KR102412325B1 - Polyethylene film for vapor deposition substrates and vapor deposition film using same - Google Patents

Abstract

It is mentioned as a subject to provide the polyethylene-type film for vapor deposition base materials which has the outstanding barrier property even if it is the vapor deposition film which vapor-deposited using the large sized vapor deposition machine.
A polyethylene film for use as a base material for a vapor deposition layer, wherein the polyethylene film has at least a laminate layer serving as a surface on the vapor deposition layer side and a sealing layer serving as the other surface, wherein the sealing layer contains inorganic particles, Mohs' Hardness of the inorganic particles contained in the sealing layer is 3 or less, and at least one of (i) and (ii) below is satisfied.
(i) the average particle diameter of the inorganic particles contained in the sealing layer is 5 µm or more and 15 µm or less
(ii) the three-dimensional surface roughness SRa of the sealing layer surface is 0.2 µm or less, and the maximum peak height SRmax of the sealing layer surface is 6 µm or less

Description

Polyethylene-based film for vapor deposition substrate and vapor deposition film using same TECHNICAL FIELD

The present invention relates to a polyethylene-based film for a deposition substrate using a polyethylene-based resin and a deposition film in which a deposition layer is deposited on the polyethylene-based film.

Polyethylene-based films subjected to vapor deposition are widely used in packaging materials such as food packaging and medical packaging, gold and silver-based films, labels, stickers, and reflective sheets, and some fabrics for vapor deposition have been proposed.

For example, in Patent Document 1, while the organic lubricant is not added and the slidability is improved by using an inorganic anti-blocking agent having a particle size of 2 to 5 µm, the type of the anti-blocking agent is not particularly limited. When the anti-blocking agent is used as a zeolite as described above, when vapor-depositing on a long film containing a zeolite, the barrier properties of the vapor-deposited film become insufficient.

Nowadays, the evaporator is being enlarged. For this reason, it is calculated|required that the vapor deposition film has barrier property even when vapor-depositing using the large sized vapor deposition machine to the vapor deposition fabric which became long and wide.

Japanese Patent Laid-Open No. 2001-225409

Even when the deposited film deposited using a large evaporator on the elongated and widened fabric for deposition has increased tension to increase the adhesion to the cooling drum, it is wound at the location where the winding is hardened due to thickness unevenness or at the core of the long winding. An object of the present invention is to provide a polyethylene-based film for vapor deposition substrates having excellent barrier properties even if it becomes hard or is excellent at one location. Moreover, providing the vapor deposition film using the said polyethylene-type film for vapor deposition base materials is mentioned as a subject.

As a result of intensive studies, the present inventors have found that, in a polyethylene-based film for use as a base material for a vapor deposition layer, the surface of the deposition layer is a laminate layer and the other surface is a sealing layer, and the sealing layer has a predetermined hardness. By containing inorganic particles, (i) the average particle diameter of the inorganic particles is within a predetermined range and/or (ii) the sealing layer has a predetermined surface shape, a film having a smooth surface of the laminate layer can be obtained, and It discovered that the said subject was solved, and came to complete this invention.

Specifically, the present invention provides a polyethylene film for use as a base material for a vapor deposition layer, wherein the polyethylene film has at least a laminate layer serving as a surface on the vapor deposition layer side and a sealing layer serving as the other surface, wherein the sealing layer is inorganic Polyethylene-based film for vapor deposition substrate comprising particles, wherein the inorganic particles contained in the sealing layer have a Mohs hardness of 3 or less, and satisfy at least one of (i) and (ii) below. characterized by being.

(i) the average particle diameter of the inorganic particles contained in the sealing layer is 5 µm or more and 15 µm or less

(ii) the three-dimensional surface roughness SRa of the sealing layer surface is 0.2 µm or less, and the maximum peak height SRmax of the sealing layer surface is 6 µm or less

The density of the polyethylene-based resin used in the laminate layer is 0.91 to 0.95 g/cm 3 , and the density of the polyethylene-based resin used in the sealing layer is preferably 0.90 to 0.94 g/cm 3 .

It is preferable that content of the inorganic particle in the said sealing layer is 0.5-3.0 mass %.

It is preferable that the three-dimensional surface roughness SRa of the surface of the sealing layer be 0.2 μm or less, and the maximum peak height SRmax of the surface of the sealing layer is 5 μm or less.

It is preferable that the density of the polyethylene-based resin used for the laminate layer is higher than the density of the polyethylene-based resin used for the sealing layer.

It is preferable that the content rate of the inorganic particle in the said lamination layer is less than 0.1 mass %.

It is preferable to have an intermediate layer interposed between the laminate layer and the sealing layer.

In addition, the present invention also includes a deposition film in which a deposition layer is deposited on the surface of the laminate layer of the polyethylene-based film for deposition substrate.

The polyethylene-based film of the present invention has excellent barrier properties over the entire length and width even when high-speed deposition is performed using a large evaporator.

The film of the present invention is a polyethylene-based film for use as a base material for a vapor deposition layer. The polyethylene-based film has at least a laminate layer (hereinafter, sometimes referred to as an A layer) serving as the surface on the side of the deposition layer, and a sealing layer (hereinafter, sometimes referred to as a “B layer”) serving as the other surface. It is preferable to have an intermediate layer interposed between the laminate layer and the sealing layer. At least the lamination layer (layer A) and the sealing layer (layer B) are formed of a polyethylene-based resin, and preferably the intermediate layer is also formed of a polyethylene-based resin. Moreover, the predetermined inorganic particle mentioned later is contained in B-layer. The thickness of the polyethylene film is preferably 300 µm or less, more preferably 10 µm or more and 200 µm or less, still more preferably 20 µm or more and 100 µm or less, and particularly preferably 30 µm or more and 50 µm or less. to be.

