JP2008087293A - Composite film, bottom material for deep drawing molding using composite film, and deep drawing package - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a composite film which has high moisture proofing properties, can carry out deep drawing molding according to a mold when the deep drawing molding is carried out, has good transparency, and is good in curling resistance even when the film includes a polyamide layer. <P>SOLUTION: In the composite film comprising an outer layer, an intermediate layer, and an inner layer, at least one polypropylene layer and/or a polyethylene layer of 30-100 μm thick are arranged in the outer layer, at least one polyamide layer and at least one cyclic polyolefin layer of 50-500 μm thick are arranged in the intermediate layer, and a heat seal resin layer is arranged in the inner layer. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a film and a deep-drawn package that can be suitably used mainly as a bottom material for deep-drawing molding. In particular, the present invention relates to a composite film and a deep-drawn package that are highly moisture-proof, highly transparent, rigid, and have good curling of the flange portion of the package when molded into a deep-drawn package.

  Conventionally, a composite film mainly composed of polypropylene (PP) or high-density polyethylene (HDPE) has been used as a deep drawing composite film requiring moisture resistance (see, for example, Patent Document 1). However, in order to impart moisture resistance to such a composite film, the layer of polypropylene (PP) or polyethylene (HDPE) must be thickened. If the layer of polypropylene (PP) or polyethylene (HDPE) is thickened, the moldability of the composite film (hereinafter also referred to as “deep drawability”) deteriorates when deep drawing is performed. There is a problem that a deep drawing molding equipment using (equipment for supplementing deep drawing moldability) is necessary, and transparency is further deteriorated.

Moreover, a composite film having a cycloolefin polymer (COP) layer and an ethylene-vinyl acetate copolymer resin (EVOH) layer is used as a composite film having good moisture resistance, transparency and moldability (Patent Document 2). The laminated film in which the polyamide (PA) layer is added to the composite film has a problem that the polyamide (PA) absorbs moisture and the film is curled (hereinafter referred to as “curling property”).
Japanese Patent Laid-Open No. 06-305099 JP 2003-191380 A

  Therefore, the object of the present invention is to have a high moisture-proof property, and when deep drawing is performed, it can be deep drawn as in the mold (deep drawing formability), has good transparency, and has a polyamide layer. An object of the present invention is to provide a composite film having good curl resistance even if it is a composite film.

  Another object of the present invention is to provide a deep-drawing molding bottom material and a deep-drawn packaging body that are excellent in moisture resistance, transparency, and curl resistance, using the composite film.

  As a result of intensive studies on the layer structure and composition of the film in order to solve the above problems, the present inventor has completed the following present invention.

  That is, an object of the present invention is to provide a composite film comprising an outer layer, an intermediate layer, and an inner layer, wherein the outer layer has at least one polypropylene layer and / or polyethylene layer of 30 μm to 100 μm, and the intermediate layer has at least one layer. This is solved by a composite film comprising a polyamide layer and a cyclic polyolefin layer having a thickness of at least 50 μm or more and 500 μm or less and a heat seal resin layer as an inner layer.

  As a preferred embodiment of the composite film of the present invention, the cyclic polyolefin has a glass transition temperature of 60 ° C. or higher and 140 ° C. or lower, and 5% by mass or more and 50% by mass or less based on the total mass of the components constituting the cyclic polyolefin layer. The low-density polyethylene and / or linear low-density polyethylene, the intermediate layer has at least one adhesive resin layer, and the heat-seal resin layer is low-density polyethylene, linear Low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer, ethylene-methyl methacrylate copolymer, ethylene- Methyl acrylate copolymer, ethylene-acrylic acid copolymer ionomer, and The heat-seal resin layer is composed of at least one selected from the group consisting of ionomers of ethylene-methacrylic acid copolymers, the heat-seal resin layer has an easy peel property, and the heat-seal resin layer having the easy peel property. A composite film having an easy peel strength of 0.8 N / 15 mm width to 15.0 N / 15 mm width at 25 ° C. is included.

  Further, the present invention provides a deep-drawing molding base material formed by using the composite film described above, a deep-drawing packaging body using the molding base material, and a plurality of depths The deep-drawn package having the draw-molded portion.

