JP2007074971A - Oxidative gas indication material and packing vessel with indication means - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an oxidative gas indication material visibly detecting a minute amount of oxidative gases (typically, oxygen, carbon dioxide, sulfur dioxide and the like) invading into a package/a vessel qualitatively and quantitatively with an oxidation reduction pigment converted to a reductant having no trace of reducibility by using fermentation actions of baker's yeast, and a packing vessel with an indication means using the same. <P>SOLUTION: The oxidative gas indication material comprises the oxidation reduction pigment and at least baker's yeast coexisting in a medium. The oxidation reduction pigment is converted to the reductant having no reducibility by the action of the baker's yeast in an anaerobic atmosphere and brought to visible detection of the oxidative gases in a package/vessel. In the packing vessel with the indication means, the oxidative gas indication material is installed at a position where the oxidative gases can invade and inside of the packing/vessel which is brought to be visible from outside. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

 The present invention uses a fermentative action of baker's yeast, and a very small amount of oxidizing gas (typically oxygen invading into a packaging / container by a redox dye converted to a reductant which does not have reductivity as traces. In addition, the present invention relates to an oxidizing gas indicator that can visually detect qualitatively and quantitatively carbon dioxide, sulfur dioxide, and the like, and a packaging container with indicator means using the same.

Foods, chemicals, pharmaceuticals, medical products, precision machine parts, electronic parts, etc. are deteriorated in quality even in a small amount of oxygen, so packaging and containers made of plastic materials that are gas-permeable (gas-impermeable) , And may be abbreviated as “packaging container”). However, the packaging container is deteriorated in quality due to air permeable scratches and the like due to many factors in the manufacturing process including the plastic material.
Therefore, a redox dye that can be reversibly converted into an oxidized form / reduced form is attached to the inside of the packaging container as a reduced form, and an oxygen detection agent by visually recognizing a color change when converted into an oxidized form by invading oxygen, Proposed (see, for example, Patent Document 1 to Patent Document 5) and industrialized.
Redox dyes used in conventional oxygen detectors are methylene blue, neutral red, indigo carmine, acid red, safranin T, phenosafranine, capri blue, nile blue, diphenylamine, xyleneamine, ferroin or N-phenylanthranilic acid (For example, see Patent Documents 1 to 5).

In conventional oxygen detectors, converting redox dyes into reductants in a short time and making them in a detectable state is considered an industrially essential characteristic. (See, for example, Patent Documents 1 to 5). As powerful reducing agents, ascorbic acid, erythorbic acid and their salts, D-arabinose, D-erythrose, D-galactose, D-xylose, D-glucose, D-mannose, D-fructose, D-lactose and other reducing sugars, stannous salts, Metal salts such as ferrous salts are used (see, for example, Patent Documents 1 to 5).
Furthermore, in order to shorten the reduction time of the redox dye, a combination of strong reducing agents such as hydroxides such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, etc. is proposed. (See, for example, Patent Document 3).

Conventional oxygen detectors using redox dyes still have the following problems (a) to (e).
(A) It is difficult (substantially difficult) to make a complete reductant by electrochemically matching the electron transfer during the reduction of the redox dye with the action of a strong reducing agent. Therefore, there are frequent cases where the reducing agent becomes excessive, and the reducing agent remains in the oxygen detecting agent, and it is difficult to remove it.
(B) When there are not enough reducing agents to reduce the redox dye, a reducing agent is added on the way to complete the conversion to the reduced form. However, even in that case, it is difficult to make the amount of the reducing agent to be added optimal, and the reducing agent often remains in the oxygen detector.
(C) If a strong reducing agent remains as a trace amount (in fact, such a case frequently occurs), the invading oxygen reacts with the remaining trace amount of the reducing agent to react with the redox dye. There are many cases where the color does not change and oxygen at the beginning of the intrusion is not detected.
(D) Methylene blue, which is a leuco-type (non-colored) reductant, is highly sensitive to oxygen. Therefore, if a trace amount of a strong reducing agent remains, it reacts with a very small amount of oxygen and is very short (practical). In the meantime, it becomes a blue-colored oxidant, but immediately returns to the non-colored state of the original reductant and does not indicate the presence of invading oxygen.

