JPH07171194A - Manufacture of deoxidation packaging body - Google Patents

Abstract

PURPOSE:To effectively trap residual oxigen in an outer covering package by making a sufficient amount of moisture coaxist so as to activate an oxigen absorbent between the inside of the heat-sealed outer covering package provided with a resin layer combined with an oxygen absorbent and a plastic inner packaging body sealingly charged with the content which is charged in the outer covering package. CONSTITUTION:As an outer covering package, such a package is used that the first laminated sheet 2 provided with a gas barrier layer 8, an oxygen absorbent compounded intermediate resin layer 7, and a heat-sealed resin inner layer 6a and the transparent second laminated sheet 3 provided with a pin hole- resistant resin layer 12, a gas barrier layer 11 and a heat-sealed resin inner layer 6b are superposed so that both heat-sealed resin layers are faced each other and both edges of the sheets are heat-sealed. And when the inner packaging body is charged in the outer covering package, the enough amount of moisture to activate the oxygen absorbent is supplied in the outer covering package.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a package having deoxidizing property, and more specifically, a plastic inner package such as an infusion container is contained in an outer bag provided with an oxygen absorbent-containing resin layer. The present invention relates to a method of manufacturing a package including

[0002]

2. Description of the Related Art An infusion container containing a liquid chemical is used by connecting a pipe or the like directly to the container. Therefore, a synthetic container is used to prevent the container from being contaminated before it is actually used. It is handled in a state where it is filled in an outer bag made of a resin film. Since the infusion container is made of a resin that allows oxygen to permeate from the viewpoint of hygiene and the like, it is necessary that the outer bag has a gas barrier property in order to prevent alteration of the content liquid by oxygen. However, there is some oxygen in the outer bag after sealing, and even if a barrier outer bag is used, it is necessary to prevent alteration of the content liquid due to oxygen permeating with time. For this reason, conventionally, not only filling the infusion container under a low oxygen concentration, but also put the oxygen absorbent in the outer bag together with the infusion container, to capture residual oxygen and further permeated oxygen by this oxygen absorbent. The amount of oxygen in the outer bag was maintained at a low level to prevent alteration of the liquid content in the infusion container (Japanese Patent Publication No. 5-33632).

[0003]

However, if the oxygen absorbent filled in the small bag is put into such an outer bag as it is, the oxygen absorbent may be mistakenly taken. On the other hand, fixing the oxygen absorbent in the outer bag so that it cannot be easily taken out from the outer bag has a problem that the manufacturing process is very complicated and the productivity is poor. Also,
Since an oxygen absorbent is used, it is not economically preferable. Therefore, it has been proposed that the outer bag itself has an oxygen absorbing function (Japanese Patent Application No. 5-27076). However, when this oxygen-absorbing outer bag is used, the presence of water is required for the oxygen absorption reaction. Therefore, it is necessary to perform heat sterilization and retort sterilization after filling the outer bag with the infusion container under a low oxygen concentration, and there is a problem that the filling process equipment needs to be changed.

Further, in some cases, it may not be preferable to carry out heat sterilization or retort sterilization after filling the infusion container into the outer packaging bag due to the nature of the content liquid to be filled in the infusion container, problems in the manufacturing process and the like. In the above method, it is also necessary to supply water into the outer bag in order to activate the oxygen absorption reaction after filling the infusion container in the outer bag.

Therefore, an object of the present invention is to effectively trap oxygen permeating from the outside and leave it in the outer bag without filling the outer bag with a plastic container and performing retort sterilization or the like. Another object of the present invention is to provide a method for producing a deoxidized package having excellent storage stability of the contents by effectively capturing even the oxygen contained therein. Another object of the present invention is to provide a suitable method for allowing a proper amount of water to be present in an outer bag filled with a plastic container.

