JP2007333742A - Carbon dioxide gas indicator and package provided with carbon dioxide gas indicator - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To easily confirm the occurrence of pin holes and defective seal. <P>SOLUTION: This carbon dioxide gas indicator using an ink composition for detecting carbon dioxide gas containing one or more types of pH indicators, a binder, and a solvent and capable of easily observing the change of coloration of an indication part by the concentration of carbon dioxide gas and a carbon dioxide gas permeable plastic container for chemicals in which a bicarbonate-containing chemical is contained are packaged, replaced with gas, in the atmosphere of carbon dioxide gas. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a carbon dioxide gas indicator for detecting that a substituted gas atmosphere in a gas replacement packaging for storing food, beverages, medicines and the like for a long period of time is maintained, and a package in which the carbon dioxide gas indicator is arranged. About.

  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 packaging is performed with a packaging material having excellent gas barrier properties.

  In this way, the contents can be stored for a long period of time by performing gas replacement packaging using a packaging material having excellent gas barrier properties. However, if a pinhole or seal failure occurs due to a defect in the packaging material itself, a failure in filling the contents, or an impact in the transportation process such as distribution, etc., the atmosphere in which the gas replacement packaging is performed changes. However, the contents may be corrupted or altered, and there is a risk that the contents may be distributed without being aware of the change in the atmosphere of the gas replacement package.

  In this way, there is no means to confirm the occurrence of pinholes and seal defects even when gas replacement packaging is performed using packaging materials with excellent gas barrier properties, and the contents are reliably stored in the gas replacement packaging atmosphere. I didn't know if it was.

  As a means for examining whether or not the gas replacement packaging atmosphere is maintained, for example, a method of detecting the carbon dioxide concentration in the replacement gas is conceivable.

  As a means for detecting the concentration of carbon dioxide, for example, Japanese Patent Application Laid-Open No. 64-69951 discloses a carbon dioxide indicator in which a filter paper is impregnated with a pH indicator, an alkali, and a solvent. However, such a carbon dioxide gas indicator has a drawback that long-term stability cannot be obtained.

  In addition, Japanese National Publication No. 5-506088 discloses a medical carbon dioxide monitor formed into a film using a pH indicator, a quaternary cation as an alkali, a polymer, and a plasticizer. Has the disadvantage that it takes time to create the indicator part.

  The present invention has been made in view of the above circumstances, and a first object of the present invention is to store a container for storing contents such as food, beverages and medicines, or an outer package made of a gas barrier material. It is an object of the present invention to provide a package in which a carbon dioxide indicator that can confirm the state of the carbon dioxide atmosphere in the container or the exterior body is disposed.

  The second object of the present invention is that the state of the carbon dioxide gas atmosphere in a container for storing contents such as foods, beverages, and medicines, or in a package formed by storing this container in an exterior body made of a gas barrier material. An object of the present invention is to provide an ink composition for detecting a carbon dioxide gas for printing an indicating section that can be confirmed.

  The third object of the present invention is to provide a carbon dioxide gas atmosphere in a container that contains contents such as food, beverages, and medicines, or in a package that contains this container in an outer package made of a gas barrier material. The object is to provide a carbon dioxide indicator whose state can be confirmed.

  Furthermore, a fourth object of the present invention is to provide a carbon dioxide gas atmosphere in a container that contains contents such as food, beverages, and medicines, or in a package that contains this container in an outer package made of a gas barrier material. The object is to provide a pinhole detection method for checking the state and detecting the occurrence of pinholes.

  The present invention firstly uses a support, an anchor coat layer provided on the support, and an ink composition for detecting carbon dioxide containing a pH indicator, a binder, and a solvent on the anchor coat layer. The formed indicator part and a carbon dioxide gas indicator having an overcoat layer provided so as to cover the indicator part are arranged in a carbon dioxide-impermeable exterior body having a carbon dioxide atmosphere. Provide packaging.

  Secondly, the present invention provides a support, an indicator formed using an ink composition for detecting carbon dioxide containing a pH indicator, a binder, and a solvent, and an overcoat provided so as to cover the indicator. An indicator for detecting carbon dioxide characterized by comprising a coating layer.

  According to the present invention, the change in the carbon dioxide gas concentration in the atmosphere in the package is detected by observing the change in the color tone of the pH indicator of the ink composition to be used. You can easily check the quality.

  The package of the present invention includes an exterior body, a carbon dioxide gas atmosphere, a carbon dioxide gas indicator, a plastic chemical solution container having carbon dioxide gas permeability at least partially, and the container. A bicarbonate-containing solution.

  The carbon dioxide gas indicator of the present invention is capable of detecting the carbon dioxide gas concentration, and is formed using a support and a carbon dioxide gas detecting ink composition on the support, and the display color according to the change in the carbon dioxide gas concentration. Has an instruction section that changes.

  According to the pinhole detection method of the present invention, the carbon dioxide detection indicator is disposed in a carbon dioxide-impermeable exterior body having a carbon dioxide atmosphere to form a package, and the display color of the indicator indicates the package Detect the occurrence of pinholes.

  The carbon dioxide detection ink composition contains a pH indicator, a binder and a solvent, or further contains an alkaline substance.

  The bicarbonate-containing chemical solution contained in the package of the present invention is a chemical having a property of losing medicinal properties by releasing carbon dioxide. For this reason, by packaging a container containing a bicarbonate-containing chemical solution in an outer package of a carbon dioxide atmosphere, the bicarbonate component and the carbon dioxide can be kept in balance and stored while preventing the release of carbon dioxide. it can.

  When the bicarbonate solution used in the present invention is accommodated, the carbon dioxide concentration in the outer package is preferably 0.5 to 10% by volume, more preferably 3 to 9% by volume.

  The bicarbonate-containing chemical solution preferably contains at least one additive component of sodium salt and citrate.

  The additive component is preferably (1) sodium chloride, (2) sodium chloride and citric acid, or (3) 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 gas atmosphere is, for example, a gas containing carbon dioxide such as a mixed gas of carbon dioxide and air of any mixing ratio is enclosed in the exterior body, or carbon dioxide generating deoxygenation such as Ageless G manufactured by Mitsubishi Gas Chemical Company, Inc. It is obtained by encapsulating the agent in the exterior body. 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, by using the above-described carbon dioxide gas detecting ink composition, by providing an indicator in a package having a carbon dioxide atmosphere, the change in carbon dioxide concentration in the carbon dioxide atmosphere is indicated by the display color of the indicator. Judging by the change in the package, it is possible to easily confirm the pinhole of the package and the occurrence of a seal failure. As the pH indicator used in the present invention, the display color is accompanied by a change in color tone due to the influence of carbon dioxide gas, or the display color is accompanied by a change in color tone in response to a change in pH according to a change in the concentration of an alkaline substance. Anything can be used.

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.

  In the presence of a suitable amount of alkaline substance, for example when the carbon dioxide concentration changes from 0 to about 10% by volume, the metacresol purple can change in the order of bluish purple, brown, yellow. Of these, bluish purple and yellow, and brown and yellow can be identified visually, but bluish purple and brown are difficult to identify instantaneously.

  As described above, when a bicarbonate-containing chemical solution is stored, the carbon dioxide gas concentration in the outer package is preferably 0.5 to 10% by volume, more preferably 3 to 9% by volume, in a relatively low concentration carbon dioxide atmosphere. Is used.

  When used in such a relatively low-concentration carbon dioxide atmosphere, it is preferable to use a pH indicator that can instantly visually identify the display color corresponding to any concentration within this range. . As such a pH indicator, a combination of two or more pH indicator components can be used.

