JP2009227296A - Method for storing article by double packaging - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for storing an article which is capable of remarkably suppressing oxidative degradation by passage of time, and also to provide a method for storing an article which is capable of well suppressing successively oxidative degradation of the stored article by passage of time after a container storing the article is opened. <P>SOLUTION: In the method for storing the article, the water-resistant container storing the article is sealed in a packaging bag formed of an oxygen-absorbing multi-layered film having an oxygen-permeable layer made of an oxygen-permeable polyolefin, an oxygen-absorbing layer made of an oxygen-absorbing resin composition mixed with an iron-based deoxidation agent, and a gas barrier layer made of a gas barrier substance in this order from the inside. The water-resistant container is a laminated tubular container which has at least a body part, a shoulder part, and a head part, and the body part is formed of a multi-layers of at least two layers, and at least one layer thereof is formed of a gas barrier substance. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a method for storing articles, and more particularly, to a method for storing articles by double packaging.

In beauty, hydroquinone, ubiquinone, vitamin A, vitamin E, carotenoids and their derivatives, substances having a polyene structure such as squalene reduce, improve appearance that seems to be aging, such as stains, wrinkles, sagging, dullness, etc. It is preferred as a healthy component and is used in health foods, quasi drugs, pharmaceuticals, cosmetics, and the like.
However, since the above-mentioned substances are easily oxidizable substances that are easily oxidized, the generation of a strange odor or discoloration due to oxidative degradation may occur, and the skin may be even irritated. Therefore, a sufficient device is required for storage.
In addition, in other components, there are very many examples in which the quality deteriorates in the presence of oxygen such as fading, coloring, smell, or change of state of the pigment.
In order to solve the above-mentioned problems, a device from the composition side, such as adding an antioxidant, an ultraviolet absorber, a chelating agent, etc., and a device from the container surface, such as a tube having an aluminum layer that shuts off the air, are performed. It has been broken. As specific examples of the device from the aspect of composition, a buffer component selected from phosphoric acid, boric acid, citric acid, glutamic acid or epsilon aminocaproic acid and alkali metal salts thereof, a nonionic surfactant and a chelating agent Patent Document 1, Patent Document 1, which discloses a stable aqueous preparation filled with a sealed container made of polypropylene or polyethylene terephthalate, having a liquidity adjusted to pH 5 to pH 8, and containing lipophilic vitamins, dibutylhydroxytoluene and butyl There exists patent document 2 etc. which disclose the comprehensive vitamin agent for intravenous injection obtained by melt | dissolving hydroxyanisole in polyoxyethylene sorbitan fatty acid ester, and then adding water and a water-soluble vitamin and freeze-drying. In addition, as a technique from the container surface, Patent Document 3 that proposed blocking of outside air, light, and metal, Patent Document that showed blocking of the body portion of the tube as well as the bonding portion of the body portion 4. Patent document 5 that proposed a multilayer film.
Furthermore, Patent Documents 6 to 8 can be cited as examples of methods for preserving the pharmaceuticals using an oxygen-absorbing multilayer film.

  As described above, conventionally, methods for improving the storage stability of an easily oxidizable article include a method by composition, a method by packaging, and a method by a combination thereof. It has been considered that a container having a gas barrier property blocks oxygen, and an airless container does not allow air to be mixed into the container, so that oxidative deterioration of an article accommodated in the container can be sufficiently suppressed.

JP 05-004918 A JP 05-124967 A JP-A-08-000986 JP 2002-370756 A Japanese Patent Laid-Open No. 11-123794 JP 07-171194 A JP 2000-84041 A Japanese Utility Model Publication No. 06-83340

However, the packaging method has a problem that oxygen is mixed in at the time of sealing and oxidative deterioration occurs with the lapse of time, and the effect is extremely reduced or eliminated once the package is opened. For this reason, there has been a demand for a packaging that can be used multiple times without depending on the amount of oxygen remaining at the time of encapsulation.
An object of the present invention is to provide a method for storing an article that can remarkably suppress oxidative deterioration of the article over time. It is another object of the present invention to provide a method for storing an article that can better suppress oxidative deterioration of the stored article over time even after the container for storing the article is opened.

The present invention
(1) An oxygen-absorbing layer made of an oxygen-absorbing resin composition containing an iron-based oxygen scavenger, an oxygen-permeable layer made of a polyolefin that is at least partially permeable to oxygen, and a water-resistant container containing an article, And a storage method for enclosing a gas barrier layer made of a gas barrier substance in a packaging bag made of an oxygen-absorbing multilayer film in this order from the inside, wherein the water-resistant container comprises at least a trunk portion, a shoulder portion, and a shoulder portion. A method for storing articles, wherein the article is a laminated tube container having a head part, and the body part is composed of two or more multilayers, at least one of which is made of a gas barrier material;

(2) The storage method according to (1), wherein the water-resistant container is a glass container at least partly made of a thermoplastic resin or an airless container (made of a thermoplastic resin and / or glass).

