JP5920844B2 - Oxygen detection agent, method for producing oxygen detection agent, and oxygen detection aqueous solution - Google Patents

Description

  The present invention relates to an oxygen detector that enables a change in the amount of oxygen in the atmosphere to be visually recognized by a change in color tone, a method for producing the oxygen detector, and an oxygen detection aqueous solution.

  When storing foods and medicines, oxygen in the atmosphere oxidizes the foods and medicines and degrades the quality of the foods and medicines. Therefore, in order to prevent quality degradation during storage, foods and pharmaceuticals, etc. are placed in a packaging container (including packaging bags) together with an oxygen scavenger and sealed, and the oxygen in the packaging container It has been practiced to store foods and pharmaceuticals in an oxygen-free state (for example, an oxygen concentration of 0.1% or less) by absorbing oxygen.

  In recent years, it has been performed to enclose an oxygen detector together with an oxygen scavenger in a packaging container and detect the presence or absence of oxygen in the packaging container by the oxygen detecting agent. The oxygen detector makes it possible to visually recognize the presence or absence of oxygen in the hermetic packaging container by changing the color tone. The user can easily confirm whether or not food, medicine, etc. are stored in an oxygen-free state based on the color tone exhibited by the oxygen detector.

  This type of oxygen detector is generally configured to include a reducing substance and a redox dye having different colors in an oxidized state and a reduced state (for example, “Patent Document 1” and “Patent Document”). 2 ”). The reducing substance is used to keep the redox dye in a reduced state when the atmosphere is in an oxygen-free state. The oxygen detector detects oxygen in the atmosphere using a mechanism in which the redox dye held in a reduced state is oxidized by oxygen in the atmosphere and changes color. Therefore, the oxygen detector is required to have a clear color tone change (color change) and a quick color change responsiveness accompanying a change in the amount of oxygen in the atmosphere. Therefore, in Patent Document 1 described above, a change in color tone exhibited by the oxygen detecting agent in the reduced state and the oxidized state is made clearer by using a pigment such as red food that is not reduced by the reducing substance.

Japanese Patent No. 2580157 JP 2007-3259 A

  However, conventionally, oxygen detectors have low heat resistance, and when stored at high temperatures (for example, temperatures above normal temperature, 35 ° C., etc.), the oxygen detection ability decreases, and the color tone changes when the amount of oxygen in the atmosphere changes. However, there was a problem that the color became unclear and the color development also decreased.

  One cause of the decrease in oxygen detection ability during high-temperature storage is deterioration of reducing substances. Conventionally, reducing saccharides have been used as reducing substances. However, reducing sugars turn brown at high temperatures. When the reducing saccharide is browned, the color change of the oxygen detecting agent is also browned, so that the color tone change becomes unclear. Further, when the reducing group of the reducing saccharide is consumed with the browning reaction, it becomes difficult to keep the redox dye in a reduced state. As a result, in the oxygen detector, a part of the redox dye may have an oxidized structure. In this case, even when oxygen is detected, the change in color tone is unclear, and the color developability may be lowered or the color change response may not be obtained. For this reason, conventionally, storing oxygen detectors at a low temperature (for example, 10 ° C. or lower) before shipment prevents browning of reducing sugars and prevents deterioration of oxygen detection ability of oxygen detectors. Was.

  On the other hand, Patent Document 2 also proposes using ascorbic acid as a reducing substance. Ascorbic acid does not cause a browning reaction, unlike reducing sugars. However, ascorbic acid has lower heat resistance than reducing saccharides and is easily oxidatively decomposed when heat is applied. Ascorbic acid gradually undergoes oxidative decomposition when stored at room temperature for a long period of time, making it difficult to keep the redox dye in a reduced state, and the oxygen detection ability of the oxygen detector is There is a problem of deterioration.

  Therefore, the present invention has a high heat resistance, can be stored at room temperature, has good color development, and can maintain an excellent oxygen detection ability regardless of the ambient temperature. It aims at providing a manufacturing method and oxygen detection aqueous solution.

  As a result of intensive studies, the present inventors have achieved the above object by employing the following oxygen detector, method for producing oxygen detector, and oxygen detection aqueous solution.

  The oxygen detection agent according to the present invention is an oxygen detection agent in which an oxygen detection aqueous solution is supported on a carrier, the oxygen detection aqueous solution comprising ascorbic acid, a stabilizer that suppresses an oxidative decomposition reaction of ascorbic acid, and ascorbine It contains a redox dye that is reduced by an acid, and rutin and / or a rutin derivative is used as the stabilizer.

  The oxygen detection agent which concerns on this invention WHEREIN: When content of ascorbic acid in the said oxygen detection aqueous solution is 100 mass parts, it is preferable to contain the said stabilizer in the range of 2 mass parts-10 mass parts.

