WO2024071092A1

WO2024071092A1 - Oriented polyethylene film, packaging material, and food packaging

Info

Publication number: WO2024071092A1
Application number: PCT/JP2023/034864
Authority: WO
Inventors: 正之櫻井; 和樹橋詰; 拓也田村; いずみ桂川; 裕之若木
Original assignee: 三井化学東セロ株式会社
Priority date: 2022-09-30
Filing date: 2023-09-26
Publication date: 2024-04-04

Abstract

An oriented polyethylene film (100) comprising a high-density polyethylene layer 1 (101), a medium-density polyethylene layer (102), and a high-density polyethylene layer 2 (103) in this order, wherein the oriented polyethylene film has a crystal thickness of 16 nm or less in the MD direction as determined by small-angle X-ray scattering (SAXS) measurement.

Description

Stretched polyethylene film, packaging material and food packaging body

The present invention relates to a stretched polyethylene film, a packaging material, and a food package.

In the field of packaging films, attempts to improve various performance features by tinkering with the materials used and layer structures are known.

Patent Document 1 discloses a laminated film that includes a base layer and a heat seal layer, has a stiffness of 70 mN or more in the TD direction measured under conditions of a loop length of 50 mm and a push-in length of 10 mm, and has a polyethylene content of 90% by mass or more, and describes that this laminated film can be recycled and can fully ensure the self-supporting properties of a standing pouch.

Patent Document 2 discloses a polyethylene laminate for packaging materials, which comprises at least an oriented polyethylene film, an adhesive layer, and a heat-sealable polyethylene layer, the adhesive layer containing a solvent-free adhesive, and the oriented polyethylene film containing at least one of high density polyethylene (HDPE) and medium density polyethylene (MDPE), and describes that this polyethylene laminate for packaging materials can significantly reduce the burden on the environment and has high printability and strength.

Patent Document 3 discloses a polyethylene co-extruded film that includes a polyethylene film substrate and a polyethylene film layer, the polyethylene film substrate being an electron beam irradiated layer that includes polyethylene, a light stabilizer, and a crosslinking agent, the polyethylene film layer including polyethylene, and the surface opposite to the surface on which the polyethylene film substrate is provided has heat sealability, and it is described that this polyethylene co-extruded film can suppress deterioration over time, and further has improved heat resistance and strength.

Patent Document 4 describes a multilayer film in which a gas barrier layer formed by applying a dispersion liquid containing an inorganic layered compound and a water-soluble polymer to at least one surface of a base layer made of a thermoplastic resin, an overcoat layer containing a cationic resin and a resin having a hydroxyl group, an adhesive layer, and a sealant layer are laminated in this order, and it is described that this multilayer film has excellent heat sealability and gas barrier properties.

JP 2022-053864 A JP 2022-079510 A JP 2018-008455 A JP 2009-241359 A

In recent years, with growing environmental awareness, and in particular the issue of marine plastic pollution coming into focus, society has been paying closer attention to packaging films. As a result, there is now a greater demand than ever before for the promotion of recycling of packaging films. In other words, there is an increasing demand to design and manufacture packaging films with "ease of recycling" in mind.

Many of the conventional packaging films have achieved the desired effects (strength, gas barrier properties, etc.) by laminating various materials. For example, the multilayer film described in Patent Document 4 has at least four layers, a gas barrier layer, an overcoat layer, an adhesive layer, and a sealant layer. However, laminating various materials makes it difficult to recycle.
From the viewpoint of facilitating recycling of packaging films, for example, it is conceivable to make the packaging film have as simple a layer structure as possible.

In terms of simplifying the layer structure, it is theoretically possible to make the packaging film a "single layer." In addition, there are examples such as Patent Documents 1 to 3 in which, even if it is not a single layer, a multi-layer structure in which a single material is blended at a high content as a whole is used in consideration of ease of recycling.
The present inventors conducted a preliminary study on various properties that may be required for packaging films using polyethylene film, which is a relatively low-cost and versatile packaging material. As a result of the study, it was found that a "single-layer" polyethylene film has poor lamination strength, which represents the force required to bond and peel the film.

The present invention provides a stretched polyethylene film with improved lamination strength and a packaging material made of such a stretched polyethylene film.

[1]
A high density polyethylene layer 1;
a medium density polyethylene layer;
A high density polyethylene layer 2;
A stretched polyethylene film comprising, in this order:
The stretched polyethylene film has a crystal thickness in the MD direction of 16 nm or less, as determined by small angle X-ray scattering (SAXS) measurement.
[2]
The stretched polyethylene film according to [1], wherein a total amount of the high density polyethylene layer 1 and the high density polyethylene layer 2 in the stretched polyethylene film is 10 mass% or more and 85 mass% or less, when the entire stretched polyethylene film is taken as 100 mass%.
[3]
The stretched polyethylene film according to [1] or [2], wherein the high-density polyethylene layer 1 and the high-density polyethylene layer 2 each have a density, as measured in accordance with JIS K 7112:1999, of 940 kg/ ^m3 or more and 970 kg/ ^m3 or less.
[4]
The stretched polyethylene film according to any one of [1] to [3], wherein the medium-density polyethylene layer has a density, as measured in accordance with JIS K 7112:1999, of 910 kg/ ^m3 or more and less than 940 kg/ ^m3 .
[5]
The stretched polyethylene film according to any one of [1] to [4], wherein the stretched polyethylene film has a full width at half maximum (FWHM) of a peak in the MD direction at a diffraction angle 2θ in the range of 0.2 to 0.4°, as determined by small angle X-ray scattering (SAXS) measurement, of 0.20° or less.
[6]
The stretched polyethylene film according to any one of [1] to [5], wherein the haze of the stretched polyethylene film per sheet, as measured in accordance with JIS K 7136:2000, is 8.0% or less.
[7]
The stretched polyethylene film according to any one of [1] to [6], wherein the haze per four sheets of the stretched polyethylene film, as measured in accordance with JIS K 7136:2000, is 33.0% or less.
[8]
The stretched polyethylene film according to any one of [1] to [7], wherein the sum of the tensile modulus of elasticity _T1 in the MD direction and the tensile modulus of elasticity T2 in the TD direction of the stretched polyethylene film, measured in accordance with JIS K7127:1999 using a tensile tester under conditions of a measurement temperature of 23±2°C, 50± ₅ % RH, and a tensile speed of 5 mm/min, is 1000 MPa or more and 3300 MPa or less.
[9]
The stretched polyethylene film according to any one of [1] to [8], wherein the stretched polyethylene film has a heat shrinkage rate in the MD direction of 3.0% or less when heat-treated at 100° C. for 15 minutes in accordance with JIS C2151:2019.
[10]
The stretched polyethylene film according to any one of [1] to [9], wherein the stretched polyethylene film has a heat shrinkage rate in the MD direction of 15.0% or less when heat-treated at 120°C for 15 minutes in accordance with JIS C2151:2019.
[11]
The stretched polyethylene film according to any one of [1] to [10], wherein at least one surface of the stretched polyethylene film is a corona-treated surface.
[12]
The stretched polyethylene film according to [11], wherein the static friction coefficient (tan θ) of the surface of the corona-treated surface of the stretched polyethylene film, as measured using a slip tester by the following method 1 (incline method), is 0.40 or more and 0.75 or less.
(Method 1)
Two pieces of the stretched polyethylene film cut to a size of 50 mm x 75 mm (hereinafter referred to as stretched polyethylene films 1 and 2) are prepared, and one of the stretched polyethylene films, the stretched polyethylene film 1, is fixed to an inclined plate so that the corona-treated surface side is on top. Next, a friction body with a bottom surface (size 41 mm x 26 mm) made of brass is fixed to the center of the surface opposite to the corona-treated surface side of the other stretched polyethylene film 2, and a weight is attached on top of the friction body so that the mass applied from the friction body to the stretched polyethylene film 2 is 150 g. Next, the corona-treated surfaces of the two stretched polyethylene films 1 and 2 are overlapped. Next, the inclined plate is inclined at a speed of 1°/sec, and the value of tan θ is calculated from the angle θ when the upper stretched polyethylene film 2 starts to slide.
[13]
The stretched polyethylene film according to any one of [1] to [12], wherein the number of pinholes generated in the stretched polyethylene film is 6000 pcs/m ^{or less, as measured in a bending test of 3000 times using a Gelbo flex tester at a bending angle of 440} ° and a bending speed of 40 times/min in an atmosphere of -30°C.
[14]
The stretched polyethylene film according to any one of [1] to [13], wherein the stretched polyethylene film has a tear strength in the MD direction of 50 mN or more and 1,500 mN or less, as measured using a light-load tear tester under the conditions of test piece size: MD direction: 63.5 mm, TD direction: 50.0 mm, pendulum weight: 96.09 g, tear length: 12.7 mm, and pendulum lift angle: 90°.
[15]
The stretched polyethylene film according to any one of [1] to [14], wherein the stretched polyethylene film has a tear strength in the TD direction of 200 mN or more and 800 mN or less, as measured using a light-load tear tester under the conditions of test piece size: MD direction: 50.0 mm, TD direction: 63.5 mm, pendulum weight mass: 96.09 g, tear length: 12.7 mm, and pendulum lift angle: 90°.
[16]
At least one surface of the stretched polyethylene film is a corona untreated surface,
The stretched polyethylene film according to any one of [1] to [15], wherein the heat fusion strength when the non-corona treated surface of the stretched polyethylene film is bonded to the other surface and heat sealed at 140°C is 10.0 N/15 mm or less.
[17]
The stretched polyethylene film according to any one of [1] to [16], wherein the stretched polyethylene film has a lamination strength of 0.92 N/15 mm or more as measured by the following method 2.
(Method 2)
A test piece measuring 297 cm x 210 cm was cut out from the stretched polyethylene film, and the corona-treated surface of the test piece was bonded to the corona-treated surface of a 50 μm-thick cast LLDPE film, one side of which had been corona-treated, with an ester-based adhesive. The resulting mixture was aged at 40°C for 3 days to obtain a sample. The sample was then cut to a width of 15 mm and peeled in the MD direction using a tensile tester in accordance with JIS Z 0238:1998 at a peel angle of 90°, a chuck distance of 100 mm, and a crosshead speed of 300 mm/min, to determine the peel strength, which is taken as the laminate strength.
[18]
The stretched polyethylene film according to any one of [1] to [17], wherein the total thickness of the stretched polyethylene film is 10 μm or more and 100 μm or less.
[19]
The stretched polyethylene film according to any one of [1] to [18], which is a food packaging film.
[20]
A packaging material using the stretched polyethylene film according to any one of [1] to [19].
[21]
[20] The packaging material according to [20],
and a food product within the packaging material.