  The present invention provides a polypropylene layer and / or a polyethylene layer having at least one predetermined thickness as an outer layer, at least one polyamide layer as an intermediate layer and at least one cyclic polyolefin layer having a predetermined thickness, and heat sealing as an inner layer. Each has a resin layer. Thereby, if it is a composite film of this invention, while having favorable moisture-proof property, a moldability, and transparency, when shape | molding in a deep drawing package, favorable curl resistance can be exhibited.

  Moreover, since the composite film is used for the deep drawing bottom material and the deep drawing package of the present invention, it is possible to exhibit excellent moisture resistance, transparency, and curl resistance.

  Hereinafter, the composite film, the deep drawing bottom material, and the deep drawing package of the present invention will be described in detail, but the present invention is not limited to the embodiments described below.

<Composite film>
The composite film in this invention means the film which has a 3 or more resin layer, and is comprised by the inner layer, the intermediate | middle layer, and the outer layer. In the present specification, the “inner layer” means, for example, a layer in contact with a content and a lid (hereinafter referred to as “content etc.”) when the composite film of the present invention is used as a bottom material for deep drawing. Say. The “inner layer” in the case of providing an easy peel property of the delamination type refers to a layer in contact with the contents, etc., as well as an adjacent layer on the surface opposite to the side in contact with the contents of this layer. The layer which also contains. The “outer layer” means a layer opposite to the inner layer, and more specifically, a polypropylene (PP) layer, a polyethylene (PE) layer, and both a polypropylene (PP) layer and a polyethylene (PE) layer. Say. The “intermediate layer” refers to a layer sandwiched between the inner layer and the outer layer.

<Inner layer>
The composite film of the present invention is provided with a heat seal resin layer as an inner layer. The heat seal resin used in the heat seal resin layer is not particularly limited as long as it is a resin that can exhibit heat seal characteristics at the time of molding. However, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), polypropylene ( PP), ethylene-vinyl acetate copolymer (EVA), ethylene-acrylic acid copolymer (EAA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methacrylic acid copolymer (EMAA), ethylene- Methyl methacrylate copolymer (EMMA), ethylene-methyl acrylate copolymer (EMA), ethylene-acrylic acid copolymer (EAA) ionomer, and ethylene-methacrylic acid copolymer (EMAA) ionomer It is preferably composed of at least one selected from the group. Among these, from the viewpoint of improving the heat seal strength, it is more preferable to use low density polyethylene (LDPE) or linear low density polyethylene (LLDPE).

  The lower limit of the thickness of the heat seal resin layer is preferably 5 μm or more, more preferably 7 μm or more, and further preferably 10 μm or more. The upper limit of the thickness of the heat seal resin layer is preferably 100 μm or less, more preferably 70 μm or less, and further preferably 50 μm or less. By setting the lower limit of the thickness to 5 μm, good heat sealability can be maintained, and by setting the upper limit to 100 μm, the thickness of the film does not become unnecessarily thick and good transparency can be maintained.

  The inner layer of the composite film of the present invention preferably imparts easy peel properties to the heat seal resin layer in consideration of opening of the package. The easy peel type to be applied may be any of cohesive failure type, delamination type, and interfacial peeling type. For example, when imparting cohesive failure type easy peel properties, a blend resin of polyethylene and polypropylene can be used for the inner layer. Further, when providing an easy peel property of the delamination type, for example, the polyethylene layer and the polypropylene layer can be arranged adjacent to each other so as to delaminate the polyethylene layer and the polypropylene layer. When providing an easy peel property of the delamination type, the inner layer has two or more layers.

  When the heat seal resin layer has an easy peel property, the lower limit of the easy peel strength at 25 ° C. is 0.8 N / 15 mm width or more, preferably 1.96 N / 15 mm width or more, more preferably 2.94 N / 15 mm width or more. The upper limit is 15.0 N / 15 mm width or less, preferably 9.81 N / 15 mm width or less, and more preferably 7.84 N / 15 mm width or less. When the easy peel strength is 0.80 N / 15 mm width or more at 25 ° C., bag breakage during transportation can be prevented. Moreover, favorable openability can be obtained by making an upper limit into 15.0 N / 15mm width.

  When the easy peel property is imparted to the heat seal resin layer, the lower limit of the thickness of the inner layer is 2 μm or more, preferably 5 μm or more, more preferably 7 μm or more, and the upper limit is 15 μm or less, preferably 12 μm or less, The thickness is preferably 10 μm or less. By making the thickness of the inner layer 2 μm or more when providing easy peel properties, it is possible to provide a sealing property that can withstand bag breakage during transportation, and by making the thickness 15 μm or less, there is no film residue, etc. Good.

