JP2002293383A - External packaging of deoxidant - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an external packaging of deoxidant which is excellent in oxygen barrier property, steam barrier property and pin-hole resistance, and suitable for storage and physical distribution. SOLUTION: In the external packaging of deoxidant which is formed of a film with oxygen barrier property and stores deoxidant therein, the film with oxygen barrier property is a multi-layered film comprising (A) a biaxially oriented polypropylene resin layer, (B) a polyvinylidene chloride coat oriented polyamide resin layer, and (C) a sealant resin layer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen-absorbing agent package containing an oxygen-absorbing agent.

[0002]

2. Description of the Related Art In recent years, a method using an oxygen scavenger has been established as a simple and reliable method for preserving easily oxidizable articles such as foodstuffs, pharmaceuticals, cosmetics, and the like, which are susceptible to microbial contamination and spoilage such as mold. Oxygen absorbers in the form of pouches, sheets, films and the like have been industrially manufactured.
These oxygen absorbers can be obtained by collecting a certain number of pouch-shaped oxygen absorbers, or by cutting a sheet-shaped or film-shaped oxygen absorber into a certain length, or by continuous packaging of a pouch-shaped oxygen absorber. Each bobbin whose body (web) has been wound up by a certain number is packaged with an oxygen barrier film and stored and subjected to a distribution process.

Conventionally, a stretched nylon (KON) / polyethylene (PE) coated with polyvinylidene chloride (hereinafter, for example, laminated in the order of a KON layer and a PE layer) has been used as an oxygen barrier container for storing an oxygen scavenger. Multilayer films are referred to as KON / PE).

However, in recent years, as a large number of packages containing oxygen scavengers have been manufactured and the distribution process of product transportation has become complicated and intense, physical handling of the conventional KON / PE package has been increasing. Insufficient strength may cause pinholes in the multilayer film during the transportation and distribution process, and the oxygen invading the oxygen scavenger may cause a situation. In order to be able to be handled practically, sufficient pinhole resistance is required, and its piercing strength needs to be 12 N or more.

On the other hand, packaging materials having excellent gas barrier properties include saponified ethylene-vinyl acetate copolymer (EV).
OH) A layer type including a resin layer and a nylon resin layer made of a blend of crystalline nylon MXD6 and another nylon is disclosed in JP-A-4-216050.
The biaxially stretched EVOH layer / biaxially stretched film layer of polypropylene, nylon or polyester is disclosed in
No. 35778, respectively. However, the saponified ethylene-vinyl acetate copolymer layer (EVOH), which is the base material of the intermediate layer, has a weak steam barrier property and is insufficient as a container for storing and distributing an oxygen scavenger.

[0006]

In an oxygen barrier film for packaging an oxygen scavenger, the oxygen scavenger sometimes contains water which is a catalyst for developing oxygen absorbing activity. High water vapor barrier properties so that it does not volatilize outside the container.Generally, because it is stored and stored under reduced pressure by degassing operation, it has high strength and pinhole resistance, and can withstand severe handling in the logistics process. Is required to have sufficient strength and pinhole resistance, and to have good operability at the time of sealing or opening.

An object of the present invention is to solve the above-mentioned problems in the prior art in the storage and distribution of an oxygen scavenger, to provide a good balance of oxygen barrier properties, water vapor barrier properties and pinhole resistance, and to improve transport and distribution processes. An object of the present invention is to provide an oxygen-absorbing agent outer package having a satisfactory function.

[0008]

As a result of studying a method for solving the above-mentioned problems, the present inventors have found that a polyvinylidene chloride-coated surface of a stretched laminated film including a stretched nylon resin layer and a sealant resin layer is coated on the surface of the polyvinylidene chloride coat. It was found that the object was achieved by using a multilayer stretched film laminated with biaxially stretched polypropylene (OPP), and completed the present invention.

That is, the present invention relates to an outer package of an oxygen-absorbing agent comprising an oxygen-barrier film containing an oxygen-absorbing agent, wherein the oxygen-barrier film comprises (A) a biaxially stretched polypropylene resin layer. And (B) a multilayer film comprising a polyvinylidene chloride-coated stretched polyamide resin layer and (C) a sealant resin layer. With this configuration, KON /
Provided is an outer package that retains the excellent oxygen barrier property and steam barrier property of PE, improves pinhole resistance to a practical level, and can safely store the oxygen scavenger and provide it to the distribution process. .