The present invention provides a stretched polyethylene film with improved lamination strength.

FIG. 1 is a cross-sectional view showing a schematic example of a structure of a stretched polyethylene film according to an embodiment of the present invention.

Below, an embodiment of the present invention will be described with reference to the drawings. In this specification, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified.

<Stretched polyethylene film>
The stretched polyethylene film (100) according to this embodiment comprises a high density polyethylene layer 1 (101), a medium density polyethylene layer (102), and a high density polyethylene layer 2 (103) in this order, and the stretched polyethylene film has a crystal thickness in the MD direction of 16 nm or less as determined by small angle X-ray scattering (SAXS) measurement.

In packaging films, high density polyethylene is sometimes blended to improve heat resistance and rigidity. However, when a film containing a high content of high density polyethylene is stretched in one direction, oriented crystallization is promoted and the molecular chains are strongly oriented in the stretching direction, which makes the film prone to tearing when stress is applied in the stretching direction, and there are cases where the laminate strength in the stretching direction is extremely reduced.
In contrast, the stretched polyethylene film according to the present embodiment can improve the lamination strength. The reason for this effect is presumably that the three-layer structure in which the medium-density polyethylene layer is sandwiched between the high-density polyethylene layer 1 and the high-density polyethylene layer 2 can suppress oriented crystallization of the surface layer of the stretched polyethylene film, that is, can suppress the molecular chains of the polyethylene from being aligned excessively in one direction.

In the stretched polyethylene film according to this embodiment, the crystal thickness in the MD direction, as determined by small angle X-ray scattering (SAXS) measurement, is, from the viewpoint of improving the laminate strength, 16 nm or less, and preferably 15 nm or less, and, from the viewpoint of further improving the heat resistance and rigidity, is preferably 3 nm or more, more preferably 5 nm or more, even more preferably 7 nm or more, even more preferably 10 nm or more, and even more preferably 13 nm or more.
The crystal thickness of the stretched polyethylene film can be adjusted, for example, by adjusting the types and content ratios of the high density polyethylene layer 1, the high density polyethylene layer 2, and the medium density polyethylene layer contained in the stretched polyethylene film, the thickness, stretching temperature, stretching ratio, etc. of the stretched polyethylene film.

The materials that make up the stretched polyethylene film are explained below.

In the stretched polyethylene film according to this embodiment, the total amount of the high density polyethylene layer 1 and the high density polyethylene layer 2, relative to the entire stretched polyethylene film, is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, even more preferably 25% by mass or more, even more preferably 28% by mass or more, even more preferably 30% by mass or more, and even more preferably 35% by mass or more, from the viewpoint of further improving the transparency, rigidity, heat resistance, and slip property, and is preferably 85% by mass or less, more preferably 83% by mass or less, even more preferably 80% by mass or less, even more preferably 75% by mass or less, even more preferably 65% by mass or less, even more preferably 55% by mass or less, and even more preferably 45% by mass or less, from the viewpoint of blending an appropriate amount of the medium density polyethylene layer to further improve the laminate strength.
Furthermore, from the viewpoint of further improving the balance between transparency, rigidity, heat resistance, heat fusion strength and laminate strength, the total amount of the high-density polyethylene layer 1 and the high-density polyethylene layer 2 is more preferably 38 mass% or more, and even more preferably 65 mass% or less, and even more preferably 55 mass% or less, of the entire stretched polyethylene film.

In the stretched polyethylene film of this embodiment, the high-density polyethylene layer 1 and the high-density polyethylene layer 2 may be formed using the same material or different materials, but if different materials are used, it is preferable that the high-density polyethylene layer 1 and the high-density polyethylene layer 2 satisfy the following configuration.

From the viewpoint of further improving transparency, rigidity, heat resistance, and slip properties, the content of high density polyethylene in high density polyethylene layer 1 and high density polyethylene layer 2 is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on the entire high density polyethylene layer 1 and high density polyethylene layer 2, respectively. There is no upper limit to the content of high density polyethylene in high density polyethylene layer 1 and high density polyethylene layer 2, but it is, for example, 100% by mass or less, respectively.

The density of the high-density polyethylene layer 1 and the high-density polyethylene layer 2, measured in accordance with JIS K 7112:1999, is preferably 940 kg/m or ^more , more preferably 943 kg/m or more, and even more preferably 945 kg/m ^or more, from the viewpoint of achieving a better balance between various performances such as heat resistance, transparency, mechanical properties, and rigidity, and is preferably 970 kg/m or less, more preferably 968 kg/ ^m ^or less, even more preferably ⁹⁶⁵ kg/m ^or less, even more preferably 960 kg/m or less, even more preferably ⁹⁵⁵ kg/m or less, and even more preferably 950 kg/m ^or ^less , from the viewpoint of achieving a better balance between laminate strength and film formability.

The density of the high density polyethylene constituting the high density polyethylene layer 1 and the high density polyethylene layer 2, as measured in accordance with JIS K 7112:1999, is preferably 940 kg/m or ^more , more preferably 943 kg/m or more, and even more preferably 945 kg/m ^or ^more , from the viewpoint of achieving a better balance between various performances such as heat resistance, transparency, mechanical properties, and rigidity, and is preferably 970 kg/m or less, more preferably 968 kg/m ^or less, even more preferably 965 kg/m ^or less, even more preferably 960 kg/m ^or less, even more preferably 955 kg/m ^or less, and even more preferably 950 kg/m ^or ^less , from the viewpoint of achieving a better balance between laminate strength and film formability.

