JP3460801B2 - Deoxidizing multilayer or method for food heating - Google Patents

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a resin composition having an oxygen absorbing function. Specifically, it is a deoxidizing resin composition comprising at least three kinds of materials of an oxygen scavenger, a polyolefin, and an antioxidant, which prevents deterioration of the polyolefin due to the oxygen scavenger, has good processing stability, and is processed. It is intended to provide a deoxidizing resin composition having a small off-flavor and a small deterioration with time of polyolefin.

[0002]

2. Description of the Related Art Conventionally, oxygen in a package for storing foods, pharmaceuticals, and other preserved items is removed to prevent oxidative deterioration, discoloration, deterioration of molds and aerobic bacteria, and insect damage. As a technique, a method of sealing an oxygen scavenger together with an object to be stored in a gas barrier bag is widely used. For this method, a deoxidizer obtained by filling a powder or granular oxygen absorber composition into a breathable sachet is usually used. However, if the oxygen scavenger in a small bag is mixed in the object to be preserved, it may be mistakenly cooked or eaten with the object to be preserved,
It also gives the user a feeling of foreign matter and a feeling of resistance.
Furthermore, there is a risk that the oxygen scavenger composition spilled by accidentally mishandling the bag may contaminate the object to be stored. For this reason, as a deoxidizing packaging technique without the above-mentioned problems, it has been considered in recent years to impart deoxidizing performance to the packaging itself.

As such an example, for example, Japanese Patent Publication No. 62-
1824, JP-A-57-146651, JP-A-4-45152, JP-A-4-90848, JP-A-7-309323 and the like, an oxygen absorber is incorporated into a resin. There are films and sheets having a multilayer structure including dispersed layers. Furthermore, Japanese Patent Examination 4-608
Japanese Patent Publication No. 26 discloses a packaging container in which a commercially available oxygen absorber is contained in a gas barrier thermoplastic resin. JP-A-2
Japanese Patent Laid-Open No. 56547 discloses a packaging material comprising an oxygen-permeable resin layer, an adhesive layer, an oxygen-absorbing sheet, an adhesive layer, and an oxygen-impermeable sheet, and an adhesive used for the oxygen-absorbing sheet. As the adhesive used for lamination, polyethylene resin, polypropylene resin, etc. are described as polyolefin-based thermoplastic resin hot-melt adhesives such as polyethylene resin, polypropylene resin.

[0004]

Generally, a packaging container containing an oxygen scavenger has a breathable isolation layer made of a thermoplastic resin,
An oxygen absorbing resin layer containing an oxygen scavenger and a gas barrier layer are laminated in this order to form an oxygen absorbing multilayer sheet having a structure of at least three layers, and an oxygen absorbing multilayer body such as an oxygen absorbing multilayer film. These deoxidizing multilayer bodies are manufactured by processes such as co-extrusion and laminating, and are thermoformed or bag-made to be used as deoxidizing multilayer packaging bodies for storage of articles such as foods and pharmaceuticals. .

When the deoxidizing multilayer body is manufactured by the above-mentioned steps, a step of extruding the thermoplastic resin forming each layer with a heated extruder is essential. A deoxidizing resin composition composed of a conventional oxygen scavenger and a polyolefin that is a thermoplastic resin is, in the extrusion step, due to the effect of the oxygen scavenger dispersed in the resin, the polyolefin melted inside the extruder. Degradation significantly progressed as compared with the state where no oxygen absorber was present, and the processing stability of the oxygen absorber resin composition sometimes deteriorated. Further, from the deoxidizing multi-layered body utilizing this deoxidizing resin composition, a bad odor is strongly generated due to the deterioration of the polyolefin in the deoxidizing resin composition, or the polyolefin constituting the deoxidizing resin composition is There has been a problem that the strength of the multilayer body deteriorates due to deterioration over time due to the oxygen scavenger.

