KR20220004821A - Polyethylene-based resin multilayer film, and vapor deposition film, laminate, and package using the same - Google Patents

Abstract

It has at least a laminate layer and a sealing layer made of a polyethylene-based resin composition, and the polyethylene-based resin composition constituting the sealing layer satisfies 1) to 3) below, and the sealing layer surface satisfies 4) and 5) below Polyethylene-based resin multilayer film.
1) A polyethylene-based resin having a density of 900 kg/m 3 or more and 935 kg/m 3 or less is included.
2) It contains the particle|grains which consist of polyethylene-type resin.
3) The content of the organic lubricant is 0.05% by weight or less.
4) Three-dimensional surface roughness SRa is 0.05-0.2 ㎛.
5) The maximum peak height SRmax is 2-8 μm.

Description

Polyethylene-based resin multilayer film, and vapor deposition film, laminate, and package using the same

The present invention relates to a polyethylene-based resin multilayer film, a vapor-deposited film in which a vapor-deposited layer is deposited on the polyethylene-based resin multilayer film, and a laminate and a package comprising the same.

A vapor deposition film in which a vapor deposition layer is installed on a polyethylene-based resin film is widely used in packaging materials such as food packaging and medical packaging, gold and silver thread, labels, stickers, and reflective sheets. Some of these have been suggested.

For example, in Patent Document 1, slidability is improved by using an inorganic anti-blocking agent having a particle size of 2 to 5 μm without adding an organic lubricant. When the performed film is wound up and it is set as a film roll, the gas-barrier property of a vapor deposition film falls easily.

These days, the size of the vapor deposition machine is also being enlarged. When a large-sized vapor deposition machine is used to perform vapor deposition on a long and wide polyethylene-based resin film, if the tension is raised to increase the adhesion to the cooling drum, the film roll on which the vapor deposition film is wound. Since the winding becomes hard due to the silver flattening, or the winding tends to become hard at one location or the core part of the film roll, the gas barrier property tends to decrease.

Japanese Patent Laid-Open No. 2001-225409

It is a problem to provide a polyethylene-based resin multilayer film having excellent gas barrier properties over the entire length and width of the vapor deposition film, even when a long and wide polyethylene-based resin film is subjected to vapor deposition using a large-sized vapor deposition machine. Moreover, it is given as a subject to provide the vapor deposition film using the said polyethylene-type resin multilayer film.

As a result of intensive studies, the present inventors have solved the above problems by controlling the height of the projections on the surface of the sealing layer and the content of the organic lubricant made of a polyethylene resin composition containing a polyethylene resin having a density within a specific range and particles made of the polyethylene resin. It has been found that possible, and came to solve the present invention.

That is, the present invention has at least a laminate layer and a sealing layer, the polyethylene-based resin composition constituting the sealing layer satisfies 1) to 3) below, and the surface of the sealing layer satisfies 4) and 5) below. It is a polyethylene-type resin multilayer film.

1) A polyethylene-based resin having a density of 900 kg/m 3 or more and 935 kg/m 3 or less is included.

2) It contains the particle|grains which consist of polyethylene-type resin.

3) The content of the organic lubricant is 0.05% by weight or less.

4) Three-dimensional surface roughness SRa is 0.05-0.2 ㎛.

5) The maximum peak height SRmax is 2 to 8 µm.

In another aspect, polyethylene having at least a laminate layer and a sealing layer, the polyethylene-based resin composition constituting the sealing layer satisfies the following 1 to 3), and the surface of the sealing layer satisfies 4) and 5) below. It is a resin-based multilayer film.

1) The density is 900 kg/m3 or more and 935 kg/m3 or less.

2) It contains the particle|grains which consist of polyethylene-type resin.

3) The content of the organic lubricant is 0.05% by weight or less.

4) Three-dimensional surface roughness SRa is 0.05-0.2 ㎛.

5) The maximum peak height SRmax is 2 to 8 µm.

In this case, it is preferable that the viscosity average molecular weight of the particle|grains which consists of polyethylene-type resin used for the said sealing layer is 1.5 million or more.

Further, in this case, it is preferable that the average particle diameter of the particles made of the polyethylene-based resin in the sealing layer is 5 to 20 µm.

Furthermore, in this case, it is preferable that the content of the particles made of the polyethylene-based resin in the polyethylene-based resin composition constituting the sealing layer is 0.4 to 2.0% by weight.

Moreover, in this case, it is preferable that the resin hardness of the particle|grains which consists of the said polyethylene-type resin is D70 or less.

Furthermore, in this case, it is preferable that the density of the polyethylene-based resin composition constituting the laminate layer is higher than the density of the polyethylene-based resin composition constituting the sealing layer.

Furthermore, in this case, the content of the organic lubricant in the polyethylene-based resin composition constituting the sealing layer is preferably 0.02 wt% or less.

