JP2003202293A - Quality control by oxygen diffusion amount - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve a problem that the storage life varies by temperature and environment, while the storage life does not indicate the actual storage deterioration of contents caused by oxygen, and we don't have a method to know the deterioration by oxygen of the contents even by an indirect method, that is, we have no method to easily judge the deterioration caused by oxygen diffused in a wrapping material for wrapping foods, preserved food, medical goods, medicines and the like, and a container. <P>SOLUTION: The deterioration of a preserved matter caused by the diffusion of oxygen is indirectly indicated by allowing color, letter, drawing and the like to be displayed in accordance with the amount of diffused oxygen by reaction with oxygen diffused and intruded to the wrapping material for wrapping foods, preserved food, medical goods, medicines and the like, and the container. Concretely, a pigment generating color or changing a color by reaction with oxygen, or an organic pigment such as phosphor is added and mixed in a resin, and applied onto an outer face of the storage container or applied onto a surface of a product, or a pigment material reactable with oxygen is added to a thermosetting resin or an ultraviolet ray curing resin, and cured on a surface of the storage container to fix the pigment or the phosphor reactable with the diffused oxygen. Or the pigment material reactable with oxygen is added in the wrapping material for storage. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a packaging material for a storage container for foods, drugs, medicines and the like.

[0002]

2. Description of the Related Art Conventionally, the deterioration of products due to oxygen in the air has been a problem in foods, preserved foods, pharmaceuticals and medicines. Therefore, to prevent oxygen in the air from diffusing, add aluminum oxide to the organic material that is the constituent material of paper and plastic containers, avoid organic materials that easily cause oxygen diffusion, or resist aluminum corrosion. Metallic films have been formed by vapor deposition, etc., to protect stored items.

Therefore, there is no other method for the deterioration of the preserved product due to oxygen diffusion during storage except to actually measure the amount of oxygen in a room temperature atmosphere to determine the preservation period. However, under normal storage conditions, both temperature and humidity change, so the actual storage deterioration due to oxygen is not accurate during the storage period estimated by these methods, and the oxygen deterioration of the content is indirectly known. There was no way.

Therefore, recently, as a hermetically-sealed bag, a part of the inner surface of a transparent thermoplastic plastic outer layer film having an oxygen gas blocking property is provided with a discolored ink print display surface that reversibly discolors in a low oxygen gas concentration range, and the printing is performed. It is proposed that a laminated sheet is formed by laminating an oxygen gas permeable heat-sealable plastic inner layer film on the entire inner surface of the transparent thermoplastic outer layer film including the surface (Saikai Sho 58 □ 27179). Gazette). Such an ink that is reversibly discolored in the low oxygen gas concentration range printed on the inner surface of the transparent outer layer film includes a thiazine-based ink, an indigoid-based dye, a thioindigoid-based dye, and a dye selected from sulfur dyes and a reducing agent. A composition in which a saccharide and an alkaline substance are mixed and dissolved or dispersed in a synthetic resin solution, and further, a composition in which glycerin is added and mixed in the composition is used. This method has a problem that deterioration due to oxygen due to the amount of oxygen that has permeated oxygen for a long time cannot be understood.

[0005] In the application number Japanese Patent Application No. Sho 60 □ 53560, a gas detector is packaged in a vacuum state for foods and pharmaceuticals, and a gas detector that changes color or precipitates due to the presence of gas generated by the decay or deterioration of the contents of the food or the like. Although described regarding a vacuum packaging bag, which is characterized in that it is enclosed in a state of being separated from the contents by a permeable film, in this method, a gas generated by alteration or deterioration is sensed, It does not evaluate the amount of oxygen that deteriorates. In addition, since the gas generated by oxygen is diverse, there is a problem that the gas detection value is difficult.Since it becomes a gas detector specified for the gas type, it is necessary to separate it for various applications and simplify it. There was a problem that was difficult to use.

In such a situation, for example, when the shelf life is several years, which is usually mentioned in medicine, the packaging container, for example, the sheet containing the individual tablets has a manufacturing date. Sometimes I don't know what the quality is, as it may not be. In addition, it was not possible to easily judge whether the packaging bag had a poor seal or the packaging bag was damaged.

In Japanese Patent Application No. 9 □ 322529, there is disclosed a method of forming a double sheet, and developing a color by a compound diffusing from one sheet and judging the elapsed time from the color development. In this patent, the preservative is oxidized. Since it is irrelevant to deterioration, it does not need to be deteriorated when stored in, for example, a nitrogen atmosphere or an Ar atmosphere, and is merely a time indicator. Japanese Patent Application No. 11-346581 shows that the color of the storage container is changed, but similarly, the coloring mechanism is not specifically known, and there is no description of oxidative deterioration.

