JPH05162776A - Oxygen removing agent package - Google Patents

Abstract

PURPOSE:To obtain a package for oxygen removing agent using the packaging material which is excellent in durability and permits this agent to display a stable oxygen removing ability. CONSTITUTION:By bonding together a laminated plastic film A having specific holes and a porous film B, an oxygen remover packaging material C having a Gurley permeability of 1-10,000 seconds/100ml is obtained. Oxygen removing agent G is wrapped and sealed in the packaging material C with the laminated film A becoming the outer film surface to obtain finished oxygen remover package. Therefore, this package suppresses contamination of the oxygen removing agent with rust and stain and prevents its deterioration to permit this agent to display a stable oxygen removing ability.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxygen scavenger package, and more particularly to a plastic laminated film having fine pores and a non-woven fabric, a microporous membrane and a water- and oil-resistant mixed paper having self-heat-sealing property. The present invention relates to an oxygen scavenger package using a film obtained by laminating a kind of microporous film selected from the group consisting of:
The oxygen scavenger package exhibits a stable oxygen scavenging performance and is therefore used in a wide range as a preservative for processed foods.

[0002]

2. Description of the Related Art An oxygen scavenger is a composition having a property of absorbing oxygen, and is usually used by being enclosed in a breathable pouch. Generally, a packaging material (hereinafter referred to as "packaging material") that constitutes a breathable sachet enclosing an oxygen scavenger includes, for example, a packaging material in which paper and a perforated polyethylene film are laminated, a perforated plastic film, paper and a perforated film. A packaging material in which polyethylene films are laminated and bonded, and a packaging material using a non-woven fabric, a microporous film, or the like are used.

[0003]

As a problem in food preservation technology using an oxygen absorber, the oxygen absorber is used in various foods such as dried foods, high-moisture foods, acidic foods, oil-processed foods and alcohol-containing foods. For use in food, moisture contained in the oxygen scavenger composition is transferred to dry food and deoxidizing performance is impaired, or water in high-moisture foods is transferred to the oxygen absorber composition, so packaging material Stain is generated on the surface of the product to impair the appearance, and oil of food permeates the packaging material, impairing the air permeability of the packaging material and deoxidizing performance. Due to such a drawback, when using an oxygen scavenger, it is the current situation that the material and structure of the packaging material are changed according to the situation.

In recent years, the application fields of oxygen scavengers have been diversified and the usage conditions have tended to become severe. Therefore, packaging materials having excellent durability, such as microporous membranes, have been widely used.
For example, as a packaging material using a conventional non-woven fabric, a microporous film or a water- and oil-resistant processed paper, a non-woven fabric, a microporous film or a water- and oil-resistant processed paper, a polyethylene, a polyethylene vinyl acetate copolymer, an ionomer resin, etc. A heat-laminated sealant film with a melting point, or a packaging material with a film layer having a low softening point of a perforated plastic laminated film having a lower softening point and a higher softening point than a microporous film as a heat laminated layer is often used. However, the low melting point film melts during the thermal lamination process, and the small-diameter holes of the perforated plastic film are closed,
It has been recognized that there are many points that should be improved as a packaging material for oxygen scavengers, such that stable air permeability cannot be ensured due to a decrease in air permeability.

The present invention has been made in view of the above-mentioned circumstances, and it is easy to manufacture and make a bag and has stable air permeability,
An oxygen scavenger package using not only sealant strength and laminate strength but also excellent durability such as water resistance and oil resistance and exhibiting stable oxygen scavenging performance. The purpose is to provide.

[0006]

Means for Solving the Problems As a result of intensive studies for achieving the above-mentioned object, the inventors of the present invention obtained by laminating a specific perforated plastic laminated film (A) and a microporous film (B). Gurley air permeability is 1 to 10,000 seconds /
Using the packaging material (C) for oxygen absorber of 100 ml, the laminated film (A) constituting the packaging material (C) is placed outside, and the oxygen absorber is packaged. The finding that the oxygen-containing package can achieve the above object,
The present invention has been completed.

