JP2003335380A - Package with oxygen indicator function - Google Patents

Abstract

(57) [Summary] [Problem] To provide a package with an oxygen indicator function that can easily confirm a change in gas atmosphere due to the occurrence of pinholes and poor sealing in a package in a deoxidized atmosphere. SOLUTION: A gas permeable container containing a medicine or food which is liable to be deteriorated by oxygen is packaged in a gas impermeable packaging material, and the inside of the package is degassed by gas replacement, vacuum, or oxygen scavenger. A package having an oxygen indicator function, characterized in that the package having an oxygen atmosphere is provided with printing an oxygen detecting portion for detecting a change in the gas atmosphere of the package by a change in color tone due to a defect of the packaging material.

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a package for storing medicines, medicines, foods (including beverages), etc. for a long period of time. More specifically, the present invention relates to a package with an oxygen indicator function, which is provided with an oxygen detector by printing.

[0002]

2. Description of the Related Art Gas substitution packaging is a general method for preventing the contents such as medicines, medicines, foods (including beverages) from being oxidized and storing them for a long time. The gas replacement packaging is, for example, a method in which nitrogen is used as a replacement gas and packaging is performed with a packaging material having excellent gas impermeability. As described above, the contents can be stored for a long period of time by performing the gas displacement packaging using the packaging material having excellent gas impermeability. However, if pinholes or poor seals occur due to defects in the packaging material itself, failure to fill the contents, or impact during transportation such as distribution, the atmosphere in which the gas is replaced is changed. However, the contents may be decomposed or deteriorated, and the gas may be distributed without noticing the change in the atmosphere filled with the gas. In this way, even when gas displacement packaging is performed using packaging materials with excellent gas impermeability, there is no means to confirm pinholes, poor sealing, etc., and the contents are reliably stored in the gas displacement packaging atmosphere. I didn't know if it was.

Therefore, in order to solve the above problems, a package containing an oxygen indicator which changes its hue depending on the presence or absence of oxygen has been developed. Conventionally, as an oxygen indicator, tablets are individually packaged,
The presence or absence of oxygen is determined by packaging a medicine or food in a small bag of a gas impermeable film by blocking external oxygen, and inserting the packaged tablet into a package. However, in the conventional tableted product, (1) the tablets must be individually packaged, (2) when the tablets are disintegrated, the disintegrated powder flows out through the holes in the pouch, ( 3)
In the case of pharmaceuticals, various problems such as accidental ingestion of tablets leading to medical malpractice, (4) it is difficult to fix the tablets inside the package, (5) the tablets move inside the package, and are difficult to be visually detected from the outside. Had a point.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides a package with an oxygen indicator function, which can easily confirm the change in the gas atmosphere in the package due to the occurrence of pinholes, poor sealing, etc. To provide.

[0005]

Means for Solving the Problems As a result of intensive studies to solve the above-mentioned problems, the present inventors have developed a gas-permeable container containing a drug or food that is easily deteriorated by oxygen with a gas-impermeable packaging material. By wrapping it and making it a packaging body with an oxygen indicator function equipped with an oxygen detection part by printing,
The inventors have found that the above problems can be solved all at once, and have conducted further studies to complete the present invention.