Table 2 below shows particularly preferable combinations of pH indicator components and color changes of the indicator when the carbon dioxide gas concentration is relatively low.

  As shown in the above table, any combination produces a color change that can be instantly identified visually, for example, with a change of 0 to 3% by volume.

  As shown in the above table, any combination produces a color change that can be instantly identified visually, for example, with a change of 0 to 3% by volume.

  The carbon dioxide gas detecting ink composition of the present invention includes a combination of two or more pH indicator components as described above, a binder, and a solvent.

  The carbon dioxide gas detection indicator of the present invention is formed using a carbon dioxide gas detection ink composition comprising a support, a combination of two or more pH indicator components as described above, a binder, and a solvent. A designated instruction unit.

  The carbon dioxide detection ink composition of the present invention and the carbon dioxide detection indicator of the present invention are the carbon dioxide concentration in the package containing the bicarbonate-containing chemical solution stored in such a low concentration carbon dioxide atmosphere. It is preferably used to detect

  When the carbon dioxide detection ink composition of the present invention and the carbon dioxide detection indicator of the present invention are applied to a package, the carbon dioxide gas in the substituted gas atmosphere has a concentration of carbon dioxide when the package is in communication with the atmosphere. Changes can be determined visually by the display color. 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 instantly identified visually can occur. For this reason, the presence of pinholes and seal defects in the package, or the presence or absence of opening, damage, etc. of the package during mischief, transportation, or storage, by the display color approaching that when there is no carbon dioxide. It can be easily confirmed.

  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 one that can uniformly and stably dissolve or disperse each component of the carbon dioxide gas detecting ink composition, for example, aromatic hydrocarbon, aliphatic hydrocarbon, Examples include esters, alcohols, and water. 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 a water-absorbing powder on a support. Examples of such a binder include polyacrylic acid, polyvinyl alcohol, and polyvinyl. Examples include butyral, polyvinyl acetal, polyvinyl acetate, polyurethane, and partially saponified vinyl acetate.

  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 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.

  The indicator used in the present invention is preferably a printing method because it is desired that the coating amount of the ink composition is relatively large and constant.

  The indication part used for this invention can be printed on an exterior body, and the package body which has an indicator can be created.

  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.

  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 unit, it can also be used as a label on which a product name or the like is printed. Further, the support may be appropriately colored in order to make the pointing part easy to see.

  The usage form of the carbon dioxide indicator used in the present invention is as follows: (1) A container made of a gas barrier material for storing contents such as foods, beverages and medicines is a carbon dioxide gas atmosphere, (2) A container made of a gas permeable material containing the contents is packaged with an exterior body made of a gas barrier material, the inside of the exterior body is in a carbon dioxide gas atmosphere, and a carbon dioxide gas indicator is placed in the exterior body The method of doing can be illustrated.

  More specifically, in the case of the above (1), as a method for arranging the carbon dioxide gas indicator, for example, paper, synthetic paper, non-woven paper, synthetic resin film, or a laminate in which at least two kinds of the above materials are combined. A method of simply putting the carbon dioxide indicator printed on the support into the container, a method of adhering the carbon dioxide indicator to the inner surface of the container, or using the material constituting the container as a support, the ink composition described above on the inner surface of the container There is a direct printing method.

  On the other hand, in the case of (2) above, the carbon dioxide indicator can be arranged on the outer surface of the container, the space between the container and the outer body, and the inner surface of the outer body. As a method for disposing carbon dioxide indicators on the outer surface of the container or the inner surface of the outer package, there are a method of adhering the indicator to these surfaces, or a method of printing the ink composition used in the present invention directly on these surfaces. .

  In the case where the ink composition is directly printed on the inner surface of the container made of the gas barrier material in (1), the outer surface of the gas permeable container in (2) or the inner surface of the exterior body made of the gas barrier material, After printing the ink composition on the film, it is possible to cover the printing surface with a gas permeable film. When coated, there is no contact with the contents or the container, and it is hygienic and prevents wear on the indicator. This is preferable.

  The carbon dioxide indicator used in the present invention is a food, beverage, medicine that may be deteriorated by contact with oxygen, or food, beverage, medicine that may lose quality or lose its medicinal properties due to the release of carbon dioxide. Can be applied.

  Examples of the food include tea, coffee, cheese, ham, miso, and raw meat. Examples of chemicals include bicarbonate-containing drug solutions, amino acid infusions, fat emulsions, antibiotic preparations, and the like.

  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. This chemical solution container has, for example, a temporary sealing portion as a partition, and this sealing portion can open the chambers by a predetermined impact, whereby the solutions contained in the respective chambers can be mixed. .

  As a combination of the chemical solutions respectively contained in the multi-chamber container, a solution containing sodium hydrogen carbonate and sodium chloride in the first chamber and a solution containing glucose and magnesium chloride in the second chamber can be mentioned.

  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.

  FIG. 1 is a front view showing a first example of a carbon dioxide indicator used in the present invention, and FIG. 2 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 by applying a circular pattern by screen printing, and the periphery thereof is surrounded by, for example, a porous film 3 having carbon dioxide gas permeability. The indicator part of the indicator is purple in normal air. In FIG. 1 and FIG. 2, the instruction unit 2 is provided on both surfaces of the support 1, but a configuration in which the instruction unit is provided only on one surface can also 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. 3 is a sectional view showing the configuration of the second example 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. Carbon dioxide gas permeability made of, for example, a polyethylene film formed so as to seal the indication part 2 obtained by applying by screen printing and the indication part 2 provided on the layer 71 having carbon dioxide impermeability. And a layer 73 having

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

Carbon dioxide permeability means having a carbon dioxide gas permeability of 500 (ml / m ² · 24 hr) or more.

  The carbon dioxide indicator 70 has a configuration in which carbon dioxide gas is transmitted and detected only from the layer 73 side having carbon dioxide permeability, and carbon dioxide gas is not transmitted from the support side. For example, a packaging body is used as a support, and a packaging body is prepared so that the carbon dioxide-impermeable layer 71 is on the outside and the carbon dioxide-permeable layer 73 is on the inside. The package can be configured such that the indicator 70 functions within 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.

If the carbon dioxide gas permeability of the layer through which carbon dioxide gas should permeate is lower than 500 (ml / m ² · 24 hr), the response to changes in the carbon dioxide gas atmosphere becomes slow, and there is a risk of erroneous determination.

For example, in the case of 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. .

Examples of the 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 include silica 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. In addition, another resin film can be laminated in order to obtain strength, heat resistance and the like according to the purpose of use. For example, a nylon film or the like can be laminated in order to obtain a piercing strength.

Examples of the film having a carbon dioxide gas permeability of 500 (ml / m ² · 24 hr) or more used in the present invention include polyolefins such as a polyethylene film and a polypropylene film. Note that low-density polyethylene and unstretched polypropylene have heat-sealing properties and are optimal as a packaging layer.

A support printed with an indicator, a film with a carbon dioxide permeability of 50 (ml / m ² · 24 hr) or less, a film with a carbon dioxide permeability of 500 (ml / m ² · 24 hr) or more, and other As a method for bonding the films, a known method can be used, and for example, dry lamination using an adhesive can be used.

  FIG. 4 is a sectional view showing the configuration of a third example of the carbon dioxide indicator used in the present invention.

