Sealant film and its uses

Abstract

The present invention addresses the problem of providing a sealant film and a packaging bag consisting of said film that have sufficient durability (oil resistance) practically required when oils and fats, in particular, oils and fats having components extracted from spices, are filled and packaged for storage, transportation, etc. The present invention relates to a single-layer or multi-layer sealant film composed of an ethylene polymer, the sealant film having, on a surface layer thereof, a layer consisting of an ethylene polymer (A) that satisfies the following requirements (i) to (iii).　(i) The density falls within the range from above 910 kg / m3 to below 940 kg / m3.　(ii) The melt flow rate (MFR) under a load of 2.16 kg at 190°C falls within the range from 0.1 to 20 g / 10 min in conformity to JIS K7210-1.　(iii) The content of a copolymer (A2) of ethylene and α-olefin having a carbon number of 4 or less is 0-50 mass%, and the content of a copolymer (A1) of ethylene and α-olefin having a carbon number of 5 or greater is 26-100 mass%.

Description

[Technical field]

[0001] The present invention relates to a sealant film suitable for a heat seal layer of a packaging body, a laminate having said sealant film, and uses thereof. More specifically, the present invention relates to a sealant film having excellent durability (oil resistance) against oils and fats containing components extracted from spices, and uses thereof. [Background technology]

[0002] Background Art For packaging liquids or viscous materials, or liquids or viscous materials containing insoluble matter, multilayer packaging films made of a laminate in which a sealant layer is laminated on a substrate via a laminate layer or an intermediate layer are used, and liquid packaging bags are known in which a liquid or the like is filled into a bag-like body with a sealant layer on the inside and the opening is closed by heat sealing.

[0003] Packaging bags are often made by heat sealing three or four sides of a film, and when liquid or the like is filled at high speed, the liquid may leak from the heat-sealed parts. For this reason, laminates for packaging bags with improved high-speed filling properties have been proposed.

[0004] Patent Documents 1 to 3 disclose a method of using a specific material that has a high viscosity at low shear rate and a low viscosity at high shear rate when used as a packaging bag for liquid or viscous material in an automatic filling machine, that is, a resin composition whose ratio of high shear rate to low shear rate measured at a temperature close to that during actual filling is in a specific range. In particular, a specific example is disclosed in which a composition of ethylene-1-hexene copolymer and high-pressure low-density polyethylene is used in an intermediate layer between a substrate and a sealant layer.

[0005] Patent Document 4 describes a density of 890 to 910 kg / m 3 The present invention proposes a laminate comprising a sealant layer (B) containing an ethylene-α-olefin copolymer having a specific heat of fusion within the above range and an intermediate layer (C) in contact with the sealant layer (B).

[0006] However, when packaging materials containing oils and fats, particularly oils and fats containing components extracted from spices, it was found that when either laminate was used as the packaging material, the oil resistance was insufficient. [Prior art documents] [Patent documents]

[0007] [Patent Document 1] JP 2012-139848 A [Patent Document 2] JP 2012-139849 A [Patent Document 3] JP 2012-139854 A [Patent Document 4] International Publication No. 2019 / 181842 Brochure Summary of the Invention [Problem to be solved by the invention]

[0008] The objective of the present invention is to provide a sealant film having sufficient durability (oil resistance) required in practical use when filling, packaging, and storing / transporting oils and fats, particularly oils and fats containing ingredients extracted from spices, and to provide a packaging bag made of the film. [Means for solving the problem]

[0009] As a result of intensive research into solving the above-mentioned problems, the inventors have found that the above-mentioned problems can be solved by providing the sealant film and a packaging bag made of the film described below, and have thus completed the present invention.

[0010] That is, the present invention includes the following aspects [1] to

[14] . [1] The sealant film is a single-layer or multi-layer sealant film composed of an ethylene-based polymer, and has, as a surface layer thereof, a layer composed of an ethylene-based polymer (A) that satisfies the following requirements (i) to (iii):

[0011] (i) Density is 910 kg / m 3 Super~940kg / m 3 Less than range. (ii) A melt flow rate (MFR) under a load of 2.16 kg at 190°C in accordance with JIS K7210-1 is in the range of 0.1 to 20 g / 10 min. (iii) The content of the copolymer (A2) of ethylene and an α-olefin having 4 or less carbon atoms is 0% by mass or more and 50% by mass or less, and the content of the copolymer (A1) of ethylene and an α-olefin having 5 or more carbon atoms is 26% by mass or more and 100% by mass or less.

[0012] [2] The density of the ethylene polymer (A) is 910 kg / m 3 Super~919kg / m 3 The sealant film according to item [1], wherein the range is

[0013] [3] Item [1]. The sealant film according to item [1], wherein the melt flow rate (MFR) of the ethylene polymer (A) is in the range of more than 1.0 g / 10 min to 3.0 g / 10 min.

[0014] [4] Item [1]. The sealant film according to item [1], wherein the ethylene polymer (A) further satisfies the following requirement (iv):

[0015] (iv) The molten resin can be wound up without breaking at a resin temperature of 190°C, a melting time of 6 minutes, and an orifice with a nozzle diameter of 2.095 mmφ and a nozzle length of 8 mm at an extrusion speed of 15 mm / min and a winding speed of 15 m / min., and the melt tension (mN), which is the resistance force generated at that time, satisfies the following formula.

[0016] Melt tension≦180×e^(-0.7×MFR)+30 [5] Item [1]. The sealant film according to item [1], wherein the ethylene-based polymer (A) has a heat of fusion ratio (Hh / Ht) of less than 10%, which is the ratio of the total heat of fusion (Ht) determined from a DSC curve in a DSC measurement to the heat of fusion (Hh) determined from a DSC curve at 120°C or higher.

[0017] [6] Item [1]. The sealant film according to item [1], which comprises two layers, a laminate layer and a heat seal layer, and at least the heat seal layer is a layer comprising an ethylene-based polymer (A).

