JP2009234623A - Exterior body for deoxidizing-packaging of easily oxidizable substance-containing film roll - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an exterior body for deoxidizing-packaging an oxidizable substance, more in detail, an oxygen indicator laminated film roll or an oxygen-absorbing resin laminated film roll which is capable of suppressing pin holes during transportation, and holding the film roll containing the oxidizable substance in a deoxidized state. <P>SOLUTION: The exterior body for deoxidizing-packaging the laminate film roll containing the oxidizable substance is an exterior body consists of a laminated film, in which a polyolefin film, a vapor-deposited nylon film, and an unoriented polyolefin film are laminated from the outer side in this order. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

The present invention relates to an oxygen indicator whose function deteriorates in the presence of oxygen, in particular oxygen, or an exterior body for deoxygenating packaging of a laminated film in which an oxygen absorbing resin is integrated with a packaging material.

Currently, there are various oxygen indicators that can easily check the occurrence of changes in gas atmosphere due to pinholes, seal defects, and oxygen absorber packaging with oxygen absorbers, by changing the color depending on the presence or absence of oxygen. It is on the market. The oxygen indicator is mainly composed of a redox indicator, a reducing agent, and a binder resin as constituent components, and various oxygen indicators in which this combination is changed are 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 oxidation-reduction indicator has 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 ambient atmosphere can be detected visually (Patent Document 1).

  On the other hand, in order to prevent the contents from being oxidized, denatured, mold generation, etc., a method of encapsulating an oxygen scavenger in the layer structure of the packaging material and performing oxygen scavenging is widely known. The oxygen scavenger uses reduced iron or an organic reducing agent as a main component, and utilizes the function of absorbing oxygen in the packaging material when they are oxidized (Patent Document 2).

Recently, an oxygen-absorbing resin film having a deoxygenating ability imparted to the film itself has been developed (Patent Document 3).
JP 2001-192592 A Japanese Patent No. 1667767 Japanese Patent No. 3362756

When the oxygen indicator is left in the atmosphere, it exhibits an oxidized color, and further, the reducing agent of the component is oxidized with the passage of time, and eventually loses its function as an indicator. Therefore, as a method for storing the oxygen indicator, a method in which the oxygen indicator is enclosed in a package having an oxygen barrier property together with a deoxidizing agent and deoxidized and packaged is the mainstream.

  In order to maintain the quality of the oxygen indicator printed on the wound film or the film having oxygen absorbing ability, it is necessary to deoxygenate the entire film winding. In this case, during transport after deoxygenation packaging, a portion where the outer package for deoxidation packaging is folded or the like rubs against the inner wall of the corrugated cardboard for packing, and there is a possibility that the quality of the contents cannot be maintained. . Further, in the case of winding the oxygen-absorbing resin laminated film integrated with the packaging material, there is a risk of quality deterioration.

  In the present invention, the structure of the exterior body for deoxidizing and packaging the easily oxidizable substance, specifically the oxygen indicator laminated film winding or the oxygen absorbing resin laminated film winding, can suppress pinholes during transportation, and is easily oxidized. An object of the present invention is to provide an exterior body that can keep the material-containing film wound in a deoxygenated state.

The easily oxidizable substance-containing film winding deoxygenation packaging exterior body in the present invention has been invented in order to solve the above problems.

  The invention according to claim 1 of the present invention is an exterior body made of a laminated film, which is laminated from the outside in the order of a polyolefin film, a vapor-deposited nylon film, and an unstretched polyolefin film. It is an outer package for film winding deoxygenation packaging.

  According to a second aspect of the present invention, there is provided the outer package for an oxidizable substance-containing film wound up and deoxygenated packaging according to the first aspect, wherein the oxidizable substance is an oxygen indicator layer.

  Invention of Claim 3 of this invention is an easily oxidized substance containing film winding | wrapping deoxygenating packaging exterior body of Claim 1 or 2 characterized by the said easily oxidizable substance being an oxygen absorption resin layer.