As a method of preventing such a problem, when extruding the deoxidizing resin composition with an extruder, it is conceivable to set the extruder as low as possible and perform the extrusion. Sometimes increased, the ejection became unstable, and the quality of the obtained molded product deteriorated. In particular, in the case of forming the deoxidizing multilayer body by extrusion laminating or the like which is usually performed at a resin temperature near 300 ° C., there is a problem that the adhesive strength between the layers becomes insufficient when the extrusion is performed at a low temperature. Furthermore, as another method for solving the above-mentioned problem, the inside of the extruder cylinder can be evacuated,
A method to prevent deterioration of the polyolefin by replacing with an inert gas and extruding is considered, but modification such as installing a vent port, a vacuum pump, a special device for introducing an inert gas in the extruder However, there is a problem that the device is complicated and the cost is high. Therefore,
Conventionally, in consideration of deterioration of the polyolefin due to extrusion in advance, for example, an adsorbent such as activated carbon is added to the deoxidizing resin composition, or an oxygen absorbing resin layer composed thereof, or a gas-permeable separating layer. Between the oxygen absorbing resin layer and the oxygen absorbing resin layer, an adsorbent layer in which an adsorbent such as activated carbon is mixed with the thermoplastic resin is provided to physically absorb the offensive odor caused by the deterioration of the polyolefin of the oxygen absorbing resin layer. However, these methods have a problem that it is necessary to add a considerably large amount of an adsorbent, and it is not possible to prevent a decrease in strength due to deterioration of the polyolefin over time.

The present invention has been made to solve the above-mentioned problems, and provides an oxygen-absorbing resin composition which is excellent in processing stability, has less offensive odor, and has little deterioration with time of the constituent polyolefin. The purpose is to provide.

[0008]

In view of the above-mentioned problems of the prior art, the inventors of the present invention stabilize the processability of the deoxidizing resin composition, reduce the offensive odor generated from the molded article, and As a result of extensive studies on prevention of deterioration of the polyolefin constituting the oxygen scavenging resin composition over time, an oxygen scavenger, by adding a certain amount of an antioxidant to the oxygen scavenging resin composition comprising the polyolefin The inventors have found that the deterioration of the polyolefin due to the oxygen scavenger is prevented, the generation of an offensive odor is reduced, and the deterioration of the polyolefin over time is reduced, and the present invention has been completed.

That is, the present invention provides at least three kinds of oxygen absorbers, polyolefins, and at least one antioxidant selected from the group consisting of phenolic antioxidants, phosphorus antioxidants and lactone antioxidants. And a deoxidizing resin composition comprising the above material.

The present invention also relates to a deoxidizing sheet or deoxidizing film comprising the above deoxidizing resin composition.

The present invention also relates to a deoxidizing property having a laminated structure of at least three layers of a gas permeable isolation layer made of a thermoplastic resin, an oxygen absorbing resin layer made of the above deoxidizing resin composition, and a gas barrier layer in this order. The present invention relates to a multi-layer body or a container made of this.

The present invention also relates to a packaging container in which a part or all of the container is composed of the above-mentioned deoxidizing multilayer body and absorbs oxygen inside the container.

[0013]

BEST MODE FOR CARRYING OUT THE INVENTION The deoxidizing resin composition of the present invention comprises
It is composed of at least three kinds of materials such as an oxygen scavenger, a polyolefin, and an antioxidant. The production of the deoxidizing resin composition,
For example, using an extruder such as a single-screw extruder or a twin-screw extruder, the above materials are melted and kneaded and extruded from a strand die or a T die, and the kneaded product is cooled by water cooling or air cooling, and then a pelletizer or the like. It can be manufactured by a conventionally known pellet manufacturing method such as pelletization.

The polyolefin used in the present invention includes low density polyethylene, linear low density polyethylene,
Various polyethylenes such as medium density polyethylene, high density polyethylene, metallocene-catalyzed polyethylene, propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random copolymer, various polypropylenes such as polypropylene with metallocene catalyst, polymethyl Penten and modified products thereof are used. These various polyolefins are excellent in processability and thermal stability and are resins suitable for the present invention. Further, depending on the purpose of use, other resin components, for example, polyamide such as polystyrene or nylon 6, polyester such as polyethylene terephthalate, or thermoplastic elastomer may be added. The content of the polyolefin in the deoxidizing resin composition is preferably 20 to 90% by weight, and 40 to 80% by weight.
Weight percent is more preferred.

