JP5469824B2 - Carbon dioxide indicator and package - Google Patents

Description

  The present invention relates to carbon dioxide using an ink composition for detecting carbon dioxide gas for detecting that a substituted gas atmosphere in a gas substitution packaging for storing foods, beverages, medicines and the like for a long period of time is maintained. The present invention relates to a gas indicator and a package using the same.

  2. Description of the Related Art Conventionally, various types of carbon dioxide indicators that can easily confirm a change in gas atmosphere due to a pinhole in a gas replacement package in which a replacement gas containing carbon dioxide is sealed and occurrence of a seal failure have been put on the market.

  This carbon dioxide indicator contains a pH indicator, and if there is enough carbon dioxide in the surrounding atmosphere, the carbon dioxide gas dissolves in the water in the carbon dioxide indicator and shows weak acidity, resulting in a low pH value. The color tone of the pH indicator changes. On the other hand, the pH value increases as the carbon dioxide concentration in the surrounding atmosphere decreases due to a pinhole or the like, and the color tone of the pH indicator changes accordingly. A change in the carbon dioxide gas concentration in the ambient atmosphere can be visually detected using the change in the color tone of the pH indicator (see, for example, Patent Document 1).

  The indicator of the carbon dioxide indicator can be printed using a carbon dioxide indicator ink composition containing a pH indicator and a binder. In addition, it is desirable that the ink layer is formed by overlapping two or more layers in order to achieve a clear change in color tone and sufficient color development.

However, these carbon dioxide indicators have a problem that, under high temperature and high humidity conditions, excessive moisture gathers in the indicator ink layer to form a water pool and the appearance is impaired. The relative humidity in the exterior body varies depending on the contents, the external temperature and humidity, and the internal space volume. In particular, it depends largely on the contents. Foods, beverages, and pharmaceuticals each have their own water activity (relative humidity (% RH) = water activity [−] × 100), which is a factor that greatly changes the humidity in the exterior body depending on the contents. For example, coffee, paste, tea, rice crackers, biscuits, chocolate 0.1-0.5, rice, caramel, boiled, medical ampoules 0.5-0.7, miso, fresh confectionery, dumplings, bread crumbs, cheese , Chikuwa, candy, beverage, medical solution bag, etc. show 0.7-1. The higher the water activity, the higher the relative humidity, causing the appearance of the indicator to be impaired.
International Publication No. 01/044385 Pamphlet

  The present invention has been made in view of the above circumstances, and a first object of the present invention is to provide a carbon dioxide gas indicator having an indicating portion whose appearance is not impaired even when used under conditions with a lot of moisture.

  A second object of the present invention is to provide a package provided with a carbon dioxide gas indicator having an indicating portion whose appearance is not impaired even when used under conditions with a lot of moisture.

The carbon dioxide indicator of the present invention comprises a support and a multilayer indicator formed on the support and laminated with two or more carbon dioxide detection layers,
The multilayer indicator includes a first carbon dioxide gas printed on the support using a first carbon dioxide detection ink composition containing a pH indicator, a binder, and a polyhydric alcohol having a first concentration. The first carbon dioxide gas detection layer using a detection layer and a second carbon dioxide gas detection ink composition containing a pH indicator, a binder, and a second concentration polyhydric alcohol different from the first concentration A carbon dioxide indicator having a second carbon dioxide sensing layer printed thereon,
The second concentration is lower than the first concentration, and the first concentration and the second concentration are 1 wt% to 10 wt% .

The package of the present invention encloses a carbon dioxide gas indicator having a support and a multilayer indicator formed on the support and having two or more carbon dioxide gas detection layers stacked therein, and a replacement gas containing carbon dioxide is enclosed. The multi-layer indicator is disposed in an exterior body, and the multilayer indicator uses the first carbon dioxide gas detecting ink composition containing a pH indicator, a binder, and a first concentration polyhydric alcohol. A second carbon dioxide detection ink composition comprising a first carbon dioxide detection layer printed thereon, a pH indicator, a binder, and a polyhydric alcohol having a second concentration different from the first concentration; second possess a carbon dioxide gas sensing layer, wherein the first lower in the second concentration than said first concentration and printed on the first carbon dioxide sensing layer using the second concentration is characterized by 10% der Rukoto 1 wt%

  By using the present invention, it is possible to obtain a carbon dioxide indicator having an indicating portion whose appearance is not impaired even when used under conditions with much moisture.

  The carbon dioxide indicator of the present invention has an indicator printed on a support using a pH indicator, a binder, and a carbon dioxide detection ink composition containing a polyhydric alcohol as a solvent.