  As shown in the figure, this carbon dioxide gas indicator 50 includes, for example, a nylon film 55 having an alumina vapor deposition layer (not shown), and an alumina vapor deposition layer (not shown) laminated thereon via an adhesive layer 56. A support 1 composed of a polyester film 57 having an anchor, an anchor coat layer 51 formed on the support 1, and thymol blue, phenolphthalein, thymolphthalein, sodium carbonate, polyvinyl acetal resin on the anchor coat layer 51, for example. An indicator 2 that is gravure-printed in a predetermined pattern using an ink composition for detecting carbon dioxide gas comprising microcrystalline cellulose and water, and the indicator 2 on the anchor coat layer 51 on which the indicator 2 is printed. And an overcoat layer 52 formed so as to seal. The indicator indicating section 2 is purple in normal air.

  The pH indicator in the indicator 2 reacts through a solvent such as a hydrophilic solvent such as water or an alcohol compound. For this reason, the instruction | indication part 2 may contain such a solvent. For this reason, the instruction | indication part 2 tends to accumulate water, and tends to raise | generate an external appearance defect. In addition, the indication unit 2 is vulnerable to external impacts and easily peels off and breaks around the indication unit 2 and its periphery. Like the carbon dioxide gas indicator 50, the indicator 2 is sandwiched between the anchor coat layer 51 and the overcoat layer 52 to protect the carbon dioxide detection ink composition constituting the indicator 2, and the appearance defect, peeling, and Breakage can be prevented. Furthermore, the long-term stability of the carbon dioxide indicator including light resistance and heat resistance is improved.

  The anchor coat layer 51 is a water-insoluble material having good adhesion between the support 1 and the indicator 2 formed thereon, and the overcoat layer 52 is carbon dioxide permeable. A material having good adhesion to the indicating unit 2 and, for example, an adhesive layer or other resin layer that can be further provided on the indicating unit 2 can be preferably used.

  As such materials, for example, urethane resins and polyvinyl acetal resins can be used alone or in combination.

  For example, the urethane resin can strengthen the adhesion between the support 1 and the indicator 2 and can effectively prevent the support 1 and the indicator 2 from being peeled off or broken. Further, the polyvinyl acetal resin has good adhesion to the support 1 and has a hydrophilic group. Due to the presence of the hydrophilic group, the polyvinyl acetal resin can prevent the moisture in the indicator 2 from being scattered and can easily take in moisture from the outside, for example, air. Thereby, polyvinyl acetal resin has the effect | action which helps maintenance of a sufficient quantity of water | moisture content for the pH indicator in the indicator part 2 to function at least.

  In addition, although the instruction | indication part was provided only in the single side | surface of the support body 1 here, the structure which provided the instruction | indication part 2 in both surfaces of the support body 1 is also applicable. Moreover, when providing an instruction | indication part only in the single side | surface of the support body 1, as needed, the layer which has the above-mentioned carbon dioxide gas impermeability as a support body, and has a carbon dioxide gas permeability | transmittance on an overcoat layer Each layer can be applied.

  FIG. 5 is a cross-sectional view showing a configuration of a fourth example of the carbon dioxide indicator used in the present invention.

  As shown in the figure, this carbon dioxide indicator 60 is an improved example of the carbon dioxide indicator 50 described above, and instead of the anchor coat layer 51, a first anchor coat layer 53 and a second anchor are provided on the support 1. Except that the laminated structure of the coat layer 54 is used, it has the same structure as the carbon dioxide indicator shown in FIG. Preferably, the peripheral portion of the first anchor coat layer 53 and the overcoat layer 52 are brought into close contact with each other so that the indication portion 2 and the second anchor coat layer 54 are enclosed in the two layers 52 and 53.

  As the first anchor coat layer, a water-insoluble material having good adhesion to the support 1 such as urethane resin is preferably used.

  In addition, the second anchor coat layer has good adhesion to the first anchor coat layer and the indicator 2, and more preferably has a hydrophilic group and has a water retention effect on the indicator 2 containing water. A material such as polyvinyl acetal resin is preferably used.

  As a method for applying the anchor coat layer and the overcoat layer, 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. .

  In this carbon dioxide gas indicator 60, the anchor coat layer is divided into two layers, so that the first anchor coat layer 53 has the effect of strengthening the adhesion between the support 1 and the indicator 2; The anchor coat layer 54 provides an action of securing a sufficient amount of moisture for at least the pH indicator in the indicator 2 to function. Therefore, the carbon dioxide indicator 60 has stronger adhesiveness and more effective water retention for the pointing portion than the case where only one anchor coat layer is formed, like the carbon dioxide indicator 50 shown in FIG. realizable. Furthermore, the long-term stability of the carbon dioxide indicator including light resistance and heat resistance is further improved.

Here, the instruction unit is provided only on one side of the support 1, but a configuration in which the double-side instruction unit 2 of the support 1 is provided can also be applied. Moreover, when providing an instruction | indication part only in the single side | surface of the support body 1, as needed, the layer which has the above-mentioned carbon dioxide gas impermeability as a support body, and has a carbon dioxide gas permeability on an overcoat layer Each layer can be applied.

In FIG. 6, the figure showing the 1st example of the gas replacement packaging body concerning this invention is shown. As shown in the figure, the gas replacement package 20 includes a carbon dioxide permeable container 11 made of carbon dioxide that contains a chemical solution, for example, 0.910 to 0.925 g / cm ³ , and carbon dioxide gas similar to FIG. The indicator 10 has a configuration in which 90 to 99.5% by volume of nitrogen and 0.5 to 10% by volume of carbon dioxide mixed gas 13 are used as a replacement gas and sealed in an outer package 12 made of a gas barrier laminated film. .

  The display color of the indicator indicating unit 2 in the package is yellow when sealed. However, if pinholes or poor seals occur in the package and the replacement gas leaks out and the surrounding air is mixed in instead, 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 pH. By visually recognizing the change in color tone, it can be easily confirmed whether or not the atmosphere containing carbon dioxide in the package is maintained at a predetermined concentration.

  Instead of the carbon dioxide indicator 10, the third and fourth examples of the carbon dioxide indicator described above can be applied.

  In FIG. 7, the 2nd example of the gas replacement packaging body concerning this invention is shown.

As shown, package 30, the low-density surface of the polyethylene container 14 to 0.910 no example of carbon dioxide permeability accommodating a drug solution 0.925 g / cm ^3, the outer portion of the container 14 support A carbon dioxide indicator 18 having an indicator 2 formed by screen printing and a coating layer 5 made of a breathable material coated on the indicator 2 is provided, and nitrogen is 90 to 99.5% by volume as a replacement gas. Further, it has a configuration in which the outer casing 12 made of a gas barrier laminated film is sealed using a mixed gas 13 of 0.5 to 10% by volume of carbon dioxide. 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 in the packaging body shown in FIG. 6, it is easy to check whether the gas atmosphere containing carbon dioxide in the packaging body is maintained at a predetermined concentration by visually recognizing the change in color tone of the display color. Can be confirmed.

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

  FIG. 8 shows a third example of the gas replacement package according to the present invention.

  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 the indicator 10 composed of the support 1 provided with the instruction part 2 is bonded to the exterior body 12. It may be used by being integrated with the package by a method such as

  The package 40 includes an outer package 12 made of a gas barrier laminated film, and a carbon dioxide gas indicator having an inner surface of the outer package 12 and an indicator 2 provided by, for example, screen printing using the outer package 12 as a support. Composed. 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 the 3rd example of the gas replacement packaging body concerning this invention is shown.

  In the case of an indicator in which the indicating unit 2 is printed using the exterior body 12 as a support, as shown in FIG. 9, the indication unit 2 is provided on the inner surface of the gas barrier layer 32 of the gas barrier material 31 constituting the exterior body 12, It is also possible to cover the inner surface side of the indicator 2 with a carbon dioxide permeable protective film 33.

  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.