The present invention has a Gurley type air permeability of 1 to 10,000 seconds / 100 ml obtained by bonding the following perforated plastic laminated film (A) and microporous film (B) together.
The deoxidizing agent packaging material (C) is used, and the deoxidizing agent is packaged and sealed with the laminated film (A) layer constituting the packaging material (C) facing outside. It is a deoxidizer package. Perforated plastic laminated film (A): It is composed of a film layer (a) to be bonded to the microporous film (B) and another film layer (b), and the softening point of the film layer (a) is the microporous film ( Perforated plastic laminate film having a softening point equal to or higher than that of B) and lower than that of the film layer (b) Microporous film (B): non-woven fabric impermeable to water at normal pressure, plastic film which is a microporous membrane, and A microporous film with self-heat sealing property selected from the group consisting of water- and oil-resistant mixed paper

The present invention will be described in detail below. In the present invention, the perforated plastic laminated film (A) is composed of a film layer (a) to be bonded to the above-mentioned microporous film (B) and another film layer (b). A perforated plastic laminated film having a softening point which is equal to or higher than the softening point of the microporous film (B) and which is lower than that of the film layer (b). The laminated film is a laminated film of two or more layers consisting of one layer of the film layer (a) and at least one layer of the film layer (b), and has a pore diameter of 10 to 500 μm, preferably 50 to 25.
Open area ratio at 0 μm 0.005 to 15%, preferably 0.01 to 5%
It is a gas permeable plastic film having fine pores and a thickness of 10 to 200 μm, preferably 12 to 50 μm.

For example, as the film of the film layer (b), one having a softening point higher than that of the film layer (a) by 10 ° C. or more is usually used. Further, as the film layer (b), polyethylene terephthalate, nylon, polypropylene or the like is used, and as the film layer (a),
LLDPE, polypropylene, etc. Further, as the film layer (a), a sealant film having a good low-temperature heat-sealing property such as LDPE, EVA copolymer, and ionomer film can be used, and the same material as that of the film (B) having mainly fine pores is preferable. Used.

As the film layer (a), one having the same or higher softening point as that of the film (B) having fine pores is used, and the film layer (a) is lower than the softening point as in the conventional case. Compared to the case of using a material with a softening point,
It becomes possible to laminate with the film (B) having fine pores without deteriorating the packaging material characteristics of the (B). The film can be laminated by fusion, adhesion, pressure bonding, dry laminating method, extrusion laminating or the like, but the thermal fusion method is more preferable mainly when the same material is used.

If the pore diameter of the perforated plastic laminated film (A) film is 10 μm or less, the air permeability will be insufficient, resulting in 500
If it is more than μm, liquids such as water, oil, acid, alcohol, etc. easily infiltrate from the outside, and the durability is deteriorated, which is not desirable. on the other hand,
If the thickness of the film is 10 μm or less, it is too thin and difficult to process, and the durability is poor, and if it is 500 μm or more, the flexibility of the film is insufficient, which is not desirable.

In the present invention, the microporous film (B) is selected from the group consisting of a water-impermeable non-woven fabric at atmospheric pressure, a plastic film which is a microporous film, and a water- and oil-resistant mixed paper having a self-heat-sealing property. It is a kind of microporous film.

A non-woven fabric that is impermeable to water at normal pressure is a non-woven fabric made of polyolefin, polyester, etc., and has a Gurley type air permeability of usually about 0.01 to 1,000 seconds / 100 ml.
However, it is water impermeable under normal pressure. For example, Tyvek (manufactured by DuPont), Luxer (manufactured by Asahi Kasei Kogyo Co., Ltd.) and the like are known.

The plastic film, which is a microporous film, has fine pores with a pore size of 0.01 to 50 μm, and has a Gurley type air permeability of usually about 0.01 to 1,000 seconds / 100 ml, which is impermeable to water at normal pressure. It is a thing. The microporous membrane is polyethylene,
It is manufactured by stretching a synthetic resin film such as polypropylene. At that time, fine powder such as silica, talc, calcium carbonate is added to stretch the film, and the fine powder is extracted from the film containing the fine powder. It is manufactured by the method of. For example, NF sheet (Tokuyama Soda Co., Ltd.)
Manufactured by Tokuyama Soda Co., Ltd., Serpore (manufactured by Sekisui Chemical Co., Ltd.), FP-2 (Asahi Kasei Co., Ltd.)
Made), NOP (made by Nippon Petrochemical Co., Ltd.), Nitoflon N
TF (manufactured by Nitto Electric Industry Co., Ltd.), polyflon paper (manufactured by Daikin Industry Co., Ltd.), Jura Guard (manufactured by Celanese), Gore-Tex (manufactured by Gore), TSF (manufactured by Kojin Co., Ltd.), etc. Are known.