  The indicator used in the present invention is a multilayer indicator in which two or more carbon dioxide detection layers are stacked. The two or more carbon dioxide gas detection layers are formed using carbon dioxide gas detection ink compositions having different polyhydric alcohol concentrations.

  In addition, the package of the present invention includes a base material and an indicator printed on the base material using a pH indicator, a binder, and a carbon dioxide gas detecting ink composition containing a polyhydric alcohol as a solvent. The carbon dioxide gas indicator is arranged in an exterior body in which a replacement gas containing carbon dioxide gas is enclosed, and the indicator used is a multilayer indicator in which two or more carbon dioxide gas detection layers are stacked. The carbon dioxide gas detection layers are formed using carbon dioxide gas detection ink compositions having different polyhydric alcohol concentrations.

  The polyhydric alcohol used as a solvent acts as a humectant, maintains moderate moisture in the ink layer as the indicator, facilitates absorption of carbon dioxide gas, and promotes the color reaction of the pH indicator. Can do.

  According to the present invention, when two or more carbon dioxide gas detection layers constituting the indicating unit are stacked, moisture such as water vapor from the contents is far from the contents via the carbon dioxide gas detection layer closer to the contents. Since it reaches the carbon dioxide gas detection layer, the distribution of the water absorption amount is appropriately controlled, and the appearance defect due to excessive water absorption in the indicator is less likely to occur.

  A carbon dioxide gas detection layer having a low polyhydric alcohol concentration is disposed closer to the contents, and a carbon dioxide gas detection layer having a higher polyhydric alcohol concentration is disposed further from the contents. Thereby, with respect to the water | moisture content, the carbon dioxide detection layer with low water absorption performance works as a buffer, and the water absorption amount to the carbon dioxide detection layer with high water absorption performance can be controlled. For this reason, it is possible to prevent an appearance defect of the instruction unit.

  As the polyhydric alcohol, glycerin, ethylene glycol, propylene glycol, polyethylene glycol and the like can be used. More preferably, glycerin can be used.

The addition amount of the polyhydric alcohol is 1% by weight to 10% by weight in the ink composition. In the present invention, the carbon dioxide gas detection layer having a lower polyhydric alcohol concentration is preferably 1 wt% to 4 wt%, and the carbon dioxide gas detection layer having a higher polyhydric alcohol concentration is preferably 4 wt% to 7 wt%.

  The multi-layer indicator used in the present invention may include a plurality of stacked carbon dioxide gas detection layers. When the number of layers increases and the amount of the ink composition increases, the amount of water that can be absorbed increases and appearance defects tend to occur. Therefore, the number of layers is preferably 2 to 3. The thickness of the carbon dioxide gas detection layer is preferably 1 μm or less. Moreover, in order to form a uniform layer by printing, the thickness of one layer is preferably 0.5 μm or more.

  Any pH indicator can be used as long as it is accompanied by a change in color tone due to the influence of carbon dioxide gas or a color change caused by a change in pH corresponding to a change in the concentration of an alkaline substance.

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

  A particularly preferred pH indicator is metacresol purple because it is easy to understand changes in safety and color reaction.

  To the ink composition of the present invention, preferably, an alkaline substance greater than 0 and 5% by weight or less can be added. Even if an alkaline substance exceeding 5% by weight is added, the effect tends to be equivalent.

  The alkaline substance used in the present invention can be selected from organic alkalis such as triethanolamine and polyethyleneimine, and alkali hydroxides, alkali carbonates, alkali hydrogen carbonates, ammonia, and the like.

  As the solvent that can be used in the present invention together with the polyhydric alcohol, a solvent that can uniformly and stably dissolve or disperse each component of the ink composition of the present invention is selected. For example, ethers, aromatics Examples include hydrocarbons, esters, alcohols, and ketones. In particular, alcohols are preferable.

  In order to obtain an ink composition by dissolving a pigment, an alkaline substance or the like and to obtain a good color as an indicator, it is preferable that the solvent further contains water. The ratio of the weight of the polyhydric alcohol and solvent used in the present invention to the weight of water is preferably 1 to 3 parts by weight of the solvent with respect to 1 part by weight of water. When the amount of the solvent added exceeds 3 parts by weight, the ratio of water decreases and the color development becomes worse, so that sufficient color development cannot be obtained and the change in color tone tends to be indistinguishable. In addition, when the solvent is less than 1 part by weight, the ratio of water increases, and appearance defects tend to occur under high humidity conditions.

