JP2005029263A - Carbon dioxide indicator, package using the same, and method of using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To enable an easy verification of whether or not contents released from an atmosphere of carbon dioxide gas are still usable. <P>SOLUTION: The carbon dioxide gas indicator includes a surface layer having a property of carbon dioxide gas permeability that allows the color-changing time of a pH indicator, when an outer packaging body is unsealed, to match the time by when the contents draw near enough to an unusable state. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention is used in a carbon dioxide gas replacement package for storing contents such as foods, beverages, and medicines for a long period of time, and causes a change in color corresponding to the deterioration of the contents after opening, and the quality of the contents The present invention relates to a method for instructing deterioration, a carbon dioxide indicator used for the method, and a package in which the indicator is disposed.

  Gas replacement packaging is a common method for preserving the contents of food, beverages, medicines, etc. for a long period of time. In this gas replacement packaging, a mixed gas of nitrogen and carbon dioxide is often used as a replacement gas, and the gas replacement packaging is packaged with a packaging material having excellent gas barrier properties.

  When a medical preparation such as a bicarbonate-containing chemical solution is used as the contents, the bicarbonate-containing chemical solution is first stored in a chemical solution container, and the chemical solution container is packaged with carbon dioxide gas in an outer package in a carbon dioxide atmosphere. Yes. Bicarbonate-containing chemicals are chemicals that have the property of losing medicinal properties by releasing carbon dioxide. By this carbon dioxide gas replacement packaging, it is possible to store the carbon dioxide component while maintaining the equilibrium between the bicarbonate component and the carbon dioxide gas and preventing the release of the carbon dioxide gas in the exterior body having excellent gas barrier properties.

  In such a gas replacement packaging, in preparation for a pinhole or a seal failure due to a defect in the packaging material itself, a failure at the time of filling the contents, or an impact in the transportation process such as distribution, for example, A carbon dioxide indicator with a pH indicator, alkali, and solvent impregnated in filter paper, etc. and partially or entirely covered with carbon dioxide permeable plastic is used to immediately detect a decrease in carbon dioxide concentration in the replacement gas. (For example, see Patent Document 1).

  The chemical solution container that contains the bicarbonate-containing chemical solution is formed of, for example, a polyethylene film. For long-term storage, the gas barrier property is insufficient, but the carbon dioxide gas is not released rapidly, and medical treatment is not possible. While being used for an application, the release of carbon dioxide can be sufficiently suppressed. For this reason, it takes a long time from opening the outer package until it is altered so that the bicarbonate-containing chemical solution cannot be used.

However, conventionally, there has been no means for examining how much the bicarbonate-containing solution has changed after the outer package has been opened.
JP-A-64-69951

  The present invention has been made in view of the above circumstances, and an object thereof is to easily confirm whether or not the contents can still be used when released from the carbon dioxide gas atmosphere.

  Another object of the present invention is to maintain the balance between bicarbonate or carbon dioxide component and carbon dioxide contained in the contents, and to open the stored package while preventing the release of carbon dioxide. Another object of the present invention is to provide a method for instructing deterioration due to the release of carbon dioxide gas.

  Still another object of the present invention is to maintain the balance between the bicarbonate or carbon dioxide component contained in the contents and carbon dioxide gas, and to open the stored package while preventing the release of carbon dioxide gas. An object of the present invention is to provide a carbon dioxide gas indicator that can easily confirm the alteration due to the release of carbon dioxide gas in a product.

  Still another object of the present invention is to provide, for example, a container for containing the contents of beverages and medical preparations, and a container in which the container is housed in an exterior body made of a carbon dioxide impermeable material. An object of the present invention is to provide a package in which a carbon dioxide indicator that can confirm the alteration of the contents in the container or the exterior body is arranged by using the exterior body.

  Another object of the present invention is to maintain the balance between the bicarbonate or carbon dioxide component contained in the contents and carbon dioxide gas, and to open the stored package while preventing the release of carbon dioxide gas. An object of the present invention is to provide a method for using a carbon dioxide gas indicator that can easily confirm the alteration due to the release of carbon dioxide gas.

First, the present invention is a method for instructing whether the contents are usable or unusable after opening the package in which the contents are packaged in an exterior body having a carbon dioxide atmosphere.
In the package, together with the contents, a carbon dioxide gas indicator formed by coating an indicator containing a pH indicator with a member having carbon dioxide permeability at least in part,
Provided is a method characterized by instructing that the contents are sufficiently close to an unusable state after opening the exterior body by changing the color tone of the carbon dioxide gas.

Secondly, the present invention is used in a method for instructing whether the contents are usable or unusable after opening the package in which the contents are packaged in an exterior body having a carbon dioxide atmosphere.
In the package, it is arranged together with the contents, and at least a part of the indicator is covered with an indicator containing a pH indicator with a carbon dioxide permeable member,
Provided is a carbon dioxide gas indicator characterized by instructing that the contents have sufficiently approached an unusable state after opening the exterior body by changing the color tone of the carbon dioxide gas.

Third, the present invention is used in a method for indicating whether the contents are usable or unusable after opening the package in which the contents are packaged in an exterior body having a carbon dioxide atmosphere.
In the package, it is arranged together with the contents, and at least a part of the indicator is covered with an indicator containing a pH indicator with a carbon dioxide permeable member,
After opening the outer package, a carbon dioxide indicator that indicates that the contents are sufficiently close to an unusable state by a change in the color tone of the carbon dioxide, and a portion having carbon dioxide permeability that contains the contents A packaging body is provided in which a container containing a carbon dioxide gas is disposed in a carbon dioxide-impermeable outer package having a carbon dioxide atmosphere.

Fourthly, in order to indicate whether the contents are usable or unusable after opening the package in which the contents are packaged in an exterior body having a carbon dioxide gas atmosphere. The body is disposed with the contents, and at least part of the body is covered with an indicator including a pH indicator with a member having carbon dioxide permeability,
Provided is a method of using a carbon dioxide gas indicator, characterized by instructing that the contents are sufficiently close to being in an unusable state after opening the exterior body by changing the color tone of the carbon dioxide gas.

  When using the carbon dioxide gas indicator of the present invention, when the stored package is opened while maintaining the balance between the bicarbonate or carbon dioxide component and carbon dioxide contained in the contents and preventing the release of carbon dioxide, Deterioration due to the release of carbon dioxide in the contents can be confirmed.

The instructing method of the present invention is a method for instructing whether the contents are usable or unusable after opening the package in which the contents are packaged in an exterior body having a carbon dioxide atmosphere,
In the package, together with the contents, arrange a carbon dioxide indicator formed by covering an indicator containing a pH indicator with a member having carbon dioxide permeability at least in part,
After opening the outer package, it is indicated by a change in the color tone of the carbon dioxide gas that the contents are sufficiently close to an unusable state.

  Moreover, the carbon dioxide gas indicator which concerns on this invention is used for the said method.