Furthermore, in this case, the content of inorganic particles in the polyethylene-based resin composition constituting the sealing layer is preferably 0.4 wt% or less.

Furthermore, the present invention also includes a laminate including a vapor deposition film in which a vapor deposition layer is deposited on the surface of a polyethylene-based resin multilayer film or a laminate layer thereof, a base film made of a thermoplastic resin composition, and a package comprising the laminate.

The polyethylene-based resin multilayer film of the present invention has excellent gas barrier properties over the entire length and width of the obtained vapor deposition film, even when vapor deposition is carried out at high speed using a large-sized vapor deposition machine. In addition, it is excellent in handling properties and deposition processability of the film before deposition.

The polyethylene-based resin multilayer film of the present invention has a sealing layer made of a polyethylene-based resin composition and a laminated layer made of a polyethylene-based resin composition, and optionally an intermediate layer interposed between the sealing layer and the laminated layer.

(Sealing layer made of polyethylene-based resin composition)

The polyethylene-type resin composition of the sealing layer in this invention contains mainly a polyethylene-type resin, and also contains the particle|grains which consist of a polyethylene-type resin. The polyethylene-based resin composition preferably contains 50% by weight or more of the polyethylene-based resin, more preferably 70% by weight or more, and still more preferably 90% by weight or more.

(polyethylene resin)

The polyethylene-based resin in the present invention is either a homopolymer of an ethylene monomer, a copolymer of an ethylene monomer and an α-olefin, or a mixture thereof, and the α-olefin is propylene, butene-1, hexene-1, 4 -Methylpentene-1, octene-1, decene-1, etc. can be illustrated.

The density range of the polyethylene-based resin is preferably 900 to 935 kg/m, more preferably 910 to 933 kg/m, still more preferably 910 to 930 kg/m, particularly preferably 915 to 928 kg/m, 915 to 925 kg/m 3 are particularly preferred. Polyethylene-based resin having a density smaller than 900 kg/m 3 tends to have poor blocking resistance.

Polyethylene-based resin having a density of 935 kg/m 3 or less does not have an excessively high heat-sealing initiation temperature, so it is easy to manufacture a bag and has excellent transparency.

More importantly, when a polyethylene-based resin having a density of 935 kg/m 3 or less is used, the three-dimensional surface roughness SRa of the sealing layer surface is 0.05 μm or more and the maximum peak height SRmax is 2 μm or more by the particles made of the polyethylene-based resin. The present inventors discovered that it becomes a film excellent in vapor deposition processability, since it becomes easy to make it easy, and since it becomes easy to obtain sliding property and blocking resistance, it is hard to generate|occur|produce wrinkles and protrusions at the time of vapor deposition process. In particular, the blocking resistance is less likely to fluctuate at each measured value of the four measurements, and becomes stable.

In addition, when a polyethylene-based resin having a density of 900 kg/m 3 or more is used, the three-dimensional surface roughness SRa of the sealing layer surface is 0.2 µm or less, and the maximum peak height SRmax is also controlled by controlling the content of the particles made of the polyethylene-based resin. It is easy to set it as 8 micrometers or less, and it is easy to improve gas barrier property.

As the polyethylene-based resin, from the viewpoint of film forming properties and the like, the melt flow rate (hereinafter, may be referred to as MFR) is preferably about 2.5 to 4.5 g/min. Here, MFR was measured based on ASTM D1893-67. In addition, this polyethylene-based resin is synthesized by a method known per se.

When a low resin such as a polyethylene resin having an MFR of 2.5 g/10 min or less is used, the blocking resistance deteriorates or the heat sealing start temperature tends to increase. Therefore, attention must be paid to the extrusion conditions. In the case of high-speed film forming with a large T-die film making machine, MFR of about 3 to 4 g/10 min is particularly preferable for film forming properties.

As a polyethylene-type resin, 85 degreeC or more is preferable from a viewpoint of heat resistance etc. to melting|fusing point, 100 degreeC or more is more preferable, and 110 degreeC or more is especially preferable.

Although the polyethylene-type resin may be a single type, it is also possible to mix|blend 2 or more types of polyethylene resins from which the density of the said density range differs. When two or more types of polyethylene-type resins from which densities differ are mix|blended, the average density and compounding ratio can be estimated by GPC measurement or density measurement. In addition, particles made of a polyethylene-based resin described above can be blended.

As a polyethylene-type resin used for a sealing layer, it is also possible to use a commercial item, For example, Ube Maruzen Polyethylene Co., Ltd. make Umerit (trademark) 2040FC, 0540F, 3540FC, Sumitomo Chemical Co., Ltd. product Sumikasen (trademark) E FV402, E FV405, etc. are mentioned.