[0006] That is, the present invention provides (1) a gas permeable container containing a drug or food which is easily deteriorated by oxygen,
In a package which is packaged in a gas impermeable packaging material and has a deoxygenated atmosphere in the package due to gas replacement, vacuum, or an oxygen scavenger, the gas atmosphere of the package due to a defect of the packaging material A packaging body with an oxygen indicator function, which is equipped with an oxygen detection unit for detecting changes by color change by printing, (2) A drug or food easily altered by oxygen is an amino acid drug solution, a sugar drug solution, or a vitamin-containing drug solution. , A bicarbonate drug solution, a fat emulsion, and one or more kinds selected from the group consisting of antibiotic preparations, and the oxygen indicator function-equipped package according to (1) above, (3) oxygen In the packaging body with an oxygen indicator function according to the above (1) or (2), wherein the medicine or food that is easily denatured is a glycyrrhizin preparation. 4) In any one of the above (1) to (3), wherein the oxygen detection part is a coating film formed by an ink composition containing an aqueous solution containing a reducing substance and a pH indicator or an organic solvent solution. (5) The packaging body with an oxygen indicator function according to (4), wherein the reducing substance is a reducing amino acid, a reducing vitamin or a reducing saccharide, 6) The packaging body with an oxygen indicator function according to the above (4) or (5), wherein the reducing substance is cysteine or cystine and the pH indicator is a thiazine dye and / or an indigo dye. (7) The oxygen indicator according to (6) above, wherein the concentration of cysteines or cystines is 100 to 100,000 ppm. Ta function package, (8) cysteines or cystine compound is L- cysteine, L- cysteine hydrochloride, DL-cysteine, DL-cysteine hydrochloride, D- cysteine, D
-One or more selected from the group consisting of cysteine hydrochloride, L-ethylcysteine hydrochloride, L-methylcysteine hydrochloride, acetylcysteine, S-carboxymethyl-L-cysteine and L-cystine. A package with an oxygen indicator function according to the above (6) or (7), (9) a thiazine dye and / or
Or the concentration of indigo dye is 100 to 100000p
(10) A package with an oxygen indicator function according to the above (6), wherein the thiazine dye or the indigo dye is ultra violet, Azure C, Azure B, methylene blue, methionine blue,
(6) or (9), which is one or more selected from the group consisting of new methylene blue, methylene green, rous violet, neomethylene blue, brilliant alizarin blue, indigo, indigo carmine, and bromindigo R. (11) A package with an oxygen indicator function according to (1) above, wherein the print is displayed on the outside of the gas permeable container or on the inside of the gas impermeable packaging material.
Oxygen indicator function packaging according to any one of (0), (12) Oxygen indicator function according to any one of (1) to (11), characterized in that the oxygen detection unit is a pinhole detection unit With packaging, (13)
A medicine or food which is easily deteriorated by oxygen contained in the gas permeable container of the package with an oxygen indicator function according to any one of (1) to (12), (14) A medicine or food which is easily deteriorated by oxygen From (1) to (1
(2) A method for storing a drug or food that is easily deteriorated by oxygen, characterized by storing and storing in a gas-permeable container of the package with an oxygen indicator function described in any of (2).

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The package with an oxygen indicator function of the present invention is characterized in that an oxygen detecting portion is provided by printing. The oxygen detection part is preferably a coating film formed by printing the ink composition on a gas permeable container or a gas impermeable packaging material. Further, the oxygen detector is preferably a pinhole detector. The color tone of this ink composition changes when oxygen is present in the atmosphere in the package. By visually observing the change in color tone from the outside of the package, the change in oxygen concentration in the atmosphere inside the package can be judged by the color tone of the oxygen detection part, and pinholes in the package and defective sealing can be easily generated. You can check.

The ink composition is preferably composed of a reducing substance, a pH indicator, a solvent, a binder, water and the like.

The reducing substance is not particularly limited, but preferably, for example, reducing amino acids,
Examples include reducing vitamins or reducing sugars. Examples of the reducing amino acids include cysteines and cystines. As reducing vitamins,
For example, vitamin E, vitamin A, vitamin C, etc. may be mentioned. Examples of the reducing sugars include monosaccharides such as glucose, fructose, galactose, xylose and mannose, disaccharides such as maltose, lactose and cellobiose, and trisaccharides such as maltotriose, cellotriose and manninotriose. further,
Isomerized sugar obtained by acting an isomerase on glucose,
And a mixture such as starch syrup obtained by hydrolyzing starch with an acid or an enzyme.

