JP2000354477A - Packed material of microwave-resistant oxygen scavenger - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a safe and practical packed material of oxygen scavenger which is a packed material of a nonferrous oxygen scavenger not to be detected by a metal detector, neither fires even by receiving microwave irradiation in heating by a microwave oven nor causes leakage of contents by destruction of bag and has excellent handleability. SOLUTION: This packed material of a microwave-resistant oxygen scavenger is a three side sealed packed material obtained by heat sealing an external material 1 in which an ethylene-based polymer layer is laminated to a heat- resistant resin layer and which has through holes to an internal material 2 obtained by laminating a paper or a nonwoven fabric to an ethylene-based polymer layer having through holes to form a double film, storing a nonferrous oxygen scavenger by heat sealing of the opposing inner material 2 of the double film. The water vapor permeability of the external material 1 is lower than that of the internal material 2 and peel strength between the external material 1 and the internal material 2 is sufficiently smaller than that between the mutual internal materials 2.

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 in a bag made of a breathable packaging material. More specifically, a microwave-resistant oxygen-absorbing agent package excellent in safety and hygiene that is not detected by a metal detector and does not ignite or leak the oxygen-absorbing agent even when heated by a microwave heating device such as a microwave oven. About the body.

[0002]

2. Description of the Related Art An oxygen scavenger package for absorbing and removing oxygen in a package to prevent deterioration of the quality of foods, medicines and the like has been widely used. The oxygen scavenger packaging is performed by enclosing the oxygen scavenger package together with the object to be preserved in a package such as a container or a bag having a high oxygen barrier property. The oxygen scavenger package is a bag made of a gas-permeable packaging material made of paper or a plastic film by heat sealing in a small bag shape, and filled with an oxygen absorber to absorb oxygen. Although various proposals have been made for oxygen absorbers, those containing iron powder as a main component from the viewpoint of safety, oxygen absorption efficiency, cost, etc. (hereinafter sometimes referred to as “iron-based oxygen absorber package” ) Has been widely used.

As oxygen scavengers, those containing an ascorbic acid compound as a main component (JP-A-54-73140, JP-A-5-269376, etc.) and those containing 1,2-glycol as a main component ( JP-A-2-284645
And glycerin as a main component (Japanese Unexamined Patent Publication No.
284646), those containing sugar alcohol as a main component (JP-A-2-284647), those containing aminoalcohol as a main component (JP-A-8-323195), and those containing gallic acid as a main component ( JP-A-8-309
No. 181) and the like that do not use iron powder have been proposed, and these can be used as a package of an oxygen scavenger that is not detected by a metal detector. Oxygen absorbers include a moisture-dependent oxygen absorber that substantially starts to absorb oxygen by receiving water from an object to be preserved, such as a food, which does not substantially contain water, and a water-absorbent, which contains a moisture donor and preserves a food, etc. There is a self-reactive oxygen scavenger package that starts oxygen absorption without receiving water supply from a product.

[0004]

As one means for providing foods that can be eaten with peace of mind, foods are placed on a metal detector before, after or during packaging, and needles, bolts, pieces of blades, bullets, and processing machines are used. It is well known to remove debris and other foreign metal contamination, which has been practiced by some food manufacturers for some time.Convenience stores and mass retailers have recently been implementing safety management of sold products. For this reason, interest in safety has been increasing, such as requiring food manufacturers to always pass metal detectors on handled food packages.

[0005] Under such circumstances, the demand for oxygen-absorbing agent packages not detected by the metal detector (hereinafter referred to as "non-ferrous oxygen-absorbing agent packages") is increasing. On the other hand, microwave ovens that can easily heat food are also widely used in homes and convenience stores, and products that are heated or cooked in a microwave oven before eating are increasing. Under such circumstances, there is a demand for a non-ferrous oxygen-absorbing agent package that does not generate heat, fire, break the package, or leak the oxygen scavenger, which is the contents, even when receiving microwaves generated from a microwave oven. It had been.

A microwave-resistant oxygen-absorbing agent package that can be heated in a microwave oven is disclosed in Japanese Patent Application Laid-Open No. 63-082967, in which an oxygen-absorbing agent package using a packaging material having a conductive layer such as an aluminum foil layer is disclosed. Proposed. However, in this method, although there is no restriction on the type of oxygen scavenger, the conductive layer is charged during microwave irradiation and discharge occurs from the end of the package, or the conductive layer hinders microwave transmission. There is a problem that the food directly under the agent package is not easily heated.

Further, Japanese Patent Application Laid-Open No. 2-413 discloses a particle size,
There has been proposed an oxygen absorber package in which an iron-based oxygen absorber composition containing a large amount of a powder filler having a specific surface area mixed therein is packaged with a breathable packaging material. This is to solve the problem that the content (iron-based oxygen scavenger) of the conventional iron-based oxygen scavenger package is heated or sparked in a very short time by microwave irradiation and easily ignited. is there. However,
If water is contained in the oxygen scavenger, it is vaporized during microwave irradiation and pressurizes the inside of the packaging bag to cause the bag to break. Therefore, the water content in the composition must be low. This method is applied to a moisture-dependent oxygen absorber that does not substantially contain moisture in the oxygen absorber package, and is not suitable for a self-reacting oxygen absorber package.

On the other hand, the non-ferrous oxygen-absorbing agent containing the organic substance as a main component, which is the content of the non-ferrous oxygen-absorbing agent package, must contain moisture, and the self-reactive type oxygen-absorbing agent that absorbs oxygen only by the composition is used. Since it is an oxygen agent, the use of a highly breathable packaging material used in this method causes a problem in that a large amount of oxygen is absorbed during handling and the ability is deactivated. Also, mixing a large amount of powder filler further increases the capacity of the oxygen scavenger, increases the size of the packaging material, and has the disadvantage of being difficult to handle and costly. That is, in the prior art, there was no means for obtaining a non-ferrous oxygen-absorbing agent package having microwave resistance.