  Moreover, the package of this invention has the carbon dioxide-impermeable exterior body of a carbon dioxide atmosphere, and the said indicator arrange | positioned in the exterior body.

  Furthermore, the usage method of this invention includes confirming whether the content in a container can be used using the said carbon dioxide gas indicator.

  A preferred carbon dioxide indicator of the present invention is capable of detecting that the content has approached an unusable state from a usable state. An indicator including a pH indicator, and a carbonic acid provided on the indicator. Including the surface layer with gas permeability, the carbon dioxide gas permeability of the surface layer matches the discoloration time of the pH indicator when the exterior body is opened to the time until the content becomes sufficiently unusable. ing.

  As the indicator, a liquid, a tablet, or a printed layer containing a pH indicator can be used.

  The indication part which consists of a liquid and a tablet can be enclosed, for example in the bag formed with the material containing the above-mentioned surface layer. Further, a solvent may be further contained.

  The indicator part which consists of a printing layer can be formed on a support body using the carbon dioxide detection ink composition containing a pH indicator.

  This carbon dioxide indicator is combined with a plastic chemical container containing a portion having carbon dioxide permeability, in which a bicarbonate-containing chemical liquid that is kept in equilibrium with the carbon dioxide atmosphere is contained in a carbon dioxide atmosphere. Can be used.

  In one embodiment of the present invention, the carbon dioxide indicator is made of a plastic including a portion having carbon dioxide permeability, in which a bicarbonate-containing chemical liquid that is kept in equilibrium with the carbon dioxide atmosphere is contained in a carbon dioxide atmosphere. Is used in combination with a chemical solution container, and is formed on a support and a carbon dioxide gas detecting ink composition on the support, and the discoloration time of the pH indicator is sufficient to make the contents unusable. It includes a surface layer having carbon dioxide permeability that matches the time to approach. The carbon dioxide detection ink composition includes a pH indicator, a binder, and a solvent, and at least a part of the surface layer that has carbon dioxide permeability is used for the surface layer.

  Further, a preferable package of the present invention includes the preferable carbon dioxide indicator, and a plastic chemical container including a portion having carbon dioxide permeability in at least a part in which the bicarbonate-containing chemical liquid is accommodated. It arrange | positions in the carbon dioxide-impermeable exterior body which has gas atmosphere.

The surface layer used in the present invention can cover at least a part on the indicating part, and at least a part having carbon dioxide gas permeability is used, and the carbon dioxide gas permeability of the surface layer is the content. For example, it is preferably greater than 50 (ml / m ² · 24 hours) and less than 20000 (ml / m ² · 24 hours), depending on the time until the chemical solution deteriorates.

  Examples of the material for the surface layer used in the present invention include polyamide, polyester, cyclic polyolefin (COC), polyvinyl chloride, polyethylene, and polypropylene.

  For example, by suitably selecting the material of the surface layer and the thickness of the surface layer, the carbon dioxide gas permeability of the surface layer is adjusted, and the discoloration time of the pH indicator is sufficiently close to the state where the contents cannot be used. Can be adjusted to the time of

For example, when low molecular weight polyethylene is used as the material of the surface layer, the carbon dioxide gas permeability is set to 50 (ml / m ² · 24 hours) or more to 500 (ml / m) by setting the thickness to about 20 μm to about 200 μm. ² · 24 hours) or 500 (ml / m ² · 24 hours) or more and less than 20000 (ml / m ² · 24 hours).

  The ink composition for detecting a carbon dioxide gas can further contain an alkaline substance.

  For example, the bicarbonate-containing chemical solution that can be stored in the package of the present invention has the property of releasing the carbon dioxide gas and losing its medicinal properties, so that the equilibrium between the bicarbonate component and the carbon dioxide gas is maintained and the release of the carbon dioxide gas is prevented. While being saved.

  In the case of containing a bicarbonate-containing solution containing 0.1 to 5% by weight of bicarbonate, the carbon dioxide concentration in the outer package is preferably 0.5 to 10% by volume, more preferably 1 to 9% by volume, Furthermore, it is preferably 1 to 7% by volume.

  When a bicarbonate-containing solution containing 5 to 20% by weight of bicarbonate is contained, the carbon dioxide concentration in the outer package is preferably 10 to 90% by volume, more preferably 20 to 80% by volume, and further Preferably, it is 30 to 70% by volume.

  The bicarbonate-containing drug solution may include an additive component that provides at least one of sodium ions and citrate ions.

  Examples of the additive component include sodium chloride, citric acid, and sodium citrate.

  Carbon dioxide gas dissolves in water and exhibits weak acidity. In the ink composition used in the package of the present invention, when the carbon dioxide in the ambient atmosphere is sufficiently present, the pH value is lowered, but the pH value is increased as the carbon dioxide concentration is lowered. The display color of the indicator changes. By observing this display color, the carbon dioxide concentration in the surrounding atmosphere can be detected. If the composition contains an alkaline substance, the change in color tone can be detected more clearly.

  The carbon dioxide atmosphere used in the present invention may be, for example, a gas containing carbon dioxide such as a mixed gas of carbon dioxide and air having an arbitrary mixing ratio is enclosed in the exterior body or, for example, AGELESS G manufactured by Mitsubishi Gas Chemical Co., Ltd. It can be obtained by enclosing a carbon dioxide generating oxygen scavenger in the exterior. In the latter case, the carbon gas concentration in the exterior body can be controlled by adjusting the concentration of a carbon dioxide gas generation source such as oxygen in the exterior body.

  According to the present invention, carbon dioxide gas is provided by providing an indicator having a surface layer having carbon dioxide permeability that matches the time required for the color change of the pH indicator to be sufficiently close to the state in which the contents cannot be used. It is possible to easily confirm the change in content caused by delay with respect to the change in density by judging the change in the display color of the indicator.

  As the pH indicator used in the present invention, the display color is accompanied by a change in color due to a change in pH of the indicator due to a change in the external carbon dioxide concentration, or a change in pH according to a change in the concentration of an alkaline substance. Any color can be used as long as it is accompanied by a color change.

Table 1 below shows preferred pH indicators and their color ranges.

  One preferred pH indicator is metacresol purple because it is easy to handle and changes in color reaction are easily understood.

  For example, when used in a relatively low concentration carbon dioxide atmosphere such as 0.5 to 10% by volume, the display color corresponding to any concentration within this range can be instantly identified visually. It is preferred to use a pH indicator. As such a pH indicator, a combination of two or more pH indicator components can be used.

The combinations of pH indicator components that can be used and the color change of the indicator when the carbon dioxide concentration is relatively low are shown in Table 2 below.

  The carbon dioxide gas detection indicator of the present invention is preferably used for detecting the carbon dioxide gas concentration in a package containing a bicarbonate-containing chemical solution stored in such a low carbon dioxide atmosphere.