[0010]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In the present invention, a multilayer film comprising (A) a biaxially stretched polypropylene resin layer, (B) a polyvinylidene chloride coated stretched polyamide resin layer, and (C) a sealant resin layer is used.

As the (A) biaxially oriented polypropylene (OPP) resin used in the present invention, a film obtained by biaxially stretching various crystalline propylene polymers can be used.
Examples of the propylene polymer include a propylene homopolymer and a copolymer of propylene with a small amount of another olefin. Auxiliary components such as antioxidants, antiblocking agents, lubricants, antistatic agents, coloring agents, concealing agents, and other additives which can be usually added to the polypropylene polymer may be used.

The stretching ratio of OPP is not particularly limited as long as the stretching effect is basically exhibited, but is usually 1.5 times or more in the warp direction, 2.0 or more in the weft direction, preferably 3.0 in the warp direction. 7.0 to 7.0 times, and the latitude direction is 5.0 to 12.0 times.

The (B) polyvinylidene chloride-coated stretched polyamide resin (KON) layer used in the present invention is obtained by adding a stretched amorphous polyamide resin or a mixture of an amorphous polyamide resin and another polyamide resin to polyvinylidene chloride. It is a resin layer whose surface is coated with a resin. (B) The polyvinylidene chloride-coated stretched polyamide resin is laminated with the polyvinylidene chloride resin surface facing the (A) OPP surface and the nylon resin surface facing the (C) sealant surface.

Amorphous nylon can be obtained by pressure-based melt polymerization, decarboxylation condensation, or the like using dicarboxylic acid, diamine, lactam, diisocyanate or the like as a raw material. Here, examples of the dicarboxylic acid include adipic acid, suberic acid, azelaic acid, terephthalic acid, and isophthalic acid. As the diamine, for example, hexamethylenediamine, trimethylhexamethylenediamine, isophoronediamine, bis-p- (aminocyclohexyl) methane, bis-p- (aminocyclohexyl) ethane and the like are used. As a lactam,
For example, caprolactam, lauroca prolactam and the like can be mentioned. As the diisocyanate, for example, diphenylmethane diisocyanate, tolylene diisocyanate and the like are used. Other polyamide resins mixed with the amorphous polyamide resin can be obtained by a polycondensation reaction of ω-aminocarboxylic acid or a polycondensation reaction of dibasic acid and dicarboxylic acid.
2, nylon 11, nylon 6-6, nylon 6-1
0, nylon 6-12, or a copolymer or mixture thereof. (A) Polyvinylidene chloride-coated stretched nylon resin is stretched under stretching conditions at which a stretching effect is exhibited, for example, at a stretching temperature of 50 to 150 ° C. and a stretching magnification of 2 to 6 times, and then coated with polyvinylidene chloride resin and dried. Obtained.

[0015] The sealant resin layer (C) used in the present invention comprises low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and medium-density polyethylene (MDP).
E), polyethylene (PE) such as high-density polyethylene (HDPE), olefin resins such as polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMM)
A), ethylene-ethyl acrylate copolymer (EE
A), ethylene-methyl acrylate copolymer (EM
A), ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMMA), ionomer (ION), etc. Ethylene copolymer resin. Among them, LD
Olefin-based resins such as PE and LLDPE are more preferably used.

Each of the layers (A), (B) and (C) can be laminated by an extrusion lamination method in which an adhesive resin (Ad) is used and is extruded and laminated between the layers. The adhesive resin (Ad) used at that time includes low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and medium-density polyethylene (MDP).
E), polyethylene (PE) such as high-density polyethylene (HDPE), olefin resins such as polypropylene (PP), ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMM)
A), ethylene-ethyl acrylate copolymer (EE
A), ethylene-methyl acrylate copolymer (EM
A), ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMMA), ionomer (ION), etc. In addition to the ethylene copolymer-based resins, modified polyolefin-based resins, for example, ethylene-vinyl acetate copolymer or ethylene-based elastomer, monobasic unsaturated fatty acid such as acrylic acid or methacrylic acid, or maleic Examples thereof include those in which an anhydride of a dibasic fatty acid such as an acid, fumaric acid or itaconic acid is chemically bound.

