JP2000062102A - Deoxidizing multilayer body of paper base material and paper container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To shut off a penetrating oxygen from outside a container and enable oxygen in the space of the container and a dissolved oxygen in an article to be removed by laminating a paper base material layer, a gas barrier layer, an oxygen absorbing resin layer consisting of a deoxidizing agent dispersed in a thermoplastic resin and an oxygen-permeable resin layer laminated in that order from the outer face side. SOLUTION: A paper base material layer, a gas barrier layer, an oxygen absorbing resin layer consisting of a deoxidizing agent dispersed in a thermoplastic resin and an oxygen- permeable resin layer are laminated in that order to form a deoxidizing multilayer body of a paper base material. In addition, the container is formed in such a manner that the oxygen-permeable resin layer becomes the inside of the container, using steps to process the end face, bond a barrel part and form a bottom part and a top part, e.g. a hemming process or the like that the bonded part of the barrel part is folded to the outside so as to keep the end face of the deoxidizing multilayer body from coming into contact with the content. The container is used as a packaging material for foods, medical supplies or the like, and the residual oxygen contained in the space part of the container or its stored article permeates through the oxygen-permeable resin layer and is absorbed by the deoxidizing agent in the thermoplastic resin. On the other hand, oxygen outside the container is shut off by the gas barrier layer to keep a low oxygen concentration level internally for a long time and thereby the qualitative deterioration of the article is prevented from occurring.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a paper base multilayer body having a deoxidizing function and a packaging paper container made of the same.
More specifically, the present invention relates to a paper base multilayer body that enables long-term storage of various foods, pharmaceuticals, cosmetics, and the like, and a paper base container made of the same.

[0002]

2. Description of the Related Art Conventionally, various packaging materials based on paper have been developed for filling and storing various foods, pharmaceuticals and the like. Specifically, for example, as shown in (1), a thermoplastic resin and a paper base material, and as shown in (2), an aluminum foil, an inorganic oxide vapor deposition film, or a thermoplastic resin having gas barrier properties. Examples thereof include those in which a gas barrier layer composed of the above is laminated as an intermediate layer, and those in which an oxygen absorbing layer whose both surfaces are coated with a thermoplastic resin as shown in (3) are laminated on a paper substrate. (1) Thermoplastic resin layer / paper base material layer / thermoplastic resin layer (2) Thermoplastic resin layer / paper base material layer / gas barrier layer / thermoplastic resin layer (3) Thermoplastic resin layer / paper base material layer / Thermoplastic resin layer / oxygen absorbing layer / thermoplastic resin layer

[0003]

However, among the above packaging materials, the one (1) has a remarkably poor gas barrier property for preventing the permeation of oxygen into the inside of the container, and therefore the article filled in the paper container is made of oxygen. There are drawbacks in that the deterioration of quality easily progresses and the storage stability of the stored article is greatly deteriorated. Further, in (2), since oxygen permeation into the container is greatly reduced by the gas barrier layer, the storage stability of the stored article is superior to (1), but oxygen in the space inside the container, Since it is not possible to remove the dissolved oxygen in the filled articles, it is difficult to completely prevent the oxidative deterioration of the stored articles. Further, the product (3) has excellent storage stability of the stored product as compared with the product (1), but the function of the oxygen absorption layer is deteriorated by the oxygen penetrating through the thermoplastic resin layer from the outside, so that the product is stored. Not suitable for long-term storage of goods.

[0004]

SUMMARY OF THE INVENTION In view of the above problems of the prior art, the inventors of the present invention have earnestly studied a paper-based packaging material which is more excellent in preservability of stored articles than before. As a result, by applying a paper container formed from a paper base multilayer body in which a gas barrier layer is laminated on a paper base material, and a thermoplastic resin layer formed by dispersing an oxygen absorber on the gas barrier layer is further laminated. In addition, it is possible to block the oxygen that enters from the outside of the container and remove the dissolved oxygen in the space inside the container and in the product, and to maintain the quality of the product stored in the container for a long period of time. I found it.

