of the stabilization solution, 1.0 g of rutin was added to 100 g of a 5% by mass aqueous sodium hydroxide solution to prepare a stabilization solution having a rutin concentration of 0.10% by mass. In the same manner as in Example 1, an oxygen detecting aqueous solution was prepared in the same manner to produce an oxygen detecting agent.

[Comparative Example]

In the comparative example, an oxygen detecting aqueous solution was prepared in the same manner as in Example 1 except that rutin was not added to a 0.5% by mass aqueous sodium hydroxide solution to produce an oxygen detecting agent.

Oxygen produced in the above Examples 1 to 4 and Comparative Examples The contents of the respective components in the test aqueous solution are shown in Table 1. Further, in Table 1, "Total" is the mass of the entire oxygen detecting aqueous solution prepared in each of the examples and the comparative examples.

〔Evaluation〕

The oxygen detecting agents produced in Examples 1 to 4 and Comparative Examples were used to evaluate the change in color tone after storage for a certain period of time at a high temperature (45 ° C). In the evaluation, first, the oxygen detecting agent obtained in each of the examples and the comparative examples was stored in an oxygen-free atmosphere, and the redox dye was brought into a reduced state by the action of ascorbic acid. Specifically, the oxygen permeability is 10 ml/m2. The KNY (coated vinylidene nylon)/PE bag is sealed with a deoxidizer and an oxygen detecting agent. Hereinafter, the samples prepared in the respective examples are referred to as Samples 1 to 4, and the samples prepared in the Comparative Examples are referred to as comparative samples. These samples were separately stored in a thermostat at 25 ° C, and the atmosphere of each oxygen detecting agent was made to be in an oxygen-free state by a deoxidizing agent. After 24 hours, the color of the oxygen detecting agent was visually confirmed for each sample, and the result was pink to red.

Next, each sample was stored in a 45 ° C thermostatic chamber, and each sample was subjected to a change in color tone accompanied by a different time. Colorimetric colorimeter ZE-2000 was measured. Each measured value (L value, a value, b value, ΔE value) is shown in Table 2. Also, the offset of the L value is shown in Fig. 1. However, the ΔE value is a color difference value expressed as a case where the value before storage in a thermostat at 45 ° C is used as a reference. Further, in Table 2, the number in parentheses indicates the rutin content in the oxygen detecting aqueous solution.

As shown in Table 2 and Fig. 1, when the oxygen detecting agents produced in Examples 1 to 4 were compared with the oxygen detecting agents produced in the comparative examples, the color difference values at 45 ° C were observed. There is little change in (ΔE). This is considered to be because the oxidative decomposition reaction of ascorbic acid can be suppressed by adding rutin to the oxygen detecting aqueous solution, and the change of the redox pigment in the oxygen detecting aqueous solution can be suppressed to an oxidized structure. In other words, it has been confirmed that rutin which can suppress the oxidative decomposition of ascorbic acid in the oxygen detecting aqueous solution can be added as a stabilizer, and an oxygen detecting agent having high heat resistance which is rarely changed even at a high temperature can be obtained. Also, since the color tone change can be reduced even if it is stored at a high temperature, it is considered to be at normal temperature. The storage time can be more stable, and the oxygen detection capability can be maintained even when the atmosphere temperature is high.

Further, as shown in Table 2 and Fig. 1, it is understood that the content of ascorbic acid in the oxygen detecting agent is increased in proportion to the rutin content, and the change in color tone is not reduced. The rutin content in the oxygen detection aqueous solution was increased in the order of Examples 1 to 4. However, the minimum change in color tone was the oxygen detecting agent of Example 2, followed by the oxygen detecting agent of Example 3. Further, when the oxygen detecting agent of Example 1 was compared with the oxygen detecting agent of Example 4, the oxidative decomposition inhibitory effect of ascorbic acid was reversed after being stored in a constant temperature layer at 45 ° C for 3 days and stored for 7 days. From these results, it is understood that if the ascorbic acid content in the oxygen detecting agent is simply increased as described above, the stabilizing effect of ascorbic acid does not become high. In addition, when the rutin concentration in the stabilization solution is about 0.5% by mass, the oxidative decomposition effect of ascorbic acid may be sharply peaked before and after the rutin is 5 parts by mass in the ascorbic acid of 100 mass parts. . Therefore, as described above, it is preferable to add arsenic in a range of 4.5 parts by mass to 5.5 parts by mass for 100 parts by mass of ascorbic acid.