Patent Document 1 JP 2004-150924 JP Patent Document 2 JP 2004-352329 JP Patent Document 3 JP 2003-327269 JP Patent Document 4 JP 2001-124758 JP Patent Document 5 JP 2000-214152 JP

Non-Patent Document 1 Hisao Yoshii, Yasuyuki Kaneko / Kazuo Yamaguchi “Food Microbiology Handbook”, Gihodo Publishing Co., Ltd., published in 1995 Non-Patent Document 2 “Revised Pan Chemical Note” by Panyuose, Inc., 2004 Patent Literature 3 Yasuo Tanaka and Hiroshi Matsumoto “Baking Chemistry <1> Science of Baking Process” Kogyo Co., Ltd. Non-Patent Literature 4 published by Yasuo Tanaka and Hiroshi Matsumoto “Baking Chemistry <11>"Science of bread process" Kogyo Co., Ltd., published in 1992

Therefore, a method for reducing the highly sensitive redox dye to a very small amount of oxygen has been studied in detail by the present inventor, and several new facts have been found. Two inventions have been invented.

The first aspect of the present invention aims at the following (i) to (vi).
(I) A first object of the present invention is to provide an oxidizing gas indicator for a redox dye of a reductant that does not remain reductive as a trace.
(I) The first aspect of the present invention is also intended to provide an oxidizing gas indicator capable of accurately controlling the conversion of the reduced form of the reduced form of the redox dye.
(iii) The first aspect of the present invention is directed by the color change due to the redox dye and the color density of the reductant which does not remain reductive, with traces of the presence of oxidizing gas at the beginning of entry into the packaging / container. An object of the present invention is to provide an oxidizing gas indicator capable of visually and quantitatively detecting an oxidizing gas.
(Iv) The first aspect of the present invention is visually recognized from the indication of the color change of the redox dye of the reductant, which does not remain reductive as a trace even to the fine shape of the portion where the oxidizing gas penetrates into the packaging / container and the indication by the color density. An object of the present invention is to provide a detectable oxidizing gas indicator.
(V) A first object of the present invention is to provide an oxidizing gas indicator in which a redox dye of a reductant that does not remain reductive as a trace contacts an oxidizing gas.
(Vi) The first aspect of the present invention is a method for producing fine scratches (oxidation) that are substantially inevitable in the process of manufacturing and distributing plastic materials, the process of manufacturing packaging and containers from the materials, and the process of distributing packaging and containers. The second present invention, which also aims to provide an oxidizing gas indicator that can easily and accurately visually detect the presence location and shape of the gas, etc. For the purpose of (b).
(A) A second object of the present invention is to provide a packaging container with an indicating means capable of easily and visually detecting an oxidizing gas entering a packaging / container.
(b) The second aspect of the present invention includes means for detecting without being restricted by the size and form of the packaging container and without being restricted by the conditions (for example, amount) of the invading oxidizing gas. Another object of the present invention is to provide a packaging container with instruction means.

The oxidizing gas indicator according to the first aspect of the present invention comprises a redox dye and at least baker's yeast coexisting in a medium, and the redox dye is reduced by fermenting the baker's yeast in an anaerobic atmosphere. It is converted into a reductant that does not have, and is used for visual detection of the oxidizing gas in the packaging / container.
The packaging container with indicating means according to the second aspect of the present invention is a portion where the oxidizing gas can enter, and is visible from the outside, and the oxidizing gas indicating material (A) below is arranged inside the packaging / container. It is characterized by that.
(A) Oxidizing gas indicator The oxidizing gas indicator is a material in which a redox dye and at least baker's yeast coexist in a medium, and the fermenting action of the redox dye by baker's yeast in an anaerobic atmosphere. Is converted into a reductant having no reducing property, and is used for visual detection of the oxidizing gas in the packaging / container.