As the reducing substance, cysteines or cystines are preferably used. As cysteines or cystines, any of L-form, DL-form and D-form can be used. In addition, L-body, DL-body, D
In addition to the -form, its salts, esters, N-acyl derivatives and the like can be used. Examples of the salts include hydrochloride. Examples of the ester include alkyl esters such as methyl ester and ethyl ester. As the N-acyl derivative,
Examples include acetyl derivatives and benzoyl derivatives.
Specific examples of these cysteines and cystines include:
For example, L-cysteine, L-cysteine hydrochloride, DL
-Cysteine, DL-cysteine hydrochloride, D-cysteine, D-cysteine hydrochloride, L-ethylcysteine hydrochloride, hydrochloric acid, L-methylcysteine, acetylcysteine, S-carboxymethyl-L-cysteine, L-cystine and the like. be able to. One of these may be used alone, or two or more thereof may be used in combination. Since cysteines or cystines are stable against heat and light and have a strong reducibility that has not been heretofore available, it is possible to increase the compounding ratio of the pH indicator described below.

For example, the concentration of the reducing substance such as cysteine or cystine is not particularly limited, but it is preferably in the range of about 100 to about 100,000 ppm.

The pH indicator is preferably one that allows the change in color tone to be easily confirmed visually. For example, methylene blue, leuco methylene blue, 2,6-dichlorophenol indophenol, methylphenazonium metasulfate, cresol violet, piocyanine, resazurin, indigo, m-cresol purple, thymol blue, cresol red, phenolphthalein,
Bromothymol blue, phenol red, dibromophenol tetrabrom, methylthymol blue, alizarin, xylitol orange, bromophenol red, congo red, sodium alizarin sulfonate, neutral red, safranin T, phenosafranin, capri blue, nile blue, diphenylamine , Xylene cyanol, nitrodiphenylamine, ferroin, N-phenylanthranilic acid and the like. More preferably, a thiazine dye such as methylene blue or an indigo dye such as indigo can be used.

As the thiazine-based dye and the indigo-based dye, dyes whose color tone in the presence of oxygen changes to colorless or another color tone in the anoxic state are preferable. Examples of thiazine dyes include ultra violet, Azure C, Azure B, methylene blue, methionine blue, new methylene blue, methylene green, rous violet, neomethylene blue, and brilliant alizarin blue. Examples of indigo dyes include indigo, indigo carmine, and bromoindigo R. These dyes may be used alone or in combination of two or more.

For example, the concentration of the pH indicator such as thiazine dye and indigo dye is not particularly limited, but it is preferably in the range of about 100 to about 100,000 ppm.

Further, in order to further clarify the change in hue due to the presence or absence of oxygen, these are conventional dyes or pigments that do not cause a change in hue regardless of the presence or absence of oxygen. It can also be used in combination with a dye or the like.

The ratio of the pH indicator such as the thiazine dye and / or indigo dye to the reducing substance such as cysteine or cystine is not particularly limited, but is usually cysteine or cystine. PH indicator such as thiazine dye and / or indigo dye to about 100 parts by weight of a reducing substance such as 1 to 1000 parts by weight, preferably about 1 to 1000 parts by weight.
A range of 10 to about 10 parts by weight is preferred. As the combination of the reducing substance and the pH indicator, cysteine or a salt thereof (especially hydrochloride) is preferably used as the reducing substance,
Methylene blue is used as a pH indicator.

The solvent is preferably one which can uniformly or stably dissolve or disperse each component of the ink composition of the present invention. For example, aromatic hydrocarbons such as toluene and xylene, cyclohexane and the like. Esters such as aliphatic hydrocarbons, ethyl acetate, butyl acetate,
Examples thereof include alcohols such as methanol and ethanol, water and a mixture thereof. In particular, at least one of water and alcohols is preferable.

The binder is used for fixing a reducing substance, a pH indicator and the like on a support, and examples of such a binder include polyacrylic acid, polyvinyl alcohol, polyvinyl butyral and polyvinyl acetal. , Polyvinyl acetate, polyurethane, partially saponified vinyl acetate, and the like.

In addition to the above reducing substance, pH indicator, solvent and binder, the ink composition may further contain an appropriate alkalizing agent, excipient or the like.