By the way, as a material for displaying the temperature / time history, Patel's US Patent No. 1 using a diacetylene-based compound that displays a range of several tens of hours at a temperature of about 100 ° C. by a change from pink to metallic green. 4,18
9,399 (issued 1982.19), U.S. Pat. No. 4,208,186 (issued 1980.6.17), U.S. Pat. No. 4,276,190 (issued 1980.6.30), room temperature U.S. Pat. No. 4,212,153 to Kidnius et al. (198) using a reaction by diffusion of an acid or alkali with a dye that develops from colorless to purple in the range of several tens of days.
0.7.15), U.S. Pat. No. 3,768,976 to Hu et al., Which uses redox dyes and oxygen diffusivity, a composition of free radical sensitive dyes and peroxides displayed by fading green. US Pat. No. 3,963 to Cartab et al.
No. 6,414, JP-B-62190447, such as Buhatta Charge, which utilizes coloring of a triarylmethane dye decolorized with a reducing agent by diffusion of oxygen, Matsuda using a microorganism that produces an acid and a pH indicator. JP-A-5 □ 6
There is 1917. In addition, patents utilizing melting point, diffusion rate, enzyme activity, etc. are disclosed.

As described above, although there has been a concept of indicating the elapsed time by actually using oxygen diffusion, reaction, etc., the deterioration of the preserved product is estimated by using the influence of the amount of oxygen diffused through the packaging wall of the container. There was nothing.

[0010]

As described above, there has been no method for easily determining deterioration due to the amount of oxygen diffused in a storage material or a container for packaging foods, preserved foods, pharmaceuticals, medicines and the like.

[0011]

[Means for Solving the Problems] Reacting with oxygen that diffuses and invades the oxygen that diffuses into the preservative materials or containers for packaging foods, preserved foods, pharmaceuticals, drugs, etc., and changes the color depending on the amount of diffused oxygen. By making the display of letters, characters, figures, etc. appear,
It indirectly indicates the deterioration of stored products due to oxygen diffusion.

[0012]

BEST MODE FOR CARRYING OUT THE INVENTION Foods, preserved foods, pharmaceuticals, medicines and the like are deteriorated by oxygen diffused from a packaging device and the degree of deterioration varies depending on the amount of oxygen. Degradation due to oxygen may occur when oxygen directly reacts with the preserved product, or when bacteria existing with the preserved product are proliferated and spoiled by the oxygen, but in any case, deterioration that is proportional to the oxygen content occurs. I found out that Therefore, in order to judge the deterioration state, for the oxygen that diffuses into the packaging material or container to be packaged, display the color, letters, figures, etc. according to the amount of oxygen that diffuses by reacting with the oxygen that diffuses. It is the present invention that a pigment material that reacts with oxygen is added as a filler.

For example, a dye that develops color when it reacts with oxygen, a dye that changes color, or an organic dye such as a fluorescent substance is added to polyethylene resin and mixed, and then applied to the outer surface of a storage container or coated on the surface of the product. It is also one way. Alternatively, it may be applied on the inner surface of the container and the amount of oxygen diffused from the bonding surface or the amount of oxygen diffused from the material itself may be observed. In addition, a dye material that reacts with oxygen is added to a thermosetting resin or an ultraviolet curable resin and cured on the surface of a storage container to immobilize a coloring dye or a phosphor that reacts with diffusing oxygen. At this time, a color-developing dye or a color-changing dye, to improve the dispersibility by binding the phosphor to the end group of the curable resin monomer or polymer, the dye or phosphor is granulated in advance with a spray dryer or the like, The same effect can be obtained by forming particles having a high affinity for the material to be coated thereon or a film layer and adding the particles as a color former. The cured resin for the surface coating varies depending on the color material, but is, for example, cellulose-based, acrylic-based,
There are aminoalkyd resins, epoxy resins, chlorinated rubber resins, vinyl chloride resins, fluorine resins, phenol resins, xylene resins, unsaturated polyester resins, and polyurethane resins. In addition to a method of using an emulsion or a water-based cross-linking type paint, a method of using a powder coating is also a method for forming a coating. Further, as the basic resin of the packaging material, there are polyethylene, polypropylene, polyvinyl chloride, polycarbonate, acrylic, polyester, polyurethane, epoxy, alkyd, polyamide, polysulfone, polyimide, polyphenylene sulfide, fluorine resin, and as the rubber, polyester. , Butyl, acrylic, urethane, silicone, etc. In particular, as the transparent substrate, an olefin film such as polyethylene or polypropylene, a polyester film represented by polyethylene terephthalate, cellophane, polyvinylidene chloride, polyvinylidene chloride copolymer, polyvinylidene fluoride, polyvinyl chloride, nylon, poly Examples thereof include plastic films such as acrylic acid and polymethacrylic acid.