(Particles made of polyethylene-based resin)

Although the polyethylene-based resin composition constituting the sealing layer contains particles made of a polyethylene-based resin, the average particle diameter of the particles made of the polyethylene-based resin can be controlled, and by using together with a polyethylene-based resin of a specific density, the sealing layer of at least one surface layer The three-dimensional surface roughness SRa of the surface may be 0.05 to 0.2 µm, and the maximum peak height SRmax may be 2 to 8 µm.

The reason is that the difference in molecular weight between the particles made of the polyethylene resin and the polyethylene resin other than the particles made of the polyethylene resin is very large. Since it is easy to maintain the shape of the particles made of the polyethylene resin even in the film, and aggregation due to fusion or adhesion between the particles made of the polyethylene resin is also unlikely to occur, the particle diameter of the particles on the surface of the sealing layer is similar to that of the inorganic particles. It is estimated that protrusions suitable for this can be formed on the surface of the sealing layer.

In this case, it is preferable that the viscosity average molecular weight of the particle|grains which consists of polyethylene-type resin is 1.5 million or more, It is more preferable that it is 1.6 million or more, and 1.7 million or more are still more preferable. Moreover, it is more preferable that it is 2.5 million or less, It is more preferable that it is 2.4 million or less, It is still more preferable that it is 2.3 million or less.

If the viscosity average molecular weight of the particles made of the polyethylene-based resin is 1.5 million or more, even if the temperature at the time of melt mixing is higher than the melting point peak, the particle size shape due to decomposition or fusion aggregation by heat or shear or partial compatibility with the base resin Since the change is difficult to occur, it is easy to form projections on the surface of the film as in the case of using inorganic particles or organic crosslinked resin particles. There is little influence on mechanical strength or heat-sealing property.

Moreover, this is also surprising, although particles made of a polyethylene-based resin having a viscosity average molecular weight of 1.5 million or more are difficult to aggregate in a polyethylene-based resin, it is difficult to fall off from the polyethylene-based resin near the film surface. It turned out that it has the characteristic which particle|grains and organic crosslinked resin particle|grains do not have.

Moreover, when the viscosity average molecular weight of the particle|grains which consists of polyethylene-type resin becomes 1.5 million or more, self-lubricating property arises in the particle|grains itself which consists of a polyethylene-type resin, and slidability improves more easily than the conventional inorganic particle.

If the viscosity average molecular weight is 1.5 million to 2.5 million, it becomes easy to set the average particle diameter to 5 to 20 µm, and when the sealing layer raw material is melt-mixed and extruded to form a film, it becomes easy to form suitable film surface projections. tends to

Polyethylene-based resin particles are softer than inorganic particles if the particle diameter is in the range of 5 to 20 µm, and even when the vapor deposition film is wound into a roll and in strong contact with the vapor deposition layer provided on the side of the laminate layer, the projections can easily remove the vapor deposition layer. will not penetrate. For this reason, there are cases where cracks in the deposition layer occur slightly in the portion where the deposition layer is pressed against the large projections and stretched. easy.

It is preferable that the resin hardness of the particle|grains which consists of a polyethylene-type resin is D70 or less. When hardness is 70 or less, it becomes more difficult to generate|occur|produce a defect in a vapor deposition layer, and gas-barrier property is hard to fall. As for hardness, D68 or less is more preferable.

Moreover, when the hardness of the particle|grains which consists of polyethylene-type resin is D60 or more, slidability improves, and even if it receives the heat|fever at the time of vapor deposition, it is hard to deteriorate slidability.

Particles made of polyethylene resin are homopolymers of ethylene monomers, copolymers of ethylene monomers and α-olefins, and mixtures thereof, and α-olefins include propylene, butene-1, hexene-1, and 4-methylpentene-1. , octene-1, decene-1, and the like can be exemplified.

930 to 950 kg/m3 is preferable, as for the density range of the particle|grains which consists of polyethylene-type resin in this invention, 935-945 kg/m3 is more preferable, 937-942 kg/m3 is still more preferable. Particles made of a polyethylene resin having a density of less than 930 kg/m 3 are soft and difficult to maintain the shape of the particles during melt extrusion, so that the blocking resistance tends to decrease. In addition, particles made of a polyethylene resin having a density greater than 950 kg/m3 are hard particles and thus scratch resistance tends to decrease, and affinity with the polyethylene resin as a base decreases, so the drop resistance may decrease. There is a possibility.

As for the average particle diameter of the particle|grains which consists of polyethylene-type resin, 5 micrometers or more are preferable, 6 micrometers or more are more preferable, and 7 micrometers or more are still more preferable. Further, the average particle diameter is preferably 20 µm or less, more preferably 15 µm or less, still more preferably 14 µm or less, and particularly preferably 13 µm or less.

When the average particle diameter of the particle|grains which consists of polyethylene-type resin shall be 5 micrometers or more, sliding property and blocking resistance can be improved.