[0018] [7] Item [6]. The sealant film according to item [6], wherein the laminate layer is a layer made of an ethylene-based polymer (C) that satisfies the following requirements (a) and (b):

[0019] (a) Density is 900-940kg / m 3 is in the range. (b) The melt flow rate (MFR) measured in accordance with JIS K7210-1 under conditions of 190°C and a load of 2.16 kg is in the range of 0.01 to 20 g / 10 min.

[0020] [8] Item [1]. The sealant film according to item [1], which comprises at least three layers, namely, a laminate layer, an intermediate layer and a heat seal layer, and at least the heat seal layer is a layer comprising an ethylene-based polymer (A).

[0021] [9] Item [8]. The sealant film according to item [8], wherein the laminate layer is a layer made of an ethylene-based polymer (C) that satisfies the following requirements (a) and (b):

[0022] (a) Density is 900-940kg / m 3 is in the range. (b) The melt flow rate (MFR) measured in accordance with JIS K7210-1 under conditions of 190°C and a load of 2.16 kg is in the range of 0.01 to 20 g / 10 min.

[0023]

[10] Item [8]. The sealant film according to item [8], wherein the intermediate layer is a layer made of an ethylene-based polymer (C) that satisfies the following requirements (a) and (b):

[0024] (a) Density is 900-940kg / m 3 is in the range. (b) The melt flow rate (MFR) measured in accordance with JIS K7210-1 under conditions of 190°C and a load of 2.16 kg is in the range of 0.01 to 20 g / 10 min.

[0025]

[11] A laminate obtained by laminating a base layer and the sealant film according to any one of items [1] to

[10] .

[0026]

[12] Item

[11] The laminate according to item

[11] , wherein the substrate layer and the sealant film are laminated by dry lamination.

[0027]

[13] A packaging bag formed from the laminate according to item

[11] or

[12] and having a sealant film as an inner surface.

[0028]

[14] A packaging bag as described in item

[13] , the contents of which contain ingredients derived from spices. Effect of the Invention

[0029] The sealant film of the present invention has sufficient durability (oil resistance) required for practical purposes when filling, packaging, storing, transporting, etc., oils and fats, particularly oils and fats containing ingredients extracted from spices, and is therefore particularly suitable as a packaging material. Packages using the sealant film of the present invention have excellent durability and can be stored in higher temperature environments or for longer periods of time (in accordance with Arrhenius' law). DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0030] <Ethylene-based polymer (A)> The ethylene polymer (A) forming the surface layer (hereinafter also referred to as the "heat seal layer, laminate layer") of the sealant film of the present invention is an ethylene polymer that satisfies the following requirements (i) to (iii).

[0031] In the present invention, the expression 0 to 2 includes 0 and also includes 1 and 2. <Requirement (i)> Density 910kg / m 3 Super~940kg / m 3 Less than 910 kg / m 3 Super~930kg / m 3 , more preferably 910 kg / m 3 Super~920kg / m 3 , most preferably 910 kg / m 3 Super~919kg / m 3 is in the range.

[0032] When the density satisfies the above range, a sealant film having excellent low-temperature heat sealability, heat seal strength, and oil resistance can be obtained. <Requirement (ii)> The melt flow rate (MFR) at 190°C under a load of 2.16 kg according to JIS K7210-1 is in the range of 0.1 to 20 g / 10 min, preferably 0.3 to 15 g / 10 min, more preferably 0.5 to 10 g / 10 min, even more preferably 0.5 to 5 g / 10 min, and most preferably more than 1.0 g / 10 min to 3.0 g / 10 min.

[0033] When the MFR satisfies the above range, a sealant film having good film formability and good appearance can be obtained. In particular, when an ethylene-based polymer (A) having an MFR within the most preferred range is used, a sealant film having better oil resistance can be obtained. <Requirement (iii)> In the ethylene-based polymer (A), the content of copolymer (A2) of ethylene and an α-olefin having 4 or less carbon atoms is in the range of 0 to 50 mass%, preferably 0 to 40 mass%, more preferably 0 to 30 mass%, and even more preferably 0 mass%, and the content of copolymer (A1) of ethylene and an α-olefin having 5 or more carbon atoms is in the range of 26 to 100 mass%, preferably 30 to 100 mass%, more preferably 50 to 100 mass%, and even more preferably 75 to 100 mass%, and the total amount of copolymer (A2) and copolymer (A1) is 100 mass%.

[0034] The ethylene polymer (A) according to the present invention may contain an ethylene polymer (A3) described below in addition to the above-mentioned copolymer (A2) and copolymer (A1). When the ethylene polymer (A) according to the present invention contains an ethylene polymer (A3) in addition to the above-mentioned copolymer (A2) and copolymer (A1), the total amount of the copolymer (A2), the copolymer (A1) and the ethylene polymer (A3) is taken as 100% by mass.

[0035] The ethylene polymer (A) according to the present invention preferably satisfies the following requirement (iv) in addition to the above requirements (i) to (iii). <Requirement (iv)> The ethylene polymer (A) can be extruded from an orifice having a nozzle diameter of 2.095 mmφ and a nozzle length of 8 mm at a resin temperature of 190°C, a melting time of 6 minutes, a speed of 15 mm / min, and a winding speed of 15 m / min without the molten resin being broken. The melt tension (mN), which is the resistance force generated at that time, satisfies the following formula:

[0036] Melt tension≦180×e^(-0.7×MFR)+30 <Requirement (v)> The ethylene polymer (A) according to the present invention preferably satisfies the following requirement (v) in addition to the requirements (i) to (iv).

[0037] The heat of fusion ratio (Hh / Ht), which is the ratio of the total heat of fusion (Ht) determined from a DSC curve in a DSC measurement to the heat of fusion (Hh) determined from a DSC curve at 120°C or higher, is less than 10.

