JP2015123993A - Alkali-proof packing material and alkali-proof packing container - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a packing material having excellent barrier properties and alkali-proof properties and a medical packing container comprising the packing material and having excellent barrier properties and alkali-proof properties.SOLUTION: A medical alkali-proof packing material comprises, in this order, a substrate layer, a barrier layer comprising an inorganic substance or inorganic oxide, and a heat-sealing resin layer having a thickness of 3-50 μm and comprising cyclic polyolefin.

Description

  The present invention relates to an alkali-resistant packaging material, and more particularly to a packaging material excellent in barrier properties and alkali resistance used for medical packaging containers.

  Conventionally, a glass container has been used as a container for storing a liquid preparation, but in recent years, an alternative to a resin container has been desired due to problems of disposal and light weight. However, compared with glass containers, resin containers have poor barrier properties, and due to problems such as adsorption of active ingredients to the inner surface, storage stability of liquid preparations, reduction of active ingredients, and active ingredient There are concerns about elution to the outside.

  In response to these problems, a chemical bag having a cyclic olefin in the inner layer has been proposed (see Patent Document 1). In addition, it has been proposed to form a plastic ampoule using a polycyclic olefin having a glass transition temperature of 110 ° C. or less on the inner wall surface side by a blow-fill-seal method (see Patent Document 2).

  In the case of a glass container, when the content is a highly alkaline solution, the alkali in the container may be eluted, and a phenomenon in which a fine silica film on the glass surface is peeled off (flake phenomenon) may occur.

JP 2011-111178 A JP 2012-135612 A

  As a result of examining the inventions of Patent Documents 1 and 2, the present inventors have found that the barrier property of the packaging container is not sufficient when considering the long-term storage of the contents, and there is a problem in the storage stability of the contents. I found out. Therefore, development of a packaging container that can achieve both barrier properties and alkali resistance is desired.

  This invention is made | formed in view of said technical subject, The objective is to provide the packaging material excellent in barrier property and alkali resistance. Moreover, it is providing the medical packaging container excellent in the barrier property and alkali resistance which consist of this packaging material.

  As a result of intensive studies to solve the above-mentioned problems, the inventors have made the thickness of the polyolefin resin layer disposed on the contents side within a specific range when a packaging container is formed, and the base material layer and It has been found that the above problem can be solved by a packaging material in which a barrier layer is provided between polyolefin resin layers. The present invention has been completed based on such findings.

That is, according to one aspect of the present invention,
A base material layer;
A barrier layer made of an inorganic substance or an inorganic oxide;
A heat-sealable resin layer having a thickness of 3 to 50 μm and comprising a cyclic polyolefin;
In this order, an alkali-resistant packaging material is provided.

  In the aspect of the present invention, it is preferable that the heat-sealable resin layer further contains a polyolefin.

  In the aspect of the present invention, the barrier layer is preferably made of a vapor deposition film of an inorganic substance or an inorganic oxide.

  In the aspect of this invention, it is preferable that the said barrier layer consists of metal foil.

  In the aspect of the present invention, it is preferable that an adhesive layer is further included between the base material layer and the heat-sealable resin layer.

  In the aspect of the present invention, it is preferable that a polyamide resin layer is further included between the base material layer and the heat-sealable resin layer.

  In the aspect of the present invention, it is preferable that a polyolefin resin layer is further included between the base material layer and the heat-sealable resin layer.

  Moreover, according to the other aspect of this invention, the alkali-proof packaging container which consists of said alkali-resistant packaging material and the said heat-sealable resin layer is arrange | positioned at the contents side is provided.

  In another aspect of the present invention, the content is preferably an alkaline solution having a pH of 12 or higher.

  In another aspect of the present invention, the content is preferably a liquid preparation.

  ADVANTAGE OF THE INVENTION According to this invention, the packaging material excellent in barrier property and alkali resistance can be provided. Moreover, the medical packaging container excellent in the barrier property and alkali resistance which consist of this packaging material can be provided.