That is, according to the present invention, a paper base material layer, a gas barrier layer, an oxygen absorbing resin layer in which a deoxidizer is dispersed in a thermoplastic resin, and an oxygen permeable resin layer are laminated in this order from the outer surface side. The present invention relates to a paper-based deoxidizing multilayer body. The present invention also relates to a deoxidizing paper container comprising the paper-based deoxidizing multilayer body according to claim 1 in at least a part of the packaging container.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention is described in detail below.
The paper substrate deoxidizing multilayer body of the present invention has at least four layers of a paper substrate layer, a gas barrier layer, an oxygen absorbing resin layer formed by dispersing an oxygen absorber in a thermoplastic resin, and an oxygen permeable resin layer. These are laminated in this order. When manufacturing a paper container from this paper-based deoxidizing multilayer body, the process of punching out the paper container in the expanded state, the process of making a ruled line, the adhesive part of the body part so that the contents and the end face of the multilayer body do not contact Oxygen permeation of normal container manufacturing processes such as end face treatment processes such as hemming method that bends the outside to the outside, skive hemming method, fin seal method, tape sticking method, body body bonding step, bottom and head molding step, etc. The target paper container can be obtained by performing the process so that the conductive resin layer is inside the container. In particular, the end face treatment step is preferably performed because it is possible to prevent contact between the oxygen absorbing resin layer in which the oxygen absorber is dispersed and the contents. If necessary, a one-piece type or two-piece type spout or the like can be attached to the paper container of the present invention. By using the paper container thus obtained as a packaging material for foods, pharmaceuticals, etc., oxygen remaining in the space inside the container and the stored articles permeates the oxygen permeable layer resin layer, and the thermoplastic resin It is absorbed by the oxygen scavenger dispersed inside, and the oxygen outside the container is blocked by the gas barrier layer, so the inside of the container is kept at a low oxygen concentration for a long time, and the quality of the stored items deteriorates for a long time. Can be prevented.

The oxygen-permeable resin layer in the deoxidizing multilayer body for forming a paper container of the present invention functions as an isolation layer for separating the contents from the oxygen-absorbing resin layer, and as a heat-sealing layer when forming a container. The oxygen absorber in the oxygen-absorbing resin layer has a role of absorbing oxygen and efficiently transmitting oxygen. The material forming the oxygen-permeable resin layer in the paper-based deoxidizing multilayer body of the present invention is not particularly limited, and various thermoplastic resins can be used, but the layer is in direct contact with the contents such as foods. Therefore, polyolefins excellent in hygiene and versatility are preferably used alone or as a mixture of two or more kinds. Examples of the polyolefins include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, various polyethylenes exemplified by polyethylene with a metallocene catalyst, polypropylene homopolymer, propylene-ethylene block copolymer, propylene. -Various polypropylenes exemplified as the ethylene random copolymer, polymethylpentene, ethylene-vinyl acetate copolymer, ethylene-α olefin copolymer, ionomer resin and the like can be mentioned. Among these, a system containing various polyethylene as a main component is particularly preferably used from the viewpoint of handleability. Also, if necessary, this oxygen-permeable resin layer,
Thermoplastic resins other than polyolefins such as thermoplastic elastomers, pigments such as titanium oxide and carbon black, antioxidants, slip agents, fillers, ultraviolet absorbers, adsorbents, other additives may be added, Further, the oxygen-permeable resin layer may be a single layer or multiple layers made of the above resins.

The film thickness of the oxygen permeable resin layer in the paper-based deoxidizing multilayer body of the present invention is preferably in the range of 10 to 200 μm, irrespective of the type of resin constituting the layer and the number of layers. It is preferably in the range of 20 to 150 μm. When the film thickness of the oxygen permeable resin layer is less than 10 μm, the heat seal strength may be reduced, and the strength of the paper container may be reduced. On the other hand, if it is thicker than 200 μm, the oxygen permeability may be lowered, and the oxygen absorbing resin layer may not be able to absorb oxygen efficiently.

The oxygen permeability of the oxygen permeable resin layer in the paper-based deoxidizing multilayer body of the present invention at 25 ° C. is 400 cc / m ² · atm regardless of the number of layers, the film thickness, and the constituent material.
・ Day or more is preferable, and 5 is particularly preferable.
It is more than 00cc / m ² · atm · day. Oxygen permeability of the oxygen permeable resin layer is 400 cc / m ² · atm · d
When it is lower than ay, the rate is limited to the oxygen absorption performed by the oxygen absorber in the oxygen-absorbing resin layer, and the oxygen absorption rate of the packaging container decreases, which is not preferable.