<Sealing layer (B layer)>

(polyethylene resin)

The polyethylene-based resin is a resin mainly composed of polyethylene, and specifically refers to a resin having an ethylene-derived component in 100% by mass of the polyethylene-based resin in an amount greater than 50% by mass and not more than 100% by mass. It is preferable that an ethylene-derived component is 60 mass % or more and 100 mass % or less, It is more preferable that they are 70 mass % or more and 100 mass % or less, It is still more preferable that they are 80 mass % or more and 100 mass % or less. The polyethylene-based resin of the sealing layer (layer B) is preferably low-density polyethylene (LDPE), and more preferably linear low-density polyethylene (LLDPE).

The polyethylene-based resin may be polyethylene obtained by polymerizing only ethylene, or may be an ethylene/α-olefin copolymer obtained by copolymerizing ethylene and an α-olefin other than ethylene, but is preferably an ethylene/α-olefin copolymer. Specifically, the ethylene/α-olefin copolymer refers to an ethylene/α-olefin copolymer containing, as a main component, a structural unit derived from ethylene, and having one or two or more types of structural units derived from an α-olefin other than ethylene. The ethylene/?-olefin copolymer is preferably a linear ethylene/?-olefin copolymer.

α-olefins other than ethylene that form the linear ethylene/α-olefin copolymer used for layer B may be represented by the general formula R-CH=CH ₂ (wherein R represents an alkyl group having 1 to 14 carbon atoms), For example, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-1-hexene, etc. can be heard The α-olefin other than ethylene is preferably an α-olefin having 3 to 10 carbon atoms, and more preferably an α-olefin having 3 to 8 carbon atoms. The number of α-olefins other than ethylene may be one or two or more.

The polyethylene-based resin used in layer B is preferably polyethylene (metallocene catalyst-based polyethylene) polymerized using a metallocene catalyst. Metallocene catalyst-based polyethylene has a narrow molecular weight distribution compared to polyethylene produced by other manufacturing methods such as polyethylene polymerized using a Ziegler-Natta catalyst, so it is difficult to transfer low molecular weight components to layer A. It can be suppressed and it becomes a film with a smooth surface.

The metallocene catalyst is not particularly limited, and a metallocene, that is, a transition metal component consisting of a complex composed of two substituted or unsubstituted cyclopentadienyl rings and various transition metals, and an organoaluminum component, particularly aluminoxane As a generic name for the catalyst consisting of, a known metallocene catalyst can be used.

The density of the polyethylene-based resin used for layer B is preferably 0.94 g/cm 3 or less, more preferably 0.90 to 0.94 g/cm 3 , still more preferably 0.90 to 0.93 g/cm 3 , and 0.90 to 0.92 g/cm 3 It is particularly preferred. By using low-density polyethylene having a density of 0.94 g/cm 3 or less, the polyethylene-based film becomes a film excellent in vapor deposition processability in which wrinkles and bumps do not easily occur during vapor deposition. In addition, by using low-density polyethylene, a laminate film in which another film such as a polyethylene terephthalate film or a nylon film is further laminated on the deposited film (hereinafter simply referred to as a laminate film) after the aging of the low-temperature heat sealing property ( Hereinafter, simply referred to as low-temperature heat sealing property) is excellent. In addition, by using low-density polyethylene, adhesion (blocking) does not occur between the films even when the polyethylene-based films are superimposed, and even if they occur, they can be easily peeled off (that is, excellent in blocking resistance). When the density of the polyethylene-based resin is less than 0.90 g/cm 3 , there is a possibility that the vapor deposition processability may decrease or the blocking resistance may decrease. Moreover, when the density of polyethylene-type resin exceeds 0.94 g/cm<3>, there exists a possibility that low-temperature heat sealing property may become inadequate.

The polyethylene-based resin used for layer B has a melt flow index (MFR) of preferably 1 to 10 g/10 min, more preferably 2 to 8 g/10 min, and 3.5 to 6 g/10 min. more preferably. When MFR is less than 1 g/10min, there exists a possibility that the extrudability of resin at the time of film preparation may deteriorate and film-forming property may deteriorate. Moreover, when MFR exceeds 10 g/10min, there exists a possibility that vapor deposition processability may fall or blocking resistance may fall. In addition, in this specification, MFR is measured based on JISK7210.

The melting point of the polyethylene-based resin used for the layer B is preferably 80°C or higher, more preferably 100°C or higher, still more preferably 105°C or higher, and particularly preferably 110°C or higher. It will become easy to raise|generate blocking that melting|fusing point is less than 80 degreeC. Although the upper limit of melting|fusing point of a polyethylene-type resin is not specifically limited, For example, it is 150 degrees C or less, Preferably it is 130 degrees C or less. When melting|fusing point is 150 degrees C or less, it is excellent in the film-forming property of a film. In addition, when there are two or more melting|fusing point peaks, let the highest temperature be melting|fusing point.

As the polyethylene-based resin used for the B layer, a commercially available product can be used, for example, Ube-Maruzen Polyethylene Co., Ltd. Umerit (registered trademark) 2040FC, 0540F, Prime Polymer Co., Ltd. Evolu (registered trademark) SP2040, etc. can be heard

(inorganic particles)

The Mohs' Hardness of the inorganic particle used for B-layer is 3 or less, and it is preferable that it is 2 or less. Protrusions are formed on the surface of layer B with inorganic particles to impart sliding properties to the film. It becomes easy to generate|occur|produce a defect, and barrier property will fall further further. Although the lower limit of the Mohs' Hardness of an inorganic particle is not specifically limited, For example, it is 0.1 or more, Preferably it is 0.5 or more. Moreover, it is preferable that the Mohs' Hardness of an inorganic particle is below the Mohs' Hardness of the said vapor deposition material.