The melt flow rate (MFR) of the high density polyethylene layer 1 and the high density polyethylene layer 2, measured in accordance with ASTM D1238 under conditions of 190°C and a load of 2.16 kg, is preferably 0.01 g/10 min or more, more preferably 0.1 g/10 min or more, even more preferably 0.5 g/10 min or more, and even more preferably 1.0 g/10 min or more, from the viewpoint of further improving the fluidity and moldability, and is preferably 20 g/10 min or less, more preferably 10 g/10 min or less, even more preferably 5 g/10 min or less, even more preferably 3 g/10 min or less, even more preferably 2 g/10 min or less, and even more preferably 1.5 g/10 min or less, from the viewpoint of improving the stiffness of the stretched polyethylene film while maintaining the tearability of the stretched polyethylene film.
The melting points of the high-density polyethylene layer 1 and the high-density polyethylene layer 2, as measured by a differential scanning calorimeter (DSC), are preferably 120° C. or higher, more preferably 125° C. or higher, and preferably 135° C. or lower, from the viewpoint of further improving the balance of thermal dimensional stability, heat resistance, mechanical properties, rigidity, bag-formability, fluidity, moldability, and the like.

The melt flow rate (MFR) of the high density polyethylene constituting the high density polyethylene layer 1 and the high density polyethylene layer 2, measured in accordance with ASTM D1238 under conditions of 190°C and a load of 2.16 kg, is preferably 0.01 g/10 min or more, more preferably 0.1 g/10 min or more, even more preferably 0.5 g/10 min or more, and even more preferably 1.0 g/10 min or more, from the viewpoint of further improving fluidity and moldability, and is preferably 20 g/10 min or less, more preferably 10 g/10 min or less, even more preferably 5 g/10 min or less, even more preferably 3 g/10 min or less, even more preferably 2 g/10 min or less, and even more preferably 1.5 g/10 min or less, from the viewpoint of improving the stiffness of the stretched polyethylene film while maintaining the tearability of the stretched polyethylene film.
The melting points of the high density polyethylene constituting the high density polyethylene layer 1 and the high density polyethylene layer 2, as measured by a differential scanning calorimeter (DSC), are preferably 120°C or higher, more preferably 125°C or higher, and preferably 135°C or lower, from the viewpoint of further improving the balance of thermal dimensional stability, heat resistance, mechanical properties, rigidity, bag-formability, fluidity, moldability, and the like.

When two or more types of polyethylene are used as the polyethylene constituting the high-density polyethylene layer, the density, MFR and melting point of the high-density polyethylene layer can be measured values for a mixture obtained by melt-blending two or more types of polyethylene using a known method. The melting point of the high-density polyethylene layer can be the peak temperature of the maximum melting peak.

The medium-density polyethylene content in the medium-density polyethylene layer is preferably 80% by mass or more, more preferably 85% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, and even more preferably 98% by mass or more, based on the entire medium-density polyethylene layer, from the viewpoint of suppressing oriented crystallization of the surface layer of the stretched polyethylene film and further improving the laminate strength. There is no upper limit to the medium-density polyethylene content in the medium-density polyethylene layer, but it is, for example, 100% by mass or less.

The density of the medium-density polyethylene layer, measured in accordance with JIS K 7112:1999, is preferably 910 kg/ ^m3 or more, more preferably 915 kg/ ^m3 or more, even more preferably 920 kg/ ^m3 or more, and still more preferably 925 kg/ ^m3 or more, from the viewpoint of improving the mechanical properties, rigidity, and flexibility, and is preferably less than 940 kg/ ^m3 , more preferably 933 kg/ ^m3 or less, and still more preferably 930 kg/ ^m3 or less, from the viewpoint of improving the balance between laminate strength and flexibility.

The density of the medium-density polyethylene constituting the medium-density polyethylene layer, measured in accordance with JIS K 7112:1999, is preferably 910 kg/ ^m3 or more, more preferably 915 kg/ ^m3 or more, even more preferably 920 kg/ ^m3 or more, and still more preferably 925 kg/ ^m3 or more, from the viewpoint of improving the mechanical properties, rigidity, and flexibility, and is preferably less than 940 kg/ ^m3 , more preferably 933 kg/ ^m3 or less, and still more preferably 930 kg/ ^m3 or less, from the viewpoint of improving the balance between laminate strength and flexibility.

The melt flow rate (MFR) of the medium-density polyethylene layer, measured in accordance with ASTM D1238 under conditions of 190°C and a load of 2.16 kg, is preferably 0.01 g/10 min or more, more preferably 0.1 g/10 min or more, even more preferably 0.5 g/10 min or more, and even more preferably 1.0 g/10 min or more, from the viewpoint of further improving processability, and is preferably 20 g/10 min or less, more preferably 10 g/10 min or less, even more preferably 5 g/10 min or less, even more preferably 3 g/10 min or less, and even more preferably 2 g/10 min or less, from the viewpoint of improving the stiffness of the stretched polyethylene film while maintaining the tearability of the stretched polyethylene film.
The melting point of the medium-density polyethylene layer, as measured by a differential scanning calorimeter (DSC), is preferably 120° C. or higher, and more preferably 125° C. or higher, from the viewpoint of improving heat resistance and stiffness while maintaining processability and adhesiveness, and is preferably 135° C. or lower, and more preferably 130° C. or lower, from the viewpoint of improving adhesiveness while maintaining heat resistance.

The melt flow rate (MFR) of the medium-density polyethylene constituting the medium-density polyethylene layer, measured in accordance with ASTM D1238 under conditions of 190°C and a load of 2.16 kg, is preferably 0.01 g/10 min or more, more preferably 0.1 g/10 min or more, even more preferably 0.5 g/10 min or more, and even more preferably 1.0 g/10 min or more, from the viewpoint of further improving processability, and is preferably 20 g/10 min or less, more preferably 10 g/10 min or less, even more preferably 5 g/10 min or less, even more preferably 3 g/10 min or less, and even more preferably 2 g/10 min or less, from the viewpoint of improving the stiffness of the stretched polyethylene film while maintaining the tearability of the stretched polyethylene film.
The melting point of the medium-density polyethylene constituting the medium-density polyethylene layer, as measured by a differential scanning calorimeter (DSC), is preferably 120° C. or higher, more preferably 125° C. or higher, from the viewpoint of improving heat resistance and stiffness while maintaining processability and adhesiveness, and is preferably 135° C. or lower, more preferably 130° C. or lower, from the viewpoint of improving adhesiveness while maintaining heat resistance.

When two or more types of polyethylene are used as the polyethylene constituting the medium-density polyethylene layer, the density, MFR and melting point of the medium-density polyethylene layer can be measured values for a mixture obtained by melt-blending two or more types of polyethylene using a known method. The melting point of the medium-density polyethylene layer can be the peak temperature of the maximum melting peak.

It is preferable that at least one surface of the stretched polyethylene film of this embodiment is a corona-treated surface (a surface that has been surface-modified by exposure to corona discharge). By making at least one surface of the stretched polyethylene film of this embodiment a corona-treated surface, the printing characteristics, coating characteristics, lamination characteristics with other films, etc. of the stretched polyethylene film of this embodiment can be further improved.

The high density polyethylene layer 1, the high density polyethylene layer 2 and the medium density polyethylene layer may contain various additives within the scope of the present invention. Examples of additives include heat stabilizers, weather stabilizers, antioxidants, UV absorbers, lubricants, slip agents, nucleating agents, antiblocking agents, antistatic agents, antifogging agents, pigments, dyes, inorganic or organic fillers, etc.