The oxygen-absorbing resin layer in the paper-based deoxidizing multilayer body of the present invention comprises a deoxidizing agent dispersed in a thermoplastic resin. The deoxidizing agent and the thermoplastic resin are melt-kneaded. Is formed by extruding a compound prepared in advance in a film form from an extruder, in the present invention, the role of absorbing oxygen dissolved in the container, or in the food, also absorbs a small amount of oxygen invading from the outside of the container. Has a role of preventing oxygen permeation into the container. The compound for forming the oxygen-absorbing resin layer can be produced by a conventionally known method, for example, a method of melt-kneading with an extruder, extruding from a strand die, and then pelletizing through a cooling step.

The oxygen scavenger used in the present invention can be used without limitation as long as it can cause an oxygen absorption reaction and can be dispersed in a thermoplastic resin. An oxygen scavenger composed of a combination of an oxidizable main agent and an auxiliary agent is preferably used.
As the main ingredient, metal powder, sulfite, dithionite, catechol, gallic acid, polyhydric alcohol, ascorbic acid ester and the like are used, and among them, metal powder is preferable, and iron powder is particularly preferable. As the auxiliary agent, a chemical substance that accelerates the oxygen absorption reaction of the main agent, such as a metal halide or an alkaline agent, is used.

As the iron powder as the main component, any iron powder capable of causing an oxygen absorption reaction can be used without any particular limitation on the purity and the like. For example, a part of the surface may be already oxidized, and other iron powders may be used. It may contain a metal. Also,
The iron powder is preferably granular, and examples thereof include reduced iron powder, atomized iron powder, iron powder such as electrolytic iron powder, and crushed products of various irons such as cast iron and steel and grinding products. The average particle size thereof may be in the range of 1 to 150 μm in consideration of handleability, thinning of the oxygen-absorbing resin layer, and prevention of unevenness of the oxygen absorber appearing on the container appearance as much as possible. Preferably
It is particularly preferable that the thickness is in the range of 1 to 100 μm.

In the case of an oxygen scavenger containing iron powder as the main agent, the metal halide as an auxiliary agent acts catalytically on the oxygen absorption reaction of the main agent. As the metal halide, for example,
Alkali metal or alkaline earth metal chlorides, bromides,
Iodide is used, and chlorides or iodides of lithium, sodium, potassium, magnesium, calcium, or barium are preferably used. The metal halide content is preferably 0.1 to 20 parts by weight, and particularly preferably 0.1 to 5 parts by weight, per 100 parts by weight of iron powder.

The metal halide is used together with the iron powder as an essential component of the oxygen scavenger containing iron powder as a main component, but it is preferable to add it in advance so as not to adhere to the iron powder and separate easily. For example, a method of mixing the metal halide and the iron powder using a ball mill, a speed mill, etc., a method of embedding the metal halide in the uneven portion of the iron powder surface, a method of attaching the metal halide to the iron powder surface using a binder. ,
A method of adhering the metal halide to the surface of the iron powder by mixing the aqueous metal halide solution and the iron powder and then drying the mixture can be employed. A preferred oxygen absorber is an iron powder-based composition containing iron powder and a metal halide, and particularly preferably a metal halide-coated iron powder composition in which a metal halide is attached to iron powder.

If necessary, the oxygen scavenger used in the present invention may be an alkaline earth metal oxide, a silane or titanate dispersant, a filler such as clay, mica, silica or calcium carbonate, activated carbon, An adsorbent such as zeolite can be added.

As the thermoplastic resin constituting the oxygen-absorbing resin layer in the paper-based deoxidizing multilayer body of the present invention, various thermoplastic resins can be used without particular limitation. Polyolefins and adhesive resins, which are versatile and have excellent adhesiveness to the oxygen permeable resin layer, are preferably used alone or as a mixture. Examples of the polyolefins include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, various polyethylenes exemplified by polyethylene with a metallocene catalyst, polypropylene homopolymer, propylene-ethylene block copolymer, propylene. -Various polypropylenes exemplified as the ethylene random copolymer,
Polymethylpentene, ethylene-vinyl acetate copolymer,
An ethylene-alpha olefin copolymer is mentioned.