[0038] When the ethylene polymer (A) according to the present invention has Hh / Ht of less than 10, the sealant film having a layer made of the ethylene polymer (A) is superior in terms of strength. The ratio of heat of fusion (Hh / Ht) of the ethylene polymer (A) in the present invention was calculated as the ratio of heat of fusion at 120°C or higher (Hh / Ht), which is the ratio showing the amount of components at 120°C or higher, from the total heat of fusion (Ht) determined from a DSC curve in a DSC measurement and the heat of fusion (Hh) determined from a DSC curve at 120°C or higher.

[0039] Ethylene-α-olefin copolymer (A1) One of the polymers contained in the ethylene-based polymer (A) according to the present invention, the ethylene-α-olefin copolymer (A1) (hereinafter sometimes abbreviated as "copolymer (A1)"), is a copolymer of ethylene and an α-olefin having 5 or more carbon atoms, and the copolymer (A1) may be one type or a mixture (composition) of two or more types of copolymers (A1). The mixture (composition) of two or more types of copolymers (A1) can be prepared by various known methods, such as mixing two or more types of copolymers (A1) in the polymerization stage of a multi-stage process, dry blending two or more types of copolymers (A1), or melt mixing using an extruder.

[0040] The α-olefin having 5 or more carbon atoms constituting the copolymer (A1) according to the present invention is preferably an α-olefin having 5 to 20 carbon atoms, such as 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, and 1-decene. Among these α-olefins, α-olefins having 5 to 10 carbon atoms are particularly preferred. These α-olefins may be contained alone or in combination of two or more α-olefins.

[0041] Furthermore, the copolymer (A1) according to the present invention alone satisfies the above requirements (i) to (iii), preferably the above requirements (i) to (v), which the ethylene polymer (A) according to the present invention has. Ethylene-α-olefin copolymer (A2) One of the polymers contained in the ethylene polymer (A) according to the present invention, the ethylene-α-olefin copolymer (A2) (hereinafter sometimes abbreviated as "copolymer (A2)"), is a copolymer of ethylene and an α-olefin having 4 or less carbon atoms.

[0042] The α-olefins having 4 or less carbon atoms constituting the copolymer (A2) are propylene and 1-butene. The copolymer (A2) according to the present invention has a density and MFR that are not particularly limited as long as the ethylene polymer (A) containing the copolymer (A2) and the copolymer (A1) satisfies the above requirements (i) to (iii), preferably the above requirements (i) to (v). Generally, the density is 910 kg / m 3 Super~940kg / m 3 Less than 915-940 kg / m 3 Less than 920-930 kg / m 3 Usually, the MFR is in the range of 0.1 to 20 g / 10 min, preferably 0.3 to 15 g / 10 min, more preferably 0.5 to 10 g / 10 min, and further preferably 0.5 to 5 g / 10 min.

[0043] Ethylene polymer (A3) Examples of the ethylene polymer (A3) other than the copolymer (A2) and the copolymer (A1) that may be contained in the ethylene polymer (A) according to the present invention include ethylene homopolymers and high-pressure low-density polyethylene (HP-LDPE).

[0044] The copolymer (A3) according to the present invention has a density and MFR that are not particularly limited as long as the ethylene polymer (A) containing the copolymer (A3), the copolymer (A1) and the copolymer (A2) satisfies the above requirements (i) to (iii), preferably the above requirements (i) to (v). Generally, the density is 900 to 940 kg / m3 , preferably 910 to 930 kg / m 3 , more preferably 914 to 927 kg / m 3 The MFR is usually in the range of 0.01 to 70 g / 10 min, preferably 0.05 to 20 g / 10 min, and more preferably 0.1 to 5 g / 10 min.

[0045] <<Production method of ethylene-α-olefin copolymer (A1)>> The ethylene-α-olefin copolymer (A1) according to the present invention can be prepared using an olefin polymerization catalyst such as a metallocene, titanium, chromium or phenoxyimine catalyst. This copolymer (A1) may be a linear or branched low-density polyethylene. In particular, when prepared using a metallocene olefin polymerization catalyst, a polymer with a narrow molecular weight distribution is obtained, so that the production of low molecular weight and low density components is reduced. The copolymer (A1) thus prepared is effective for the application related to the present invention, i.e., for packaging packaging materials such as food and medicine.

[0046] Metallocene catalysts are usually formed from a metallocene catalyst component (a1) consisting of a transition metal compound of Group IVB of the periodic table having at least one ligand having a cyclopentadienyl skeleton, an organoaluminum oxy-compound catalyst component (b), a fine particle support (c), and, if necessary, an organoaluminum compound catalyst component (d) and an ionizing ionic compound catalyst component (e).

[0047] The copolymer (A1) according to the present invention can be produced by copolymerizing ethylene and an α-olefin having 5 or more carbon atoms in the presence of a so-called metallocene-based olefin polymerization catalyst containing a metallocene catalyst component described, for example, in JP-A-6-9724, JP-A-6-136195, JP-A-6-136196, JP-A-6-207057, etc.

[0048] <Sealant film> The sealant film of the present invention is a single-layer or multi-layer sealant film made of an ethylene polymer, and has a layer made of the above-mentioned ethylene polymer (A) on the surface layer of the sealant film.

[0049] The sealant film of the present invention is a film having a heat seal surface capable of heat sealing (sealing) a packaged material to a laminate surface to be laminated with a substrate layer described below. The sealant film of the present invention has excellent heat fusion properties (heat sealability) and oil resistance, particularly resistance to oils and fats containing components extracted from spices, and can therefore be suitably used as a packaging material, particularly as a sealant layer of a packaging material.

[0050] When the sealant film of the present invention is a single layer, the sealant film is made of the above-mentioned ethylene polymer (A). The thickness of the sealant film can be appropriately selected depending on the type of the packaged material, but is usually in the range of 5 to 100 μm.