According to 1st this invention, the effect represented by following (A)-(E) etc. is acquired.
(A) In an anaerobic atmosphere and in a temperature range below the heat-resistant temperature of the redox dye, the fermenting action of baker's yeast is controlled (for example, resting, life and death, etc.), and the redox dye of the oxidizing gas indicator is used. It can be converted into a reductant in which reducibility does not remain as a trace, and an oxidizing gas such as oxygen can be visually detected by the redox dye of the reductant that does not remain reducible.
(B) Since an oxidizing gas such as oxygen reacts with the redox dye of the reductant that does not remain as traces of reductivity, even if a very small amount of oxidizing gas such as oxygen enters the packaging / container, The presence can be visually detected by the color change of the redox dye and the color density in particular (at the very beginning).
(C) By selecting a redox dye (for example, by selecting a thiazine dye of a leuco-type reductant), even the minute shape of the invading portion of the oxidizing gas (for example, a scratch) is visually recognized as the color density of the redox dye. Can be detected.

(D) It is possible to detect an oxidant gas intrusion site caused by a flaw or the like generated in the manufacturing process / distribution process in the packaging container, and use of the information can eliminate the occurrence of a flaw or the like. For example, it is possible to detect an oxidative gas intrusion portion generated in container manufacturing due to uneven thickness, uneven thickness, distortion due to thermal and physical stress, and the like. For example, it is possible to detect an oxidizing gas intrusion portion (for example, a gas permeation portion due to friction) generated in film formation caused by mechanical friction with a winding roller, a tension control roller, or the like. For example, oxidizing gas intrusion due to poor sealing (due to dirt on the hot melt seal), cutting of the seal (due to excessive heat / pressure load, etc.), stress / strain concentration on the seal due to thermal history, etc. The location can be detected. It is possible to detect an oxidizing gas intrusion portion generated in the packaging container due to a difference in material characteristics (for example, a difference in stretchability and heat shrinkage).
Therefore, metal oxides (for example, aluminum / aluminum oxide) and inorganic substances (for example, silicon dioxide) are deposited or coated, and oxidized gas intrusion points (for example, scratches) generated due to differences in stretchability and heat shrinkage Can be detected visually.
(E) An oxidizing gas intrusion portion (for example, a pinhole or the like) generated in the distribution process due to a handling failure can be visually detected.
According to the packaging container with instruction means according to the second aspect of the present invention, the effects represented by the following (1) and (2) can be obtained in addition to the effects of the first aspect of the present invention.
(1) The packaging container has the ability to perform visual detection with high sensitivity to the intruding oxidizing gas regardless of its form.
(2) The packaging container has the ability to visually detect at the desired level and area for the intruding oxidizing gas.

< Oxidizing gas indicator according to the first invention >
The oxidizing gas indicator according to the first aspect of the present invention comprises a medium in which at least a redox dye (particularly a thiazine dye) and a fermentable baker's yeast coexist, and the redox dye is used in an anaerobic atmosphere. It is converted into a reductant that does not have reducibility by fermentation of yeast (in particular, it is converted to a reductant that does not have reductivity as a trace by controlling the fermenting action), and visual detection of oxidizing gas in packaging and containers is performed. To be served. Note that the anaerobic atmosphere refers to an atmosphere in which there is no air or a minute amount even when air is present.

< Redox dye >:
A thiazine dye (representative), which is a redox dye that reversibly changes the color of oxidized and reduced forms (including changes from no color) in the visible wavelength range (maximum wavelength is about 400 to 670 nm). Specifically, azine dyes such as methylene blue, new methylene blue, toluidine blue, thionine, resorcin blue, etc.) and oxazine dyes (for example, resaludine), indigoid dyes and thioindigoid dyes are suitable. In the following, the term “redox dye” is used in the sense of a redox dye suitable for use in the present invention unless otherwise specified.
In addition, when the reduced form is a leuco-type thiazine dye methylene blue redox dye, it can be easily converted to the reduced form, and the color change and color density can be detected with high sensitivity. (See the actual example below).

< Bread yeast >
As baker's yeast, cerevissia species, xiguuss species, Candidamilleri species, rosei species, Torulopsis celluculosa species, and Torulopsis candida species belonging to Saccharomyces are suitable. Used in an optimal combination with a reducing dye (especially a chromophoric group). The optimal combination is easy to control the conversion of redox dyes into reductants by fermentation of baker's yeast in an aerobic atmosphere, and the color change between redox dyes and reductants is easily visible Thus, a redox dye having a structure that can be converted into an oxidant with a very small amount of oxidizing gas is provided, for example, a combination of a redox dye of thiazine dye and a Saccharomyces cerevissia species.
In baker's yeast in han dough, more than 50 kinds of enzyme action proceed in anaerobic conditions under conditions suitable for the substrate, temperature, time, pH, etc., and the semi-solid dough is expanded by the generated carbon dioxide gas ( For example, see p256 to 258 of Non-Patent Document 1 and p87 to 89 of Non-Patent Document 2).