  When the carbon dioxide gas detection indicator of the present invention is applied to a package, when the package is opened, the decrease in carbon dioxide concentration due to the release of carbon dioxide gas is instantly visually confirmed by the display color, depending on the degree of alteration of the contents. I can judge. For example, even when used in a relatively low-concentration carbon dioxide atmosphere of about 0.5 to 10% by volume, a color change that can be sufficiently visually identified can occur. For this reason, the alteration of the contents can be easily confirmed by approaching the color when the display color is not carbon dioxide.

  The alkaline substance used in the present invention is preferably composed of any one of alkali hydroxide, alkali carbonate, and alkali hydrogen carbonate.

  The solvent used in the present invention is preferably a solvent that can uniformly and stably dissolve or disperse each component contained in the indicator containing the pH indicator, for example, an aromatic hydrocarbon or an aliphatic hydrocarbon. , Esters, alcohols, water and the like. In particular, at least one of water and alcohol is preferable.

  The ink composition for detecting carbon dioxide gas may further contain a water absorbing agent.

  By blending a water-absorbing agent in the ink composition, it is possible to hold a solvent such as water in the ink layer serving as an indicator, facilitating the absorption of carbon dioxide gas, and to promote the color reaction of the pH indicator. .

  As the water-absorbing agent used in the present invention, a substance having high whiteness and not exhibiting extremely acidic or basic properties when containing a solvent such as water can be desirably used. As such a substance, for example, starch, kaolin, synthetic silica, glass, microcrystalline cellulose, ion exchange cellulose, aluminum silicate, and the like can be used.

  The binder used in the present invention is used for fixing a pH indicator, an alkaline substance, and an absorbent on a support. Examples of such a binder include polyacrylic acid, polyvinyl alcohol, and polyvinyl butyral. , Polyvinyl acetal, polyvinyl acetate, polyurethane, partially saponified vinyl acetate, and the like.

  Moreover, as this binder, what has the property to melt | dissolve or disperse | distribute to a solvent can be selected. For example, when water or alcohol is used as a solvent, it is preferable to use a solvent having a property of being dissolved or dispersed in at least one of water and alcohol.

  Moreover, it is preferable that the carbon dioxide detection ink composition used in the present invention further contains glycerin. This glycerin acts as a moisturizing agent, and can hold a solvent such as water in the ink layer serving as the indicator to facilitate absorption of carbon dioxide gas and promote the color reaction of the pH indicator.

  The pH indicators shown in Table 1 can be determined not only by the change in color tone of the indicator itself, but also by the change in color tone due to color mixing with other color pigments.

  For this purpose, a colorant can be added to the carbon dioxide gas detecting ink composition.

  When a colorant is added and mixed with the color of the carbon dioxide gas detection ink composition, for example, when the change in the color tone of the indicator itself is difficult to visually determine, or when the design is not a desired color tone, It can be changed to a color tone that is easy to visually determine, or a color tone that is desired in design.

  For the same purpose, a colored support other than white can be applied, and an indicator using the carbon dioxide gas detecting ink composition can be provided thereon.

  Examples of colorants include edible red No. 2 (Amaranth), edible red No. 3 (erythrosin), edible red No. 40 (Arla Red AC), edible red No. 102 (New Coxin), edible red No. 104 (Phloxine), edible Red No. 106 (Acid Red) and red colorants such as natural cochineal pigments, edible yellow No. 4 (tartrazine), edible yellow No. 5 (Sunset Yellow FCF), and yellow colorants such as natural red safflower yellow Blue colorants such as Food Blue No. 1 (Brilliant Blue FCF) and Food Blue No. 2 (Indigo Carmine) can be mentioned.

  In addition to adding a colorant to the ink composition, the same change in color tone can be obtained by using a colored support.

  In addition, in order to improve the coatability of other inks, various agents such as surfactants, varnishes, compounds, drying inhibitors, and dryers may be added within a range that does not affect the color development of the carbon dioxide detection ink. Is possible.

  As a method for applying the ink to the support, a printing method such as a screen printing method, an intaglio printing method, a gravure printing method, or a coating method such as roll coating, spray coating, or dip coating is preferably used.

Since the indicator used in the present invention is desired to have a relatively large coating amount of the ink composition and to be constant, it is preferable to use a printing method as the coating method of the ink composition. The preferable ranges of the coating amount and the film thickness vary depending on the printing method employed, but generally, the coating amount is about 0.1 to 20 g / m ² and the film thickness is about 0.1 to 10 μm. This coating amount and film thickness can be preferably adopted by any of the above-described printing methods.

  The indicator having the indicator can be produced by printing the indicator used in the present invention on the exterior body and forming a surface layer so as to cover at least a part of the indicator.

  For example, when a packaging body is processed by continuously printing an indicator on a support, heat sealing, and cutting, gravure printing or flexographic printing is suitable because the support can be wound and supplied.

  As the support, one that does not react with the ink composition and that does not inhibit the coloration of the reagent can be selected. As such a support, for example, paper, synthetic paper, non-woven cloth, synthetic resin film, or the like can be used in accordance with the purpose and use form. The support is also controlled as part of a carbon dioxide permeable surface layer that adjusts the color change time of the pH indicator to the time until the contents are sufficiently close to being unusable when the exterior is opened. Carbon dioxide permeability.

  Moreover, it is preferable that an instruction | indication part consists of an ink layer which has patterns, such as a character and a pattern.

  In particular, when a character is selected as the instruction section, it can also be used as a label printed with a product name or the like. Further, the support may be appropriately colored in order to make the pointing part easy to see.

  As a use form of the carbon dioxide gas indicator used in the present invention, for example, a container made of a gas permeable material containing contents such as carbonated beverages and bicarbonate solution is packaged with an exterior body made of a carbon dioxide impermeable material, A method of placing the exterior body in a carbon dioxide atmosphere and disposing a carbon dioxide indicator in the exterior body can be exemplified.

  More specifically, as a method of arranging the carbon dioxide indicator, for example, when the exterior body is opened with a liquid containing a pH indicator or a tablet containing a pH indicator, the discoloration time of the pH indicator, Application, printing, etc., using a carbon dioxide gas indicator that includes a carbon dioxide gas permeable surface layer that matches the time until it becomes sufficiently unusable, or a carbon dioxide gas detection ink composition that contains a pH indicator on the support And a surface layer having carbon dioxide permeability that matches the time required for the content of the pH indicator formed on the indicator to change to a time when the content is sufficiently close to being unusable. The above ink composition is directly applied to the inner surface of the container by simply bonding the carbon dioxide indicator to the container surface or by using the material constituting the container as a support. An indicator formed by printing, and a surface layer having carbon dioxide gas permeability that matches the time required for the content of the pH indicator formed on the indicator to change sufficiently to the state in which the contents cannot be used. There is a method of providing a carbon dioxide gas indicator having

  The carbon dioxide indicator used in the present invention can be applied to chemicals such as carbonated beverages or bicarbonate-containing solutions that may lose quality and lose their efficacy due to the release of carbon dioxide.