<Intermediate layer>
The intermediate layer of the composite film of the present invention is provided with at least one cyclic polyolefin layer or a plurality of cyclic polyolefin layers for the purpose of improving the moisture resistance of the composite film. Cyclic polyolefin is a polymer having an alicyclic hydrocarbon group in the molecule. The cyclic polyolefin used for the cyclic polyolefin layer has a glass transition temperature (hereinafter also referred to as Tg) of 60 ° C. or higher, preferably 65 ° C. or higher, more preferably 70 ° C. or higher, and an upper limit of 140 ° C. or lower, preferably 135. ° C or lower, more preferably 130 ° C or lower. By setting the Tg of the cyclic polyolefin to 60 ° C or higher, there is no softening of the film even when the temperature is high during storage of the film, and it is possible to prevent squeezing in a state where the film is wound around a paper tube due to the softening of the film at a high temperature. In addition, the package due to the softening of the film at a high temperature does not soften and the shape of the package cannot be maintained. In addition, by setting the Tg of the cyclic polyolefin to 140 ° C. or less, good deep drawability can be imparted, and it is not necessary to set the extrusion temperature high during film formation. Since heat is not applied as necessary, it is possible to suppress defects, gels, and the like due to thermal degradation.

  The lower limit of the thickness of the cyclic polyolefin layer is 50 μm or more, preferably 70 μm or more, and more preferably 100 μm or more. The upper limit is 500 μm or less, preferably 400 μm or less, and more preferably 350 μm or less. By setting the lower limit of the thickness of the cyclic polyolefin layer to 50 μm or more, sufficient moisture resistance and moldability can be obtained, and by combining the upper limit of the thickness of the cyclic polyolefin layer to 500 μm or less, a composite that can be deep drawn It can be a film.

  As the cyclic polyolefin, a cycloolefin copolymer (COC) and a cycloolefin polymer (COP) can be used. Here, the cycloolefin copolymer (COC) refers to a cyclic polyolefin obtained by addition polymerization of dicyclopentadiene or a dicyclopentadiene derivative and an α-olefin. The cycloolefin polymer (COP) refers to a cyclic polyolefin obtained by ring-opening polymerization of a cyclic olefin. From the viewpoint that the Tg of COC can be controlled by adjusting the content of the cyclic olefin monomer, it is desirable to use a cycloolefin copolymer, but this is not the main purpose of adding a limitation.

  The cyclic polyolefin may contain low density polyethylene (LDPE) and / or linear low density polyethylene (LLDPE). It is possible to moderately soften the film by incorporating low density polyethylene (LDPE) and / or linear low density polyethylene (LLDPE) into the cyclic polyolefin.

  The lower limit of the content of the low-density polyethylene (LDPE) and / or the linear low-density polyethylene (LLDPE) is 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass of the total components constituting the cyclic polyolefin layer. The upper limit is 50% by mass or less, preferably 45% by mass or less, and more preferably 40% by mass or less. When the content is 5% by mass or more, the composite film can be moderately softened, and when the content is 50% by mass or less, it is possible to suppress a decrease in deep drawability due to softening. In addition, the component which comprises a cyclic polyolefin layer means all things, such as resin which comprises the cyclic polyolefin layer, and an additive.

  In the composite film of the present invention, at least one polyamide (PA) layer is disposed in the intermediate layer from the viewpoint of imparting pinhole resistance and deep drawability.

  The polyamide constituting the polyamide (PA) layer is not particularly limited, and a polyamide (PA) layer containing a lactam having a three-membered ring or more, a polymerizable ω-amino acid, a diamine and a dicarboxylic acid as main components (50 mol% or more) may be used. preferable. The polyamide may be a copolymer of a polyamide component and other components (for example, ω-amino acid, diamine and dicarboxylic acid as main components (50 mol% or more)). The mol% is preferably 80 mol% or more, more preferably 85 mol% or more, and further preferably 90 mol% or more. The upper limit of the polyamide component is a typical copolymer. The upper limit is 99 mol% or less. The polyamide may be a polymer blend. In that case, the polyamide component is preferably 70% by mass or more and 75% by mass or more based on the mass of the entire polymer blend (100% by mass). More preferably, the upper limit value of the polyamide component, more preferably 80% by mass or more, is the upper limit value of a typical copolymer, and is 99% by mass or less.