The present invention solves this problem and provides a non-ferrous oxygen-absorbing agent package which is not detected by a metal detector. An object of the present invention is to provide a safe and practical oxygen-absorbing agent package which does not ignite even when irradiated and does not cause leakage of contents due to bag breakage, and is excellent in handleability.

[0010]

Means for Solving the Problems The inventors of the present invention made use of the development technology of oxygen scavengers and conducted repeated evaluation studies of various non-ferrous oxygen scavengers. A non-ferrous oxygen scavenger that does not lead to odor. However, it was inevitable that the moisture contained in the composition was heated and vaporized by microwaves. As a result, although it does not ignite, the inside of the bag is pressurized by the steam generated suddenly, the bag expands and eventually the heat seal part is broken and the bag is broken, and the contents are non-ferrous oxygen absorbers. Was at risk of leakage.

Therefore, as a result of further intensive research, it was found that by combining the outer and inner pouches using a packaging material having different air permeability and seal strength with the above-mentioned non-ferrous oxygen scavenger, steam was added during microwave irradiation. When pressure is reached,
Even if the bag expands, it releases pressure by breaking only the seal between the two breathable packaging materials,
It has been found that there is obtained an oxygen scavenger package in which the inner packaging bag for packaging the contents is not damaged and the contents do not leak. Also, by this method, it is possible to obtain a non-ferrous oxygen-absorbing agent package excellent in handleability with little deactivation even if left as it is, since the small bag as a whole can obtain a small air permeability, and the present invention completed.

The present invention relates to an oxygen-absorbing agent package which contains moisture in the composition and is not detected by a metal detector. An object of the present invention is to provide a microwave-resistant oxygen-absorbing agent package excellent in practical use, which does not ignite or leak the contents due to breakage of the packaging bag.

That is, a first aspect of the present invention is that an outer material 1 having an ethylene polymer layer and a heat resistant resin layer laminated thereon and having a hole penetrating therethrough, and an ethylene polymer layer having a hole penetrating paper or nonwoven fabric. Is a package formed by housing a non-ferrous oxygen-absorbing agent by heat sealing the facing inner members 2 of a double film heat-sealed at the peripheral edge. Wherein the moisture permeability of the outer material 1 is smaller than the moisture permeability of the inner material 2 and the peel strength between the outer material 1 and the inner material 2 is smaller than the peel strength between the inner materials 2. The present invention relates to an agent package.

A second aspect of the present invention is that an ethylene-based polymer layer and a heat-resistant resin layer are laminated and have an outer material 1 having a hole penetrating therethrough, and an ethylene-based polymer layer having a hole penetrating paper or nonwoven fabric. The inner member 2 facing the inner member 2 formed by laminating the inner member 2 and the film having the inner member 3 made of an ethylene-based polymer,
And a package formed by storing a non-ferrous oxygen-absorbing agent by heat sealing between the inner member 3 and the outer member 1, wherein the moisture permeability of the outer member 1 is smaller than the moisture permeability of the inner member 2, and The peel strength between the inner material 2 and the inner material 3 is smaller than the peel strength between the inner material 2 and the inner material 3.

The product of the present invention has good handleability as a self-reacting non-ferrous oxygen-absorbing package that is not detected by a metal detector, so that it can be favorably used for oxygen-absorbing packaging regardless of the moisture content of the food. Even if the oxygen scavenger package is microwave-heated with a microwave oven before eating, the oxygen scavenger package does not ignite, and even if the moisture inside the oxygen scavenger package rapidly evaporates and expands, the pressure does not increase. Shall eat the heated food safely without breaking the food by breaking the bag to break and break only the seal between the two packaging materials and thus without damaging or contaminating the food It has various properties that are extremely practical.

[0016]

Embodiments of the present invention will be described below in detail. The outer material 1 is composed of an ethylene polymer layer and a heat resistant resin layer. The ethylene-based polymer layer used in the present invention is a heat-sealing resin layer that creates an adhesive effect by melting when the outer material 1 and the inner material 2 are heat-sealed,
Low density, medium density, high density polyethylene, ethylene-
Vinyl acetate copolymer, ethylene-acrylic acid copolymer,
Examples thereof include an ethylene-methacrylic acid copolymer, an ethylene-methyl methacrylic acid copolymer, and an ionomer. The thickness of the ethylene polymer layer is preferably from 10 to 50 microns.

Further, the heat-resistant resin layer constituting the outer material 1 means that when the outer material 1 and the inner material 2 or the inner materials are heat-sealed, the outer appearance is maintained without being melted by heat and a smooth heat seal is achieved. It is a resin layer for performing, stretched or unstretched polypropylene, polyester, polyamide, ethylene-
Examples include vinyl alcohol copolymers and cellophane. Among them, a film made of polyester or polyamide is preferable from the viewpoint of easy handling in production. The thickness of the heat-resistant resin layer is preferably from 10 to 40 microns. It is preferable that this layer is printed on one side to improve the appearance, and then laminated with the polyethylene or a resin layer having a lower softening point by dry lamination, extrusion lamination, or the like to form the outer material 1. For printing, it is more preferable to perform pattern printing and concealed solid printing on the side to be laminated so that the ink does not appear on the surface of the external material.