In addition, when the average particle diameter is 20 µm or less, the three-dimensional surface roughness SRa and the maximum projection height SRmax do not become excessively large, and compared with the case where particles made of a polyethylene-based resin of the same weight are added, the number of projections increases, It is easy to obtain sufficient slipperiness for vapor deposition.

Furthermore, since particles made of polyethylene-based resin are less likely to break or agglomerate due to extrusion kneading than relatively soft inorganic particles such as talc and calcium carbonate, the particle diameter is less likely to change, and the average particle diameter before and after extrusion is easy to control. .

When the average particle diameter of the particles made of the polyethylene-based resin is in the range of 5 to 20 µm, the projections due to the coarse particles are almost eliminated, and the hardness of the projections itself on the film surface is lower than that of the inorganic particles, so the other side (laminate Defects, such as cracks, of the vapor deposition layer provided in layer) are suppressed, and the fall of gas barrier property is suppressed more.

It is preferable that the ratio of the particle|grains of 30 micrometers or more to the particle|grains which consists of a polyethylene-type resin is 10 % or less, and it is more preferable that the particle|grains of 30 micrometers or more do not contain the particle|grains which consist of a particle diameter. By doing so, it is easy to make the maximum peak height of the sealing layer surface 8 micrometers or less.

The addition amount of the particles made of the polyethylene resin in the polyethylene-based resin composition constituting the sealing layer is preferably 0.4% by weight or more, more preferably 0.5% by weight or more, and 0.6% by weight relative to the polyethylene-based resin composition constituting the sealing layer. % or more is more preferable. Moreover, 2 weight% or less is preferable, 1.5 weight% or less is more preferable, and 1.0 weight% or less is still more preferable.

If the content of the particles made of the polyethylene-based resin is 0.4 wt% or more, the number of particles tends to decrease, and the maximum peak height of the sealing layer surface is easily set to 2 µm or more per designated area (0.2 mm2), so that blocking resistance and sliding properties are obtained. easy. In addition, when the content of the particles made of the polyethylene-based resin is 2% by weight or less, the protrusions on the surface of the sealing layer do not increase too much, and it is easy to be excellent in transparency and low-temperature sealing property. Moreover, the screw load of extrusion becomes small and it is excellent in high-speed film forming property.

It is preferable that the content rate of the organic-type lubricant in the polyethylene-type resin composition which comprises a sealing layer is 0.05 weight% or less. When the content of the organic lubricant is 0.05% by weight or less, the adhesion with the vapor deposition layer provided on the laminate layer is less likely to decrease with time.

Examples of the organic lubricant include unsaturated fatty acid amides such as oleic acid amide, erucic acid amide, stearic acid amide, behenic acid amide, ethylenebisoleic acid amide, and ethylenebiserucic acid amide and polymer wax.

Further, in the sealing layer, the content of the organic lubricant is more preferably 0.03% by weight or less, still more preferably 0.02% by weight or less, particularly preferably 0.01% by weight or less, and 0% by weight (i.e., if sliding properties can be ensured) , the sealing layer does not contain organic lubricants).

In addition to the particle|grains which consist of polyethylene-type resin, you may use together inorganic particle for the purpose of improving slidability. Examples of the inorganic particles that may be used in combination include talc, calcium carbonate, silica, and diatomaceous earth, and the lower the Mohs hardness is, the more preferable, and the Mohs hardness 3 or less is particularly preferable.

The average particle diameter of the inorganic particles used in combination is smaller than that of the polyethylene-based resin particles, and is particularly preferably 2 to 10 µm from the viewpoint of sliding properties and gas barrier properties, and more preferably 3 to 6 µm. In this case, inorganic particles can be obtained at a lower price than particles made of polyethylene-based resin, and due to the small particle diameter, the contact distance with the deposition layer is smaller than that of particles made of polyethylene-based resin, suppressing the occurrence of scratches on the deposition layer, It is possible to improve the slidability.

The content in the polyethylene-based resin composition constituting the sealing layer of the inorganic particles is preferably 0.5 wt% or less, more preferably 0.4 wt% or less, and furthermore 0.3 wt% or less from the viewpoint of gas barrier properties after the deposition layer is installed. Preferably, 0.2 wt% or less is particularly preferred, and 0 wt% (ie, no inorganic particles are contained in the sealing layer) is most preferred.

In the polyethylene-based resin film of the present invention, when the sealing layer contains organic crosslinked resin particles, the reduction of gas barrier properties after vapor deposition is suppressed, scratch resistance, die drool prevention of die slip, and particles are not dropped. It is preferable to contain in the range which does not impair the addition effect of the particle|grains which consist of resin. The crosslinked organic particles as used herein are organic crosslinked particles typified by polymethyl acrylate resin and the like, and the proportion of the crosslinked organic particles in the entire polyethylene-based resin multilayer film of the present invention is preferably 2% by weight or less, and 0.1 It is more preferably not more than weight %, and more preferably 0 weight % (that is, the sealing layer does not contain organic crosslinked resin particles).