[0051] When the sealant film of the present invention is a multilayer film, it comprises a layer to be laminated (attached) to a substrate layer described below (hereinafter, may be referred to as a "laminate layer") and a heat seal layer, and at least the heat seal layer comprises the above-mentioned ethylene polymer (A).

[0052] Even when the sealant film of the present invention is a two-layer film having a laminate layer and a heat seal layer, the thickness of the film can be appropriately selected depending on the type of packaged material, but the thickness of the laminate layer is usually in the range of 1 to 50 μm, preferably 5 to 30 μm, the thickness of the heat seal layer is usually in the range of 1 to 50 μm, preferably 5 to 30 μm, and the thickness of the entire layer is in the range of 5 to 100 μm.

[0053] When the sealant film of the present invention is a multi-layer film having three or more layers, it comprises a laminate layer, an intermediate layer and a heat seal layer, and at least the heat seal layer comprises the above ethylene polymer (A).

[0054] Furthermore, even when the sealant film of the present invention is a multilayer film having three or more layers having a laminate layer, an intermediate layer, and a heat seal layer, the thickness of the film can be appropriately selected depending on the type of packaged material, but typically, the thickness of the laminate layer is in the range of 1 to 50 μm, preferably 5 to 30 μm, the thickness of the intermediate layer is in the range of 1 to 50 μm, preferably 5 to 30 μm, or 1 to 50 μm, preferably 5 to 30 μm, and the thickness of all layers is in the range of 5 to 100 μm.

[0055] In addition, when the sealant film of the present invention is a two-layer film having a laminate layer and a heat seal layer, or a multi-layer film having three or more layers having a laminate layer, an intermediate layer and a heat seal layer, at least the heat seal layer is a layer comprising the above-mentioned ethylene polymer (A).

[0056] Of course, all layers of the sealant film of the present invention may be layers composed of the above-mentioned ethylene-based polymer (A). In that case, all layers may be layers composed of the same ethylene-based polymer (A), or each layer may be composed of a different ethylene-based polymer (A).

[0057] When the sealant film of the present invention is a two-layer film having a laminate layer and a heat seal layer, or a multi-layer film having three or more layers having a laminate layer, an intermediate layer and a heat seal layer, the laminate layer or the intermediate layer may be a layer composed of an ethylene-based polymer other than the above-mentioned ethylene-based polymer (A).

[0058] As the ethylene-based polymer other than the ethylene-based polymer (A) constituting the laminate layer and / or intermediate layer of the sealant film of the present invention, the polymer forming said layer is preferably an ethylene-based polymer (C).

[0059] <Ethylene-based polymer (C)> When the sealant film of the present invention is multilayered, the ethylene-based polymer (C) which may form a portion of the layers, preferably a laminate layer and an intermediate layer, is a homopolymer of ethylene or a copolymer of ethylene and an α-olefin having 3 or more carbon atoms, which is a polymer mainly composed of ethylene and is an ethylene-based polymer containing polyethylene resins (ethylene-based polymers) manufactured and sold under the names of high-pressure low-density polyethylene (HP-LDPE), linear low-density polyethylene (LLDPE), medium-density polyethylene (MDPE) and high-density polyethylene (HDPE).

[0060] These ethylene polymers may be a single polymer or a composition (mixture) of two or more kinds of ethylene polymers. The α-olefin having 3 or more carbon atoms forming the ethylene polymer (C) according to the present invention is preferably an α-olefin having 3 to 20 carbon atoms, and examples of the α-olefin include propylene, 1-butene, 1-hexene, 1-pentene, 4-methyl-1-pentene, 1-heptene, 1-octene, and 1-decene. These may be used alone or in combination of two or more.

[0061] The ethylene polymer (C) according to the present invention is not particularly limited as long as it satisfies the object of the present invention, but preferably has a density and MFR that satisfy the following requirements (a) and (b). (a) Density is 900-940kg / m 3 , preferably 910 to 930 kg / m 3 , more preferably 920 to 930 kg / m 3 is in the range. (b) The melt flow rate (MFR) measured in accordance with JIS K7210-1 under conditions of 190° C. and a load of 2.16 kg is in the range of 0.01 to 20 g / 10 min, preferably 0.05 to 20 g / 10 min, and more preferably 0.1 to 5 g / 10 min.

[0062] <Method of manufacturing sealant film> The sealant film of the present invention may be produced by any of various known film production methods (molding methods), for example, a casting method using a flat die such as a T-die, or an inflation method using a circular die.

[0063] When the sealant film is a two-layer film, it can be produced by a so-called co-extrusion molding method in which the ethylene polymer (A) forming the laminate layer and the ethylene polymer (A) forming the heat seal layer are melted separately by two extruders to produce a two-layer film from one die, and when the sealant film is a three-layer or more multilayer film, it can be produced by a so-called co-extrusion molding method in which the ethylene polymer (A) forming the laminate layer, the ethylene polymer (A) forming the intermediate layer, and the ethylene copolymer (A) forming the heat seal layer are melted separately by three or more extruders to produce a three-layer or more multilayer film from one die. Among them, the co-extrusion molding method is preferred because it can easily produce a multilayer film and the resulting multilayer film has excellent interlayer adhesion.

[0064] The coextrusion molding method may be either a cast method using a flat die such as a T-die, or an inflation method using a circular die. The method for producing the two or more layer sealant film of the present invention is not limited to the above. For example, a method may be adopted in which a film to be a laminate layer is produced (molded) in advance, and then the above ethylene-based copolymer (A) to be an intermediate layer and a heat seal layer, if necessary, is extrusion laminated on the surface of the film.

[0065] The molding temperature for the sealant film is not particularly limited as long as the ethylene polymer (A) and the like can be melt-extruded at this temperature, but is usually in the range of 130 to 350°C, and preferably 160 to 250°C.

[0066] <Laminate> The laminate of the present invention is a laminate in which a substrate layer and the above-mentioned sealant film are laminated together, and is usually in the form of a film or sheet.