It is the schematic sectional drawing which showed one Embodiment of the alkali-resistant packaging material by this invention. It is the schematic sectional drawing which showed one Embodiment of the alkali-resistant packaging material by this invention.

<Alkali-resistant packaging material>
The alkali-resistant packaging material according to the present invention comprises a base material layer, a barrier layer, and a heat-sealable resin layer having a specific thickness and containing a specific resin in this order. Such a packaging material is excellent in barrier properties and alkali resistance. The alkali-resistant packaging material may further include an adhesive layer between the base material layer and the heat-sealable resin layer, or may further include another resin layer.

  First, an embodiment of the alkali-resistant packaging material according to the present invention will be described with reference to a schematic cross-sectional view. The alkali-resistant packaging material 11 shown in FIG. 1 includes a base material layer 14, a barrier layer 13, and a heat sealable resin layer 12 in this order.

  2 includes a base material layer 26, a polyolefin resin layer 25, a barrier layer 24, a polyolefin resin layer 23, and a heat sealable resin layer 22 in this order. Hereinafter, each layer constituting the alkali-resistant packaging material will be described in detail.

<Base material layer>
Although the base material layer which comprises the alkali-resistant packaging material by this invention is not specifically limited, It is preferable to form using resin which has a moldability and transparency. For example, low density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer resin, ionomer resin, ethylene-acrylic acid copolymer resin, ethylene-ethyl acrylate copolymer Copolymer resin, ethylene-methacrylic acid copolymer, ethylene-propylene copolymer, methylpentene resin, polybutene resin, acid-modified polyolefin resin, polyamide resin, polystyrene resin, low crystalline saturated polyester or amorphous It can be formed using a polyester resin or the like. Of these, polyester resins, polybutylene terephthalate resins, polyethylene naphthalate resins, particularly polyethylene terephthalate (PET) resins are preferred because of good moldability and transparency. Usually, the thickness of the base material layer is preferably 5 to 100 μm and more preferably 10 to 50 μm from the viewpoint of moldability and transparency.

<Barrier layer>
The barrier layer constituting the alkali-resistant packaging material according to the present invention is made of an inorganic material or an inorganic oxide, and is preferably made of a vapor deposited film of an inorganic material or an inorganic oxide or a metal foil. Since the alkali-resistant packaging material has a barrier layer, gas barrier properties that prevent permeation of oxygen gas, water vapor, and the like can be improved. In addition, if necessary, light shielding properties that prevent transmission of visible light, ultraviolet light, and the like can be imparted. Note that the alkali-resistant packaging material may have two or more barrier layers. When two or more barrier layers are provided, each may have the same composition or a different composition. Usually, the thickness of the barrier layer is preferably 0.01 to 500 μm, more preferably 1 to 300 μm from the viewpoint of gas barrier properties and transparency.

  A conventionally known metal foil can be used as the inorganic or inorganic metal foil. Aluminum foil or the like is preferable from the viewpoint of gas barrier properties that prevent the transmission of oxygen gas, water vapor, and the like, and light shielding properties that prevent the transmission of visible light, ultraviolet light, and the like.

  A vapor deposition film can be formed by a conventionally known method using a conventionally known inorganic substance or inorganic oxide, and its composition and formation method are not particularly limited. As a method for forming a vapor deposition film, for example, a physical vapor deposition method (Physical Vapor Deposition method, PVD method) such as a vacuum vapor deposition method, a sputtering method, and an ion plating method, or a plasma chemical vapor deposition method, a thermochemical method, or the like. Examples thereof include a chemical vapor deposition method (chemical vapor deposition method, CVD method) such as a vapor phase growth method and a photochemical vapor deposition method.