A hole is formed in the outer member 1 to provide air permeability. The shape of the hole is not limited as long as it penetrates the outer material 1. Usually, after laminating the ethylene-based polymer layer and the heat-resistant resin layer, a hole is formed with a needle before bag making. The shape of the needle tip is conical, polygonal, or the like, and the size of the hole can be appropriately adjusted by changing the thickness or length of the needle, or by heating the needle to melt the outer material 1. The air permeability is set appropriately according to the oxygen absorbing capacity of the oxygen absorber, but the oxygen absorption rate is too fast and the heat generation is large, and the moisture in the oxygen absorber evaporates unnecessarily. Therefore, by reducing the number of holes or reducing the size of the holes and setting the air permeability to be low so that the deactivation during production and during standing is reduced, it is possible to obtain an oxygen absorber package with good handleability. it can. Therefore, the air permeability is preferably smaller than that of the inner member 2 described later in terms of moisture permeability, and more preferably 70% or less of the moisture permeability of the inner member 2.

The moisture permeability is measured as follows. 1) Each packaging material is individually applied to the automatic filling and packaging machine used for the product of the present invention and the comparative product, and is not filled with an oxygen scavenger.
The automatic filling and packaging machine is operated without heat sealing one of the bag mouths to obtain an empty bag having the same dimensions and the same opening conditions as the product of the present invention and the comparative product. Each of these empty bags is filled with anhydrous calcium chloride, and the bag mouth is heat-sealed with an impulse sealer, and then the weight of each package is precisely weighed. 2) Immediately put each obtained package at 25 ° C and 75% RH.
Transfer to a constant temperature and humidity chamber and store. 3) Measure the weight over time, and determine the moisture permeability of each packaging material (0/75% RH, 25 ° C., unit) from the value of the weight change and the area obtained by removing the area of the seal portion from the surface area of each package. g / m
² · 24h) seek.

The inner material 2 is made of paper or non-woven fabric, and a perforated ethylene polymer. As the paper constituting the inner material 2 used in the present invention, a mixed paper with Japanese paper, Western paper, rayon or the like is used. Paper basis weight from 20 g / m ² to 100 g
/ Things m ² is used, those from the packaging suitability and the like from 30 g / m ² of 60 g / m ² is preferably used. As the nonwoven fabric constituting the inner material 2, any of nonwoven fabrics such as a wet type, a dry type, and a spun bond nonwoven type can be used, and any material such as polyamide, polyester, polyolefin, rayon or a composite thereof can be used. A nonwoven fabric having a basis weight of 20 g / m ² to 100 g / m ² is used,
Those having 30 g / m ² to 80 g / m ² are preferably used from the viewpoint of packaging suitability and the like. In order to impart water repellency or oil repellency to the paper or nonwoven fabric, paper or nonwoven fabric processed with a water repellent or oil repellent may be used.

The ethylene polymer resin layer constituting the inner material 2 is a layer that serves as a sealant when the inner material 2 is formed.
The hole is opened so as not to impair the air permeability. As the resin material, low-density, medium-density, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylic acid copolymer, An ionomer or the like is used. In order to secure the layer sealing strength, the thickness of the ethylene polymer layer is preferably 20 to 50 microns. The ethylene polymer constituting the inner material 2 may be the same resin or a different resin as the ethylene polymer constituting the outer material 1.

The method for opening the holes is to make a hole in the ethylene polymer film in advance and then heat or dry laminate the paper or nonwoven fabric with the paper or nonwoven fabric. Alternatively, a method of extruding and laminating a molten ethylene-based polymer resin and then forming a hole can be used.

The shape of the hole formed in the ethylene polymer resin layer constituting the inner material 2 is not limited as long as it penetrates the ethylene polymer resin layer. Since the air permeability needs to be large in order to allow the water vapor generated rapidly during microwave irradiation to pass smoothly, it is preferable to increase the open area per unit area within a range that does not hinder the adhesiveness as a sealant. The size and number of holes are set so that the opening ratio becomes 10 to 30%. In addition, if the opening area per hole is too small, the air permeability at the time of pressurization is poor, which may cause bag breakage. Therefore, the opening area per hole is preferably 0.03 mm ² or more. The moisture permeability of the inner material 2 is preferably 100 g / m ² · 24 h or more. The method of measuring the moisture permeability will be described later. The Gurley air permeability of the inner material 2 is 60
Seconds / 100 cc or less is preferable.

The outer material 1 and the inner material 2 are heat-sealed at the peripheral edge of the package to form a double film. That is, in the present invention, a space through which gas flows is formed between the outer member 1 and the inner member 2.

The multilayer film having the inner material 3 is a multilayer film in which a film composed of an ethylene-based polymer layer is used as the inner material 3 and is combined with another film. The hole may be provided to provide air permeability, or may not be provided. When the holes were not opened, a film composed of an ethylene-based polymer layer (inner material 3) and a film composed of a heat-resistant resin such as polypropylene, polyester, polyamide, ethylene-vinyl alcohol copolymer, and cellophane were laminated. A laminated film of at least two layers is preferably used. When providing air permeability by opening holes, a film (inner material 3), a paper or nonwoven fabric, and a polypropylene, polyester, polyamide, ethylene-
A laminated film of at least three layers in which an apertured film made of a heat-resistant resin such as a vinyl alcohol copolymer or cellophane is laminated is preferably used. Examples of the resin material of the ethylene polymer layer constituting the inner material 3 include low-, medium-, and high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-
Methacrylic acid copolymer, ethylene-methyl methacrylic acid copolymer, ionomer and the like are used. It is preferable that the resin is of the same type as the ethylene-based polymer constituting the inner material 2.