(Polyethylene-based resin composition)

The density range of the polyethylene-based resin composition constituting the sealing layer is preferably 900 to 935 kg/m3, more preferably 910 to 933 kg/m3, still more preferably 910 to 930 kg/m3, and still more preferably 915 to 928 kg/m3. m 3 is particularly preferred, and 915 to 925 kg/m 3 is particularly preferred. Polyethylene-based resin having a density smaller than 900 kg/m 3 tends to have poor blocking resistance.

The polyethylene-based resin composition having a density of 935 kg/m 3 or less does not have a high heat-sealing initiation temperature, is easy to manufacture, and has excellent transparency. More importantly, when a polyethylene-based resin having a density of 940 kg/m3 or less is used, stable blocking resistance or stable sliding properties of the polyethylene-based resin multilayer film are easily obtained, and wrinkle and protrusion are less likely to occur during deposition processing. It makes an excellent film.

As the polyethylene-based resin composition, from the viewpoint of film forming properties, etc., the melt flow rate (hereinafter, may be referred to as MFR) is preferably about 2.5 to 4.5 g/min. Here, MFR was measured based on ASTM D1893-67. In addition, this polyethylene-based resin is synthesized by a method known per se.

(Laminate layer)

In the polyethylene-based resin composition constituting the laminate layer, a homopolymer of an ethylene monomer, a copolymer of an ethylene monomer and an α-olefin, or a mixture thereof, and the α-olefin include propylene, butene-1, hexene-1, 4-methyl Pentene-1, octene-1, decene-1, etc. can be illustrated.

On the other hand, the density of the polyethylene-based resin used for the laminate layer can be selected from a range different from that of the sealing layer, and specifically, it is preferably 910 to 950 kg/m 3 , and from the viewpoint of reducing the bleed-out of low molecular weight components, 920 to It is more preferable that it is 950 kg/m<3>, It is still more preferable that it is 925-940 kg/m<3>, It is especially preferable that it is 930-935 kg/m<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, the density of the polyethylene used for the laminate layer is preferably higher than that of the polyethylene used for the sealing layer, and the density of the polyethylene used for the laminate layer is 10 kg/m 3 or more higher than the density of the polyethylene used for the sealing layer. more preferably.

The polyethylene-based resin used for the laminate layer preferably has a melt flow rate (MFR) of 1 to 10 g/10 min, more preferably 2 to 8 g/10 min, and more preferably 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 not good, 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, as for melting|fusing point of the polyethylene-type resin used for a lamination layer, it is more preferable that it is 115 degreeC or more, 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 laminate layer 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 140 degrees C or less, Preferably it is 130 degrees C or less. When melting|fusing point is 140 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 the laminate layer 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 manufacturing methods such as polyethylene polymerized using a Ziegler-Naphtha 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 a sealing layer.

It is preferable that the content rate of the particle|grains which consists of a polyethylene-type resin in the polyethylene-type resin composition which comprises a laminate layer, and an inorganic particle, respectively is 0.1 weight% or less. When the content of the particles made of the polyethylene-based resin and the inorganic particles is 0.1 wt% or less, the surface of the laminate layer tends to be flat, the vapor deposition layer provided thereon has a dense structure, and the oxygen transmittance and water vapor transmittance tend to be small. Further, in the polyethylene-based resin composition constituting the laminate layer, the content of the particles made of the polyethylene-based resin and the inorganic particles is more preferably 0.05% by weight or less, respectively, and 0% by weight from the gas barrier property after the deposition layer is provided. It is more preferable that

Specific examples of the particles include the same polyethylene-based resin and inorganic particles as those described for the sealing layer.

When the polyethylene-based resin composition constituting the laminate layer contains crosslinked organic particles, the effects such as suppression of reduction in gas barrier properties after vapor deposition, scratch resistance, die drool prevention of die slip, and non-dropping of particles are not prevented. It is preferable to contain in the range. The crosslinked organic particles as used herein are organic crosslinked particles typified by polymethyl acrylate resin and the like, and the content of the crosslinked organic particles is preferably 0.1% by weight or less, more preferably 0.05% by weight or less, and most preferably 0% by weight. do.

The content of the organic lubricant in the polyethylene-based resin composition constituting the laminate layer is preferably 0.02% by weight or less, more preferably 0% by weight. When the content of the organic lubricant is 0.02% by weight or less, the adhesion with the vapor deposition layer provided on the laminate layer is less likely to decrease with time. Examples of the organic lubricant include unsaturated fatty acid amides such as oleic acid amide, erucic acid amide, stearic acid amide, behenic acid amide, ethylenebisoleic acid amide, and ethylenebiserucic acid amide and polymer wax.