  According to the storage method of the present invention, it is possible to remarkably suppress oxidative deterioration of a stored article over time. In addition, even after the container for storing the stored article is opened, the oxidative deterioration of the stored article can be suppressed more favorably by storing the article in the container.

[Packaging bag made of oxygen-absorbing multilayer film]
In the present invention, a packaging bag for enclosing a water-resistant container containing an article has an oxygen-absorbing resin in which at least a part thereof is blended with an oxygen-permeable layer made of polyolefin that transmits oxygen and an iron-based oxygen scavenger. It consists of an oxygen-absorbing multilayer film having an oxygen-absorbing layer made of the composition and a gas-barrier layer made of the gas-barrier substance in this order from the inside.

Oxygen-permeable layer The oxygen-permeable layer constituting the oxygen-absorbing multilayer film is a portion that becomes a sealant when the oxygen-absorbing multilayer film of the present invention is used for a part or all of a packaging bag, and is also water-resistant containing articles. Role as a separating layer that separates the container having the properties from the oxygen absorbing layer described later, and the role of allowing oxygen to permeate efficiently because oxygen in the packaging bag is quickly absorbed by the oxygen absorbent in the oxygen absorbing layer Have

  The oxygen permeable layer can be used without limitation as long as it is a polyolefin having oxygen permeability that can play the above-mentioned role. Specifically, various polyethylenes such as low density polyethylene, linear low density polyethylene, ultra low density polyethylene, polyethylene by metallocene catalyst, ethylene-vinyl acetate copolymer, ionomer, ethylene-methyl acrylate copolymer, Ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, propylene homopolymer, propylene-ethylene block copolymer, propylene-ethylene random Examples include copolymers, various polypropylenes such as polypropylene using a metallocene catalyst, polymethylpentene, thermoplastic elastomers, and the like, and these can be used alone or in combination.

Among these, in consideration of oxygen permeability and heat sealability, various polyethylenes such as low-density polyethylene, linear low-density polyethylene, ultra-low-density polyethylene, and metallocene-catalyzed polyethylene are preferable.
For the oxygen permeable layer, if necessary, coloring pigments such as titanium oxide, additives such as antioxidants, slip agents, antistatic agents, stabilizers, fillers such as calcium carbonate, clay, mica and silica, deodorization An agent or the like can be added.

  The thickness of the oxygen permeable layer is preferably 10 to 100 μm, more preferably 20 to 60 μm. When the film thickness of the oxygen permeable layer is 10 μm or more, the oxygen absorbent of the oxygen absorbing layer is sufficiently covered without being exposed on the surface, and the heat seal strength can be maintained. Further, when the film thickness of the oxygen permeable layer is 100 μm or less, lamination can be easily performed, oxygen permeability can be maintained, deterioration of the oxygen absorption performance of the film can be suppressed, and there is no cost problem.

Oxygen absorbing layer The oxygen absorbing layer constituting the oxygen absorbing multilayer film is composed of an oxygen absorbing resin composition in which iron powder is blended. However, a material obtained by dispersing an iron-based oxygen scavenger in a thermoplastic resin is preferably used. It is done. The oxygen absorbing layer has a role of absorbing oxygen dissolved in the packaging bag or in the stored article, and also has a role of preventing a small amount of oxygen entering from the outside of the packaging bag and preventing oxygen from penetrating into the inside.

Examples of the thermoplastic resin constituting the oxygen absorbing layer of the present invention include various polyethylenes such as low density polyethylene, linear low density polyethylene, ultra-low density polyethylene, polyethylene using a metallocene catalyst, and ethylene-vinyl acetate copolymer. , Ionomer, ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-acrylic acid copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, propylene homopolymer, Examples include propylene-ethylene block copolymer, propylene-ethylene random copolymer, various polypropylenes such as polypropylene by metallocene catalyst, polymethylpentene, thermoplastic elastomer, etc., and these may be used alone or in combination. it can
Among these, it is preferable to use the same type of resin as that used for the oxygen permeable layer in consideration of compatibility with the oxygen permeable layer.

As the iron-based oxygen absorber compounded in the oxygen-absorbing resin composition, a composition comprising iron powder and a metal halide is preferably used.
The iron powder that is the main component of the iron-based oxygen scavenger can be used without any particular limitation on the purity, etc., as long as it can cause an oxygen absorption reaction. For example, a part of the surface may be already oxidized, It may contain a metal. The iron powder is preferably granular, and for example, iron powder such as reduced iron powder, sprayed iron powder, and electrolytic iron powder, pulverized products of various iron such as cast iron and steel, and ground products are used. The average particle size should be in the range of 1 to 100 μm in consideration of handling properties, reducing the film thickness of the oxygen absorbing layer, and minimizing the irregularities of the iron-based oxygen absorber appearing on the film appearance. Is preferable, and the range of 1 to 80 μm is particularly preferable. The average particle size can be measured with a laser diffraction / scattering particle size analyzer.