In the present invention, the oxygen absorber stored in the inner bag formed by heat sealing between the inner materials is a non-ferrous oxygen absorber containing water. A preferred non-ferrous oxygen absorber is a composition in which an organic compound and water are supported on an adsorptive non-conductive carrier. The adsorptive non-conductive carrier constituting the oxygen scavenger according to the present invention is a substance that is not itself a good conductor of electricity, and can adsorb and hold an aqueous solution of an organic compound, amorphous silica, petal-like crystalline silica, Silica compounds such as diatomaceous earth, activated clay, sepiolite, silica / alumina compounds such as zeolite, mica, bentonite, perlite, vermiculite, alkaline earth metal compounds such as calcium carbonate, magnesium carbonate, dolomite, calcium hydroxide, magnesium hydroxide, etc. Can be exemplified.

The adsorptive nonconductive carrier of the present invention can be used in the form of powder or granules. In the case of powder, when the aqueous solution of the organic compound of the present invention is supported on the carrier and used as an oxygen scavenger, it can be smoothly filled and packed. Since the fluidity is required for filling in the packaging material, it is preferable to perform granulation in the step of using an oxygen scavenger. In the case of granular, there is an advantage that the fluidity can be easily obtained even after being used as a deoxidizer, and a granulating step is not required. In addition, since some of these compound components include an oxidized compound which reacts with the metal detector as an impurity, it is preferable that the content of the heavy metal compound, particularly, the iron compound is small. Of the iron compounds, iron sulfide and triiron tetroxide are particularly susceptible to reaction with metal detectors, so the smaller their content, the better. From these viewpoints, diatomaceous earth, sepiolite, zeolite, calcium hydroxide, and magnesium hydroxide are preferable, and granular form is more preferable than powder. In the process of producing the adsorptive non-conductive carrier, iron may be mixed in equipment such as a pulverizer and a baking furnace, which may cause the metal detector to react easily. It is preferable to take measures such as prevention of contamination, installation of an iron removal machine, and washing with an acid.

The oxidizable organic compound constituting the oxygen scavenger of the present invention is a main agent of the oxygen scavenger which oxidizes and absorbs oxygen in an alkaline environment, and includes ascorbic acid, sodium ascorbate, sodium erythorbate and the like. Polyhydric phenols such as ascorbic acid, catechol, gallic acid, pyrogallol, glycerin, ethylene glycol,
Polyhydric alcohols such as propanediol can be used, but sodium ascorbate and glycerin are preferred from the viewpoint of availability, safety, solubility in water, and the like.

Various additives can be added to the oxygen scavenger of the present invention as needed. Examples of additives that are added as necessary to the oxygen scavenger of the present invention are described below. The additives are not limited to these, and can be added as appropriate while taking into consideration that they are not detected by the metal detector, that microwave resistance is reduced, and that ignition and spark do not occur. 1) Alkaline substance The oxidizable organic compound used in the oxygen scavenger of the present invention includes:
Oxygen is absorbed under the condition of an alkaline aqueous solution. For this purpose, alkaline substances such as caustic soda, sodium carbonate and calcium hydroxide can be added. The method of adding the alkaline substance to the organic compound aqueous solution, the method of adding the alkaline substance as a powder after supporting the organic compound, and the like can be adopted.
When the adsorptive nonconductive carrier itself is alkaline, and when other additives are alkaline, the alkaline substance may not be added.

2) Catalyst As a catalyst for activating the oxygen absorption reaction, water-soluble salts of transition metals such as iron, copper, cobalt and manganese, phenols,
It is preferable to add one or more selected from quinones and activated carbon. However, if the addition amount is too large, the microwave resistance, safety and the like are reduced, so the total addition amount is preferably 10% by weight or less in the oxygen scavenger composition.
Activated carbon also has the effect of adsorbing trace amounts of odorous components generated by the oxygen absorption reaction. 3) Lubricants Lubricants such as talc, magnesium stearate, and calcium stearate can be added in order to improve the flowability of the oxygen scavenger and improve the productivity of the oxygen scavenger and the suitability for filling and packaging.

The oxygen scavenger according to the present invention is not detected by the metal detector, and when irradiated with microwaves, the water in the oxygen scavenger is rapidly heated and vaporized by the microwave, but other components Is characterized by no rapid heating, ignition or sparking and no contamination or damage to food or food packaging. With respect to the above-mentioned heating and vaporization of water, microwave heating of foods primarily heats the water in foods, and therefore does not cause contamination or damage to foods or food packages. A particularly preferred oxygen absorber in the present invention is a non-ferrous oxygen absorber composition comprising granular slaked lime, glycerin, a transition metal compound and water.

The oxygen scavenger of the present invention can be obtained, for example, by supporting the organic compound and water on the adsorptive nonconductive carrier. The supporting method is a method in which a powdery adsorbent non-conductive carrier, an organic compound, and water are mixed, and the mixture is granulated by a method such as extrusion granulation or tumbling granulation. A method of impregnating with a compound aqueous solution can be used. The higher the amount of the organic compound per unit volume as the oxygen scavenger, the better the package that is small and has a high oxygen absorption capacity. Therefore, the higher the concentration of the aqueous solution of the organic compound, the better. The water content of the oxygen scavenger of the present invention is preferably 2
% Or more, more preferably 5 to 50% by weight. If the water content is too small, the oxygen absorbing ability is reduced.

In order to manufacture the microwave-resistant oxygen-absorbing agent package according to the first aspect of the present invention, generally, a three-side sealing method in which three sides of the package are sealed or a four-side sealing method in which four sides are sealed Is adopted. Preferably, a three-side sealing method using a known vertical or horizontal three-side seal automatic filling and packaging machine is used.