From the viewpoint of achieving a more appropriate range of oriented crystallinity, the thicknesses of the high-density polyethylene layer 1 and the high-density polyethylene layer 2 are each preferably 1 μm or more, more preferably 2 μm or more, and preferably 17 μm or less, more preferably 15 μm or less, even more preferably 13 μm or less, even more preferably 10 μm or less, even more preferably 9 μm or less, and even more preferably 7 μm or less.
The thicknesses of high-density polyethylene layer 1 and high-density polyethylene layer 2 may be the same or different, but it is preferable that they are the same from the viewpoint of making the amount of distortion on the front and back of the stretched polyethylene film uniform on the high-density polyethylene layer 1 side and the high-density polyethylene layer 2 side.
From the viewpoint of achieving a more appropriate range of oriented crystallinity, the thickness of the medium-density polyethylene layer is preferably 2 μm or more, more preferably 3 μm or more, even more preferably 5 μm or more, and even more preferably 10 μm or more, and is preferably 30 μm or less, more preferably 25 μm or less, even more preferably 20 μm or less, and even more preferably 15 μm or less.
The overall thickness of the stretched polyethylene film is, from the viewpoints of maintaining the tearability and further improving the mechanical strength of the stretched polyethylene film, preferably 10 μm or more, more preferably 13 μm or more, and even more preferably 15 μm or more, and from the viewpoints of further improving the tearability, handleability, formability, bag-making suitability, lightness, etc. of the stretched polyethylene film, it is preferably 100 μm or less, more preferably 70 μm or less, even more preferably 50 μm or less, even more preferably 40 μm or less, and even more preferably 30 μm or less.

Next, we will explain the physical properties of stretched polyethylene film.

In the stretched polyethylene film of this embodiment, the full width at half maximum (FWHM) of the peak in the MD direction at a diffraction angle 2θ in the range of 0.2 to 0.4°, as determined by small angle X-ray scattering (SAXS), is preferably 0.20° or less, more preferably 0.19° or less, from the viewpoint of suppressing oriented crystallization of the surface layer of the stretched polyethylene film and further improving the balance of performance of tear strength, lamination strength, transparency, thermal dimensional stability, and slip property. The full width at half maximum (FWHM) of the peak in the MD direction at a diffraction angle 2θ in the range of 0.2 to 0.4° of the stretched polyethylene film is preferably 0.05° or more, more preferably 0.10° or more, even more preferably 0.13° or more, even more preferably 0.14° or more, and even more preferably 0.15° or more, from the viewpoint of further improving film formability, bag formability, lamination strength, and thermal dimensional stability.
The full width at half maximum (FWHM) of the peak in the MD diffraction angle 2θ range of 0.2 to 0.4°, which is determined from such small angle X-ray scattering (SAXS) measurement, can be adjusted, for example, by adjusting the types and contents of the high density polyethylene layer 1, the high density polyethylene layer 2, and the medium density polyethylene layer contained in the stretched polyethylene film, the thickness of the stretched polyethylene film, the stretch ratio, etc.

In the stretched polyethylene film of this embodiment, the haze per sheet of stretched polyethylene film measured in accordance with JIS K 7136:2000 is preferably 8.0% or less, more preferably 7.5% or less, even more preferably 7.0% or less, even more preferably 6.5% or less, even more preferably 6.0% or less, even more preferably 5.5% or less, even more preferably 5.0% or less, and even more preferably 4.5% or less, from the viewpoint of further improving the transparency of the stretched polyethylene film. There is no lower limit for the haze per sheet of stretched polyethylene film, but it is, for example, 0.1% or more, and may be 1.0% or more, or 3.0% or more.

In the stretched polyethylene film of this embodiment, the haze per four sheets of stretched polyethylene film measured in accordance with JIS K 7136: 2000 is, from the viewpoint of further improving the transparency of the stretched polyethylene film, preferably 33.0% or less, more preferably 30.0% or less, even more preferably 28.0% or less, even more preferably 25.0% or less, even more preferably 23.0% or less, even more preferably 20.0% or less, and even more preferably 18.0% or less. There is no lower limit for the haze per four sheets of stretched polyethylene film, but it may be, for example, 1.0% or more, or may be 5.0% or more, 10.0% or more, or may be 15.0% or more.
Such haze can be adjusted, for example, by adjusting the types and contents of the high density polyethylene layer 1, the high density polyethylene layer 2 and the medium density polyethylene layer contained in the stretched polyethylene film, the thickness and the stretch ratio of the stretched polyethylene film, etc.

In the stretched polyethylene film of the present embodiment, the total value of the tensile modulus T1 in the MD direction and the tensile modulus _T2 in the TD direction of the stretched polyethylene film, measured in accordance with JIS K7127:1999 using a tensile tester under conditions of a measurement temperature of ₂₃ ±2°C, 50±5% RH, and a tensile speed of 5 mm/min, is preferably 1000 MPa or more, more preferably 1300 MPa or more, even more preferably 1500 MPa or more, even more preferably 1550 MPa or more, even more preferably 1600 MPa or more, and even more preferably 1800 MPa or more, from the viewpoints of improving the performance balance of the transparency and thermal dimensional stability of the stretched polyethylene film and improving the stiffness of the stretched polyethylene film; and from the viewpoints of making troubles such as breakage less likely to occur during molding of the stretched polyethylene film, facilitating continuous stretch molding of the film, and further improving industrial continuous productivity, is preferably 3300 MPa or less, more preferably 3100 MPa or less, even more preferably 3000 MPa or less, and even more preferably 2950 MPa or less.
In addition, from the viewpoint of further improving the balance between transparency, rigidity, heat resistance, and heat fusion strength and laminate strength, the sum of the tensile modulus _T1 in the MD direction and the tensile modulus _T2 in the TD direction of the stretched polyethylene film is more preferably 1830 MPa or more, more preferably 1840 MPa or more, and more preferably 2800 MPa or less, more preferably 2600 MPa or less, more preferably 2400 MPa or less, and more preferably 2200 MPa or less.
Such a tensile modulus is a substitute value for quantitatively measuring the stiffness of a film, and can be adjusted, for example, by adjusting the types and contents of the high density polyethylene layer 1, high density polyethylene layer 2, and medium density polyethylene layer contained in the stretched polyethylene film, the thickness of the stretched polyethylene film, the stretching ratio, etc.

The tensile modulus _T1 in the MD direction of the stretched polyethylene film is, from the viewpoint of further improving the balance of the thermal dimensional stability, formability, mechanical properties, transparency, bag-formability, handleability and packaging suitability of the stretched polyethylene film, preferably 500 MPa or more, more preferably 600 MPa or more, even more preferably 630 MPa or more, even more preferably 650 MPa or more, even more preferably 670 MPa or more, and even more preferably 700 MPa or more; and, from the viewpoint of further improving the balance of the thermal dimensional stability, bag-formability and packaging suitability of the stretched polyethylene film, it is preferably 1500 MPa or less, more preferably 1480 MPa or less, even more preferably 1450 MPa or less, even more preferably 1430 MPa or less, and even more preferably 1400 MPa or less.
The tensile modulus _T2 in the TD direction of the stretched polyethylene film is preferably 600 MPa or more, more preferably 700 MPa or more, even more preferably 730 MPa or more, even more preferably 750 MPa or more, even more preferably 770 MPa or more, even more preferably 800 MPa or more, and even more preferably 830 MPa or more, from the viewpoint of further improving the balance of the formability, mechanical properties, transparency, bag-formability, handleability, and packaging suitability of the stretched polyethylene film. Also, from the viewpoint of further improving the balance of the bag-formability and packaging suitability of the stretched polyethylene film, it is preferably 1800 MPa or less, more preferably 1750 MPa or less, even more preferably 1700 MPa or less, even more preferably 1650 MPa or less, even more preferably 1600 MPa or less, and even more preferably 1550 MPa or less.

In the stretched polyethylene film of this embodiment, the heat shrinkage rate in the MD direction of the stretched polyethylene film when heated at 100°C for 15 minutes is, from the viewpoint of further improving the thermal dimensional stability and bag-formability, preferably 3.0% or less, more preferably 2.8% or less, and even more preferably 2.5% or less, and may be 0.1% or more, 0.5% or more, 1.0% or more, 1.5% or more, 1.6% or more, or 1.7% or more.
From the viewpoint of further improving the balance between transparency, rigidity, heat resistance, and heat fusion strength and laminate strength, the heat shrinkage rate in the MD direction of the stretched polyethylene film when heat-treated at 100°C for 15 minutes is more preferably 2.4% or less, and may be 2.0% or more.
The heat shrinkage rate of the stretched polyethylene film can be measured in accordance with JIS C2151:2019.