Further, when the coloration of the oxygen detecting agent was visually determined, the color of the oxygen detecting agent of the example in which rutin was added was better than that of the oxygen detecting agent produced in the comparative example, which showed a stronger color. colour. Specifically, the oxygen detecting agent of the comparative example was shown in pink, and the oxygen detecting agents of Example 3 and Example 4 were shown in red. The oxygen detecting agent of Example 1 and Example 2 in which the amount of rutin added was smaller than that of Example 3 and Example 4 exhibited an intermediate color of pink and red. In any case, the color added by the rutin is good, and the color development can be maintained even when stored at a high temperature for a long time.

Further, in the above examples, the example using the rutin derivative was not shown, and the same result was obtained when the rutin derivative was used.

[Industrial Availability]

According to the oxygen detecting agent, the oxygen detecting agent manufacturing method, and the oxygen detecting aqueous solution of the present invention, it contains ascorbic acid, a stabilizer for inhibiting oxidative decomposition reaction of ascorbic acid, and a redox dye which is reduced by ascorbic acid. In the oxygen detecting aqueous solution, ascorbic acid can be stabilized by the stabilizer, and the redox dye can be maintained in a reduced state in an oxygen-free state to prevent the change to an oxidized structure. Thereby, the oxygen detecting agent of the present invention has high heat resistance, can be stored at room temperature, and can maintain excellent oxygen detecting ability without being affected by the atmospheric temperature. Moreover, since it can be stored at normal temperature, the storage cost of the product before shipment can be reduced. Further, it is possible to provide an oxygen detecting agent which exhibits a clear color tone change and rapid color change response depending on the oxygen content change in the atmosphere, and which has excellent color rendering properties, even when it is used in a high-temperature atmosphere such as summer.

Claims (6)

An oxygen detecting agent which is an oxygen detecting agent for supporting an oxygen detecting aqueous solution as a carrier, characterized in that the oxygen detecting aqueous solution contains ascorbic acid, a stabilizer for inhibiting oxidative decomposition reaction of ascorbic acid, and redox property by reduction of ascorbic acid As the coloring matter, the aforementioned stabilizer is rutin and/or rutin derivative. In the oxygen detecting agent according to the first aspect of the invention, wherein the content of the ascorbic acid in the oxygen detecting aqueous solution is 100 parts by mass, the content of the stabilizer is in the range of 2 parts by mass to 10 parts by mass. The oxygen detecting agent according to claim 1, wherein the total mass of the carrier and the oxygen detecting aqueous solution carried by the carrier is 100 parts by mass, and includes 10 parts by mass of ascorbic acid to 30 parts by mass, and the stabilizer is 0.2. The mass portion is up to 3 mass portions, and the redox pigment is 0.01 mass portion to 0.1 mass portion. The oxygen detecting agent according to claim 1, further comprising a dye which cannot be reduced by the reducing sugar. A method for producing an oxygen detecting agent, which is a method for producing an oxygen detecting agent for supporting an oxygen detecting aqueous solution as a carrier, comprising the steps of: dissolving an ascorbic acid stabilizer in a solvent to prepare a stabilization solution; The stabilization solution is mixed with the ascorbic acid solution obtained by dissolving ascorbic acid in a solvent to prepare an ascorbic acid stabilization solution; and the ascorbic acid solution is mixed with the redox pigment solution obtained by dissolving the redox pigment in a solvent. Modulating the oxygen detection solution And a step of carrying the oxygen detecting aqueous solution as a carrier, and as the stabilizer, rutin and/or rutin derivative are used. An oxygen detecting aqueous solution which is an oxygen detecting aqueous solution for an oxygen detecting agent, characterized in that the oxygen detecting aqueous solution contains ascorbic acid, a stabilizer for inhibiting oxidative decomposition reaction of ascorbic acid, and a redox pigment reduced by ascorbic acid, The tranquilizer uses rutin and/or rutin derivatives.