  As the metal halide that is an auxiliary agent for the iron-based oxygen scavenger, for example, alkali metal or alkaline earth metal chloride, bromide or iodide is used, and lithium, sodium, potassium, magnesium, calcium or barium chloride is used. Or iodide is preferably used. The blending amount of the metal halide is preferably 0.1 to 20 parts by mass, particularly preferably 0.1 to 5 parts by mass per 100 parts by mass of the iron powder.

  In the present invention, a preferable iron-based oxygen scavenger is an iron powder-based composition containing iron powder and a metal halide, and more preferably a metal halide-coated iron powder composition in which a metal halide is attached to the iron powder. It is. Thus, it is preferable to add the metal halide in advance mixed with the iron powder so as not to adhere to the iron powder and easily separate. As a method of attaching the iron powder, for example, a method in which a metal halide and iron powder are mixed using a ball mill, a speed mill, etc., and the metal halide is embedded in the uneven portion of the iron powder surface, or a metal halide using a binder. The method of adhering to the iron powder surface, the method of adhering the metal halide to the iron powder surface by drying after mixing the metal halide aqueous solution and the iron powder can be employed.

The blending amount of the iron-based oxygen scavenger in the oxygen absorbing layer is preferably in the range of 10 to 70% by mass from the viewpoint that the oxygen absorbing ability is sufficient and the oxygen absorbing layer is easy to form. The range of 10-60 mass% is more preferable.
The thickness of the oxygen absorbing layer is preferably in the range of 20 to 100 μm, more preferably in the range of 30 to 80 μm, regardless of the constituent materials. If the film thickness of the oxygen absorption layer is 20 μm or more, film formation is easy, the amount of iron-based oxygen scavenger per unit area of the film is appropriate, and sufficient oxygen absorption performance is obtained. Moreover, if it is 100 micrometers or less, it will become the thing excellent in the handleability from the point of the film total thickness, and there is no problem also on cost.

  In the oxygen-absorbing resin composition constituting the oxygen-absorbing layer, if necessary, various additives such as coloring pigments such as titanium oxide, antioxidants, slip agents, antistatic agents, stabilizers, clay, mica, A filler such as silica, calcium carbonate, calcium sulfate, and barium sulfate, a deodorant, an adsorbent such as activated carbon and zeolite, and an antifoaming agent such as calcium oxide and magnesium oxide can be added.

Gas barrier layer In the present invention, the gas barrier layer constituting the oxygen-absorbing multilayer film is a layer that blocks oxygen entering from the outside of the packaging bag. For example, a metal foil such as an aluminum foil, polyvinylidene chloride, and ethylene-vinyl acetate are used together. Polymer saponified product, ethylene-vinyl alcohol copolymer, nylon 6, nylon 6,6, nylon MXD6, polyethylene terephthalate (PET) or other gas barrier resin, aluminum vapor deposited film, silica vapor deposited film or other vapor deposited film alone or Can be used in combination. Among these, metal foil such as aluminum foil is particularly preferable.
The thickness of the gas barrier layer is preferably in the range of 5 to 30 μm, more preferably in the range of 7 to 25 μm, regardless of the constituent materials, from the viewpoint of oxygen barrier properties and bag-making processability.

Oxygen-absorbing multilayer film The oxygen-absorbing multilayer film is composed of an oxygen-permeable layer composed of the above-mentioned oxygen-permeable polyolefin, an oxygen-absorbing layer composed of an oxygen-absorbing resin composition containing an iron-based oxygen scavenger, and a gas barrier material. At least three gas barrier layers are provided in this order from the inside.
In the present invention, if necessary, other layers can be added in addition to the above three layers. For example, in order to prevent damage to the gas barrier layer and pinholes, it is preferable to provide a protective layer made of a thermoplastic resin outside the gas barrier layer. Examples of the thermoplastic resin used in the protective layer include polyethylenes such as high-density polyethylene, polypropylenes such as propylene homopolymer, propylene-ethylene random copolymer, propylene-ethylene block copolymer, nylon 6, nylon 6, Polyamides such as 6, and polyesters such as PET, or combinations thereof.
The laminated film of each of the above layers can be obtained, for example, by a method of laminating a gas barrier layer by dry lamination or the like on a laminate film obtained by extrusion lamination or the like of an oxygen permeable layer and an oxygen absorption layer.