  Examples of the deposited film include silicon (Si), aluminum (Al), magnesium (Mg), calcium (Ca), potassium (K), tin (Sn), sodium (Na), boron (B), and titanium (Ti). ), Lead (Pb), zirconium (Zr), yttrium (Y) and other inorganic or inorganic oxide vapor deposition films can be used. In particular, an aluminum metal vapor-deposited film or a silicon oxide or aluminum oxide vapor-deposited film is preferably used as a packaging material.

Notation inorganic oxides, _e.g., SiO X, as such AlO _X MO _X (In the formula, M represents an inorganic element, the value of X, varies each of an inorganic element range.) In expressed. As a range of the value of X, silicon (Si) is 0 to 2, aluminum (Al) is 0 to 1.5, magnesium (Mg) is 0 to 1, calcium (Ca) is 0 to 1, 0 to 0.5 for potassium (K), 0 to 2 for tin (Sn), 0 to 0.5 for sodium (Na), 0 to 1,5 for boron (B), titanium (Ti) Can take values in the range of 0 to 2, lead (Pb) in the range of 0 to 1, zirconium (Zr) in the range of 0 to 2, and yttrium (Y) in the range of 0 to 1.5. In the above, when X = 0, it is a complete inorganic simple substance (pure substance) and is not transparent, and the upper limit of the range of X is a completely oxidized value. Silicon (Si) and aluminum (Al) are preferably used for the packaging material, silicon (Si) is in the range of 1.0 to 2.0, and aluminum (Al) is in the range of 0.5 to 1.5. Values can be used.

  In the present invention, the film thickness of the inorganic material or inorganic oxide vapor-deposited film as described above varies depending on the kind of inorganic material or inorganic oxide used, but is, for example, about 10 to 2000 mm, preferably about 10 to 1000 mm. It is desirable to select and form arbitrarily within the range. Specifically, in the case of an aluminum deposited film, the film thickness is preferably about 10 to 600 mm, more preferably about 10 to 400 mm. In the case of a silicon oxide or aluminum oxide deposited film, the film thickness is preferably about 10 to 500 mm, more preferably 10 to 300 mm.

Hereinafter, as a preferred embodiment of the present invention, a deposited film of silicon oxide will be described in more detail. The deposited film (thin film) of silicon oxide is represented by the general formula: SiO _x (wherein x represents a number from 0 to 2), and the value of x is preferably 1.3 to 1.9. The silicon oxide thin film may be mainly composed of silicon oxide, and may further contain at least one kind of compound composed of one kind of carbon, hydrogen, silicon or oxygen, or two or more kinds of elements by chemical bonding or the like. For example, when a compound having a C—H bond, a compound having a Si—H bond, or a carbon unit is in the form of graphite, diamond, fullerene, or the like, the raw material organosilicon compound or a derivative thereof is further added. It may be contained by a chemical bond or the like. Examples thereof include hydrocarbons having a CH ₃ site, hydrosilica such as SiH ₃ silyl and SiH ₂ silylene, and hydroxyl derivatives such as SiH ₂ OH silanol. As content which said compound contains in the vapor deposition film | membrane of a silicon oxide, it is 0.1-50 mass%, Preferably it is 5-20 mass%. Moreover, when a silicon oxide thin film contains the said compound, it is preferable that content of a compound is reducing toward the depth direction from the surface of the vapor deposition film | membrane of a silicon oxide. As a result, the impact resistance and the like are enhanced by the above compound on the surface of the silicon oxide vapor deposition film, and on the other hand, the vapor deposition of the base material layer and the silicon oxide at the interface with the base material layer due to the low content of the above compound. The tight adhesion with the film becomes strong.