Here, the alkalizing agent functions as an agent that promotes the oxidation of reducing substances such as cysteine and cystine and an agent that promotes the absorption of oxygen, and can make the system of the ink composition alkaline. Any of these can be used. For example, alkali metal or alkaline earth metal hydroxides, carbonates, hydrogen carbonates,
Examples thereof include water-soluble compounds such as phosphate and borate. These may be hydrous or anhydrous. For example, sodium borate, sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, lithium hydroxide,
Examples thereof include calcium phosphate, barium hydroxide, magnesium hydroxide and calcium phosphate. Among these, sodium borate, sodium hydroxide, sodium carbonate and the like are preferable. These may be used alone or in combination of two or more. When an alkalizing agent is added, the color change reaction of the pH indicator in the ink composition is promoted, a vivid color tone is developed, and the presence or absence of oxygen may be more reliably detected.

As the excipient, any of various known excipients that can be prepared in a form that the ink composition can take can be used. For example, zeolites, activated clays, calcium silicates, crystalline celluloses and the like which serve to provide a reaction site. The excipient preferably has a color tone that does not hinder visual confirmation of the discoloration of the dye of the oxygen indicator as much as possible, for example, a colorless or pale color.

The coating film formed by printing the ink composition, together with the water present in the coating film itself and the package in which it is used, usually has a desired oxygen detection ability or a desired oxygen detection ability and oxygen absorption ability. Although it can be exerted, it has a deliquescent property such as calcium chloride in order to obtain it from the atmosphere when the water necessary for the oxygen detection or reaction for oxygen absorption is insufficient in the package. Substances can also be further incorporated into the ink composition.

To dissolve or disperse the reducing substance, the pH indicator, the binder and the like in a solvent, all the above components are mixed and the mixture is kneaded by a general mixing and dispersing means such as a sand mill, a ball mill, a roll mill or an attritor. do it. By dissolving or dispersing, the ink composition becomes an ink composition that uniformly contains a reducing substance, an aqueous solution containing a pH indicator, or an organic solvent solution.

The method of applying the ink composition onto the support is a printing method, for example, a screen printing method, an intaglio printing method, a letterpress printing method, a gravure printing method, a flexographic printing method and an offset printing method, and a coating method. , For example,
Roll coating, spray coating, dip coating, solid coating and the like can be mentioned, but a printing method is preferably used. The ink composition can be printed on a support which is, for example, a gas-impermeable packaging material to prepare an oxygen detection part. For example, when the packaging is processed by continuously printing the oxygen detection unit on the support and then heat-sealing and cutting the support, the support may be wound and supplied, and thus gravure printing or flexographic printing is suitable. There is.

The support is preferably one which does not react with the ink composition and does not impair the color developability of the reagent. For example, paper, synthetic paper, non-woven fabric, synthetic resin film, or the like can be used depending on the purpose and usage. Further, it is preferable that the oxygen detecting section is composed of an ink layer having a pattern such as letters and pictures. Especially when you select letters as the shape of the oxygen detector, the product name, ingredient name,
It is also possible to display the usage instructions. Further, the support can be appropriately colored to make the oxygen detection part easier to see.

The oxygen indicator packaging is preferably a container made of a gas permeable material for containing contents such as medicines, medicines, foods (including beverages), which is packaged with a gas impermeable packaging material. It can be manufactured by setting a deoxygenated atmosphere in the package and arranging an oxygen detector in the package. The oxygen detector can be provided on the outer surface of the gas permeable container, the space between the gas permeable container and the gas impermeable packaging material, and the inner surface of the gas impermeable packaging material. As a method of arranging the oxygen detection part on the outer surface of the gas permeable container or the inner surface of the gas impermeable packaging material, a method of adhering the oxygen detection part prepared by printing the ink composition to these surfaces, or an ink composition Can be printed directly on these surfaces. Preferably, printing is performed directly on the surface of these containers or packaging materials. The gas permeable container itself may be used as a support, the ink composition may be applied to the outer surface of the gas permeable container, and the gas permeable container itself may be used as the oxygen detector. It is also possible to use the gas-impermeable packaging material itself as a support, apply the ink composition to the inner surface of the gas-impermeable packaging material, and use the gas-impermeable packaging material itself as the oxygen detector. When directly printing the ink composition on the outer surface of the gas-permeable container or the inner surface of the gas-impermeable packaging material, after printing the ink composition on the outer surface of the gas-permeable container or the inner surface of the gas-impermeable packaging material, printing It is also possible to cover the surface with a gas permeable film, and when covered with a skin, there is no contact with the contents or the container, it is hygienic and wear of the indicator can be prevented, which is preferable. Examples of the gas permeable film used here include low density polyethylene, linear low density polyethylene, polypropylene, ionomer, and ethylene-vinyl acetate copolymer.