  In the oxygen detection agent according to the present invention, when the total mass of the carrier and the oxygen detection aqueous solution carried on the carrier is 100 parts by mass, the ascorbic acid is 10 parts by mass to 30 parts by mass, and the stabilizer is 0 parts by mass. 2 to 3 parts by mass, preferably 0.01 to 0.1 parts by mass of the redox dye.

  The oxygen detector according to the present invention preferably further includes a dye that is not reduced by the reducing saccharide.

  The method for producing an oxygen detecting agent according to the present invention is a method for producing an oxygen detecting agent in which an oxygen detecting aqueous solution is supported on a carrier, wherein a stabilizing solution is prepared by dissolving an ascorbic acid stabilizer in a solvent. A step of preparing an ascorbic acid stabilization solution by mixing the stabilization solution and an ascorbic acid solution in which ascorbic acid is dissolved in a solvent; and dissolving the ascorbic acid solution and the redox dye in the solvent A step of preparing an oxygen detection aqueous solution by mixing the oxidized redox dye solution and a step of supporting the oxygen detection aqueous solution on a carrier, and using rutin and / or a rutin derivative as the stabilizer. Features.

  The oxygen detection aqueous solution according to the present invention is an oxygen detection aqueous solution for an oxygen detection agent, comprising ascorbic acid, a stabilizer that suppresses the oxidative decomposition reaction of ascorbic acid, and a redox dye that is reduced by ascorbic acid; And rutin and / or rutin derivatives are used as the stabilizer.

  According to the oxygen detector, the oxygen detector manufacturing method, and the oxygen detection aqueous solution according to the present invention, ascorbic acid, a stabilizer that suppresses the oxidative degradation reaction of ascorbic acid, and a redox dye that is reduced by ascorbic acid Including. Therefore, ascorbic acid can be stably held by a stabilizer in an oxygen detection aqueous solution, and the redox dye can be held in a reduced state in an oxygen-free state to prevent the change to an oxidized structure. Can do. Thereby, the oxygen detection agent according to the present invention has high heat resistance, can be stored at room temperature, and can maintain excellent oxygen detection ability regardless of the ambient temperature. Moreover, since the storage at normal temperature is possible, the product storage cost before shipment can be reduced. Furthermore, even when used in a high-temperature atmosphere such as in summer, it is possible to provide an oxygen detector that exhibits a vivid color tone change and a quick color change response in response to changes in the amount of oxygen in the atmosphere, and has good color development. It becomes possible.

It is a figure which shows the color tone change of the oxygen detection agent which concerns on this invention.

  Hereinafter, embodiments of the present invention will be described. The oxygen detection agent according to the present invention is obtained by supporting an oxygen detection aqueous solution on a carrier, and the change in the oxygen amount in the atmosphere can be visually recognized by changing the color tone according to the change in the oxygen amount in the atmosphere. Is.

1. First, the oxygen detection aqueous solution will be described. The oxygen detection aqueous solution according to the present invention is an aqueous solution containing ascorbic acid, a stabilizer that suppresses the oxidative degradation reaction of ascorbic acid, and a redox dye that is reduced by ascorbic acid. And / or a rutin derivative.

Ascorbic acid: Ascorbic acid includes L-form and D-form. In the present invention, L-form L-ascorbic acid is mainly used. L-ascorbic acid is widely used as an antioxidant for food additives, and can be used safely as a component of an oxygen detector enclosed in a packaging container together with food and the like. The ascorbic acid content in the oxygen sensing aqueous solution is adjusted so as to be sufficient to keep all the redox dyes in the reduced structure in the oxygen sensing aqueous solution. In the present invention, holding in a reduced state means holding all redox dyes in a reduced structure.

  Ascorbic acid is easily oxidized by various oxidizing agents. In the present invention, utilizing this property, ascorbic acid is used as a reducing agent for maintaining the redox dye in a reduced state. Ascorbic acid is a relatively stable substance in a dry state, but gradually becomes colored and decomposes when it absorbs moisture. The oxygen detector makes it possible to visually recognize a change in the amount of oxygen in the atmosphere as a change in color tone by utilizing a change in color accompanying a redox reaction of the redox dye. In order to react with the redox dye and oxygen in the atmosphere, the presence of appropriate moisture is required as a reaction site. Therefore, when ascorbic acid is used as a reducing agent, ascorbic acid is always placed in an environment where moisture exists, so it is unstable even at room temperature and easily oxidatively decomposes. For this reason, conventionally, it has been proposed that ascorbic acid can be used as a reducing agent for redox dyes, but in reality it has been difficult to use ascorbic acid as a reducing agent.