Nutritional components required for the fermentation of baker's yeast are supplemented from the components contained in baker's yeast itself and the wheat in the dough. Nutritional components of baker's yeast include carbon sources (sugars such as glucose, fructose, sucrose, and maltose), nitrogen sources (typically free amino acids such as aspartic acid, glutamic acid, alanine, arginine, and glycine), inorganic components ( Typically, phosphorus, magnesium, potassium) and vitamins are representative. In the fermentation of baker's yeast with han dough, maltose fermentation is induced by maltase contained in wheat or maltase previously contained in the microbial cell after fermentation that consumes the sugar of the substrate.
Some baker's yeast contains a large amount of protein and vitamin B group in the cells, for example, by taking it from the medium. The following Table 1 shows the vitamin content of published baker's yeast (see Table 2-2 on p64 of Non-Patent Document 4).

In the fermentation of baker's yeast in bread dough under anaerobic atmosphere, higher alcohol production from nitrogen sources has been reported, and Table 2 is published data (Table 4-4 of p135 of Non-Patent Document 3 reference).

In addition, about 38 types of esters, about 19 types of organic acids and about 16 types of carbonyl compounds have been reported in bread fermentation in bread dough (Tables 4-9 and 6-7 of Non-Patent Document 3). See Tables 6-9 and 6-10).
It is involved in electron transfer between baker's yeast fermentation in anaerobic atmosphere and redox dye during reductant conversion (especially electron transfer during excitation of conjugated double bond of chromogen functional group) The present invention has been examined by the present invention as a subject of experiment, and it has been found in the present invention that an electron transfer of excitation upon oxidation from the oxidation of the redox dye occurs due to the fermentation action of baker's yeast.
Furthermore, it has been found in the present invention that conversion of an oxidation-reduction pigment from an oxidized form to a reduced form is also caused by a fermentation action utilizing nutrient components contained in baker's yeast cells. Therefore, even if it is a fermenting action which replenishes a nutrient, conversion can be advanced.
Therefore, the “baker yeast” of the present invention may be a baker's yeast that can be fermented by the nutrient components contained in the cells of the baker's yeast, etc., and the carbon source, nitrogen source, inorganic component, It may be baker's yeast that is fermentable by adding vitamins or the like to the medium. Further, a coenzyme, yeast food or the like may be added to the medium.
If the redox dye is a methylene blue strain of thiazine dye, a leuco-type reductant, it is converted to a highly sensitive reductant by fermentation using nutrient components contained in baker's yeast itself, and a very small amount of oxidation is obtained. Even if the property gas invades, blue shades corresponding to the unevenness and shape of the intrusion portion are shown.

< Type and form of baker's yeast >
Bakers' yeast is roughly classified into raw baker's yeast (ie, raw yeast) containing about 60% or more of moisture and dry baker's yeast (ie, dry yeast) containing about 8% or less of water. Any type of baker's yeast can be used in the present invention.
The use of dry baker's yeast is suitable because the fermentation action is easy to control and the reductant is highly sensitive to oxidizing gases. Active dry baker's yeast also exists in dry baker's yeast, but can be used in the present invention. The dried baker's yeast may be instant dried baker's yeast that has improved the fermentative power for bread dough. Compressed baker's yeast, cream baker's yeast, and freeze-resistant baker's yeast can also be used.

Baker's yeast “ie Bakers Yeast” is generally called “yeast” because the English name of yeast is “Yeast” and the majority of yeast is baker's yeast. (See, for example, Non-Patent Documents 1 to 4), "yeast" and "baker's yeast" are substantially synonymous.