In the transportation process, by using a laminated film laminated from the outside in the order of polyolefin film, vapor-deposited nylon film, and unstretched polyolefin film, as an outer package for deoxidizing and packaging laminated film winding containing an easily oxidizable substance In addition, it is possible to suppress the inflow of oxygen into the exterior body due to bag breakage and the like, and to maintain the quality of the easily oxidizable substance-containing film winding.

Next, an example of an embodiment 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. When a seal layer is necessary, a material having oxygen permeability and water vapor permeability, such as polyethylene and polypropylene, can be appropriately selected.

  The substrate used for the oxygen indicator laminated film is preferably a substrate that does not react with the oxygen indicator and does not inhibit the coloration of the reagent. As such a base material, a synthetic resin film, for example, polyester, polyamide, polyvinyl alcohol, cellophane, ethylene vinyl alcohol copolymer, polyethylene, polypropylene, polymethylpentene, and a transparent vapor deposition layer such as silica and alumina are provided on these. A transparent vapor deposition film or the like can be used in accordance with the purpose of use and the form of use.

In particular, when used as a package with an oxygen indicator, it is necessary to provide an oxygen barrier property to the base material, so silica, alumina vapor-deposited base material, polyvinyl alcohol, ethylene vinyl alcohol copolymer, polyamide, etc. are used as the base material. It is preferable to use as. Furthermore, it is preferable that the oxygen permeability of the base material to be used is 20 cc / m ² · day · MPa or less.

An anchor coat layer and / or an overcoat layer can be provided on the base material for the purpose of protecting the oxygen indicator layer and preventing occurrence of poor appearance, peeling, and breakage. The anchor coat layer is a water-insoluble material having good adhesion between the substrate and the oxygen indicator layer formed thereon, and the overcoat layer is an oxygen permeable, oxygen indicator layer. Materials having good adhesion and good adhesion to 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.

  As for the material of the oxygen-absorbing resin laminated film, the one in which reduced iron is dispersed in a thermoplastic resin to absorb oxygen, the one using oxidative decomposition or oxygen addition of a thermoplastic resin having an unsaturated bond, the inorganic oxide is thermoplastic. There is no particular limitation as long as it oxidizes when continuously exposed to oxygen, such as a resin dispersed in a resin and utilizing oxygen bonds to its lattice defects.

  As oxygen scavengers used for oxygen scavenging packaging of films containing easily oxidizable substances, both organic oxygen scavengers and iron oxygen scavengers can be used. Accordingly, the size and number of oxygen scavengers may be adjusted. When the function of the oxygen indicator depends on pH, it is preferable to select an iron-based oxygen scavenger. The method of attaching the oxygen scavenger is not particularly limited as long as it does not impair the capacity of the oxygen scavenger, but the film end surface portion (FIG. 1), the film side surface portion (FIG. 2), paper tube or plastic A method of fixing the inside of the tube (FIG. 3) with an arbitrary pressure-sensitive adhesive, paper tape or the like can be mentioned. Further, the oxygen absorbent amount may be kneaded into a paper tube or a plastic tube and integrated.

  The material configuration of the easily oxidizable substance-containing film winding deoxygenation packaging outer body of the present invention is such that a polyolefin film, a vapor-deposited nylon film, and an unstretched polyolefin film are laminated in this order from the outside.

  The lamination method is not particularly limited, but a dry laminate method and an extruder laminate method can be suitably used.

  The outermost polyolefin film imparts flexibility and a function of preventing pinholes due to rubbing to the laminate, and is not particularly limited as long as the film has a thickness of 20 to 60 μm. Among them, a biaxially stretched polypropylene film, A uniaxially stretched polypropylene film, an unstretched polypropylene film, and an unstretched polyethylene film can be used conveniently.

The vapor-deposited nylon film is for imparting oxygen barrier properties to the exterior body, and a polyamide film having a thickness of 15 to 40 μm obtained by vapor-depositing silicon oxide and aluminum oxide can be suitably used. The oxygen barrier may be 20.0 cc / m ² · day · MPa (30 ° C., 70% RH) or less.