  In the present invention, it is preferable to further provide a barrier coating film on the silicon oxide vapor deposition film in order to enhance the gas barrier property. The gas barrier coating film can be formed by coating with a solution containing at least a water-soluble polymer having a hydroxyl group and alkoxysilane. Examples of the water-soluble polymer having at least a hydroxyl group include polyvinyl alcohol, polyvinyl pyrrolidone, starch, methyl cellulose, carboxymethyl cellulose, sodium alginate, an ethylene-vinyl alcohol copolymer, and the like. Polyvinyl alcohol is preferred. These resins may be commercially available. For example, as an ethylene / vinyl alcohol copolymer, Kuraray Co., Ltd., Eval EP-F101 (ethylene content: 32 mol%), Nippon Synthetic Chemical Industry Co., Ltd., Soarnol D2908 (ethylene content; 29 mol%) and the like can be used. Moreover, as polyvinyl alcohol, RS-110 (degree of saponification = 99%, degree of polymerization = 1,000) manufactured by Kuraray Co., Ltd., Kuraray Poval LM-20SO (degree of saponification = 40%) manufactured by Kuraray Co., Ltd. Polymerization degree = 2,000), Gohsenol NM-14 manufactured by Nippon Synthetic Chemical Industry Co., Ltd. (degree of saponification = 99%, degree of polymerization = 1,400) and the like can be used.

As alkoxysilane, the general formula:
R _1n Si (OR ₂ ) _m
(In the formula, R ₁ and R ₂ each independently represent an organic group having 1 to 8 carbon atoms, n represents an integer of 0 or more, m represents an integer of 1 or more, and n + m represents an Si atom. Can be suitably used. In the above formula, specific examples of the organic group represented by R ₁ include, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group. , T-butyl group, n-hexyl group, n-octyl group, and other alkyl groups. Specific examples of the alkoxysilane include, for example, tetramethoxysilane: Si (OCH ₃ ) ₄ , tetraethoxysilane: Si (OC ₂ H ₅ ) ₄ , tetrapropoxysilane: Si (OC ₃ H ₇ ) ₄ , tetrabutoxysilane. : Si (OC ₄ H ₉ ) ₄ or the like can be used.

  The above-mentioned water-soluble polymer and alkoxysilane are mixed, and a solution to which a sol-gel method catalyst, water, and an organic solvent are added as desired is applied to the surface of a thin film made of aluminum oxide or silicon oxide. By condensation, a gas barrier coating film can be formed. In the present invention, a composite polymer layer in which two or more of the above-described coating films are stacked may be formed on a thin film made of aluminum oxide or silicon oxide.

  Moreover, in this invention, a silane coupling agent can be added to said coating liquid for gas barrier coating-film formation, The gas barrier coating film obtained by this is especially preferable. As the silane coupling agent, known organic reactive group-containing organoalkoxysilanes can be used. In particular, an organoalkoxysilane having an epoxy group is suitable, for example, γ-glycidoxypropyltrimethoxy. Silane, γ-glycidoxypropylmethyldiethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, or the like can be used. The above silane coupling agents may be used alone or in combination of two or more. In this invention, the usage-amount of the above silane coupling agents can be used within the range of about 1-20 mass parts with respect to 100 mass parts of said alkoxysilane.

  As a coating method of the coating liquid for forming a gas barrier coating film, conventionally known means such as roll coating such as a gravure roll coater, spray coating, spin coating, dipping, brush, bar code, applicator and the like are used. . Although the thickness of a coating film changes with kinds of coating liquid, the thickness after drying becomes like this. Preferably it is the range of 0.01-100 micrometers, More preferably, it is 0.01-50 micrometers. If the thickness after drying is 100 μm or less, the occurrence of cracks can be suppressed.

  As a sol-gel method catalyst for polycondensation with a coating solution, a tertiary amine that is substantially insoluble in water and soluble in an organic solvent is used. Specifically, for example, N, N-dimethylbenzylamine, tripropylamine, tributylamine, tripentylamine and the like can be used. In particular, N, N-dimethylbenzylamine is suitable, for example, 0.01 to 1.0 part by weight, particularly about 0.03 part by weight, per 100 parts by weight of the total amount of alkoxysilane and silane coupling agent. It is preferable to use it.