Examples of the adhesive resin include acid-modified polyolefins obtained by modifying an olefin resin with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid and maleic anhydride. Among these, a system containing various polyethylene as a main component is particularly preferably used from the viewpoint of handleability. Further, in the oxygen-absorbing resin layer, if necessary, a thermoplastic resin other than the above, such as a thermoplastic elastomer, a pigment such as titanium oxide or carbon black, an alkaline earth metal oxide, an antioxidant, a slip agent, and a filling agent. Agents, ultraviolet absorbers, adsorbents, and other additives may be added.

The oxygen absorber concentration in the oxygen-absorbing resin layer in the present invention is preferably in the range of 10 to 70% by weight, more preferably 10 to 60% by weight. When the concentration of the oxygen scavenger is lower than 10% by weight, the oxygen absorption performance is low, so that sufficient storage stability of the content may not be exhibited. On the other hand, if it is more than 70% by weight, the workability is deteriorated and it becomes difficult to form an oxygen-absorbing resin layer having a uniform film thickness, or the weight per container becomes heavy, which causes inconvenience in handling. There are cases.

The film thickness of the oxygen-absorbing resin layer is preferably set within a range not exceeding the particle size of the oxygen scavenger dispersed in the thermoplastic resin, specifically 10 to 400 μm, more preferably 10 μm. Is about 200 μm. When the film thickness of the oxygen-absorbing resin layer is thinner than 10 μm, the oxygen absorber is likely to be exposed on the surface of the oxygen-permeable resin layer, and unevenness due to the oxygen absorber is likely to occur on the surface of the oxygen-permeable resin layer or the outermost layer. Become. If it is thicker than 400 μm, the workability is deteriorated and the cost is increased, which is not preferable.

The paper base material layer in the paper base material deoxidizing multilayer body of the present invention serves as a base material layer constituting a container, and has moldability, flex resistance, rigidity, stiffness, strength and the like. It is something that makes you. The paper base material that can be used is not particularly limited as long as it is obtained by paper-making a natural fiber, a synthetic fiber or a mixture thereof, and the natural fiber used for paper-making includes, for example, softwood pulp and hardwood pulp. Wood fiber, cotton yarn, sugar cane, vegetable fiber made from pulp of bamboo, wool,
Examples include animal fibers such as silk thread. Examples of synthetic fibers include polyethylene, polypropylene, polyester, polyamide, and cellulose acetate. In the present invention, the above paper base material may be printed with a desired pattern such as characters, figures, symbols, patterns, patterns, and the like.

The gas barrier layer in the deoxidizing multilayer body for forming a paper container of the present invention has a role of blocking oxygen invading from the outside of the container when the multilayer body of the present invention is used as a container. Materials for forming the gas barrier layer include metal foil such as aluminum foil, polyvinylidene chloride, saponified ethylene-vinyl acetate copolymer, nylon 6, nylon 66, MX nylon, polyamide such as amorphous nylon, polyethylene terephthalate, etc. Inorganic oxide vapor-deposited films such as polyester and aluminum vapor-deposited films and silica vapor-deposited films can be used alone or in combination, and the oxygen permeability thereof is preferably as small as processability and cost allow. 100 cc / m ² regardless of thickness
・ Atm · day (25 ° C., 100% RH) or less is necessary, and more preferably 50 cc / m ² · a
It is below tm · day (25 ° C., 100% RH). By doing so, when a paper container is produced using the paper container-forming deoxidizing multilayer body according to the present invention, it is possible to reduce the amount of oxygen entering from the outside of the packaging container, and The storability can be improved.

The paper-based deoxidizing multilayer body of the present invention preferably has an outermost layer laminated as necessary. Various thermoplastic resins can be used as the material forming the outermost layer, but since they may play a role as an adhesive layer in the case of packaging as a packaging paper container, they may be melted together with the oxygen permeable resin layer. It is preferred to use a thermoplastic resin that can be worn. Specifically, for example, low density polyethylene, linear low density polyethylene, medium density polyethylene,
High density polyethylene, various polyethylene exemplified by polyethylene with metallocene catalyst, polypropylene homopolymer, propylene-ethylene block copolymer, various polypropylene exemplified by propylene-ethylene random copolymer, polymethylpentene, ethylene-vinyl acetate copolymer Examples thereof include polymers and polyolefins such as ethylene-α olefin copolymers.