[0006]

According to the present invention, a plastic inner package filled with a content and sealed is filled in a heat-sealable outer package having an oxygen absorbent blending layer, and the outer package and the inner package are provided. Another object of the present invention is to provide a method for producing a deoxygenated package, characterized in that a sufficient amount of water for activating the oxygen absorbent is allowed to coexist therewith, and then the outer bag is sealed by heat sealing.

In the present invention, the space between the outer bag and the inner bag is replaced or filled with nitrogen which is humidified, or water is supplied in the form of droplets or spray, or the label of the inner bag is attached. It is preferable that moisture is allowed to coexist between the outer bag and the inner packet by preliminarily absorbing moisture.

[0008]

The present invention provides an oxygen absorbent between a heat-sealable outer bag provided with a resin layer containing an oxygen absorbent and a plastic inner package filled with the contents filled in the outer bag. By allowing a sufficient amount of water to be activated to coexist, it is possible to effectively capture the residual oxygen in the outer bag, and it is possible to provide a deoxygenated package having excellent storage stability of the content liquid. Of.

As described above, the presence of water is indispensable for the oxygen absorbent to capture oxygen. In the conventional outer packaging bag, after filling the plastic inner packaging body, retort sterilization or the like is performed to Although the water generated at this time was used, if the retort sterilization or the like must be performed before filling the plastic inner package, it is necessary to supply the water together with the inner package into the outer bag. In the present invention, by providing the oxygen absorbent-containing resin layer as one layer of the laminate constituting the outer bag, the misidentification of the oxygen absorbent is prevented, and the troublesome work of putting it in the outer bag is unnecessary. In addition, when water coexists directly in the outer bag,
The leakage of the oxygen absorbent is effectively prevented.

FIG. 1 is a graph showing the change over time in the oxygen concentration in the outer bag when water is present by changing the supply amount in the outer bag used in the present invention. As can be seen from this graph, in the case of not adding water at all, the oxygen concentration gradually increases without decreasing, whereas in the case of adding water, the oxygen concentration increases from the time of filling to 15 days. The concentration is gradually reduced to prevent alteration of the contents due to oxygen. Especially 1.5g / l and 3g of water
It is understood that the oxygen concentration is further reduced after 30 days, and the residual oxygen in the outer bag is trapped for a long time. This degree of oxygen reduction naturally varies depending on the container configuration, material configuration, and container size.

[0011]

Preferred embodiment of the present invention The outer bag used in the present invention is a heat-sealable outer bag provided with an oxygen absorbent as described above. Specifically, it suppresses the permeation of oxygen from the outside. In order to do so, the outer layer must have gas barrier properties, and the inner layer must have moisture resistance because it supplies water into the outer bag. Preferably, the first laminated sheet 2 provided with the gas barrier layer 8, the oxygen absorbent-containing resin intermediate layer 7 and the heat-sealable resin inner layer 6a proposed by the present inventors as shown in FIG. Pinhole resin layer 1
2, gas barrier layer 11 and heat sealable resin inner layer 6
It is particularly preferable to use an outer packaging bag in which the transparent second laminated sheet 3 provided with b is overlapped so that the heat-sealable resin layers face each other and the edges are heat-sealed.
Since this outer bag has transparency, the state of the contents can be grasped without opening the outer bag, and since it has excellent pinhole resistance, the outer bag is also sealed. It is well retained. It should be noted that in FIG. 3, an infusion container 13 (a label 14 that has absorbed moisture) is placed on the outer bag 1 by the method of the present invention.
Is attached) is shown as an example.