When the Mohs' Hardness of the inorganic particles is 3 or less, and the lower the Mohs' Hardness of the inorganic particles, the projections formed on the layer B by the inorganic particles strongly contact the deposition layer provided on the side of the layer A, the projections are formed on the deposition layer It does not simply penetrate through the layer, but slowly squeezes in as if torn by pressing the deposited layer to elongate it. For this reason, some cracks may occur in the portion where the vapor deposition layer is pressed and stretched. Even if a recess is formed in the vapor deposition layer due to the projections, the vapor deposition layer tends to remain except for the cracks. In addition, when a separate film such as a polyethylene terephthalate film or a polyamide film is laminated on the vapor deposition layer, cracks in the vapor deposition layer that exist slightly are blocked, so that it has high barrier properties.

On the other hand, when the Mohs' Hardness of the inorganic particles exceeds 3, the projections momentarily penetrate the deposition layer, and the deposition layer is pushed to the periphery of the hole created by the projections, and the barrier properties are lowered, for example, on the deposition layer. Even if the separate film is laminated, the barrier property is not recovered.

As an inorganic particle, a talc, a calcium carbonate, etc. are mentioned, for example, Mohs' Hardness will not specifically limit if it is an inorganic particle of 3 or less.

By satisfying at least one of the following (i) and (ii), the appearance and barrier properties of the film can be improved.

(i) the average particle diameter of the inorganic particles contained in the sealing layer is 5 µm or more and 15 µm or less

(ii) the three-dimensional surface roughness SRa of the sealing layer surface is 0.2 µm or less, and the maximum peak height SRmax of the sealing layer surface is 6 µm or less

When the average particle diameter of the inorganic particles used for the layer B is 5 µm or more and 15 µm or less, not only the appearance and barrier properties of the film, but also the sliding properties and the blocking resistance can be improved. The average particle diameter of the inorganic particles is preferably 6 µm or more and 12 µm or less, and more preferably 7 µm or more and 10 µm or less.

Moreover, since the three-dimensional surface roughness SRa of the B-layer surface is 0.2 micrometer or less and the maximum peak height SRmax of the B-layer surface is 6 micrometers or less, the external appearance and barrier property of a film can be made compatible. From a viewpoint of a barrier property improvement, it is more preferable that three-dimensional surface roughness SRa is 0.05-0.17 micrometers, and it is still more preferable that it is 0.10-0.15 micrometers. In addition, from the viewpoint of improving barrier properties and slidability, the maximum peak height SRmax is more preferably 5 μm or less, still more preferably 1 to 5 μm, particularly preferably 1 to 4.5 μm, and particularly preferably 2 to 4.5 μm. Most preferred. The three-dimensional surface roughness SRa and the maximum peak height SRmax can be adjusted by the average particle size and the amount of inorganic particles added. In addition, the three-dimensional surface roughness SRa is the average value of absolute values obtained by taking the difference in the height direction of the roughness curved surface and the center plane of the roughness curved surface, and the maximum peak height SRmax is the difference between the maximum and minimum values of the roughness curved surface.

In order to satisfy the said surface roughness, it is preferable that content of the inorganic particle in B-layer is 0.5-3.0 mass %. When it is less than 0.5 mass %, there exists a possibility that barrier property may fall, blocking resistance may fall, or vapor deposition processability may fall. When it is more than 3.0 mass %, the external appearance of a film may deteriorate, or there exists a possibility that a filter may become clogged when melt|melting the polyester supplied to an extruder and filtering with a filter. As for content of an inorganic particle, it is more preferable that it is 1.0-2.0 mass %.

It is preferable that it is 0.2 mass % or less, and, as for the content rate of the organic lubricant in B-layer, it is more preferable that it is less than 0.1 mass %. When the content rate of an organic lubricant exceeds 0.2 mass %, when it is set as a laminate film, there exists a possibility that adhesiveness may fall. Examples of the organic lubricant include unsaturated fatty acid amides and polymer waxes such as oleic acid amide, erucic acid amide, stearic acid amide, behenic acid amide, ethylenebisoleic acid amide, and ethylenebiserucic acid amide. Further, the content rate of the organic lubricant in the layer B is more preferably 0.05 mass% or less, and still more preferably 0 mass% (the organic lubricant is not contained in the layer B).

In the polyethylene film of the present invention, layer B can be used as a sealing layer of a packaging material. That is, it can be set as a packaging material by sealing B-layers. Therefore, it is preferable that the polyethylene-type film of this invention has low-temperature heat sealing property.

<Lamination layer (Layer A)>

(polyethylene resin)

The polyethylene-based resin forming the laminate layer (layer A) is composed of the same monomers (polyethylene, α-olefin, etc.) as the polyethylene-based resin forming the sealing layer (layer B), and the proportion of polyethylene is also the sealing layer (layer B). It can be selected from the range equivalent to the range shown by.

Further, similarly to the case of layer B, the polyethylene-based resin of layer A may also be polyethylene obtained by polymerizing only ethylene, or may be an ethylene/α-olefin copolymer obtained by copolymerizing ethylene and α-olefins other than ethylene, or ethylene/α -It is preferable that it is an olefin copolymer. Specific examples of the α-olefin are also the same as in the case of the B layer.