  In addition, the chemical solution container used in the package of the present invention has a single chamber container or a partition wall that has two or more storage chambers that can each independently store a chemical solution and that can communicate between adjacent chambers. A multi-chamber container can be used.

  In the case of a single-chamber container, it is possible to mix magnesium salt and calcium salt in addition to sodium hydrogen carbonate. In that case, citric acid and citrate can be added to prevent precipitation.

  In the case of a multi-chamber container, for example, it has a temporary sealing portion, and this sealing portion can release the space between the chambers by a predetermined impact, so that the solution stored in each chamber can be mixed. As a combination of the chemical solutions respectively accommodated in the subchamber container, a solution containing sodium hydrogen carbonate in the first chamber, a magnesium salt, and optionally a calcium salt in the second chamber can be mentioned. Other combinations include a solution containing sodium bicarbonate, magnesium salt, calcium salt and sodium citrate in the first chamber and a solution containing oxyglutathione in the second chamber. As these magnesium salts, magnesium sulfate and magnesium chloride can be suitably used, and as the calcium salt, calcium chloride can be suitably used.

  Other combinations include a solution containing sodium bicarbonate and sodium citrate in the first chamber and a solution containing oxyglutathione in the second chamber.

  Hereinafter, the present invention will be specifically described with reference to the drawings.

  In FIG. 1, the schematic sectional drawing showing one form of the carbon dioxide gas indicator used for this invention is shown.

As shown in the figure, this carbon dioxide gas indicator has a thickness of 20 to 200 μm, for example, and its carbon dioxide permeability is larger than 500 (ml / m ² · 24 hours) and 20000 (ml / m ² · 24 hours). ) A bag 63 made of less polyethylene film, and a material in which a pH indicator such as metacresol purple and a moisturizing agent are soaked in a filler mainly composed of crystalline cellulose, for example, enclosed in the bag. And a tablet 62 molded from the raw material.

  Moreover, the schematic sectional drawing showing one form of the carbon dioxide gas indicator used for this invention at FIG. 2 is shown.

  As shown in the figure, this carbon dioxide indicator is, for example, metacresol purple in a bag body 64 made of a polyethylene film having a thickness of 20 to 200 μm and a solvent mainly containing propylene glycol, for example, enclosed in the bag body. And a liquid 65 obtained by mixing a pH indicator or the like.

  FIG. 3 is a front view showing an embodiment of the carbon dioxide indicator used in the present invention, and FIG. 4 is a sectional view thereof.

  As shown in the figure, this indicator 10 is an ink composition for detecting carbon dioxide gas, for example, comprising metacresol purple, sodium carbonate, polyvinyl acetal resin, microcrystalline cellulose, and water on both sides of a support 1 made of, for example, a polyethylene terephthalate film. Is provided with an indicator 2 obtained by screen printing in a circular pattern, and the surrounding area is set to the time until the discoloration time of the pH indicator is sufficiently close to the state in which the contents cannot be used. It has the structure enclosed by the surface film 3 which has permeability | transmittance. The indicator part of the indicator is purple in normal air. 3 and 4, the instruction unit 2 is provided on both sides of the support 1, but a configuration in which the instruction unit is provided only on one side may be applied. Moreover, although this indicator is surrounded by the air permeable film 3, it can be used as it is without using the air permeable film 3.

  FIG. 5 is a cross-sectional view showing an embodiment of the carbon dioxide indicator used in the present invention.

  As shown in the figure, this carbon dioxide indicator 70 is an example in which an indicator is provided only on one side, and as a support, for example, a layer 71 having carbon dioxide impermeability made of a film obtained by vapor-depositing silica on a polyester resin, A carbon dioxide detection ink composition comprising, for example, metacresol purple, ortho-cresolphthalein, sodium carbonate, polyvinyl acetal resin, microcrystalline cellulose, and water in a circular pattern on the layer 71 having carbon dioxide impermeability. It consists of, for example, a polyethylene film formed so as to seal the indicator 2 obtained by screen printing and the indicator 2 provided on the carbon dioxide-impermeable layer 71. Carbon dioxide permeability that matches the time required for the discoloration time to sufficiently approach the state in which the contents cannot be used. It consists of that surface layer 73.

Here, the carbon dioxide impermeability means having a carbon dioxide permeability of less than 50 (ml / m ² · 24 hr).

Carbon dioxide permeability means having a carbon dioxide gas permeability of 50 (ml / m ² · 24 hr) or more.

  The carbon dioxide gas indicator 70 detects carbon dioxide through the carbon dioxide gas only from the surface layer 73 side having carbon dioxide permeability, which matches the time required for the color change of the pH indicator to be sufficiently close to the state in which the contents cannot be used. The carbon dioxide gas does not permeate from the support side. For example, using a package outer body or the like as a support, creating a package so that the carbon dioxide-impermeable layer 71 is on the outside, and the controlled carbon dioxide-permeable layer 73 is on the inside, The package can be configured such that the carbon dioxide indicator 70 functions inside the package. The package thus obtained has excellent responsiveness to changes in the atmosphere and excellent carbon dioxide retention, so that the contents can be stored well.

Further, for example, when forming a package, if the carbon dioxide permeability of the layer that should be impermeable to carbon dioxide is higher than 50 (ml / m ² · 24 hr), the carbon dioxide atmosphere in the package cannot be maintained. .

As a resin film having a carbon dioxide gas permeability of 50 (ml / m ² · 24 hr) or less that can be used in the present invention, a silica film is formed on a base film made of a synthetic resin such as a polyester (PET) film or a nylon (Ny) film. And a transparent vapor-deposited film obtained by vapor-depositing alumina and the like, a polyvinylidene chloride (PVDC) film, a polyvinyl alcohol (PVA) film, an ethylene vinyl acetate copolymer (EVOH) film, and the like.

  These films can be used alone or laminated. Moreover, in order to obtain the strength, heat resistance, etc. according to the intended purpose, other resin films can be laminated. For example, a nylon film or the like can be laminated to obtain a piercing strength.

  Examples of the surface layer used in the present invention include polyolefins such as polyethylene film and polypropylene film. Note that low-density polyethylene and unstretched polypropylene have heat-sealing properties and are optimal as a packaging layer.

A support instruction unit is printed, and carbon dioxide permeability ^{50 (ml / m 2 · 24hr} ) or less of the film, the time of the color change time of the pH indicator, until the contents are sufficiently close to unusable As a method of laminating a film having carbon dioxide permeability and other films to be bonded to each other, a known method can be used, for example, dry lamination using an adhesive.