The density of the polyethylene-based resin composition constituting the laminate layer can be selected from a range different from that of the sealing layer, and specifically, it is preferably 910 to 950 kg/m 3 , and 920 to 950 from the viewpoint of reducing the bleed-out of low molecular weight components. It is more preferable that it is kg/m3, It is still more preferable that it is 925-940 kg/m3, It is especially preferable that it is 930-935 kg/m3. 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, the density of the polyethylene-based resin composition constituting the laminate layer is preferably higher than that of the polyethylene-based resin composition constituting the sealing layer, and the density of the polyethylene-based resin composition constituting the laminate layer is the polyethylene-based resin composition constituting the sealing layer. It is more preferable that it is 10 kg/m<3> or more higher than the density of a resin composition.

(middle floor)

The polyethylene-type resin multilayer film of this invention may have an intermediate|middle layer as needed between a lamination layer and a sealing layer, 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 composition constituting the intermediate layer includes a homopolymer of an ethylene monomer, a copolymer of an ethylene monomer and an α-olefin, and a mixture thereof. Examples of the α-olefin include propylene, butene-1, hexene-1, 4-methylpentene. -1, octene-1, decene-1, etc. can be used.

The density of the polyethylene-based resin used for the intermediate layer is preferably 940 kg/m3 or less, more preferably 900 to 940 kg/m3, and still more preferably 910 to 930 kg/m3. MFR, melting point, etc. of the polyethylene-type resin of an intermediate|middle layer can be set in the same range as a sealing layer.

The polyethylene-based resin used for the intermediate layer preferably has a melt flow rate (MFR) of 1 to 10 g/10 min, more preferably 2 to 8 g/10 min, and furthermore preferably 3.5 to 6 g/10 min. desirable. When MFR is less than 1 g/10min, the extrudability of resin at the time of film preparation is not good, and there exists a possibility that film-forming property may be inferior. Moreover, when MFR exceeds 10 g/10min, the film forming property in a multilayer structure may be inferior.

The melting point of the polyethylene-based resin used for the intermediate layer is preferably 110°C or higher, more preferably 115°C or higher, and still more preferably 120°C or higher. When the melting point is less than 110° C., the surface of the laminate layer 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 140 degrees C or less, Preferably it is 130 degrees C or less. When melting|fusing point is 140 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.

Moreover, it is preferable that the content rate of the organic type lubricant and the inorganic particle in the polyethylene-type resin composition which comprises an intermediate|middle layer is less than 0.1 weight%, respectively. Specific examples of the organic lubricant and inorganic particles are the same as those described for the sealing layer. Further, in the intermediate layer, the content of the organic lubricant and the inorganic particles is more preferably 0.05% by weight or less, respectively, and more preferably 0% by weight (the intermediate layer does not contain the organic lubricant and inorganic particles).

It is preferable that the density of the polyethylene-type resin composition which comprises an intermediate|middle layer is 940 kg/m3 or less, It is more preferable that it is 900-940 kg/m3, It is more preferable that it is 910-930 kg/m3.

(Polyethylene-based resin multilayer film thickness)

The thickness of the polyethylene-based resin multilayer film is preferably in the range of 6 to 100 µm.

As thickness of a sealing layer, it is preferable that it is 3 micrometers or more, 5 micrometers or more are more preferable, and 7 micrometers or more are especially preferable. If the thickness of the sealing layer is 3 µm or more, it is particularly preferable because the sliding properties and the blocking resistance are stable. If it is 7 mu m or more, the effect of the particles made of the polyethylene resin is sufficiently obtained, and the effect of blocking resistance and slidability can be easily achieved even without adding an organic lubricant.

The thickness of the sealing layer is preferably 50 µm or less, more preferably 30 µm or less, and particularly preferably 20 µm or less from the viewpoint of cost.

As thickness of a lamination layer, it is preferable that it is 3 micrometers or more, 5 micrometers or more are more preferable, and 7 micrometers or more are especially preferable. If the thickness of the laminate layer is 3 µm or more, it is particularly preferable because blocking resistance and gloss during vapor deposition are stable. Moreover, when it is 3 micrometers or more, the smoothness of a lamination layer becomes easy to be maintained, and when a vapor deposition layer is provided, it becomes easy to express gas barrier property.

As thickness of a lamination layer, 50 micrometers or less are preferable, 30 micrometers or less are more preferable, and 20 micrometers or less are especially preferable from a viewpoint of cost and curling.