On the other hand, the density of the polyethylene-based resin used in the A layer can be selected from a range different from that of the B layer, specifically, it is preferably 0.91 to 0.95 g/cm 3 , and from the viewpoint of reducing the bleed-out of low molecular weight components, 0.92 to It is more preferable that it is 0.95 g/cm<3>, It is still more preferable that it is 0.925-0.94 g/cm<3>, It is especially preferable that it is 0.93-0.935 g/cm<3>. When the density is outside the above range, there is a fear that the metallic luster (hereinafter simply referred to as luster) of the vapor deposition layer may decrease or curling may occur in the film. In addition, it is preferable that the density of the polyethylene used for the A layer is higher than the density of the polyethylene used for the B layer, and the density of the polyethylene used for the A layer is 0.01 g/cm 3 or more higher than the density of the polyethylene used for the B layer. more preferably.

The polyethylene-based resin used in the A layer preferably has a melt flow index (MFR) of 1 to 10 g/10 min, more preferably 2 to 8 g/10 min, and 3.5 to 6 g/10 min. more preferably. When MFR is less than 1 g/10min, the extrudability of resin at the time of film preparation is bad, and there exists a possibility that film-forming property may be inferior. Moreover, when MFR exceeds 10 g/10min, there exists a possibility that the blocking resistance of a film may fall.

It is preferable that it is 110 degreeC or more, and, as for melting|fusing point of the polyethylene-type resin used for A-layer, it is more preferable that it is 115 degreeC or more, and it is still more preferable that it is 120 degreeC or more. When the melting point is less than 110° C., the surface of the layer A is softened when the deposition layer is formed, and there is a fear that the glossiness of the deposition layer is lowered. Although the upper limit of melting|fusing point of a polyethylene-type resin is not specifically limited, For example, it is 160 degrees C or less, Preferably it is 140 degrees C or less. If melting|fusing point is 160 degrees C or less, it is excellent in the film forming property of a film. In addition, when there are two or more melting|fusing point peaks, let the highest temperature be melting|fusing point.

The polyethylene-based resin used in layer A is preferably polyethylene (metallocene catalyst-based polyethylene) polymerized using a metallocene catalyst. Since the metallocene catalyst-based polyethylene has a narrow molecular weight distribution compared to polyethylene produced by other production methods such as polyethylene polymerized using a Ziegler-Natta catalyst, bleed-out of low molecular weight components can be reduced. In addition, the definition of a polyethylene-type resin is the same as that of B layer.

It is preferable that the content rate of the inorganic particle in A-layer is less than 0.1 mass %. Moreover, it is preferable that the content rate of the organic lubricant in A-layer is less than 0.1 mass %. Specific examples of the organic lubricant and inorganic particles include the same ones described for layer B. Further, in the layer A, the content of the organic lubricant and the inorganic particles is more preferably 0.05 mass% or less, respectively, and more preferably 0% (the organic lubricant and the inorganic particles are not contained in the layer A).

It is also possible to use a commercial item as a polyethylene-type resin used for A-layer, For example, the Umerit (trademark) 3540F and 4040FC by the Ube-Maruzen polyethylene company are mentioned.

<middle floor>

The polyethylene-type film of this invention may have an intermediate|middle layer between A-layer and B-layer as needed, and it is preferable to have one or more intermediate|middle layers. Although the resin used for an intermediate|middle layer is not specifically limited, It is preferable that it is a polyethylene-type resin.

The polyethylene-based resin forming the intermediate layer is composed of the same monomers (polyethylene, α-olefin, etc.) as the polyethylene-based resin forming the sealing layer (layer B), and the proportion of polyethylene is also equal to the range indicated by the sealing layer (layer B). You can choose from a range.

Also, as in the case of layer B, the polyethylene-based resin of the intermediate layer may also be polyethylene obtained by polymerizing only ethylene, or may be an ethylene/α-olefin copolymer obtained by copolymerizing ethylene and an α-olefin other than ethylene, or ethylene/α- It is preferable that it is an olefin copolymer. Specific examples of the α-olefin are also the same as in the case of the B layer. Further, the manufacturing method of the polyethylene-based resin is also the same as in the case of the B layer.

The density of the polyethylene-based resin is preferably 0.94 g/cm 3 or less, more preferably 0.90 to 0.94 g/cm 3 , still more preferably 0.90 to 0.93 g/cm 3 , and particularly preferably 0.90 to 0.92 g/cm 3 . MFR, melting point, etc. of the polyethylene-type resin of an intermediate|middle layer can be set in the same range as B-layer.

Moreover, it is preferable that the content rate of the organic lubricant and inorganic particle in an intermediate|middle layer is less than 0.1 mass %, respectively. Specific examples of the organic lubricant and inorganic particles include the same ones described for layer B. Further, the content of the organic lubricant and inorganic particles in the intermediate layer is more preferably 0.05 mass% or less, respectively, and more preferably 0 mass% (the intermediate layer does not contain organic lubricant and inorganic particles).

<Film production method, etc.>

The polyethylene-based film of the present invention can be produced by, for example, forming a film into a film by a melt extrusion molding method such as a T-die method and an inflation method, a cast molding method, a press molding method, etc. In order to obtain an elongated and widened film, the T-die method It is preferable to manufacture using

As a lamination method of two or more layers, the co-extrusion method is advantageous in terms of productivity, but the lamination method is not particularly limited as long as the performance can be maintained. Moreover, in order to raise the smoothness of A-layer, or to lower|hang production cost, you may use a recovered raw material.