As the oxygen absorbent compounded in the outer bag,
Although all oxygen absorbers conventionally used in this type of application can be used, those which are generally reducible and substantially insoluble in water are preferable, and suitable examples thereof include metal powders having reducibility, such as Reducing iron, reducing zinc, reducing tin powder; low metal oxides such as ferrous oxide, ferric tetroxide;
Examples thereof include reducing metal compounds such as iron carbide, silicon iron, iron carbonyl, ferrous hydroxide, and the like, which are mainly composed of one or a combination thereof. These are alkali metal, alkaline earth metal hydroxides, carbonates, sulfites, thiosulfates, tertiary phosphates, organic acid salts, halides, activated carbon, activated alumina and activated clay as required. It can also be used in combination with such auxiliaries. Alternatively, a polymer compound having a polyhydric phenol in the skeleton, such as a polyhydric phenol-containing phenol / aldehyde resin, may be used. It is preferable that these oxygen absorbents generally have an average particle size of 50 μm or less, particularly 30 μm or less.
The oxygen absorbent is preferably added to the following resin in an amount of 1 to 100% by weight, particularly 10 to 70% by weight.

As the resin containing the oxygen absorbent, various conventionally known resins capable of forming a film can be used. Above all, in order that the layer containing the oxygen absorbent can effectively absorb water, A resin having water absorbability itself, for example, an ethylene-vinyl acetate copolymer having an ethylene content of 20 to 60 mol%, particularly 25 to 50 mol%, has a saponification degree of 96 mol% or more, particularly 99 mol% or more. An ethylene vinyl alcohol copolymer, which is a saponified product obtained by saponification so that The saponified ethylene vinyl alcohol copolymer should have a molecular weight sufficient to form a film, and is generally 0.01 dl / 0.01 as measured at 30 ° C. in a mixed solvent having a phenol: water weight ratio of 85:15. It is preferable to have a viscosity of g or more, particularly 0.05 dl / g or more.

Further, resins which do not absorb water themselves, such as low-, medium-, and high-density polyethylene, isotactic polypropylene, propylene-ethylene copolymer,
Polybutene-1, ethylene-propylene copolymer, ethylene-butene-1 copolymer, propylene-butene-1 copolymer, ethylene-propylene-butene-1 copolymer,
Ethylene vinyl acetate copolymers, ion-crosslinked olefin copolymers (ionomers) or olefin resins such as blends thereof, polyacrylic acid, polymethacrylic acid, polyacrylamide, polyvinylpyrrolidone, polyvinyl methyl ether, polyvinyl alcohol, Vinyl alcohol-acrylic acid copolymer, polyethylene oxide modified product, sodium acrylate polymer, acrylic acid (salt) grafted starch, acrylonitrile grafted hydrolyzate of starch, starch such as acrylic acid (salt) grafted cellulose A highly water-absorbent resin such as a cellulose-based graft derivative can also be blended as a water-absorbing agent. In addition to these resins, inorganic salts such as sodium sulfate, magnesium sulfate, disodium phosphate, and sodium diphosphate, organic compounds such as modified casein and modified starch, silica gel, alumina gel, diatomaceous earth, and various inorganic zeolites A compound can also be added.

As the gas barrier layer provided on the outer bag,
Since the resin layer side laminate containing the oxygen absorber is colored by the oxygen absorber, it is preferable to use an opaque layer such as aluminum, tin plate, steel, metal foil such as tin or vapor deposition film. Since the other layer is preferably transparent from the perspective of seeing through the contents, conventionally known gas barrier resins such as, but not limited to, the above-mentioned ethylene vinyl alcohol copolymer and polyvinyl chloride, Vinyl chloride resins such as polyvinylidene chloride, polyamide resins, SiOx vapor-deposited polyethylene terephthalate, etc. can be preferably used.

As the heat-sealable resin, any conventionally known heat-sealable resin can be used. For example, without limitation, low-, medium-, high-density polyethylene, isotactic polypropylene, propylene-ethylene copolymer, polybutene-1, ethylene-
Propylene copolymer, ethylene-butene-1 copolymer,
An olefin resin such as a propylene-butene-1 copolymer or an ethylene-propylene-butene-1 copolymer can be used. Further, these resins may be colored with titanium white or the like, if necessary.