  The innermost polyolefin film is not particularly limited as long as it is a heat-sealing layer at the time of bag making and is a polyolefin-based film having heat-fusibility. Of these, unstretched polyethylene and unstretched polypropylene can be suitably used. The thickness is preferably about 30 to 100 μm.

  The extrusion resin at the time of extruder lamination is not limited as long as it is low density polyethylene. When the other polyolefin film of the outermost layer and the vapor-deposited nylon film are bonded, the thickness of the extruded resin is preferably about 10 to 30 μm, and the total thickness of the other polyolefin film of the outermost layer and the extruded resin may be 20 to 60 μm. preferable.

  Further, the innermost polyolefin layer may be made of an extruded resin. In this case, the thickness is preferably about 30 to 100 μm. When laminating these extruded resin layers, an adhesive anchor coat layer may be provided between the base film and the extruded resin layer.

  As the adhesive during dry lamination, known adhesives such as an isocyanate curing type of polyol and an amine curing type of epoxy can be used.

  The shape of the easily oxidized substance-containing laminated film winding deoxygenating packaging outer body of the present invention is not particularly limited, such as a three-side sealed bag, a gusset bag, etc. , Pinhole is difficult to place.

  When deoxidizing and packaging an easily oxidizable substance-containing film with the exterior body of the present invention, by using a deaeration package, the space between the exterior body and the easily oxidizable substance-containing film winding is fixed during transportation, and rubbing or bending It is preferable because it can prevent pinholes due to. In addition, even if not degassed, if the inside is in a depressurized state when deoxygenated, the space between the outer package and the oxidizable substance-containing film is fixed as in the case of degassed. Can be expected. Furthermore, nitrogen substitution can be used together.

  Because of the difference in the shape of the easily oxidizable substance-containing film winding of the contents and the outer casing, the corners of the outer casing are not in close contact with the winding, especially after deoxidation packaging, which can easily cause pinholes. A double-sided tape, adhesive, or the like can be attached or applied to the surface of the body, and the corners can be woven (FIGS. 4 and 5). When the outermost package is unstretched polyethylene or unstretched polypropylene, it may be folded and heat-sealed (FIG. 6).

  It is also possible to print and integrate an oxygen indicator on the exterior body, and confirm the deoxygenated state in the exterior body (the space where the easily oxidizable substance-containing film is wound).

Examples of the present invention will be specifically described below.

<Example 1>
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 weightAnchor coat layer, overcoat layer composition : 10 parts by weight of yellow pigment, 15 parts by weight of urethane resin 12 μm thick polyester film, 0.5 μm anchor coat layer, 1 μm indicator layer, 1 μm overcoat layer are sequentially laminated by gravure printing method, A 12 μm thick polyester film deposited with a metal oxide was laminated using a two-component curable urethane adhesive, and a 60 μm thick low-density polyethylene film was laminated to cover the printed surface. This was an oxygen indicator winding of 800 m in length.

  As shown in the cross section of FIG. 7, the outer packaging body for easy-oxidized substance-containing laminated film winding and deoxygenating packaging has a 20 μm-thick biaxially stretched polypropylene film 10, a 15 μm-thick aluminum oxide-deposited nylon film 12, a 60 μm-thick straight body. A chain low density polyethylene film 13 was sequentially laminated with a two-component curable urethane adhesive (not shown), and a three-sided bag was used. An appropriate number of iron-based oxygen scavengers were put in a paper tube for winding the oxygen indicator, and then the winding was deoxygenated and packed in a cardboard using the three-side seal bag.

<Example 2>
Oxygen indicator layer composition, anchor coat layer, overcoat layer composition: the same as in Example 1. An anchor coat layer 0.5 μm, an oxygen indicator layer 1 μm, and an overcoat layer 1 μm are sequentially laminated on one side of a 12 μm-thick polyester film by a gravure printing method, and a 12 μm-thick polyester film vapor-deposited with metal oxide is formed on the opposite side. A two-component curable urethane-based adhesive was laminated, and a low-density polyethylene film 60 μm was further laminated so as to cover the printed surface. This was an oxygen indicator winding of 800 m in length.