The packaging bag made of oxygen-absorbing multilayer film is preferably a bag made of the oxygen-absorbing multilayer film as a whole, but at least a part, for example, one side is made of the oxygen-absorbing multilayer film and one side is made of another gas barrier film. It may be a packaging bag. There is no restriction | limiting in particular as this other gas-barrier film, Any can be used if it consists of a substance which has gas barrier property normally. Moreover, there is no restriction | limiting in particular in the shape of a packaging bag, Any of a three-sided bag shape, a self-supporting bag shape, etc. can be used.

[Waterproof container]
In the present invention, the water-resistant container for storing articles is preferably made of a material having gas barrier properties, a laminated tube container that is a gas barrier multilayer container, a glass container in which a part of the container is made of a thermoplastic resin, And an airless container made of thermoplastic resin and / or glass is used.

Laminate tube container The laminate tube container mentioned as a container having water resistance has at least a body part, a shoulder part, and a head part, and the body part is composed of two or more layers, and at least one layer has gas barrier properties. It is a laminated tube container made of a substance.
As a layer which comprises the trunk | drum of such a laminated tube container, what consists of two or more layers including the layer which consists of polyethylene other than the layer which consists of the said gas-barrier substance is mentioned, for example.

Examples of the gas barrier material constituting the layer made of the gas barrier material include metal foil such as aluminum foil, polyvinylidene chloride, saponified ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer, nylon 6, nylon 6, 6, vapor barrier films such as nylon MXD6, PET, and the like, vapor deposition films that are vapor deposition films of aluminum, alumina, silica, and the like are used alone or in combination. Among the gas barrier substances, a film obtained by vapor-depositing a saponified ethylene-vinyl acetate copolymer, aluminum, alumina, silica or the like is particularly preferable.
Examples of the polyethylene constituting the layer made of polyethylene include various types of polyethylene such as linear low density polyethylene, ultra-low density polyethylene, and polyethylene using a metallocene catalyst.

In the present invention, from the viewpoint of tube processability and cost, it is preferable that the body portion of the laminate tube container having water resistance has a two-layer structure composed of the layer made of polyethylene and the layer containing the gas barrier substance. .
Moreover, in this invention, it is preferable from the point of tube processability and a sealing performance that the trunk | drum which comprises the laminated tube container which has the said water resistance has a multilayered structure which consists of three or more layers. In that case, from the same viewpoint, it is preferable that at least one of the innermost layer and the outermost layer is made of the polyethylene, and one or more intermediate layers are layers made of the gas barrier substance. More preferably, both the innermost layer and the outermost layer are made of polyethylene. In the present invention, there are no particular restrictions on the material of the shoulder portion and the head portion of the laminated tube container. However, in the present invention, the shoulder portion and the head portion are made of a gas-permeable material such as polyethylene or polypropylene from the viewpoint of storage of contents. It is preferable to use a material made of a functional substance.

From the viewpoint of processability and cost, the thickness of the polyethylene layer and the layer containing a gas barrier substance is preferably 10 μm or more in total, including the case where each layer is two or more layers.
As long as the laminated tube container has a mouth with a cap that can be used multiple times, the shape can be any of a cylindrical shape, a sheet shape, etc., and is not particularly limited. There is no particular limitation on the shape.

A glass container made of a thermoplastic resin, at least a part of which is cited as a container having water resistance, is preferably made of glass, and the cap, stopper, pump, etc. are partially thermoplastic. A container in which resin is used. These containers are suitably used for water-based articles containing water because the contents of the articles are low in viscosity.
Examples of the thermoplastic resin used in at least a part of the container include high-density polyethylene and polypropylene, and polypropylene is preferable from the viewpoint of water vapor barrier properties.
The shape, size, and thickness are not particularly limited as long as they can physically withstand use, and can be appropriately selected according to the purpose.

Airless container The airless container is filled with the contents filled in the container, and the lower part of the container rises due to internal pressure, etc., and even if the contents in the container decrease due to use, air does not enter the container. It is a container and the thing which has a trunk | drum, a shoulder part, and a head part like a laminated tube container is preferable. In the present invention, it is preferable that a thermoplastic resin such as polypropylene, polyethylene, or PET or glass is used for the material of the body portion, and the above-described thermoplastic resin is used for the head portion or the shoulder portion. The thickness of the airless container is not particularly limited as long as it can physically withstand use.
There is no restriction | limiting in particular about the shape and magnitude | size of an airless container, The thing similar to a normal airless container can be suitably selected according to the objective.

[Contained goods]
In the present invention, the article accommodated in the water-resistant container is preferably an easily oxidizable article, and examples thereof include cosmetics, pharmaceuticals, foods and the like. As such, a composition (1) comprising at least one selected from the group consisting of hydroquinone, ubiquinone, vitamin A, vitamin E, carotenoid and / or derivatives thereof, and a substance having a polyene structure such as squalene, or A composition (2) containing at least one kind of metal ion and at least one kind of organic compound that reacts with the metal ion and develops color is preferred.