As the oxygen scavenger used in the present invention, there is used a so-called moisture-dependent oxygen scavenger containing a reducing substance as a main component, which causes a oxygen scavenging reaction when supplied with moisture.
Preferably, a granular oxygen absorber composition composed of iron powder and a metal halide can be used. As iron powder,
Iron powder obtained by various manufacturing methods such as reduced iron powder and atomized iron powder can be used, and the average particle diameter of the iron powder is preferably 10 to 50 μm. As the metal halide, sodium chloride,
One or more alkali metal or alkaline earth metal halides exemplified by sodium bromide, sodium iodide, potassium chloride, potassium bromide, potassium iodide, calcium chloride, magnesium chloride and barium chloride are preferred. Used.

The content of the oxygen scavenger composition in the oxygen scavenging resin composition is preferably 10 to 80% by weight, more preferably 20 to 60% by weight. If the content of the oxygen scavenger composition is less than the above amount, the oxygen absorption performance of the oxygen scavenging multilayer structure using this will be decreased, and if it is increased, the processability will be deteriorated. Is appropriately selected within the above range.

As the antioxidant, those usually used for preventing deterioration of polyolefin can be applied as they are. As the antioxidant, one having a small odor of itself is preferable, and if classified from the bone nucleus, a phenol-based antioxidant, a phosphorus-based antioxidant, and a lactone-based antioxidant can be mentioned. Specifically, as a phenolic antioxidant, n-octadecyl-3 (3 ′, 5 ′)
-Di-t-butyl 4'hydroxyphenyl) propionate, 2,6 di-t-butyl 4-methylphenol, 2,
6-di-t-butyl-p-cresol, 2,2'-methylenebis (4-methyl-6-t-butylphenol),
4,4'-thiobis (3-methyl 6-t-butylphenol), 4,4'-butylidene bis (3-methyl-6-
t-butylphenol), stearyl-β (3,5-di-4-butyl4-hydroxyphenyl) propionate, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, octadecyl-
3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, tetrakis [methylene-3
(3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane and the like, and phosphorus-based antioxidants include triisodecyl phosphite, tris (nonylphenyl) phosphite, and tris. (Monononylphenyl) phosphite, tris (dinonylphenyl)
Phosphite, 4,4′-butylidene-bis (3-methyl6-t-butylphenyl-di-tridecyl) phosphite, cyclic neopentanetetraylbis (octadecylphosphite), cyclic neopentanetetraylbis ( 2,4-di-t-butylphenylphosphite), cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenylphosphite), 2,2-methylenebis (4,6-) Di-t-butylphenyl) octyl phosphite and the like are listed, and as the lactone-based antioxidant, 5,7-di-t-butyl-3- (3,4-dimethylphenyl) -3H-benzofuran-2- On and the like. The antioxidant in the present invention is 1,3,5-trimethyl-2,4,6-tris.
(3,5-di-t-butyl-4-hydroxybenzyl)
Benzene and tris (2,4-di-t-butylphenyl)
) Phosphite) or 5,7-di-t-butyl-
3- (3,4 dimethylphenyl) -3H-benzofuran
2-on).

In the present invention, as the antioxidant, 1, 3,
5-trimethyl-2,4,6-tris (3,5-di-t
-Butyl-4-hydroxybenzyl) benzene and tri-
Sus (2,4-di-t-butylphenyl) phosphite
Or 5,7-di-t-butyl-3- (3,4 dimethyl)
Tylphenyl) -3H-benzofuran-2-one) with
Even better due to synergistic effect by using the mixture
It can exert an antioxidant function.

The content of the antioxidant in the deoxidizing resin composition is preferably 10 to 20,000 ppm (weight),
100 to 20000 ppm is more preferable. Also when the antioxidant is composed of two or more kinds, the total content of the antioxidant is preferably 10 to 20000 ppm, more preferably 100 to 20000 ppm. By setting the content within this range, the deterioration of the polyolefin due to the oxygen scavenger composition is suppressed, and the generation of offensive odor is reduced. If it is less than 10 ppm, the effect on the deterioration of the polyolefin is hardly exerted, and 20000 ppm
If there is more, the interlayer adhesion strength and hygiene when made into a multilayer body,
There is a cost problem.