Among these, a system containing various polyethylene as a main component is particularly preferably used from the viewpoint of handleability.
Further, in the oxygen-permeable resin layer, if necessary, thermoplastic resins other than polyolefins such as thermoplastic elastomers, pigments such as titanium oxide and carbon black, antioxidants, slip agents, fillers, ultraviolet absorbers, Other additives may be added, and the oxygen-permeable resin layer may be a single layer or multiple layers made of the above resins. In the present invention, the surface of the resin layer forming the outermost layer as described above may be provided with a desired print pattern such as letters, figures, symbols, pictures, patterns, and the like.

The method for producing the paper-based deoxidizing multilayer body according to the present invention is a conventional laminating method, for example, a wet lamination method, a dry lamination method, a solventless dry lamination method, an extrusion lamination method, a coextrusion lamination method. , And other known methods. Further, in the present invention, when performing the above-mentioned lamination, if necessary, for example, a pretreatment such as corona treatment, plasma treatment, ozone treatment can be performed on the paper or the thermoplastic resin layer, and, for example, , Urethane-based, polyethyleneimine-based, polybutadiene-based, organic titanium-based anchor coating agents, or polyurethane-based, polyacrylic-based, polyester-based, epoxy-based, polyvinyl acetate-based, cellulose-based, etc. known anchor coating agents, adhesion Agents and the like can be used.

In the present invention, when laminating the gas barrier layer and the paper substrate, for example, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, ethylene-
Vinyl acetate copolymer, ionomer resin, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-extruded polyolefins such as methyl methacrylate copolymer, Alternatively, the olefin resin can be laminated using an adhesive resin such as an acid-modified polyolefin modified with an unsaturated carboxylic acid such as acrylic acid, methacrylic acid, maleic acid or maleic anhydride.

The paper-based deoxidizing multilayer body of the present invention has an oxygen-permeable resin layer side as an inner surface depending on its purpose, use, etc.
It can be used as a paper container of various forms, for example, a container for liquid packaging having a shape such as a Gobel top, a brick type, a cube, a tetrahedron, etc., other cup-shaped containers, pouch-shaped containers, etc. Not limited to the above example, the paper-based deoxidizing multilayer body of the present invention can be used by molding it into packaging containers of various shapes.

Note that these wrapping paper containers include, for example,
Liquid drinks such as milk, juice, sake, whiskey, shochu, coffee, tea, jelly drinks, health drinks, seasoning liquids,
Sauce, soy sauce, dressing, liquid soup, mayonnaise,
Miso, seasonings such as grated spices, pasty foods such as jams, creams, chocolate pastes, liquid foods such as liquid processed foods such as liquid soups, stews, pickles, stews, soba, udon, ramen, etc. Of raw noodles and boiled noodles, polished rice, moisture-conditioned rice, unwashed rice, etc., cooked cooked rice, gome rice, red rice, porridge and other processed rice products, powdered soup, soup stock, etc. High-moisture foods such as powder seasonings, other solid or solution chemicals such as pesticides and insecticides, liquid and paste medicines, lotions, cosmetic creams, lotions, hair dressings, hair dyes ,shampoo,
Various items such as soap and detergent can be stored, oxygen does not enter from the outside of the container, and oxygen inside the container is absorbed by the oxygen scavenger, preventing oxidative corrosion of the items. It is possible to maintain good quality for a long period of time.

[0028]

EXAMPLES Examples of the present invention will be shown below. The invention is not limited to these examples. First, materials used in this example are shown. Example 1 40 parts by weight of a granular oxygen scavenger obtained by coating 3 parts by weight of calcium chloride with 100 parts by weight of reduced iron powder having an average particle size of 30 μm and low-density polyethylene (manufactured by Tosoh Corp., trade name: Petrosene 204, (Hereinafter abbreviated as LDPE) 60 parts by weight was dry blended, extruded with a 35 mm twin-screw extruder, cooled with a net belt with a blower, and passed through a pelletizer to obtain a deoxidizing compound.

Next, an extruder, a T-die, a cooling roll,
Using an extrusion laminator consisting of a corona processor and a take-up machine, one side of a paper having a basis weight of 400 g / m ² was subjected to corona treatment, and then LDPE (outermost layer, 30 μm) was applied to the corona surface.
m) was extruded and laminated, and the other surface of the above paper was subjected to corona treatment to produce a laminate having an outermost layer / paper structure.