In FIG. 6, the figure showing one form of the gas replacement packaging body concerning this invention is shown. As illustrated, the gas exchange packaging body 20, to carbon dioxide permeability, e.g. 0.910 not housing the chemical liquid and low-density polyethylene container 11 of 0.925 g / cm ^3, similar to the carbon dioxide gas and 3 A configuration in which the indicator 10 is enclosed in an outer package 12 made of a carbon dioxide-impermeable laminated film using a mixed gas 13 of 90 to 99.5% by volume of nitrogen and 0.5 to 10% by volume of carbon dioxide as a replacement gas. Have

  The display color of the indicator indicating unit 2 in the package is yellow when sealed. However, when the package is opened, the carbon dioxide concentration in the package decreases. For this reason, the gas atmosphere around the indicator 10 changes, and the color of the display color of the indicator 2 changes from yellow to brown and further to purple according to the change in pH of the indicator due to the change in the external carbon dioxide concentration. . The time required for the change in the color tone is controlled by adjusting the thickness of the surface layer 3 of the indicator 10 according to the time until the content is sufficiently close to the unusable state, for example. For this reason, it can be easily confirmed whether the contents can be used or not by visually recognizing the change in color tone.

  In FIG. 7, one form of the gas replacement packaging body concerning this invention is shown.

As shown in the figure, the package 30 has a carbon dioxide-permeable container 14 made of, for example, 0.910 to 0.925 g / cm ³ , which is made of carbon dioxide and has a package 14 on its surface. The carbon dioxide gas permeability is adjusted so that the discoloration time of the indicator 2 formed by screen printing and the pH indicator coated on the indicator 2 is sufficiently close to the state in which the contents cannot be used sufficiently. Carbon dioxide indicator 18 having a surface layer 5 having carbon dioxide gas impervious laminated film using a mixed gas 13 of 90 to 99.5% by volume of nitrogen and 0.5 to 10% by volume of carbon dioxide as a replacement gas. It has the structure enclosed with the exterior body 12 which consists of. Moreover, it can also be set as the package which has the structure similar to the package 30 of FIG. 7 except not providing the coating layer 5. FIG.

  In this packaging body 30 as well as the packaging body shown in FIG. 6, it is possible to easily confirm whether the contents can be used or not, by visually recognizing the change in color tone of the display color. .

  Instead of the carbon dioxide indicator 18, the above-described second example of the carbon dioxide indicator can be applied.

  In FIG. 8, the figure showing one form of the gas replacement packaging body concerning this invention is shown.

  In addition to the package shown in FIGS. 6 and 7, the indicator 2 is printed on the exterior body 12 as shown in FIG. 8, or an indicator in which the support 1 provided with the instruction portion 2 is covered with a surface layer is provided on the exterior body 12. It may be used by being integrated with the package by a method such as adhering to the package.

  The package 40 includes an exterior body 12 made of a carbon dioxide-impermeable laminated film, and the discoloration time of the indicator 2 and the pH indicator provided on the inner surface of the exterior body 12 by, for example, screen printing using the exterior body 12 as a support. Is formed of a carbon dioxide gas indicator having a surface layer 6 having carbon dioxide permeability that matches the time until the content is sufficiently close to the unusable state. For example, the packaging body 40 is formed by arranging two laminated films with the indicator 2 inside, and after placing the contents 16 therebetween, nitrogen 90 to 99.5 vol%, carbon dioxide 0.5 to 10 vol. It can be formed by hermetically sealing the periphery of the outer package 12 by heat sealing while replacing with the% mixed gas 13.

  In FIG. 9, the figure showing an example of the structure of the carbon dioxide gas indicator which can be used for one form of the gas replacement packaging body concerning this invention is shown.

  In the case of an indicator in which the indicator 2 is printed using the exterior body 12 as a support, as shown in FIG. 9, the indicator 2 is provided on the inner surface of the gas barrier layer 32 of the carbon dioxide impermeable material 31 constituting the exterior body 12. The inner surface side of the indicator 2 is provided as a surface layer, and the discoloration time of the pH indicator is covered with a protective film 33 having carbon dioxide permeability that matches the time until the content is sufficiently close to the unusable state. Is also possible.

  By adopting a configuration in which the instruction unit 2 is not exposed in this way, the instruction unit 2 is not directly in contact with the container or the contents, and the wear of the instruction unit 2 during the manufacturing process or transportation is prevented. Can do.

  FIG. 8 shows an example in which a carbon dioxide gas indicator is provided on the exterior body. However, considering that the exterior body is discarded after opening, the carbon dioxide indicator is preferably alone in the exterior body, more preferably the contents. It is preferable to arrange | position on the container which can accommodate.

  The package obtained by the method of the present invention can indicate / confirm the time during which the contents are altered, that is, the period during which the contents can be used safely and effectively, by changing the color tone of the carbon dioxide gas indicator. In addition, the package itself has the adhesion, light resistance, and heat resistance because the indicator is completely covered with the surface layer. That is, the printed layer is vulnerable to external impact and easily peeled off. However, in the present invention, since the indicator is covered with the surface layer, there is no fear of peeling. Furthermore, the composition constituting the indicator may contain a component that is altered by light and heat. However, since the indicator is covered with a surface layer, irradiation with light and heat is possible even when these components are used. Those alterations can be reduced.

Reference Examples and Test Examples Reference Examples 1 to 8 are shown below, and the color change with respect to the carbon dioxide content was examined as a test example.

Reference example 1
An ink composition was obtained by finely dispersing an ink composition 1 for detecting carbon dioxide gas having the following composition with a paint conditioner or the like.

Carbon dioxide detection ink composition 1
Metacresol purple 0.1g
Sodium carbonate 1.5g
Polyvinyl acetal resin 17.5g
11g microcrystalline cellulose
70g of water
A JIS standard P 3801 filter paper for chemical analysis having a weight of 140 g / m ² was used as a support, and this was coated by screen printing and dried at 70 ° C. for 1 hour to form an indicator.

Next, a vinylidene chloride coated polyamide film (thickness 25 μm, manufactured by Kojin Co., Ltd .: Ponyle) / low density polyethylene film (thickness 50 μm, density 0.930 g / cm ³ (manufactured by Mitsui Chemicals, Inc .: ULT ZEXX)) The carbon dioxide gas barrier laminated film (carbon dioxide permeability: 0.3 ml / m ² · 24 hours) was used to prepare a bag-like product having an internal volume of 50 ml. The mixed gas of gas, carbon dioxide, and air was sealed with various concentrations of carbon dioxide, and the color change was observed, and the obtained results are shown in Table 3 below.

Reference example 2
In Reference Example 1, the carbon dioxide detection ink composition 1 was changed to the carbon dioxide detection ink composition 2 having the following composition, and the support was changed to a polyester film having a thickness of 12 μm (made by Unitika Ltd .: Emblem). A test package was prepared in the same manner as described above, and the color change was observed. The obtained results are shown in Table 3 below.

Carbon dioxide detection ink composition 2
Metacresol purple 0.1g
Sodium hydroxide 1.0g
Polyvinyl acetal resin 17.5g
11g microcrystalline cellulose
70g of water
Reference example 3
A test package was prepared in the same manner as in Reference Example 1 except that the carbon dioxide detection ink composition 1 in Reference Example 1 was changed to the carbon dioxide detection ink composition 3, and the color change was observed. The obtained results are shown in Table 3 below.