  In addition, the 2nd example of the above-mentioned carbon dioxide indicator, a 3rd example, and a 4th example are applicable instead of a carbon dioxide indicator.

  In FIG. 10, sectional drawing showing the example which applied the 4th example of the carbon dioxide indicator used for this invention to the exterior body of a package is shown.

  As shown in the drawing, for example, a nylon film 81 having an alumina vapor deposition layer (not shown) and a polyester film 83 having an alumina vapor deposition layer (not shown) are disposed as adhesives serving as a support through an adhesive layer 82. A laminated film obtained by laminating is used. Similar to the fourth example of the carbon dioxide indicator shown in FIG. 5 on this laminated film, the laminated structure of the first anchor coat layer 53 and the second anchor coat layer 54, the indicating section 2, and the overcoat By providing the layers 52 in order, a carbon dioxide indicator is configured. In addition, an ink layer 17 having, for example, a character such as a product name or a pattern such as an image can be arbitrarily provided in parallel with the production of the carbon dioxide indicator 80 in other regions on the exterior body. Further, a sealant layer 75 made of low density polyethylene is provided on the overcoat layer 52 and the ink layer 17 with an adhesive layer 74 interposed therebetween, for example.

  Using an exterior body provided with such a carbon dioxide indicator, the contents are sealed using, for example, a mixed gas 13 of 90 to 99.5% by volume of nitrogen and 0.5 to 1.0% by volume of carbon dioxide as a replacement gas. Thus, a package with a carbon dioxide indicator is obtained.

  In the obtained package, it is possible to realize strong adhesion of the indicating unit and effective water retention for the indicating unit. Furthermore, the long-term stability of the package with a carbon dioxide gas indicator including light resistance and heat resistance is improved.

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
As a support, a JIS standard P 3801 filter paper for chemical analysis having a weight of 140 g / m ² was used, and this was coated by screen printing and dried at 70 ° C. for 1 hour to obtain an indicator.

  Next, using a gas barrier laminated film of vinylidene chloride-coated nylon film (thickness 25 μm) / low density polyethylene film (thickness 50 μm), a bag with an internal volume of 50 ml was prepared. The above-mentioned indicator and a mixed gas of nitrogen gas and carbon dioxide gas were sealed in the obtained bag while varying the concentration of the carbon dioxide gas, and the color change was observed. The obtained results are shown in Table 2 below.

Reference example 2
A test package was prepared in the same manner as in Reference Example 1, except that carbon dioxide detection ink composition 1 in Reference Example 1 was changed to carbon dioxide detection ink composition 2 and the support was changed to a polyester film having a thickness of 12 μm. I saw the color change. 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.

Test Examples Hereinafter, test examples 2-1 to 2-7, and test example 3- using the ink composition for detecting carbon dioxide gas as a part of the outer package of the package (Reference Example 9-25). 1 to 3-8 are shown.

  Test Examples 2-1 to 2-7 have a configuration in which an indicator is printed with various carbon dioxide impermeable films with carbon dioxide detection ink, and various carbon dioxide permeable films are further laminated thereon. The example which formed the exterior body is shown.

Reference Example 9 and Test Example 2-1
The following ink composition 9 for carbon dioxide gas detection was finely dispersed with a paint conditioner or the like to obtain an ink composition.

Carbon dioxide detection ink composition 9
Metacresol purple 1g
Polyvinyl acetal resin 7g
92g of water
21g of propanol
Sodium hydroxide 4g
Glycerin 5g
A silica-deposited polyester film having a polyester layer having a thickness of 12 μm and a silica-deposited layer having a thickness of 40 nm deposited on one surface thereof is prepared, and the above ink composition is used on the polyester layer side. The indicator was printed by a gravure printing method, and a low-density polyethylene film having a thickness of 25 μm was laminated as a sealant on the polyester layer on which the indicator was formed using a urethane adhesive to obtain a laminate.

  Using this laminate, it was arranged so that the sealant was inside, and a packaging bag was produced (100 mm × 100 mm), and 50 ml of nitrogen gas added with 5% by volume of carbon dioxide was filled and sealed. About the obtained packaging bag, the responsiveness of the instruction | indication part and the carbon dioxide gas concentration in a packaging bag were measured.

  Responsiveness was determined to be good when the color changed from purple to yellow within 30 minutes after gas filling, and poor otherwise.

  The carbon dioxide concentration was measured after storage for 30 days in an environment of 40 ° C. and 75% humidity, and the indicator was also observed at the same time. Table 4 shows the obtained results.

  Moreover, the carbon dioxide gas permeability | transmittance of the silica vapor deposition polyester film and sealant similar to what was used was measured, respectively, and it described together in following Table 4.

Reference Example 10 and Test Example 2-2
A polyester film having a thickness of 12 μm was prepared, and an indicator and a sealant were laminated in the same manner as in Test Example 2-1. Furthermore, an alumina vapor-deposited nylon film having an alumina vapor-deposited layer with a thickness of 20 nm on a nylon film with a thickness of 15 μm is placed on the opposite side of the polyester film indicating section, and the vapor-deposited surface is in close contact with the polyester film. Lamination was performed using a system adhesive to obtain a laminate.

  Using the obtained laminate, a packaging bag was prepared in the same manner as in Test Example 2-1, responsiveness and carbon dioxide concentration were measured, and the indicator was observed. The results are shown in Table 3 below.

  Further, the carbon dioxide gas permeability of the laminate and sealant of the same polyester film and alumina-deposited nylon film as used was measured and listed in Table 4 below.

Reference Example 11 and Test Example 2-3
A polyester film having a thickness of 12 μm similar to that in Test Example 2-2 was prepared, and an instruction part was printed in the same manner as in Test Example 2-1. Thereafter, an unstretched polypropylene film having a thickness of 25 μm as a sealant was laminated on the indicator side using a urethane-based adhesive. Further, the opposite surface with an instruction of the polyester film, the coated surface K coated nylon film is nylon film having a thickness of 15μm coated with polyvinylidene chloride 1 g / m ² is so as to contact with the polyester film Lamination was performed using a urethane adhesive to obtain a laminate.

  Using the obtained laminate, a packaging bag was prepared in the same manner as in Test Example 2-1, the responsiveness and the carbon dioxide concentration were measured, and the indicator was observed. The results are shown in Table 3 below.

  Further, the carbon dioxide gas permeability of each of the laminate of the same polyester film and polyvinylidene chloride coated nylon film as used and the unstretched polypropylene film was measured and listed in Table 4 below.

Reference Example 12 and Test Example 2-4
A polyester film having a thickness of 12 μm similar to that in Test Example 2-2 was prepared, and an indicator and an unstretched polypropylene film were laminated in the same manner as in Test Example 2-3. Furthermore, a polyvinyl alcohol film having a thickness of 15 μm was laminated on the surface opposite to the indicator portion of the polyester film using a urethane-based adhesive. Furthermore, a polyester film having a thickness of 12 μm was similarly laminated on the polyvinyl alcohol film to obtain a laminate.

  Using the obtained laminate, a packaging bag was prepared in the same manner as in Test Example 2-1, the responsiveness and the carbon dioxide concentration were measured, and the indicator was observed. The results are shown in Table 3 below.

  Moreover, the laminated body of the polyester film similar to what was used, the polyvinyl alcohol film, and the polyester film was created, the laminated body and the unstretched polyethylene film carbon dioxide gas transmittance | permeability were measured, and it described together in following Table 4.

Reference Example 13 and Test Example 2-5
A polyester film similar to Test Example 2-2 was prepared, and similarly, an indicator and a low density polyethylene film were laminated.