In the stretched polyethylene film of this embodiment, the heat shrinkage rate in the MD direction of the stretched polyethylene film when heated at 120°C for 15 minutes is, from the viewpoint of further improving the thermal dimensional stability and bag-formability, preferably 15.0% or less, more preferably 13.0% or less, and even more preferably 11.0% or less, and may be 1.0% or more, 3.0% or more, 5.0% or more, or 8.0% or more.
Furthermore, from the viewpoint of further improving the balance between transparency, rigidity, heat resistance, and heat fusion strength and laminate strength, the heat shrinkage rate in the MD direction of the stretched polyethylene film when heat-treated at 120°C for 15 minutes is more preferably 10.5% or less, and more preferably 9.0% or more, and even more preferably 9.5% or more.

When either the high density polyethylene layer 1 or the high density polyethylene layer 2 of the stretched polyethylene film has been corona treated, the static friction coefficient (tan θ) of the surfaces of the stretched polyethylene film may be measured between treated surfaces, between untreated surfaces, or between treated and untreated surfaces.
In particular, from the viewpoint of facilitating the formation of a thin and uniform layer, it is preferable that the static friction coefficient (tan θ) of the corona-treated surface of the stretched polyethylene film is within the above range. The static friction coefficient (tan θ) of the corona-treated surface of the stretched polyethylene film is preferably 0.40 or more, more preferably 0.42 or more, and even more preferably 0.45 or more, and is preferably 0.75 or less, more preferably 0.70 or less, even more preferably 0.65 or less, even more preferably 0.60 or less, even more preferably 0.56 or less, and even more preferably 0.54 or less.
In order to improve the handleability of the stretched polyethylene film, it is preferable that the static friction coefficient (tan θ) of the surface on the non-corona treated side of the stretched polyethylene film is within the above range. The static friction coefficient (tan θ) of the non-corona treated side of the stretched polyethylene film is preferably 0.40 or more, more preferably 0.42 or more, and even more preferably 0.45 or more, and is preferably 0.75 or less, more preferably 0.70 or less, even more preferably 0.65 or less, even more preferably 0.60 or less, even more preferably 0.56 or less, and even more preferably 0.54 or less.

The static friction coefficient (tan θ) of the corona-treated surface of the stretched polyethylene film is measured by the following method.
Two pieces of stretched polyethylene film cut to a size of 50 mm x 75 mm (hereinafter referred to as stretched polyethylene film 1 and 2) are prepared, and one of the stretched polyethylene films, the stretched polyethylene film 1, is fixed to an inclined plate so that the corona-treated surface side is on top. Next, a friction body with a bottom surface (size 41 mm x 26 mm) made of brass is fixed to the center of the surface opposite to the corona-treated surface side of the other stretched polyethylene film 2, and a weight is attached on top of the friction body so that the mass applied from the friction body to the stretched polyethylene film 2 is 150 g. Next, the corona-treated surfaces of the two stretched polyethylene films 1 and 2 are overlapped. Next, the inclined plate is inclined at a speed of 1°/sec, and the value of tan θ is calculated from the angle θ when the upper stretched polyethylene film 2 starts to slide.
When the static friction coefficient (tan θ) of the corona-untreated surface is measured, the static friction coefficient (tan θ) of the corona-treated surface is measured in the above-mentioned method for measuring the static friction coefficient (tan θ) of the corona-treated surface, except that the corona-treated surface is replaced with the corona-untreated surface.

In the stretched polyethylene film of this embodiment, the number of pinholes generated in the stretched polyethylene film, measured using a Gelbo flex tester at a bending angle of 440 degrees, a bending speed of 40 times/min, and an atmosphere of -30°C, 3000 times, is preferably 6000 pcs/m or ^less , more preferably 5000 pcs/m or ^less , even more preferably 4000 pcs/m ^or less, even more preferably 3000 pcs/m ^or less, even more preferably 2800 pcs/m ^or less, and even more preferably 2500 pcs/m ^or less.
There is no lower limit to the number of pinholes generated in the stretched polyethylene film, but it is, for example, 100 pinholes/ ^m2 or more, or 300 pinholes/ ^m2 or more, or 500 pinholes/ ^m2 or more, or 1000 pinholes/ ^m2 or more.
The number of pinholes generated represents an index of the flex resistance of the stretched polyethylene film of this embodiment, and the fewer the number of pinholes generated, the better the flex resistance.
By ensuring that the number of pinholes generated in the stretched polyethylene film is within the above range, the generation of pinholes due to bending during filling at low temperature or transportation at low temperature can be further suppressed.
The Gelbo flex tester may be, for example, a product manufactured by Tester Sangyo Co., Ltd.

The tear strength in the MD direction of the stretched polyethylene film measured using a light-load tear tester under the conditions of test piece size: MD direction: 63.5 mm, TD direction: 50.0 mm, pendulum weight mass: 96.09 g, tear length: 12.7 mm, pendulum lift angle: 90° is preferably 50 mN or more, more preferably 55 mN or more, even more preferably 60 mN or more, even more preferably 65 mN or more, and even more preferably 70 mN or more, from the viewpoint of improving film-forming and bag-making processability, and is preferably 1500 mN or less, more preferably 1200 mN or less, even more preferably 1000 mN or less, even more preferably 800 mN or less, even more preferably 600 mN or less, even more preferably 400 mN or less, and even more preferably 200 mN or less, from the viewpoint of improving tearability while maintaining the heat sealability and stiffness of the stretched polyethylene film.

The tear strength in the TD direction of the stretched polyethylene film, measured using a light-load tear tester under conditions of test piece size: MD direction: 50.0 mm, TD direction: 63.5 mm, pendulum weight mass: 96.09 g, tear length: 12.7 mm, and pendulum lift angle: 90°, is preferably 200 mN or more, more preferably 250 mN or more, even more preferably 300 mN or more, even more preferably 310 mN or more, even more preferably 320 mN or more, and even more preferably 330 mN or more, from the viewpoint of improving the film-forming property and bag-making processability, and is preferably 800 mN or less, more preferably 750 mN or less, even more preferably 700 mN or less, preferably 650 mN or less, even more preferably 630 mN or less, even more preferably 600 mN or less, and even more preferably 500 mN or less, from the viewpoint of improving the tearability while maintaining the heat sealability and stiffness of the stretched polyethylene film.
The light load tear tester may be, for example, Model D manufactured by Toyo Seiki Seisakusho Co., Ltd.
In order to achieve such a tear strength, the density, thickness, etc. of each of the high density polyethylene layer 1, the high density polyethylene layer 2 and the medium density polyethylene layer contained in the stretched polyethylene film may be appropriately adjusted.

When at least one of the stretched polyethylene films is a corona untreated surface, the heat fusion strength when the corona untreated surfaces of the stretched polyethylene films are bonded together and heat fused at 140° C. is preferably 10.0 N/15 mm or less, more preferably 9.0 N/15 mm or less, even more preferably 7.0 N/15 mm or less, even more preferably 6.8 N/15 mm or less, even more preferably 6.5 N/15 mm or less, even more preferably 6.3 N/15 mm or less, and even more preferably 6.0 N/15 mm or less, from the viewpoint of improving heat resistance. There is no lower limit for the heat fusion strength, but it is, for example, 0.5 N/15 mm or more.
The heat fusion strength is measured as follows.
The non-corona treated surfaces of two sheets of stretched polyethylene film cut to a width of 15 mm are heat-sealed to each other under conditions of 140°C, pressure of 2.0 kgf, and sealing time of 1.0 second to obtain a laminated film. Next, the two sheets of stretched polyethylene film are peeled off using the laminated film cut to a width of 15 mm under conditions of 90° peeling, peeling speed of 300 mm/min, and pulling in the MD direction, and the peel strength at this time is taken as the heat fusion strength (N/15 mm).