The package of the present invention is a layered material having a thickness of 250 μm or less. (A) The thickness of the biaxially stretched polypropylene resin layer is 20 to
A range of 30 μm is preferred. If it is less than 20 μm, the pinhole resistance is reduced, and if it is more than 30 μm, the total thickness of the laminated film is increased, and the handleability is reduced. (B) The polyvinylidene chloride-coated stretched polyamide resin (KON) layer is preferably functionally and costly in the range of 10 to 30 μm. (C) The thickness of the sealant is preferably in the range of 30 to 50 μm. If it is 30 μm or less, the sealing strength is reduced, and there is a concern that the seal may be damaged during use. If it exceeds 50 μm, the cost will increase, and the total thickness of the film will increase, resulting in poor handling. When an adhesive resin layer (Ad) for bonding these layers is used, its thickness is 10 to 25 μm.
Is preferable in terms of workability, economy and handling.

In the present invention, the thicknesses of the layers (A) and (C) are set to 20 μm ≦ (A) ≦ 30 μm and 30 μm <
(C) ≦ 50 μm, and simultaneously the layer (A) and the layer (C)
Ratio of layer thickness of (A) layer to total layer thickness X = (A) /
[(A) + (C)] is preferably in a specific range of 0.29 ≦ X <0.40.

As a method for producing the outer package of the present invention, for example, in the case of a three-layer, five-layer film of (A) / (Ad) / (B) / (Ad) / (C), first, (A) While sending OPP film and (B) KON film by roll, OPP film
After the adhesive resin layer (Ad) is melt-extruded between the surface and the polyvinylidene chloride coated surface and laminated and adhered,
The adhesive resin layer (Ad) is extruded between the nylon surface of the (B) KON film and the (C) sealant film and laminated and adhered to obtain the above-mentioned three-layer, five-layer multilayer package.

Here, a film composed of the number of base film types (n) and the number of adhesive resin layers (m) is referred to as an n-type m-layer film. The adhesive resin layer has a thickness of 5 μm or more and 25
It is a layer of 0 μm or less. It does not include a layer having a thickness of less than 5 μm, such as a dry lamination adhesive or a coating agent.

The multilayer film used in the present invention comprises (A) OPP, (B) KON, (C)
Each layer of the sealant is manufactured by individually manufacturing a film corresponding to each layer, and then attaching the layers with an adhesive resin or an adhesive. At that time, as a method of pasting (lamination),
An extrusion lamination method in which the adhesive resin layer (Ad) is extruded and laminated between the layers, and a dry lamination method in which an adhesive is applied to each layer or a part thereof, pressed and dried, and the like are exemplified. Specifically, as a method of laminating between the A / B layers,
(A) Biaxially stretched polypropylene (OPP) resin layer and (B) Polyvinylidene chloride coated stretched polyamide resin (KON)
Extrusion lamination method in which an adhesive resin layer (Ad) that has a thickness between layers and also serves as a cushion and also has a role of improving adhesiveness, because the direct adhesiveness with the resin layer is not good and the flexibility is somewhat lacking. Is more preferable than the dry lamination method in which the adhesive is thinly applied (generally, several μm or less) and attached. In addition, the extrusion lamination method and the dry lamination method can be applied between the B / C layers, but the extrusion lamination method is more preferable because the package needs some flexibility.

The outer package obtained by the present invention has a water vapor permeability of 1.0 g / m ² · 2 at 25 ° C. and 0 → 75% RH.
4 hr or less, oxygen permeability is 20 m at 25 ° C. and 60% RH
1 / m ² · 24 hr · atm or less, and the piercing strength is 12 N / pen tip radius 0.5 mm and 50 mm / min or more. As a result of the study by the present inventors, it has been found that pinhole occurrence accidents are sharply reduced at a puncture strength of 10 N. So, in anticipation of the safety factor,
When the piercing strength is 12 N or more, it can be determined that the pinhole has practically good pinhole resistance in handling.

The oxygen absorber to be packaged is a material obtained by wrapping an oxygen-absorbing substance exemplified by iron and ascorbic acid with a breathable packaging material or blending it with a thermoplastic resin. It is an oxygen absorber in any form such as a shape and a film. Specifically, it is an accumulation of a pouch-shaped oxygen absorber, a bobbin wound around a continuous bag (web) of the pouch-shaped oxygen absorber, or a bundle or roll of the oxygen absorber in the form of a sheet or a film. .

The exterior package of the present invention is a package for storing and distributing the produced oxygen absorber, but can be widely used as a package for other food and drink bottles and barrels. The outer package is usually sealed with the sealant layers and sealed by various heat-sealing methods, for example, a method such as a heat bar seal, an impulse seal, and a high-frequency seal, to obtain a bag-shaped container. Then, a certain amount of the produced oxygen scavenger is stored therein, and if necessary, a vacuum operation or a degassing operation is performed, and then the container is sealed and subjected to a storage and distribution process.