Stabilizer: The present invention is characterized by using rutin and / or a rutin derivative as a stabilizer for suppressing the oxidative degradation reaction of ascorbic acid in view of the above circumstances. By adding a stabilizer to the oxygen detection aqueous solution, oxidative decomposition of ascorbic acid can be effectively suppressed, and ascorbic acid can be kept stable in the oxygen detection aqueous solution. As a result, it becomes possible to keep the redox dye in a reduced state in an oxygen-free state and prevent the redox dye from changing to an oxidized structure, and actually use ascorbic acid as a reducing agent. Made it possible. Furthermore, by using rutin and / or a rutin derivative, the color of the oxygen detection solution can be made clearer, and an oxygen detector excellent in color developability can be obtained.

Here, rutin is a kind of citrus flavonoid. The molecular formula is represented by C ₂₇ H ₃₀ O ₁₆ , which is a glycoside in which β-lutinose (6-O-α-L-rhamnosyl-D-β-glucose) is bound to the oxygen at the 3-position of quercetin. Examples of rutin derivatives include α-glucosyl-rutin. Rutin is one of the natural extract components widely contained in higher plants, vegetables and fruits, and since it is a kind of polyphenol, it has an excellent antioxidant effect, and ascorbic acid is oxidized in an oxygen sensing aqueous solution. It is possible to effectively suppress decomposition. In addition, rutin is sometimes used as a health food and the like, and thus is a very preferable component as a constituent component of an oxygen detector used for storing food and pharmaceuticals.

  The content of the stabilizer in the oxygen detection aqueous solution is preferably a sufficient amount that can suppress the oxidative decomposition reaction of ascorbic acid in the oxygen detection aqueous solution. Specifically, when the content of ascorbic acid in the oxygen detection aqueous solution is 100 parts by mass, the stabilizer is preferably contained in the oxygen detection aqueous solution in a range of 2 parts by mass to 10 parts by mass. Part-7 mass parts is more preferable, and it is most preferable to set it as around 5 mass parts. When the ascorbic acid content is 100 parts by mass, if the stabilizer content is less than 2 parts by mass, the stabilizer content is small relative to the ascorbic acid content, and sufficient stabilization is achieved. The effect is not obtained, which is not preferable. Even if the stabilizer is added in an amount exceeding 10 parts by mass with respect to 100 parts by mass of ascorbic acid, the effect of suppressing oxidative degradation of ascorbic acid is not increased in proportion to the amount of stabilizer added. This is not preferable because the agent is wasted. When compared with the case where 2 parts by mass of a stabilizer (rutin) is added to the case where 10 parts by mass is added to 100 parts by mass of ascorbic acid in the short term of about a few days, the stabilizer When 10 parts by mass is added, the effect of inhibiting oxidative degradation of ascorbic acid is higher. However, when viewed for a long period of one week or longer, the effect of suppressing the oxidative degradation of ascorbic acid is higher when 2 parts by mass is added than when 10 parts by mass is added with respect to 100 parts by mass of ascorbic acid. . Thus, the oxidative degradation inhibitory effect of ascorbic acid does not increase in proportion to the added amount of the stabilizer, but a value that becomes a peak with respect to the oxidative degradation inhibitory effect of ascorbic acid around 5 parts by mass within the above-mentioned range. It is estimated that there is. Therefore, the content of the stabilizer is preferably added in the range of 2 to 10 parts by mass, preferably in the range of 4 to 7 parts by mass, with respect to 100 parts by mass of ascorbic acid. More preferably, it is most preferable to add within the range of 4.5 parts by mass to 5.5 parts by mass.

Basic substance: Here, when rutin is used as a stabilizer, rutin is slightly soluble in water. Therefore, after preparing a stabilized solution in which rutin is dissolved in an alkaline aqueous solution, it is mixed with other components. Thus, it is preferable to prepare an oxygen detection aqueous solution. As a basic substance used when preparing the alkaline aqueous solution which dissolves rutin, sodium hydroxide or potassium hydroxide can be mentioned, for example. On the other hand, when α-glucosyl-rutin described above is used as a stabilizer, the rutin derivative has high solubility in water, and thus a basic substance may not be used when preparing an oxygen detection aqueous solution.

Redox dye: The redox dye used in the present invention is a dye that is reduced by ascorbic acid and reversibly changes coloration between an oxidized state and a reduced state. Examples of such pigments include methylene blue, new methylene blue, phenosafranine, rous violet, and methylene green.

  In addition, when a dye that exhibits colorlessness in a reduced state, such as methylene blue or phenosafranine, is used as the redox dye, it is preferable to use a dye that is not reduced by ascorbic acid in order to make it easier to visually determine the presence or absence of oxygen. For example, when using a redox pigment that exhibits blue in an oxidized state such as methylene blue, it is preferable to use a red pigment such as red food as a pigment that is not reduced by ascorbic acid. Crimson is a pigment that exhibits a red color regardless of the presence or absence of oxygen in the atmosphere. On the other hand, when using a redox dye that exhibits red in an oxidized state, such as phenosafranine, it is preferable to use a dye that exhibits blue or green as a dye that is not reduced by ascorbic acid, regardless of the presence or absence of oxygen in the atmosphere. .