  The binder resin is used to fix a component such as a pH indicator on a support, and a resin that swells or dissolves in water after film formation is unsuitable. Use a resin that holds Examples of such a binder include polyacrylic acid, polyvinyl alcohol, polyvinyl butyral, polyvinyl acetal, polyvinyl acetate, polyurethane, and partially saponified vinyl acetate.

  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 such a purpose, a colorant can be added to the carbon dioxide gas detecting ink composition of the present invention.

  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 a carbon dioxide detection layer using the carbon dioxide detection ink composition of the present invention can be provided thereon.

  Examples of the colorant used in the present invention include edible red No. 2 (Amaranth), edible red No. 3 (erythrosin), edible red No. 40 (Arla Red AC), edible red No. 102 (New Coxin), and edible red 104. No. (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 natural red safflower yellow And blue colorants such as Food Blue No. 1 (Brilliant Blue FCF) and Food Blue No. 2 (Indigo Carmine).

  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.

  For the formation of the multilayer indicator used in the present invention, it is preferable to use a printing method because the amount of the ink composition applied is relatively large and is desired to be constant.

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

  For example, when processing a packaging bag by continuously printing a multilayer 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 of the present invention and does not inhibit the coloration of the reagent can be selected. As such a support, for example, paper, synthetic paper, non-woven cloth, or synthetic resin film can be used. Synthetic resin films include, for example, polyester, polyamide, polyvinyl alcohol, cellophane, ethylene vinyl alcohol copolymer, polyethylene, polypropylene, polymethylpentene, and the like, and transparent deposited films provided with silica or alumina deposited layers on these films. Etc. can be used in accordance with the purpose and usage.

  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.

  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 atmosphere, and a carbon dioxide indicator is provided in the container. (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.

  Examples of foods, beverages, and chemicals to which the carbon dioxide indicator of the present invention can be applied include those that may be altered by contact with oxygen, or those that may lose quality or lose their efficacy due to the release of carbon dioxide. There is.

  Examples of foods and beverages 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.

  Since the carbon dioxide gas indicator used in the present invention has an indicating portion with adjusted water absorption so as not to cause poor appearance, the package of the present invention has a relative humidity of 50% or less in the outer package. The contents that can be 100% can be enclosed.

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

  FIG. 1 is a cross-sectional view of a multi-layer indicator of a carbon dioxide indicator of the present invention.

  As shown in the figure, the indicator of this carbon dioxide indicator is a support 5 in a circular pattern of an ink composition for detecting carbon dioxide comprising, for example, metacresol purple, sodium carbonate, polyvinyl acetal resin, microcrystalline cellulose, and water. It is composed of a multi-layer indicator 4 in which a carbon dioxide gas detection layer 1 and a carbon dioxide gas detection layer 2 obtained by coating by screen printing are laminated.

  FIG. 2 is a front view showing a first example, and FIG. 3 is a sectional view thereof.

  As shown in the figure, this indicator 10 has a structure in which, for example, the indicator 4 is provided on both surfaces of a support 5 made of, for example, a polyethylene terephthalate film, and its periphery is surrounded by, for example, a porous film 7 having carbon dioxide permeability. Have. The indicator part of the indicator is purple in normal air. In FIGS. 2 and 3, the instruction unit 4 is provided on both sides of the support 1, but a configuration in which the instruction unit is provided only on one side can also be applied. The indicator is surrounded by the air permeable film 7 but can be used as it is without using the air permeable film 7.

  FIG. 4 is a sectional view showing the configuration of a second example of the carbon dioxide indicator of 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, Carbon dioxide made of, for example, a polyethylene film formed so as to seal the indicator 4 and the indicator 4 provided on the carbon dioxide-impermeable layer 71 on the carbon-gas-impermeable layer 71. A layer 73 having gas permeability.

Here, carbon dioxide impermeability means having a carbon dioxide permeability of 50 (ml / m ² · 24 hours) or less at about 23 ° C. and about 40% RH.

Carbon dioxide permeability means having a carbon dioxide gas permeability of 500 (ml / m ² · 24 hours) or more at about 23 ° C. and about 40% RH.

  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 hours), the response to changes in the carbon dioxide gas atmosphere is delayed, 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 hours), the carbon dioxide atmosphere in the package can be maintained. Can not.

The resin film having a carbon dioxide gas permeability of 50 (ml / m ² · 24 hours) or less that can be used in the present invention is a base film made of a synthetic resin such as a polyester (PET) film or a nylon (Ny) film. Examples thereof include a transparent vapor-deposited film on which silica or alumina is vapor-deposited, 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 film having a carbon dioxide gas permeability of 500 (ml / m ² · 24 hours) or more 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 bag inner layer.