As the pinhole-resistant resin layer, nylon 6, nylon 6,6, nylon 6-6,6 copolymer, metaxylylene adipamide, nylon 6,10, nylon 11, nylon 12, nylon are used. Polyamides such as 13 and the like, polyesters such as polyethylene terephthalate and polybutylene terephthalate, polycarbonates,
ABS resin, polyacetal, polymethylmethacrylate, isotactic polypropylene, polystyrene resin and the like can be preferably used. If sufficient adhesion cannot be obtained between the layers, use an adhesive resin composed of a thermoplastic resin having a carbonyl group in the main chain or in the side chain at a concentration of 1 to 700 milliequivalent / 100 g resin. You can

In a preferred embodiment of the present invention, a gas barrier layer (hereinafter referred to as an RG layer), an oxygen absorbent-containing resin layer (hereinafter referred to as an AO layer), a heat seal layer (hereinafter referred to as an HS layer), and a pinhole resistant layer. The thickness of the layer (hereinafter referred to as RP layer) is R
G layer is 5 to 30 μm, AO layer is 20 to 70 μm, H
It is preferable that the S layer has a thickness in the range of 5 to 100 μm and the RP layer has a thickness in the range of 5 to 30 μm. The layer structure of the sheet forming the outer bag can be variously modified as long as it has a basic layer. For example, a first sheet and a second sheet having the following layer structure can be combined and molded. The AD layer is an adhesive layer. First sheet (outer) RG layer / AD layer / AO layer / AD layer / HS layer (inner) (outer) protective layer / RG layer / AD layer / AO layer / AD layer / H
S layer (inside) (outside) Protection layer / AD layer / RG layer / AD layer / AO layer / H
S layer (inside) Second sheet (outside) RP layer / AD layer / RG layer / AD layer / HS layer (inside)

The outer bag used in the present invention can be manufactured by a method known per se except that it has the above-mentioned layer structure. After melt-kneading with an extruder corresponding to each resin layer, a lamination method such as dry lamination, sandwich lamination, and extrusion coating can be adopted. The formed laminated sheets are overlapped with each heat seal layer inside, and the periphery is heat-sealed by a conventionally known heat-sealing means such as a heat-seal bar to be molded. In the present invention, the laminated sheets are heat-sealed while leaving the filling port of the inner package, and after supplying the inner package and water, the filling port of the inner package is heat-sealed to seal the outer bag.

In the present invention, the outer bag is formed first, and water is supplied into the outer bag when the inner bag is filled or before and after the inner bag is filled. The amount of water to be supplied to the outer bag is appropriately determined depending on the blending amount of the oxygen absorbent used in the outer bag.
1 to 3.0 g / liter, especially 0.3 to 2.0 g / liter
It is preferably in the range of liters. This is because if the water content is more than this range, it may be mistaken that the inner solution leaks because the water remains in the outer bag, and if the water content is less than this range. This is because the oxygen absorbent may not be able to capture oxygen sufficiently, and the oxygen in the outer bag may not be efficiently kept at a low level.

As a method of supplying water, the droplets may be directly supplied into the outer bag, or the water may be sprayed and supplied by using a spray or the like. Further, water may be allowed to coexist by replacing the inside of the outer bag with highly humidified nitrogen or filling the outer bag with highly humidified nitrogen. Further, when a label is attached to the outer surface of the inner package, the label may be made to absorb moisture in advance, or the label itself may be moistened with moisture. In this case, it is necessary that the label itself has water absorbability, and a highly water-absorbent resin capable of forming paper or a film as described above, or a label in which these other resins are laminated is used for moisture of paper or the like. It is preferable to use by sticking to a container so that the part containing is the surface.

The outer bag of the present invention is, of course, not limited to this, but is preferably used for filling an infusion container used for infusion or the like. In general, the infusion container is made of polyolefins such as polyethylene and polypropylene from the viewpoint of moisture resistance and hygiene. Although these resins are excellent in moisture resistance and hygiene, they are inferior in gas barrier property.
As described above, the outer bag of the present invention has excellent gas barrier properties and can effectively reduce the residual oxygen in the outer bag, so that the inner solution of the infusion container may be deteriorated by oxygen. Even if it is filled with a certain content liquid, since oxygen hardly exists in the outer bag, the inner solution can be stored without being altered.