[0067] The laminate of the present invention is a laminate in which a base layer and the above-mentioned sealant film are laminated together, and since the above-mentioned sealant film has thermal fusion properties (heat sealability), it can be suitably used as a packaging material.

[0068] The materials that can be packaged with the packaging material of the present invention are not limited to foods and medicines, but include various other items that can be packaged, such as daily necessities, detergents, agricultural chemicals, etc. The form of the materials to be packaged may be either liquid or solid.

[0069] In addition, the laminate of the present invention has excellent oil resistance as well as thermal fusion (heat sealability), and is therefore particularly suitable as a packaging material for oily foods, such as oils and fats containing ingredients extracted from spices, whether liquid or solid.

[0070] 《Base material layer》 The base material layer constituting the laminate of the present invention is a material having relatively high rigidity and strength, which is one of the outer surfaces of the packaging material. Specifically, it is a film containing at least one thermoplastic resin selected from the group consisting of polyamide resins such as nylon 11 and nylon 12, polyester resins such as polyethylene terephthalate and polybutylene terephthalate, polyolefin resins such as polyethylene resins and polypropylene resins, polyvinylidene chloride resins, saponified ethylene-vinyl acetate copolymers, polycarbonate resins, polystyrene resins, and acrylic resins, and the film may be a non-stretched film or a uniaxially or biaxially stretched film. In addition, it may be a laminate with metal foils, metal-deposited films, ceramic-deposited films such as inorganic oxide-deposited films, paper, nonwoven fabrics, and films containing thermoplastic resins, without being limited to the above films.

[0071] The thickness of the substrate layer according to the present invention is usually in the range of 5 to 50 μm. The metal foil is not particularly limited by its material or thickness, and examples of the metal foil that can be used include aluminum foil, tin foil, lead foil, zinc-plated thin-layer steel sheet, a thin film of ionized metal formed by electrolysis, iron foil, and the like, each having a thickness of 5 to 50 μm.

[0072] The metal deposition film is not particularly limited in terms of material or thickness, and examples of the metal to be deposited include aluminum and zinc, and the thickness is usually preferably 0.01 to 0.2 μm. The deposition method is also not particularly limited, and well-known methods such as vacuum deposition, ion plating, and sputtering can be used.

[0073] In the ceramic vapor deposition film, examples of the ceramic to be vapor deposited include silicon oxides represented by the general formula SiOx (0.5≦x≦2), as well as glass, alumina, metal oxides such as magnesium oxide and tin oxide, and metal fluorides such as fluorite and selenium fluoride. Metal oxides may contain trace amounts of metals, other metal oxides, and metal hydroxides. Vapor deposition can also be performed by applying the above-mentioned various vapor deposition methods to at least one side of the film. In addition, the film to be vapor deposited is not particularly limited, and examples thereof include transparent films such as (stretched) polyester film, (stretched) polypropylene film, and (stretched) polyamide film.

[0074] When laminating (bonding) the base layer according to the present invention and the sealant film of the present invention, in order to improve the adhesion between the base layer and the sealant film of the present invention, the laminate surface of the base layer of the sealant film or the surface in contact with the laminate layer may be subjected to a surface activation treatment such as corona treatment, flame treatment, plasma treatment, undercoat treatment, etc., and may be coated with one or more adhesives selected from the group consisting of urethane type adhesives, isocyanate adhesives, polyesters, and mixtures and reaction products of polyols and isocyanate compounds.

[0075] <Method of manufacturing laminate> The laminate of the present invention can be produced by various known production methods. For example, the laminate surface of the base layer of the sealant film of the present invention or the surface in contact with the laminate layer is subjected to a surface activation treatment such as corona treatment, flame treatment, plasma treatment, ozone treatment, undercoat treatment, etc., or is not subjected to the surface activation treatment, and then one or more adhesives selected from the group consisting of urethane adhesives, isocyanate adhesives, polyesters, and mixtures and reaction products of polyols and isocyanate compounds are applied, or is not applied, to the sealant film by melt extrusion (extrusion lamination) to bond the base layer and the sealant film together (lamination). When the substrate layer is made of a thermoplastic resin, a method of co-extrusion molding the thermoplastic resin that will become the substrate layer and the above-mentioned ethylene-based polymer (A) that will become the sealant film of the present invention using a multi-layer die to form a laminated film can be used. Alternatively, a method of laminating (laminating) the sealant film of the present invention previously obtained by the above-mentioned production method (molding method) and the substrate layer via one or more adhesives selected from the group consisting of a urethane type adhesive, an isocyanate type adhesive, polyester, and a mixture and reaction product of a polyol and an isocyanate compound (dry lamination method) can be used.

[0076] <Packaging bag> The packaging bag of the present invention is a bag having the sealant film of the laminate as the inner surface. The shape of the packaging bag of the present invention is not particularly limited as long as the sealant film is the inner surface, and the bag may have various known shapes.

[0077] Specifically, the above laminate can be folded so that the sealant film is on the inside, one side of the folded body is heat-sealed to form a tube, and then the bottom side is heat-sealed to form a bag; two laminates are overlapped so that the sealant films face each other and three sides are heat-sealed to form a bag; or the sealant film of the above laminate is overlapped with a film or sheet that can be heat-sealed and three sides are heat-sealed to form a bag. Various known manufacturing methods can be used to make the packaging bag.

[0078] The packaging material that can be packaged in the packaging bag of the present invention may be liquid or solid, regardless of its shape. Examples of liquids or viscous materials include food and medicine. In addition, the liquid or viscous material may contain solid matter, such as a dressing containing granules. EXAMPLES

[0079] The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. [Example 1] A laminate (packaging film) was produced by the dry lamination method as follows.