  Specific examples of the composition (1) include hydroquinone, ubiquinone, ubiquinol, retinol, retinol acetate, retinol palmitate, vitamin A oil, tocopherol, tocopherol nicotinate, tocotrienol, β-carotene, lycopene, xanthofur, rhodo Xanthine, bixin and the like can be mentioned, and these derivatives have a basic skeleton of hydroquinone, ubiquinone, vitamin A, vitamin E, and carotenoid, and are substances whose stability, solubility, pharmacological properties and the like are changed. In particular, the effect of the present invention can be effectively obtained for a composition containing ubiquinone, vitamin A, carotenoid and derivatives thereof (retinol, retinol palmitate, β-carotene, lycopene, astaxanthin).

  In addition, these oxidizable articles are generally devised to prevent oxidation by the composition by blending dibutylhydroxytoluene, which is a powerful antioxidant compound, etc. Concentration formulation may raise safety concerns. According to the present invention, it is possible to maintain the stability of an easily oxidizable article even when the blending amount of the antioxidant compound is reduced or when it is not blended.

  In the present invention, a composition (2) containing at least one kind of metal ion and at least one kind of organic compound that develops color by reacting with the metal ion can be preferably used as the containing article. Examples of the metal ion include ions of each metal such as iron, copper, silver, aluminum, and zinc. The organic compound used together with the metal ion may be an element as long as it develops color, but in the present invention, Substances that easily become metal ions such as ferrous sulfate, ferric sulfate, ferrous chloride, ferric chloride, copper sulfate, copper nitrate, silver chloride, silver sulfate, silver nitrate, and silver citrate are preferably used.

  Organic compounds that react with metal ions to develop color, such as hematein, pyrogallol, tannin, catechol, shikonin, etc. , Hypericum, yellowfin, walnut, keihi, gentiana, gennoshouko, tea, kohone, koganebana, konotegasiwa, quintuplet, pomegranate, hawthorn, zion, peonies, gills, honeysuckle, suso, yarrow, sardine, crested dragonfly, senna Crested beetle, betel nut, dandelion, brazil wood, henna, button, mugwa, moss, octopus, melissa, bayberry, yukinoshita, green tea, forsythia, rosemary Shikonekisu, it is possible to use the extract such as tea extract and log wood.

The containing article has alcohols such as ethanol, glycerin, sorbitol, glucose, isomerized sugar, sodium riboflavin phosphate, ascorbic acid, L-ascorbyl magnesium phosphate, tetra 2-amino acid as long as the effects of the present invention are not impaired. Vitamin and its derivatives such as ascorbyl hexyldecanoate, amino acids and derivatives such as aspartic acid, cationion, methionine, lysine and trimethylglycine, polyquaternium-51, chitosan, sodium carboxymethylcellulose, carboxyvinyl polymer, water-soluble such as methylcellulose and sodium hyaluronate Polymer, glycyrrhizic acid and its derivatives, glycyrrhetinic acid and its derivatives, allantoin and its derivatives, nylon powder and cross-linked Corn / Reticulated silicone block copolymer, powders such as talc and iron oxide, pigments such as tar pigments, plant extracts such as sicon extract and scorpion extract, fragrance, pearl agent, preservative and fungicide, fungal metabolite, It is also possible to add a reducing agent, γ-oryzanol, ceramide, sodium pyrrolidonecarboxylate and the like.
In the present invention, the containing article may be any of cream, emulsion, liquid, powder and the like, and its dosage form is not limited.

[Preservation method of the present invention]
In the preservation method of the present invention, a water-resistant container containing the article is enclosed in a packaging bag having the oxygen-absorbing multilayer film. Each container having water resistance, the oxygen-absorbing multilayer film, and the articles contained in the container having water resistance are as described above.
That is, the present invention is a storage method in which the water-resistant container containing articles such as cosmetics, pharmaceuticals, and foods is sealed in a packaging bag using at least a part of the oxygen-absorbing multilayer film and sealed. .
In the present invention, it is preferable that water is allowed to coexist with a water-resistant container in the packaging bag made of the oxygen-absorbing multilayer film in terms of promoting the oxidation reaction of the oxygen-absorbing multilayer film. The amount of water to be coexisted is preferably 1 to 10 g, more preferably 2 to 5 g with respect to 100 cc of air from the viewpoint of promoting the oxidation reaction of the oxygen-absorbing multilayer film.