[0025]

The present invention will be described below in detail with reference to examples. The physical properties of the multilayer film or the oxygen-absorbing agent exterior package obtained in the examples were measured by the following methods. (1) Water vapor permeability Unit: g / m ² · 24 hr The obtained multilayer film was measured according to JIS-Z-0208. Oxygen permeability Unit: ml / m ² · 24 hr The obtained multilayer film is subjected to an oxygen permeability measurement apparatus (OXY-TRAN, manufactured by Modern Control Co., Ltd.) at 25 ° C. and 60% RH
100 type).

(3) Puncture strength (pinhole resistance)
Unit: N (Newton) / Pin tip radius 0.5 mm, 50
mm / min The obtained multilayer film is 1 mm in diameter and has a radius of curvature of 0.1 mm.
A 5 mm pin was pierced under a speed condition of 50 mm / min, and the load (N) when the hole was opened was measured. (4) Drop test A roll body formed by spirally winding a continuous bag (web) consisting of 3,000 small bag-shaped oxygen absorber packages (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name: Ageless Z-23PTR) in series on a bobbin Was sealed by a heat sealing method while performing a depressurizing operation using the obtained multilayer film to obtain 10 samples of the oxygen-absorbing exterior package, and these oxygen-absorbing exterior packages were placed on a concrete floor from a height of 2 m. After the natural film was repeatedly dropped 10 times, the multilayer film was observed for damage or pinholes.

Example 1 A biaxially oriented polypropylene (OPP) having a thickness of 20 μm (trade name: U-1 manufactured by Tosello Co., Ltd.) was applied to a film having a thickness of 15 μm.
m, a low-density polyethylene-based adhesive while sending the polyvinylidene chloride film of a biaxially stretched nylon film (trade name: N-812AE, manufactured by Toyobo Co., Ltd.) coated with polyvinylidene chloride on one surface by a hot roll so as to face each other Water-soluble resin (Misolan 11P, manufactured by Mitsui Chemicals, Inc.)
It is melt-extruded at 00 ° C., and OPP / adhesive resin / KON = 20/15/15 by an extrusion lamination method.
A laminated film of μm was obtained. Next, the nylon side of the obtained film and linear low density polyethylene (LLDPE) as a sealant resin (trade name: TU, manufactured by Tocelo Co., Ltd.)
X-FCD) film, while being fed by a hot roll, while the low-density polyethylene-based adhesive resin is melt-extruded and bonded by an extrusion lamination method, and finally OPP / adhesive resin / KON / An adhesive resin / LLDPE = 20/15/15/15/40 μm three-layer, five-layer film (total thickness: 105 μm) was obtained. The obtained multilayer film has a water vapor permeability,
Oxygen permeability and piercing strength (pinhole resistance) were measured. The results are shown in Table 1. Each measurement was performed 10 times and the range of the numerical value was shown.

From Table 1, it was found that the pinhole resistance can be greatly improved and improved to 12 N or more, which is a reference value capable of practically handling, while maintaining the steam barrier property and the oxygen barrier property. Next, the obtained three kinds 5
A drop test was performed using the layer film. After the drop test, there was no breakage or pinhole in the oxygen absorber package. Furthermore, the adhesive resin layer (Ad) between the (A) layer and the (B) layer improved the adhesiveness in a cushioning manner, and had high flexibility and handleability (handleability).

[0029]

[Table 1]

Comparative Example 1 In Example 1, a KON single film was used in place of the OPP / adhesive resin / KON laminated film, and (C) a linear low-density polyethylene (LLDPE) having a thickness of 60 μm (LLDPE) (Tokyo Cello) Co., Ltd., trade name TUX-
Except for using FCD), a multilayer film was prepared in exactly the same manner except that the film was adhered by the extrusion lamination method, and the water vapor permeability, oxygen permeability, and piercing strength (pinhole resistance) were measured. The results are shown in Table 1. Next, a drop test was performed using the obtained multilayer film. After the drop test, pinholes were observed in the multilayer film of two samples among the ten samples of the oxygen-absorbing agent outer package.

Comparative Example 2 In Example 1, a 10 μm-thick biaxially oriented polypropylene (OPP) (trade name: U-1 manufactured by Tosello Co., Ltd.) was used as the (A) layer, and (C) a sealant resin layer was used. A multilayer film was prepared in exactly the same manner except that linear low-density polyethylene (LLDPE) having a thickness of 50 μm (Tux-FCD, trade name of Tocelo Co., Ltd.) was used, and water vapor permeability, oxygen permeability, and piercing strength (resistance to puncture) Pinhole property) was measured. The results are shown in Table 1.