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

  FIG. 5 is a sectional view showing the configuration of the third example of the carbon dioxide gas indicator of 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 body 1 made of a polyester film 57 having an anchor coat layer 51 formed on the support body 1, and on the anchor coat layer 51 on which the indicator section 4 and the instruction section 4 are printed. The overcoat layer 52 is formed so as to seal the indicating portion 4. The indicator indicating section 4 is purple in normal air.

  The pH indicator in the indicator 4 reacts via a solvent, for example, a hydrophilic solvent such as water or an alcohol compound. For this reason, the instruction | indication part 4 can contain such a solvent. For this reason, the instruction | indication part 4 tends to accumulate water, and tends to raise | generate an external appearance defect. In addition, the indicating unit 4 is vulnerable to external impacts, and is easily peeled off and broken around the indicating unit 4 and its periphery. Like the carbon dioxide gas indicator 50, the indicator 4 is sandwiched between the anchor coat layer 51 and the overcoat layer 52, so that the carbon dioxide detection ink composition constituting the indicator 4 is protected. Breakage can be prevented. Furthermore, the long-term stability of the carbon dioxide indicator including water resistance, light resistance, and heat resistance is improved.

  The anchor coat layer 51 is made of a water-insoluble material having good adhesion between the support 5 and the indicator 4 formed thereon, and the overcoat layer 52 is carbon dioxide permeable. A material having good adhesion to the indicating unit 4 and optionally, for example, an adhesive layer or other resin layer that can be further provided on the indicating unit 4 can be preferably used.

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

  Here, the instruction unit is provided only on one side of the support 4, but a configuration in which the instruction unit 4 is provided on both sides of the support 5 can also be applied. Moreover, when providing an instruction | indication part only in the single side | surface of the support body 5, if necessary, 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.

  Moreover, FIG. 6 is sectional drawing showing the structure of the 4th example of a carbon dioxide gas indicator.

  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 gas 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 4 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 5 such as a urethane resin is preferably used. In addition, the second anchor coat layer has good adhesion to the first anchor coat layer and the indicator 4, and more preferably has a hydrophilic group and has a water retention effect on the indicator 5 containing water. For example, a butyral resin or the like is preferably used.

  As the overcoat layer, for example, urethane resin can be 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 5 and the indicating portion 4, the second The anchor coat layer 54 provides an effect of securing a sufficient amount of moisture for at least the pH indicator in the indicator 4 to function. Therefore, the carbon dioxide indicator 60 has stronger adhesion and more effective water retention with respect to the indicator 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.

  In addition, although the instruction | indication part was provided only in the single side | surface of the support body 5 here, the structure which provided the instruction | indication part 4 in both surfaces of the support body 5 is also applicable. Moreover, when providing an instruction | indication part only in the single side | surface of the support body 5, if necessary, 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. 7, the figure showing the 1st example of the gas replacement packaging body concerning this invention is shown. As shown in the figure, this gas replacement package 20 is made of, for example, a polyethylene container 11 containing contents such as chemicals and beverages, and a carbon dioxide gas indicator 10 with 50% nitrogen and 50% carbon dioxide as replacement gases. % Mixed gas 13 is used to enclose the outer package 12 made of a gas barrier laminated film.

  The indicator indicating section 4 in the package is yellow when enclosed. 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 tone of the indicator 4 changes from yellow to light brown, and further to purple according to pH. By visually recognizing the change in the color tone, it can be easily confirmed whether or not the atmosphere containing carbon dioxide in the package is maintained.

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

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

  As shown in the figure, the package 30 is formed by using the ink composition of the present invention on the surface of a polyethylene film container 14 in which contents such as raw block meat are vacuum-packaged, with the exterior portion of the container 14 as a support. A carbon dioxide gas indicator 18 having an indicator 4 formed by screen printing and a coating layer 8 made of a breathable material coated on the indicator 4 is provided, and 50% by volume of nitrogen and 50% of carbon dioxide are used as replacement gases. % Of the mixed gas 13 is used to enclose the outer package 12 made of a gas barrier laminated film. Moreover, it can also be set as the package which has the structure similar to the package 30 of FIG. 8 except not providing the coating layer 8. FIG.

  Even in the package 30, as in the package shown in FIG. 7, it is possible to easily confirm whether or not the gas atmosphere containing the carbon dioxide gas in the package is maintained by visually recognizing the change in the color tone.