The contents include medicines, medicines, foods (including beverages) that are easily deteriorated by contact with oxygen, or medicines, medicines, foods (including beverages) that may deteriorate in quality or lose their medicinal effects. ) And the like. These medicines, medicines, foods (including beverages), etc. are not particularly limited. Examples of the medicines and drugs include amino acid drug solutions, sugar drug solutions, vitamin-containing drug solutions, bicarbonate drug solutions, fat emulsions, and antibiotic preparations. Examples of the amino acid drug solution include amino acid infusions containing essential amino acids and the like, glycyrrhizin preparations, and examples of the sugar drug solution include sugar infusion solutions containing reducing sugars and the like,
Examples of the vitamin-containing drug solution include mixed vitamin preparations, and examples of the bicarbonate drug solution include artificial kidney dialysate, perfusate and replenisher, peritoneal dialysate, dental root canal expander, artificial cerebrospinal fluid, Organ preservative, intraocular perfusate, cardiac perfusate,
Examples of the fat emulsion include cardioplegic solution, peritoneal lavage fluid, antidote, and the like, and vegetable oil emulsion and the like. Examples of foods (including beverages) include tea, coffee, cheese, ham, miso, and raw meat.

As the gas permeable container for containing or filling medicines, medicines, foods (including beverages) and the like, those conventionally used in the technical field can be used. Preferably, a gas permeable plastic container is used. Examples thereof include those made of polyethylene, ethylene vinyl acetate copolymer, polypropylene, polyethylene, and those prepared by mixing or laminating these at an appropriate ratio. The shape and size of these containers are not particularly limited. For example, a rectangular shape or a cylindrical shape can be used. Further, the content volume thereof is not particularly limited, but a container having a range of about 2 mL to about 3 L is preferably used.

The term "gas impermeable" in the gas impermeable packaging material of the present invention does not necessarily mean that gas is not exactly permeable, but its gas impermeable property is larger than that of the gas permeable container. This means that even if the same material as the above-mentioned container has a large thickness, it can be used as the gas impermeable packaging material in the present invention. The material of such a gas-impermeable packaging material is not particularly limited, and is preferably generally used as such a packaging material, for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyvinyl alcohol. (PVA), ethylene vinyl alcohol copolymer (EVOH), polyvinylidene chloride (PVDC), nylon, and other materials, those on which inorganic materials such as silicon oxide and aluminum oxide are further deposited, and these Examples thereof include those made of multi-layer films (laminate films) of various materials. The shape and size of these gas-impermeable packaging materials are not particularly limited as long as the gas-permeable container can be housed therein. Preferably about 1.
The size is preferably about 2 to about 3 times the volume.

According to the present invention, it is possible to easily detect a defect in a package made of a gas impermeable packaging material. Defects include, for example, changes in the gas atmosphere due to pinholes, poor seals, and the like. More specifically, the intrusion of oxygen into the package due to the occurrence of pinholes in the package made of gas impermeable packaging, air leakage due to poor sealing of the package, incomplete deaeration, etc. included.

