JP2666381B2 - Packaging film for oxygen scavenger - Google Patents

Description

Description: TECHNICAL FIELD The present invention relates to a packaging film for an oxygen scavenger, particularly to a packaging film for an oxygen scavenger used for dried foods and the like, and a chemical agent for producing an oxygen scavenger. It belongs to manufacturing technology and also food preservation technology.

[Related Art] In recent years, various oxygen scavengers capable of preserving foods have been developed. These oxygen absorbers are usually used in a state where an oxygen-absorbing agent is contained in a package made of a breathable packaging material. The oxygen absorber contained in a package made of a breathable packaging material is used in a sealed state in a bag or container made of a packaging material having high gas barrier properties together with the food to be stored, and absorbs oxygen from the oxygen-absorbing drug. It absorbs oxygen in the gas-barrier bag by its ability to prevent oxidation and spoilage of foods to be preserved.

Usually, the oxygen scavenger has a disadvantage that the oxygen absorbing ability is reduced under dry conditions, and is not suitable for use in an extremely low humidity state. For this reason, a self-reacting oxygen scavenger has been developed, but when used for preserving extremely dry foods, it does not have a sufficient effect as an oxygen scavenger and the inside of the container is completely deoxidized. In many cases, it is difficult to use because it has a drawback that it cannot be oxygenated or that oxygen in the container can be removed, but the essential product is discouraged.

In addition, when an oxygen absorber is used in foods containing a large amount of oil, the package of the oxygen absorber may be stained with oil during use, resulting in a very poor appearance.

As a method for solving these problems, a method has been proposed in which paper is coated with an oil-resistant chemical and oil-resistant paper is used as a breathable packaging material. Is difficult.

There is also a proposal to use a plastic film having a large number of pores (Japanese Patent Publication No. 56-44644), but there is a problem that oil oozes from the hole.

Therefore, when an oxygen absorber is used for preserving a food containing a large amount of oil, it is necessary to take a method of preventing direct contact between the oxygen absorber and the food.

[Problems to be Solved by the Invention] An object of the present invention is to improve the performance of a breathable packaging material used for packaging an oxygen scavenger, overcome the above-mentioned drawbacks of the conventional oxygen scavenger package, and dry A breathable packaging material that can prevent a decrease in oxygen absorption capacity under water, can be applied to foods with extremely low water activity, and can provide an oxygen absorber that can be applied to foods with a high oil content. It was made to seek.

[Means for Solving the Problems] The inventors of the present invention have conducted various studies in order to obtain an excellent breathable packaging material as described above, and as a result, a laminated film having a specific structure has solved the above-mentioned problems, and has achieved excellent results. The inventors have found that the present invention can be used as a packaging material for deoxygenation and completed the present invention.

That is, according to the present invention, paper or nonwoven fabric is used as the middle layer, and the outer layer is substantially non-permeable and has a moisture permeability of 70 g / m ² · 24Hr (JIS Z 02
08) A packaging film for an oxygen scavenger characterized by laminating the following plastic film and a plastic film having air permeability and heat fusibility as an inner layer.

○ substantially at impermeable moisture permeability ^{70g / m 2 · 24Hr (JIS} Z 02
08) The following plastic film (hereinafter also referred to as (1) layer) The plastic film having a moisture permeability of 70 g / m ² · 24Hr (JIS Z 0208) or less in the present invention is defined as JIS-Z-0208 (moisture permeability of the moisture-proof packaging material). This is a plastic film having a moisture permeability of 70 g / m ² · 24Hr or less measured according to the test method). The preferred film for the present invention has a moisture permeability of 30 g / m ² · 24 Hr (JIS Z 0208) or less. Particularly preferred are films having a property of substantially not allowing water vapor to pass therethrough.

When the oxygen scavenger moisture permeability is wrapped with a film of 70g / m ² · 24Hr or plastic is used for drying food,
Moisture transfer in the oxygen scavenger is so severe that the oxygen scavenger targeted by the present invention can hardly be achieved.

As such a plastic film, polyethylene,
Films made from polypropylene, polybutadiene, ethylene / butadiene copolymer, ethylene / vinyl acetate copolymer, polyethylene terephthalate, polyvinyl chloride, polyvinyl acetate, polyvinylidene chloride, etc., or a laminate of two or more of these films Examples thereof include a laminated film and the like whose film thickness is adjusted so that the moisture permeability falls within the above range. Examples of other specific films include a single film of vinylidene chloride, polyester, or the like, and a film in which vinylidene chloride is coated on stretched polypropylene, polyester, vinylon, or the like. Also, on the plastic film surface,
A film obtained by evaporating aluminum to reduce moisture permeability, a film obtained by laminating aluminum foil, and the like can also be mentioned as the plastic film in the present invention.

