JP4590922B2 - Oxygen indicator packaging - Google Patents

Description

  The present invention relates to an oxygen indicator that prevents deterioration due to sunlight or the like.

At present, various oxygen indicators that can easily confirm changes in the gas atmosphere due to the occurrence of pinholes in a deoxygenated package encapsulating an oxygen scavenger, poor sealing, and oxygen scavenger failure are on the market.
As the oxygen indicator, an oxygen indicator in which a combination of a redox indicator, a reducing agent, a binder resin, or the like is changed as a constituent component is known. The oxygen indicator utilizes the property that the redox indicator exhibits a different color tone between the reduced type and the oxidized type. When oxygen in the ambient atmosphere is sufficiently present, the oxygen indicator suppresses the action of the reducing agent and the redox indicator takes an oxidized structure, but oxygen exists in the ambient atmosphere by the action of the oxygen scavenger. When it disappears, the reducing agent works and the redox indicator becomes a reduced structure. By utilizing this change in color tone, a change in oxygen concentration in the surrounding atmosphere can be detected visually.

The known literature is shown below.
JP 2000-214155 A JP 2001-192592 A

  Several oxygen indicators using a redox indicator are known, but many of these have faded and decomposed due to light irradiation, which may cause deterioration of the indicator. For example, there is a problem that reduced methylene blue that is colorless is easily deteriorated by light, and the deteriorated methylene blue does not show the blue color of oxidized methylene blue even in the presence of oxygen. The light shielding property in the visible region can be realized by using ink containing pigments such as yellow and red, but it is not sufficient when long-term storage is required or when exposed to ultraviolet rays such as sunlight. Therefore, it is desired to provide light shielding properties in the ultraviolet region. However, when an ultraviolet blocking layer is added to the anchor coat and overcoat of the indicator, the work process such as addition of a printing unit increases.

  The present invention has been made in view of the above circumstances, and an object thereof is to provide an oxygen indicator packaging material in which deterioration of the indicator due to light is suppressed without increasing the number of work steps.

  The present invention has been conceived in order to solve the above-mentioned problems. By adding an ultraviolet blocking function to the adhesive layer, the indicator is prevented from being deteriorated by light without changing the conventional work process.

The invention according to claim 1 is characterized in that an oxygen indicator having an oxygen detection function is laminated on one side of a base material, and the content surrounded by the base material is oxygen oxygen in the oxygen indicator packaging material without contact with the oxygen indicator. An adhesive layer in which one or more base materials are laminated on the indicator lamination surface and the base materials are laminated covers the oxygen indicator, and the ultraviolet absorber is contained in an amount of 5 to 95 parts by weight as a ratio to the solid content of the ultraviolet shielding adhesive layer. Oxygen indicator wrapping material that is characterized by being.

The invention according to claim 2 is an oxygen indicator packaging material in which an oxygen indicator having an oxygen detection function is laminated on one side of a base material, and the content surrounded by the base material is not in contact with the oxygen indicator. The adhesive layer in which one or more base materials are laminated on the surface where the indicator is not laminated and the base material is bonded covers the oxygen indicator, and the ultraviolet absorber is 5 to 95 as a ratio with respect to the solid content of the ultraviolet blocking adhesive layer. The oxygen indicator packaging material is characterized by being contained in parts by weight.

According to a third aspect of the present invention, an oxygen indicator having an oxygen detection function is laminated on one side of a base material, and the content surrounded by the base material is an oxygen indicator packaging material having no contact with the oxygen indicator. One or more base materials are laminated on both surfaces of the base material on which the indicator is laminated, and the adhesive layer that bonds the base material covers the oxygen indicator, and the ultraviolet absorber is in proportion to the solid content of the ultraviolet light shielding adhesive layer. The oxygen indicator packaging material is characterized by containing 5 to 95 parts by weight.

  The invention according to claim 4 is characterized in that the light transmittance of the adhesive layer having the role of blocking ultraviolet rays is less than 40% in the wavelength region of 290 nm to 400 nm. The oxygen indicator packaging material described in 1.

  By blocking light irradiation in the ultraviolet region such as sunlight with an adhesive layer containing an ultraviolet absorber, it is possible to prevent deterioration of the indicator due to ultraviolet rays without changing the conventional work process.