To the polyethylene film of the present invention, an antioxidant, a heat stabilizer, an ultraviolet inhibitor, an ultraviolet absorber, a nucleating agent, etc. may be added to the polyethylene-based film of the present invention as long as the adhesion strength between the vapor deposition layer and the A layer does not deteriorate and the low-temperature heat sealability does not deteriorate. However, when performing the said addition to the composition for A-layer, it is made so that the content rate of the inorganic particle in A-layer does not become 0.1 mass % or more.

In order to increase the adhesion strength between the vapor deposition layer and the A layer, a known surface treatment may be performed before vapor deposition on the surface of the A layer of the film, for example, corona discharge treatment, flame treatment, plasma treatment, ozone treatment, etc. You may perform a process on the A-layer surface. In the case of the above-mentioned surface treatment, it is preferable to treat so that the wetting tension measured according to JIS K 6768 after discharging becomes 37 mN/m or more, and more preferably to process it so that it becomes 39 mN/m or more.

<Deposition layer>

When a vapor deposition material is vapor-deposited on the surface of layer A of the polyethylene film of the present invention, since the surface of layer A containing little or no inorganic particles is flat, a vapor deposition film having a dense vapor deposition layer is obtained. On the other hand, although there are protrusions due to inorganic particles on the surface of layer B, they are not sharp protrusions, but gentle protrusions. For this reason, even if the projections are transferred to the vapor deposition layer when the vapor deposition film is wound on a roll, since the hardness of the inorganic particles is lower than that of the vapor deposition material, defects are unlikely to occur in the vapor deposition layer, and barrier properties can be maintained. Furthermore, since the B-layer and the A-layer are less likely to block because the projections are provided on the surface of the B-layer, that is, the blocking resistance is improved, the film is taken out from the film roll made of the film for vapor deposition substrates. Thus, the vapor deposition process can be smoothly performed, and wrinkles and bumps are less likely to occur in the obtained vapor deposition film.

The method of vapor-depositing the vapor deposition material on the polyethylene film of the present invention is not particularly limited, and may be carried out using a known means, for example, electrothermal heating, sputtering, or ion plating by a continuous or batch-type vacuum vapor deposition machine. , an ion beam or the like. The thickness of the vapor deposition layer of the vapor deposition film obtained in this way is not particularly limited, but is generally several hundreds of angstroms or about 2 to 4 in terms of optical density (OD value) in terms of adhesion, durability, and economy.

The deposition material to be deposited on the surface of the layer A is preferably a metal. Although the metal is not particularly limited, for example, aluminum, gold, silver, copper, zinc, nickel, chromium, titanium, selenium, germanium, tin, etc. are mentioned, and from the viewpoint of workability, luster, safety, cost, etc. It is preferably aluminum.

This application claims the benefit of priority based on Japanese Patent Application No. 2017-043096 filed on March 7, 2017. The entire contents of the specification of Japanese Patent Application No. 2017-043096 filed on March 7, 2017 are incorporated herein by reference.

Example

The present invention will be described in more detail by way of examples below, but the examples below do not limit the present invention, and all modifications and implementations within the scope that do not deviate from the spirit of the present invention are included in the present invention.

First, the measurement and evaluation methods used in Examples will be described below.

<Mohs hardness>

As inorganic particles, the Mohs hardness of the mineral before pulverization was calculated|required from a Mohs hardness table. Specifically, the hardness of the measured object was determined by rubbing the minerals before pulverization in order starting with the standard material with the smallest hardness, and visually confirming whether or not there was a scratch on the measured object.

Mohs hardness was also measured by a method other than the above determination method. A Raman spectrum was measured for the residue obtained by incineration of the film or the residue obtained by melting the film in a hot solvent and then filtering the film by the measuring method described later. And the Mohs' Hardness of the matching mineral was calculated|required from the Mohs' Hardness table by Raman spectroscopy. The Mohs' Hardness calculated by Raman spectroscopy also became the same hardness as the Mohs' Hardness of the mineral before pulverization.

Raman spectrum was obtained by microscopic Raman scattering measurement using RAMAN-11 manufactured by Nanophoton, which is a laser Raman microscope. In addition, the measurement conditions for the Raman scattering measurement were as follows, and the laser intensity was adjusted with a filter so that an appropriate Raman scattering intensity was obtained.

<Measurement conditions for Raman scattering measurement>

Irradiation light wavelength: 532 nm

Aperture: 50 μm Φ

Magnification of objective lens: 50 times

The numerical aperture of the objective lens: 0.6

Exposure time: 30 seconds

Number of exposures (accumulation number): 2 times

<Average particle size>

The average particle diameter of the inorganic particles was measured in a wet manner on the basis of volume distribution using a laser diffraction type particle size distribution analyzer (SALD-3100 manufactured by Shimadzu Corporation).

<Density>

The density of the polyethylene resin was measured with the extrudate of a melt indexer according to JIS K 6922-1.

<Surface roughness>

According to JIS B 0601, using a three-dimensional surface roughness meter (Surfcorder ET4000A manufactured by Kosaka Research Institute), 100 measurements were made with cutoff 0.08 mm, 1 µm length, and 2 µm pitch, and three-dimensional surface roughness SRa of the surface of the B layer, The maximum peak height SRmax was obtained.