As the plastic film, a single-layer film made of nylon, cellophane, polystyrene, polycarbonate, or the like is difficult to use because of high moisture permeability, but a laminate with another film or coated with polyvinylidene chloride. If the moisture permeability falls within the above range, it can be used in the present invention.

The thickness of these plastic films is inevitably determined according to the material and the desired moisture permeability, but the thickness is 5 μm or more in consideration of functionality and economy.
It is preferably 50 μm or less. That is, the strength is too low at 5μ or less, and the stiffness of the packaging material becomes too strong at 50μ or more,
In any case, workability in the packaging machine is reduced.

Further, since these plastic films are substantially air-impermeable, the effects aimed at by the present invention are more effectively exhibited.

JIS refers to a substantially non-breathable plastic film
-A plastic film whose Gurley air permeability measured according to the standard of P-8117 (Test method for air permeability of paper and paperboard) is 100,000 seconds / 100 ml or more, and Gurley air permeability is practically unmeasurable That is.

○ Paper or non-woven fabric (hereinafter also referred to as (2) layer) As the paper or non-woven fabric in the present invention, those generally used as packaging materials are applied. Examples of paper include Japanese paper, kraft paper, Pure white roll paper, oil-resistant paper, and the like can be used, but are not limited thereto.

In addition, as long as the nonwoven fabric has a higher melting point than a plastic film having air permeability and heat fusibility described later, it can be used without being restricted by a raw material fiber or a manufacturing method. , Polyamide, polypropylene, polyethylene, acrylic and the like. Examples of the production method include a dry method, a wet method, a spun bond method, and a needle punch method, and those produced by combining them can be used. Further, those which are formed on the film by various methods and are commercially available as microporous membranes are also used as paper or nonwoven fabric in the present invention.

Air permeability (JIS-P-8117) 10,000 seconds / 100ml for paper
Those having the following air permeability and having a thickness of 10 μm to 500 μ and a basis weight of 10 g to 500 g / m ² are preferable. In addition, air permeability (JIS-P-8117) 10,000 seconds / 10
Preferably, it has a gas permeability of 0 ml or less, and has a thickness of 10 μm to 500 μ and a weight of 10 g to 500 g / m ² .

Paper or non-woven fabric can be adjusted in air permeability by selecting its thickness and type. When the packaging film of the present invention is finally used as a packaging material for an oxygen scavenger, it can be removed. This makes it possible to adjust the deoxygenation rate of the oxygen agent.

○ Plastic film having air permeability and heat fusibility (hereinafter also referred to as (3) layer) The plastic film having air permeability and heat fusibility in the invention, when used as a package for an oxygen scavenger, Constituent, generally used as a sealant, in order to be able to heat seal, the moisture permeability constituting the outer layer
A plastic film having a softening point lower than that of a plastic film of 70 g / m ² · 24Hr (JIS-Z-0208) or less is preferable, and a film having air permeability through a through hole is preferable. Those having a size of at least 500 μm are preferred.

Specific examples include a polyethylene film, a polypropylene film, an ethylene-vinyl acetate copolymer film, and an ionomer film.

In the film with the pores as through holes, the shape of the pores,
Although there is no particular condition such as the number, the diameter is 3 mm or less, preferably about 0.5 mm pores, the number is preferably 1 cm
2 to 300 per ^2, more preferably preferably taken present invention those two is 100, the size and type of pores can be selected in accordance with the deoxygenation rate desired.

○ Lamination method Although the packaging film for an oxygen scavenger of the present invention is a laminated film composed of the above-described film and paper or nonwoven fabric,
As a lamination method for obtaining the film of the present invention, an ordinary film lamination method can be applied. That is, (1)-
Each method of wet lamination, dry lamination, hot melt lamination, and extrusion lamination can be applied to each of (2) interlayer and (2)-(3) interlayer. Further, since the layer (3) has a heat-fusing property between the layers (2) and (3), bonding (thermal lamination) using only heat is also possible.

The order of lamination is not particularly limited. Even if (1) layer and (2) layer are bonded and then (2) layer and (3) layer are bonded, (2) layer and (3) layer are bonded. After that, the layers (1) and (2) may be bonded together, or three layers may be bonded together. Also, like extrusion sand lamination (1)
It is also possible to laminate the layer (2) while forming a laminated film as a layer.