  As a method of imparting ultraviolet resistance to the indicator, a method of coating an ink having ultraviolet resistance on the undercoat layer and the overcoat layer of the indicator can be considered. However, when printing ink having ultraviolet resistance, the number of units for printing general symbols is reduced because the number of printing units for each apparatus is determined in a normal gravure printing machine.

  When the adhesive has ultraviolet resistance as in the present invention, no additional printing unit is required, and therefore it is possible to impart ultraviolet resistance without changing the printing process.

  Next, embodiments of the present invention will be specifically described. As a redox indicator that is a component of the oxygen indicator, methylene blue, new methylene blue, neutral red, indigo carmine, acid red, safranin T, phenosafranine, capri blue, nile blue, diphenylamine, xylene cyanol, nitrodiphenylamine, ferroin, N-phenylanthranilic acid or the like can be used.

  Moreover, as a reducing agent, ascorbic acid, ascorbate, erythorbic acid, erythorbate, D-arabinose, D-erythrose, D-galactose, D-xylose, D-glucose, D-mannose, D-fructose Further, reducing sugars such as D-lactose, metal salts such as stannous salts and ferrous salts can be used.

  Moreover, it is necessary to set the light transmittance of the ultraviolet blocking layer to be less than 40% at 290 nm to 400 nm, whereby the ultraviolet blocking function is sufficiently exerted and deterioration of the redox indicator can be suppressed. .

  The ultraviolet absorber added to the adhesive includes an organic type and an inorganic type. Examples of the organic ultraviolet absorber include benzophenone derivatives, benzotriazole derivatives, paramethylbenzoic acid derivatives, methoxycinnamic acid derivatives, salicylic acid derivatives, urocanic acid derivatives, and the like. Examples of the inorganic ultraviolet absorber include zinc oxide, titanium oxide, iron oxide, cerium oxide, kaolin, talc, calcium carbonate, magnesium carbonate and the like. Of these, zinc oxide and titanium oxide are particularly preferable.

  The ratio of the ultraviolet absorber to the solid content of the ultraviolet blocking layer is preferably 5 to 95 parts by weight. When the ratio of the ultraviolet absorber is 5 parts by weight or less, a sufficient ultraviolet blocking effect is not exhibited. Moreover, when the ratio of a ultraviolet absorber exceeds 95 weight part, there exists a possibility that the contact | adherence with a ultraviolet shielding layer and a to-be-adhered base material may become weak.

  An anchor coat layer and an overcoat layer can be provided for the purpose of protecting the oxygen indicator layer and preventing appearance defects, peeling, and breakage. As the anchor coat layer, a material that is water-insoluble and has good adhesion between the base material and the oxygen indicator layer formed thereon, and as the overcoat layer, oxygen permeability and an oxygen indicator layer are used. Materials having good adhesion and good adhesion with an adhesive layer or other resin layer that can optionally be further provided on the oxygen indicator layer can be preferably used. Two or more anchor coat layers and / or overcoat layers may be provided as necessary.

  The substrate to be laminated is preferably a substrate that does not react with the oxygen indicator and does not inhibit the coloration of the reagent. Examples of such a substrate include paper, synthetic paper, non-woven fabric, or synthetic resin film, such as polyester, polyamide, polyvinyl alcohol, cellophane, ethylene vinyl alcohol copolymer, polyethylene, polypropylene, polymethylpentene, and silica thereof. A transparent vapor deposition film such as alumina can be laminated as necessary according to the purpose and usage. In this case, as the adhesive layer to which the substrate is bonded, an ultraviolet blocking adhesive layer and an adhesive layer having no ultraviolet blocking function can be arbitrarily selected.

  As a method for laminating the oxygen indicator on the substrate, 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, dip coating or the like is preferably used.

  Similarly, a gravure printing method or the like, or a coating method such as roll coating, spray coating, dip coating, or the like is also suitably used for the adhesive layer to which the substrate is bonded.

  Examples of the usage form of the oxygen indicator packaging material of the present invention include a method in which a container made of a gas barrier material that contains contents such as foods, beverages, and medicines is made a deoxygenated atmosphere, and the oxygen indicator is disposed in the container. be able to. More specifically, as shown in FIG. 1, for example, the oxygen indicator is arranged on both sides of the base material 31 on which the oxygen indicator (including the anchor coat layer and the overcoat layer) 1 is laminated. Paper, synthetic paper, non-woven fabric, synthetic resin film, or oxygen indicator wrapping material (FIG. 1) in which at least one of the above materials 32, 33 is bonded together by adhesive layers 21, 22 having the role of an ultraviolet blocking layer It is simply a method of putting in a container.