Examples of the infusion agent which may be deteriorated by oxygen include L-isoleucine, L-loin, L-lysine and L.
-Methionine, L-phenylalanine, L-threonine, L-valine, L-tyrosine, L-tryptophan,
L-arginine, L-histidine, L-alanine, L-
In addition to those containing amino acid components such as asparagine sun, aminoacetic acid, L-proline, L-serine, etc., in addition to those containing sugars, lipids, vitamins, cardiovascular agents such as dobutamine hydrochloride and dopamine hydrochloride And the content adjusting agents thereof, and in the present invention, an outer bag capable of storing these without deterioration can be produced.

[0024]

【Example】

Example 1 An iron-based oxygen-absorbing composition having an average particle size of 25 μm was coated on the aluminum foil side of a laminated film composed of a polyethylene terephthalate film (12 μm) and an aluminum foil (7 μm).
Linear low density polyethylene blended with 0% by weight (LLDP
50 μm thick oxygen-absorbing resin layer containing E) as a main component, and further a titanium white-containing LLD having a thickness of 50 μm on the outside thereof.
First sheet with a laminated PE layer and polyethylene terephthalate (PET) / ethylene vinyl alcohol copolymer (EVOH) / polyamide / polypropylene (PP)
The second laminated film having a total thickness of about 90 μm at 12: 15: 15: 50 is replaced with L of the first laminated film.
The LDPE layer and the PP layer of the second laminated film are laminated so that they face each other, and the three sides are bonded by heat sealing,
A 0 × 150 mm bag was made. The bag was filled with 200 ml of water, and a PP flat bottle sealed under nitrogen substitution and 0.3 ml of water were put therein, and the bag was sealed and heat-sealed under nitrogen substitution. As a result, the inside of the bag and the PP bottle as the filling material have a low oxygen concentration. The nitrogen substitution rate was about 90%.

As a control product, a product prepared in the same manner except that water was not added (control product 1) and a product in which an LLDPE layer was used instead of the oxygen absorbing layer and water was not added (control product 2) were prepared. . These were stored under a storage condition of 22 ° C.-60% RH for a certain period, and the atmospheric gas composition inside the bag was measured by a gas chromatograph. As shown in Table 1, the oxygen concentration in the bag is understood to decrease with time in the product of the present invention, but in the control product 1 to which water is not added, the increase in concentration due to oxygen permeating from the second laminated film is suppressed, It cannot be reduced. Further, it can be seen that in the control product 2, the oxygen concentration increases with time.

[0026]

[Table 1]

Example 2 Using the bag prepared in Example 1, a flat bottle, which is the content product of Example 1, was put in a nitrogen atmosphere in which fine water droplets were suspended and sealed in the same manner as in Example 1. . 22 ° C-60%
It was stored under the storage condition of RH, and after a certain period of time, the gas composition inside the bag was analyzed by a gas chromatograph. The amount of water present in the initial bag was 0.3 g / 200 ml. The oxygen concentration in the bag decreased with time and did not exceed the initial oxygen concentration even after 6 months.

Example 3 The PP flat bottle used in Example 1 was added with 60 × 100 mm
The paper label of No. 2 was attached using an adhesive, and hot water was sprayed onto the label to make it hydrate. The water content was 30 wt%. The bag was placed in the three-sided sealed bag prepared in Example 1 and sealed under nitrogen substitution. The nitrogen substitution rate in the bag atmosphere was about 95%. When stored at 22 ° C.-60% RH and the oxygen concentration in the bag was measured at regular intervals, it was confirmed that the oxygen concentration in the bag decreased with time. The results are shown in Table 2. As a control product, a label not containing water was prepared and the oxygen concentration was measured in the same manner.