Next, using a co-extruder comprising a first to a fifth extruder, a feed block, a T-die, a chill roll and a winder, the white pigment added LDPE (oxygen permeable resin layer) was fed from the first extruder. ), The deoxidizing compound (oxygen absorbing resin layer) from the second extruder, and the adhesive polyethylene (manufactured by Mitsubishi Chemical Corporation, trade name: Modic M503, adhesive resin layer A) from the third extruder. From the fourth extruder to a gas barrier polyamide (manufactured by Mitsubishi Gas Chemical Co., Inc., trade name: MX Nylon 600)
7, gas barrier layer) from the fifth extruder LDPE
(Adhesive resin layer B) is extruded, and the layer structure is from the inside surface of the container. Oxygen permeable resin layer / oxygen absorbing resin layer / adhesive resin layer A / gas barrier layer / adhesive resin layer A / adhesive resin A multilayer molten state is formed through a feed block so that the layers B are in order, and co-extrusion lamination is performed so that the adhesive resin layer B is laminated on the corona surface of the paper on which LDPE has been extruded and laminated in advance. A material deoxidizing multilayer body was obtained. The composition of the obtained paper-based deoxidizing multilayer body was such that an oxygen-permeable resin layer (50 μm) / oxygen-absorbing resin layer (50 μm) / adhesive resin layer A (10 μm) from the inside surface of the container.
m) / gas barrier layer (15 μm) / adhesive resin layer A (1
0 μm) / Adhesive resin layer B (20 μm) / Basis weight 400 g /
m ² of paper / outermost layer (30 μm).

Next, the laminated body is made into a sleeve shape through the steps of punching, ruled line, skive hemming method, and heat-sealing body section from the paper-based deoxidizing multilayer body, and then a molding and filling machine. Fill 1.5 liters of sake from the upper opening using, and fold the opening and heat seal to fill a Gabeltop type package (internal volume 1.
8 liters, dimensions: 8.5 cm x 8.5 cm x 25.7
cm) was manufactured. The packaged product was stored at 25 ° C. for 3 months, the oxygen concentration in the space inside the container was measured, the container was opened, and the flavor of sake was investigated. The results are shown in Table 1.

Comparative Example 1 Same as Example 1 except that the oxygen absorbing resin layer is not laminated.
In this way, a paper base multilayer body was obtained. Obtained paper-based multilayer body
The configuration of the oxygen permeable resin layer from the surface that is the inside of the container
(50 μm) / Adhesive resin layer A (10 μm) / Gas burr
A layer (15 μm) / adhesive resin layer A (10 μm) / adhesion
Resin layer B (20μ) / grammage 400g / m ²Paper / outermost
It was a layer (30 μm). Next, in the same manner as in Example 1,
Manufactures Gobeltop-type filled and packed products filled with sake
Stored at 25 ° C for 3 months, and oxygen concentration in the space inside the container
After measuring, open the container and check the flavor of sake.
It was The results are shown in Table 1.

Comparative Example 2 A paper-based deoxidizing multilayer body was obtained in the same manner as in Example 1 except that the gas barrier layer was not laminated. The composition of the obtained paper-based deoxidizing multilayer body is such that an oxygen-permeable resin layer (50 μm) / oxygen-absorbing resin layer (50 μm)
m) / adhesive resin layer A (10 μm) / adhesive resin layer A
(10 μm) / adhesive resin layer B (20 μ) / basis weight 400
It was g / m ² of paper / outermost layer (30 μm). Next, a Goebeltop-type filled package filled with sake was produced in the same manner as in Example 1, stored at 25 ° C. for 3 months, and the oxygen concentration in the space inside the container was measured, and then the container was opened. Then, I investigated the flavor of sake. The results are shown in Table 1.

Comparative Example 3 An extrusion laminator comprising an extruder, a T-die, a cooling roll, a corona treatment machine and a take-up machine was used and the basis weight was 4
After corona treatment on both sides of 00g / m ² paper, LDPE (50μm) is extruded on both sides and laminated.
A paper-based multilayer having a PE / paper / LDPE construction was produced. Next, in the same manner as in Example 1, a Goebeltop-type filled packaged product filled with sake was produced and kept at 25 ° C. for 3 months.
The container was opened, the container was opened, and the flavor of sake was investigated. The results are shown in Table 1.