(Method for forming a polyethylene-based resin multilayer film)

As the manufacturing method of the polyethylene-based resin multilayer film of the present invention, for example, a step of mixing and melt-kneading particles made of a polyethylene-based resin and a polyethylene-based resin having a density in a specific range other than the particles made of a polyethylene-based resin , a step of melt-extruding the melt-kneaded polyethylene-based resin composition to form a sealing layer made of a molten polyethylene-based resin composition, similarly a step of forming a laminate layer made of a molten polyethylene-based resin composition, an intermediate layer made of a molten polyethylene-based resin composition in the same manner It is preferable to employ a step of making a fusion layer, a step of extruding a three-layer molten polyethylene-based resin composition laminated sheet by merging the sealing layer, an intermediate layer, and a laminate layer, and a step of cooling and solidifying the three-layer molten polyethylene-based resin composition laminated sheet.

(Sealing layer raw material mixing process)

In the case of mixing particles made of a polyethylene-based resin and a polyethylene-based resin other than particles made of a polyethylene-based resin, it is sufficient as long as they are uniformly mixed. and a method of mixing using When the particles made of the polyethylene resin are directly added, the particles made of the polyethylene resin may be attached to the polyethylene resin to which the adhesive is attached, or may be added directly to the extruder by side feeding or the like.

A method of using a small amount of a masterbatch obtained by mixing particles made of a polyethylene resin with a polyethylene resin other than particles made of a polyethylene resin at a high concentration with a polyethylene resin other than particles made of a polyethylene resin is used in a method of using a dispersibility degree good and easy However, dispersibility is obtained depending on the method of addition, even in a method of directly mixing particles made of polyethylene resin with a linear low-density polyethylene, a homopolymer of ethylene, or a copolymer of ethylene and α-olefin without using a master batch. Therefore, in order to lower the cost, it is preferable to directly add it by a side feeding method that joins at the inlet of the extruder. A lamination layer and an intermediate|middle layer can also be performed similarly by changing a raw material.

(Sealing layer raw material melt-kneading process)

First, as a film raw material, it is dried or hot air dried as needed so that the moisture content of the particles made of the polyethylene-based resin and the polyethylene-based resin other than the particles made of the polyethylene-based resin is less than 1000 ppm. Next, each raw material is measured and mixed, supplied to an extruder, and melt-kneaded.

The lower limit of the melt mixing temperature of the polyethylene-based resin composition is preferably 200°C, more preferably 210°C, still more preferably 220°C. If it is less than the above, discharge may become unstable. The upper limit of the resin melting temperature is preferably 260°C. When the above is exceeded, the decomposition of the resin proceeds, and the amount of foreign substances such as crosslinked organic matter, so-called gel, produced as a result of recombination increases. When the above-mentioned antioxidant is contained in a polyethylene-type resin composition, although melt extrusion at a higher temperature becomes possible, it is preferable to set it as 270 degrees C or less. A lamination layer and an intermediate|middle layer can also be performed similarly by changing a raw material.

Although the melting point of the particles made of the polyethylene resin used in the present invention is about 150 ° C. or less, and mixed with a polyethylene resin other than the particles made of the polyethylene resin, the melting point of the particles is much lower than the temperature at the time of melt kneading. , Surprisingly, it is not dispersed at the molecular level in a polyethylene-based resin other than the particles made of a polyethylene-based resin, and is extruded from a T-die, and in a polyethylene-based resin film obtained through a cooling step, particles made of a polyethylene-based resin are It exists with the particle diameter and shape before addition to polyethylene-type resin other than the particle|grains formed substantially maintained.

(Sealing layer filtration)

In a melt-kneading process, in order to remove the foreign material contained in the molten polyethylene-type resin composition, high-precision filtration can be performed. The filter media used for high-precision filtration of molten resin is not particularly limited, but in the case of a stainless steel sintered filter media, Si, Ti, Sb, Ge, Cu derived from additives such as catalysts in addition to foreign substances such as so-called gels are the main components. It is suitable because it has excellent removal performance of aggregates. Moreover, it is preferable that the filtration precision is 200 micrometers or less. The filtration accuracy here is nominal filtration accuracy, and means the ability to capture about 60 to 98% of particles (here, 200 µm or more) having a size greater than or equal to the indicated filtration accuracy. A lamination layer and an intermediate|middle layer can also be performed similarly by changing a raw material.

(sealing layer filter boost)

It is preferable that the pressure increase amount during the step of melt-kneading the polyethylene-based resin composition is small. A lamination layer and an intermediate|middle layer can also be performed similarly by changing a raw material.

The method of measuring the amount of pressure increase was performed by the method described in Examples.

(melt lamination process)

As a specific method for laminating the sealing layer, the laminate layer, and, if necessary, the intermediate layer, a general multilayering device (multilayer feed block, static mixer, multilayer multi-manifold, etc.) can be used. For example, a method of laminating the molten polyethylene-based resin composition sent from different flow paths using two or three extruders in two or three layers using a feed block, a static mixer, a multi-manifold die, etc. can

(melt extrusion process)

Next, the molten three-layer polyethylene-based resin composition laminated sheet is melt-extruded from, for example, a T-die, cast on a cooling roll, and cooled and solidified to obtain an unstretched sheet. As a specific method for this, casting on a cooling roll is preferable.