  Moreover, an acid can also be used as a catalyst of a sol-gel method, for example, mineral acids, such as a sulfuric acid, hydrochloric acid, nitric acid, organic acids, such as an acetic acid and tartaric acid, and others can be used. The amount of the acid used is preferably 0.001 to 0.05 mol, and more preferably 0.01 to 0.05 mol with respect to the total molar amount of alkoxysilane and the alkoxysilane content (for example, silicate moiety) of the silane coupling agent. 0.03 mol.

  The water contained in the coating solution is preferably added in a proportion of 0.1 to 100 mol, more preferably 0.8 to 2 mol, with respect to 1 mol of the total molar amount of the solution alkoxide. Moreover, it is preferable that the polyvinyl alcohol and the ethylene-vinyl alcohol copolymer contained in the coating liquid for forming a gas barrier coating film are in a state dissolved in a coating liquid containing the above alkoxysilane, silane coupling agent, and the like. Therefore, an organic solvent may be appropriately selected and added. For example, as the organic solvent, methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butanol and the like can be used.

<Heat seal layer>
The heat seal layer constituting the alkali-resistant packaging material according to the present invention comprises a cyclic polyolefin and has a thickness of 3 to 50 μm. The thickness of the heat seal layer is preferably 4 μm to 40 μm, more preferably 5 μm to 30 μm. By disposing the cyclic polyolefin resin layer on the contents side when the packaging container is formed, the non-adsorption property for the drug can be increased and the alkali resistance can be improved.

  Specifically, the cyclic polyolefin is a polymer obtained by hydrogenating a ring-opening (co) polymer of a cyclic olefin as necessary, an addition (co) polymer of a cyclic olefin, a cyclic olefin, and an α such as ethylene or propylene. -Means a random copolymer with olefin, or a graft modified product obtained by modifying the above (co) polymer with an unsaturated carboxylic acid or a derivative thereof. Among these, a cyclic olefin copolymer (COC) obtained by addition polymerization of norbornene and an ethylene unit and a cyclic olefin polymer (COP) obtained by ring-opening polymerization of cyclopentadiene and stabilization by hydrogenation can be suitably used. .

  The formation method of a cyclic polyolefin resin layer is not specifically limited, It can form by a conventionally well-known method. For example, the cyclic polyolefin resin layer may be formed by extrusion molding a cyclic polyolefin resin or a cyclic polyolefin resin film. Commercially available cyclic polyolefin resin films may be used. For example, as COC, TOPAS (manufactured by Polyplastics Co., Ltd.) and Apel (manufactured by Mitsui Chemicals) are used, and as COP, ZEONEX ( Nippon Zeon Co., Ltd.), ZEONOR (Nihon Zeon Co., Ltd.), etc. can be used conveniently.

  The heat-sealable resin layer may further contain a polyolefin. Examples of polyolefin resins include low-density polyethylene, linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, polymethylpentene, etc., or a mixture of polypropylene and low-density polyethylene, or polypropylene and high-density polyethylene. And the like.

  The content of the cyclic polyolefin in the heat-sealable resin layer is preferably 50 to 100% by mass, more preferably 60 to 99% by mass, and still more preferably based on the entire resin in the heat-sealable resin layer. Is 70-97 mass%. The polyolefin content in the heat-sealable resin layer is preferably 1 to 40% by mass, more preferably 3 to 30% by mass.

<Adhesive layer>
The adhesive layer constituting the alkali-resistant packaging material according to the present invention is an adhesive layer or an adhesive resin layer formed in order to bond any two layers by lamination. As an adhesive for laminating, for example, one or two-component cured or non-cured vinyl type, (meth) acrylic type, polyamide type, polyester type, polyether type, polyurethane type, epoxy type, rubber type, Other adhesives such as solvent type, aqueous type, and emulsion type can be used. Examples of the coating method for the adhesive include a direct gravure roll coating method, a gravure roll coating method, a kiss coating method, a reverse roll coating method, a fountain method, a transfer roll coating method, and other methods. As the coating ^{amount, 0.1g / m 2 ~10g / m} 2 ( dry state) position are ^{preferred, 1g / m 2 ~5g / m} 2 ( dry state) position is more preferred.