<blocking resistance>

A 12 cm×10 cm polyethylene film is stacked on the surface of layer B and layer A, and then 10 cm×10 cm paper is placed as one set. sandwiched between A load of 50 kg was applied on this glass plate, and it was left to stand at 40 degreeC for 48 hours. After returning to room temperature, the laminate was cut to a width of 25 mm. Using an autograph (registered trademark) manufactured by Shimadzu Corporation, the peel strength (unit: N/25 mm) when the cut laminate was peeled at 180° at a tensile rate of 200 mm/min was measured, and the following criteria were used. was evaluated as

◎: 0.2 N/25 mm or less

○: Greater than 0.2 N/25 mm and less than 0.5 N/25 mm

△: Greater than 0.5 N/25 mm and less than 1 N/25 mm

X: Larger than 1 N/25 mm

<Glossiness of the vapor deposition layer>

Based on JISK5600-4-7 using the glossmeter (Nippon Denshoku Kogyo Co., Ltd. type VG2000 type), the metallic glossiness of the vapor deposition layer in a vapor deposition film was measured, and the following reference|standard evaluated.

◎: 1,000% or more

○: 700% or more and less than 1,000%

△: 500% or more and less than 700%

×: Less than 500%

<Peel strength of laminate film (adhesion)>

TM569/CAT10L, an adhesive manufactured by Toyo Morton, was applied to a nylon film having a thickness of 15 µm (“N1100” manufactured by Toyobo Co., Ltd.) at a solid content of 3 g/m 2 . Next, the deposition surface of the deposition film was pasted on the adhesive to form a laminate film, and then aged at 40° C. for 48 hours. Peel strength between the deposited layer and the A layer when the above-mentioned aging was performed with a tensile tester (Autograph (registered trademark) AGS-J 100NJ, manufactured by Shimadzu Corporation) and peeled at 180° under the condition of a tensile rate of 200 mm/min. (unit: N/15 mm) was measured.

<Deposition processability>

A roll of 500 m was produced using the vapor deposition film. The state of the vapor deposition film of the obtained roll was observed, and it evaluated as follows.

◎: Almost no wrinkles or bumps

○: Some wrinkles and bumps occurred

△: A lot of wrinkles and bumps occurred

x: A lot of wrinkles and bumps were generated.

<Oxygen permeability of vapor-deposited film>

A roll of 500 m was produced using the vapor deposition film. Next, the roll hardness was measured at a pitch of 2 cm in the width direction of a 500 m roll using a Parotester manufactured by Prosec. Then, the sample was taken out from the location used as roll hardness 600-650. Finally, in accordance with the JIS K 7126-2A method, the oxygen permeability of the sample was measured using an oxygen permeability measuring device (OX-TRAN2/21 manufactured by MOCON) under conditions of a temperature of 23° C. and a humidity of 65%. When measuring oxygen permeability, layer B, which is a non-deposition surface, was mounted to be the humidity control side.

<Water vapor permeability of vapor-deposited film>

A roll of 500 m was produced using the vapor deposition film. Next, the roll hardness was measured at a pitch of 2 cm in the width direction of a 500 m roll using a Paro tester manufactured by Prosec. Then, the sample was taken out from the location used as roll hardness 600-650. Finally, according to the JIS K 7129B method, using a water vapor transmission rate measuring device (PERMATRAN-W3/33 manufactured by MOCON), the vapor transmission rate of the vapor deposition film was measured under conditions of a temperature of 37.8° C. and a humidity of 90%. When measuring water vapor permeability, layer B, which is a non-evaporated surface, was mounted so as to be on the high-humidity side.

<Low-temperature heat-sealing property of laminate film after aging>

A roll of 500 m was produced using the vapor deposition film, and then left to stand for one month in an environment of 30°C. Next, TM569/CAT10L, an adhesive manufactured by Toyo Morton, was applied to a nylon film having a thickness of 15 µm (“N1100” manufactured by Toyobo Co., Ltd.) at a thickness of 3 g/m 2 as a solid content. Then, after sticking the vapor deposition surface of the vapor deposition film left on the adhesive for one month to form a laminate film, it was aged at 40° C. for 48 hours. Finally, the B layer of the aged laminate film was heat-sealed at a sealing temperature of 150° C., a sealing pressure of 0.2 MPa, and a sealing time of 1 second, and then the laminate film was cut to a width of 15 mm. Peel strength between the deposited layer and A layer when the cut laminate film is peeled 180° at a tensile speed of 200 mm/min with a tensile tester (Autograph (registered trademark) AGS-J 100NJ, manufactured by Shimadzu Corporation) (unit is N/15 mm) was measured.

(Example 1)

[Composition for layer B]

Sumitomo Chemical Co., Ltd. Sumikasen (registered trademark) E FV402 (metallocene catalyst-based LLDPE, density: 0.913 g/cm 3 , MFR: 3.8 g/10 min, melting point: 116°C) was mixed with talc having Mohs hardness 1 and average particle size of 8 μm. By mixing, a masterbatch containing 15% by mass of talc was prepared. Next, Ube-Maruzen Polyethylene Co., Ltd. Umerit (registered trademark) 2040FC (metallocene catalyst-based LLDPE, density: 0.918 g/cm 3 , MFR: 4.0 g/10 min, melting point: 116°C) 90% by mass; A composition for layer B was prepared using a composition in which 10% by mass of the masterbatch was mixed. Although 1.5 mass % of talc was contained in 100 mass % of the composition for B-layer, the organic lubricant was not added to the composition for B-layer.

[Composition for Layer A]

A composition for layer A was prepared using only Umerit (registered trademark) 3540FC (metallocene catalyst-based LLDPE, density: 0.931 g/cm 3 , MFR: 4.0 g/10 min, melting point: 123°C) manufactured by Ube-Maruzen Polyethylene Co., Ltd. . In addition, inorganic particles and organic lubricant were not added to the composition for A-layer.