Moreover, the method which adhere | attaches what laminated | stacked the oxygen indicator on the film-form base material on the inner surface with the ultraviolet-ray blocking adhesive on the inner surface can be illustrated. There is also a method of directly printing the adhesive on the inner surface of the container. In this case, after printing the adhesive on the inner surface of the container, an oxygen indicator laminated on a film-like substrate is attached to the adhesive. FIG. 2 is an explanatory view showing such an example in cross section. When printing the ultraviolet blocking adhesive 23 directly on the inner surface of the container 4 made of a gas barrier material, the oxygen indicator (including the anchor coat layer and the overcoat layer) 10 is laminated on the film (oxygen indicator print base material) 34 ( This may also be printed and laminated), and the laminated surface can be covered with the gas permeable film 6, and then the film 34 surface is attached to the adhesive 23 printed on the inner surface of the container 4. In this case, since the oxygen indicator 10 is covered with the gas permeable film 6, there is no contact with the contents 5 or the container, and it is hygienic and can prevent wear of the indicator. Is preferred. Note that an ultraviolet blocking adhesive may be used for the adhesive 23.

Oxygen indicator layer composition:
Methylene blue 3 parts by weight, L-ascorbic acid 7.5 parts by weight, binder resin 10 parts by weight, glycerin 7.5 parts by weight, synthetic silica 0.6 parts by weight Anchor coat layer, overcoat layer composition:
10 parts by weight of yellow pigment, 15 parts by weight of urethane resin Composition of UV blocking adhesive layer:
25 parts by weight of zinc oxide, 20 parts by weight of urethane resin Polyester film with an anchor coat layer, indicator layer, and overcoat layer sequentially laminated by gravure printing method, polyethylene on the indicator lamination surface via an ultraviolet blocking adhesive layer Films were laminated to form an oxygen indicator packaging material.

Oxygen indicator layer composition:
Methylene blue 3 parts by weight, L-ascorbic acid 7.5 parts by weight, binder resin 10 parts by weight, glycerin 7.5 parts by weight, synthetic silica 0.6 parts by weight Anchor coat layer, overcoat layer composition:
10 parts by weight of yellow pigment, 15 parts by weight of urethane resin Composition of UV blocking adhesive layer:
25 parts by weight of zinc oxide, 20 parts by weight of urethane resin An anchor coat layer, an indicator layer, and an overcoat layer are sequentially laminated on one side of a polyester film by a gravure printing method, and an ultraviolet blocking adhesive layer is provided on the surface on which no indicator is laminated. Then, a polyester film on which a metal oxide was deposited was bonded. Further, a polyethylene film was laminated on the indicator lamination surface via a two-component curable urethane adhesive to obtain an oxygen indicator packaging material.

Oxygen indicator layer composition:
Methylene blue 3 parts by weight, L-ascorbic acid 7.5 parts by weight, binder resin 10 parts by weight, glycerin 7.5 parts by weight, synthetic silica 0.6 parts by weight Anchor coat layer, overcoat layer composition:
10 parts by weight of yellow pigment, 15 parts by weight of urethane resin Composition of UV blocking adhesive layer:
25 parts by weight of calcium carbonate, 20 parts by weight of urethane resin An anchor coat layer, an indicator layer, and an overcoat layer are sequentially laminated on one side of a polyester film by a gravure printing method. The polyester film was bonded together. Furthermore, a polyethylene film was laminated on the indicator lamination surface via an ultraviolet blocking adhesive layer to obtain an oxygen indicator packaging material.

This example is an example for comparison.
<Comparative example>
Oxygen indicator layer composition:
Methylene blue 3 parts by weight, L-ascorbic acid 7.5 parts by weight, binder resin 10 parts by weight, glycerin 7.5 parts by weight, synthetic silica 0.6 parts by weight Anchor coat layer, overcoat layer composition:
10 parts by weight of yellow pigment and 15 parts by weight of urethane resin A polyester film on which metal oxide is vapor-deposited is sequentially laminated with an anchor coat layer, an indicator layer, and an overcoat layer by gravure printing. A polyethylene film was laminated through the film to obtain an oxygen indicator packaging material.

[Experiment 1]
The oxygen indicator packaging material was released from the deoxidized state to the aerobic state, and the discoloration was confirmed. The results are shown below.