When using the oxygen-absorbing wrapping film of the present invention to form an oxygen-absorbing wrapper, insert the laminated film with the plastic film having air permeability and heat sealability inside and insert the oxygen-absorbing agent. A method in which the three sides are sealed with a heat sealer or the like to form a bag, or a method in which a plastic film having air permeability and heat sealability is placed inside and opposed to each other, and an oxygen-absorbing agent is put therebetween and the four sides are sealed is applied. Is done.

The oxygen-absorbing agent packaging film of the present invention can provide the most excellent effect when the oxygen-absorbing agent is a self-reactive oxygen-absorbing agent containing water as an essential component. Sexual drugs are generally and widely used, and the oxygen-absorbing agent packaging film of the present invention is effectively used for those known.

Self-reactive oxygen-absorbing agents include, for example, iron, NaC
l, Iron powder-based drugs mainly containing water, ascorbic acid, alkali, water, or polyhydric alcohols, alkalis, organic drugs mainly containing water, and the like.

Further, the packaging film for an oxygen scavenger of the present invention can also be applied to a carbon dioxide-generating type oxygen-absorbing agent or a carbon dioxide-absorbing type oxygen-absorbing agent.

[Operation] The oxygen-absorbing agent packaging film of the present invention, when used for a self-reactive oxygen-absorbing agent containing water as an essential component, efficiently suppresses the evaporation of water as a constituent component. The function of the oxygen absorber is sufficiently maintained, and furthermore, the adverse effect of moisture on the dried food can be prevented.The oxygen absorber packaged by the oxygen absorber packaging film of the present invention is effective for the dried food. Demonstrates excellent functions.

Further, the oxygen absorber package using the oxygen absorber packaging film of the present invention can be used for oily foods because the entire package is covered with a plastic film.

Deoxidation by the oxygen absorber package using the oxygen absorber packaging film of the present invention is performed through a sealed portion of the package. That is, the entire surface of the package is covered with the plastic film, but in the sealed portion, the cut surface of the paper or nonwoven fabric of the intermediate layer is exposed to the outside, and oxygen passes through this portion to be deoxygenated. Accordingly, the rate of the oxygen scavenger is controlled by the thickness and type of the paper, and is controlled by the air permeability of the inner plastic film.

Example 1 Polyester film 12μ (Gurley air permeability 100,000 seconds /
Or 100 ml; moisture permeability 56g / m ² · 24Hr) and basis weight 50 g / m ² kraft paper laminated by dry lamination, and further, adhered by heat lamination the polyethylene film 30μ open of said laminated film and holes from the kraft paper side It was set as the packaging film for the oxygen scavenger of the present invention.

The polyethylene film layer of the film was folded inward, iron powder 5 g as an oxygen absorbing agent, sodium chloride 0.
A mixture of 5 g, diatomaceous earth 5 g, and water 2 g was added, and the three sides were heat-sealed to obtain an oxygen scavenger package having a length of 80 mm × a width of 80 mm and a seal width of 5 mm.

The oxygen scavenger package obtained in this manner was sealed in a KOP / PE bag with the oxygen scavenger package and the cracker in close contact with 100 g of a cracker (water content: 3.5%) and left at 30 ° C.
One week later, the oxygen concentration in the bag was measured and found to be 0.0%. The water content of the cracker around the oxygen absorber was 3.5%. Food taste was also good.

Comparative Example 1 A 12 μm perforated polyester film and 50 g / m ² basis weight kraft paper were bonded by dry lamination, and the laminated film and a 30 μm perforated polyethylene film were bonded together by thermal lamination from the kraft paper side. The laminated film was used as a packaging film for an oxygen scavenger.

The polyethylene film layer of the film was folded inward, iron powder 5 g as an oxygen absorbing agent, sodium chloride 0.
A mixture of 5 g, diatomaceous earth 5 g, and water 2 g was added, and the three sides were heat-sealed to obtain an oxygen-absorbing agent package having a length of 80 mm, a width of 80 mm and a seal width of 5 mm.

The oxygen scavenger package obtained in this manner was sealed in a KOP / PE bag with the oxygen scavenger package and the cracker in close contact with 100 g of a cracker (water content: 3.5%) and left at 30 ° C.
One week later, the oxygen concentration in the bag was measured and was found to be 4.2%. The water content of the crackers around the oxygen absorber was 4.4%. The taste of the food was stale.

Reference Example 1 A packaging film for an oxygen absorber was obtained in the same manner as in Example 1,
The same test as in Example 1 was performed on 200 g of tea (water content: 4.0%). One week later, the oxygen concentration in the bag was measured to be 0.0%, and the water content of the tea around the oxygen absorber was 4.0%.
%, Tea flavor and taste were good.