[Composition for Intermediate Layer]

A composition for an intermediate layer was prepared using only Umerit (registered trademark) 2040FC (metallocene catalyst-based LLDPE, density: 0.931 g/cm 3 , MFR: 4.0 g/10 min, melting point: 123°C) manufactured by Ube-Maruzen Polyethylene Co., Ltd. . In addition, inorganic particles and organic lubricants were not added to the composition for the intermediate layer.

Using an extruder having a T die for the composition for layer A, the composition for the intermediate layer, and the composition for the layer B, the thickness ratio of the layer A, the intermediate layer, and the B layer is 1 : Melt-extrusion was carried out at 240 degreeC so that it might become 1:2. Thereafter, corona discharge treatment was performed on the surface of the layer A. Then, it wound on the roll at the speed|rate of 150 m/min, and obtained the laminated|multilayer film whose thickness is 40 micrometers, and the wet tension of the treated surface is 45 mN/m.

Next, the roll of the laminated film obtained was set in a vacuum vapor deposition machine, and aluminum vapor deposition was performed on the corona-treated surface of the laminated film at a vacuum degree of 10 ^-4 torr or less, and wound around a roll to obtain a vapor deposition film provided with an aluminum vapor deposition layer. The thickness of the deposition layer was adjusted so that the aluminum deposition layer had a gloss concentration (OD value) of 3. Aluminum has a Mohs hardness of 2.75.

Table 1 shows the evaluation results of this film. The three-dimensional surface roughness SRa was 0.12 μm and the maximum peak height SRmax was 4.3 μm. The deposition film of Example 1 increased the number of holes in the deposition layer by transfer of inorganic particles even in locations with high sound damping hardness (where the hardness measured with a paro tester is 600 to 650) (with a high-brightness LED light, the surface layer or damping hardness There was almost no defect condition compared with a location with a low value), and the barrier property was excellent. In addition, the vapor deposition film of Example 1 exhibited a value equivalent to the oxygen barrier properties of the film in which aluminum was deposited on a biaxially stretched nylon film.

In addition, the laminated film of Example 1 was excellent in blocking resistance, and the vapor deposition film of Example 1 was excellent in deposition processability and glossiness. In addition, the laminate film produced using the vapor deposition film of Example 1 was excellent in adhesiveness and low-temperature heat sealing properties.

(Example 2)

A laminated film and a vapor deposition film were obtained like Example 1 except that the addition amount of the talc in the composition for B-layers was 0.5 mass %. Although somewhat inferior to Example 1 in blocking resistance and deposition processability, it was a sufficiently high performance. Moreover, it was excellent in barrier property, glossiness, adhesiveness, and low-temperature heat sealing property.

(Example 3)

Laminated film and vapor-deposited film were prepared in the same manner as in Example 1 except that the inorganic particles contained in the composition for layer B were changed from talc to CUBE-80KAS manufactured by Maruo Calcium Co., Ltd. (calcium carbonate particles with Mohs hardness 3 and average particle diameter of 8 µm). got it Also in Example 3, it was excellent in barrier property, blocking resistance, vapor deposition processability, glossiness, adhesiveness, and low temperature heat sealing property.

(Example 4)

The resin contained in the B-layer composition is from Ube-Maruzen Polyethylene Co., Ltd. Umerit (registered trademark) 2040FC to Ube-Maruzen Polyethylene Co., Ltd. Umerit (registered trademark) 0540F (density: 0.904 g/cm 3 , MFR: 4.0 g/ 10 min, melting|fusing point: 111 degreeC) except having changed into it, it carried out similarly to Example 1, and obtained the laminated|multilayer film and vapor deposition film. Also in Example 4, it was excellent in barrier property, blocking resistance, vapor deposition processability, glossiness, adhesiveness, and low temperature heat sealing property.

(Example 5)

The resin contained in the composition for layer A is from Ube-Maruzen Polyethylene Co., Ltd. Umerit (registered trademark) 3540FC to Ube-Maruzen Polyethylene Co., Ltd. Umerit (registered trademark) 4040FC (density: 0.938 g/cm 3 , MFR: 3.5 g/ 10 min, melting|fusing point: 126 degreeC) except having changed into it, it carried out similarly to Example 1, and obtained the laminated|multilayer film and vapor deposition film. Although the glossiness was inferior to Example 1, it was a performance high enough. Moreover, it was excellent in barrier property, blocking resistance, vapor deposition processability, adhesiveness, and low-temperature heat sealing property.

(Example 6)

Ube-Maruzen Polyethylene Co., Ltd. Umerit (registered trademark) 2040FC 　 89.9 mass %, organic lubricant 0.1 mass % erucic acid amide as an organic lubricant, except that the composition for the B layer was prepared using a composition mixed with 10 mass % of the masterbatch It carried out similarly to Example 1, and obtained the laminated|multilayer film and vapor deposition film. Also in Example 6, it was excellent in barrier property, blocking resistance, vapor deposition processability, glossiness, and low temperature heat sealing property.

(Example 7)

Resin contained in the composition for layer B is Umerit (registered trademark) 2040FC manufactured by Ube-Maruzen Polyethylene Co., Ltd. Exelene (registered trademark) FX307 manufactured by Sumitomo Chemical Corporation (density: 0.89 g/cm 3 , MFR: 3.2 g/10 min, melting point: 83 degreeC), it carried out similarly to Example 1, and obtained the laminated|multilayer film and vapor deposition film. Although the glossiness was inferior to Example 1, it was a performance high enough. Moreover, it was excellent in barrier property, adhesiveness, and low-temperature heat-sealing property.