[0080] The extruders for the inner layer (heat seal layer), middle layer, and outer layer (laminate layer) of an Alpine three-type three-layer inflation molding machine (die diameter: 225 mmφ, extruder: 50 mmφ × 3 units) were filled with Evolue (registered trademark) SP1523 (Prime Polymer Co., Ltd., density (JIS K7112) = 0.916 g / cm), an ethylene-1-hexene copolymer produced by multistage gas phase polymerization. 3 , MFR (JIS K7210, 190°C) = 2.0g / 10min] was fed into the extruder and molded under the conditions of extruder set temperature: 190°C, die set temperature: 200°C, take-up speed: 25m / min, and fold width: 700mm to form a sealant film consisting of three layers with an inner layer / middle layer / outer layer thickness ratio of 1 / 1 / 1 and a thickness of 50μm.

[0081] A three-layer film was obtained in which the laminate layer side (outer layer) was subjected to a corona treatment (45 dyn). A 15 μm-thick stretched nylon base film (EMBLEM manufactured by Unitika Ltd.) was dry laminated to the laminate layer side of the three-layer film using a dry laminator (adhesive: Takelac A315, coating amount 3 g / m). 2 ) to obtain a packaging film for evaluation.

[0082] The oil resistance of the resulting packaging film was evaluated by the method described below, and the results are shown in Table 1. [Example 2] A laminate (packaging film) was produced by extrusion lamination as follows.

[0083] Using an extrusion lamination device set so that the temperature of the resin extruded from the T-die of the 60 mmφ extruder was 295°C, the extrusion amount was adjusted so that the coating thickness would be 25 μm at a processing speed of 80 m / min under conditions of a cooling roll surface temperature of 30°C, a die width of 500 mm, and a die lip opening of 0.9 mm. While spraying ozone in the lamination section, the laminate layer material was extruded onto the substrate coated with the anchor coating agent at a take-up speed of 80 m / min and a coating thickness of 25 μm to perform extrusion lamination processing to form a laminate layer. The substrate coated with the anchor coating agent was a biaxially oriented nylon film (ONY #15 manufactured by Toyobo) with a width of 500 mm and a thickness of 15 μm, coated with an isocyanate-based anchor coating agent (Takelac® A-3210, Takenate® A-3075 manufactured by Mitsui Chemicals, Inc.) using a gravure roll. The laminate layer material was Evolue® SP13100C (Prime Polymer Co., Ltd., density (JIS K7112) = 0.914 g / cm), an ethylene-1-hexene copolymer produced by multistage gas phase polymerization. 3 , MFR (JIS K7210, 190°C) = 8.0 g / 10 min] was used.

[0084] Further, on the laminate layer, a heat seal layer was extruded using the above-mentioned extrusion lamination device at an extrusion resin temperature of 295°C, a take-up speed of 80 m / min, and a coating thickness of 25 μm to perform extrusion lamination to obtain a laminate. As the heat seal layer, EVOLUE (registered trademark) SP13100C [manufactured by Prime Polymer Co., Ltd., density (JIS K7112) = 0.914 g / cm 3 , MFR (JIS K7210, 190°C) = 8.0 g / 10 min] was used. The laminate was aged in an oven at 40°C for 24 hours to obtain a packaging film for evaluation.

[0085] The liquid filling suitability of the resulting packaging film was evaluated by the method described below, and the results are shown in Table 1. [Example 3] In Example 1, an ethylene-1-butene copolymer, Neozex (registered trademark) 2512F (manufactured by Prime Polymer Co., Ltd., density (JIS K7112) = 0.924 g / cm), was used in the extruder for the intermediate layer of the inflation molding machine. 3 , MFR (JIS K7210, 190 ° C) = 1.3 g / 10 min] 80 parts by mass, and Santec LD (registered trademark) M1920 (Asahi Kasei Corporation, density (JIS K7112) = 0.921 g / cm 3 A packaging film for evaluation was prepared in the same manner, except that 20 parts by mass of a resin having a molecular weight of 1.0 kg / mole (MFR (JIS K7210, 190°C) = 2.0 g / 10 min) was mixed in a Henschel mixer and added, and the oil resistance was evaluated. The results are shown in Table 1.

[0086] [Example 4] In Example 3, an ethylene-1-butene copolymer, Neozex (registered trademark) 2512F (manufactured by Prime Polymer Co., Ltd., density (JIS K7112) = 0.924 g / cm), was used in the extruder for the outer layer of the inflation molding machine. 3 , MFR (JIS K7210, 190 ° C) = 1.3 g / 10 min] 80 parts by mass, and Santec LD (registered trademark) M1920 (Asahi Kasei Corporation, density (JIS K7112) = 0.921 g / cm 3 A packaging film for evaluation was prepared in the same manner, except that 20 parts by mass of a resin having a molecular weight of 1.0 kg / mole (MFR (JIS K7210, 190°C) = 2.0 g / 10 min) was mixed in a Henschel mixer and added, and the oil resistance was evaluated. The results are shown in Table 1.

[0087] [Example 5] In Example 4, an ethylene-1-butene copolymer, Neozex (registered trademark) 2512F (manufactured by Prime Polymer Co., Ltd., density (JIS K7112) = 0.924 g / cm), was used as the extruder for the inner layer of the inflation molding machine. 3, MFR (JIS K7210, 190 ° C) = 1.3 g / 10 min] 50 parts by mass, and Santec LD (registered trademark) M1920 (Asahi Kasei Corporation, density (JIS K7112) = 0.921 g / cm 3 20 parts by mass of ethylene-1-hexene copolymer (MFR (JIS K7210, 190°C) = 2.0 g / 10 min) produced by multistage gas phase polymerization method (manufactured by Prime Polymer Co., Ltd., density (JIS K7112) = 0.916 g / cm 3 A packaging film for evaluation was prepared in the same manner, except that 30 parts by mass of a resin having a molecular weight of 1.0 kg / mole (MFR (JIS K7210, 190°C) = 2.0 g / 10 min) was mixed in a Henschel mixer, and the oil resistance was evaluated. The results are shown in Table 1.