As a method for adding the antioxidant in the production of the deoxidizing resin composition, conventionally known methods such as dry blending and side feeding can be used. It can also be added in advance in the production process of polyolefin.

In the deoxidizing resin composition of the present invention, if necessary, a coloring agent such as an organic dye or an inorganic dye, a pigment or the like, a dispersant such as a silane or titanate or a water absorbing agent such as a polyacrylic acid compound or the like. It is also possible to add agents, clay, mica, silica, alumina, calcium sulfate, barium sulfate, calcium carbonate, calcium oxide, fillers such as starch, zeolite, activated carbon, deodorant and the like.

The oxygen scavenging resin composition of the present invention is stored in a bag having gas barrier properties together with articles such as foods, beverages and pharmaceuticals in the same manner as the conventional pouch-shaped oxygen scavenger, and is then stored in a bag. It absorbs oxygen in the interior, prevents oxidative deterioration of stored items, and enables long-term storage. When using the oxygen scavenger resin composition of the present invention, it is preferable to use it as an oxygen scavenging sheet or oxygen scavenging film obtained by molding it into a sheet or film and then cutting it into an appropriate size.
Since the oxygen scavenger or the oxygen scavenging film of the present invention has the oxygen scavenger dispersed in the resin, the oxygen scavenger, which has been a problem in the conventional pouch-shaped oxygen scavenger, does not spill. When it is feared that the stored material is contaminated by the oxygen scavenger contained in the resin, the molded product of the oxygen scavenger resin composition of the present invention may be stored in a highly breathable pouch or used. It may be used by being attached to the inside of a lid, a container, a bag, etc., and covered with a highly air-permeable isolation film.

Further, a sheet-shaped or film-shaped deoxidizing multilayer body in which a breathable isolation layer is arranged inside the oxygen absorbing resin layer made of the oxygen scavenger resin composition is manufactured by various molding methods, and this is used. Tray, cup, case, bottle,
It is also possible to form a multilayer package such as a tube, a top film or a bag. Furthermore, if a gas barrier layer is provided on the outer layer side of the above-mentioned multilayer body, a higher performance deoxidizing multilayer body can be obtained, and it becomes possible to store the preserved object for a long period of time. The oxygen scavenger resin composition of the present invention is not limited to these use examples, and can be used in various forms as a material for preventing oxidative deterioration of articles.

[0024]

The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In Examples and Comparative Examples,
The following materials were used. (1) Polyethylene; manufactured by Nippon Polychem Co., Ltd., trade name:
Novatec LD-LC720 (2) Phenolic antioxidant A; Asahi Denka Co., Ltd.
Product name: ADEKA STAB A0-50 (Chemical name: n-octadecyl-β- (4′-hydroxy-3 ′, 5′-di-
t-butylphenyl) propionate) (3) Phenolic antioxidant B; manufactured by Nippon Ciba Geigy Ltd., trade name: Irganox 1330 (chemical name:
1,3,5-Trimethyl-2,4,6-tris (3,5
-Di-t-butyl-4-hydroxybenzyl) benzene) (4) Phosphorus antioxidant A; manufactured by Asahi Denka Co., Ltd., trade name: ADEKA STAB PEP-36 (chemical name: cyclic neopentanetetraylbis) (2,6-di-t-butyl-4-methylphenylphosphite)) (5) Phosphorus antioxidant B; Nippon Ciba Geigy Co., Ltd.
Product name: Irgafos168 (Chemical name: tris (2,4-di-t-butylphenyl) phosphite) (6) Lactone-based antioxidant; Retec, USA, trade name: HP-136 (Chemical name: 5,7-di-t-butyl-3- (3,4dimethylphenyl) -3H-benzofuran-2-one)

Reference Example 1 Reduced iron powder having an average particle size of 35 μm was placed in a vacuum mixing dryer with a heating jacket, and dried under heating at 130 ° C. under a reduced pressure of 10 mmHg, while 100 parts by weight of iron powder was mixed with calcium chloride. : Sodium chloride: Water = 1: 1: 5 (parts by weight)
The mixed aqueous solution mixed in the ratio of was sprayed to obtain a granular oxygen scavenger composition in which calcium chloride and sodium chloride were attached to the surface of the iron powder.