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

  In addition to the package shown in FIGS. 7 and 8, the indicator 4 is printed on the exterior body 12 as shown in FIG. 9, or the indicator 10 including the support 5 provided with the instruction part 4 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 exterior body 12 made of a gas barrier laminated film, and an indicator provided on the inner surface of the exterior body 12 by, for example, screen printing using the ink composition of the present invention with the exterior body 12 as a support. 4 and a carbon dioxide gas indicator. For example, the packaging body 40 is formed by arranging two laminated films with the indicating unit 4 inside and placing the contents 16 therebetween, and then replacing the mixed gas 13 with 50% by volume of nitrogen and 50% by volume of carbon dioxide. It can be formed by hermetically sealing the periphery of the exterior body 12 by heat sealing.

  In FIG. 10, 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 indicator 12 is printed using the ink composition of the present invention using the outer package 12 as a support, as shown in FIG. 10, the gas of the laminate 31 including the gas barrier layer constituting the outer package 12. It is also possible to provide the indicating unit 4 on the inner surface of the barrier layer 32 and cover the inner surface side of the indicating unit 4 with a protective film 33 that is permeable to carbon dioxide gas.

By adopting a configuration in which the indication unit 4 is not exposed in this way, the indication unit 4 is not directly in contact with the container or the contents, and the indication unit 4 is prevented from being worn during the manufacturing process or during transportation. 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. 11, sectional drawing showing the example which applied the 4th example of the carbon dioxide gas indicator which concerns on this invention to the exterior body of a package is shown.

  As shown in the figure, 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. 6 on this laminated film, the laminated structure of the first anchor coat layer 53 and the second anchor coat layer 54, the indicator 4, 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 trade name or a pattern such as an image can be provided in other regions on the exterior body in parallel with the production of the carbon dioxide indicator 80. Further, a sealant layer 75 made of low-density polyethylene is provided on the overcoat layer 52 and the ink layer 17 through an adhesive layer 74, for example.

  A package with a carbon dioxide indicator is obtained by sealing the contents using, for example, 50% by volume of nitrogen and 50% by volume of carbon dioxide as a replacement gas using an exterior body provided with such a carbon dioxide indicator. It is done. 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 indicator including water resistance, light resistance, and heat resistance is improved.

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

Example 1
Ink compositions having the following compositions were respectively prepared.

Carbon dioxide gas detection layer a composition:
1 part by weight of metacresol purple, 4 parts by weight of sodium hydroxide, 7 parts by weight of binder resin, 4 parts by weight of glycerol, 84 parts by weight of n-propanol, 28 parts by weight of water Carbon dioxide detection layer b Composition:
Metacresol purple 1 part, sodium hydroxide 4 parts, binder resin 7 parts, glycerin 1 part, n-propanol 84 parts, water 28 parts by weight Anchor coat layer, overcoat layer composition:
4 parts by weight of urethane resin, 5 parts by weight of isopropyl alcohol, 10 parts by weight of ethyl acetate, 5 parts by weight of methyl ethyl ketone, 10 parts by weight of toluene An anchor coat layer 0.5 μm on one side of a 12 μm thick polyester film, a carbon dioxide gas detection layer a 1 μm, A carbon dioxide gas indicator having the same configuration as in FIG. 5 is obtained by sequentially laminating a carbon dioxide gas detection layer b 1 μm and an overcoat layer 1 μm by gravure printing, and forming a carbon dioxide gas permeable layer made of, for example, a polyethylene film thereon. It was. The carbon dioxide gas detection layer b of the obtained carbon dioxide gas indicator has a lower content of glycerin, that is, polyhydric alcohol than the carbon dioxide gas detection layer a.

  The obtained carbon dioxide indicator is put into a transparent outer casing made of a gas barrier base material, the inside is replaced with carbon dioxide 50% nitrogen 50%, the content containing the sodium bicarbonate solution is enclosed, and the internal humidity is 70%. A package was obtained.

  The resulting package was allowed to stand for 2 weeks under high-temperature and high-humidity conditions at 60 ° C. and 75% Rh, and the appearance and color development were observed. As a result, the appearance and color development were not deteriorated.

  The obtained results are shown in Table 2 below.

  In the table, the appearance was evaluated as ◎ when there was no problem with the appearance, ◯ when the appearance was slightly deteriorated, and × when the appearance was poor.

  The color development was evaluated as ◯ when the visibility of color development was good, and x when it was insufficient.

Example 2
Ink compositions having the following compositions were respectively prepared.