  Examples of the lactam having 3 or more members include ε-caprolactam, ω-enantolactam, ω-laurolactam, α-pyrrolidone and the like. Examples of the polymerizable ω-amino acid include ω-aminocaproic acid, ω-aminoheptanoic acid, ω-aminononanoic acid, ω-aminoundecanoic acid, and ω-aminododecanoic acid. Examples of the diamine include tetramethylene diamine, hexamethylene diamine, heptamethylene diamine, octamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, and 2,2,4-tochimethyl hexamethylene diamine. Aliphatic amines such as 2,4,4-totimethylhexamethylenediamine, 1,3 / 1,4-bis (aminomethyl) cyclohexane, isophoronediamine, piperazine, bis (4-aminocyclohexyl) methane, 2,2 Examples include alicyclic diamines such as -bis- (4'-aminocyclohexyl) propane, and aromatic diamines such as metaxylylenediamine and paraxylylenediamine. Examples of the dicarboxylic acid include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, nonanedioic acid, decanedioic acid, undecanedioic acid, dodecanedioic acid and other aliphatic dicarboxylic acids, hexahydroterephthalic acid, Hexahydroisophthalic acid and other alicyclic carboxylic acids, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid (1,2-form, 1,3-form, 1,4-form, 1,5-form, 1,6- , 1,7-isomer, 1,8-isomer, 2,3-isomer, 2,6-isomer, 2,7-isomer), and aromatic dicarboxylic acids such as metal-isophthalsulfonic acid.

  In the polyamide (PA) layer, a lactam having three or more members, a polymerizable ω-amino acid, a polyamide homopolymer or copolymer derived from diamine and dicarboxylic acid can be used alone or as a mixture. Specifically, for example, 4 nylon, 6 nylon, 7 nylon, 11 nylon, 12 nylon, 46 nylon, 66 nylon, 69 nylon, 610 nylon, 611 nylon, 6T nylon, 6I nylon, MXD6 nylon, 6-66 Nylon, 6-610 nylon, 6-611 nylon, 6-12 nylon, 6-612 nylon, 6-6T nylon, 6-6I nylon, 6-66-610 nylon, 6-66-12 nylon, 6-66- 612 nylon, 66-6T nylon, 66-6I nylon, 6T-6I nylon, 66-6T-6I nylon and the like.

  For the polyamide (PA) layer, it is preferable to use a nylon resin from the viewpoint of pinhole resistance, and it is particularly preferable to use 6 nylon or 6-66 nylon. Two or more polyamide (PA) layers can be provided, and in this case, each layer may be formed of different types of nylon resins.

  The lower limit of the thickness of the polyamide (PA) layer is preferably 10 μm or more, more preferably 15 μm or more, and further preferably 20 μm or more. The upper limit is preferably 200 μm or less, more preferably 170 μm or less, and even more preferably 150 μm or less. When the lower limit of the thickness of the polyamide (PA) layer is 10 μm or more, good pinhole resistance is obtained, and when the upper limit is 200 μm or less, the deep drawability can be maintained well.

  The intermediate layer in the composite film of the present invention can be provided with an adhesive resin layer as necessary for the purpose of increasing the delamination strength of each layer. The adhesive resin layer in the intermediate layer may be one layer or plural. Moreover, as a layer which an adhesive resin layer distributes, it can arrange | position suitably between an intermediate | middle layer and an outer layer, between an intermediate | middle layer and an inner layer, and between each layer which comprises an intermediate | middle layer.

  Adhesive resins that can be used in the adhesive resin layer are polyethylene (PE) such as low density polyethylene (LDPE), linear low density polyethylene (LLDPE), medium density polyethylene (MDPE), and high density polyethylene (HDPE), and polypropylene (PP). Olefin resins such as ethylene-vinyl acetate copolymer (EVA), ethylene-methyl methacrylate copolymer (EMMA), ethylene-ethyl acrylate copolymer (EEA), ethylene-methyl acrylate copolymer (EMA) , Ethylene-ethyl acrylate-maleic anhydride copolymer (E-EA-MAH), ethylene-acrylic acid copolymer (EAA), ethylene-methacrylic acid copolymer (EMMA), ethylene ionomer (ION), etc. Examples of other ethylene copolymer resins are other examples. Polyolefin resin such as ethylene-vinyl acetate copolymer or ethylene elastomer, monobasic unsaturated fatty acid such as acrylic acid or methacrylic acid, or dibasic fatty acid such as maleic acid, fumaric acid or itaconic acid. Examples include chemically bonded anhydrides. Among them, it is preferable to use an adhesive resin based on polyethylene.