The laminate strength of the stretched polyethylene film, measured in accordance with JIS Z 0238:1998, is preferably 0.92 N/15 mm or more, more preferably 0.93 N/15 mm or more, even more preferably 0.94 N/15 mm or more, even more preferably 0.95 N/15 mm or more, even more preferably 1.00 N/15 mm or more, and even more preferably 1.05 N/15 mm or more, and from the viewpoint of achieving a better balance between adhesion and easy-opening properties, it is preferably 1.20 N/15 mm or less, more preferably 1.18 N/15 mm or less, preferably 1.15 N/15 mm or less, preferably 1.13 N/15 mm or less, and preferably 1.10 N/15 mm or less.
The laminate strength is measured as follows: A test piece measuring 297 cm x 210 cm is cut out from a stretched polyethylene film, and the corona-treated side of the test piece is bonded to the corona-treated side of a 50 μm-thick cast LLDPE film, one side of which has been corona-treated, with an ester adhesive, and aged for 3 days at 40° C. to obtain a sample. The sample is cut to a width of 15 mm, and peeled in the MD direction using a tensile tester in accordance with JIS Z 0238:1998 at a peel angle of 90°, a chuck distance of 100 mm, and a crosshead speed of 300 mm/min, to determine the peel strength, which is the laminate strength.

<Identification of high density polyethylene layer and medium density polyethylene layer>
The fact that the stretched polyethylene film of this embodiment is composed of a high-density polyethylene layer 1, a medium-density polyethylene layer, and a high-density polyethylene layer 2 can be determined, for example, by cutting a cross-section of the stretched polyethylene film and measuring the melting point of each layer.
The melting points of the high density polyethylene layers 1 and 2 are, for example, in the range of 130°C or higher and 140°C or lower, and the melting point of the medium density polyethylene layer is, for example, in the range of 110°C or higher and 129°C or lower.

<Method of producing stretched polyethylene film>
The stretched polyethylene film of the present embodiment is stretched uniaxially or biaxially from the viewpoint of improving the orientation crystallinity and increasing the mechanical strength, and is preferably stretched uniaxially from the viewpoint of improving productivity. Moreover, by stretching uniaxially in the MD direction, the tensile modulus _T1 in the MD direction can be further improved.
The stretched polyethylene film can be obtained, for example, by co-extrusion molding a high-density polyethylene resin for forming the high-density polyethylene layer 1, a medium-density polyethylene resin for forming the medium-density polyethylene layer, and a high-density polyethylene resin for forming the high-density polyethylene layer 2, in that order, into a film, and stretching the film obtained by using a known stretched film production method such as a uniaxial stretching method, simultaneous biaxial stretching method, or sequential biaxial stretching method.
The molding apparatus and molding conditions are not particularly limited, and conventionally known molding apparatus and molding conditions can be used. As the molding apparatus, a T-die extruder, a multi-layer T-die extruder, an inflation molding machine, a multi-layer inflation molding machine, etc. can be used.
The conditions for the uniaxial stretching method and the biaxial stretching method may be, for example, the manufacturing conditions for known stretched polyethylene films. More specifically, in the case of the uniaxial stretching method, for example, the longitudinal stretching temperature may be set to 100° C. to 145° C., and the longitudinal stretching ratio may be set to a range of 4.5 to 6 times. In the case of the sequential biaxial stretching method, for example, the longitudinal stretching temperature may be set to 100° C. to 145° C., the longitudinal stretching ratio may be set to a range of 4.5 to 6 times, the transverse stretching temperature may be set to 110° C. to 160° C., and the transverse stretching ratio may be set to a range of 9 to 11 times.

<Applications of oriented polyethylene film/packaging materials/food packaging>
Specifically, the stretched polyethylene film of the present embodiment can be suitably used as a food packaging film.
The stretched polyethylene film of the present embodiment can also be suitably used as a packaging material.
When used as a packaging material, the stretched polyethylene film of the present embodiment may be used alone, or other layers may be laminated to form the packaging material. Examples of the other layers include a base layer, a coating layer, an adhesive layer, and a heat seal layer. From the viewpoint of ease of recycling, when these layers are laminated, they are preferably formed of a polyethylene-based resin.
The packaging material of the present embodiment can also be suitably used for food packaging. The food packaging is used for the purpose of packaging food, for example, and specifically includes the packaging material of the present embodiment and the food inside the packaging material.
Depending on the application, only a portion of the food package may be made of the packaging material of this embodiment, or substantially the entire food package may be made of the packaging material of this embodiment.

There are no particular limitations on the method for producing food packages from oriented polyethylene films and packaging materials. Methods well known in the field of packaging materials/packages, such as heat sealing and melt cutting, can be used as appropriate.

The stretched polyethylene film according to this embodiment is preferably used for food packaging that requires good laminate strength. The food packaging can be in the form of, for example, a two-sided bag or a standing pouch (pouch packaging). These forms are preferred because they can provide good laminate strength.

Furthermore, when a food package (such as a packaging bag) is formed using the stretched polyethylene film or packaging material of this embodiment, it is preferable that the corona-treated surface is the inner surface and the non-corona-treated surface is the outer surface.
As described above, when another layer is laminated on the stretched polyethylene film, it is preferable to laminate it on the corona-treated surface side. That is, when a laminate using the stretched polyethylene film of this embodiment is used for a food package (such as a packaging bag), it is preferable that the stretched polyethylene film side of this embodiment is the outermost layer of the food package.

There are no limitations on the foods that can be packaged in the food packaging, but examples include baked goods, rice crackers, snacks, sprinkles, grain powders, etc.

The above describes the embodiments of the present invention, but these are merely examples of the present invention, and various configurations other than those described above can be adopted. Furthermore, the present invention is not limited to the above-described embodiments, and modifications and improvements within the scope of the present invention are included in the present invention.

<Ingredients>
The raw materials used in the examples and comparative examples are shown below.
The density was measured in accordance with JIS K 7112: 1999. The MFR was measured in accordance with ASTM D1238 under conditions of 190°C and a load of 2.16 kg. The melting point was measured using a differential scanning calorimeter (DSC).

(High density polyethylene)
High density polyethylene (HDPE1): density: 949 kg/m ³ , MFR: 1.1 g/10 min, melting point: 130° C.
(medium density polyethylene)
Medium density polyethylene (MDPE1): density: 928 kg/m ³ , MFR: 1.7 g/10 min, melting point: 127°C

<Production of oriented polyethylene film>
In the examples and comparative examples, high density polyethylene (HDPE1), medium density polyethylene (MDPE1), and high density polyethylene (HDPE1) were extruded in this order by T-die to form a film in the composition shown in Table 1, and then the cast sheet was subjected to uniaxial stretching. The high density polyethylene layer 2 side of the cast sheet after uniaxial stretching was then subjected to corona treatment to produce the stretched polyethylene film of each example. The extrusion conditions and uniaxial stretching conditions are shown below.
Multi-layer extrusion molding machine: 75 mmφ multi-layer T-die extrusion molding machine (L/D=29, manufactured by Mitsubishi Heavy Industries, Ltd.)
Extrusion temperature: 230°C, processing speed: 70m/min
Longitudinal stretching temperature: 110 to 130°C
For each of the stretched polyethylene films obtained in the respective examples, the densities of the high density polyethylene layer 1, the high density polyethylene layer 2 and the medium density polyethylene layer were measured. The following evaluations were also carried out. The results are shown in Table 1.