  As an outer packaging body for taking up an oxidizable substance-laminated film and deoxygenating packaging, an adhesive anchor coating agent 14 is applied to a biaxially stretched polypropylene film 10 having a thickness of 25 μm, and a low-density polyethylene 15 having a thickness of 30 μm is extruded to 15 μm. A thick aluminum oxide-deposited nylon film 12 was adhered. Further, a three-side bag was made by laminating a 30 μm-thick linear low-density polyethylene film 13 on an aluminum oxide vapor-deposited nylon film 12 with a two-component curable urethane adhesive. An appropriate number of iron-based oxygen scavengers were put in a paper tube for winding the oxygen indicator, and then the winding was deoxygenated and packed in a cardboard using the three-side seal bag.

<Example 3>
Oxygen indicator layer composition, anchor coat layer, overcoat layer composition: the same as in Example 1.

  An anchor coat layer of 0.5 μm, an indicator layer of 1 μm, and an overcoat layer of 1 μm are sequentially laminated on one side of a 12 μm-thick polyester film by gravure printing, and a 12 μm-thick polyester film on which the metal oxide is vapor-deposited on the opposite side. Lamination was performed using a liquid curable urethane-based adhesive, and a low-density polyethylene film having a thickness of 60 μm was further laminated so as to cover the printed surface. This was an oxygen indicator winding of 800 m in length.

  As an exterior body for easy-oxidized substance-containing laminated film winding and deoxygenating packaging, a 20 μm thick biaxially oriented polypropylene film 10 and a 15 μm thick aluminum oxide-deposited nylon film 12 are sequentially laminated with a two-component curable urethane adhesive. Further, the adhesive anchor coating agent 14 was applied, and then a 60 μm-thick low density polyethylene 15 was extruded to form a heat-sealing layer. An appropriate number of iron-based oxygen scavengers were put in a paper tube for winding the oxygen indicator, and then the winding was deoxygenated and packed in a cardboard using the three-side seal bag.

<Example 4>
Oxygen indicator layer composition, anchor coat layer, overcoat layer composition: the same as in Example 1. An anchor coat layer of 0.5 μm, an indicator layer of 1 μm, and an overcoat layer of 1 μm are sequentially laminated on one side of a 12 μm-thick polyester film by gravure printing, and a 12 μm-thick polyester film on which the metal oxide is vapor-deposited on the opposite side. A 60 μm thick low density polyethylene film was laminated so as to cover the printed surface by laminating using a liquid curable urethane-based adhesive. This was an oxygen indicator winding of 800 m in length.

  As an exterior body for easy-oxidized substance-containing laminated film winding and deoxygenating packaging, a 20 μm thick biaxially oriented polypropylene film 10 and a 15 μm thick aluminum oxide-deposited nylon film 12 are sequentially laminated with a two-component curable urethane adhesive. Further, after the adhesive anchor coating agent 14 was applied, a 30 μm-thick low-density polyethylene 15 was extruded and laminated with a 60 μm-thick linear low-density polyethylene film 13 to form a three-sided bag. An appropriate number of iron-based oxygen scavengers were put in a paper tube for winding the oxygen indicator, and then the winding was deoxygenated and packed in a cardboard using the three-side seal bag.

<Comparative Example 1>
Oxygen indicator layer composition, anchor coat layer, overcoat layer composition: the same as in Example 1.

An anchor coat layer of 0.5 μm, an indicator layer of 1 μm, and an overcoat layer of 1 μm are sequentially laminated on one side of a 12 μm-thick polyester film by gravure printing, and a 12 μm-thick polyester film on which the metal oxide is vapor-deposited on the opposite side. Lamination was performed using a liquid curable urethane-based adhesive, and a low-density polyethylene film having a thickness of 60 μm was further laminated so as to cover the printed surface. This was an oxygen indicator winding of 800 m in length.