(Example 8)

It carried out similarly to Example 1, and obtained the laminated|multilayer film. High-adhesion aluminum vapor deposition was performed on the laminated|multilayer film obtained in Example 1, and the vapor deposition film was obtained. Specifically, without corona treatment on the surface of layer A, after plasma discharge treatment by introducing argon into a low-temperature plasma processing apparatus in a vacuum evaporator, aluminum deposition on the plasma treatment surface of the laminated film at a vacuum degree of 10 ^-4 torr or less Except having carried out, it carried out similarly to Example 1, and obtained the vapor deposition film provided with the aluminum vapor deposition layer. Also in Example 8, it was excellent in barrier property, blocking resistance, vapor deposition processability, glossiness, adhesiveness, and low temperature heat sealing property, and was excellent in barrier property and adhesiveness than Example 1.

(Comparative Example 1)

A laminated film and a vapor deposition film were obtained in the same manner as in Example 1 except that the inorganic particles contained in the composition for layer B were changed from talc to a zeolite having a Mohs hardness of 4 and an average particle diameter of 5 µm. Although three-dimensional surface roughness SRa and maximum peak height SRmax were substantially equivalent to Example 1, the significant fall of the barrier property of the vapor deposition film whose roll hardness is 600 or more and 650 or less was confirmed.

(Comparative Example 2)

A laminated film and a vapor deposition film were obtained in the same manner as in Example 1 except that the inorganic particles contained in the composition for layer B were changed from talc to amorphous silica having a Mohs hardness of 7 and an average particle diameter of 5 µm. Although three-dimensional surface roughness SRa and maximum peak height SRmax were substantially equivalent to Example 1, the significant fall of the barrier property of the vapor deposition film whose roll hardness is 600 or more and 650 or less was confirmed.

(Comparative Example 3)

A laminated film and a vapor deposition film were obtained in the same manner as in Example 1 except that the average particle diameter of the talc contained in the composition for layer B was 20 µm. The oxygen barrier properties of the vapor deposition films having roll hardness of 600 or more and 650 or less were dropped significantly, and the glossiness of the vapor deposition layer was also low.

Table 1 shows the configuration and various physical properties of Examples and Comparative Examples.

The polyethylene-based film for vapor deposition substrate of the present invention has excellent barrier properties over the entire length and width even when high-speed deposition is performed using a large evaporator with a winding length exceeding 10,000 m, so its productivity is high and industrially It is of high use value. For this reason, it can be used as an industrial material in addition to packaging materials, such as food, a pharmaceutical, and miscellaneous goods.

Claims (10)

A polyethylene-based film for use as a base material for a vapor deposition layer, comprising:
The polyethylene-based film has at least a laminate layer serving as a surface on the side of the deposition layer and a sealing layer serving as the other surface,
The sealing layer contains inorganic particles, the Mohs hardness of the inorganic particles contained in the sealing layer is 3 or less, and at least one of (i) and (ii) below is satisfied. Polyethylene-based film for substrate.
(i) the average particle diameter of the inorganic particles contained in the sealing layer is 5 µm or more and 15 µm or less
(ii) the three-dimensional surface roughness SRa of the sealing layer surface is 0.2 µm or less, and the maximum peak height SRmax of the sealing layer surface is 6 µm or less A polyethylene-based film for use as a base material for a vapor deposition layer, comprising:
The polyethylene-based film has at least a laminate layer serving as a surface on the side of the deposition layer and a sealing layer serving as the other surface,
The sealing layer contains inorganic particles, the Mohs hardness of the inorganic particles contained in the sealing layer is 3 or less, and the average particle diameter of the inorganic particles contained in the sealing layer is 5 µm or more and 15 µm or less Polyethylene-based film for vapor deposition substrate. A polyethylene-based film for use as a base material for a vapor deposition layer, comprising:
The polyethylene-based film has at least a laminate layer serving as a surface on the side of the deposition layer and a sealing layer serving as the other surface,
The sealing layer contains inorganic particles, the Mohs' Hardness of the inorganic particles contained in the sealing layer is 3 or less, and the three-dimensional surface roughness SRa of the surface of the sealing layer is 0.2 µm or less, and the sealing layer surface A polyethylene film for a vapor deposition substrate having a maximum peak height SRmax of 6 μm or less. 4. The method according to any one of claims 1 to 3,
The density of the polyethylene-based resin used in the laminate layer is 0.91 to 0.95 g/cm 3 , and the density of the polyethylene-based resin used in the sealing layer is 0.90 to 0.94 g/cm 3 A polyethylene-based film for vapor deposition substrates. 4. The method according to any one of claims 1 to 3,
The content of inorganic particles in the sealing layer is 0.5 to 3.0 mass% of the polyethylene-based film for vapor deposition substrate. 4. The method according to any one of claims 1 to 3,
The three-dimensional surface roughness SRa of the sealing layer surface is 0.2 μm or less, and the maximum peak height SRmax of the sealing layer surface is 5 μm or less. 4. The method according to any one of claims 1 to 3,
A polyethylene-based film for a vapor deposition substrate in which the density of the polyethylene-based resin used for the laminate layer is higher than that of the polyethylene-based resin used for the sealing layer. 4. The method according to any one of claims 1 to 3,
The polyethylene-based film for vapor deposition substrates, wherein the content rate of inorganic particles in the laminate layer is less than 0.1 mass %. 4. The method according to any one of claims 1 to 3,
A polyethylene-based film for vapor deposition having an intermediate layer interposed between the laminate layer and the sealing layer. The vapor deposition film by which the vapor deposition layer was vapor-deposited on the laminate layer surface of the polyethylene-type film for vapor deposition base materials in any one of Claims 1-3.