  When the adhesive resin layer is provided, the lower limit of the thickness of the adhesive resin layer is preferably 3 μm or more, more preferably 5 μm or more, and further preferably 8 μm or more. The upper limit is not particularly limited, but is preferably 30 μm or less, more preferably 25 μm or less, and further preferably 20 μm or less. When the thickness of the adhesive resin layer is 3 μm or more, the delamination strength can be improved. In addition, if the adhesive resin layer is too thick, the total thickness of the bottom material is increased, and the physical and chemical characteristics of the adhesive resin are expressed in the entire composite film. Therefore, the upper limit is preferably 30 μm.

  The intermediate layer of the composite film of the present invention may have at least one poreimide (PA) layer and cyclic polyolefin layer, and may further be provided with other layers. Examples of the other layer include an ethylene-vinyl acetate copolymer resin layer, a polyethylene layer, and a polypropylene layer.

<Outer layer>
The outer layer of the composite film of the present invention is provided with a polypropylene (PP) layer and / or a polyethylene (PE) layer in order to suppress the occurrence of curling of the composite film due to moisture absorption of the polyamide layer. When a polypropylene (PP) layer and a polyethylene (PE) layer are laminated, the outer layer has two layers.

  Examples of the polypropylene (PP) used in the polypropylene (PP) layer include homopolymers, block copolymers, and random copolymers. A homopolymer is preferably used from the viewpoint of rigid properties, and a random copolymer is preferably used from the viewpoint of transparency and deep drawability.

  The polyethylene (PE) used in the polyethylene (PE) layer is not particularly limited, and various polyethylene (PE) can be used. For example, low density polyethylene (LDPE), linear low density polyethylene (LLDPE), high density polyethylene (HDPE), ethylene-vinyl acetate copolymer (EVA), ethylene-ethylene acrylate copolymer, ethylene-acrylic acid copolymer It is preferable to use a polymer, an ethyl-methyl acrylate copolymer, an ethylene-methyl methacrylate copolymer, an ethylene ionomer resin, or a mixture thereof. It is more desirable to use linear low density polyethylene (LLDPE) in terms of transparency, film forming property and cost.

  The lower limit of the thickness of the outer layer in the composite film of the present invention is preferably 30 μm or more, more preferably 35 μm or more, further preferably 40 μm or more, and the upper limit is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 70 μm or less. . By setting the lower limit value to 30 μm or more, it is possible to maintain a state where no curling occurs in the package, and by setting the upper limit value to 100 μm or less, the film is not unnecessarily thickened. The thickness of the outer layer in which polypropylene (PP) and polyethylene (PP) are laminated is also 30 μm or more and 100 μm or less.

  The inner layer, the intermediate layer, and the outer layer of the composite film of the present invention can contain other resins and additives as long as the effects of the present invention are not impaired. For example, additives such as a heat resistance stabilizer, an oxidation resistance stabilizer, a weather resistance stabilizer, an ultraviolet absorber, a pigment, and a dye may be included as appropriate.

<Layer structure>
The layer structure of the composite film of the present invention comprises at least one polyamide layer and at least one cyclic polyolefin layer as an intermediate layer, a heat seal resin layer as an inner layer, at least one polypropylene (PP) layer and / or polyethylene as an outer layer. It has a (PE) layer. If the thickness of the outer polypropylene layer and / or polyethylene layer is 30 μm or more and 100 μm or less, and the thickness of the cyclic polyolefin layer is 50 μm or more and 500 μm or less, the other layer configuration is not particularly limited.

  For example, a cyclic polyolefin layer (A), a polyamide layer (B), a polyethylene layer (C), a polypropylene layer (D), a heat seal resin layer (E) imparted with easy peel properties, an adhesive resin layer (F), and When represented by the heat seal resin layer (G), the following layer structure can be formed. Among these, a preferable layer configuration is the following (2), (3), (4), (7) or (8), and a more preferable layer configuration is (4) or (8).