According to the present invention, there is no particular limitation on the pressure, oxygen concentration, etc. in the packaging bag made of an oxygen-absorbing multilayer film enclosed in a water-resistant container, and it may be a case where air or the like is packaged as it is. The effect of the present invention can be achieved without depending on the oxygen remaining amount at the time of encapsulation, and the effect of the present invention can be effectively obtained in such a case.
In addition, according to the preservation method of the present invention, even after the packaging bag containing the water-resistant container containing the preserved article is once opened, the article is stored in the water-resistant container to reduce the oxidative deterioration. It can continue to be suppressed. This is a case where an article is stored in a water-resistant container without being externally packaged from the beginning. Is an unexpected effect.

[Multiple packaging container]
The present invention also provides (1) (a) a laminate having at least a body part, a shoulder part, and a head part, wherein the body part is composed of two or more layers, and at least one layer is made of a gas barrier material. A tube container, (b) a glass container made of at least a part of a thermoplastic resin, and (c) an airless container made of a thermoplastic resin and / or glass, and a container having water resistance for containing articles, and (2) An oxygen-absorbing resin composition comprising a packaging bag containing the container according to (1), wherein at least a part of the oxygen-permeable layer is composed of an oxygen-permeable polyolefin and an iron-based oxygen scavenger. A compound type for storing an oxidizable article having an oxygen-absorbing layer comprising, and a packaging bag comprising an oxygen-absorbing multilayer film having a gas barrier layer comprising a gas barrier substance in this order from the inside. On instrumentation container.

Water-resistant containers for storing articles, oxygen-permeable layers made of oxygen-permeable polyolefin, oxygen-absorbing layers made of an oxygen-absorbing resin composition containing an iron-based oxygen absorber, and gas barriers made of a gas-barrier substance The layers, the oxygen-absorbing multilayer film having these, and the packaging bag comprising the oxygen-absorbing multilayer film are all as described above. Moreover, as an easily oxidizable article, any of those listed as articles accommodated in the water-resistant container can be used.
As described above, it is preferable that the storage double packaging container preferably has water in the packaging bag made of the oxygen-absorbing multilayer film together with the water-resistant container.
By using such a duplex packaging container and storing an easily oxidizable article to be stored in a container having water resistance, excellent storability can be obtained.

The present invention will be described more specifically with reference to the following examples, but the present invention is not limited thereto.
Production Example 1 (Production of oxygen-absorbing multilayer film)
1000 kg of iron powder with an average particle size of 30 μm is put into a vacuum dryer equipped with a heating jacket, mixed with 140 kg at a reduced pressure of 10 mmHg at 140 ° C., sprayed with 50 kg of 50% by weight aqueous solution of calcium chloride, dried, sieved, and coarsened Excluding the grains, an iron-based oxygen absorbent having an average particle diameter of 30 μm was obtained.
Next, using a twin screw extruder with a vent, iron-based oxygen absorbent and calcium oxide are supplied by side feed while extruding linear low-density polyethylene (manufactured by Nippon Polychem Co., Ltd .; trade name Kernel KC580). Polyethylene: iron-based oxygen absorbent: calcium oxide = 58: 40: 2 After being kneaded so as to have a weight ratio, extruded from a strand die, cooled, pelletized with a pelletizer, and an oxygen-absorbing resin composition was obtained. Obtained.

  Next, using an extrusion laminator device composed of two single-screw extruders, a T die, a cooling roll and a slitter, and a winder, an unstretched polyethylene film fed out as a heat seal layer 50 μm (manufactured by Okamoto Co., Ltd .; trade name LRW) As an oxygen absorbing layer, an oxygen absorbing resin composition was extruded and laminated with a thickness of 30 μm to obtain a laminated film in which the oxygen absorbing layer surface was subjected to corona discharge treatment. On the laminate film, an aluminum foil having a thickness of 9 μm, a nylon having a thickness of 15 μm, and a PET film having a thickness of 12 μm were sequentially laminated by dry lamination to produce an oxygen-absorbing multilayer film.

Example 1
200 g of the retinol-containing cosmetic solution shown in Table 1 below is substantially mixed with air into a gas barrier laminate tube container in which the shoulder portion and the head portion are made of polyethylene, and the trunk portion is made of polyethylene / aluminum-deposited PET film / polyethylene. It is filled without being sealed, and this is sealed with a cap made of polyethylene, and it is a three-sided bag having a length of 130 mm and a width of 185 mm made using the oxygen-absorbing multilayer film produced in Production Example 1, with an air amount of about 50 cc. After sealing and sealing, the container containing the cosmetic liquid was opened after standing at 40 ° C. for 6 months, and the residual amount of retinol was quantified.
Thereafter, the amount of retinol remaining after one month of use once a day was quantified, and the results of evaluating its odor and appearance are shown in Table 2. Here, the residual amount of retinol was quantified by liquid chromatography equipment (Waters 2690 HPLC system, detector: Waters 996 Photodiode Array Detector, column: SHISEIDO CAPCELL PAK C18 MG 3 mm ID × 150 mm, developing solvent: methanol). (The same applies hereinafter).