As a water- and oil-resistant mixed paper having a self-heat-sealing property, a Gurley type air permeability of 1 to 1,000 seconds / 10
It is a gas permeable film made by selecting two or more materials consisting of a thermoplastic plastic impermeable to water at normal pressure and water-insoluble plastic or paper, which is 0 ml, and papermaking. Examples of such packaging materials include paper / thermoplastic-based mixed paper made from pulp and paper made of polyethylene, polypropylene, etc., but so-called synthetic resin paper made solely of polypropylene, etc., and heat of polyethylene terephthalate, etc. It is also possible to use a non-woven fabric or the like made of fibers having a core of insoluble or high melting point thermoplastic and coated with a low melting point thermoplastic such as polyethylene. Further, such a mixed paper is subjected to water repellency, oil repellency treatment, etc., and has a basis weight of 10 to 150 g / m ² , preferably 12 to 100 g / m ² , and a mixed paper ratio of thermoplastics.
It is a water- and oil-repellent gas-permeable film having a content of 20 to 80%, preferably 30 to 70%.

Further, such a microporous membrane having a self-heat-sealing property, a non-woven fabric or a water- and oil-resistant mixed paper is
It is used as a packaging material for oxygen scavenger by laminating it with a perforated plastic laminated film (A), and a microporous membrane, a non-woven fabric or a water- and oil-resistant mixed paper is packaged as a film with fine pores having self-heat-sealing property. It not only imparts air permeability to the material, but also acts as a sealing layer of the oxygen scavenger packaging material (C). Therefore, for the purpose of improving the bag-making property and heat-sealing property of the packaging material for oxygen absorber, it is necessary to newly provide a seal layer inside the oxygen absorber packaging material and a reinforcing material such as a wallif for reinforcement. Absent. However, as a sealing layer inside the oxygen scavenger packaging material, a large number of streaks or fine meshes are formed by laminating a perforated plastic film, extrusion laminating a resin, printing method, coating method, or the like. It doesn't matter what you do. However, the softening point of the resin of the seal layer must be equal to or lower than that of the film (B) having fine pores.

The Gurley type air permeability of the oxygen scavenger packaging material (C) used in the present invention is 1 to 10,000 seconds / 100 ml.
The range is. The air permeability is determined by the size of the pore diameter of the perforated plastic laminated film (A), the number of pores, the type of the film (B) having fine pores used, and the bonding conditions with the perforated plastic laminated film (A). .. In addition to the air permeability of the oxygen scavenger packaging material, in consideration of various factors such as adhesive strength, ease of bag making, the sealed oxygen absorber does not spill, and durability such as rust resistance. The packaging composition is determined.

According to the present invention, the oxygen absorber packaging material (C) is
The (A) of the packaging material is used as the outside and used as both sides or one side of the packaging material of the oxygen absorber, and in the case of one side, the oxygen absorber is packaged by using a plastic laminated film or a film having fine pores on the other side, Since it is a sealed oxygen scavenger package, the characteristics of the film (B) having fine pores can be utilized, and thus the packaging material can be appropriately selected in consideration of the intended use, the form of use, the working method and the like. In addition, when the oxygen scavenger packaging material is used on one side, a non-breathable plastic laminated film is mainly used on the other side, but if necessary, fine pores may be used as long as there is no practical problem such as durability. You may use the film which has.

As the oxygen scavenger to be packaged in the oxygen scavenger packaging material (C), metals such as sulfite, bisulfite, nithionite, hydroquinone, catechol, resorcin, pyrogallol, gallic acid and iron powder can be used. A substance containing powder, ascorbic acid, or the like is used and is not particularly limited.