< Medium >
The medium is a liquid such as water, aqueous solution and solvent that can contain redox dye and baker's yeast by dissolution, etc., and may be used in a liquid state and is supported on a carrier such as a gel, semi-solid, or solid. You may use it. There is no restriction | limiting about the characteristic and shape of a support material, For example, natural or a synthetic fiber may be sufficient, and the support material which consists of a polymer absorber etc. may be sufficient.
When the redox pigment and fermentable baker's yeast containing liquid (for example, water, aqueous solution) is adjusted to a pH of about 4 to 8 from the beginning, and the redox pigment is converted to a reductant, it is reduced as a trace. It is easy to convert to a reductant with no remaining properties. In fermentation of bread dough, the bread dough is best at pH 6 and the dough's carbon dioxide retention is best at pH 5.0 to 5.5, and the dough's carbon dioxide retention decreases sharply at pH 5 or less, so the pH is around 5. Be constrained.
However, in the present invention, if it is within the range of about pH 4 to 8, the conversion to the reductant can proceed accurately at a moderate rate that can be controlled. In addition, the temperature range of conversion of the redox dye to the reduced form is the growth temperature of psychrophilic bacteria (for example, upper limit temperature 20 ° C.), mesophilic bacteria (for example 35 ° C.), and heat-resistant bacteria (for example 42 ° C.). Any area may be used.

< Control of conversion to reductant>
When converting the redox dye into a reduced form, if the conversion is completed by controlling the yeast action of baker's yeast (for example, inactivation of the yeast action), the reduced form becomes a reductant that does not remain as traces and is oxidized. Has a high level of sensitivity to sex gases.
As a method of completing the conversion by inactivating the yeast action of baker's yeast, (1) measuring the color change of the redox dye, the time required for the completion of conversion, and the amount of baker's yeast required for the completion of the conversion, based on previous experiments. In this method, conversion is completed based on the measurement data, and (2) color change in the conversion of the redox dye to the reductant is traced with a colorimetric measuring device (for example, molar extinction coefficient). Identifying baker's yeast required for the complete conversion from the change and its working conditions, and a method for completing the conversion based on the data; (3) Electron transfer of the conversion of the redox dye to the reductant Measuring (for example, measurement based on the principle of coulometry), identifying baker's yeast necessary for electron transfer required for excitation at the time of conversion and its operating conditions, and completing the conversion based on the data, (Four There is a method of terminating the conversion by forcibly stopping the fermentation of baker's yeast.
For industrial implementation, the method (4) of terminating the conversion by forcibly stopping the fermentation of baker's yeast is convenient. For example, when methylene blue, a thiazine pigment of a leuco-type reductant, is converted to a reductant, even if the conversion proceeds by fermentation of baker's yeast and becomes a colorless leuco-type reductant, the fermentative action is definitely enforced. By applying the stopping action, the yeast action of baker's yeast can be inactivated completely and easily to complete the conversion.
In addition, the compulsory stopping means of the fermenting action may be any means as long as the fermenting action can be stopped, but it is a temperature that does not affect the function of the redox pigment and the temperature at which the action of baker's yeast is stopped. It is convenient to add an amount of heat (for example, 55 to 95 ° C.).

< Oxidizing gas >
Oxidizing gas causes quality degradation due to oxidation of objects (for example, foods, chemicals, pharmaceuticals, medical products, precision mechanical parts, electronic parts, etc.), and the reduced form of the redox dye is converted into an oxidized form. The gas to be converted. The oxidizing gas is typically oxygen or air containing oxygen, but may be carbon dioxide, sulfur dioxide, or a gas containing one or more of them.

<Packaging / containers >
Packaging and containers are gas barriers used for materials and products that require prevention of quality deterioration due to the presence of oxidizing gas (for example, materials and products such as food, chemicals, pharmaceuticals, medical products, precision machine parts, and electronic parts). A packaging / container made of a material (for example, a gas barrier plastic material and others).
The gas barrier packaging / container is arbitrary in form, and may have a soft or hard structure. The packaging / container needs to be able to visually recognize the color change of the internal redox dye from the outside.

< Packaging container with instruction means of the second invention >
The packaging container with instruction means according to the second aspect of the present invention (the packaging container is synonymous with packaging / container) is a place where an oxidizing gas can enter, and is visible from the outside and is first inside the packaging / container. The oxidizing gas indicator according to the present invention is arranged.
The oxidizing gas indicator is disposed by adhering it in a layer having a desired thickness to a portion of the packaging / container where the oxidizing gas can enter (for example, a corner or the entire surface of the packaging / container). Further, even if an oxidizing gas indicator is stored in a liquid-impermeable gas-permeable bag or the like and stored in a packaging / container, the invading oxidizing gas can be visually detected.