  In addition, a resin layer made of a thermoplastic resin layer is used as the adhesive resin layer. Specifically, the material of the adhesive resin layer includes a low density polyethylene resin, a medium density polyethylene resin, a high density polyethylene resin, a linear low density polyethylene resin, and an ethylene-α olefin polymerized using a metallocene catalyst. Copolymer resin, ethylene-polypropylene copolymer resin, ethylene-vinyl acetate copolymer resin, ethylene-acrylic acid copolymer resin, ethylene-ethyl acrylate copolymer resin, ethylene-methacrylic acid copolymer resin, Graft polymerization of unsaturated carboxylic acid, unsaturated carboxylic acid, unsaturated carboxylic acid anhydride, ester monomer to ethylene-methyl methacrylate copolymer resin, ethylene-maleic acid copolymer resin, ionomer resin, polyolefin resin, Or graft copolymerized resin, maleic anhydride to polyolefin resin It can be used sexual resin or the like. These materials can be used alone or in combination.

  In the present invention, it is preferable to use a polyolefin-based adhesive resin having a polar group introduced as the adhesive resin layer. By introducing a polar group into nonpolar polyolefin, it is possible to improve the adhesion between the barrier layer made of an inorganic substance or an inorganic oxide and the heat-sealable resin layer containing the polyolefin. In the present invention, a commercially available polyolefin adhesive resin into which a polar group is introduced can be used, and examples thereof include Admer (manufactured by Mitsui Chemicals, Inc.).

<Other resin layers>
Examples of other resin layers constituting the alkali-resistant packaging material according to the present invention include polyamide resin layers and polyolefin resin layers. As the polyamide resin layer, nylons such as nylon 6, nylon 6, 6, and nylon 12 are preferably used. By using nylons, it is possible to impart flex resistance to the alkali-resistant packaging material. As the polyolefin resin layer, low density polyethylene, linear low density polyethylene, medium density polyethylene, high density polyethylene, polypropylene, polymethylpentene, etc., or a mixture of polypropylene and low density polyethylene, polypropylene and high density Examples thereof include a mixture with polyethylene. The formation method of another resin layer is not specifically limited, It can form by a conventionally well-known method. For example, the other resin layer may be formed by extrusion molding of a resin or a resin film.

<Additives>
Various conventionally known additives such as a light stabilizer, an ultraviolet absorber, an antioxidant, a filler, a lubricant and the like may be appropriately added to the resin layer constituting the alkali-resistant packaging material according to the present invention as necessary. it can. Conventionally known light stabilizers and ultraviolet absorbers can be used. For example, phenol-based, phosphorus-based, hindered amine-based light absorbers, benzotriazole-based, benzophenone-based, and salicylic acid ester-based ultraviolet absorbers are used. it can.

<Alkali resistant packaging container>
The alkali-resistant packaging container according to the present invention is made of the alkali-resistant packaging material according to the present invention, and the heat-sealable resin layer of the alkali-resistant packaging material is arranged on the content side. Alkali resistance can be improved by arrange | positioning a heat-sealable resin layer in the contents side.

<Application>
The alkali-resistant packaging container according to the present invention can accommodate various contents, and the contents are not particularly limited. Since the alkali-resistant packaging container according to the present invention is excellent in alkali resistance, it can be accommodated even in a highly alkaline solution having a pH of 12 or more. For example, it can be suitably used as a medical packaging container, and can also contain a liquid formulation or the like that requires long-term storage. An example of the medical packaging container is a chemical solution bag.