[0020]

The present invention relates to a film (A) having a perforated plastic layer, a non-woven fabric, a microporous film, and a film (B) having one kind of micropores selected from the group consisting of water- and oil-resistant mixed papers having self-sealing properties. ) Is used as a packaging material for an oxygen absorber package on both sides or one side, and the oxygen absorber is packaged with (A) facing outward, and the film is used as the oxygen absorber. The packaging material does not employ a material having no self-heat-sealing property for the film (B) itself having fine pores inside the packaging material, and is limited to a packaging material having self-heat-sealing property, and the outer perforated plastic laminate is used. Film (A)
Also, the film layer (a) having a low softening point of the film constituting (A) has the same or a high softening point as the (B) and is limited to a laminated film having a heat-sealable resin layer. It is processed in a packaging material configuration.

The perforated plastic laminated film (A) is
Since it is a step of laminating the film (B) having pores in the pore-opening step after laminating the films, it is possible to perform once in the step of processing the oxygen absorber packaging material after the pore-opening step. Since only the laminating process is performed, damage to the packaging material due to heating at the time of lamination is suppressed, and the softening points of the film layers (a) and (b) of the perforated plastic laminated film (A) are The layer (a) is lower than (b) and the film layer (a) is equal to or higher than the softening point of the microporous film (B),
Unlike the case where the film (B) having fine pores has the lowest softening point, the perforated plastic laminated film (A) can also be prevented from closing. That is, stable packaging material performance can be secured without an extreme decrease in air permeability of the film (B) having fine pores.

After laminating a perforated plastic laminated film having a small pore size and a film having micropores as in the conventional case, a film layer having a low softening point of the perforated plastic laminated film is laminated as an adhesive layer, and further having micropores. In the packaging material composition such as a method of laminating a perforated low-melting-point sealant film on the other side of the film, a plurality of heat histories are generated after opening, so a film layer having a low softening point due to heat during laminating The resin melts and the small pores are blocked, and stable air permeability cannot be obtained. In addition, even if the processing order is changed, for the same reason, a hole in the sealant film having a low melting point or any hole in the perforated plastic laminated film is blocked, ensuring air permeability, difficult to adjust, and difficult to process. Solved some drawbacks.

The film (B) having fine pores is simply
Only one side is laminated with the perforated plastic laminated film (A), and the other side is not processed at all and is held as it is. Therefore, it is a nonwoven fabric, a microporous membrane, or a self-heat-sealing water and oil resistant product. The oxygen absorbing agent package has a stable oxygen scavenging performance because it retains the stable air permeability without significantly lowering the air permeability that it originally has, while making full use of the characteristics of mixed papermaking. Can be demonstrated.

Further, the perforated plastic laminated film (A) is laminated with the film (B) having fine pores, and also has a function as a reinforcing material for the film (B) having fine pores. And it is easy to use due to its bag-making properties. The packaging material can be appropriately selected in consideration of the intended use, usage form, working method, etc., and can be applied to a wide range of fields.

The packing material for the oxygen scavenger, which is formed by laminating the perforated plastic laminated film (A) so as to cover the film (B) having fine pores, has a fine outer laminated plastic film (A). Not only does it protect the film (B) that has holes, prevents contamination from the outside and prevents rust from rising inside the oxygen absorber package, but it can also be printed on the back, which gives the oxygen absorber durability and hygiene. There is expected.

Therefore, in the present invention, the oxygen scavenger packaging material has an air permeability, durability,
While maintaining the properties such as bag-making properties as they are, they are reproduced, so that a deoxidizing agent package having stable deoxidizing performance and having extremely excellent water resistance and oil resistance can be obtained.

[0027]

EXAMPLES The present invention will be described more specifically with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited to these examples. (1) Sample and comparative sample

Sample-1 Perforated PET / P which is a perforated plastic laminated film (A)
E film [thickness: 37 μm (PET; 12 μm, PE; 25 μ
m), pore diameter: 100 μm, 2 × 2 m / m grid-like openings] and TSF-EU [thickness: 60 μm, PE microporous membrane manufactured by Kojin Co., Ltd.] which is a film (B) having fine pores. And (A) through the film layer (a) having a low softening point of 100 to
Lamination was carried out at 120 ° C. to prepare a laminated film: sample-1.