  Furthermore, a co-extruded film of nylon (NY) and ethylene vinyl acetate copolymer (EVOH) having a thickness of 30 μm on the surface opposite to the display portion of the polyester film so that the EVOH adheres to the polyester film. Lamination was performed using a urethane adhesive to obtain a laminate.

  Using the obtained laminate, a packaging bag was prepared in the same manner as in Test Example 2-1, the responsiveness and the carbon dioxide concentration were measured, and the indicator was observed. The results are shown in Table 4 below.

  Moreover, the laminated body of the polyester film similar to what was used, and the NY / EVOH coextruded film was created, the carbon dioxide gas transmittance | permeability of the laminated body and a low density polyethylene film was measured, and it described together in following Table 4.

Reference Example 14 and Test Example 2-6
The indicator was printed in the same manner on a polyester film having a thickness of 12 μm as in Test Example 2-2. Thereafter, a silica-deposited nylon film having a thickness of 40 μm is laminated on the nylon film having a thickness of 15 μm on the indicator side using a urethane adhesive, and further, using a urethane adhesive as a sealant, A low density polyethylene film having a thickness of 25 μm was laminated.

  Using the obtained laminate, a packaging bag was prepared in the same manner as in Test Example 2-1, the responsiveness and the carbon dioxide concentration were measured, and the indicator was observed. The results are shown in Table 4 below.

  Also, make a laminate of silica-deposited nylon film and low-density polyethylene film similar to those used, and measure the carbon dioxide gas permeability of the polyester film similar to that used and the resulting laminate, respectively. These are also shown in Table 4 below.

Reference Example 15 and Test Example 2-7
The indicator was printed in the same manner on a polyester film having a thickness of 12 μm as in Test Example 2-2. Thereafter, a low-density polyethylene film was laminated using a urethane-based adhesive as a sealant having a thickness of 25 μm on the indicator side.

Using the obtained laminate, a packaging bag was prepared in the same manner as in Test Example 2-1, the responsiveness and the carbon dioxide concentration were measured, and the indicator was observed. The results are shown in Table 3 below. Moreover, the carbon dioxide gas permeability | transmittance of the polyester film and low density polyethylene film similar to what was used was measured. The results obtained are shown in Table 4 below.

  As shown in Table 4, all of the packaging bags of Test Examples 2-1 to 2-5 have good responsiveness, there is no problem with the concentration of carbon dioxide after storage, and the color tone of the indicator also shows the concentration of carbon dioxide. It corresponded to.

  However, if the carbon dioxide gas permeability inside the packaging bag is low as in Test Example 2-6, the responsiveness deteriorates, and if the carbon dioxide gas permeability of the entire packaging bag is high as in Test Example 2-7, Storability is poor and carbon dioxide escapes from the packaging bag.

As is clear from Test Examples 2-1 to 2-5, the laminate outside the packaging bag indicating portion has a carbon dioxide gas permeability of 50 (ml / m ² · 24 hr) or less, and the packaging bag indicating When the laminate inside the part has a carbon dioxide permeability of 500 (ml / m ² · 24 hr) or more, an indicator that can respond sensitively to changes in the carbon dioxide atmosphere in the packaging bag can be realized, and the packaging bag It turned out that it becomes the packaging bag excellent in the holding | maintenance of the carbon dioxide gas in the inside, and excellent in the preservation | save of the contents.

  Furthermore, after forming an anchor coat layer on a support, various examples of carbonic acid indicators having a configuration in which an indicator is printed and an overcoat layer is further provided are shown.

  Moreover, the coloration property of the package using this indicator, water resistance, heat resistance, and a transport test are shown as Test Example 3.

Reference Example 16 and Test Example 3-1.
An ink composition was prepared by finely dispersing the following carbon dioxide detection ink composition 10 with a paint conditioner or the like.

Metacresol purple 1g
Polyvinyl acetal resin 7g
92g of water
21g of propanol
Sodium hydroxide 4g
Glycerin 5g
As a support, a 12 μm-silica-deposited polyester film comprising a silica-deposited layer having a thickness of 40 nm and a polyester layer was prepared. On the surface of the polyester layer, a first anchor coat agent composed mainly of urethane resin and a second anchor coat agent composed of vinyl acetal resin were respectively applied by gravure printing, and the first anchor coat layer and A second anchor coat layer was obtained.

  Then, the above-mentioned ink composition was apply | coated by the gravure printing method on the 2nd anchor coat layer, and the instruction | indication part was formed.

  A first overcoat agent made of vinyl acetal resin is applied on the obtained indicator, and in order of a second overcoat agent made of urethane resin, each is applied by gravure printing, and the first and second An overcoat layer was formed. After drying these, a low-density polyethylene film having a thickness of 25 μm was bonded using a urethane adhesive using a dry laminating method to obtain a laminate.

  The following evaluation tests 1 to 3 were performed on the obtained laminate.

Evaluation test 1
Using the obtained laminate, 50 ml of a mixed gas having a nitrogen gas / carbon dioxide concentration ratio of 95/5 was sealed inside the package, and the bag was completely produced to prepare a test packaging bag. The coloration of the resulting packaging bag was confirmed. The results are shown in Table 5 below.

Evaluation test 2
About the packaging bag similar to the evaluation test 1, light resistance and heat resistance were confirmed. The light resistance was equivalent to 1,200,000 lx * hr, and the heat resistance was 60 ° C. for 2 weeks, and it was confirmed that the indicator of the packaging bag opened to the atmosphere after the test was changed from yellow to purple.

  In the water resistance test, the obtained laminate was allowed to stand for 1 day under high temperature and high humidity at a temperature of 40 ° C. and a humidity of 75% in the atmosphere, and the surface of the indicator was observed. The obtained results are shown in Table 5 below.

Evaluation test 3
Test Example 2-1 except that 50 ml of carbon dioxide-permeable plastic ampoule-containing distilled water is put inside, 50 ml of a mixed gas having a nitrogen gas / carbon dioxide concentration ratio of 92/8 is enclosed, and the bag is made. Similarly, a packaging bag containing a plastic ampule was obtained. Twenty of these packaging bags were boxed, and a transport test of 200 km in a round trip by a truck was performed. The obtained results are shown in Table 6 below.

Reference Example 17 and Test Example 3-2
A laminate was obtained in the same manner as in Test Example 3-1, except that the first overcoat layer made of vinyl acetal resin was omitted.

  Evaluation tests 1 to 3 were performed in the same manner as in Test Example 3-1, using the obtained laminate. The obtained results are shown in Tables 5 and 6 below.

Reference Example 18 and Test Example 3-3
A laminate was obtained in the same manner as in Test Example 3-1, except that the second overcoat layer made of urethane resin was omitted.

  Evaluation tests 1 to 3 were performed in the same manner as in Test Example 3-1, using the obtained laminate. The obtained results are shown in Tables 5 and 6 below.

Reference Example 19 and Test Example 3-4
A laminate was obtained in the same manner as in Test Example 3-1, except that the first and second overcoat layers were omitted.

  Evaluation tests 1 to 3 were performed in the same manner as in Test Example 3-1, using the obtained laminate. The obtained results are shown in Tables 5 and 6 below.

Reference Example 20 and Experimental Example 3-5
As the anchor coat layer and the overcoat layer, a laminate is formed in the same manner as in Test Example 3-1, except that only the first anchor coat layer made of urethane resin and the second overcoat layer are made of urethane resin. Got.

  Evaluation tests 1 to 3 were performed in the same manner as in Test Example 3-1, using the obtained laminate. The obtained results are shown in Tables 5 and 6 below.