[Example 1]
<Preparation of alkali-resistant packaging material>
A biaxially stretched polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., model number: T-4102) having a thickness of 12 μm was prepared as a base material layer. One surface of the polyethylene terephthalate film and an aluminum foil (made in Japan) One surface of Foil Co., Ltd .: 1N30 material) was bonded with polyethylene extruded at 300 ° C. by extrusion lamination (Ube Maruzen Polyethylene Co., Ltd .: Z568, thickness 15 μm). Next, after coating an anchor coating agent (acid-modified polyolefin, manufactured by Unitika Ltd., model number: SE-1200) on the other surface of the aluminum foil, a linear low density polyethylene resin (thickness 20 μm, (Manufactured by Prime Polymer Co., Ltd., model number: SP2020) and cyclic polyolefin resin (thickness 5 μm, containing 3-5% by mass of linear low density polyethylene resin, heat-sealable resin layer, manufactured by Polyplastics Co., Ltd., Model No. TOPAS 8007F-500) was coextruded at 300 ° C. to obtain an alkali-resistant packaging material of Example 1. The layer structure of the alkali-resistant packaging material of Example 1 was as shown in FIG.

<Preparation of alkali-resistant packaging container>
A pouch with a spout and a four-way pouch were prepared using the alkali-resistant packaging material of Example 1 prepared above.

[Example 2]
<Preparation of alkali-resistant packaging material>
A biaxially stretched polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., model number: T-4102) having a thickness of 12 μm was prepared as a base material layer. One surface of the polyethylene terephthalate film and an aluminum foil (made in Japan) One surface of Foil Co., Ltd .: 1N30 material) was bonded with polyethylene extruded at 300 ° C. by extrusion lamination (Ube Maruzen Polyethylene Co., Ltd .: Z568, thickness 15 μm). Next, after coating an anchor coating agent (acid-modified polyolefin, manufactured by Unitika Ltd., model number: SE-1200) on the other surface of the aluminum foil, a linear low density polyethylene resin (thickness 20 μm, (Manufactured by Prime Polymer Co., Ltd., model number: SP2020), cyclic polyolefin resin (thickness 10 μm, containing 3-5% by mass of linear low density polyethylene resin, heat-sealable resin layer, manufactured by Polyplastics Co., Ltd., No. TOPAS 8007F-500) was coextruded at 300 ° C. to obtain an alkali-resistant packaging material of Example 2. The layer structure of the alkali-resistant packaging material of Example 2 was as shown in FIG.

<Preparation of alkali-resistant packaging container>
Using the alkali-resistant packaging material of Example 2 produced above, a pouch with a spout and a 4-way pouch were produced in the same manner as in Example 1.
[Example 3]
<Preparation of alkali-resistant packaging material>
A biaxially stretched polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., model number: T-4102) having a thickness of 12 μm was prepared as a base material layer. One surface of the polyethylene terephthalate film and an aluminum foil having a thickness of 7 μm (made in Japan) One surface of Foil Co., Ltd .: 1N30 material) was bonded with polyethylene extruded at 300 ° C. by extrusion lamination (Ube Maruzen Polyethylene Co., Ltd .: Z568, thickness 15 μm). Next, after coating an anchor coating agent (acid-modified polyolefin, manufactured by Unitika Ltd., model number: SE-1200) on the other surface of the aluminum foil, a linear low density polyethylene resin (thickness 20 μm, (Manufactured by Prime Polymer Co., Ltd., model number: SP2020), cyclic polyolefin resin (thickness 20 μm, containing 3-5% by mass of linear low density polyethylene resin, heat-sealable resin layer, manufactured by Polyplastics Co., Ltd., Model No. TOPAS 8007F-500) was coextruded at 300 ° C. to obtain an alkali-resistant packaging material of Example 3. The layer structure of the alkali-resistant packaging material of Example 3 was as shown in FIG.

<Preparation of alkali-resistant packaging container>
Using the alkali-resistant packaging material of Example 3 produced above, a pouch with a spout and a 4-way pouch were produced in the same manner as in Example 1.