Examples of means for putting a package in which a gas permeable container is packaged in a gas impermeable packaging material into a deoxidizing atmosphere include a gas replacement method, a vacuum packaging method, and an oxygen scavenging method. Examples of the gas replacement method include a method of enclosing a mixed gas containing carbon dioxide gas such as nitrogen gas, carbon dioxide gas, or a mixed gas of carbon dioxide gas and nitrogen gas in a package. Examples of the vacuum packaging method include a method using a vacuum packaging machine. As the vacuum packaging machine, one generally used in the technical field can be used. Examples of the oxygen scavenger method include a method using a oxygen scavenger. As the oxygen scavenger, Ageless (manufactured by Mitsubishi Gas Chemical Co., Inc.) or the like can be used.
The package of the present invention is manufactured by a method known per se, which is obvious from the above. Preferably, a drug or food (including beverage) that is easily deteriorated by oxygen is contained in a gas permeable container, which is further packaged with a gas impermeable packaging material to create a deoxygenated atmosphere in the gas impermeable packaging. It is manufactured by printing an ink composition on a support to provide an oxygen detector. When cysteines or cystines are used as the reducing substance, they also serve as an oxygen scavenger, so it is not necessary to use an oxygen scavenger.

[0032]

EXAMPLES Examples and test examples of the present invention will be described below, but the following examples and test examples are merely preferred embodiments of the present invention and do not limit the technical scope of the present invention. .

Example 1 L-Cysteine hydrochloride (Wako Pure Chemical Industries, Ltd.) 6.0 g Methylene blue (Wako Pure Chemical Industries, Ltd.) 4.0 g Isopropyl alcohol (Osaka Printing Ink Co., Ltd.) 33.0 g Water 100.0 g Obtained by mixing the above components. 1 part by weight of the solution was mixed with 50 parts by weight of polyvinyl alcohol (JIP41C), and 5 parts by weight of a yellow ink (WS Yellow 2RN-1T manufactured by Toyo Ink Co., Ltd.) containing an ultraviolet absorber was added. The ink composition using the water-soluble binder resin was obtained by kneading the meat for 1 hour with a sand mill. Oxygen permeability 1m
The oxygen detecting ink composition was printed by a gravure printing method PVA film l ^/ m 2 ^/ 24hr ^/ atm or less is oxygen-impermeable packaging material, laminated with LLDPE film on the printing surface and sealant layer. Also, P on the surface
An ET film was laminated, and a gas impermeable packaging material having an oxygen detection portion by printing was obtained.

As a content, a polyethylene container containing 500 mL of an amino acid infusion solution having the composition shown below was packaged with the packaging material prepared as described above with the surface having the oxygen detecting portion facing inward. Space (volume approx. 100 m
L) is replaced with nitrogen gas, and then the oxygen scavenger ageless (ZH-1
00P) and the packaging material was sealed to obtain the packaging body with the oxygen indicator function of the present invention. Amino acid infusion L-leucine 7.0 g, L-isoleucine 4.0
g, L-valine 4.0 g, L-lysine acetate 7.4
g, L-threonine 2.85 g, L-tryptophan 1.0 g, L-methionine 1.95 g, L-phenylalanine 3.5 g, L-cysteine 0.5 g, L
-Tyrosine 0.25 g, L-arginine 5.25 g,
L-histidine 2.5 g, L-alanine 4.0 g,
L-proline 2.5 g, L-serine 1.5 g, aminoacetic acid 2.95 g, L-aspartic acid 0.5 g,
L-glutamic acid 0.5 g and glacial acetic acid 1.45 g
Was dissolved in distilled water to obtain a 500 mL solution.

Twenty-four hours after the sealing, the space became anoxic, which was confirmed by the fact that the oxygen detection portion, which was blue immediately after sealing, turned yellow after sealing for 24 hours.

Comparative Example 1 A PVA film, which is a gas impermeable packaging material, is laminated with an LDPE film to form a sealant layer, and the surface layer surface is PE.
The T film was laminated to obtain a gas impermeable packaging material.
As an oxygen indicator, Mitsubishi Gas Chemical's Ageless Eye Type: Paper Eye P Eye-M was used.
A polyethylene container containing 500 mL of the amino acid infusion is packed with the packing material prepared above, and an oxygen scavenger AGELESS (ZH-100P) is put together with AGELESS EYE.
The space between the container and the packaging material (volume: about 100 mL) was replaced with nitrogen gas, then sealed in an oxygen-free state, and stored under each condition. Twenty-four hours after sealing, the space became anoxic, which means that the ageless eye, which was purple immediately after sealing,
It was confirmed that the color changed to pink 24 hours after the sealing.