Carbon dioxide detection ink composition 3
Metacresol purple 0.1g
Sodium carbonate 1.5g
Polyvinyl acetal resin 17.5g
78.8g of water
Reference example 4
A test package was prepared in the same manner as in Reference Example 1 except that the carbon dioxide detection ink composition 1 in Reference Example 1 was changed to the carbon dioxide detection ink composition 4, and the color change was observed. The obtained results are shown in Table 3 below.

Carbon dioxide detection ink composition 4
Metacresol purple 0.1g
Sodium carbonate 1.5g
Polyvinyl acetal resin 19.7g
78.8g of water
Glycerin 11g
Reference Example 5
A test package was prepared in the same manner as in Reference Example 1 except that the carbon dioxide detection ink composition 4 in Reference Example 4 was changed to the carbon dioxide detection ink composition 5, and the color change was observed. The obtained results are shown in Table 3 below.

Carbon dioxide detection ink composition 5
Metacresol purple 0.1g
Sodium carbonate 1.5g
Polyvinyl acetal resin 19.7g
11g microcrystalline cellulose
78.8 g of 2- (2-n-butoxyethoxy) ethyl acetate
Glycerin 11g

  As shown in Table 3, when the carbon dioxide gas detecting ink composition used in the present invention is used, a change in color tone that can easily recognize a change in the gas atmosphere is obtained.

Reference Example 6
A test package was prepared in the same manner as in Reference Example 1 except that the carbon dioxide detection ink composition 1 in Reference Example 1 was changed to the following carbon dioxide detection ink composition 6, and the color change was observed. The results obtained were as follows.

Carbon dioxide detection ink composition 6
Cresol red 0.1g
Sodium carbonate 1.5g
Polyvinyl acetal resin 19.7g
78.8g of water
The color developability was reddish brown in an atmosphere with carbon dioxide, and reddish purple in an atmosphere without carbon dioxide.

Reference Example 7
A test package was prepared in the same manner as in Reference Example 1 except that the carbon dioxide detection ink composition 1 in Reference Example 1 was changed to the following carbon dioxide detection ink composition 7, and the color change was observed. The results obtained were as follows.

Carbon dioxide detection ink composition 7
Bromothymol blue 0.1g
Urethane resin 26.1g
61.3g of water
The coloration was blue in an atmosphere with carbon dioxide, and purple in an atmosphere without carbon dioxide.

Reference Example 8
A test package was prepared in the same manner as in Reference Example 1 except that the carbon dioxide detection ink composition 1 in Reference Example 1 was changed to the following carbon dioxide detection ink composition 8, and the color change was observed. The results obtained were as follows.

Carbon dioxide detection ink composition 8
α-Naphtholphthalein 0.1g
Urethane resin 26.2g
11g microcrystalline cellulose
61.3g of water
The coloration was light blue in an atmosphere with carbon dioxide, and blue in an atmosphere without carbon dioxide.

Example Example 1
A polyethylene terephthalate layer having a thickness of 12 μm (manufactured by Unitika Ltd .: “Emblem”) and an adhesive layer provided on this layer (manufactured by Toyo Morton Co., Ltd .: “AD-393 / TCS”), thickness: 5 μm ) And a releasable support sheet (Iwata Label: Varnish coated tack label, 50 μm), and a 20 mm × 20 mm tack seal is prepared, and an ink composition having the following formulation is formed at the center of the polyethylene terephthalate layer surface. A 10 mm × 10 mm circular shape was printed at a thickness of 1 μm by a gravure printing method to form an indicator with a water content of 0.5 g. On the layer where the indicator is formed, a linear low density polyethylene film (LLDPE, thickness 60 μm, carbon dioxide permeability 6900 ml / m ² · 24 hours) is laminated as a surface layer by dry lamination to provide a tack seal indicator Got.

  The structure of the cross section is: support sheet / adhesive layer / polyethylene terephthalate (PET) (12 μm) / indicator ink / LLDPE (60 μm).

Indicator ink formula Metacresol Purple 0.9g
Sodium hydroxide 3.1g
Glycerin 4.5g
100.0 g of water
The obtained tack-seal type carbon dioxide gas indicator is affixed to the side of the suspension 94 of the double bag 90 having a size of about 20 cm × 30 cm, which has a communicating partition wall as shown in FIG. Folded into a laminated film bag of nylon (thickness 15 μm) / polyvinyl alcohol (thickness 18 μm) / polyethylene (thickness 60 μm) approximately 26 × 28 cm, 10% carbon dioxide gas and air Gas replacement packaging with 90% by volume mixed gas was performed to obtain a package having the same configuration as in FIG.

  As shown in the figure, this double bag 90 has a bag shape composed of a pair of films whose peripheral edges are sealed, and the inside of the bag is divided into a first chamber 92 and a second chamber 93. It has a possible partition wall 91. The layer structure of the film is 110 μm LLDPE (made by Mitsui Chemicals), 20 μm PP (made by Mitsui Chemicals), and LLDPE (made by Mitsui Chemicals) in order from the outer layer. Each of the first chamber 92 and the second chamber 93 of the bag contains a chemical solution having the following composition.

Chemical composition of chamber 1 Oxyglutathione 0.09g
Dextrose 0.46g
Sodium chloride 3.32g
Potassium chloride 0.19g
Hydrochloric acid appropriate amount Sodium hydroxide appropriate amount Sterile purified water Amount to make 150 ml of total pH 4.5
Chemical solution composition of chamber 2 Sodium bicarbonate 1.05g
Sodium acetate trihydrate 0.30g
Sodium citrate dihydrate 0.50g
Calcium chloride dihydrate 0.08g
Magnesium chloride hexahydrate 0.10g
Hydrochloric acid appropriate amount Sodium hydroxide appropriate amount Sterile purified water Amount to make 350 ml of total pH 7.8
The chemical solution contained in the first chamber and the second chamber has a pH immediately after mixing of 7.45, and if the pH is in the range of 7.1 to 8.1, it can be used sufficiently and effectively. it can. If this pH exceeds 8.1, there is a problem that the intended effect of the chemical solution cannot be exhibited during use.

  A suspension 94 that can be suspended from a hook or the like is provided at the end of the double back 90 on the first chamber 92 side. Further, at the end portion on the second chamber 93 side, a takeout port 95 communicating with the second chamber 93 and a cap 96 capable of opening and closing the takeout port are provided.

Create a total of seven similar packages, open them simultaneously, break the partition, mix the two liquids, immediately after opening, 30 minutes, 1 hour, 2 hours, 3 hours, 6 hours later After 12 hours, the CO ₂ concentration was measured for a gas containing CO ₂ that was in the space in the chemical solution container and kept in equilibrium with the chemical solution, and the pH of the chemical solution at that time was measured. The results are shown in Table 4 below. The color tone of the indicator at that time is also shown in Table 4 below.