  For example, when these dyes are used together with the above methylene blue, the oxygen detection aqueous solution changes the color tone as follows depending on the presence or absence of oxygen in the atmospheric gas. First, in the anoxic state, methylene blue is colorless (leucomethylene blue) because it is held in a reduced state by reducing saccharides. At this time, the oxygen detection aqueous solution exhibits a red color due to the red pigment. On the other hand, in the aerobic state, methylene blue is oxidized and colored blue. At this time, the oxygen detection aqueous solution exhibits purple to blue. In this way, when using a redox dye that becomes colorless in the reduced state, a dye that is not reduced by reducing saccharides is added to the oxygen detection aqueous solution, so that the change in the color tone of the oxygen detection agent accompanying the change in the amount of oxygen can be further improved. It is possible to clearly determine the presence or absence of oxygen with the naked eye.

2. Next, the oxygen detection agent according to the present invention will be described. The oxygen detection agent is obtained by supporting the above-described oxygen detection aqueous solution on a carrier.

Carrier: In the present invention, the material constituting the carrier is not particularly limited as long as it is an absorber that can be impregnated with a liquid oxygen detection aqueous solution. As a material constituting such a carrier, for example, an organic polymer material, an alkaline earth metal, silicon dioxide, or the like can be used. In the present invention, an organic polymer material is particularly preferable as the material constituting the carrier in consideration of the absorbability and stability of the oxygen detection aqueous solution. The organic polymer material is particularly preferably an ion exchange resin or a cellulose material. Here, the ion exchange resin is an insoluble and porous synthetic resin having an acidic group or a basic group capable of performing ion exchange. Moreover, as a cellulose material, it is preferable that it is Sarashi kraft paper. If it is the support | carrier which consists of Sarashi kraft paper, oxygen detection aqueous solution can be hold | maintained in a preferable state as an oxygen detection agent. Further, since the Sarashi kraft paper is a bleached paper, the coloring of the dye contained in the oxygen detection aqueous solution such as a redox dye becomes clear. Thereby, the change in the color tone of the oxygen detector can be made clearer as the oxygen amount in the atmosphere changes.

  In the present invention, the shape of the carrier is not particularly limited, and various shapes such as a sheet shape, a tablet shape, and a powder shape can be used depending on the material constituting the carrier. In particular, a form having a sufficient surface area relative to the volume is preferable, and a form excellent in handleability is preferable. From such a viewpoint, in the present invention, the shape of the carrier is more preferably a sheet shape. Since the carrier has a sufficient surface area relative to the volume, the contact area between the atmospheric gas and the oxygen sensing aqueous solution can be increased, and even when the oxygen sensing agent is miniaturized, sufficient oxygen sensing ability is exhibited. Can do.

  The thickness of the carrier is preferably 200 μm or more, more preferably 200 μm to 500 μm. When the thickness of the carrier is thinner than 200 μm, the amount of impregnation of the oxygen detection aqueous solution is reduced, so that the oxygen detection ability of the oxygen detection agent is lowered. Moreover, when the thickness of the carrier exceeds 500 μm, the certainty of packaging when the sheet-like carrier is packaged with the encapsulating material may be impaired.

Moisture content: In the oxygen detection agent according to the present invention, the oxygen detection aqueous solution is supported on the carrier, and then dried so that the moisture content becomes a predetermined amount. The water content of the oxygen detector is not particularly limited and can be appropriately changed according to the use conditions. However, it is preferable that the amount of water is such that the amount of water can be supported on the carrier, and the concentration is such that the oxidation-reduction reaction of the oxidation-reduction dye is smoothly performed. That is, the concentration of the redox dye in the oxygen sensing aqueous solution supported on the carrier is such that the redox reaction of the redox dye is smoothly performed in the presence of other components adjusted to a predetermined amount. It is preferable to adjust the amount of water so that By smoothly performing the oxidation-reduction reaction, it is possible to ensure quick discoloration responsiveness and clear color tone change, and when the amount of oxygen in the atmosphere changes, it can be immediately detected.

  As such a moisture content, it is preferable that it is 450 mass parts-1050 mass parts with respect to 100 mass parts of basic substances, for example, Most preferably, it is 550 mass parts-950 mass parts. When the water content is 450 parts by mass to 1050 parts by mass, as described above, it is the amount of water that can be supported on the carrier, and in the presence of other components, the redox reaction of the redox dye is performed smoothly. be able to. In particular, when the water content is 550 parts by mass to 950 parts by mass, an oxygen detection aqueous solution having a concentration suitable for the oxidation reaction of the redox dye can be supported on the support in a good state, and at the time of oxygen detection It is possible to obtain a quick color change response and a clear color tone change.