Example 2
In Example 1, it was stored and evaluated in the same manner except that 3 g of water was sealed in a three-sided bag together with about 50 cc of air. The results are shown in Table 2.

Example 3
In Example 1, instead of the gas barrier laminate tube container in which the body part is composed of three layers of polyethylene / aluminum-deposited PET film / polyethylene, the body part is composed of three layers of polyethylene / ethylene-vinyl alcohol copolymer saponified product / polyethylene. It was stored and evaluated in the same manner except that a gas barrier laminate tube container was used. The results are shown in Table 2.

Example 4
In Example 1, instead of the gas barrier laminate tube container, the airless container made of polypropylene was filled without substantially mixing air, and stored in the same manner except that it was sealed with a cap made of polyethylene. And evaluated. The results are shown in Table 2.

Comparative Example 1
In Example 1, instead of the gas barrier laminate tube container, a gas barrier container made of a glass bottle was filled without substantially mixing air and sealed with a cap made of polyethylene, and this was used as a three-sided bag. The samples were stored and evaluated in the same manner except that they were not encapsulated. The results are shown in Table 2.

Comparative Example 2
In Example 1, instead of the gas barrier laminate tube container, the body portion is filled without substantially mixing air into the gas barrier laminate tube container composed of three layers of polyethylene / ethylene-vinyl alcohol copolymer / polyethylene. Then, it was stored and evaluated in the same manner except that the one sealed with a cap made of polyethylene was used and this was not enclosed in a three-sided bag. The results are shown in Table 2.

Comparative Example 3
In Example 1, instead of the gas barrier laminate tube container, it was stored in the same manner except that a polyethylene single-layer tube container was filled without substantially mixing air and sealed with a cap made of polyethylene. And evaluated. The results are shown in Table 2.

  According to Table 2, each of Examples 1 to 4 showed a high retinol residual amount even after one month of continuous use at the time of opening, and there was no particularly clear change in color and odor. On the other hand, in Comparative Examples 1 and 2, since it is a normal state of storage in the air and is a test result in the presence of oxygen, at the time of opening, the residual amount is greatly reduced due to oxidation of retinol, and the color and odor The change was also clear. In Comparative Example 3, it was in a deoxygenated state until opening, showing a high residual amount of retinol, and there was no particularly clear change in color and odor, but the amount of retinol was clearly reduced after 1 month of continuous use. The change in color and odor was also clear. Further, in the conventional storage method, about 0.1% by mass of dibutylhydroxytoluene needs to be blended to prevent the cosmetic liquid from being oxidized, but the blending amount of dibutylhydroxytoluene is reduced to 0 by using the preservation method of the present invention. Even when the amount was reduced to 0.02% by mass, it was possible to store the serum for a long period as in Example 1.

Example 5
200 g of ubiquinone-containing emulsion shown in Table 3 below was filled in a glass container whose pump was made of polypropylene without substantially mixing air, and sealed with a cap made of polyethylene, which was produced in Production Example 1. Sealed in a three-sided bag made of oxygen-absorbing multilayer film with a length of 130mm and a width of 185mm along with about 60cc of air, left at 40 ° C for 6 months, and then opened the container containing the emulsion and opened ubiquinone. The remaining amount of was quantified.
Thereafter, the amount of ubiquinone remaining after one month of use once a day was quantified, and the results of evaluating its odor and appearance are shown in Table 4. The residual amount of ubiquinone was quantified by liquid chromatography similar to the residual amount of retinol (hereinafter the same).

Example 6
In Example 5, instead of using a glass container, the gas barrier laminate tube container used in Example 3 was filled without substantially mixing air and sealed with a cap made of polyethylene. It preserve | saved similarly and evaluated. The results are shown in Table 4.

Comparative Example 4
In Example 5, instead of a glass container, a gas barrier container made of a glass bottle was filled without substantially mixing air, and sealed with a cap made of polyethylene, and this was enclosed in a three-sided bag. It was stored in the same manner except that it was not evaluated. The results are shown in Table 4.

Comparative Example 5
In Example 5, instead of the glass container, the gas barrier laminate tube container used in Example 3 was filled without substantially mixing air and sealed with a polyethylene cap, and this Was stored in the same manner except that it was not enclosed in a three-sided bag and evaluated. The results are shown in Table 4.

Comparative Example 6
In Example 5, instead of using a glass container, the head part and the body part were filled in a polyethylene single-layer tube container without substantially mixing air and sealed with a cap made of polyethylene. It preserve | saved similarly and evaluated. The results are shown in Table 4.

  At the time of opening, there was no difference in odor and appearance between the example and the comparative example, but the effectiveness of the present invention appeared after one month of use. In addition, since Examples 5 and 6 showed higher ubiquinone residual rate than Comparative Examples 4 to 6, it can be seen that oxidation of ubiquinone, which is an easily oxidizable substance, was suppressed according to the present invention.