  As the outer packaging for deoxygenation packaging, three-sided bag made of 15 μm thick aluminum oxide-deposited nylon 12 and 60 μm thick linear low-density polyethylene film 13 sequentially laminated with a two-component curable urethane adhesive Was used. An appropriate number of iron-based oxygen scavengers were put in a paper tube for winding the oxygen indicator, and then the winding was deoxygenated and packed in a cardboard using the three-side seal bag.

[Experiment 1]
The cardboard packed in Examples 1 to 4 and Comparative Example 1 was subjected to a vibration test under the following conditions.
Vibration condition: ± 4G (11Hz), total 60 minutes (vertical direction 30 minutes + vertical 15 minutes + horizontal 15 minutes)
Evaluation method: A vibration test was performed under the above conditions, and the cardboard was unpacked to confirm whether the deoxygenated state in the exterior body was maintained. In addition, the number of exterior bodies in which the deoxygenated state was not maintained (oxygen flowed into the inside) was counted. (It was defined as the number of broken bags, and 20 cardboard inspections were conducted for each condition). The results are shown in Table 1 together with the numerical value (cc / m ² · day · MPa) of the oxygen barrier property of the outer package.

From the above results, it can be seen that Examples 1 to 4 have a reduced number of broken bags in the vibration test as compared with Comparative Example 1. The rate of bag breakage in the actual transportation process is much less than that occurring under the experimental conditions, which is on the order of ppm, but the results under these conditions are considered to reflect this relatively. Furthermore, if it was a structure like Examples 1-4, there were many things with a deoxygenation state maintained, and the film which had high oxygen barrier property was obtained.

  Thereby, as an exterior body for deoxidizing and packaging a laminated film winding containing an easily oxidizable substance, from the outside, by using a laminated film laminated in order of a polyolefin film, a vapor-deposited nylon film, and an unstretched polyolefin film, Providing an outer package for easy-oxidizing substance-containing laminated film winding deoxygenating packaging that can suppress the inflow of oxygen into the outer package due to broken bags in the transport process and maintain the quality of easily-oxidized substance-containing film winding. It has become possible.

Schematic showing an example of an oxygen scavenger application site Schematic showing an example of an oxygen scavenger application site Schematic showing an example of an oxygen scavenger application site Schematic showing an example of folding the winding corner (fixed with adhesive) Schematic showing an example of folding the winding corner (fixed with adhesive tape) Schematic showing an example of folding the winding corner (fixed with heat seal) Schematic cross-sectional view of an example of the outer packaging for deoxygenating packaging of the present invention Schematic cross-sectional view of an example of the outer packaging for deoxygenating packaging of the present invention Schematic cross-sectional view of an example of the outer packaging for deoxygenating packaging of the present invention Schematic cross-sectional view of an example of the outer packaging for deoxygenating packaging of the present invention Cross-sectional schematic diagram of an example of an outer packaging for deoxygenating packaging of a comparative example

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Winding roll end surface 2 ... Deoxidation agent 3 ... Winding roll side surface 4 ... Winding roll paper tube (or plastic tube) inner surface 5 ... Deoxygenation packaging exterior body 6 ... Easy-oxidation substance containing film winding 7 ... Adhesion Agent 8 ... Adhesive tape 10 ... Biaxially stretched polypropylene film 11 ... Aluminum oxide vapor deposition layer 12 ... Nylon film 13 ... Linear low density polyethylene film 14 ... Adhesive anchor coat layer 15 ... Low density polyethylene

Claims (3)

An outer packaging body made of a laminated film, which is laminated from the outside in the order of a polyolefin film, a vapor-deposited nylon film, and an unstretched polyolefin film. The package for deoxidized packaging according to claim 1, wherein the oxidizable substance is an oxygen indicator layer. The package for deoxidized packaging according to claim 1 or 2, wherein the easily oxidizable substance is an oxygen-absorbing resin layer.