As is apparent from Table 4, the CO ₂ concentration of the gas that maintains equilibrium with the mixed chemical solution in the chemical solution container gradually decreases with time, and after 6 hours have elapsed after opening the package, the CO ₂ concentration Was 0.1% and its pH was 8.1. Further, the indicator part of the indicator, which was yellow immediately after opening, turned brown after 2 hours and changed to blue after 6 hours. Thus, when the indicator was yellow and brown, the pH was 7.7 to 8.0, which was sufficiently usable. Moreover, when it was blue, it turned out that it was in the state (pH 8.1) sufficiently close to the state which cannot be used, or the state which cannot be used (value larger than pH 8.1).

Comparative Example 1
Instead of LLDPE (thickness 60 μm, carbon dioxide permeability 6900 ml / m ² · 24 hours) used as the surface layer in Example 1, LLDPE (thickness 25 μm, carbon dioxide permeability 15000 m / m ² · 24 hours) In the same manner, a tack seal type carbon dioxide indicator was obtained.

Using the obtained tack-seal type carbon dioxide indicator, a package was prepared in the same manner as in Example 1, and the gas CO2 concentration and the pH of the chemical solution present in the space in the chemical solution container were measured in the same manner. The color change of the indicator was observed. The obtained results are shown in Table 5 below.

  As shown in Table 5 above, in Comparative Example 1, since the indicator color tone turns blue in 2 hours, even when the chemical solution can still be used sufficiently (pH 7.9), it is determined that it cannot be used by mistake. There was a disadvantage of doing.

Example 2
Lamination comprising the same LLDPE as in Example 1 (thickness 30 μm), COC (cyclic olefin copolymer, thickness 30 μm (Mitsui Chemicals, Inc .: “Apel”)) and LDPE identical to Example 1 (thickness 30 μm) ^Two films (carbon dioxide permeability of 490 ml / m ² · 24 hours) are overlapped and heat sealed on three sides to create a bag-like material. In this bag, a liquid having the same composition as the ink composition of Example 1 is prepared. After enclosing the product, the remaining one was heat-sealed to obtain a liquid carbon dioxide indicator.

Liquid Indicator Formula Metacresol Purple 0.9g
Sodium hydroxide 3.1g
Glycerin 4.5g
100.0 g of water
Using the obtained liquid carbon dioxide indicator, a package was prepared in the same manner as in Example 1, and the CO ₂ concentration of the gas present in the space in the chemical solution container and the pH of the chemical solution were measured in the same manner. The color change of the indicator was observed. The obtained results are shown in Table 6 below.

  As shown in the above table, the same result as in Example 1 was obtained. When the indicator was yellow and brown, it was found that the chemical solution was sufficiently usable, and when the indicator was blue, the chemical solution was not usable. It was found that the state was sufficiently close to the state (pH 8.1) or not usable (value greater than pH 8.1).

Comparative Example 2
A liquid carbon dioxide indicator was obtained in the same manner using LLDPE (thickness 60 μm, carbon dioxide permeability 6900 m) m ² · 24 hours) instead of the laminated film composed of LLDPE / COC / LLDPE.

Using the obtained liquid content liquid indicator, a package was prepared in the same manner as in Example 1, and the gas CO ₂ concentration and the pH of the chemical liquid present in the space in the chemical liquid container were measured in the same manner. The change in the color of the indicator was observed. The obtained results are shown in Table 7 below.

  In Comparative Example 2, as in Comparative Example 1, since the indicator color changes to blue in 2 hours, even when the chemical solution can still be used sufficiently (pH 7.9), it is determined that it cannot be used by mistake. There was a disadvantage.

Example 3
An ink composition was obtained by finely dispersing a carbon dioxide gas detection ink having the same composition as in Example 1 with a paint conditioner or the like. An analysis filter paper was prepared as a support, and an ink layer was applied to a 1 × 1 cm ² area with a thickness of 1 μm by screen printing on the filter paper, followed by drying at 70 ° C. for 1 hour to form an indicator. .

The filter paper on which the indicator was formed was drawn polypropylene (OPP) (thickness 20 μm (Mitsui Chemicals Co., Ltd .: “B355”)), polyvinyl alcohol (PVA) (thickness 20 μm (Nippon Synthetic Rubber Co., Ltd .: “ Poplon ”) and LLDPE (thickness 20 μm) laminated film (carbon dioxide permeability 490 ml / m ² · 24 hours), sandwiched between two sheets, and sealed on four sides of the film to form a bag (2 × 2 cm ² ) Housed in a carbon dioxide indicator.

  A bicarbonate-containing chemical solution having the following formulation was filled into an ampule container made of LDPE (manufactured by Mitsui Chemicals) having a thickness of 400 μm as a chemical solution container and closed. The obtained ampule was sterilized with a hot water shower.

Bicarbonate-containing chemical composition 1
Sodium bicarbonate 7g
93g of water
pH 7.9
The chemical contained in the ampoule can be used sufficiently safely as a bicarbonate chemical when the pH is in the range of 7.9 to 8.6.

  Next, a carbon dioxide indicator is attached to the surface of the ampoule container using Toyo Morton Co., Ltd. product: “ADG93 / TCS” as an adhesive, and the resulting container is a silica-deposited polyester having a thickness of 12 μm. Put into a bag made of carbon dioxide gas barrier laminated film (carbon dioxide gas permeability 0.3 ml / m 2 · 24 hours) made of a film, a silica-deposited polyester film having a thickness of 12 μm, and LLDPE having a thickness of 25 μm. The inside was replaced with a mixed gas consisting of 50% by volume of carbon dioxide gas and 50% by volume of air and packaged to obtain a package body packed with carbon dioxide gas.

A total of seven similar packages are prepared, and these are opened at the same time, immediately after opening, 1 day, 2 days, 3 days, 4 days, 5 days, and 6 days later. The CO ₂ concentration and pH were measured, and the color change of the indicator was observed. The obtained results are shown in Table 8 below.

As apparent from Table 8 above, the CO ₂ concentration in the gas in equilibrium with the drug solution in the ampoule gradually decreases with time, and after 5 days from opening the package, the CO ₂ concentration is 5 0.0% and its pH was 8.6. Moreover, the indicator part of the indicator, which was yellow immediately after opening, turned brown after 3 days and turned blue after 5 days. Thus, when the indicator is yellow and brown, the pH is 8.1 to 8.5, so that it can be used sufficiently, and when it becomes blue, the pH is 8.6 or more, so it cannot be used. It was found that the condition was close enough (pH 8.6) or not usable (greater than pH 8.6).

Comparative Example 3
Example using a perforated polyethylene bag (2 × 2 cm ² , carbon dioxide permeability cannot be measured because the atmosphere can freely enter and exit) instead of a bag-like product made of an OPP / PVA / LLDPE laminated film In the same manner as in No. 3, a paper print carbon dioxide indicator was obtained.