[0088] [Example 6] In Example 4, an ethylene homopolymer (high-pressure low-density polyethylene) Santech LD (registered trademark) M1920 (Asahi Kasei Corporation, density (JIS K7112) = 0.921 g / cm 3 ) was used as the extruder for the inner layer of the inflation molding machine. 3 25 parts by mass of ethylene-1-hexene copolymer (MFR (JIS K7210, 190°C) = 2.0 g / 10 min), and EVOLUE (registered trademark) SP1523 (manufactured by Prime Polymer Co., Ltd., density (JIS K7112) = 0.916 g / cm) produced by a multistage gas phase polymerization method. 3 A packaging film for evaluation was prepared in the same manner, except that 75 parts by mass of a resin having a molecular weight of 1.0 kg / mole (MFR (JIS K7210, 190°C) = 2.0 g / 10 min) was mixed in a Henschel mixer, and the oil resistance was evaluated. The results are shown in Table 1.

[0089] [Example 7] In Example 4, an ethylene homopolymer (high-pressure low-density polyethylene) Santech LD (registered trademark) M1920 (Asahi Kasei Corporation, density (JIS K7112) = 0.921 g / cm 3 ) was used as the extruder for the inner layer of the inflation molding machine. 350 parts by mass of ethylene-1-hexene copolymer (MFR (JIS K7210, 190°C) = 2.0 g / 10 min), and 50 parts by mass of EVOLUE (registered trademark) SP1523 (manufactured by Prime Polymer Co., Ltd., density (JIS K7112) = 0.916 g / cm) produced by a multistage gas phase polymerization method. 3 A packaging film for evaluation was prepared in the same manner, except that 50 parts by mass of a resin having a molecular weight of 1.0 kg / mole (MFR (JIS K7210, 190°C) = 2.0 g / 10 min) was mixed in a Henschel mixer and added, and the oil resistance was evaluated. The results are shown in Table 1.

[0090] [Comparative Example 1] In Example 4, an ethylene-1-butene copolymer, Neozex (registered trademark) 2512F (manufactured by Prime Polymer Co., Ltd., density (JIS K7112) = 0.924 g / cm), was used as the extruder for the inner layer of the inflation molding machine. 3 , MFR (JIS K7210, 190 ° C) = 1.3 g / 10 min] 80 parts by mass, and Santec LD (registered trademark) M1920 (Asahi Kasei Corporation, density (JIS K7112) = 0.921 g / cm 3 A packaging film for evaluation was prepared in the same manner, except that 20 parts by mass of a resin having a molecular weight of 1.0 kg / mole (MFR (JIS K7210, 190°C) = 2.0 g / 10 min) was mixed in a Henschel mixer and added, and the oil resistance was evaluated. The results are shown in Table 1.

[0091] [Comparative Example 2] In Example 4, an ethylene-1-butene copolymer, Neozex (registered trademark) 2512F (manufactured by Prime Polymer Co., Ltd., density (JIS K7112) = 0.924 g / cm), was used as the extruder for the inner layer of the inflation molding machine. 3 A packaging film for evaluation was prepared in the same manner, except that the oil used was 1.3 g / 10 min., MFR (JIS K7210, 190° C.)=1.3 g / 10 min., and the oil resistance was evaluated. The results are shown in Table 1.

[0092] [Comparative Example 3] In Example 4, the inner layer of the inflation molding machine The extruder was fed with Santec LD (registered trademark) M1920 (Asahi Kasei Corporation, density (JIS K7112) = 0.921 g / cm), which is an ethylene homopolymer (high-pressure low-density polyethylene). 3 A packaging film for evaluation was prepared in the same manner, except that the oil resistance was evaluated using the same composition as in Example 1. The results are shown in Table 1.

[0093] [Comparative Example 4] In Example 4, an ethylene homopolymer (high-pressure low-density polyethylene) Santech LD (registered trademark) M1920 (Asahi Kasei Corporation, density (JIS K7112) = 0.921 g / cm 3 ) was used as the extruder for the inner layer of the inflation molding machine. 3 75 parts by mass of ethylene-1-hexene copolymer (MFR (JIS K7210, 190°C) = 2.0 g / 10 min), and EVOLUE (registered trademark) SP1523 (manufactured by Prime Polymer Co., Ltd., density (JIS K7112) = 0.916 g / cm) produced by a multistage gas phase polymerization method. 3 A packaging film for evaluation was prepared in the same manner, except that 25 parts by weight of a resin having a molecular weight of 1.0 g / 10 min and a molecular weight of 1.0 g / 10 min were mixed in a Henschel mixer, and the oil resistance was evaluated. The results are shown in Table 1.

[0094] The melt tensions (mN) of the ethylene-based polymers and compositions (mixtures) used in the examples and comparative examples were measured by the measurement method described above. [Oil resistance evaluation] Two pieces of packaging film for evaluation cut into a size of 90 mm x 120 mm were stacked so that the heat seal layers were in contact with each other, and 10 mm from the ends of the three sides were heat sealed under conditions of 160°C, 0.5 seconds, and 0.5 MPa. 100 g of a mixed liquid prepared by mixing vinegar, water, and chili oil in a 1 / 1 / 1 weight ratio was filled into the bag, and the remaining side was heat sealed in the same manner as the other three sides to obtain a packaging bag containing the mixed liquid. After heating for 30 minutes in water at a specified temperature, a test was performed three times with a load of 100 kg applied. The maximum heating temperature at which no appearance defects, including bag breakage, delamination, or seal peeling, occurred in all three cases was evaluated.

[0095] [Table 1] [Industrial Applicability]

[0096] The sealant film of the present invention and packaging bags made from the film have excellent durability compared to conventional packaging materials for oils and fats, particularly oils and fats containing ingredients extracted from spices, and are characterized by their ability to be stored in higher temperature environments or for longer periods of time (in accordance with Arrhenius' law).