  In the oxygen detection agent manufactured as described above, when the total mass is 100 parts by mass, ascorbic acid is 10 to 30 parts by mass, the stabilizer is 0.2 to 3 parts by mass, and oxidation is performed. It is preferable to contain a reducing pigment in the range of 0.01 parts by mass to 0.1 parts by mass. Moreover, when a basic substance is included, it is preferable that the basic substance is included in the range of 0.5 to 3.0 parts by mass when the total mass is 100 parts by mass. The oxygen detector contains ascorbic acid, a stabilizer and a redox dye as solid components within the above ranges, so that the redox reaction of the redox dye can be smoothly carried out in the presence of ascorbic acid and a stabilizer. It is possible to obtain a quick color change response and a clear color tone change upon oxygen detection. However, the “total” mass refers to the total mass of the mass of the “carrier” and the mass of the “oxygen detection aqueous solution” carried on the carrier, and covers the carrier such as a transparent film described below. It does not contain packaging materials or oxygen scavengers.

Packaging material: The oxygen detection agent of the present invention preferably has a structure in which at least the surface of a carrier carrying an oxygen detection aqueous solution is covered with a transparent film (packaging material). This is because by covering the surface of the carrier with a transparent film, the oxygen-detecting aqueous solution does not come into contact with food even if it is in contact with a substance to be preserved such as food, so that it is hygienic.

  Any transparent film can be used as long as it has a certain strength. For example, a film made of polyethylene, polypropylene, polyvinyl chloride, polystyrene, cellulose acetate, cellophane, or the like can be used.

  The oxygen detector of the present invention may be configured such that a carrier carrying an oxygen detection aqueous solution is hermetically sealed in a flat oxygen detector bag made of a transparent film. In this way, by sealingly sealing the carrier carrying the oxygen detection aqueous solution in the flat oxygen detection agent bag made of a transparent film, it is possible to prevent the oxygen detection function from being impaired by the components of the preserved substance such as food. Can do. That is, when the carrier carrying the oxygen detection aqueous solution is exposed to the outside or partially exposed, if moisture such as food, oil, alcohol, etc. are present, these enter the carrier from the exposed part, The color of the oxygen detection aqueous solution changes, and the oxygen detection function is impaired. Such a problem does not occur when the carrier carrying the oxygen sensing aqueous solution is hermetically sealed in a flat oxygen sensing agent bag made of a transparent film to constitute the oxygen sensing agent.

  The transparent film used here needs to be oxygen permeable and impermeable 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. However, a film made of polyester, polyamide, or the like having a small amount of oxygen permeation is hardly affected by moisture, alcohol, oil, or the like. It is preferable to use a very small pinhole. More specifically, low density polyethylene (LDPE) and linear low density polyethylene (LLDPE) are preferably used as polyethylene, and unstretched polypropylene (OPP), biaxially stretched polypropylene (CPP), etc. are preferably used as polypropylene. These synthetic resin films are used not only as a single layer film but also as a laminated film in which films of different materials are laminated. As these laminated films, three or more layers such as OPP / CPP, OPP / LDPE, PET / LDPE, PET / CPP, etc., LDPE / OPP / LDPE, LDPE / CPP / LDPE, CPP / OPP / LDPE, etc. Film.

  The oxygen detector according to the present invention may be used alone, or may be integrated with the oxygen absorber and used as a composite oxygen absorber. In a sheet-like oxygen detecting agent using a sheet-like carrier, the oxygen-absorbing agent is integrated with the oxygen-absorbing agent so as to be enclosed in a packaging container such as food (including packaging bags). It is not necessary to separately enclose the oxygen detector and the oxygen detector, and the oxygen scavenger and the oxygen detector can be enclosed at the same time, thereby eliminating the complexity of handling. Moreover, any one of the enclosure leakages can be prevented.

  The oxygen detector according to the present invention and the oxygen absorber used in an integrated manner are not particularly limited, and may be an organic oxygen absorber as long as it functions well as an oxygen absorber. However, it may be an iron powder-based inorganic oxygen scavenger.

  As a method for integrating the oxygen detector and the oxygen absorber, for example, it is conceivable to attach the oxygen detector to a desired position of the oxygen absorber bag in which the oxygen absorber is sealed by an appropriate application means. The sticking means is not particularly limited, and for example, a double-sided pressure-sensitive adhesive tape, an adhesive, a paste, or the like is preferably used.

3. Next, a method for producing an oxygen detector according to the present invention will be described. The oxygen detection agent is manufactured by preparing the above-described oxygen detection aqueous solution and supporting the oxygen detection aqueous solution.