Even if a curable resin is not used, a resin or plastic of the same material as a storage material or a container for packaging foods, preserved foods, pharmaceuticals, medicines, etc. is melted at a melting point or dissolved in an organic solvent, The same effect can be obtained by adding it and coating it on clothes or protective equipment. The same applies when these color materials are added as an additive when making a storage package or container.

At this time, the product is previously manufactured in a usual manner,
A method of coating the surface to form a multilayer film, and kneading as a single additive to the composition of a thin plastic film, for example, when the raw materials are melted and molded by a mold or roll press in the process of manufacturing the product in advance. The same effect can be obtained by mixing and mixing them, rolling them into a film, and coating the other additive on the film to immobilize it, or laminating the film of the other additive. can get.

As a material which causes a color change, a fluorescent material,
It may be a dye, a chromic material, a pigment or a pigment. Specific materials include disperse dyes, direct dyes, reactive dyes, cationic dyes and vat dyes as dyes, and particularly representative compounds are azo dyes, anthraquinone dyes, stilbene dyes, indigoid dyes and triphenylmethane. dye,
Xanthene dye, styrine dye, phthalocyanine dye,
Examples include quinophthalone dyes, nitro dyes, oxazane dyes, stilbene dyes, cyanine dyes, and triphenyl dyes. Examples of intermediates between dyes and pigments include aromatic sulfonic acids, aromatic carboxylic acids, and anthraquinone derivatives. As the pigment, there are an organic pigment and an inorganic pigment, and there are an azo pigment and a condensed polycyclic pigment. Among these, for example, safranin T, indigosulfonic acid, methylene blue, ferroin, neutral red, diphenylamine, and o-phenanthroline iron complex salts are among those that are discolored by oxygen. Conversely, it is also possible to visualize the deterioration of the packaging material caused by oxidation due to oxidation, and in this case, the coloring material is a compound based on anilines or phenols such as oxidation dyes. There are certain 4-aminodiphenylamine, 4-aminophenol, diaminobenzene, diaminotoluene, aminophenol, diaminonitrobenzene and the like, and examples of the oxidation accelerator include ammonium vanadate, copper sulfate and iron salt. It is also a method to increase the change by adding a sensitizer when causing such a color change by the dye.

These uses are not limited to vinyl bags and plastic containers for storage of pharmaceuticals, medicines, stored foods, sweets, etc. which are deteriorated by oxygen invading from the outside of the storage container at the time of storage. It can also be deployed in containers that prevent the diffusion and invasion of oxygen to eradicate the microorganisms that propagate.

[0018]

【Example】

Example 1 An ultraviolet-curable acrylic resin containing 1% by weight of a color material powder of a triarylmethane dye decolorized with a reducing agent was coated on a polyester film having a thickness of 20 μm by 5 μm to form a film cured by ultraviolet rays. After preparation, they were laminated in an Ar atmosphere so that the coating surface was on the inside. The size of the bag is 30 cm square, with 100 cc of Ar inside.
Absorbent water absorbent oxygen absorbent and iron powder 1g
I put it in. At this time, the relationship between the degree of oxidation of iron powder and the degree of color change was examined at room temperature. As a result, the following results were obtained for the elapsed days. The oxidation degree of the iron powder was expressed as 100 after 12 months. From this result, it was found that the amount of oxygen in the bag can be estimated from the change in the film-formed coloring material. Similarly, when the above-mentioned coloring material coated as a film is put into a 30 cm square bag made of a polyester film having a thickness of 20 μ and evaluated under the same conditions, similar results are obtained. Was given.