(1) C / A / F / B / F / G
(2) C / F / A / F / B / E
(3) C / F / A / F / B / F / G
(4) C / F / B / F / A / F / G
(5) D / A / F / B / F / G
(6) D / F / A / F / B / G
(7) D / F / A / F / B / F / G
(8) D / F / B / F / A / F / G
(9) D / C / F / A / F / B / F / G
(10) D / C / F / B / F / A / F / G

<Production method of composite film>
The composite film of the present invention can be produced using a known method. For example, an extrusion lamination method, a coextrusion inflation method, a coextrusion T die method, and the like can be used, and it is particularly preferable to use a method that combines the extrusion lamination method and the coextrusion T die method. For example, when the composite film of the present invention is produced by the coextrusion T-die method, the raw materials (pellets) used for the outer layer, the intermediate layer, and the inner layer are respectively filled in an extruder and melted at 180 to 300 ° C. It can be co-extruded to produce a composite film.

  The composite film of the present invention is an unstretched film suitable for deep drawing. The deep drawn package is composed of a lid material and a bottom material, but the composite film of the present invention is preferably used for the bottom material. This is because in general deep drawing packaging, the bottom material film is deep drawn, so that a film having good moldability such as the composite film of the present invention is used.

  The deep-drawn package using the composite film of the present invention has good moisture resistance and is suitable for filling medicines and foods inside the package. Further, since the composite film of the present invention has good transparency, it is suitable for packaging medical products such as foods and cotton swabs and pharmaceutical products.

  The composite film of the present invention is suitably used for deep drawing packaging. For example, a package having a part that has been deep-drawn in one place, filled with a food, medicine, medical product, or the like, or a package having parts that have been deep-drawn in two places, and a drug in one place One with a cotton swab in the other part.

Examples of the present invention will be described below, but the present invention is not limited thereto. <Example 1>
(Production of composite film)
A composite film of the present invention having the following layer structure was produced by a coextrusion method.
PP1 (50 μm) / Adhesive resin 1 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / COC1 (250 μm) / LLDPE1 (20 μm)

  Here, “PP1” is Novatec PP (random copolymer) manufactured by Nippon Polypro. “Ny1” is Novamid 6Ny manufactured by Mitsubishi Engineering Plastics. “Adhesive resin 1” is Admer (PP base) manufactured by Mitsui Chemicals. “COC1” is manufactured by Mitsui Chemicals, Inc. (Tg = 80 ° C.). “Adhesive resin 2” is Admer (LLDPE base) manufactured by Mitsui Chemicals. “LLDPE1” is Novatec C6 made by Nippon Polyethylene.

(Production of deep drawn package)
The composite film prepared above is deep-drawn into a shape of 50 mm in length, 50 mm in width and 10 mm in depth by a deep-drawing packaging machine (FV6300, manufactured by Omori Machine Industry Co., Ltd.) to form a bottom material, and 20 g of 10% popidone iodine preparation. The cover was covered and a frame seal with a width of 10 mm was applied. The packaging conditions were an aerated package with a deep drawing temperature of 115 ° C., a molding heating time of 2 seconds, a sealing temperature of 130 ° C., and a sealing time of 2 seconds. In addition, the cover material used what dry-laminated laminated film EVOH (10 micrometers) / Ny1 (10 micrometers) / adhesive resin 2 (10 micrometers) / LLDPE1 (30 micrometers) on transparent vapor deposition PET (16 micrometers).

  Here, “transparent vapor deposition PET” is a tech barrier L manufactured by Mitsubishi Plastics. “EVOH” is Soarnol manufactured by Nippon Synthetic Chemical Co., Ltd.

<Example 2>
A film for heat treatment of the present invention having the following layer constitution was produced by a coextrusion method.
PP1 (80 μm) / Adhesive resin 1 (10 μm) / COC1 (250 μm) / Adhesive resin 2 (10 μm) / Ny1 (30 μm) / LLDPE1 (15 μm) / Easy peel 1 (5 μm)

  Here, “Easy Peel 1” is a blend of 65% by mass of Novatec EVA (Vac = 8%) manufactured by Nippon Polyethylene and 35% by mass of Novatec PP (random copolymer) manufactured by Nippon Polypro.

<Example 3>
LLDPE1 (50 μm) / Adhesive resin 2 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / COP (250 μm) / LLDPE1 (15 μm) / Easy peel 2 (5 μm)
Here, “COP” is ZEONOR 750R (Tg = 70 ° C.) manufactured by ZEON Corporation. “Easy Peel 2” is a heat seal resin layer laminated in the order of Nippon Polyethylene Co., Ltd., Novatec LD 2 μm, Nihon Polypro Co., Ltd. and Novatec PP (random copolymer) 3 μm from the LLDPE 1 side.