Using the obtained paper-printed carbon dioxide indicator, seven packaging bodies were prepared in the same manner as in Example 3, and in the same manner as in Example 1, the gas CO ₂ concentration and the chemical solution present in the space in the chemical solution container were used. And the change in color of the indicator was observed. The obtained results are shown in Table 9 below.

  In Comparative Example 3, since the indicator color changes to blue in 4 hours, there is a disadvantage that even if the pH is still 8.1 and the chemical solution can be used sufficiently, it is determined that it cannot be used by mistake. It was.

Example 4
The carbon dioxide gas detection ink was finely dispersed with crystalline cellulose or the like to obtain an ink composition in powder form.

The obtained powder is filled into a sealing bag (2 × 2 cm ² ) obtained using two laminated films similar to those in Example 3, and a carbon dioxide gas indicator in powder form is obtained by sealing all sides. It was.

Using the obtained carbon dioxide gas indicator, seven packaging bodies were prepared in the same manner as in Example 3, and the CO ₂ concentration of the gas present in the space in the chemical solution container and the pH of the chemical solution in the same manner as in Example 3. And the change in color tone of the indicator was observed. The obtained results are shown in Table 10 below.

After confirming that the color of the indicator is yellow, measure the CO ₂ concentration of the gas present in the space in the chemical solution container and the pH of the chemical solution in the same manner as in Example 3 and observe the change in the color tone of the indicator. did. The obtained results are shown in Table 10 below.

As is apparent from the above table, the CO ₂ concentration in the gas in equilibrium with the chemical solution in the one bag gradually decreases with time, and after 5 days from opening the package, the CO ₂ concentration is 5 0.0% and its pH was 8.6. Moreover, the indicator part of the indicator, which was yellow immediately after opening, turned brown after 3 days and turned blue after 5 days. Thus, when the indicator is yellow and brown, the pH is 8.1 to 8.5, so it can be used sufficiently, and when it becomes blue, the pH is 8.6 or more, so it cannot be used immediately. Or was found to be in a state where it cannot be used.

Comparative Example 4
A powdered carbon dioxide indicator was used in the same manner as in Example 4 except that the same porous polyethylene bag (2 × 2 cm ² ) as in Comparative Example 3 was used instead of the two laminated films as in Example 3. Obtained.

Using the obtained carbon dioxide gas indicator, seven packaging bodies were prepared in the same manner as in Example 3, and the CO ₂ concentration of the gas present in the space in the chemical solution container and the pH of the chemical solution in the same manner as in Example 3. And the change in color tone of the indicator was observed. The obtained results are shown in Table 11 below.

    In Comparative Example 3, since the indicator color tone changes to blue in 6 hours, there is a disadvantage that even if the pH is still 8.1 and the chemical solution can be used sufficiently, it is determined that it cannot be used by mistake. It was.

  As shown in the table, in this case, since the indicator color changes to blue in 6 hours, it is erroneously determined that the product cannot be used.

Sectional drawing showing the one aspect | mode of the carbon dioxide indicator used for this invention Sectional drawing showing the one aspect | mode of the carbon dioxide indicator used for this invention Sectional drawing showing the one aspect | mode of the carbon dioxide indicator used for this invention Sectional view of FIG. Sectional drawing showing the one aspect | mode of the carbon dioxide indicator used for this invention The figure showing the one aspect | mode of the gas replacement packaging body concerning this invention The figure which shows the one aspect | mode of the gas replacement packaging body concerning this invention The figure which shows the one aspect | mode of the gas replacement packaging body concerning this invention The figure showing an example of the structure of the carbon dioxide indicator which can be used for the one aspect | mode of the gas replacement packaging body concerning this invention The top view showing the container for chemical | medical solutions used for this invention

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Support body 2,62,65 ... Instruction | indication part 3,5,6 ... Surface layer 10 ... Indicator 11, 14, 16 ... Container for chemical | medical solution 12 ... Exterior body 13 ... Carbon dioxide containing gas

Claims (16)

A method for indicating whether the contents are usable or unusable after opening the package in which the contents are packaged in an exterior body having a carbon dioxide atmosphere,
In the package, together with the contents, a carbon dioxide gas indicator formed by coating an indicator containing a pH indicator with a member having carbon dioxide permeability at least in part,
A method characterized by instructing that the contents are sufficiently close to an unusable state after opening the exterior body by changing the color tone of the carbon dioxide gas.   The content is a bicarbonate-containing chemical solution that is kept in equilibrium with the carbon dioxide atmosphere, and is contained in a plastic chemical solution container including a portion having carbon dioxide permeability, and is disposed in the package. The method according to claim 1, wherein:   The chemical solution container has two or more storage chambers each capable of storing a chemical solution independently, and is composed of a multi-chamber container having a partition wall that can communicate between adjacent chambers, and the first chamber is sodium bicarbonate. The method according to claim 2, wherein the second chamber contains a solution containing sodium sulfate and sodium chloride, and the second chamber contains a solution containing magnesium sulfate or magnesium chloride and glucose.   The chemical solution container has two or more storage chambers each capable of storing a chemical solution independently, and is composed of a multi-chamber container having a partition wall that can communicate between adjacent chambers, and the first chamber is sodium bicarbonate. And a solution containing citric acid, the second chamber contains a solution containing oxyglutathione.   The method according to any one of claims 1 to 4, wherein the indicator is a powder or a printed layer and further contains a humectant.   The method according to claim 1, wherein the indication unit is one of a liquid and a tablet, and further contains a solvent.   The method according to claim 1, wherein the indicator is a printing layer, and is formed on the support using a carbon dioxide detection ink composition containing a pH indicator, a binder, and a solvent. .   The said instruction | indication part is a printing layer, and is formed using the carbon dioxide detection ink composition containing a pH indicator, a binder, and a solvent on a support body. The method according to claim 1.   The method according to claim 8, wherein the support is at least one of a part of the chemical solution container and a support sheet that can be attached to the chemical solution container.   The method according to claim 7, wherein the carbon dioxide gas detecting ink composition further includes at least one of a water absorbing agent and an alkaline substance.   The method according to claim 7, wherein the solvent is at least one of water and alcohol.   The method according to any one of claims 7 to 11, wherein the binder has a property of being dissolved or dispersed in at least one of water and alcohol.   A carbon dioxide indicator used in the method according to claim 1.   The carbon dioxide indicator according to claim 13 and a container containing a carbon dioxide-permeable portion containing the contents are disposed in a carbon dioxide-impermeable exterior body having a carbon dioxide atmosphere. Packaging.   The package according to claim 14, wherein the content of the container is a bicarbonate-containing chemical solution.   The carbon dioxide gas indicator according to claim 13 for indicating whether the contents are usable or unusable after opening the package in which the contents are packaged in an exterior body having a carbon dioxide atmosphere. How to use.

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