Example 2 An ink composition was prepared in exactly the same manner as in Example 1. This was applied onto an alumina vapor-deposited PET film by a screen printing method in the same manner as in Example 1, dried at 70 ° C. for 1 hour, the print surface was laminated with an LDPE film to form a sealant layer, and the surface layer surface was laminated with a PET film. Then, a gas-impermeable packaging material having an oxygen detection part was obtained. As a content, a polyethylene container containing 20 mL of a glycyrrhizin preparation containing cysteine shown below was packaged with the surface having the oxygen detection part inside by the packaging material formed with the oxygen detection part prepared above, and removed. Oxygen agent Ageless (Z
H-10P), and replace the space between the container and the packaging material (volume of about 30 mL) with nitrogen gas, and then seal the packaging material.
A package with an oxygen indicator function of the present invention was obtained. Glycyrrhizic acid preparation Glycyrrhizin 40 mg, aminoacetic acid 400 mg and L-cysteine 20 mg were dissolved in distilled water to obtain 20 m.
An L solution was obtained.

24 hours after the sealing, the space became anoxic, which was confirmed by the fact that the oxygen detection member, which was blue immediately after the sealing, turned yellow 24 hours after the sealing.

Comparative Example 2 A polyethylene container containing 20 mL of the glycyrrhizin preparation was packaged in the same manner as in Example 2 with a gas impermeable packaging material composed of an alumina vapor-deposited PET film on which an oxygen detection member was not printed to obtain an ageless eye. The oxygen absorber was put together with Ageless (ZH-10P), the space between the container and the packaging material (volume: about 30 mL) was replaced with nitrogen, and then the packaging material was sealed to obtain Comparative Example 2. Twenty-four hours after sealing, the space became anoxic, which was confirmed by the fact that the ageless eye, which was purple immediately after sealing, turned pink after sealing for 24 hours.

Test Example 1 A wrapping material of the wrapping body produced in Examples 1 and 2 and Comparative Examples 1 and 2 was pinhole (diameter about 500 μm, minor axis about 50 μm) with an injection needle (27 G, Terumo, Neorus). ) Was opened and the discoloration of the color of the oxygen detection part in the package was visually observed from the outside. The results are shown in the table below. The color change time represents the time until the color change reaction is completed after the pinhole.

[Table 1]

Test Example 2 An ink composition was prepared and its stability to light and heat was investigated. In the same manner as in Test Example 1, a polyethylene container containing 500 mL of an amino acid infusion solution was wrapped with the packaging material of the packaging body of the present invention produced in Examples 1 and 2, and an oxygen scavenger Ageless (ZH-100P) was added, and nitrogen was added. After the replacement, the container was sealed and kept in an oxygen-free state under each condition. As a comparative example, a polyethylene container containing 500 mL of the paper eye and amino acid infusion solution was wrapped with the packaging material produced in Comparative Examples 1 and 2, and the oxygen scavenger Ageless (ZH-100P) was put therein, and the container was sealed after nitrogen replacement, It was stored under each condition in an anoxic state.

(1) Light Stability Test The change in color tone was investigated by sticking and storing on a window glass irradiated with sunlight. The results are shown in the table below.

[Table 2]

In Comparative Examples 1 and 2, the color tone became unstable after 3 days, whereas in Examples 1 and 2, the anoxic color tone of yellow was exhibited even after 5 days. When the package wrapped with the gas impermeable packaging material was opened 14 days later, it returned to blue in Examples 1 and 2, but no color change in Comparative Examples 1 and 2.

(2) Stability test Changes in color tone were investigated with the passage of time at 40 ° C. under oxygen-free storage. The results are shown in the table below.

[Table 3]

In Comparative Examples 1 and 2, the color tone shown in the absence of oxygen was poor after 2 months, whereas in Examples 1 and 2, the oxygen-free color tone was yellow even after 3 months.
When the package wrapped with the gas impermeable packaging material was opened 3 months later, it returned to blue in Examples 1 and 2, but did not discolor in Comparative Examples 1 and 2.