Next, the oxygen scavenger composition 40 obtained above.
35 parts by weight and 35 ppm of phenolic antioxidant A in advance
Dry blend 60 parts by weight of kneaded polyethylene,
Extruder was extruded at a resin temperature of 230 ° C. with a 45 mmφ co-rotating twin-screw extruder, cooled with a net belt with a blower, and then passed through a pelletizer to obtain an oxygen absorber blended pellet 1. The concentration of antioxidant in the obtained oxygen absorber-containing pellet 1 was 21 ppm.

Reference Example 2 40 parts by weight of the oxygen scavenger composition obtained in Reference Example 1 and 60 parts by weight of polyethylene in which 200 ppm of the phenolic antioxidant A was previously kneaded were dry blended, and the same method as in Reference Example 1 was performed. Then, the oxygen absorber blended pellet 2 was obtained. The concentration of the antioxidant in the obtained oxygen absorber blended pellet 2 was 120.
It was ppm.

Reference Example 3 40 parts by weight of the oxygen absorber composition obtained in Reference Example 1 and 60 parts by weight of polyethylene in which 100 ppm of the phenolic antioxidant A and 100 ppm of the phosphorus antioxidant A were kneaded in advance were dry blended. Then, in the same manner as in Reference Example 1, oxygen absorber-containing pellets 3 were obtained. The concentration of antioxidants in the obtained oxygen absorber blended pellets 3 was 120 ppm in total.

Comparative Example 1 40 parts by weight of the oxygen scavenger composition obtained in Reference Example 1 and 60 parts by weight of polyethylene to which no antioxidant was added were dry blended, and in the same manner as in Reference Example 1, Oxygen absorber-containing pellet 4 was obtained.

Reference Example 4 Extruder, feed block, T-die, cooling roll,
In a film manufacturing apparatus including a film take-up machine, an aluminum foil laminated film having a structure of polyethylene terephthalate (PET) / aluminum foil / polyethylene (PE) and a film made of PE are unwound, and the extruding machine is used in Reference Example 1 The oxygen absorbing compound-containing pellet 1 thus obtained was extrusion-laminated between the two types of films to obtain an oxygen absorbing multilayer film 1. This deoxidizing multilayer film 1 is composed of PET (12 μm) / aluminum foil (9 μm) / PE (20 μm) / oxygen absorbing resin layer (50
μm) / PE (40 μm). () Shows the film thickness of each layer.

Next, the PE of the deoxidizing multilayer film 1
Three-sided seal deoxidizing bag (inside dimension; length 23)
0 mm × width 170 mm) was produced. Into this three-sided seal deoxidizing bag, 200 g of rice cake was stored and heat-sealed so that the air amount in the bag was about 100 cc and sealed.
Store this in a room at 25 ℃ for 1 month, the oxygen concentration in the bag,
The appearance of Kakuri Mochi and the odor when the bag was opened were investigated. The results are shown in Table 1.

Reference Example 5 PET (12 μm) was prepared in the same manner as in Reference Example 4 except that the oxygen absorber blended pellet 2 obtained in Reference Example 2 was used.
/ Aluminum foil (9 μm) / PE (20 μm) / Oxygen absorbing resin layer (50 μm) / PE (40 μm) The oxygen concentration in the bag, the appearance of the cut rice cake, and the odor when the bag was opened were investigated. The results are shown in Table 1.

Reference Example 6 PET (12 μm) was prepared in the same manner as in Reference Example 4 except that the oxygen absorber-containing pellet 3 obtained in Reference Example 3 was used.
/ Aluminum foil (9 μm) / PE (20 μm) / Oxygen absorbing resin layer (50 μm) / PE (40 μm) The oxygen concentration in the bag, the appearance of the cut rice cake, and the odor when the bag was opened were investigated. The results are shown in Table 1.

Comparative Example 2 PET (12 μm) / Aluminum foil (9 μm) / PE (40
(3 μm) with the PE side of the multi-layer film having the configuration inside as a three-sided seal bag (internal size; length 230 mm × width 170 m)
m) was prepared, and a storage test of the cut rice cake was carried out in the same manner as in Reference Example 4, and the oxygen concentration in the bag after 1 month storage, the appearance of the cut rice cake, and the odor when the bag was opened were examined. The results are shown in Table 1.