[0035]

[Table 1] Oxygen concentration in container after 3 months (%) Flavor of sake Example 1 <0.1% Good Comparative Example 1 20% Flavor reduction Comparative Example 2 10% Slightly flavor reduction Comparative Example 3 21% Large flavor reduction

As is clear from these results, when a container formed of a paper-based deoxidizing multilayer body in which oxygen absorbing resin layers are laminated is used, oxygen in the container is absorbed by the oxygen scavenger. Therefore, oxidative deterioration of sake, which is the content, was prevented, and the original flavor was retained even after long-term storage.
On the other hand, in Comparative Example 1 in which the oxygen-absorbing resin layer is not laminated, although the oxygen that intrudes from the outside is blocked by the gas barrier layer, the sake, which is the content of the sake, is oxidatively deteriorated by the oxygen remaining in the container. Upon receiving it, the flavor deteriorated.

Further, in Comparative Example 2 in which the gas barrier layer is not laminated, the oxygen absorbing function compounded in the oxygen absorbing resin layer is gradually deteriorated by the oxygen invading from the outside and the oxygen absorbing function is deteriorated. The sake, which is a product, was subjected to oxidative deterioration and the flavor was slightly deteriorated. In Comparative Example 3 in which the oxygen-absorbing resin layer and the gas barrier layer were not laminated, the sake was oxidatively deteriorated by the oxygen remaining inside the container and the oxygen invading from the outside, and the flavor was greatly deteriorated.

Example 2 Extruder, T-die, chill roll, corona processor and puller
Use a tandem extrusion laminator consisting of a scraper
200 g / m2, corona treated on one side ²Paper
And 9 μm thick aluminum with corona treatment on both sides separately
LDPE extruded from T-die (30
(μm) is used for sand lamination, and then aluminum
LDPE (20μm) is extruded and laminated on the foil.
And has a structure of paper / LDPE / aluminum foil / LDPE
A multilayer body was produced.

Next, an oxygen absorbing compound is extruded and laminated on the LDPE of the multilayer body to laminate an oxygen absorbing resin layer, and a white LDP is further formed on the oxygen absorbing resin layer.
E was extruded and laminated to laminate an oxygen-permeable resin layer to produce a paper-based deoxidizing multilayer body. The composition of the obtained paper-based deoxidizing multi-layered body was as follows: paper having a basis weight of 200 g / m ² / LDPE (30 μm) / aluminum foil (9 μm) / LDPE (20 μm) / oxygen absorption Resin layer (30 μm) / oxygen permeable resin layer (50 μm). Next, from the paper-based deoxidizing multilayer body, the length is 17 cm and the width is 10 cm so that the oxygen-permeable resin layer is the inner surface.
A four-sided sealed bag (inner size) was produced. Next, chestnut yokan 1
00 g was sealed in a bag and stored at 25 ° C. for 3 months, the oxygen concentration in the space inside the bag was measured, the bag was opened, and the appearance and taste of chestnut yokan were examined. The results are shown in Table 2.

Comparative Example 4 A paper base multilayer body was produced in the same manner as in Example 2 except that the oxygen absorbing resin layer was not laminated. The composition of the obtained paper-based multi-layer body is 200 g / m ² basis weight paper / LDPE (3
0 μm) / Aluminum foil (9 μm) / LDPE (20 μm)
/ Oxygen permeable resin layer (50 μm). Next, in the same manner as in Example 2, a four-sided sealed bag in which chestnut yokan was enclosed was prepared, stored at 25 ° C. for 3 months, the oxygen concentration in the space inside the bag was measured, and then the bag was opened to make chestnut yokan. Was examined for appearance and taste. The results are shown in Table 2.

Comparative Example 5 A paper-based deoxidizing multilayer body was produced in the same manner as in Example 2 except that the aluminum foil was not laminated. The composition of the obtained paper-based deoxidizing multilayer body is 200 g / m ² basis weight paper / L.
DPE (30 μm) / LDPE (20 μm) / oxygen absorbing resin layer (30 μm) / oxygen permeable resin layer (50 μm)
Met. Next, in the same manner as in Example 2, a four-sided sealed bag in which chestnut yokan was enclosed was prepared, stored at 25 ° C. for 3 months, the oxygen concentration in the space inside the bag was measured, and then the bag was opened to make chestnut yokan. Was examined for appearance and taste. The results are shown in Table 2.