Reference Example 21 and Test Example 3-6
As the anchor coat layer and the overcoat layer, a laminate was formed in the same manner as in Test Example 3-1, except that only the second anchor coat layer and the first overcoat layer made of urethane resin were formed from the vinyl acetal resin. Got.

  Evaluation tests 1 to 3 were performed in the same manner as in Test Example 3-1, using the obtained laminate. The obtained results are shown in Tables 5 and 6 below.

Reference Example 22 and Test Example 3-7
A laminate was obtained in the same manner as in Test Example 3-1, except that only the second overcoat agent made of urethane resin was used for the overcoat layer and the anchor coat layer was omitted.

  Evaluation tests 1 to 3 were performed in the same manner as in Test Example 3-1, using the obtained laminate. The obtained results are shown in Tables 5 and 6 below.

Reference Example 23 and Test Example 3-8
A laminate was obtained in the same manner as in Experimental Example 8 except that the overcoat layer and the anchor coat layer were omitted.

  Evaluation tests 1 to 3 were performed in the same manner as in Test Example 3-1, using the obtained laminate. The obtained results are shown in Tables 5 and 6 below.

Reference Example 24 and Test Example 3-9
Except for using only the first anchor coat agent composed mainly of an acrylic resin, the second anchor coat agent composed of a vinyl acetal resin, and the overcoat agent composed mainly of an acrylic resin for the overcoat layer, A laminate was obtained in the same manner as in Test Example 3-7.

  Evaluation tests 1 to 3 were performed in the same manner as in Test Example 3-1, using the obtained laminate. The obtained results are shown in Tables 5 and 6 below.

Experimental Example 17
For anchor coat layers, only the first anchor coat agent composed mainly of urethane resin, the second anchor coat agent composed of acrylic resin, and overcoat agent composed mainly of urethane resin for overcoat layer A laminate was obtained in the same manner as in Test Example 3-1, except that was used.

Evaluation tests 1 to 3 were performed in the same manner as in Test Example 3-1, using the obtained laminate. The obtained results are shown in Tables 5 and 6 below.

Diagonal line: Light resistance not tested ○: Good, indicator section turns purple △: Indicator section purple to gray (degradation of function is observed but detectable) ×: Indicator section yellow (not detectable)
Heat resistance ○: Good, indicator part changes to purple △: Indicator part purple to gray (degradation of function is observed, but can be detected) ×: Indicator part yellow (not detectable)
Water resistance ○: Good △: Slight puddle phenomenon occurs in the carbon dioxide indicator section ×: Severe puddle phenomenon occurs in the carbon dioxide indicator section In Test Examples 3-1 to 3-8, the carbon dioxide indicator is purple in the atmosphere. Yellowish under carbon dioxide. Moreover, light resistance, heat resistance, and water resistance were good or detectable. In Test Example 3-9, water accumulated in the indicator portion and appearance defects occurred. On the other hand, as shown in Test Example 3-10, when an acrylic resin is used for the anchor coat agent or overcoat agent, the indicator portion is purple in the atmosphere and yellow in the carbon dioxide gas, but has no light resistance and heat resistance. , Lack of stability.

Shaded portion: not tested From the result of Evaluation Test 1, it was confirmed that when a preferable overcoat layer and anchor coat layer were used, the carbon dioxide indicator and the package were excellent in coloration. From the evaluation test 2, it was confirmed that when a preferable overcoat layer and anchor coat layer were used, the carbon dioxide indicator and its package were excellent in light resistance, heat resistance and water resistance. Vinylacetal resin improved heat resistance, and urethane resin improved water resistance. In addition, from the evaluation test 3, it was confirmed that the strength of the indicating portion was improved even in actual use, and peeling did not occur, and the appearance defect could be prevented.

Example 1
A bicarbonate-containing chemical solution having the following formulation was filled in a carbon dioxide-permeable polyethylene bag (one bag) (with a space of 400 ml) and closed. The obtained one bag was sterilized with a hot water shower. Thereafter, the one bag is put into a laminated film bag of nylon (thickness 15 μm) / polyvinyl alcohol (thickness 18 μm) / polyethylene (thickness 60 μm) together with the indicator of Reference Example 1, and a mixed gas containing carbon dioxide. The gas replacement packaging was carried out to obtain a package having the same configuration as in FIG. The mixed gas was carbon dioxide gas 5 volume% and air 95 volume%.

Bicarbonate-containing chemical composition 1
Sodium chloride 3.00 g
Calcium chloride 0.10g
Sodium bicarbonate 1.20g
Citric acid 0.07g
Amount to make 500 ml of sterilized purified water pH 7.3
Example 2
Instead of the one bag, a carbon dioxide permeable polyethylene double bag having a partition wall as shown in FIG. 11 is used, a chemical solution having the following composition is used, and the composition of the mixed gas is 10% by volume of carbon dioxide and 90% of air. A package was obtained in the same manner as in Example 1 except that the volume percentage was changed.

  As shown in the figure, this double bag 90 has a bag shape composed of a pair of polyethylene 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 the partition wall 91 which can communicate. Each of the first chamber 92 and the second chamber 93 contains a chemical solution having the following composition. 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.

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 The amount to make the whole 350ml
Example 3
A package was obtained in the same manner as in Example 1 except that a chemical solution having the following composition was used and a double bag having the same configuration as in Example 2 was used.

Chemical composition of the first chamber Magnesium chloride hexahydrate 0.11g
Dextrose 0.30g
Sterile purified water Amount to make the total volume 150ml pH 4.5
Chemical composition of the second chamber Sodium hydrogen carbonate 1.00g
Sodium chloride 3.60g
pH 7.3
Examples 4 to 6
Example 1 thru | or 3 each except using the one back or double back (space amount 400ml) using the laminated body of the reference example 9 which provided the indicator in part instead of the indicator and the laminated film bag body. A package was obtained in the same manner.

Examples 7 to 9
Example 1 thru | or 3 each except using the one back or double back (space amount 400ml) using the laminated body of the reference example 16 which provided the indicator in part instead of the indicator and the laminated film bag body. A package was obtained in the same manner.

Example 10
A package was obtained in the same manner as in Example 2 except that the mixed gas composition was 4% by volume of carbon dioxide and 96% of air.

Example 11
A package was obtained in the same manner as in Example 5 except that the mixed gas composition was 4% by volume of carbon dioxide and 96% of air.

Example 12
The following ink composition 11 for detecting carbon dioxide gas was finely dispersed with a paint conditioner or the like to obtain an ink composition.

Carbon dioxide detection ink composition 11
Thymolphthalein 0.05g
卜 Lopeolin OOONo. 2 0.05g
Sodium hydroxide 0.40g
Polyvinyl alcohol 50.00g
Isopropyl alcohol 34.00 g
100.00 g of water
An alumina-deposited polyethylene terephthalate (PET) film was prepared as a support. On the alumina-deposited PET film, the above carbon dioxide detection ink is applied by screen printing to a thickness of 1 μm in an area of 1 cm in length and 1 cm in width, and dried at 70 ° C. for 1 hour, whereby a carbon dioxide gas detection unit Thus, an alumina-deposited PET film having a film formed thereon was obtained.

  Using the alumina vapor-deposited PET film as a packaging material, a chemical solution container (made of polyethylene (PE), content capacity: 1200 mL) containing an infusion solution containing 0.3% sodium hydrogen carbonate, a surface having a carbon dioxide gas detection unit After packaging inside, replacing the space between the chemical solution container and the alumina-deposited PET film (volume: about 300 mL) with a mixed gas of 3% carbon dioxide and 97% air, the packaging material is sealed, and the present invention A package was obtained. The display color of the carbon dioxide gas detection unit was purple at the beginning of manufacture, but turned yellow after 1 hour.