Comparative Example 2 A laminated film obtained by laminating a kraft paper having a basis weight of 50 g / m ² and a polyethylene film having a hole of 30 μm by thermal lamination was used as a packaging film for an oxygen scavenger.

Using the film, an oxygen-absorbing agent package similar to that of Example 1 was prepared, and a test similar to that of Reference Example 1 was performed using the oxygen-absorbing agent package. One week later, the oxygen concentration in the bag was 5.6
%, And the water content of the tea around the oxygen absorber is 4.5%,
The flavor and taste of the tea were normal.

Reference Example 2 As an oxygen-absorbing drug, catechol 2.0 g, activated carbon 4.0 g,
The test was performed in the same manner as in Example 1 except that a mixture of 10 g of sodium carbonate and 1.0 g of water was used. When the oxygen concentration after one week was measured, it was 0.0%.

Reference Example 3 As an oxygen-absorbing drug, sodium ascorbate 2.
The test was conducted in the same manner as in Example 1 except that a mixture of 0 g, 4.0 g of coal, and 2.0 g of water was used. The oxygen concentration measured one week later was 0.0%.

Example 2 KPET (vinyl chloride coated polyester) film
12μ (Gurley air permeability 100,000 sec / 100ml or more; moisture permeability 15g / m
²・ 24Hr) and 50g / m ² pure white roll paper are bonded together by dry lamination, and a polyethylene film 30 having a hole from the pure white roll paper side of the laminated film.
μ was laminated by dry lamination to obtain a packaging film for an oxygen scavenger of the present invention. The polyethylene film layer of the film was folded inside, and a mixture of 5 g of iron powder, 0.5 g of sodium chloride, 5 g of diatomaceous earth and 1 g of water was added as an oxygen-absorbing agent, and heat-sealed on all three sides.
An oxygen absorber package having a size of mm and a seal width of 5 mm was obtained. The oxygen scavenger package obtained in this way is put together with 200 g of butter peanuts in a state in which the oxygen scavenger package and the butter peanuts are in close contact with each other.
It was sealed in a P / PE bag and left at 30 ° C. One week later, the oxygen concentration in the bag was measured and found to be 0.0%. The taste of the food was good. No oil bleeding was observed on the surface of the packaging material.

Comparative Example 3 A laminated film obtained by laminating a pure white roll paper having a basis weight of 50 g / m ² and a polyethylene film having a hole of 30 μm by dry lamination was used as a packaging film for an oxygen scavenger.

The polyethylene film layer of the film was folded inward, iron powder 5 g as an oxygen absorbing agent, sodium chloride 0.
A mixture of 5 g, diatomaceous earth 5 g, and water 1 g was added, and the three sides were heat-sealed to obtain an oxygen-absorbing agent package having a length of 80 mm, a width of 80 mm and a seal width of 5 mm.

The oxygen scavenger package obtained in this way is buttered with peanuts.
With the oxygen absorber package and butter peanuts in close contact with 200 g, it was sealed in a KOP / PE bag and left at 30 ° C. 1
One week later, the oxygen concentration in the bag was measured to be 2.3%. The taste of the food was stale. Oil bleeding was observed on the surface of the packaging material.

Example 3 KOP (vinylidene coated stretched polypropylene chloride) film 25.mu.; the basis weight 50 g / m ² Oil paper (the Gurley air permeability 100,000 seconds / 100ml or higher moisture permeability 8g / m ² · 24Hr) laminated by dry lamination, further , An ionomer resin film 30μ perforated from the oil-resistant paper side of the laminated film
Was laminated by dry lamination to obtain a packaging film for an oxygen scavenger of the present invention.

The film is folded with the ionomer resin film layer inside, and a mixture of 5 g of iron powder, 0.5 g of sodium chloride, 5 g of coal extinguisher, and 0.5 g of water as an oxygen-absorbing agent is placed. An oxygen absorber package having a size of 80 mm and a seal width of 5 mm was obtained.

The oxygen scavenger package thus obtained was sealed in a KOP / PE bag with 500 g of coffee immediately after sooting and the oxygen scavenger package in tight contact with the coffee, and allowed to stand at 30 ° C. One month later, the oxygen concentration in the bag was measured to be 0.0%, and the carbon dioxide concentration was 2.7%. The bag was in a vacuum state. No oil seepage was observed on the surface of the packaging material.

Comparative Example 4 A kraft paper having a basis weight of 50 g / m ² and a perforated polyester film 12 μ were bonded together by dry lamination, and a polyethylene film 30 μ having a perforated hole from the kraft paper side of the laminated film was bonded together by dry lamination. The laminated film was used as a packaging film for an oxygen scavenger.