<Example 4>
PP1 (50 μm) / LLDPE1 (50 μm) / Adhesive resin 2 (10 μm) / Ny2 (30 μm) / Adhesive resin 2 (10 μm) / COC2 (250 μm) / LLDPE1 (20 μm)

  Here, “Ny2” is Novamid 6-66Ny manufactured by Mitsubishi Engineering Plastics. The copolymerization ratio of 6Ny and 66Ny is 6Ny: 66Ny = 85: 15. “COC2” is manufactured by Mitsui Chemicals, Inc. (Tg = 105 ° C.).

<Example 5>
LLDPE1 (50 μm) / PP1 (50 μm) / Adhesive resin 1 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / COC2 (250 μm) / LLDPE1 (20 μm)

<Example 6>
PP1 (50 μm) / Adhesive resin 1 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / COC1 (100 μm) / LLDPE1 (20 μm)

<Example 7>
PP1 (50 μm) / Adhesive resin 1 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / COC1 (400 μm) / LLDPE1 (20 μm)

<Example 8>
PP1 (50 μm) / Adhesive resin 1 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / COC3 (250 μm) / LLDPE1 (20 μm)

  Here, “COC3” is obtained by blending 80% by mass of Mitsui Chemicals, Inc. (Tg = 80 ° C.) with 20% by mass of Novatec LD manufactured by Nippon Polyethylene.

<Example 9>
PP1 (50 μm) / Adhesive resin 1 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / COC4 (250 μm) / LLDPE1 (20 μm)

  Here, “COC4” is a blend of 90% by mass of Mitsui Chemicals, Inc. (Tg = 105 ° C.) and 10% by mass of Novatec LL, manufactured by Nippon Polyethylene.

<Example 10>
PP1 (50 μm) / Adhesive resin 1 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / COC5 (250 μm) / LLDPE1 (20 μm)

  Here, “COC5” is 80% by mass of Mitsui Chemicals, Appel (Tg = 80 ° C.), 10% by mass of Nippon Polyethylene, Novatec LL, 10% by mass of Nippon Polyethylene, Novatec LD It is a thing.

<Example 11>
PP1 (80 μm) / Adhesive resin 1 (10 μm) / Ny1 (25 μm) / Adhesive resin 2 (10 μm) / Ny1 (25 μm) / Adhesive resin 2 (10 μm) / COC2 (250 μm) / LLDPE1 (20 μm)

<Example 12>
PP1 (80 μm) / Adhesive resin 1 (10 μm) / Ny1 (25 μm) / Adhesive resin 2 (10 μm) / EVOH (10 μm) / Adhesive resin 2 (10 μm) / COC2 (250 μm) / LLDPE1 (20 μm)
Here, “EVOH” is Soarnol manufactured by Nippon Synthetic Chemical Co., Ltd.

<Comparative Example 1>
PP1 (10 μm) / Adhesive resin 1 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / COC1 (250 μm) / LLDPE1 (20 μm)

<Comparative example 2>
PP1 (150 μm) / Adhesive resin 1 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / COC1 (250 μm) / LLDPE1 (15 μm) / Easy peel 1 (5 μm)

<Comparative Example 3>
PP1 (50 μm) / Adhesive resin 1 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / COC1 (40 μm) / LLDPE1 (20 μm)

<Comparative Example 4>
PP1 (50 μm) / Adhesive resin 1 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / COC1 (600 μm) / LLDPE1 (20 μm)

<Comparative Example 5>
PP1 (50 μm) / Adhesive resin 1 (10 μm) / COC2 (250 μm) / LLDPE1 (20 μm)

<Comparative Example 6>
Ny1 (50 μm) / adhesive resin 2 (10 μm) / EVOH (10 μm) / adhesive resin 2 (10 μm) / COC2 (250 μm) / LLDPE1 (20 μm)

<Comparative Example 7>
COC1 (250 μm) / Adhesive resin 2 (10 μm) / Ny1 (30 μm) / Adhesive resin 2 (10 μm) / EVOH (10 μm) / Adhesive resin 2 (10 μm) / LLDPE1 (20 μm)

<Evaluation method>
(Curl property)
The deep-drawn package was stored for 48 hours under conditions of 25 ° C. and humidity 60% RH, placed on a flat surface with the lid facing down, and the height of the curl (warpage) was measured. For each of the 10 packaged bodies, four corners were measured, and an average value was obtained and evaluated. 0-5 mm was evaluated as “◯”, and those exceeding 5 mm were evaluated as “x”.