In the three-way sealing method, the ethylene-based polymer resin layer side of the outer material 1 and the paper or nonwoven fabric side of the inner material 2 are overlapped so as to face each other and guided to a three-side seal automatic filling and packaging machine, and the inner material 2 is turned inside. The bag is manufactured by folding it in half and heat-sealing portions corresponding to two separated sides of the bag periphery, filling an appropriate amount of an oxygen scavenger, and heat-sealing the remaining sides of the bag periphery. At this time, it is preferable that the size of the outer material 1 be larger than the size of the inner material 2 by 1 mm or more, preferably 2 mm or more, since the inner material 2 does not protrude from the outer material 1. In addition, external material 1
If no holes have been previously formed in the outer material 1, an appropriate number of holes are formed in the outer material 1 by a punching device provided in the three-side seal automatic filling and packaging machine.

In order to manufacture the microwave-resistant oxygen-absorbing agent package according to the second aspect of the present invention, a four-side sealing method in which four sides are sealed is generally employed. Preferably, a four-side sealing method using a known vertical or horizontal three-side seal automatic filling and packaging machine is used. In the four-sided sealing method, the ethylene-based polymer resin layer side of the outer material 1 and the paper or non-woven fabric side of the inner material 2 are superimposed so as to face each other and guided to a four-sided seal automatic filling and packaging machine, and the inner material comprising the ethylene-based polymer layer is formed. The film having 3 is overlapped so that the inner material 3 faces the inner material 2, heat-sealed the bag peripheral portion, filled with an appropriate amount of oxygen scavenger, and heat-sealed the remaining side equivalent portion. Manufactured. If the outer material 1 has not been previously drilled, an appropriate number of holes are formed in the outer material 1 by a punching device provided in the four-side seal automatic filling and packaging machine.

In the present invention, the moisture permeability of the outer member 1 and the inner member 2, the outer member 1 and the inner member 2 in the heat-sealed portion of the oxygen absorber package, and between the inner members 2 or between the inner members 2. The peel strength with the material 3 is important. Since the seal portion between the outer member 1 and the inner member 2 is selectively destroyed, the moisture permeability of the outer member 1 is smaller than that of the inner member 2, and the peel strength between the outer member 1 and the inner member 2 is lower than that of the inner member. Is required to be smaller than the peel strength. The part where the peel strength between the outer material 1 and the inner material 2 is weak is the outer material 1
It may be a part of the entire circumference of the seal portion between the inner member 2 and the inner member 2. If the difference in strength is small, the selectivity of the fracture point becomes uncertain,
The peel strength between the outer member 1 and the inner member 2 is determined by the inner member 2 or the inner member 2.
It is preferably 70% or less of the peel strength between the material and the inner material 3. Further, the peel strength between the inner members 2 or between the inner members 2 and the inner member 3 may be 0.8 kg or more in order to prevent the seal portion between the inner members from peeling when the oxygen absorber package is expanded. preferable. In addition, during the normal handling,
It is preferable that the peel strength between the outer material 1 and the inner material 2 is 0.1 kg or more in order to prevent the peeling of the material.

The peel strength of these seals is adjusted by adjusting the ethylene copolymer resin layer of the outer material 1, the paper or nonwoven fabric layer of the inner material 2, or the ethylene copolymer resin layer of the inner material 2 or the inner material 3. Appropriately selecting the material and thickness of each layer of
It can be carried out by appropriately selecting the heat sealing method of the bag making and filling machine, and by appropriately selecting the temperature and time during the heat sealing.

When the oxygen scavenger package according to the present invention is irradiated with microwaves together with food, the moisture in the oxygen scavenger is heated, rapidly evaporates and expands, and quickly passes through the inner material 2 having high air permeability. However, since the speed at which the outer material 1 having low air permeability passes outside is lower than the speed at which it evaporates, the material stays between the outer material 1 and the inner material 2 and pressurizes the outer material 1 from the inside. The outer material 1 is pushed outward, but the outer material 1 and the inner material 2 are sealed at the periphery of the package, so that the entire oxygen absorber package expands to its limit, thereby absorbing the initial increase in internal pressure. . Further, when the vaporization of the moisture from the oxygen absorber continues, the pressure in the oxygen absorber package continues to increase, and finally, the sealing portion between the outer member 1 and the inner member 2 having a relatively weak seal strength is limited. And selectively destroyed, releasing water vapor.
At this time, since the sealed portion between the inner materials forming the inner bag is not broken, the oxygen scavenger as the contents remains in the inner bag. Therefore, the oxygen scavenger does not leak from the oxygen scavenger package of the present invention even when microwave heating is performed. After outgassing,
Moisture that subsequently evaporates quickly passes through the inner material and evaporates to the outside air, so that the pressure no longer increases.

[0039]

The present invention will be described more specifically with reference to examples and comparative examples of the present invention, but the present invention is not limited to these examples. Example 1 96 parts by weight of glycerin pharmacopoeia and 10 parts by weight of water were mixed, and a solution of 1 part by weight of manganese chloride and 1 part by weight of gallic acid was impregnated into granular slaked lime having an average particle diameter of 1 mm.
5 parts by weight of powdered activated carbon and 0.5 parts by weight of magnesium stearate powder were mixed to obtain a deoxidizer A. After printing on one side of a polyethylene terephthalate film (Toyobo Co., Ltd., thickness 12 μm) in the order of character printing and solid printing, a low-density polyethylene (Nihon Unicar Co., Ltd.) 15 μm thickness is printed on the printing surface. And an ethylene-methacrylic acid copolymer (manufactured by Dow Chemical Co., Ltd.) was extruded in this order with a thickness of 15 μm and laminated to obtain a film-shaped outer material 10, which was cut into a width of 110 mm and a length of 500 m, and wound around a paper tube. . On the other hand, a hole having a diameter of 0.8 mm was formed on a water-resistant and oil-resistant paper coated with a sizing agent and an oil-proof agent at a porosity of 25%.
% Open medium-density polyethylene (TUX manufactured by Tocelo Co., Ltd.)
(TC, thickness 30 μm) was thermally laminated to obtain a film-like inner material 20, which was cut into a width of 105 mm and a length of 500 m, and wound around a paper tube. Gurley air permeability of inner material 20 is 30
Seconds.