(1) Preparation method of oxygen detection aqueous solution First, the preparation example of oxygen detection aqueous solution is demonstrated. When preparing the oxygen detection aqueous solution, first, a stabilizing solution (A) containing the above-mentioned stabilizer at a predetermined concentration, an ascorbic acid aqueous solution (B) containing ascorbic acid at a predetermined concentration, and as required An aqueous solution (C) containing a dye that is not reduced by ascorbic acid added at a predetermined concentration and an aqueous redox dye solution (D) containing a redox dye at a predetermined concentration are prepared. And oxygen detection aqueous solution is prepared by mixing these solutions (A)-(D) in order.

  Next, the stabilization solution (A) and the ascorbic acid aqueous solution (B) are mixed to prepare an ascorbic acid stabilization solution (E). The aqueous solution (C) containing the pigment | dye which is not reduce | restored with a reducing saccharide | sugar as needed is mixed with this ascorbic acid stabilization solution (E) (F). And the oxygen detection aqueous solution (G) which concerns on this invention is prepared by mixing the aqueous solution ((E) or (F)) prepared in this way, and redox dye aqueous solution (D). However, the mixing amount of each solution (A)-(D) is prepared so that the content of each component in the oxygen detector is within the preferred range described above.

  As described above, when preparing the oxygen sensing aqueous solution (G), the stabilizing solution (A) is preferably prepared as follows. First, “water” is preferably used as the solvent of the stabilizing solution (A). This is because the solvents of the other solutions (B) to (D) are also “water” and have good affinity when mixing the solutions. Here, when rutin is used as a stabilizer, as described above, rutin is slightly soluble in water, so it is difficult to directly dissolve it in water. In this case, a solution obtained by dissolving rutin in an alkaline aqueous solution is used as a stabilizing solution. Of course, when a rutin derivative having high solubility in water is used as a stabilizer, it may be dissolved directly in water.

  As the alkaline aqueous solution, a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution can be used. Regardless of whether an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution is used, the concentration of these alkaline aqueous solutions is preferably 0.2% by mass to 0.8% by mass. When the concentration of the alkaline solution is less than 0.2% by mass, it becomes difficult to dissolve rutin at room temperature (20 ° C. ± 15 ° C. (JIS Z 8703)). On the other hand, there is no particular problem even if the concentration of the alkaline aqueous solution exceeds 0.8% by mass. However, when the alkaline component leaches out from the packaging material or the like to the side of food or the like that is a preserved product, Since it may affect, it is not preferable.

  Moreover, it is preferable that the density | concentration of the stabilizer in a stabilization solution is 0.2 mass%-1 mass%. When the concentration of the stabilizer is less than 0.2% by mass, the addition of a small amount cannot suppress the oxidative degradation of ascorbic acid, and the stabilization solution necessary for obtaining a sufficient stabilizing effect of ascorbic acid The amount of increases. As a result, when the stabilizer is dissolved in the alkaline aqueous solution, the amount of the alkaline component in the stabilized aqueous solution may exceed the upper limit of the above range, which is not preferable. On the other hand, when the concentration of the stabilizing agent in the stabilizing solution exceeds 1% by mass, the peak value of the ascorbic acid stabilizing effect by the stabilizing agent is exceeded in consideration of the amount of ascorbic acid in the oxygen detection aqueous solution. Depending on the addition amount of the stabilizing solution, the ascorbic acid stabilizing effect may be reduced.

(2) Production of oxygen detector The oxygen detector aqueous solution prepared as described above is supported on a carrier and dried appropriately so that the amount of water falls within the above-described range, whereby the oxygen detector according to the present invention is obtained. can get. In addition, although drying may be performed by natural drying, it is preferably performed by heat drying or vacuum drying from the viewpoint of improving productivity.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the present invention is not limited to the following examples.

1. Preparation of Oxygen Detection Aqueous Solution The oxygen detection aqueous solutions of Examples were prepared as follows.
First, 95.5 g of water (distilled water) and 0.5 g of sodium hydroxide were mixed to prepare a 0.5 mass% sodium hydroxide aqueous solution (alkaline aqueous solution). 100 g of this 0.5% by mass aqueous sodium hydroxide solution and 0.25 g of rutin were mixed to prepare a stabilized solution having a rutin concentration of 0.2% by mass. The rutin used was rutin trihydrate manufactured by Tokyo Chemical Industry Co., Ltd.

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

  Among the solutions prepared as described above, first, 10 g of the stabilizing solution and 50 g of a 2 mass% ascorbic acid aqueous solution were mixed to prepare an ascorbic acid stabilizing solution. Next, 10 g of 0.4% by mass reddish aqueous solution was mixed with this ascorbic acid stabilization solution, and finally 10 g of 0.8% by mass methylene blue aqueous solution was mixed to obtain the oxygen detection aqueous solution of Example 1.