In the present invention, it is in accordance with the object of the present invention, and any modification or partial change and addition is optional as long as the effects of the present invention are not particularly impaired. It is. EXAMPLES Next, although this invention is demonstrated concretely based on an Example, an Example is an illustration and does not restrain this invention.

<Example 1>
Methylene blue (thiazine-based redox dye) and dried baker's yeast (dry yeast) were added to a phosphate buffer diluted aqueous solution to prepare a mixed and uniform test solution. A plurality of test solutions were prepared by changing the quantitative ratio between methylene blue and dried baker's yeast (mainly Saccharomyces cerevissia species) and the concentration in the aqueous solution. As dry baker's yeast, commercially available dry yeast was used.
Methylene blue and dry yeast have a dry yeast weight / methylene blue weight ratio in the range of 4-8.
Each test solution is placed in a plastic bag made of a high gas barrier plastic material to remove air and bubbles as much as possible and the opening is thermally welded and sealed, and the test solution is stored in an anaerobic bag. A test bag was prepared. Each test bag had a growth temperature region (30-35 ° C.) of mesophilic bacteria as a core temperature region, and observed a change in blue color of methylene blue (coloration of oxidized form) with time in different temperature regions in the vicinity.
Over time (about 5 to 8 hours), there were test bags in which the blue color of methylene blue disappeared and became colorless (that is, leuco-type methylene blue) and test bags in which the discolored blue color remained.
From this, when the conversion reaction of the redox dye and the fermentation action of baker's yeast match electrochemically and stoichiometrically, the entire redox dye must be converted into a leuco-type reductant over time. Became clear.

<Example 2> Complete conversion to reductant <br/> Opening portion of test bag in the state where the blue color of the oxidant of Example 1 does not disappear (insufficient conversion to leuco reductant) Was opened, sugar was added, then the air was expelled to make the test bag anaerobic and left in the same temperature range for time. As a result, the blue color of methylene blue disappeared and the whole was converted to a leuco type. That is, the fermentation effect of dry yeast was controlled to make the entire methylene blue leuco.

<Example 3> Oxygen sensitivity of methylene blue reductant The oxygen sensitivity of methylene blue of the reductant (leuco type) obtained in Example 1 was tested. In Example 1, the test bag for the leuco-type reductant was allowed to stand for a long time, and the color change of methylene blue with respect to invading oxygen was observed. The test bag into which oxygen had invaded changed to a clear blue color from the beginning.

<Example 4> Forcible stop of fermentation action An experiment was carried out to forcibly stop the fermentation action of dry yeast by heat-treating the test bag in which sugar was added in excess in Example 2.
The baker's yeast was killed by means such as placing the test bag against hot air from a dryer or immersing it in warm water to forcibly stop the fermentation. A heating temperature of about 80 ° C. and its vicinity was sufficient. Although the experiment was conducted for a heating time of 2 to 20 minutes, the fermentation action was forcibly stopped in about 5 minutes. When baker's yeast was killed by heating, no reductivity remained in the oxidizing gas instruction of the test bag.

<Example 5> Observation of oxygen intrusion into test bag A test bag of a gas barrier plastic bag containing a test solution containing leuco-type methylene blue was prepared. The gas barrier plastic bag was provided with a high gas barrier property by laminating PET on an OPP / CPP laminated film by vapor deposition and forming it from a gas barrier laminate.
In test bag A, the stoichiometric agreement of Example 1 and the leuco-type methylene blue-containing test solution over time are stored, and in test bag B, the fermenting action of Example 4 is compulsory. By stopping, a test solution containing leuco-type methylene blue, which does not have any reductivity derived from fermentation, was stored.
When oxygen invades after the elapse of time, the test bags A and B clearly showed discoloration of methylene blue to blue as a trace of invasion from the very beginning of oxygen invasion. However, in the test bag B, the fine shape due to the blue coloration of methylene blue appeared more clearly.