Pinhole detection test As a pinhole detection test, a pinhole having a diameter of about 500 μm and a short diameter of about 50 μm was opened on the packaging material of the obtained package with an injection needle (trade name: 27G, Terumo, Neolas). The change in display color of the carbon dioxide indicator was visually observed from the outside. The results are shown in Table 7.

Example 13
A package was obtained in the same manner as in Example 12 except that the following carbon dioxide detection ink composition 13 was used instead of the carbon dioxide detection ink composition 12.

Carbon dioxide detection ink composition 12
Thymol blue 0.05g
Phenolphthalein 0.25g
Thymolphthalein 0.025g
Sodium hydroxide 0.40g
Polyvinyl alcohol 50.00g
Isopropyl alcohol 34.00 g
Ethanol 50.00g
50.00 g of water
The display color of the carbon dioxide gas detection unit was purple at the beginning of manufacture, but turned yellow after 1 hour.

  A pinhole detection test was performed on the resulting package in the same manner as in Example 12. The results are shown in Table 7 below.

Example 14
The following ink composition 13 for detecting carbon dioxide gas was finely dispersed with a paint conditioner or the like to obtain an ink composition.

Carbon dioxide detection ink composition 13
Thymolphthalein 0.025g
Tropeolin OOONo. 2 0.075g
Sodium hydroxide 0.40g
Polyvinyl alcohol 50.00g
Isopropyl alcohol 34.00 g
Ethanol 40.00g
50.00 g of water
As a support, JIS standard P 3801 filter paper for chemical analysis having a weight of 140 g / m ² was used. On the filter paper, the ink composition was applied to an area of 1 cm in length and 1 cm in width with a thickness of 1 μm by screen printing, and dried at 70 ° C. for 1 hour.

  The filter paper was filled in a perforated polyethylene bag (1.5 cm × 1.5 cm) and sealed in three directions with a heat sealer to obtain a carbon dioxide detection indicator impregnated in the filter paper.

  Alumina-deposited PET film using an alumina-deposited PET film as a packaging material and containing an infusion solution containing 0.3% sodium hydrogencarbonate (polyethylene (PE), content: 1200 mL) together with the obtained carbon dioxide indicator After packaging with the packaging material made of the product, and replacing the space between the chemical solution container and the packaging material (volume of about 300 mL) with a mixed gas of 3% carbon dioxide and 97% air, the packaging material is sealed and An inventive package was obtained. The display color of the carbon dioxide indicator was purple at the beginning of production, but turned yellow after 1 hour.

  A pinhole detection test was performed on the resulting package in the same manner as in Example 12. The results are shown in Table 7 below.

Example 15
The following ink composition 14 for detecting carbon dioxide gas was finely dispersed with a paint conditioner or the like to obtain an ink composition.

Carbon dioxide detection ink composition 14
Metacresol purple 0.05g
Orthocresolphthalein 0.02g
Sodium hydroxide 0.40g
10.00g of water
10 g of this ink is impregnated into 50 g of microcrystalline cellulose, mixed well, filled into a perforated polyethylene bag (3 cm × 4 cm), and sealed in three directions with a heat sealer, so that the carbon dioxide detection ink is microcrystalline cellulose. The carbon dioxide indicator in the form of impregnated with was obtained.

  A package of the present invention was obtained in the same manner as in Example 14 except that the obtained carbon dioxide indicator was used. A pinhole detection test was conducted in the same manner as in Example 12 on the package obtained with the carbon dioxide gas indicator having a purple color at the beginning of production. The results are shown in Table 7 below.

However, it turned yellow after 1 hour.

Example 16
The following ink composition 15 for detecting carbon dioxide gas was finely dispersed with a paint conditioner or the like to obtain an ink composition.

Carbon dioxide detection ink composition 15
Timor Blue 0.075g
Tropeolin OOONo. 2 0.025g
Sodium hydroxide 0.40g
10.00g of water
10 mL of this ink was filled in a carbon dioxide-permeable low-density polyethylene bag (3 cm × 4 cm) and sealed three-way with a heat sealer to obtain a carbon dioxide indicator with a liquid form of carbon dioxide detection ink sealed therein.

  A package of the present invention was obtained in the same manner as in Example 14 except that the obtained carbon dioxide indicator was used. The display color of the carbon dioxide indicator was purple at the beginning of production, but turned yellow after 1 hour.

  A pinhole detection test was performed on the resulting package in the same manner as in Example 12. The results are shown in Table 7 below.

Example 17
The following ink composition 16 for detecting carbon dioxide gas was finely dispersed with a paint conditioner or the like to obtain an ink composition.

Carbon dioxide detection ink composition 16
Thymolphthalein 0.05g
Tropeolin OOONo. 2 0.05g
Sodium hydroxide 0.40g
Polyvinyl alcohol 50.00g
Isopropyl alcohol 34.00 g
100.00 g of water
A packaging material was obtained in the same manner as in Example 12 except that a mixed gas of 50% carbon dioxide and 50% air was used instead of the mixed gas of 3% carbon dioxide and 97% air using the obtained ink. Then, a packaging body of the present invention having an alumina-deposited PET film on which a carbon dioxide gas detection part was formed was obtained. The carbon dioxide gas detector was purple at the beginning of manufacture, but turned yellow after 1 hour.

  A pinhole detection test was performed on the resulting package in the same manner as in Example 12. The results are shown in Table 7 below.

Example 18
The following ink composition 17 for detecting carbon dioxide gas was finely dispersed with a paint conditioner or the like to obtain an ink composition.

Carbon dioxide detection ink composition 17
Thymol blue 0.05g
Phenolphthalein 0.25g
Thymolphthalein 0.025g
Sodium hydroxide 0.40g
Polyvinyl alcohol 50.00g
Isopropyl alcohol 34.00 g
Ethanol 50.00g
50.00 g of water,
Using the obtained ink, in the same manner as in Example 17, a package including a carbon dioxide gas detection indicator impregnated in filter paper was obtained. The carbon dioxide gas detector was purple at the beginning of manufacture, but turned yellow after 1 hour.

  A pinhole detection test was performed on the resulting package in the same manner as in Example 12. The results are shown in Table 7 below.

Example 19
The following ink composition 18 for detecting carbon dioxide gas was finely dispersed with a paint conditioner or the like to obtain an ink composition.

Carbon dioxide detection ink composition 18
Thymolphthalein 0.025g
卜 Lopeolin OOONo. 2 0.075g
Sodium hydroxide 0.40g
Polyvinyl alcohol 50.00g
Isopropyl alcohol 34.00 g
Ethanol 40.00g
50.00 g of water
Carbon dioxide gas was obtained in the same manner as in Example 14 except that the obtained ink composition was used and a mixed gas of 50% carbon dioxide and 50% air was used instead of a mixed gas of 3% carbon dioxide and 97% air. A package including a carbon dioxide detection indicator in a form in which filter paper was impregnated with detection ink was obtained. The display color of the carbon dioxide indicator was purple at the beginning of production, but turned yellow after 1 hour.

  A pinhole detection test was performed on the resulting package in the same manner as in Example 12. The results are shown in Table 7 below.

Example 20
The following ink composition 19 for detecting carbon dioxide gas was finely dispersed with a paint conditioner or the like to obtain an ink composition.