Folded with the polyethylene film layer of the film inside, 5 g of oxygen-absorbing drug and iron powder, 0.5 g of sodium chloride,
A mixture of 5 g of coal extinguisher and 0.5 g of water was added, and heat sealing was performed on all three sides to obtain an oxygen absorber package having a length of 80 mm, a width of 80 mm and a seal width of 5 mm.

The oxygen scavenger package thus obtained was sealed in a KOP / PE bag with 500 g of coffee immediately after sooting and the oxygen scavenger package in tight contact with the coffee, and allowed to stand at 30 ° C. One week later, the oxygen concentration in the bag was measured to be 2.1%, and the carbon dioxide concentration was 26.6%. The bag was slightly inflated.
Oil oozing was observed on the surface of the packaging material.

Reference Example 4 An oxygen absorber package similar to that of Example 1 was prepared, and the oxygen absorber package was sealed in a KOP / PE bag together with 200 g of tea with the oxygen absorber package and tea in close contact at 30 ° C. Left down. 2
A month later, the oxygen concentration in the bag was measured to be 0.23%.

Example 4 A polyester film (12 μm) and a kraft paper having a basis weight of 50 g / m ² were bonded to each other through polyethylene by extrusion sand lamination. The moisture permeability of the formed laminated film of polyester and polyethylene was 28 g / m ² · 24 hr.

This three-layer laminated film and a polyethylene film having a hole of 30 μm were adhered from the kraft paper side by dry lamination to obtain a packaging film for an oxygen scavenger of the present invention.

Using the film, an oxygen-absorbing agent package similar to that of Example 1 was prepared, and a test similar to that of Reference Example 4 was performed using the oxygen-absorbing agent package. Two months later, the oxygen concentration in the bag is 0.05
%Met.

Example 5 A vinylidene chloride-coated polyester film (12 μm) and a kraft paper having a basis weight of 50 g / m ² were adhered to each other via polyethylene by extrusion sand lamination.

At this time, the formed laminate film of vinylidene chloride polyester and polyethylene had a moisture permeability of 12 g / m ² · 24 hr. This three-layer laminated film and a polyethylene film having a hole of 30 μm were adhered from the kraft paper side by dry lamination to obtain a packaging film for an oxygen scavenger of the present invention.

Using the film, an oxygen-absorbing agent package similar to that of Example 1 was prepared, and a test similar to that of Reference Example 4 was performed using the oxygen-absorbing agent package. Two months later, the oxygen concentration in the bag is 0.0
%Met.

Comparative Example 5 oriented nylon film 15.mu. (moisture permeability 320g / m ² · 24Hr)
And a basis weight of 50 g / m ² kraft paper were laminated by dry lamination, and further, a laminated film obtained by laminating a polyethylene film 30 μm with a hole from the kraft paper side of the laminated film by dry lamination was used as a packaging film for an oxygen agent. .

Using the film, an oxygen-absorbing agent package similar to that of Example 1 was prepared, and a test similar to that of Reference Example 4 was performed using the oxygen-absorbing agent package. Two months later, the oxygen concentration in the bag is 4.2
%Met.

[Effect] A package made by using the oxygen-absorbing agent packaging film of the present invention effectively suppresses the evaporation of moisture in the package, so that the oxygen-absorbing agent applicable to dry food is supplied. can do.

In addition, since the entire surface of the package is covered with a plastic film, even if this surface is brought into contact with oily food, transfer of stains from the food can be prevented. To supply an applicable oxygen scavenger. In addition, it is possible to prevent the transfer of stains to food having a high moisture content.

The oxygen-absorbing agent packaging film of the present invention can be a suitable oxygen-absorbing agent package.
It can also be used for fragrances and heating elements.

[Brief description of the drawings]

FIGS. 1 and 2 are cross-sectional views of an example of an oxygen absorber packaged with the packaging film for an oxygen absorber of the present invention. The symbols in the figure indicate the following. 1 ...... outer layer (substantially non-breathable moisture permeability 70g / m ² · 24Hr
(JIS Z 0208) The following plastic film 2) Middle layer (paper or nonwoven fabric) 3 Inner layer (plastic film having air permeability and heat sealability) 4 ... Oxygen-absorbing agent 5 ... Air permeability imparted Through holes for

Claims (1)

(57) [Claims] 1. An intermediate layer of paper or non-woven fabric and a substantially non-permeable and moisture-permeable 70 g / m ² · 24 hr (JIS Z 0208) as an outer layer.
A packaging film for an oxygen scavenger, comprising a laminate of the following plastic films and a plastic film having air permeability and heat fusibility as an inner layer.