2. Production of Oxygen Sensing Agent Next, an oxygen sensing aqueous solution prepared by the above steps was impregnated into a filter paper having a width of 15 mm and a length of 50 mm and dried at 35 ° C. for 3 hours to produce an oxygen sensing agent. At this time, the oxygen detection agent A was blue. Moreover, the oxygen detector A manufactured in this way has a total mass (mass of the mass of the filter paper and the mass of the oxygen detection aqueous solution G impregnated in the filter paper after drying) of 100 parts by mass. 0.03 parts by mass of rutin, 1.25 parts by mass of ascorbic acid, 0.63 parts by mass of sodium hydroxide, 0.05 parts by mass of red food, and 0.10 parts by mass of methylene blue which is a redox pigment It has a configuration.

  In Example 2, when preparing the stabilization solution, 0.50 g of rutin was added to 100 g of 5 mass% sodium hydroxide aqueous solution, and the stabilization solution having a rutin concentration of 0.5 mass% was added. Except that it was prepared, an oxygen detection aqueous solution was prepared in the same manner as in Example 1 to produce an oxygen detection agent.

  In Example 3, when preparing the stabilization solution, 0.75 g of rutin was added to 100 g of 5 mass% sodium hydroxide aqueous solution, and the stabilization solution having a rutin concentration of 0.7 mass% was prepared. Except that it was prepared, an oxygen detection aqueous solution was prepared in the same manner as in Example 1 to produce an oxygen detection agent.

  In Example 4, when preparing the stabilization solution, 1.0 g of rutin was added to 100 g of 5% by mass aqueous sodium hydroxide solution to obtain a stabilization solution having a rutin concentration of 0.10% by mass. Except that it was prepared, an oxygen detection aqueous solution was prepared in the same manner as in Example 1 to produce an oxygen detection agent.

Comparative example

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

  Table 1 shows the content of each component in the oxygen detection aqueous solutions produced in Examples 1 to 4 and Comparative Examples. In Table 1, “Total” indicates the mass of the entire oxygen detection aqueous solution prepared in each Example and Comparative Example.

[Evaluation]
Using the oxygen detectors produced in Examples 1 to 4 and Comparative Examples, evaluation was made regarding changes in color tone when stored for a certain period of time at a high temperature (45 ° C.). When performing the evaluation, first, the oxygen detectors obtained in the respective Examples and Comparative Examples were stored in an oxygen-free atmosphere, and the redox dye was brought into a reduced state under the action of ascorbic acid. More specifically, a KNY (vinylidene coated nylon) / PE bag having an oxygen permeability of 10 ml / m ² · day was sealed with an oxygen detector and one oxygen detector. Hereinafter, samples prepared for each example are referred to as Sample 1 to Sample 4, and samples prepared in Comparative Examples are referred to as comparative samples. Each of these samples was stored in a constant temperature bath at 25 ° C., and the atmosphere of each oxygen detector was made oxygen-free by a deoxidizing agent. After the lapse of 24 hours, the color of the oxygen detection agent was visually observed for each sample, and the color changed from pink to red.

  Next, each sample was stored in a 45 ° C. thermostat, and the change in color tone with time for each sample was measured with a color measurement color difference meter ZE-2000 manufactured by Nippon Denshoku Industries Co., Ltd. Table 2 shows each measured value (L value, a value, b value, ΔE value). FIG. 1 shows the transition of the L value. However, the ΔE value indicates a color difference value based on a value before being stored in a 45 ° C. constant temperature bath. In Table 2, the number in parentheses indicates the rutin content in the oxygen detection aqueous solution.

  As shown in Table 2 and FIG. 1, the oxygen detectors manufactured in Examples 1 to 4 have a color difference value (ΔE) when stored at 45 ° C. when compared with the oxygen detectors manufactured in Comparative Examples. It can be seen that there is little change in. This is because the addition of rutin in the oxygen detection aqueous solution can suppress the oxidative degradation reaction of ascorbic acid and suppress the oxidation-reduction dye in the oxygen detection aqueous solution from changing to an oxidized structure. It is thought that it was made. That is, by adding rutin, which suppresses oxidative degradation of ascorbic acid, as a stabilizer in the oxygen detection aqueous solution, it is confirmed that an oxygen detection agent with high heat resistance with little color change can be obtained even when stored at high temperatures. It was done. In addition, even when stored at high temperatures, the change in color tone can be reduced, so it can be stored more stably at room temperature, and oxygen detection capability can be maintained even when the ambient temperature is high. It is thought that.