Comparative Example 6 Using an extrusion laminator consisting of an extruder, a T-die, a chill roll, a corona treatment machine and a take-up machine, LDPE was applied on one side of corona treated paper having a basis weight of 200 g / m ^2. (50 μm) was extrusion-laminated to produce a paper-based multilayer body having a structure of paper / LDPE (50 μm) having a basis weight of 200 g / m ² . Next, Example 2
In the same manner as above, make a four-sided seal bag enclosing chestnut yokan,
After storing at 25 ° C. for 3 months and measuring the oxygen concentration in the space inside the bag, the bag was opened and the appearance and taste of chestnut yokan were examined. The results are shown in Table 2.

[0043]

[Table 2] Oxygen concentration in container after 3 months (%) Appearance and taste of chestnut yokan Example 2 <0.1% No discoloration / good Comparative Example 4 20% Slightly discolored / taste reduced Comparative Example 5 10% Slightly discolored・ Taste reduction Comparative Example 6 21% Large discoloration / taste reduction

As is clear from these results, in Example 2 in which the bag-shaped container formed of the paper-based deoxidizing multilayer body in which the oxygen-absorbing resin layer was laminated was used, the oxygen in the container was deoxidized. Since it is absorbed by the agent, oxidative deterioration of the chestnut yokan, which is the content, is prevented, and the original color and taste are retained even after long-term storage. On the other hand, in Comparative Example 4 in which the oxygen-absorbing resin layer is not laminated, the oxygen invading from the outside is blocked by the gas barrier layer, but the residual sugar in the container causes oxidative deterioration of the chestnut yokan. As a result, a slight discoloration was observed and the taste was deteriorated.

Further, in Comparative Example 5 in which the gas barrier layer is not laminated, the oxygen absorbing function compounded in the oxygen-absorbing resin layer is gradually deteriorated by the oxygen penetrating from the outside and the oxygen absorbing function is deteriorated. The chestnut yokan, which is a product, was subjected to oxidative deterioration, some discoloration was observed, and the taste was slightly deteriorated. In Comparative Example 6 in which the oxygen-absorbing resin layer and the gas barrier layer were not laminated, the chestnut yokan was oxidatively deteriorated by the oxygen remaining in the container and the oxygen invading from the outside, and the appearance was greatly changed and the taste was deteriorated. It was

[0046]

EFFECTS OF THE INVENTION The paper-based deoxidizing multilayer body and the paper container comprising the same according to the present invention eliminate long-term storage by eliminating the oxidative deterioration of stored items such as various foods and pharmaceuticals, which was a problem in the conventional example. It is possible and extremely useful.

Continued front page    F term (reference) 3E067 AA03 AA04 AA05 AA11 AB01                       AB20 AB21 AB23 AB26 AB27                       AB28 AB81 AB96 AB97 BA06A                       BA07A BB01A BB14A BB15A                       BB16A BB22A BB25A BC06A                       CA06 CA24 CA30 EE02 EE25                       EE32 GD01 GD02 GD10                 4F100 AA06H AB02H AK01C AK01D                       AK01E AK04 AK06 AK48                       AR00B BA04 BA05 BA07                       BA10A BA10D BA10E CA09C                       CA23 DE01 DG10A EH20                       GB16 GB23 GB66 JB03 JB16C                       JB16E JD02B JD03D JD14C                       JD14H JL00

Claims (3)

[Claims] 1. A paper base material layer, a gas barrier layer, and
A paper-based deoxidizing multilayer body in which an oxygen-absorbing resin layer obtained by dispersing an oxygen absorber in a thermoplastic resin and an oxygen-permeable resin layer are laminated in this order. 2. The paper base deoxidizing multilayer body according to claim 1, wherein an outermost layer made of a thermoplastic resin is laminated on the outer surface side of the paper base layer. 3. A deoxidizing paper container using the paper-based deoxidizing multilayer body according to claim 1 in at least a part of the packaging container.