The outer material 10 and the inner material 20 are unwound, and the ethylene-methacrylic acid copolymer layer of the outer material 10 and the paper layer of the inner material 20 face each other in a horizontal three-side seal rotary automatic filling and packaging machine (manufactured by Topak Co., Ltd.). To overlap, inner material 2
Is folded inside so that the outer material 10 is opened with a 0.7 mm diameter conical needle at the bottom before heat sealing, and the width is 55 m.
An oxygen-absorbing agent package (hereinafter referred to as product 1 of the present invention) containing m, 45 mm in length, and 2.5 g of oxygen-absorbing agent A was produced. The oxygen scavenger package was sealed and stored in a bag made of a plastic film laminated with aluminum foil within 10 minutes after production to prevent deterioration due to oxygen absorption. Measure the moisture permeability of the packaging material, the peel strength of each oxygen absorber package, the oxygen absorption capacity of each oxygen absorber package, and the storage stability by the procedure described below, and pass the metal detector of each oxygen absorber package. Tested.

Example 2 Biaxially stretched nylon film (manufactured by Unitika Ltd., thickness 1)
After printing on one side (5 microns) in the order of letter printing and solid printing, a low-density polyethylene film (20 microns thick) was dry-laminated on the printing side, and holes were formed with a heated 1 mm diameter needle. Outer material 11 was obtained. Width 120
External material 11 cut to 500 mm in length and wound on a paper tube
And the inner material 20 cut into a width of 115 mm and a length of 500 m and wound up on a paper tube is passed through a vertical three-side seal automatic filling and packaging machine (manufactured by Sanko Machine Co., Ltd.) to form a low-density polyethylene layer of the outer material 11 and a paper of the inner material 20. The layers are opposed to each other, the inner material 2 is set so that it is folded inside, and the oxygen absorber A is put into the filling hopper, and the oxygen absorber package (width 60 mm, length 80 mm, oxygen absorber A 9 g containing 9 g) is used. Invention product 2) was obtained. Example 1
Store in the same manner as above and measure the moisture permeability of the packaging material, the peel strength of each oxygen absorber package, the oxygen absorption capacity of each oxygen absorber package and the storage stability, and detect the metal of each oxygen absorber package. A container passing test was performed.

Example 3 100 parts by weight of sodium 1-ascorbate was added to water 120
100 parts of a solution of 15 parts by weight of ferrous sulfate and 25 parts by weight of sodium carbonate was impregnated with 100 kg of granulated and calcined diatomaceous earth washed with hydrochloric acid.
The resulting mixture was mixed to obtain oxygen scavenger B. After printing on one side of a polyethylene terephthalate film (12 μm thick) in the order of character printing and solid printing, 20 μm of an ethylene-vinyl acetate copolymer was extruded and laminated on the printing side to obtain an outer material 12. On the other hand, medium-density polyethylene (thickness: 30 μm) in which holes having a diameter of 1 mm were formed at a porosity of 20% was dry-laminated on a polyester-based nonwoven fabric (basis weight: 30 g) to obtain an inner material 21. The Gurley air permeability of the inner material 21 was 30 seconds or less.

An outer material 12 cut into a width of 130 mm and a length of 500 m and wound on a paper tube, and a width of 123 mm and a length of 500 m
The inner material 21 cut into a paper tube and wound into a paper tube, the ethylene-vinyl acetate copolymer layer of the outer material 12 and the nonwoven fabric layer of the inner material 21 face each other in a horizontal three-side seal rotary automatic filling and packaging machine,
The inner material 2 is set so as to be folded inside, the oxygen absorber B is put into the filling hopper, and the outer material 12 is opened with a conical needle having a diameter of 0.7 mm at the bottom before heat sealing, and the inner material 2 has a width of 6 mm.
A package of oxygen absorber (0 mm, length 45 mm, containing 2.5 g of oxygen absorber B) (hereinafter referred to as product 3 of the present invention) was obtained. Stored in the same manner as in Example 1, and measured the moisture permeability of the packaging material, the peel strength of each oxygen-absorbing agent package, the oxygen absorption capacity and the storage stability of each oxygen-absorbing agent package, and measured the oxygen-absorbing agent packages. Was tested for pass through a metal detector.

Comparative Example 1 As a comparative example of the present invention, the following oxygen absorber package was prepared. Each oxygen-absorbing agent package and each oxygen-absorbing agent were sealed and stored in a bag made of a plastic film laminated with an aluminum foil within 10 minutes after production to prevent deterioration due to oxygen absorption. After printing on one side of a polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., thickness 12 μm) in the order of character printing and solid printing, a low-density polyethylene 15 μm was extruded on the printing side and heated to a two-layer film. The hole was opened with a needle having a diameter of 1 mm. Water-resistant oil-resistant paper is heat-laminated on the polyethylene side of the apertured two-layer film, and a low-density polyethylene film (30 micron) is opened on the water-resistant oil-resistant paper side with a heated needle having a diameter of 1 mm. Material 30 was obtained. Instead of the outer material 10 and the inner material 20, width 110mm,
The packaging material 30 wound up to a length of 500 m is set in a horizontal three-side-seal rotary automatic filling and packaging machine with the low-density polyethylene film side folded inward, and an oxygen scavenger A is placed in a filling hopper, and the width is 55 mm and the length is 55 mm. 45mm,
An oxygen scavenger package containing 2.5 g of oxygen scavenger A (Comparative product 1) was obtained. Stored in the same manner as in Example 1, and measured the moisture permeability of the packaging material, the peel strength of each oxygen-absorbing agent package, the oxygen absorption capacity and the storage stability of each oxygen-absorbing agent package, and measured the oxygen-absorbing agent packages. Was tested for pass through a metal detector.