<Small angle X-ray scattering (SAXS) measurement of stretched polyethylene film>
For the stretched polyethylene film of each example, the MD direction of the film was set to the top and bottom, the TD direction was set to the left and right, and the angle between the X-ray source direction and the film surface was perpendicular. Small angle X-ray scattering (SAXS) measurements were performed with the following equipment and conditions.
Device: RIGAKU Corporation, product name: Ultima IV (small angle scattering attachment system)
X-ray incidence direction: normal to the film X-ray wavelength: 0.15418 nm
Optical unit specifications:
1. Optical system selection slit; 0.03 mm (= ^1st slit) for small angle scattering
2. DS: Anti-scattering slit 1.00 mm (= ^2nd slit)
3. Soller slit on the entrance side: 5° flexible optical system used 4. Distance between ^1st and ^2nd slits: 70 mm
^5.2nd . ~ Sample distance: 98 mm
6. Vacuum path length: 100 mm (installed on a dedicated stand in front of the receiving slit box)
7. RS, SS: scattering slit 0.20 mm, receiving slit 0.10 mm
8. Camera length: 285mm
9. Solar slit on the receiving side: 5° flexible optical system used 10. Monochromatization: None (monochromatization on the incident side by multilayer mirror)
11. Detector: RIGAKU scintillation detector (HV: 762 V) (one-dimensional)
X-ray irradiation conditions:
A. Scan axis: 2theta
B. Measurement method: Continuous C. Scan start angle: 0.1°
D. Scan end angle: 1.0°
E. Sampling width: 0.02°
F. Scan speed: 0.5°/min
G. Voltage and current: 40kV-40mA
H. Number of sample stacks: In order to obtain sufficient scattering intensity, the samples were stacked to a thickness of about 0.5 mm with the sample orientation aligned.
The X-ray scattering pattern obtained under the above measurement conditions was corrected for air scattering by the detector to obtain a SAXS profile I(q). The diffraction angle θ was calculated from the magnitude of the scattering vector of the peak derived from the crystal long period of the SAXS profile I(q) using formula (1), and this was substituted into Bragg's formula (2) to calculate the crystal long period (d).
q = 4π sin θ / λ (1)
θ: diffraction angle q: scattering vector magnitude λ: X-ray wavelength 2d sin θ=λ (2)
d: Crystal long period θ: Diffraction angle λ: X-ray wavelength Also, referring to the structural analysis of crystalline polymer materials by scattering method in Nichias Technical Review (2014) No. 2 No. 365, the electron density correlation function γ(r) was calculated by Fourier transforming the SAXS profile I(q) using the following formula (3). γ(r) has a special property that can be directly used for structural characterization, and the amorphous thickness (da) of each example of the stretched polyethylene film obtained as structural information was calculated. Also, r indicates distance (nm).

The crystal thickness (dc) was calculated by subtracting the amorphous thickness (da) from the crystal long period (d).
In addition, the full width at half maximum (FWHM) of the peak in the range of 0.2 to 0.4° diffraction angle 2θ in the MD direction was calculated using X-ray analysis software PDXL-2 (manufactured by RIGAKU Corporation). Specifically, air scattering was removed from the SAXS profile I(q) obtained above. Using the obtained values, the above software separated the data into crystalline scattering and amorphous scattering, and the full width at half maximum (FWHM) of the peak in the range of 0.2 to 0.4° diffraction angle 2θ in the MD direction was calculated from the peak fitting results of crystalline scattering under the following (analysis conditions).
(Analysis conditions)
Fitting peak shape: split pseudo-Voigt function Crystallite size distribution type: Lorentz model

<HAZE>
In accordance with JIS K7136:2000, the haze was measured using a haze meter (NDH5000, manufactured by Nippon Denshoku Industries Co., Ltd.) for one sheet of stretched polyethylene film and for four sheets stacked together in each example.
Here, the four sheets of stretched polyethylene film were stacked together with the orientations of the MD and TD directions of the stretched polyethylene films aligned, and the measurements were performed.

<Tensile modulus>
A test piece of 15 mm x 15 cm was cut out from each stretched polyethylene film. Then, using a tensile tester manufactured by Orientec Co., Ltd., the tensile modulus of elasticity in the MD direction _T1 and the tensile modulus of elasticity in the TD direction _T2 of the test piece were measured in accordance with JIS K7127:1999 under the conditions of a measurement temperature of 23±2°C, 50±5% RH, and a tensile speed of 5 mm/min. The total value of _T1 and _T2 was calculated from the obtained values.

<Heat shrinkage rate in MD direction of stretched polyethylene film at 100° C.>
The heat shrinkage rate in the MD direction of the stretched polyethylene film at 100°C was measured in accordance with JIS C2151:2019.
A test piece of 10 cm x 10 cm was cut out from the stretched polyethylene film of each example. At this time, the test piece was heated in a hot air circulation type thermostatic chamber (manufactured by ADVANTEC, product name: DRM620DE) while hanging without applying force. The test piece was then heat-treated at 100°C for 15 minutes. The length in the MD direction of the test piece after the heat treatment was taken as MD ₁₀₀ [cm], and the heat shrinkage rate in the MD direction [%] was calculated by 100 x (10 - MD ₁₀₀ ) / 10. The above measurement was carried out three times, and the average value of the obtained measured values was adopted as the heat shrinkage rate of the stretched polyethylene film at 100°C.

<Heat shrinkage rate in MD direction of stretched polyethylene film at 120°C>
The heat shrinkage rate in the MD direction of the stretched polyethylene film at 120°C was measured in accordance with JIS C2151:2019.
A test piece of 10 cm x 10 cm was cut out from the stretched polyethylene film of each example. At this time, the test piece was heated in a hot air circulation type thermostatic chamber (manufactured by ADVANTEC, product name: DRM620DE) while hanging without applying force. The test piece was then heat-treated at 120°C for 15 minutes. The length of the test piece in the MD direction after the heat treatment was taken as MD ₁₂₀ [cm], and the heat shrinkage rate in the MD direction [%] was calculated by 100 x (10 - MD ₁₂₀ ) / 10. The above measurement was carried out three times, and the average value of the obtained measured values was adopted as the heat shrinkage rate of the stretched polyethylene film at 120°C.

<Static friction coefficient (corona treated surface/corona treated surface)>
The static friction coefficient of the corona-treated surface was measured as follows.
Two pieces of stretched polyethylene film of each example cut to a size of 50 mm x 75 mm (hereinafter referred to as stretched polyethylene film 1 and 2) were prepared, and one of the stretched polyethylene films, the stretched polyethylene film 1, was fixed to an inclined plate so that the corona-treated surface side was on top. Next, a friction body with a bottom surface (size 41 mm x 26 mm) made of brass was fixed to the center of the surface opposite to the corona-treated surface side of the other stretched polyethylene film 2, and a weight was attached on top of the friction body so that the mass applied from the friction body to the stretched polyethylene film 2 was 150 g. Next, the corona-treated surfaces of the two stretched polyethylene films 1 and 2 were overlapped. Next, the inclined plate was tilted at a speed of 1°/sec, and the value of tan θ was obtained from the angle θ when the upper stretched polyethylene film 2 started to slide.

<Tear strength>
A test piece of 63.5 mm in the MD direction and 50.0 mm in the TD direction was cut out from each stretched polyethylene film. The tear strength (mN) in the MD direction of each test piece was measured using a light-load tear tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., Model-D) under the following conditions: pendulum weight: 96.09 g, tear length: 12.7 mm, pendulum lift angle: 90°.
Further, a test piece having a length of 50.0 mm in the MD direction and 63.5 mm in the TD direction was cut out from each stretched polyethylene film. The test piece was subjected to measurement of tear strength (mN) in the TD direction in the same manner as in the measurement of tear strength (mN) in the MD direction.

<Flexibility>
A test piece measuring 297 cm x 210 cm was cut out from the stretched polyethylene film of each example, and a bending test was performed 3,000 times using a Gelbo Flex Tester (manufactured by Tester Sangyo Co., Ltd.) at a bending angle of 440 degrees and a bending speed of 40 times/minute in an atmosphere of -30°C. After the bending test, bags were made from the test pieces, and the number of pinholes generated was measured using Ageless Seal Check Liquid (manufactured by Mitsubishi Gas Chemical Co., Ltd.).