Claims

1. A multi-layer sealant film composed of an ethylene-based polymer, A sealant film comprising two layers, a laminate layer and a heat seal layer, wherein at least the heat seal layer is a layer made of an ethylene-based polymer (A) that satisfies the following requirements (i) to (iii): (i) Density is 910 kg / m 3 Super ~921kg / m 3 Less than range. (ii) A melt flow rate (MFR) of 0.1 to 10 g / 10 min at 190° C. under a load of 2.16 kg according to JIS K7210-1. (iii) The content of the copolymer (A2) of ethylene and an α-olefin having 4 or less carbon atoms is 0 mass%, and the content of the copolymer (A1) of ethylene and an α-olefin having 5 or more carbon atoms is 50 mass% or more and 100 mass% or less.

2. A multi-layer sealant film composed of an ethylene-based polymer, A sealant film comprising two layers, a laminate layer and a heat seal layer, wherein at least the heat seal layer is a layer made of an ethylene polymer (A) that satisfies the following requirements (i) to (iii): (i) Density is in the range of more than 910 kg / m 3 and less than 921 kg / m 3 . (ii) A melt flow rate (MFR) of 0.1 to 10 g / 10 min at 190° C. under a load of 2.16 kg according to JIS K7210-1. (iii) The content of the copolymer (A2) of ethylene and an α-olefin having 4 or less carbon atoms is 50% by mass, and the content of the copolymer (A1) of ethylene and an α-olefin having 5 or more carbon atoms is 26% by mass or more and 50% by mass or less.

3. A multi-layer sealant film composed of an ethylene-based polymer, The sealant film comprises at least three layers, namely, a laminate layer, an intermediate layer and a heat seal layer, which are laminated in this order, and at least the heat seal layer is a layer made of an ethylene-based polymer (A) that satisfies the following requirements (i) to (iii), and the laminate layer and the intermediate layer are made of the same ethylene polymer. (i) Density is 910 kg / m 3 Super ~921kg / m 3 Less than range. (ii) A melt flow rate (MFR) of 0.1 to 10 g / 10 min at 190° C. under a load of 2.16 kg according to JIS K7210-1. (iii) The content of the copolymer (A2) of ethylene and an α-olefin having 4 or less carbon atoms is 0 mass%, and the content of the copolymer (A1) of ethylene and an α-olefin having 5 or more carbon atoms is 50 mass% or more and 100 mass% or less.

4. A multi-layer sealant film composed of an ethylene-based polymer, The sealant film comprises at least three layers, namely, a laminate layer, an intermediate layer and a heat seal layer, which are laminated in this order, and at least the heat seal layer is a layer made of an ethylene-based polymer (A) that satisfies the following requirements (i) to (iii), and the laminate layer and the intermediate layer are made of the same ethylene polymer. (i) Density is in the range of more than 910 kg / m 3 and less than 921 kg / m 3 . (ii) A melt flow rate (MFR) of 0.1 to 10 g / 10 min at 190° C. under a load of 2.16 kg according to JIS K7210-1. (iii) The content of the copolymer (A2) of ethylene and an α-olefin having 4 or less carbon atoms is 50% by mass, and the content of the copolymer (A1) of ethylene and an α-olefin having 5 or more carbon atoms is 26% by mass or more and 50% by mass or less.

5. The density of the ethylene polymer (A) is 910 kg / m 3 Super ~919kg / m 3 The sealant film according to any one of claims 1 to 4, wherein the range is

6. The sealant film according to any one of claims 1 to 4, wherein the ethylene polymer (A) has a melt flow rate (MFR) in the range of more than 1.0 g / 10 min to 3.0 g / 10 min.

7. The sealant film according to any one of claims 1 to 4, wherein the ethylene polymer (A) further satisfies the following requirement (iv): (iv) The molten resin can be wound up without being broken at a resin temperature of 190°C, a melting time of 6 minutes, through an orifice having a nozzle diameter of 2.095 mmφ and a nozzle length of 8 mm, at an extrusion speed of 15 mm / min and a winding speed of 15 m / min, and the melt tension (mN) which is the resistance force generated at that time satisfies the following formula: Melt tension≦180×e^(-0.7×MFR)+30

8. The sealant film according to any one of claims 1 to 4, wherein the ethylene-based polymer (A) has a heat of fusion ratio (Hh / Ht) of less than 10%, which is the ratio of the total heat of fusion (Ht) determined from a DSC curve in a DSC measurement to the heat of fusion (Hh) determined from a DSC curve at 120°C or higher.

9. 3. The sealant film according to claim 1, wherein the laminate layer is a layer made of an ethylene polymer (C) which satisfies the following requirements (a) and (b): (a) Density is 900 to 940 kg / m 3 is in the range. (b) The melt flow rate (MFR) measured in accordance with JIS K7210-1 under conditions of 190° C. and a load of 2.16 kg is in the range of 0.01 to 20 g / 10 min.

10. 5. The sealant film according to claim 3, wherein the laminate layer and the intermediate layer are layers made of an ethylene polymer (C) which satisfies the following requirements (a) and (b): (a) Density is 900 to 940 kg / m 3 is in the range. (b) The melt flow rate (MFR) measured in accordance with JIS K7210-1 under conditions of 190° C. and a load of 2.16 kg is in the range of 0.01 to 20 g / 10 min.

11. A laminate comprising a substrate layer and the sealant film according to any one of claims 1 to 10, and a laminate layer of the sealant film laminated on the substrate layer.

12. A laminate as described in claim 11, wherein the base layer and the laminate layer of the sealant film are bonded together by dry lamination.

13. A packaging bag formed from the laminate according to claim 11 or 12 and having a sealant film as an inner surface.

14. The packaging bag according to claim 13, wherein the contents contain a spice-derived ingredient.

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