[Comparative Example 1]
<Preparation of alkali-resistant packaging material>
A biaxially stretched polyethylene terephthalate film (manufactured by Toyobo Co., Ltd., model number: T-4102) having a thickness of 12 μm was prepared as a base material layer. One surface of the polyethylene terephthalate film and an aluminum foil having a thickness of 7 μm (made in Japan) One surface of Foil Co., Ltd .: 1N30 material) was bonded with polyethylene extruded at 300 ° C. by extrusion lamination (Ube Maruzen Polyethylene Co., Ltd .: Z568, thickness 15 μm). Next, the other surface of the aluminum foil and a surface subjected to a corona treatment of a 25 μm-thick low-density polyethylene film (manufactured by Nippon Polyethylene Co., Ltd .: Novatec) are bonded to an anchor coating agent (acid-modified polyolefin, unitica ( It was bonded via a product, model number: SE-1200) to obtain an alkali-resistant packaging material of Comparative Example 1.

<Preparation of alkali-resistant packaging container>
Using the alkali-resistant packaging material of Comparative Example 1 produced above, a pouch with a spout and a 4-way pouch were produced in the same manner as in Example 1.

<Evaluation of alkali-resistant packaging container>
The pouches prepared in the above examples and comparative examples were filled with a sodium hydroxide aqueous solution of pH 13 and sealed to prepare a sample. Samples were retorted (121 ° C. for 20 minutes or 110 ° C. for 30 minutes) for heat sterilization. After the retort treatment, an acceleration test was conducted for 3 weeks in a dry environment at 60 ° C. From the retort treatment to the end of the acceleration test, the change in the mass of the sample was measured several times (−%, the amount of decrease with respect to the sample mass immediately after production). The results are shown in Table 1. The mass change after completion of the acceleration test is preferably 5% by mass or less.

  Next, the laminate strength of the sample was measured before the retort treatment, after the retort treatment, and after the acceleration test was completed. The laminate strength is measured by cutting each sample into a width of 15 mm, and using a tensile tester (Orientec Co., Ltd .: Tensilon RTC-125A) to measure the laminate strength (N / 15 mm) at a speed of 50 mm / min. did. The results are shown in Table 2.

  As shown in Table 2, in Examples 1 to 3, no significant decrease in delamination strength or delamination occurred. However, in Comparative Example 1, it was found that delamination occurred and the alkali resistance was poor.

DESCRIPTION OF SYMBOLS 11 Alkali-resistant packaging material 12 Heat sealable resin layer 13 Barrier layer 14 Base material layer 21 Alkali resistant packaging material 22 Heat sealable resin layer 23 Polyolefin resin layer 24 Barrier layer 25 Polyolefin resin layer 26 Base material layer

Claims (10)

A base material layer;
A barrier layer made of an inorganic substance or an inorganic oxide;
A heat-sealable resin layer having a thickness of 3 to 50 μm and comprising a cyclic polyolefin;
An alkali-resistant packaging material comprising   The alkali-resistant packaging material according to claim 1, wherein the heat-sealable resin layer further comprises a polyolefin.   The alkali-resistant packaging material according to claim 1, wherein the barrier layer is formed of an inorganic or inorganic oxide vapor deposition film.   The alkali-resistant packaging material according to claim 1, wherein the barrier layer is made of a metal foil.   The alkali-resistant packaging material according to any one of claims 1 to 4, further comprising an adhesive layer between the base material layer and the heat-sealable resin layer.   The alkali-resistant packaging material according to any one of claims 1 to 5, further comprising a polyamide resin layer between the base material layer and the heat-sealable resin layer.   The alkali-resistant packaging material according to any one of claims 1 to 6, further comprising a polyolefin resin layer between the base material layer and the heat-sealable resin layer.   The alkali resistant packaging container which consists of an alkali resistant packaging material as described in any one of Claims 1-7, and the said heat-sealable resin layer is arrange | positioned at the contents side.   The alkali-resistant packaging container according to claim 8, wherein the content is an alkaline solution having a pH of 12 or more.   The alkali-resistant packaging container according to claim 8 or 9, wherein the content is a liquid preparation.

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