Sample-2, 3 In the preparation of Sample-1 above, the perforated PET / PE film (described above) used as the perforated plastic laminated film (A) was replaced with the perforated PET / PP film [thickness: 37 μm ( PET;
12 μm, PP; 25 μm), pore size: 100 μm, 2 × 2 m / m grid-shaped openings], and TSF-EU (described above) used as a film (B) having fine pores is NF sheet S140.
[Thickness: 140 μm, PP microporous membrane manufactured by Tokuyama Soda Co., Ltd.],
Serpore [thickness: 100 μm, PP manufactured by Sekisui Chemical Co., Ltd.
Microporous Membrane] was laminated in the same manner as Sample-1 except that it was used instead, and a laminated film: Sample-2,
3 was produced.

Sample-4 TSF-EU (described above) used as the film (B) having fine pores in the preparation of Sample-1 was Tyvek 1059B (polyethylene nonwoven fabric manufactured by DuPont).
A laminated film: Sample-4 was prepared by laminating in the same manner as Sample-1 except that the film was used instead.

Sample-5 The TSF-EU (previously used) used as the film (B) having fine pores in the preparation of the above-mentioned Sample-1 was pulp / PE mixed paper [grammage: 60 g / m ² , pulp. Laminated film: sample laminated in exactly the same manner as Sample-1 except that PE is mixed at a ratio of 60% and mixed with gas permeability and water and oil repellency -5 was produced.

Sample-6 In the preparation of Sample-1 above, the hole diameter and the opening pattern of the perforated PET / PE film (described above) used as the perforated plastic laminated film (A) were changed, and the hole diameter was 300 μm.
m, 2.5 × 2.5 m / m Lattice perforated in a lattice pattern: Laminated film: Sample-laminated in exactly the same way as Sample-1 except that a perforated PET / PE film of 37 μm is used.
6 was produced.

Sample-A PET (thickness: 12 μm) and PE were prepared by the extrusion laminating method.
A non-breathable PET / PE film sample-A having a thickness of 25 μm was prepared.

Sample-B Sample B of a packaging material in which PE was extrusion-laminated to a thickness of 20 μm on the aluminum surface of a laminated film obtained by laminating PET (previously described) and aluminum foil (thickness: 15 μm) by the dry lamination method. Was produced. Table 1 shows the contents of each sample in the present invention manufactured as described above.

[0035]

[Table 1]

Comparative Sample-1 In the preparation of Sample-1 above, the hole diameter and the opening pattern of the perforated PET / PE film (described above) used as the perforated plastic laminated film (A) were changed, and the hole diameter was 50 μm.
m, 2 × 2 m / m grid-shaped holes with a thickness of 37 μm
Laminated film comparative sample-1 by laminating in exactly the same way as sample-1 except using PET / PE film
Was produced.

Comparative Sample-2 In the preparation of Sample-1 above, the hole diameter and the opening pattern of the perforated PET / PE film (described above) used as the perforated plastic laminated film (A) were changed, and the hole diameter was 500 μm.
m, 2 × 2 m / m grid-shaped holes with a thickness of 37 μm
Sample-1 except that the PET / PE film was used as the film (B) having fine pores and TSF-EU (described above) was used instead of the wet non-woven fabric (basis weight: 60 g / m ² , made of polyethylene). A laminated film: Comparative sample-2 was prepared by laminating in the same manner as in.

Comparative Sample-3 In the preparation of Sample-5, the pulp / PE mixed paper (previously used) used as the film (B) having fine pores was mixed with 90-percent low-density polyethylene (B-hole). Thermal lamination was carried out at 100 ° C. to prepare a laminated film: Comparative sample-3.

Comparative Sample-4 In the preparation of Sample-1 above, TSF-EU (previously used) used as the film (B) having fine pores was mixed with perforated low density polyethylene (hole B) at 90 to 100 ° C. Was heat-laminated to prepare a laminated film: Comparative sample-4.

Comparative Sample-5 Tyvek 1059B (supra) used as a film (B) having fine pores in the preparation of Sample-4 above.
A low density polyethylene with holes (hole B) was heat-laminated at 90 to 100 ° C. to prepare a laminated film: Comparative sample-5. Table 2 shows the contents of each sample in the comparative samples 1 to 5 prepared above.