(Dampproof)
The deep-drawn package was stored for 60 days under conditions of 40 ° C. and humidity 75% RH, and the reduction rate of the 10% povidone iodine preparation as the contents was measured.
When the rate of decrease was 0.5% or less, “◯” was evaluated, and when the reduction rate exceeded 0.5%, “X” was evaluated.

(Deep drawing formability)
Those that could be molded according to the mold were evaluated as “◯”, and those that could not be evaluated as “×”.

(All haze)
The haze of the composite film was measured according to JIS K7105. A haze value of 7% or less was evaluated as “◎”, a haze value exceeding 7% was evaluated as “◯”, and a value exceeding 10% was evaluated as “x”.

  From Tables 1 and 2, in Examples 1 to 12, all of the curled resistance, moisture resistance, moldability, and transparency of the packed product were good.

  On the other hand, Comparative Example 1 was inferior in curl resistance because the thickness of the outer polypropylene layer was 10 μm. In Comparative Example 2, since the outer polypropylene layer had a thickness of 150 μm, the moldability was poor and the transparency was low. In Comparative Example 3, since the thickness of the cycloolefin copolymer was 40 μm, a sufficient moisture-proof effect could not be obtained. Moreover, since the cycloolefin copolymer was 600 micrometers in the comparative example 4, the moldability was inferior. Moreover, since the comparative example 5 did not contain a polyamide layer in an intermediate | middle layer, the pinhole generate | occur | produced. In Comparative Example 6, since the outer layer did not have a polypropylene layer or a polyethylene layer, the polyamide layer absorbed moisture and curled. In Comparative Example 7, since the cycloolefin copolymer layer was disposed on the outer layer, it was embrittled with hand fat, solvent, etc., and cracks occurred.

  While the present invention has been described in connection with embodiments that are presently the most practical and preferred, the present invention is not limited to the embodiments disclosed herein. However, the present invention can be appropriately changed without departing from the gist or concept of the invention that can be read from the claims and the entire specification, and composite films accompanying such changes are also included in the technical scope of the present invention. Must be understood.

Claims (10)

  In a composite film comprising an outer layer, an intermediate layer, and an inner layer, the outer layer has at least one polypropylene layer and / or polyethylene layer of 30 μm or more and 100 μm or less, and the intermediate layer has at least one polyamide layer and at least one layer thickness. A composite film having a cyclic polyolefin layer having a thickness of 50 μm or more and 500 μm or less and a heat seal resin layer as an inner layer.   The composite film according to claim 1, wherein the cyclic polyolefin has a glass transition temperature of 60 ° C. or higher and 140 ° C. or lower.   The cyclic polyolefin contains 5% by mass or more and 50% by mass or less of low density polyethylene and / or linear low density polyethylene with respect to the total mass of the components constituting the cyclic polyolefin layer. Item 3. The composite film according to Item 1 or 2.   The composite film according to claim 1, wherein the intermediate layer has at least one adhesive resin layer.   The heat seal resin layer is made of low density polyethylene, linear low density polyethylene, polypropylene, ethylene-vinyl acetate copolymer, ethylene-acrylic acid copolymer, ethylene-ethyl acrylate copolymer, ethylene-methacrylic acid copolymer. At least one selected from the group consisting of a polymer, an ethylene-methyl methacrylate copolymer, an ethylene-methyl acrylate copolymer, an ethylene-acrylic acid copolymer ionomer, and an ethylene-methacrylic acid copolymer ionomer It is comprised from these, The composite film in any one of Claims 1-4 characterized by the above-mentioned.   The composite film according to claim 1, wherein the heat seal resin layer has an easy peel property.   The composite film according to claim 6, wherein an easy peel strength of the heat seal resin layer is 0.8 N / 15 mm width or more and 15.0 N / 15 mm width or less at 25 ° C.   A bottom material for deep drawing, which is molded using the composite film according to claim 1.   A deep drawn package using the deep drawing bottom material according to claim 7.   The deep drawn package according to claim 9, comprising a plurality of deep drawn molded parts.