Carbon dioxide gas detection layer a composition:
Metacresol purple 1 part, sodium hydroxide 4 parts, binder resin 7 parts, glycerin 7 parts, n-propanol 84 parts, water 28 parts by weight Carbon dioxide detection layer b composition:
Metacresol purple 1 part, sodium hydroxide 4 parts, binder resin 7 parts, glycerin 2 parts, n-propanol 84 parts, water 28 parts by weight Anchor coat layer, overcoat layer composition:
As in Example 1, each ink composition was used, and a package was obtained in the same manner as in Example 1. The resulting package was allowed to stand for 2 weeks under high-temperature and high-humidity conditions at 60 ° C. and 75% Rh, and the appearance and color development were observed. As a result, the appearance and color development were not deteriorated.

  The obtained results are shown in Table 2 below.

Example 3
Ink compositions having the following compositions were respectively prepared.

Carbon dioxide gas detection layer a composition:
1 part by weight of metacresol purple, 4 parts by weight of sodium hydroxide, 7 parts by weight of binder resin, 5 parts by weight of glycerin, 84 parts by weight of n-propanol, 28 parts by weight of water Carbon dioxide detection layer b composition:
Metacresol purple 1 part, sodium hydroxide 4 parts, binder resin 7 parts, glycerin 1 part, n-propanol 84 parts, water 28 parts by weight Anchor coat layer, overcoat layer composition:
As in Example 1, each ink composition was used, and a package was obtained in the same manner as in Example 1. The resulting package was allowed to stand for 2 weeks under high-temperature and high-humidity conditions at 60 ° C. and 75% Rh, and the appearance and color development were observed. As a result, the appearance and color development were not deteriorated.

  The obtained results are shown in Table 2 below.

Reference example 1
Ink compositions having the following compositions were respectively prepared.

Carbon dioxide gas detection layer a composition:
Metacresol purple 1 part by weight, sodium hydroxide 4 parts by weight, binder resin 7 parts by weight, glycerin 2 parts by weight, n-propanol 84 parts by weight, water 28 parts by weight Carbon dioxide detection layer b composition:
Metacresol purple 1 part, sodium hydroxide 4 parts, binder resin 7 parts, glycerin 7 parts, n-propanol 84 parts, water 28 parts by weight anchor coat layer, overcoat layer composition:
As in Example 1, each of the above ink compositions was used to obtain a packaged body as in Example 1. The carbon dioxide gas detection layer b of the obtained carbon dioxide gas indicator has a higher content of glycerin, that is, polyhydric alcohol than the carbon dioxide gas detection layer a.

Using the above ink compositions, a package was obtained in the same manner as in Example 1 obtained. 2 weeks after leaving the resulting package to a high temperature and high humidity conditions of 60 ° C. 75% Rh, appearance was observed color development, some deterioration in appearance was observed, and Tsu good der visibility of color It was.

  The obtained results are shown in Table 2 below.

Reference example 2
Ink compositions having the following compositions were respectively prepared.

Carbon dioxide gas detection layer a composition:
1 part by weight of metacresol purple, 4 parts by weight of sodium hydroxide, 7 parts by weight of binder resin, 1 part by weight of glycerin, 84 parts by weight of n-propanol, 28 parts by weight of water Carbon dioxide detection layer b Composition:
Metacresol purple 1 part by weight, sodium hydroxide 4 parts by weight, binder resin 7 parts by weight, glycerin 5 parts by weight, n-propanol 84 parts by weight, water 28 parts by weight anchor coat layer, overcoat layer composition:
Similar to Example 1 A package was obtained in the same manner as Example 1. 2 weeks after leaving the resulting package to a high temperature and high humidity conditions of 60 ° C. 75% Rh, appearance was observed color development, some deterioration in appearance was observed, and Tsu good der visibility of color It was.

  The obtained results are shown in Table 2 below.

Example 4
Ink compositions having the following compositions were respectively prepared.

Carbon dioxide gas detection layer a composition:
1 part by weight of metacresol purple, 4 parts by weight of sodium hydroxide, 7 parts by weight of binder resin, 7 parts by weight of glycerin, 84 parts by weight of n-propanol, 28 parts by weight of water Carbon dioxide detection layer b Composition:
Metacresol purple 1 part by weight, sodium hydroxide 4 parts by weight, binder resin 7 parts by weight, glycerin 5 parts by weight, n-propanol 84 parts by weight, water 28 parts by weight anchor coat layer, overcoat layer composition:
As in Example 1, each ink composition was used, and a package was obtained in the same manner as in Example 1. 2 weeks after leaving the resulting package to a high temperature and high humidity conditions of 60 ° C. 75% Rh, appearance was observed color development, some deterioration in appearance was observed, and Tsu good der visibility of color It was.