[Table 1]
Deoxygenation Aerobic Example 1 Yellow Green Example 2 Yellow Green Example 3 Yellow Green Comparative Example Yellow Green * The color after standing for 1 day in an aerobic state was shown.
* After 1 day, all showed aerobic color.

[Experiment 2]
The oxygen indicator packaging material is placed in a polyvinylidene chloride-coated stretched polypropylene / polyethylene packaging material with an oxygen scavenger, deoxygenated, exposed to 200 W · hr / cm ² of ultraviolet light, and the packaging material is opened. The color change was confirmed.
For the samples of Examples 1 and 2 having an ultraviolet blocking layer only on one side of the indicator, a metal foil that does not transmit ultraviolet rays was placed on the surface without the ultraviolet blocking layer.

[Table 2]
Deoxygenation Aerobic Example 1 Yellow Green Example 2 Yellow Green Example 3 Yellow Green Comparative Example 1 Yellow Yellow * The color after standing for 1 day in an aerobic state was shown.
Those having an ultraviolet blocking layer showed an aerobic color in one day, but those not printed with an ultraviolet blocking layer as in Comparative Example 1 showed an aerobic color even after one day had elapsed after opening. There wasn't.

  From Experiment 1, the oxygen indicator wrapping material of the present invention detected oxygen when the oxygen state changed from the deoxygenated state, and discoloration was confirmed within one day. Further, from Experiment 2, when the ultraviolet ray was irradiated in a deoxygenated state, the oxygen indicator packaging material having the ultraviolet blocking layer as in the example changed to an aerobic color after 1 day from the aerobic state. On the other hand, the oxygen indicator wrapping material having no ultraviolet blocking layer as in the comparative example did not show an aerobic color even after one day had passed since it was in an aerobic state. From the above, an oxygen indicator packaging material that is resistant to ultraviolet rays is made possible by adding an ultraviolet absorber having a low transmittance in the ultraviolet region to the adhesive layer.

It is explanatory drawing which shows the example of the oxygen indicator packaging material which has an ultraviolet-ray blockade adhesive layer of this invention in a cross section. It is explanatory drawing which shows the cross section of the other example of the oxygen indicator packaging material which has the ultraviolet-ray shielding adhesive layer of this invention.

Explanation of symbols

1, 10 ... Oxygen indicators 21, 22, 23 ... UV-blocking adhesive layers 31, 32, 33, 34 ... Base material 4 ...・ ・ ・ ・ ・ ・ Packaging base material 5 with gas barrier property ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Content 6 ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Gas permeable film 7 ・ ・・ ・ ・ ・ ・ ・ ・ ・ ・ ・ ・ Adhesive layer

Claims (4)

An oxygen indicator having an oxygen detection function is laminated on one side of a base material, and the content surrounded by the base material is one or more layers on the oxygen indicator lamination surface in an oxygen indicator packaging material that is not in contact with the oxygen indicator The adhesive layer that laminates the base material and covers the base material covers the oxygen indicator, and the ultraviolet absorber is contained in an amount of 5 to 95 parts by weight as a proportion of the solid content of the ultraviolet blocking adhesive layer. Oxygen indicator packaging material. An oxygen indicator having an oxygen detection function is laminated on one side of the base material, and the content surrounded by the base material is a surface on which the oxygen indicator is not laminated in the oxygen indicator packaging material that is not in contact with the oxygen indicator. An adhesive layer in which one or more base materials are laminated on each other and the base material is bonded covers the oxygen indicator, and the ultraviolet absorber is contained in an amount of 5 to 95 parts by weight as a ratio to the solid content of the ultraviolet blocking adhesive layer. Oxygen indicator packaging characterized by things. An oxygen indicator having an oxygen detection function is laminated on one side of the base material, and the content surrounded by the base material is a base material on which the oxygen indicator is laminated in an oxygen indicator packaging material that is not in contact with the oxygen indicator. The adhesive layer in which one or more base materials are laminated on both sides of the substrate and the base materials are bonded covers the oxygen indicator, and the ultraviolet absorber is contained in an amount of 5 to 95 parts by weight as a ratio to the solid content of the ultraviolet blocking adhesive layer. Oxygen indicator packaging material characterized by being made.   The oxygen indicator packaging material according to any one of claims 1 to 3, wherein the light transmittance of the adhesive layer having a function of blocking ultraviolet rays is less than 40% in a wavelength region of 290 nm to 400 nm. .

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