[0029]

[Table 2]

Example 4 L-leucine and L-leucine were added to the PP bottle used in Example 1.
-Isoleucine, lysine acetate, L-methionine, L-phenylalanine, L-threonine, L-tryptophan, L-valine, L-arginine, L-histidine, L
-Alanine and glucose were filled with 200 ml of an amino acid preparation model liquid dissolved in water and sealed under nitrogen substitution. Then, the bag prepared in Example 1 was filled with 0.3 ml of water under nitrogen substitution. The nitrogen substitution rate in the bag was 98%. After a certain period of time, the oxygen concentration in the bag and the color change of the contents in the PP bottle were examined. The results are shown in Table 3. The oxygen concentration in the bag was lower than the initial oxygen concentration, and there was almost no color change in the contents, indicating good performance. As a control product, the same bag was used, except that the oxygen absorbent layer was not provided, and the same examination was performed.

[0031]

[Table 3]

[0032]

EFFECTS OF THE INVENTION According to the present invention, a heat-sealable outer packaging bag provided with a resin layer containing an oxygen absorbent is filled with a plastic inner package which is filled and sealed with the content to sufficiently activate the oxygen absorbent. If the outer bag is sealed by heat sealing after allowing a certain amount of water to coexist, it is possible to effectively block the permeation of oxygen from the outside without filling the outer bag with the plastic inner bag and performing retort sterilization. Oxygen remaining in the bag can also be effectively captured to provide a deoxidized package having excellent storage stability of the content.

[Brief description of drawings]

FIG. 1 is a diagram showing a time-dependent change in oxygen concentration in an outer bag depending on an amount of water in the outer bag.

FIG. 2 is a cross-sectional view showing an example of an outer bag used in the present invention.

FIG. 3 is a view showing a deoxidizing package in which an infusion container is contained in an outer bag.

[Explanation of sign]

 1 Outer Bag 2 First Laminated Sheet 3 Second Laminated Sheet 4 Storage Part 5 Heat Sealing Part 6a, 6b Heat Sealing Layer 7 Oxygen Absorber Blend Resin Intermediate Layer 8, 11 Gas Barrier Layer 9 Protective Layer 12 Pinhole Resistance Resin layer 13 Infusion container 14 Label

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location B65D 77/04 F 81/20 K

Claims (8)

[Claims] 1. A heat-sealable outer packaging bag having an oxygen absorbent blending layer is filled with a plastic inner packaging body filled with a content, and the oxygen absorbent is activated between the outer packaging bag and the inner packaging body. A method for producing a deoxidized package, which comprises allowing an outer bag to be sealed by heat sealing after allowing a sufficient amount of water to coexist. 2. The production method according to claim 1, wherein 0.1 to 3.0 g / liter of water coexists based on the volume of the outer bag. 3. The production method according to claim 1, wherein water is made to coexist by replacing the space between the outer packet and the inner packet with highly humidified nitrogen or by filling highly humidified nitrogen. 4. The method according to claim 1, wherein water is made to coexist by supplying water in the form of droplets or spray between the outer bag and the inner packet. 5. The method according to claim 1, wherein the inner package is a container having a label on the outer surface thereof, and the label is preliminarily absorbed or moistened with water so that water coexists. 6. The production method according to claim 1, wherein the inner package is a polyolefin bottle. 7. The production method according to claim 1, wherein the content is an amino acid preparation or a cardiovascular agent. 8. A first laminated sheet having an outer bag including a gas barrier layer, an oxygen absorbent-containing resin intermediate layer and a heat sealable resin inner layer, a pinhole resistant resin layer, a gas barrier layer and a heat sealable resin. The production method according to claim 1, wherein a transparent second laminated sheet having an inner layer is laminated so that the heat-sealable resin layers face each other, and heat-sealed to form a bag.