[0019]

Example 2 A polyester film having a thickness of 20 .mu.
Apply 5μ of UV-curable acrylic resin containing 1% by weight of phenylenediamine dye color material powder, prepare a UV-cured film, and bond them in Ar atmosphere with the coating surface facing inside. It was Similarly, toluene-2,
A bag containing 3% by weight of 5-diamine was also prepared. The size of the bag was 30 cm square, and 100 cc of Ar was put therein. Further, a 1% by weight bag was filled with absorbent cotton absorbing water as an oxygen absorbent and iron powder. Only iron powder was put into the 10% by weight bag as an oxygen absorbent. Further, the relationship between the degree of oxidation of the iron powder and the degree of color change of the two bags at this time was examined at room temperature. As a result, the iron powder showed the same degree of oxidation and a similar color change with the lapse of days.

[0020]

[Example 3] Based on the result of the amount of oxidation according to the amount of oxygen in Example 1, 0.5% by weight of indigosulfonic acid type pigment powder was mixed with polyvinyl chloride resin as a pigment that reacts with oxygen and changes color. Was heated in a non-oxidizing atmosphere to be melted, and then a sheet having a thickness of 200 μm was produced by a rolling press. The sheets were stuck together and fused by heating to produce a vinyl container. Chocolate was put into this sheet, the vacuum was drawn, and the sheet was left at room temperature. After examining the standing time and the color condition of the sheet, the color of the sheet added after 12 months was discolored. As a result of evaluating the change in color by changing the added weight of this color material, the results are as follows. The amount of oxygen diffused at this time was 55.0 using the oxidation degree of Example 1. When confirming the change of the dye from this result, it is at least 90% or less, preferably 10% or less. Similarly, similar results were obtained with Safranin T, methylene blue, ferroin, neutral red and diphenylamine.

Next, a polyethylene film was formed without adding an indigosulfonic acid type dye which changes color by reacting with oxygen, and 1% by weight of a diaminonitrobenzene type dye dispersed in polyethylene was formed inside the film to be "deteriorated". "" Was written in a thickness of 100 μm and fused. A container of 500 CC was made from this film, iron powder as an oxygen absorbent was put in the container, and the discoloration of the letters was observed. As a result, the letters "deteriorated" turned out in 12 months. I was able to confirm that On the other hand, the oxygen amount estimated from Example 1 is 6 when the oxidation degree of Example 1 is used.
It was estimated to be 5.0, and the state of the amount of oxidation in the container could be visually observed.

[0022]

Example 4 A color material of a triarylmethane dye decolorized with a reducing agent on a polycarbonate film having a thickness of about 50 μm was added to an ultraviolet curable acrylic resin in an amount of 0.25% by weight.
The dispersed material was applied to a thickness of about 10 μm and cured with ultraviolet rays. Using this film, a packaging sheet container was prepared with the acrylic resin film surface cured by ultraviolet rays on the inside. The inside of this container was evacuated, and the container was sealed to check the color change. As a result, it was found that the color developed in about several months. As for the amount of oxygen diffused at this time, as a result of the test as in Example 1, the oxidation degree after 12 months was 10
When set to 0, it became 18.0.

[0023]

Example 5 Example 3 is placed inside the container prepared in Example 4.
Indigo sulfonic acid dye to polyethylene like 3
What was dispersed by weight% was written with the character "no effect of oxygen" in a thickness of 10 μm and fused. After introducing nitrogen gas into the container to reduce oxygen to 1% or less, the state of discoloration and fading was examined. As a result, it was found that the color of the character "no effect of oxygen" changed after 18 months. . From this result, when the effect of oxygen diffused from the outside was quantified, the degree of oxidation was estimated to be 88.0 based on Example 1, and the effect of the oxygen amount could be visually observed.

[0024]

Example 6 0.3% by weight of para-phenylenediamine, which is an oxidation dye as a dye that reacts with oxygen to develop color, was mixed with polyvinyl chloride resin, and this was heated in a non-oxidizing atmosphere and mixed, A sheet having a thickness of 200 μm was produced by a rolling press. The sheets were stuck together and fused by heating to produce a vinyl container. Chocolate was put into this sheet, the vacuum was pulled, and the sheet was allowed to stand at room temperature, and the standing time and the color condition of the sheet were examined. As a result, the color of the sheet added in 12 months was colored. The oxygen amount at this time was estimated to be 32.0 based on Example 1.

Next, a 200-micron polyethylene film was formed without adding an indigosulfonic acid dye that changes color by reacting with oxygen, and 5% by weight of the indigosulfonic acid dye was dispersed in polyethylene inside the film. The character "no deterioration" was written in a thickness of 20 μm and fused. With this film, make a container of 500CC,
As a result of putting iron powder, which is an oxygen absorber, into the container, introducing nitrogen gas, and observing the discoloration of the characters, it was confirmed that the characters "no deterioration" were discolored in 24 months. The oxidation degree at this time was 35.0 based on Example 1. As a result, oxygen entered the container, and the state of the amount of oxygen in the container could be visually checked.