<Heat fusion strength>
Two sheets of the stretched polyethylene film of each example cut to a width of 15 mm were heat-sealed together with their corona-untreated surfaces at 140° C., a pressure of 2.0 kgf, and a sealing time of 1.0 second to obtain a laminated film. The two sheets of stretched polyethylene film were then peeled off under conditions of 15 mm width, 90° peeling, a peeling speed of 300 mm/min, and pulling in the MD direction, and the peel strength at this time was recorded as the heat-sealing strength (N/15 mm).

<Lamination strength>
A 297 cm x 210 cm test piece was cut out from the stretched polyethylene film of each example, and the corona-treated side of the test piece was bonded to the corona-treated side of a 50 μm thick cast LLDPE film (TUX FCS #50 manufactured by Mitsui Chemicals Tohcello) with one side corona-treated, with an ester-based adhesive (Takelac A310/Takenate A3/ethyl acetate manufactured by Mitsui Chemicals) = 12/1/7), and aged at 40 ° C for 3 days to obtain a sample. The sample was cut to a width of 15 mm, and in accordance with JIS Z 0238: 1998, a tensile tester (Tensilon universal tester RTC-1225 manufactured by Orientec Co., Ltd.) was used to measure the peel strength when peeled in the MD direction under the conditions of a peel angle of 90 °, a chuck distance of 100 mm, and a crosshead speed of 300 mm / min, and this was taken as the laminate strength.

When the stretched polyethylene film of the embodiment was used, a food packaging film with improved laminate strength was obtained. It was also found that when the stretched polyethylene film of the embodiment was used, bending resistance could also be improved.

This application claims priority based on Japanese Patent Application No. 2022-157673, filed on September 30, 2022, the entire disclosure of which is incorporated herein by reference.

100 Stretched polyethylene film 101 High density polyethylene layer 1
102 Medium density polyethylene layer 103 High density polyethylene layer 2

Claims

A high density polyethylene layer 1;
a medium density polyethylene layer;
A high density polyethylene layer 2;
A stretched polyethylene film comprising, in this order:
The stretched polyethylene film has a crystal thickness in the MD direction of 16 nm or less, as determined by small angle X-ray scattering (SAXS) measurement.
The stretched polyethylene film according to claim 1, wherein the total amount of the high-density polyethylene layer 1 and the high-density polyethylene layer 2 in the stretched polyethylene film is 10% by mass or more and 85% by mass or less, when the entire stretched polyethylene film is taken as 100% by mass.
3. The stretched polyethylene film according to claim 1, wherein the first and second high-density polyethylene layers each have a density, measured in accordance with JIS K 7112:1999, of 940 kg/ m3 or more and 970 kg/ m3 or less.
The stretched polyethylene film according to any one of claims 1 to 3, wherein the medium-density polyethylene layer has a density, measured in accordance with JIS K 7112:1999, of 910 kg/ m3 or more and less than 940 kg/ m3 .
The stretched polyethylene film according to any one of claims 1 to 4, wherein the full width at half maximum (FWHM) of the peak in the MD direction diffraction angle 2θ range of 0.2 to 0.4°, as determined by small angle X-ray scattering (SAXS) measurement, is 0.20° or less.
The stretched polyethylene film according to any one of claims 1 to 5, wherein the haze per sheet of the stretched polyethylene film measured in accordance with JIS K 7136:2000 is 8.0% or less.
The stretched polyethylene film according to any one of claims 1 to 6, wherein the haze per four sheets of the stretched polyethylene film measured in accordance with JIS K 7136:2000 is 33.0% or less.
The stretched polyethylene film according to any one of claims 1 to 7, wherein the sum of the tensile modulus T1 in the MD direction and the tensile modulus T2 in the TD direction of the stretched polyethylene film, measured in accordance with JIS K7127:1999 using a tensile tester under conditions of a measurement temperature of 23 ± 2 °C, 50±5% RH, and a tensile speed of 5 mm/min, is 1000 MPa or more and 3300 MPa or less.
The stretched polyethylene film according to any one of claims 1 to 8, wherein the thermal shrinkage rate in the MD direction of the stretched polyethylene film is 3.0% or less when heat-treated at 100°C for 15 minutes in accordance with JIS C2151:2019.
The stretched polyethylene film according to any one of claims 1 to 9, wherein the thermal shrinkage rate in the MD direction of the stretched polyethylene film is 15.0% or less when heat-treated at 120°C for 15 minutes in accordance with JIS C2151:2019.
The stretched polyethylene film according to any one of claims 1 to 10, wherein at least one surface of the stretched polyethylene film is a corona-treated surface.
The stretched polyethylene film according to claim 11, wherein the static friction coefficient (tan θ) of the surface of the corona-treated surface of the stretched polyethylene film, as measured using a slip tester by the following method 1 (incline method), is 0.40 or more and 0.75 or less.
(Method 1)
Two pieces of the stretched polyethylene film cut to a size of 50 mm x 75 mm (hereinafter referred to as stretched polyethylene films 1 and 2) are prepared, and one of the stretched polyethylene films, the stretched polyethylene film 1, is fixed to an inclined plate so that the corona-treated surface side is on top. Next, a friction body with a bottom surface (size 41 mm x 26 mm) made of brass is fixed to the center of the surface opposite to the corona-treated surface side of the other stretched polyethylene film 2, and a weight is attached on top of the friction body so that the mass applied from the friction body to the stretched polyethylene film 2 is 150 g. Next, the corona-treated surfaces of the two stretched polyethylene films 1 and 2 are overlapped. Next, the inclined plate is inclined at a speed of 1°/sec, and the value of tan θ is calculated from the angle θ when the upper stretched polyethylene film 2 starts to slide.
13. The stretched polyethylene film according to any one of claims 1 to 12, wherein the number of pinholes generated in the stretched polyethylene film is 6000 pcs/ m2 or less, as measured in a bending test of 3000 times using a Gelbo flex tester at a bending angle of 440° and a bending speed of 40 times/min in an atmosphere of -30°C.
The stretched polyethylene film according to any one of claims 1 to 13, wherein the tear strength in the MD direction of the stretched polyethylene film is 50 mN or more and 1500 mN or less, measured using a light-load tear tester under the following conditions: test piece size: MD direction: 63.5 mm, TD direction: 50.0 mm, pendulum weight: 96.09 g, tear length: 12.7 mm, pendulum lift angle: 90°.
The stretched polyethylene film according to any one of claims 1 to 14, wherein the tear strength in the TD direction of the stretched polyethylene film is 200 mN or more and 800 mN or less, as measured using a light-load tear tester under the following conditions: test piece size: MD direction: 50.0 mm, TD direction: 63.5 mm, pendulum weight mass: 96.09 g, tear length: 12.7 mm, pendulum lift angle: 90°.
At least one surface of the stretched polyethylene film is a non-corona treated surface,
The stretched polyethylene film according to any one of claims 1 to 15, wherein the heat fusion strength when the non-corona treated surface of the stretched polyethylene film is bonded to the non-corona treated surface and heat sealed at 140°C is 10.0 N/15 mm or less.
The stretched polyethylene film according to any one of claims 1 to 16, wherein the stretched polyethylene film has a lamination strength of 0.92 N/15 mm or more as measured by the following method 2.
(Method 2)
A test piece measuring 297 cm x 210 cm was cut out from the stretched polyethylene film, and the corona-treated surface of the test piece was bonded to the corona-treated surface of a 50 μm-thick cast LLDPE film, one side of which had been corona-treated, with an ester-based adhesive. The resulting mixture was aged at 40°C for 3 days to obtain a sample. The sample was then cut to a width of 15 mm and peeled in the MD direction using a tensile tester in accordance with JIS Z 0238:1998 at a peel angle of 90°, a chuck distance of 100 mm, and a crosshead speed of 300 mm/min, to determine the peel strength, which is taken as the laminate strength.
The stretched polyethylene film according to any one of claims 1 to 17, wherein the total thickness of the stretched polyethylene film is 10 μm or more and 100 μm or less.
The stretched polyethylene film according to any one of claims 1 to 18, which is a food packaging film.
　A packaging material using the stretched polyethylene film according to any one of claims 1 to 19.
A packaging material according to claim 20;
and a food product within the packaging material.