Carbon dioxide detection ink composition 19
Metacresol purple 0.05g
Orthocresolphthalein 0.02g
Sodium hydroxide 0.40g
10.00g of water
Except for using the obtained ink composition and using a mixed gas of 50% carbon dioxide and 50% air instead of a mixed gas of 3% carbon dioxide and 97% air, in the same manner as in Example 15, A package having a carbon dioxide indicator in a form in which microcrystalline cellulose was impregnated with carbon dioxide detection ink was obtained.

  The display color of the carbon dioxide indicator was purple at the beginning of production, but turned yellow after 1 hour.

  A pinhole detection test was performed on the resulting package in the same manner as in Example 12. The results are shown in Table 7 below.

Example 21
The following ink composition 20 for detecting carbon dioxide gas was finely dispersed with a paint conditioner or the like to obtain an ink composition.

Carbon dioxide detection ink composition 20
Timor Blue 0.075g
Tropeolin OOONo. 2 0.025g
Sodium hydroxide 0.40g
10.00g of water
Except for using the obtained ink composition and using a mixed gas of 50% carbon dioxide and 50% air instead of a mixed gas of 3% carbon dioxide and 97% air, in the same manner as in Example 16, A package including a carbon dioxide indicator enclosing a liquid form of carbon dioxide detection ink was obtained.

  The display color of the carbon dioxide indicator was purple at the beginning of production, but turned yellow after 1 hour.

  A pinhole detection test was performed on the resulting package in the same manner as in Example 12. The results are shown in Table 7 below.

Example 22
A package using an alumina-deposited PET film having a carbon dioxide gas detection portion formed as a package in the same manner as in Example 12 except that the following carbon dioxide gas detection ink composition 21 is used instead of the carbon dioxide gas detection ink composition 12. Got the body.

Carbon dioxide detection ink composition 21
Thymolphthalein 0.05g
Tropeolin OOONo. 2 0.05g
Sodium hydroxide 1.00g
Polyvinyl acetal resin 17.5g
Microcrystalline cellulose 11.00g
70.00g of water
The display color of the obtained carbon dioxide gas detection part was purple at the beginning of manufacture, but turned yellow after 1 hour.

  A pinhole detection test was performed on the resulting package in the same manner as in Example 12. The results are shown in Table 7 below.

Example 23
A package using an alumina-deposited PET film having a carbon dioxide gas detection portion formed as a package in the same manner as in Example 12 except that the following carbon dioxide gas detection ink composition 22 is used instead of the carbon dioxide gas detection ink composition 12. Got the body.

Carbon dioxide detection ink composition 22
Thymol blue 0.05g
Phenolphthalein 0.25g
Thymolphthalein 0.025g
Sodium hydroxide 1.00g
Polyvinyl acetal resin 17.5g
Microcrystalline cellulose 11.00g
70.00g of water
The display color of the obtained carbon dioxide gas detection part was purple at the beginning of manufacture, but turned yellow after 1 hour.

A pinhole detection test was performed on the resulting package in the same manner as in Example 12. The results are shown in Table 7 below.

The front view showing the 1st example of the carbon dioxide indicator used for the present invention Sectional view of FIG. Sectional drawing showing the structure of the 2nd example of the carbon dioxide gas indicator used for this invention Sectional drawing showing the structure of the 3rd example of the carbon dioxide gas indicator used for this invention Sectional drawing showing the structure of the 4th example of the carbon dioxide gas indicator used for this invention The figure showing the 1st example of the gas replacement packaging body concerning this invention The figure which shows the 2nd example of the gas replacement packaging body concerning this invention The figure which shows the 3rd example of the gas replacement packaging body concerning this invention The figure showing an example of the structure of the carbon dioxide gas indicator which can be used for the 3rd example of the gas replacement packaging body concerning this invention Sectional drawing showing the example which applied the 4th example of the carbon dioxide gas indicator used for this invention to the exterior body of a package The top view showing the container for chemical | medical solutions used for this invention.

Explanation of symbols

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

Claims (22)

  A support, an anchor coat layer provided on the support, an indicator formed on the anchor coat layer using a carbon dioxide detection ink composition containing a pH indicator, a binder, and a solvent; and A package comprising a carbon dioxide gas indicator having an overcoat layer provided so as to cover an instruction portion and disposed in a carbon dioxide-impermeable outer package having a carbon dioxide atmosphere.   The package according to claim 1, wherein a plastic chemical solution container having carbon dioxide permeability is further disposed in at least a part of the exterior body containing the bicarbonate-containing chemical solution.   3. The carbon dioxide gas concentration in the outer package is 0.5 to 10% by volume, and the bicarbonate-containing chemical solution includes at least one additive component of sodium salt and citrate. The package described in 1.   The package according to claim 3, wherein the additive component is (1) sodium chloride, (2) sodium chloride and citric acid, or (3) sodium citrate.   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. 5. The package according to claim 2, wherein the second chamber contains a solution containing sodium chloride and the second chamber contains a solution containing glucose and magnesium chloride.   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 package according to any one of claims 2 to 4, wherein the solution containing sodium citrate and the second chamber contain a solution containing oxyglutathione.   The package body according to any one of claims 1 to 6, wherein a concentration of carbon dioxide in the outer package is 3 to 9% by volume.   8. The carbon dioxide gas indicator is disposed between the chemical solution container and a carbon dioxide-impermeable outer package for packaging the chemical solution container. Packaging.   The package according to any one of claims 1 to 7, wherein the outer package is applied as the support, and the indicator is formed on at least a part of the inner surface of the outer package. The support includes a carbon dioxide impermeable layer having a carbon dioxide permeability of 50 (ml / m ² · 24 hr) or less, and 500 (ml / m ² · 24 hr) or more provided on the overcoat layer. The package according to any one of claims 1 to 8, further comprising a carbon dioxide permeable layer having a carbon dioxide permeability of the following.   The package according to any one of claims 1 to 10, wherein the anchor coat layer contains a vinyl acetal resin. The anchor coat layer is provided on the support, and includes a first anchor coat layer containing urethane resin, and a second anchor coat layer containing vinyl acetal resin laminated on the first anchor coat. The package according to claim 11.   The package according to any one of claims 1 to 12, wherein the overcoat layer contains a urethane resin.   The package according to any one of claims 1 to 13, wherein the carbon dioxide detection ink composition further includes at least one of a water absorbing agent and an alkaline substance.   The package according to any one of claims 1 to 14, wherein the solvent is at least one of water and alcohol.   The package according to any one of claims 1 to 15, wherein the binder has a property of being dissolved or dispersed in at least one of water and alcohol.   The package according to any one of claims 1 to 16, wherein the carbon dioxide gas detecting ink composition further contains glycerin.   A support, an anchor coat layer provided on the support, and an indicator formed on the anchor coat layer using a carbon dioxide detection ink composition containing a pH indicator, a binder, and a solvent; An indicator for detecting carbon dioxide, comprising an overcoat layer provided to cover the indicator. The support includes a carbon dioxide impermeable layer having a carbon dioxide permeability of 50 (ml / m ² · 24 hr) or less, and 500 (ml / m ² · 24 hr) or more provided on the overcoat layer. 19. The carbon dioxide gas detection indicator according to claim 18, further comprising a carbon dioxide gas permeable layer having a carbon dioxide permeability of the following.   The carbon dioxide detection indicator according to claim 18 or 19, wherein the anchor coat layer contains a vinyl acetal resin.   The anchor coat layer is provided on the support, and includes a first anchor coat layer containing urethane resin, and a second anchor coat layer containing vinyl acetal resin laminated on the first anchor coat. The carbon dioxide detection indicator according to any one of claims 18 to 20, wherein the indicator is for detecting carbon dioxide. The carbon dioxide detection indicator according to any one of claims 18 to 21, wherein the overcoat layer contains a urethane resin.

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