Examples 7-13
200 g of a cosmetic composition having the composition shown in each of the following Tables 5 to 11 (Examples 7 and 8 are creams, Example 9 is a gel, Example 10 is a lotion, Example 11 is a permeation solution of a pack with a sheet, Example 12 is hair art and Example 13 is hair cream) in a laminated tube container in which the shoulder part and the head part are made of polyethylene, and the trunk part is made of three layers of polyethylene / ethylene-vinyl alcohol copolymer / polyethylene. A laminate tube container was obtained in which air was filled without being substantially mixed and the head portion was sealed with aluminum foil. Filling and sealing a laminate tube container filled with the cosmetic composition together with an air amount of about 60 cc and 3 g of water in a three-sided bag of 130 mm length and 185 mm width created using the oxygen-absorbing multilayer film produced in Reference Example 1 Stored for 1 month. When the preserved material inside the tube was observed after opening the bag, the appearance and scent before filling were well maintained for any composition. Moreover, when the filling inside the laminated tube was observed after 1 month of opening, a product having no problem in use was obtained for any of the compositions with a slight decrease in appearance.
Examples 7 to 13 are examples using the compositions shown in Tables 5 to 11, respectively.

  The storage method of the present invention is capable of suppressing oxidative deterioration of stored articles, and also stores the articles in the container after opening the outer bag enclosing the container for storing the stored articles. Therefore, since the oxidative deterioration of the stored article can be continuously suppressed, it is suitably used as a method for storing the article.

Claims (9)

  A water-resistant container containing an article, an oxygen-permeable layer made of a polyolefin that at least partially contains oxygen, an oxygen-absorbing layer made of an oxygen-absorbing resin composition containing an iron-based oxygen absorber, and gas barrier properties A storage method in which a gas barrier layer made of a substance is enclosed in a packaging bag made of an oxygen-absorbing multilayer film in this order from the inside, wherein the water-resistant container has at least a body part, a shoulder part, and a head part. A method for storing an article, which is a laminated tube container in which the body portion is formed of a multilayer of two or more layers, and at least one layer thereof is formed of a gas barrier material.   The preservation | save method of Claim 1 with which the trunk | drum of the said laminate tube container has at least 2 layer structure which consists of a layer containing polyethylene and a layer containing a gas-barrier substance.   The body of the laminate tube container has a multilayer structure of three or more layers, at least one of the innermost layer and the outermost layer is made of polyethylene, and at least one of the intermediate layers is made of a gas barrier material. The storage method described.   The storage method according to claim 3, wherein both the innermost layer and the outermost layer are made of polyethylene.   A water-resistant container containing an article, an oxygen-permeable layer made of a polyolefin that at least partially contains oxygen, an oxygen-absorbing layer made of an oxygen-absorbing resin composition containing an iron-based oxygen absorber, and gas barrier properties A storage method in which a gas barrier layer made of a substance is enclosed in a packaging bag made of an oxygen-absorbing multilayer film in this order from the inside, wherein the water-resistant container is a glass at least partly made of a thermoplastic resin A method for storing an article, which is a container.   A water-resistant container containing an article, an oxygen-permeable layer made of a polyolefin that at least partially contains oxygen, an oxygen-absorbing layer made of an oxygen-absorbing resin composition containing an iron-based oxygen absorber, and gas barrier properties A storage method in which a gas barrier layer made of a substance is enclosed in a packaging bag made of an oxygen-absorbing multilayer film in this order from the inside, wherein the water-resistant container is an airless container made of a thermoplastic resin and / or glass A method for storing an article.   7. The composition according to claim 1, wherein the article is a composition containing at least one selected from the group consisting of hydroquinone, ubiquinone, vitamin A, vitamin E, carotenoids and / or derivatives thereof, and a substance having a polyene structure. The storage method according to the above.   The storage method according to any one of claims 1 to 6, wherein the article is a composition containing at least one metal ion and at least one organic compound that reacts with the metal ion and develops color. (1) (a) A laminated tube container having at least a body part, a shoulder part, and a head part, wherein the body part is composed of two or more layers, and at least one layer is made of a gas barrier material, (b) A water-resistant container for housing articles selected from a glass container at least partially made of a thermoplastic resin, and (c) an airless container made of a thermoplastic resin and / or glass, and (2) the above (1 ) A packaging bag containing the container described above, at least a part of which is an oxygen permeable layer made of an oxygen permeable polyolefin, an oxygen absorbing layer made of an oxygen absorbing resin composition containing an iron-based oxygen scavenger, And a packaging bag made of an oxygen-absorbing multilayer film having a gas barrier layer made of a gas barrier material in this order from the inside,
A multi-packaging container for storing easily oxidizable articles.