  The obtained results are shown in Table 2 below.

Example 5
Ink compositions having the following compositions were respectively prepared.

Carbon dioxide gas detection layer a composition:
1 part by weight of metacresol purple, 4 parts by weight of sodium hydroxide, 7 parts by weight of binder resin, 7 parts by weight of glycerin, 84 parts by weight of n-propanol, 28 parts by weight of water Carbon dioxide detection layer b Composition:
Metacresol purple 1 part, sodium hydroxide 4 parts, binder resin 7 parts, glycerin 2 parts, n-propanol 84 parts, water 28 parts by weight anchor coat layer, overcoat layer composition:
As in Example 1, using each of the above ink compositions, an anchor coat layer of 0.5 μm, a carbon dioxide gas detection layer a of 1 μm, and a carbon dioxide gas detection layer b of 1 μm are coated on one side of a 12 μm polyester film. One layer of 1 μm was sequentially laminated by gravure printing. A carbon dioxide gas permeable layer was formed thereon to obtain a carbon dioxide indicator having the same configuration as in FIG.

  Using the obtained carbon dioxide indicator, a package was obtained in the same manner as in Example 1.

The resulting package was allowed to stand under high temperature and high humidity conditions of 60 ° C. and 75% Rh for 2 weeks, and the appearance and color development were observed. Some deterioration in appearance was observed, and was Tsu good der visibility of the color.

  The obtained results are shown in Table 2 below.

Comparative Example 1
Ink compositions having the following compositions were respectively prepared.

Carbon dioxide gas detection layer a composition:
1 part by weight of metacresol purple, 4 parts by weight of sodium hydroxide, 7 parts by weight of binder resin, 7 parts by weight of glycerin, 84 parts by weight of n-propanol, 28 parts by weight of water Carbon dioxide detection layer b Composition:
Metacresol purple 1 part, sodium hydroxide 4 parts, binder resin 7 parts, glycerin 7 parts, n-propanol 84 parts, water 28 parts by weight anchor coat layer, overcoat layer composition:
Similar to Example 1 A package was obtained in the same manner as Example 1. The resulting package was allowed to stand for 2 weeks under high-temperature and high-humidity conditions at 60 ° C. and 75% Rh. The appearance and color development were observed. As a result, water accumulated in the indicator part, resulting in poor color development.

  The obtained results are shown in Table 2 below.

Comparative Example 2
Ink compositions having the following compositions were respectively prepared.

Carbon dioxide gas detection layer a composition:
1 part by weight of metacresol purple, 4 parts by weight of sodium hydroxide, 7 parts by weight of binder resin, 1 part by weight of glycerin, 84 parts by weight of n-propanol, 28 parts by weight of water Carbon dioxide detection layer b Composition:
Metacresol purple 1 part by weight, sodium hydroxide 4 parts by weight, binder resin 7 parts by weight, glycerin 1 part by weight, n-propanol 84 parts by weight, water 28 parts by weight anchor coat layer, overcoat layer composition:
Similar to Example 1 A package was obtained in the same manner as Example 1. Discoloration of the indicator part did not occur during carbon dioxide gas replacement. Discoloration occurred after standing for 24 hours.

  The obtained results are shown in Table 2 below.

Comparative Example 3
Ink compositions having the following compositions were respectively prepared.

Carbon dioxide gas detection layer a composition:
1 part by weight of metacresol purple, 4 parts by weight of sodium hydroxide, 7 parts by weight of binder resin, 1 part by weight of glycerin, 84 parts by weight of n-propanol, 28 parts by weight of water Carbon dioxide detection layer b Composition:
Metacresol purple 1 part by weight, sodium hydroxide 4 parts by weight, binder resin 7 parts by weight, glycerin 15 parts by weight, n-propanol 84 parts by weight, water 28 parts by weight anchor coat layer, overcoat layer composition:
Similar to Example 1 A package was obtained in the same manner as Example 1. The resulting package was allowed to stand for 2 weeks under high-temperature and high-humidity conditions at 60 ° C. and 75% Rh. The appearance and color development were observed. As a result, water accumulated in the indicator part, resulting in poor color development.

  The obtained results are shown in Table 2 below.

Comparative Example 4
Ink compositions having the following compositions were respectively prepared.