As a result of a drop test using the obtained multilayer film, pinholes were observed in two out of ten samples. That is, (A) the OPP resin layer is 10 μm, and (C) the sealant LLDPE resin layer is 50 μm.
By increasing the thickness to m, the steam barrier property and the oxygen barrier property were at practical levels. However, when the thickness of the OPP layer was reduced to 10 μm, the pinhole resistance was reduced, so that the OPP layer was not practically satisfactory in the transportation and distribution process.

Example 2 In Example 1, a 30 μm-thick biaxially oriented polypropylene (OPP) (trade name U-1 manufactured by Tosello Co., Ltd.) was used as the (A) layer, and (C) a sealant resin layer was used as the layer. A multilayer film was prepared in exactly the same manner except that a linear low-density polyethylene (LLDPE) having a thickness of 30 μm (trade name: TUX-FCD, manufactured by Tocelo Co., Ltd.) was used.
Oxygen permeability and piercing strength (pinhole resistance) were measured. The results are shown in Table 1. Next, a drop test was performed using the obtained multilayer film. After the drop test, there was no breakage or pinhole in the oxygen absorber package. From the above results, the steam barrier property, oxygen barrier property, and pinhole resistance were excellent.

Example 3 In Example 1, (A) a 30 μm-thick biaxially oriented polypropylene (OPP) (manufactured by Tosello Co., Ltd., trade name U-1) was used as the (A) layer, and (C) a sealant resin layer was used as the layer. S 50
A linear low-density polyethylene (LLDPE) (trade name: TUX-FCD, manufactured by Tocelo Co., Ltd.) and a layer (A) and a layer (B) having a thickness of 20 μm and a low-density polyethylene-based adhesive resin (Mitsui Chemicals, Inc. Co., Ltd., trade name Mirason 11P), the layer (B) and the layer (C) were dry-laminated urethane-based adhesives having a thickness of 3 μm (Trade name: A5
A multilayer film was prepared in exactly the same manner except that the film was adhered according to 15 / A12), and the water vapor permeability, oxygen permeability, and piercing strength (pinhole resistance) were measured. The results are shown in Table 1. Next, a drop test was performed using the obtained multilayer film. As a result, no breakage or pinholes were found in the oxygen-absorbing agent outer package after the drop test. From the above results, the water vapor barrier property, oxygen barrier property, and pinhole resistance were excellent.

[0035]

According to the present invention, the water vapor barrier property and the oxygen barrier property can be maintained, and at the same time, the piercing strength (pinhole resistance) can be improved and improved to a sufficiently practical level. A package of an oxygen-absorbing agent that can store the article in the storage and distribution process can be realized.

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Claims (5)

[Claims] 1. An outer package for an oxygen-absorbing agent comprising an oxygen-barrier film containing an oxygen-absorbing agent, wherein the oxygen-barrier film comprises (A) a biaxially stretched polypropylene resin layer, and (B) An oxygen-absorbing agent outer package, which is a multilayer film comprising a polyvinylidene chloride-coated stretched polyamide resin layer and (C) a sealant resin layer. 2. The oxygen barrier film according to claim 1, wherein (A) a resin layer and (B) a resin layer, or (B) a resin layer and (C) a resin layer, laminated by (Ad) an adhesive polyolefin resin layer. The outer package according to claim 1, wherein the outer package is a laminated multilayer film. 3. The oxygen barrier film is a multilayer film in which (A) a resin layer and (B) a resin layer or (B) a resin layer and (C) a resin layer are laminated by a dry lamination method. The outer package according to claim 1. 4. The oxygen barrier film according to claim 1, wherein (A) the resin layer has a thickness of 10 to 30 μm, and (B) the resin layer has a thickness of 1 to 30 μm.
The outer package according to claim 1, wherein the resin package has a thickness of 5 to 30 m and the resin layer has a thickness of 20 to 60 m. 5. The oxygen barrier film has a water vapor permeability of 1.0 g / m ² · 24 hr (25 ° C., 0 → 75%
RH) or less and an oxygen permeability of 20 ml / m ² · 2
4 hr.atm (25 ° C., 60% RH) or less, and
The piercing strength is 12N / ballpoint pen tip radius 0.5mm,
The outer package according to claim 1, which is at least 50 mm / min.