Comparative Example 2 The heat sealing temperature of the vertical three-side seal automatic filling and packaging machine was increased.
An oxygen scavenger package having a width of 60 mm, a length of 80 mm and an oxygen scavenger B of 9 g using the same material and method as that of the product 2 of the present invention except that the peeling strength of the heat seal portion is set to be high by decreasing the filling and packaging speed. (Comparative product 2) was obtained. Stored in the same manner as in Example 1, and measured the moisture permeability of the packaging material, the peel strength of each oxygen-absorbing agent package, the oxygen absorption capacity and the storage stability of each oxygen-absorbing agent package, and measured the oxygen-absorbing agent packages. Was tested for pass through a metal detector.

COMPARATIVE EXAMPLE 3 100 parts by weight of sodium 1-ascorbate was added to water 120
100 parts of a solution of 15 parts by weight of ferrous sulfate and 25 parts by weight of sodium carbonate was impregnated into 70 kg of zinc-activated granular activated carbon to obtain a deoxidizer C. Using the same material and method as the product 3 of the present invention except that the oxygen scavenger C was used instead of the oxygen scavenger B, the width was 60 mm,
An oxygen absorber package (comparative product 3) having a length of 45 mm and containing 2.5 g of oxygen absorber B was obtained. Stored in the same manner as in Example 1, and measured the moisture permeability of the packaging material, the peel strength of each oxygen-absorbing agent package, the oxygen absorption capacity and the storage stability of each oxygen-absorbing agent package, and measured the oxygen-absorbing agent packages. Was tested for pass through a metal detector.

COMPARATIVE EXAMPLE 4 The same material and method as in Example 1 of the present invention were used except that iron powder-based oxygen absorber D was used instead of oxygen absorber A.
An oxygen absorber package (comparative product 4) having a length of 45 mm and containing 2.5 g of oxygen absorber D was obtained. Stored in the same manner as in Example 1, and measured the moisture permeability of the packaging material, the peel strength of each oxygen-absorbing agent package, the oxygen absorption capacity and the storage stability of each oxygen-absorbing agent package, and measured the oxygen-absorbing agent packages. Was tested for pass through a metal detector.

COMPARATIVE EXAMPLE 5 The same material and method as in the product 1 of the present invention except that the number of holes was increased when the outer material 10 was opened with a 0.7 mm diameter conical needle at the bottom, and the width was 55 mm, the length was 45 mm, Deoxidizer A2.5g
An oxygen-absorbing agent-containing package (comparative product 5) was obtained. Stored in the same manner as in Example 1, and measured the moisture permeability of the packaging material, the peel strength of each oxygen-absorbing agent package, the oxygen absorption capacity and the storage stability of each oxygen-absorbing agent package, and measured the oxygen-absorbing agent packages. Was tested for pass through a metal detector.

[Measurement Method] [Measurement of moisture permeability of packaging material] Outer materials 10 to 12, inner materials 20 and 21, and packaging material 30 used in each of the oxygen absorber packages of the present invention products 1 to 3 and comparative products 1 to 5 Each of the packaging materials was independently applied to the automatic filling and packaging machine used in the present invention product and the comparative product, and the automatic filling and packaging machine was operated without filling with the oxygen scavenger and without heat sealing one of the bag mouths. Thus, an empty bag having the same dimensions and the same opening conditions as the product of the present invention and the comparative product was obtained. Each of these empty bags was filled with anhydrous calcium chloride, and the bag mouth was heat-sealed with an impulse sealer, and then immediately weighed precisely. This was stored in a thermo-hygrostat at 25 ° C. and 75% RH, and each packaging material was obtained from the weight change measured over time and the area of the surface area of each package excluding the area of the seal portion. Moisture permeability (0/75% RH, 25 ° C, unit g / m
² · 24h) was determined. The results are shown in Table 1.

[Measurement of Peeling Strength of Each Oxygen Oxygen Packing Body] Each of the oxygen absorbing agent packages of the above-mentioned products 1 to 3 of the present invention and comparative products 1 to 5
Cut each side of the seal into strips 15mm wide,
Peel strength was measured using a push-pull gauge. still,
The sealing portion between the outer material and the inner material was measured for each of the three sides on the front and back. Table 1 shows the numerical value (unit kg / 15 mm) of the portion having the weakest peel strength among the seal portions of the respective oxygen absorber packages.

[Measurement of Oxygen Absorbing Ability and Storage Stability of Each Oxygen Desorbent Package] Each of the oxygen absorbers of the present invention products 1 to 3 and comparative products 1 to 5 was placed in a gas barrier bag with air. 300 ml (but 900 ml of air for the product 2 of the present invention and the comparative product 2) and an oxygen detector (manufactured by Mitsubishi Gas Chemical Co., Ltd., trade name "Ageless Eye"), which indicates the presence or absence of oxygen by a change in color tone. After being left in a room at a temperature of 48 ° C., the color tone of the oxygen detector was observed after 48 hours and 240 hours, and the state of deoxygenation was measured. After leaving each oxygen absorber package in the air for 20 minutes, the same oxygen absorption capacity measurement was performed.
The storage stability was measured. In both cases, the results are shown in Table 2 as x when the oxygen detector has a color tone with oxygen at the time of observation, and as で あ れ ば when the oxygen detector has a color tone without oxygen.