Comparative Example 3 PET (12 μm) was prepared in the same manner as in Reference Example 4, except that the oxygen absorber blended pellet 4 obtained in Comparative Example 1 was used.
/ Aluminum foil (9 μm) / PE (20 μm) / oxygen absorbing resin layer (50 μm) / PE (40 μm) The oxygen concentration in the bag, the appearance of the cut rice cake, and the odor when the bag was opened were investigated. The results are shown in Table 1.

[0036]

[Table 1]

As is clear from these Reference Examples and Comparative Examples, the oxygen absorbing multilayer composition having oxygen absorbing resin layers formed of oxygen absorbing resin-containing pellets containing an appropriate amount of antioxidant added to the oxygen absorbing resin composition. I used a packaging bag made of film
In Reference Example 4 to Reference Example 6, since the oxygen in the bag is absorbed, the sliced rice cake is excellent in storability, and deterioration of polyethylene is suppressed during extrusion lamination of the oxygen absorbing resin layer, the oxygen-absorbing multilayer film. No offensive odor was generated. In Comparative Example 2 in which a packaging bag having no oxygen-absorbing resin layer was used, mold was generated on the cut rice cake, and a rotten smell was generated when the bag was opened. In Comparative Example 3 antioxidant deoxidizer compounded pellets constituting the oxygen absorbing resin layer is not added, to absorb oxygen likewise the bag as in Reference Example 4 to Example 6, the appearance of the corners rice cake is Although it was good, the polyethylene constituting the pellets mixed with the oxygen scavenger deteriorated during the production of the oxygen scavenging multilayer film, so that a resin odor was generated from the packaging bag and the flavor of the cut rice cake was deteriorated.

Example 1 40 parts by weight of the oxygen scavenger composition obtained in Reference Example 1 and propylene-ethylene random copolymer (PP) 60, which was previously kneaded with 500 ppm of phenol antioxidant B and 500 ppm of phosphorus antioxidant B. By dry blending with parts by weight, an oxygen absorber blending pellet 5 was obtained in the same manner as in Reference Example 1. The concentration of antioxidant in the obtained oxygen absorber blended pellets 5 was 600 ppm in total.

[0039] Example 2 and oxygen absorbing composition 40 parts by weight obtained in Reference Example 1, PP60 parts by weight of a previously phenolic antioxidant B500ppm and lactone-based antioxidant 500ppm kneaded by dry blending, or less, by reference By the same method as in Example 1, an oxygen absorber-containing pellet 6 was obtained. The total concentration of the antioxidant in the obtained oxygen scavenger-containing pellet 6 was 600 ppm.

Example 3 In a film production apparatus comprising an extruder, a feed block, a T die, a cooling roll and a film take-up machine,
Unwinding unstretched polypropylene film (CPP),
White P with 10% by weight of titanium oxide added from the extruder
P is extruded and laminated to form a white PP layer, and subsequently the oxygen absorbing agent-containing pellet 5 obtained in Example 1 is extruded and laminated on the white PP layer to form an oxygen absorbing resin layer, and a stack of three layers is formed. Got the body Then, an oxygen absorbing multilayer film 5 was obtained by dry laminating the oxygen absorbing resin layer side of the laminate and the aluminum foil side of an aluminum foil laminated film having a PET / aluminum foil structure. This deoxidizing multilayer film 5 has a structure of PET (12 μm) / aluminum foil (9 μm) / oxygen absorbing resin layer (40 μm) / white PP (20 μm) / CPP (40 μm). () Shows the film thickness of each layer.

Next, the CP of the deoxidizing multilayer film 5
Three sided seal deoxidizing bag with P side as the inside (inside dimension; length 2)
30 mm × width 170 mm) was produced. 250 g of porridge was stored in this three-way seal deoxidizing bag and heat-sealed so that the amount of air in the bag was about 10 cc. After heat-sterilizing this for 30 minutes at 120 ° C,
It was stored in a room at 25 ° C for one month, and the oxygen concentration in the bag, the odor when the bag was opened, and the appearance of porridge were examined. The results are shown in Table 2.