FIG. 1 is an enlarged explanatory view showing a state in which methylene blue is colored due to oxygen intrusion in the test bag B. FIG. In FIG. 1, the state where the heat-sealed portion of the outer peripheral region on the side surface of the test bag B is colored blue as a square line 1 is shown as a tear line formed in the gas barrier laminate due to heat and pressure. Yes.
In FIG. 1, the combination of the long short line in the vertical direction in the right lateral direction of the square frame line 1, the square point, and the short short line in the diagonally lower right direction shows that the scratch 2 caused by the deformation stress cracking of the test bag B is It appears clearly due to the shade of blue color of methylene blue. Note that the horizontally long quadrilateral frame-like line 3 only shows a region surrounding the deformation stress cracking flaw 2 in the middle.
In FIG. 1, the oblique line 4 on the lower left side and the short line 5, 6, 7 on the lower side indicate vapor deposition cracks originating from “displacement” and “bending” that occurred during processing of the gas barrier laminate. Yes.

FIG. 2 is an enlarged explanatory view of a region of a quadrangular frame-like line 3 surrounding the deformation stress cracking flaw 2 of FIG. In FIG. 2, many flaws 8, 9, 10, 11, and 12 are also clearly displayed around the deformation stress cracking flaw 2 by the shade of blue color of methylene blue.

By the oxidizing gas indicator of the present invention, a small amount of oxidizing gas entering the packaging / container is detected visually and qualitatively and quantitatively at the initial stage of entry (particularly at the very beginning), and the invasion point of the oxidizing gas is detected. Even a minute shape can be visually detected.
Further, the packaging container with instruction means of the present invention gives the packaging / container the ability to visually detect the invading oxidizing gas with high sensitivity regardless of the form.

FIG. 6 is an enlarged explanatory view showing a state where blue color of methylene blue is developed due to oxygen intrusion of the test bag B. FIG. 2 is an enlarged explanatory view of a region surrounding a deformation stress cracking flaw of FIG.

Explanation of symbols

1 Square border line
2
Scratches due to deformation stress cracking
3 Horizontal square frame line surrounding the deformed stress cracking wound
4 Lower left diagonal line
5 Lower horizontal short line
6 Lower horizontal short line
7
Lower horizontal short line
8
Wound
9 wounds
10 wounds
11 wounds
12 wounds

Claims (4)

The redox dye and at least baker's yeast coexist in the medium, and the redox dye is converted into a reductant having no reducing property by the fermenting action of baker's yeast in an anaerobic atmosphere. An oxidizing gas indicator characterized by being used for visual detection of oxidizing gas. A packaging container with indicating means, characterized in that an oxidizing gas indicator of the following (A) is disposed on the inside of a packaging / container so as to be visible from the outside where the oxidizing gas can enter.
(A) Oxidizing gas indicator The oxidizing gas indicator is a material in which a redox dye and at least baker's yeast coexist in a medium, and the fermenting action of the redox dye by baker's yeast in an anaerobic atmosphere. Is converted into a reductant having no reducing property, and is used for visual detection of the oxidizing gas in the packaging / container. The oxidizing gas indicator according to claim 1, comprising one or more of the following features (1) to (7).
(1) The conversion to the reduced form having no reducing property is due to the control of the fermentation action of baker's yeast.
(2) The baker's yeast is cerevissia species, xiguuss species, Candidamilleri species, rosei species, Torulopsis celluculosa species and Torulopsis species belonging to Saccharomyces
It consists of one or more candida species.
(3) The redox dye is a thiazine dye whose reduced form is a leuco type.
(4) The oxidizing gas is composed of one or more of oxygen, carbon dioxide and sulfur dioxide or a gas containing them.
(5) The baker's yeast comprises one or plural kinds of dry baker's yeast, active dry baker's yeast, instant dry baker's yeast, fresh baker's yeast, cream baker's yeast, freezing-resistant baker's yeast, and compressed baker's yeast.
(6) The liquid of the medium is adjusted to pH 4-8.
(7) The packaging / container is made of a gas barrier plastic. 4. The oxidizing gas indicator according to claim 3, comprising one or more of the following features (i) to (ii).
(I) The control of the fermentation effect of the baker's yeast consists of cessation of the fermenting action of the baker's yeast or death / activation.
(Ii) The control of the fermenting action of the baker's yeast consists of stopping the fermenting action by heat load on the baker's yeast in a temperature range where the fermenting temperature of the baker's yeast is lower than the heat resistance temperature of the redox dye.