Carbon dioxide gas detection layer a composition:
Metacresol purple 1 part by weight, sodium hydroxide 4 parts by weight, binder resin 7 parts by weight, glycerin 15 parts by weight, n-propanol 84 parts by weight, water 28 parts by weight Carbon dioxide detection layer b Composition:
Metacresol purple 1 part, sodium hydroxide 4 parts, binder resin 7 parts, glycerin 1 part, n-propanol 84 parts, water 28 parts by weight anchor coat layer, overcoat layer composition:
Similar to Example 1 A package was obtained in the same manner as Example 1. The resulting package was allowed to stand for 2 weeks under high-temperature and high-humidity conditions at 60 ° C. and 75% Rh. The appearance and color development were observed. As a result, water accumulated in the indicator part, resulting in poor color development.

  The obtained results are shown in Table 2 below.

Comparative Example 5
Ink compositions having the following compositions were respectively prepared.

Carbon dioxide gas detection layer a composition:
Metacresol purple 1 part by weight, sodium hydroxide 4 parts by weight, binder resin 7 parts by weight, glycerin 5 parts by weight, n-propanol 84 parts by weight, water 28 parts by weight Carbon dioxide detection layer b composition:
Metacresol purple 1 part, sodium hydroxide 4 parts, binder resin 7 parts, glycerin 7 parts, n-propanol 84 parts, water 28 parts by weight anchor coat layer, overcoat layer composition:
Similar to Example 1 A package was obtained in the same manner as Example 1. The resulting package was allowed to stand for 2 weeks under high-temperature and high-humidity conditions at 60 ° C. and 75% Rh. The appearance and color development were observed. As a result, water accumulated in the indicator part, resulting in poor color development.

  The obtained results are shown in Table 2 below.

  Note that the present invention is not limited to the above-described embodiment as it is, and can be embodied by modifying the constituent elements without departing from the scope of the invention in the implementation stage. In addition, various inventions can be formed by appropriately combining a plurality of components disclosed in the embodiment. For example, some components may be deleted from all the components shown in the embodiment. Furthermore, you may combine the component covering different embodiment suitably.

  The present invention can be applied to detect that a substituted gas replacement atmosphere in a gas replacement package for storing foods, beverages, and medicines for a long period of time is maintained.

Sectional drawing of the indicator of the carbon dioxide indicator of the present invention The front view which shows the 1st example of the carbon dioxide indicator of this invention Cross section of FIG. Sectional drawing showing the structure of the 2nd example of the carbon dioxide gas indicator of this invention Sectional drawing showing the structure of the 3rd example of the carbon dioxide gas indicator of this invention Sectional drawing showing the structure of the 4th example of a carbon dioxide indicator The figure showing the 1st example of the gas replacement packaging body concerning this invention The figure showing the 2nd example of the gas replacement packaging body concerning this invention The figure showing 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 concerning this invention to the exterior body of a package

Explanation of symbols

DESCRIPTION OF SYMBOLS 1, 2 ... Carbon dioxide gas detection layer, 4 ... Instruction | indication part 5 ... Support body, 73, 73 ... Carbon dioxide gas permeable film, 8 ... Covering layer 10, 18, 50, 60, 70, 80 ... Carbon dioxide gas indicator, 11 , 14, 16 ... container, 12 ... exterior body, 13 ... carbon dioxide-containing gas, 17 ... ink layer, 20, 30, 40 ... packaging body, 31 ... laminate, 32 ... gas barrier layer, 33 ... protective film, 51 ... anchor coat layer, 52 ... overcoat layer, 53 ... first anchor coat layer, 54 ... second anchor coat layer, 55, 81 ... nylon film, 56, 74, 82 ... adhesive layer, 57, 83 ... Alumina-deposited polyester film, 71 ... Carbon dioxide impermeable film, 75 ... Sealant layer

Claims (3)

A support, and a multilayer indicator formed on the support and laminated with two or more carbon dioxide gas detection layers;
The multilayer indicator includes a first carbon dioxide gas printed on the support using a first carbon dioxide detection ink composition containing a pH indicator, a binder, and a polyhydric alcohol having a first concentration. The first carbon dioxide gas detection layer using a detection layer and a second carbon dioxide gas detection ink composition containing a pH indicator, a binder, and a second concentration polyhydric alcohol different from the first concentration A carbon dioxide indicator having a second carbon dioxide sensing layer printed thereon,
The carbon dioxide indicator, wherein the second concentration is lower than the first concentration, and the first concentration and the second concentration are 1 wt% to 10 wt%.   A packaging body, wherein the carbon dioxide indicator according to claim 1 is disposed in an outer package enclosing a replacement gas containing carbon dioxide. The package according to claim 2, wherein contents having a relative humidity of 50% or more in the outer package are enclosed.

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