[0026]

[Example 7] A 20 μm thick polyester film was coated with 5 μm of an ultraviolet-curable acrylic resin containing 1% by weight of indigosulfonic acid-based pigment powder, and a film cured by ultraviolet rays was prepared. Then, the surfaces of the coating films were stuck together so that the relationship between the degree of color change and the oxygen concentration in the container was examined at room temperature. The size of the bag was 30 cm square, and 100 cc of Ar was put therein. As a result, the following oxygen concentration and color change results were obtained with respect to the elapsed days.
The oxygen concentration was expressed as 100 after 12 months. From this result, it was found that the amount of oxygen in the bag can be estimated from the change in the film-formed coloring material. Similarly, when the above-mentioned coloring material coated as a film is put into a 30 cm square bag made of a polyester film having a thickness of 20 μ and evaluated under the same conditions, similar results are obtained. Was given.

[0027]

Example 8 As a result of examining the color change after 12 months using the films having different oxygen permeability in Example 7, the results are shown below.
When the oxygen permeability is low, the change in color is small, and the result is shown in Example 4.
In the case of the above material, it was about 8 cc / m ² day. The results of examining the change in color after 12 months with films having different oxygen permeability are shown. From this result, it was found that a change in color can be confirmed even if the density is 20 cc / m ² day or less. As can be seen from the above, the oxygen permeable membrane is not suitable for the storage of chemicals and foods.
It is good to apply to the thing of about cc / m ² day or less.

[0028]

Example 9 Using the result of the color change obtained in Example 7, a blue pigment ultramarine powder was used and attached as a color sample. As a result of investigating the effects of temperature, oxygen and atmosphere on the state after 12 months by putting a cold medicine in the polyester film used in Example 5, the following results were obtained. From this result, it can be seen that there is no change in the absence of oxygen and no deterioration due to oxygen has occurred. Also, it was found that the deterioration progresses when the temperature is high,
It was possible to judge the deterioration depending on the amount of oxygen. At this time, 2
The degree of oxidation is 100 when the storage container is placed in 0 ° C air.
It was shown based on the time. From the color sample, it could not be determined that the degree of oxidation, which indicates the amount of oxidation, was 100 or more, but the degree of oxidation was almost estimated.

[0029]

[Effects of the Invention] Due to the change of the pigment due to oxygen diffusion of the present invention, the packaging container, the medicine or the preserved food packaged in the packaging material may have an unknown date of manufacture, or may have a date of manufacture. It is possible to easily determine what the quality of the product is, and also to determine whether the packaging bag has a poor seal or the packaging bag is damaged.

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Claims (8)

[Claims] 1. A material to be preserved stored in a packaging material is packed by adding a material that causes a color change such as discoloration, color development, color fading, and transparency to an organic material forming the packaging material by reacting with oxygen that diffuses. A method characterized by judging from a degree of change of a color-changing material to which a state of deterioration due to the amount of oxygen diffused through the material is added. 2. A method of reacting with oxygen that diffuses during storage by adding a material that reacts with oxygen that diffuses to an organic material that constitutes a packaging material in order to determine a state in which a stored material deteriorates depending on the amount of oxygen that diffuses Then, a symbol indicating the storage state is displayed by using color changes such as discoloration, coloring, fading, and transparency. 3. A storage container, characterized in that a dye changing material is installed in the container so that the amount of oxygen entering the container can be visually confirmed as a color change amount. 4. The estimated amount of oxygen diffused from the packing material by using the change amount of the color changing material according to claim 1, 10 cc per unit area of the packing material.
/ M ² day or less. 5. A packaging container for food or medicine, which uses the packaging material for storage according to claims 1 and 2. 6. The color-changing material according to claim 1,
A packaging container characterized by comprising 90% by weight or less of a packaging material containing one or more materials selected from organic dyes and inorganic materials. 7. The color change according to claims 1 and 2 or 3 depending on the kind of a preserved substance such as liquid, solid, raw fish, preserved food, etc., depending on the degree of deterioration due to decomposition by fungi or the like. , A method of adding a material that causes a color change such as coloring, fading, and transparency. 8. The method according to claim 1, wherein a color sample for visually confirming the amount of oxygen diffused in the container is attached to the storage container or the dye changing material.