[0046]

EFFECTS OF THE INVENTION According to the present invention, it is possible to easily confirm the discoloration of the oxygen detection portion from the outside, and further to obtain a package with an oxygen indicator function which is excellent in light stability and discoloration speed.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kohei Yuyama             20-1 Kitahari, Hiroshima, Matsushige-cho, Itano-gun, Tokushima Prefecture F-term (reference) 2G042 AA01 BB09 CA01 CB01 DA03                       DA08 FA05 FA12 FB07 FC03                       FC07 GA04 HA01 HA10                 2G054 AA01 AB10 CA08 EA06 GB04                       GE10                 3E067 AB01 AB81 BB14C CA06                       EA06 EE02 FA04 FC01 GB13                       GD01 GD02 GD10

Claims (14)

[Claims] 1. A gas-permeable container containing a drug or food that is easily deteriorated by oxygen is packaged with a gas-impermeable packaging material, and the inside of the package is replaced by gas replacement, vacuum, or an oxygen scavenger. A package with an oxygen indicator function, characterized in that a package having an oxygen-free atmosphere is provided with an oxygen detection unit for detecting a change in the gas atmosphere of the package due to a malfunction of the packaging material by a color tone change by printing. 2. A drug or food which is easily altered by oxygen is one or more selected from the group consisting of amino acid drug solutions, sugar drug solutions, vitamin-containing drug solutions, bicarbonate drug solutions, fat emulsions, and antibiotic preparations. The packaging body with an oxygen indicator function according to claim 1, wherein the packaging body has an oxygen indicator function. 3. The packaging body with an oxygen indicator function according to claim 1, wherein the drug or food that is easily deteriorated by oxygen is a glycyrrhizin preparation. 4. The coating film formed by an ink composition containing an aqueous solution containing a reducing substance and a pH indicator or an organic solvent solution, as the oxygen detecting part. Package with oxygen indicator function described. 5. The packaging body with an oxygen indicator function according to claim 4, wherein the reducing substance is a reducing amino acid, a reducing vitamin, or a reducing saccharide. 6. The package with an oxygen indicator function according to claim 4, wherein the reducing substance is cysteine or cystine, and the pH indicator is a thiazine dye and / or an indigo dye. . 7. The package with an oxygen indicator function according to claim 6, wherein the concentration of cysteine or cystine is 100 to 100,000 ppm. 8. The cysteines or cystines are L-cysteine, L-cysteine hydrochloride, DL-cysteine,
Selected from the group consisting of DL-cysteine hydrochloride, D-cysteine, D-cysteine hydrochloride, L-ethylcysteine hydrochloride, L-methylcysteine hydrochloride, acetylcysteine, S-carboxymethyl-L-cysteine, L-cystine. One or two or more types, The package with an oxygen indicator function of Claim 6 or 7 characterized by the above-mentioned. 9. The package with an oxygen indicator function according to claim 6, wherein the concentration of the thiazine dye and / or the indigo dye is 100 to 100000 ppm. 10. The thiazine-based dye or the indigo-based dye is ultra violet, Azure C, Azure B, methylene blue, methionine blue, new methylene blue,
The oxygen indicator according to claim 6 or 9, wherein the oxygen indicator is one or more selected from the group consisting of methylene green, rous violet, neomethylene blue, brilliant alizarin blue, indigo, indigo carmine, and bromindigo R. Functional packaging. 11. The packaging body with an oxygen indicator function according to claim 1, wherein the printing is displayed on the outer surface of the gas permeable container or the inner surface of the gas impermeable packaging material. 12. The package with an oxygen indicator function according to claim 1, wherein the oxygen detector is a pinhole detector. 13. A medicine or food which is easily deteriorated by oxygen contained in the gas permeable container of the package with an oxygen indicator function according to any one of claims 1 to 12. 14. A medicine or food which is easily deteriorated by oxygen is stored in the gas-permeable container of the package with an oxygen indicator function according to any one of claims 1 to 12, and is preserved, thereby being deteriorated by oxygen. A method of storing medicines or foods that is easy to do.