  Further, as shown in Table 2 and FIG. 1, it can be seen that the change in color tone does not decrease in proportion to the increase in the rutin content with respect to the ascorbic acid content in the oxygen detector. The rutin content in the oxygen detection aqueous solution increases in the order from Example 1 to Example 4. However, the change in the color tone was the least in the oxygen detector of Example 2, and then in the oxygen detector of Example 3. Moreover, when the oxygen detector of Example 1 and the oxygen detector of Example 4 are compared, the oxidative degradation inhibitory effect of ascorbic acid is observed after 3 days storage in a 45 ° C. constant temperature layer and after 7 days storage. Was reversed. From these results, it can be seen that, as described above, simply increasing the rutin content relative to the ascorbic acid content in the oxygen detector does not increase the ascorbic acid stabilizing effect. Based on the above results, the rutin concentration in the stabilizing solution is about 0.5% by mass, and the peak value of the oxidative degradation effect of ascorbic acid is about 5 parts by mass with respect to 100 parts by mass of ascorbic acid. You can see that it exists. Therefore, from the result, as described above, it is most preferable to add rutin in the range of 4.5 parts by mass to 5.5 parts by mass with respect to 100 parts by mass of ascorbic acid.

  Furthermore, when the color of the oxygen detector is judged visually, the oxygen detector of the example with the addition of rutin has a better color and shows a darker color than the oxygen detector produced in the comparative example. It was. Specifically, the oxygen detection agent of the comparative example showed a pink color, whereas the oxygen detection agents of Examples 3 and 4 showed a red color. The oxygen detectors of Examples 1 and 2 in which the amount of rutin added was small compared to Examples 3 and 4, exhibited a color intermediate between pink and red. In any case, the color was better when rutin was added, and it was possible to maintain a clear color even when stored at a high temperature for a long time.

  In addition, in the above-mentioned Example, although the example using a rutin derivative is not shown, the same result was obtained also when the rutin derivative was used.

  According to the oxygen detector, the oxygen detector manufacturing method, and the oxygen detection aqueous solution according to the present invention, ascorbic acid, a stabilizer that suppresses the oxidative degradation reaction of ascorbic acid, and a redox dye that is reduced by ascorbic acid Including. Therefore, ascorbic acid can be stably held by a stabilizer in an oxygen detection aqueous solution, and the redox dye can be held in a reduced state in an oxygen-free state to prevent the change to an oxidized structure. Can do. Thereby, the oxygen detection agent according to the present invention has high heat resistance, can be stored at room temperature, and can maintain excellent oxygen detection ability regardless of the ambient temperature. Moreover, since the storage at normal temperature is possible, the product storage cost before shipment can be reduced. Furthermore, even when used in a high-temperature atmosphere such as in the summer, the oxygen detector has a vivid color tone change and a quick color change response according to a change in the amount of oxygen in the atmosphere, and has excellent color development. Can be provided.

Claims (6)

An oxygen detection agent having an oxygen detection aqueous solution supported on a carrier,
The oxygen detection aqueous solution includes ascorbic acid, a stabilizer that suppresses the oxidative decomposition reaction of ascorbic acid, and a redox dye that is reduced by ascorbic acid,
As the stabilizer, rutin and / or a rutin derivative is used.   The oxygen detection agent of Claim 1 which contains the said stabilizer in the range of 2 mass parts-10 mass parts, when content of ascorbic acid in the said oxygen detection aqueous solution is 100 mass parts.   When the total mass of the carrier and the oxygen detection aqueous solution supported on the carrier is 100 parts by mass, ascorbic acid is 10 to 30 parts by mass, and the stabilizer is 0.2 to 3 parts by mass. The oxygen detector according to claim 1 or 2, comprising 0.01 part by mass to 0.1 part by mass of the redox dye.   The oxygen detection agent according to any one of claims 1 to 3, further comprising a dye that is not reduced by the reducing saccharide. A method for producing an oxygen sensing agent comprising an oxygen sensing aqueous solution supported on a carrier,
Preparing a stabilizing solution by dissolving a stabilizer of ascorbic acid in a solvent;
Mixing the stabilization solution and an ascorbic acid solution in which ascorbic acid is dissolved in a solvent to prepare an ascorbic acid stabilization solution;
Mixing the ascorbic acid solution and a redox dye solution in which a redox dye is dissolved in a solvent to prepare an oxygen detection aqueous solution;
Supporting the oxygen sensing aqueous solution on a carrier;
With
A method for producing an oxygen detector, wherein rutin and / or rutin derivatives are used as the stabilizer. An oxygen sensing aqueous solution for an oxygen sensing agent,
Ascorbic acid, a stabilizer that suppresses the oxidative degradation reaction of ascorbic acid, and a redox dye that is reduced by ascorbic acid,
An oxygen detection aqueous solution characterized by using rutin and / or a rutin derivative as the stabilizer.

Images