[Passage test of each oxygen absorber package with a metal detector] Metal detector (ND-800 manufactured by Nissin Denshi Kogyo KK)
Mold) is set to the condition that the iron 0.7 mmφ test piece is not detected and the iron 0.8 mmφ test piece is detected. Each was passed. The results are shown in Table 2 as ○ if not detected and × if detected.

[Microwave resistance test of various oxygen scavenger packages] Each of the oxygen scavenger packages of the products 1 to 3 of the present invention and the comparative products 1 to 5 was subjected to standard heating conditions for food, that is, 1) output. 500W microwave oven (RR manufactured by Mitsubishi Electric Corporation)
-50 type) for 1 minute 2) 1700W microwave oven (Matsushita Electric Industrial Co., Ltd.)
(NE-1700) manufactured by Microwave Engineering Co., Ltd. for 2 seconds under heating conditions for 30 seconds. After the irradiation, the appearance of the oxygen scavenger package was observed. The results are shown in Table 2.

[0054]

[Table 1]

[0055]

[Table 2]

[0056]

The oxygen scavenger package of the present invention is excellent in oxygen absorption capacity and handleability, is not only highly practical as an oxygen scavenger package, but is not detected by a metal detector and is heated in a microwave oven. Even if receiving microwave irradiation such as, there is no problem such as leakage of contents or burning due to bag breakage,
Has excellent features. Therefore, the oxygen-absorbing agent package of the present invention can be suitably used particularly in the field of microwave-heated packages of various foods or medicines in which foreign substances are checked using a metal detector. That is, bento, microwave cooked or microwaved before eating, rice rice such as rice balls, rice cake, yakisoba, noodles such as spaghetti, various dishes, cooking bread, pizza, cake, buns, dumplings and other confectionery, Various foods such as sausages, fried chicken, yakitori and other processed meat products, etc., are highly effective in preventing oxidation and suppressing microbial growth during storage of various pharmaceuticals that are sterilized by microwave before use or softened by microwave heating. .

[Brief description of the drawings]

FIG. 1 is an example of a packaging material of the present invention.

FIG. 2 shows an example of the oxygen absorber package of the present invention.

[Description of Signs] 1 Outer material 1 1a Ethylene polymer layer 1b Heat resistant resin layer 2 Inner material 2a Paper or nonwoven fabric 2b Ethylene polymer layer 90 Non-ferrous oxygen scavenger

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI theme coat ゛ (Reference) B32B 27/18 B32B 27/18 G 27/32 27/32 Z 29/00 29/00 B65D 81/26 B65D 81/26 RF term (reference) 3E067 AA05 AB97 BA12A BB01A BB06A BB14A BB25A CA17 CA24 EA06 EA08 EA09 EE25 EE48 GB02 GB13 GD08 4B021 LA15 LA16 LA24 MC04 MK08 MP07 MP08 4F100 AK01 BA04A04 BA04 AK04 BA10 AK04 BA10 AK04 DB02 DC11 DG10C DG15C GB15 GB23 JD04 JJ03B JK06 YY00 4G066 AA11B AA14D AA17B AA32B AB06B AB06D AB23D BA13 CA37 DA03 EA07

Claims (8)

[Claims] 1. An inner layer formed by laminating an ethylene-based polymer layer and a heat-resistant resin layer, and laminating an outer material 1 having a through-hole and a paper or nonwoven fabric and an ethylene-polymer layer having a through-hole. The material 2 is a package formed by housing a non-ferrous oxygen-absorbing agent by heat sealing between the facing inner materials 2 of a double film which is heat-sealed at the peripheral portion, and the moisture permeability of the outer material 1 is formed. Is smaller than the moisture permeability of the inner material 2 and the outer material 1
The peeling strength between the inner material 2 and the inner material 2 is smaller than the peeling strength between the inner materials 2. 2. The oxygen absorber package according to claim 1, wherein the package is a three-side seal package. 3. The package according to claim 1, wherein the peel strength between the outer material 1 and the inner material 2 is 70% or less of the peel strength between the inner materials 2. . 4. An inner layer formed by laminating an ethylene-based polymer layer and a heat-resistant resin layer, and laminating an outer material 1 having a through hole and an ethylene-based polymer layer having a through hole with paper or nonwoven fabric. The non-ferrous material is removed by heat-sealing the inner material 2 and the inner material 3 which face each other between the double film having the inner material 3 heat-sealed at the peripheral portion and the multilayer film having the inner material 3 made of the ethylene polymer. A package formed by storing an oxygen agent, wherein the moisture permeability of the outer material 1 is smaller than the moisture permeability of the inner material 2 and the peel strength between the outer material 1 and the inner material 2 is lower than that of the inner material 2. 3. An oxygen scavenger package characterized by having a peel strength of less than 3. 5. The oxygen absorber package according to claim 4, wherein the package is a four-sided seal package. 6. The removal method according to claim 4, wherein the peel strength between the outer material 1 and the inner material 2 is 70% or less of the peel strength between the inner material 2 and the inner material 3. Oxygen package. 7. The non-ferrous oxygen scavenger comprises an adsorbable non-conductive carrier carrying an oxidizable organic compound and water,
The oxygen absorber package according to claim 1 or 4, wherein the oxygen absorber is a non-ferrous oxygen absorber containing water. 8. The deoxidizer according to claim 1, wherein the non-ferrous oxygen scavenger is a non-ferrous oxygen scavenger containing water, comprising granular slaked lime, glycerin, a transition metal compound and water. Oxygen package.