[0041]

[Table 2]

(2) Packaging material test The air permeability, adhesive strength, heat seal strength, bag-making property, processability and durability of each sample and comparative sample prepared in the above (1) were measured. .. The measurement results are shown in Table 3 (Examples) and Table 4 (Comparative Examples).

(3) Oxygen scavenger package The samples 1 to 6 and the comparative samples 1 to 5 of the packaging material prepared in the above (1) are used for both sides of the oxygen scavenger package, and in the case of one side, sample-A or Using sample-B together, make a bag of 50 × 50 mm with the perforated plastic laminated flume (A) on the outside, and use iron powder as the main ingredient with an oxygen absorption capacity of 100 ml.
The oxygen absorber of the present invention was filled in to prepare the oxygen absorber package of the present invention. Each of these oxygen absorber packages and 500 ml of air are placed in a bag of oxygen barrier packaging material (KON / PE, 15 x 30 cm), sealed, and allowed to stand at 25 ° C until the oxygen concentration reaches zero. Was measured. The number of samples is 10 in each of the examples and comparative examples.
The measurement results are shown in Table 3 (Examples) and Table 4 (Comparative Examples).

[0044]

INDUSTRIAL APPLICABILITY The present invention provides a oxidizer for rusting, stains, even when used in severe applications under various conditions such as high-moisture foods, dry foods, acidic foods, oil-processed foods and alcohol-containing foods. Suppression of pollution due to adhesion, deterioration of oxygen absorber, etc.
Since it has stable oxygen scavenging performance, it can be used in a wide range as a preservative that can be applied to applications where it has been difficult to use oxygen scavengers. Therefore, its industrial significance, including the food field, is extremely significant.

[0045]

[Brief description of drawings]

FIG. 1 shows a cross-sectional view of a packaging material for an oxygen scavenger used in the present invention.

[Explanation of symbols]

A: Perforated plastic laminated film (A) B: Microporous film (B) C: Oxygen absorber packaging material (C) D Perforated plastic laminated film (A) laminate layer E: Perforated plastic laminated film (A) ) And a microporous film (B) laminated layer a: a film layer (a) constituting a laminated film (A) b: a film layer (b) constituting a laminated film (A) X: a perforated plastic laminated film (A) ) Hole

FIG. 2 and

FIG. 3 is an oxygen absorber packaging body of the present invention in which the oxygen absorber packaging material used in the present invention is used as both or one side of a oxygen absorber packaging material, filled with an oxygen absorber, packaged, and sealed. Each sectional view of is shown. (Both sides: Figure 2, One side: Figure 3)

[Explanation of symbols]

A: Perforated plastic laminated film (A) B: Microporous film (B) E: Laminated layer of perforated plastic laminated film (A) and microporous film (B) F: Heat seal layer of oxygen absorber package G : Oxygen scavenger H: Oxygen scavenger Packaging material on one side of package (hereinafter referred to as margin)

[Table 3]

[Table 4]

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Yoichi Yamakawa 2-2-1 Otemachi, Chiyoda-ku, Tokyo Nippon Soda Co., Ltd.

Claims (2)

[Claims] 1. An oxygen scavenger having a Galerian air permeability of 1 to 10,000 seconds / 100 ml obtained by laminating a perforated plastic laminated film (A) and a microporous film (B) described below. A packaging material (C) for packaging, a packaging film (C), the laminated film (A) layer being placed outside, and a deoxidizer packaged and sealed. body. Perforated plastic laminated film (A): It is composed of a film layer (a) to be bonded to the microporous film (B) and another film layer (b), and the softening point of the film layer (a) is the microporous film ( Perforated plastic laminate film having a softening point equal to or higher than that of B) and lower than that of the film layer (b) Microporous film (B): non-woven fabric impermeable to water at normal pressure, plastic film which is a microporous membrane, and A microporous film with self-heat sealing property selected from the group consisting of water- and oil-resistant mixed paper 2. The oxygen absorber package according to claim 1, wherein the perforated plastic laminated film (A) has a pore size of 10 to 500 μm and a porosity of 0.005 to 15%.