Example 4 PET (12 μm) was obtained in the same manner as in Example 3 except that the oxygen absorber-containing pellet 6 obtained in Example 2 was used.
/ Aluminum foil (9 μm) / Oxygen absorbing resin layer (40 μm) /
A deoxidizing multilayer film 6 having a structure of white PP (20 μm) / CPP (40 μm) was obtained, a deoxidizing bag was manufactured, a storage test of porridge was performed, and the oxygen concentration in the bag after storage for 1 month, The odor when the bag was opened and the appearance of the porridge were investigated. The results are shown in Table 2.

[0043]

[Table 2]

[0044]

EFFECTS OF THE INVENTION The deoxidizing resin composition of the present invention suppresses the deterioration of the polyolefin resin during processing and storage, which is a problem in the conventional example, and thus prevents the generation of offensive odors and the reduction in strength. It is possible to improve the production stability and quality. In addition, a deoxygenating sheet using this deoxidizing resin composition, a deoxidizing film and a packaging comprising the deoxidizing multilayer body, not only suppress the generation of offensive odor, but also a conventional sachet-shaped deoxidizing agent. It is extremely useful because there is no sense of foreign matter, which is a problem in the case of using, and there is no contamination of stored articles due to spilling of the oxygen scavenger.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI B32B 27/32 B32B 27/32 Z B65D 81/26 B65D 81/26 C08K 3/08 C08K 3/08 5/13 5/13 5 / 49 5/49 C08L 23/00 C08L 23/00 (56) Reference JP-A-9-268235 (JP, A) JP-A-9-227730 (JP, A) JP-B-56-25934 (JP, B1) ) (58) Fields surveyed (Int.Cl. ⁷ , DB name) B32B 1/00-35/00 C08L 1/00-101/16 C08K 1/00-13/08

Claims (6)

(57) [Claims] 1. A breathable separator made of a thermoplastic resin in order.
Layer, oxygen-absorbing resin layer and gas barrier layer
The oxygen absorbing resin layer is composed of iron powder and a metal halide, and the oxygen absorber is 10 to 80% by weight, the polyolefin is 20 to 90% by weight, and 1,3 as an antioxidant. , 5-trimethy
Ru-2,4,6-tris (3,5-di-t-butyl-4)
-Hydroxybenzyl) benzene and tris (2,4-
Di-t-butylphenyl) phosphite or 5,7
-Di-t-butyl-3- (3,4 dimethylphenyl)-
3H-benzofuran-2-one) Mixture 10-20
Food additive which is a deoxidizing resin composition consisting of 000 ppm
Deoxidizing multilayer body for heat. 2. The content of the antioxidant is 100 to 2000.
It is 0 ppm, and the deoxidizing multilayer for food heating according to claim 1.
body. 3. The deoxidizing multilayer body for food heating according to claim 1, wherein the oxygen absorber content is 20 to 60% by weight and the polyolefin content is 40 to 80% by weight . 4. A breathable separator made of a thermoplastic resin in order.
Layer, oxygen-absorbing resin layer and gas barrier layer
In the multilayer body having the above laminated structure, the oxygen absorbing resin layer is made of iron powder and a metal halide.
Oxygen agent 10-80% by weight, polyolefin 20-90%
%, And 1,3,5-trimethy as an antioxidant
Ru-2,4,6-tris (3,5-di-t-butyl-4)
-Hydroxybenzyl) benzene and tris (2,4-
Di-t-butylphenyl) phosphite or 5,7
-Di-t-butyl-3- (3,4 dimethylphenyl)-
3H-benzofuran-2-one) Mixture 10-20
Food additive which is a deoxidizing resin composition consisting of 000 ppm
A method for heating and storing porridge using a thermal deoxidizing multilayer body . 5. The antioxidant content is 100 to 2000.
The method for heating and storing porridge according to claim 4, wherein the porridge content is 0 ppm. 6. An oxygen absorber content of 20 to 60% by weight,
The content of the re-olefin is 40 to 80% by weight.
4. The method for heating and storing porridge according to 4.