Since the particles made of the polyethylene-based resin used in the present invention are hydrophobic resins from the beginning, the hydrophobicity of the surface of the particles does not change even after melt-kneading and extrusion processes. Deposition of thermal degradation products in the lip, so-called die drool, is very unlikely to occur.

A method of melt-extruding a molten three-layer polyethylene-based resin composition laminated sheet by a T-die method or an inflation method to obtain a film is mentioned. is particularly preferred.

(lip contamination)

It is preferable that there is little contamination of the lip entrance of T-die at the time of melt-extruding a three-layer polyethylene-type resin composition lamination sheet from T-die by the T-die method. The measurement method of lip contamination was performed by the method described below.

(Cooling and solidification process)

For example, it is preferable to perform cooling by casting the three-layer polyethylene-type resin composition lamination sheet melt-extruded from the T-die on a cooling roll. The lower limit of the cooling roll temperature is preferably 10°C. If it is 10° C., not only the crystallization inhibitory effect is sufficient, but also problems such as dew condensation occur, which is not preferable. The upper limit of the cooling roll temperature is preferably 70°C or less. If it is 70 degrees C or less, since crystallization does not advance easily and transparency does not worsen easily, it is preferable. In addition, when the temperature of the cooling roll is within the above range, it is preferable to lower the humidity of the environment in the vicinity of the cooling roll to prevent dew condensation.

In casting, since hot resin comes into contact with the surface, the temperature of the surface of a cooling roll rises. Usually, the cooling roll is cooled by flowing cooling water through the pipe inside, and by securing a sufficient amount of cooling water, devising the arrangement of the pipe, and performing maintenance to prevent sludge from adhering to the pipe, the width direction of the surface of the cooling roll is It is necessary to reduce the temperature difference.

(Characteristics of polyethylene-based resin multilayer film)

The characteristics of the polyethylene-based resin multilayer film of the present invention will be described below.

(3D surface roughness SRa)

The three-dimensional surface roughness (SRa) of the sealing layer of the polyethylene-based resin multilayer film of the present invention is preferably 0.05 µm or more. When the SRa is 0.05 µm or more, the sliding property and the blocking resistance are excellent. As for SRa, it is more preferable that it is 0.07 micrometer or more, and it is especially preferable that it is 0.1 micrometer or more.

The three-dimensional surface roughness (SRa) of the sealing layer of the polyethylene-based resin multilayer film of the present invention is preferably 0.2 µm or less. When SRa is 0.2 micrometer or less, transparency is hard to fall. As for SRa, it is more preferable that it is 0.18 micrometer or less, and it is especially preferable that it is 0.16 micrometer or less. The measuring method is performed by the method described in an Example.

(maximum peak height SRmax)

It is preferable that the maximum peak height SRmax of the sealing layer of the polyethylene-type resin multilayer film of this invention is 2 micrometers or more. If the maximum peak height SRmax is 2 µm or more, sliding properties and blocking resistance are easily obtained. As for SRmax, it is more preferable that it is 3 micrometers or more, and it is still more preferable that it is 4 micrometers or more.

It is preferable that the maximum peak height SRmax of the sealing layer of the polyethylene-type resin multilayer film of this invention is 8 micrometers or less. If the maximum peak height SRmax is 8 μm or less, the gas barrier property is hardly lowered even after the deposition layer is installed on the laminate layer and then wound up with a film roll, and appearance defects such as no flicker do not occur. desirable. As for SRmax, it is more preferable that it is 7 micrometers or less, It is still more preferable that it is 6 micrometers or less, It is especially preferable that it is 5 micrometers or less. The measuring method is performed by the method described in an Example.

(blocking strength)

The film roll made of the multilayer film for vapor deposition substrates of the present invention has excellent blocking resistance and also excellent sliding properties. hard to do

The lower limit of the blocking strength of the polyethylene-based resin multilayer film is preferably lower, and the most preferred is 0 mN/20 mm, and the upper limit of the blocking strength is preferably 200 mN/20 mm or less, more preferably 150 mN/20 mm, and more preferably 100 mN/20 mm. When the above is exceeded, feeding property may deteriorate. The measuring method is performed by the method described in an Example.

(Deposition layer)

Providing a vapor deposition layer on the surface of the laminate layer of the polyethylene-based resin multilayer film of the present invention is effective in reducing the oxygen transmittance and the water vapor transmittance. For the deposition of the deposition layer, a method of depositing an inorganic deposition material, for example, a continuous or batch type vacuum deposition machine, electrothermal heating, sputtering, ion plating, ion beam, or the like can be used. The thickness of the vapor deposition layer of the vapor deposition film obtained in this way is preferably in the range of 500 to 1200 angstroms from the viewpoint of adhesiveness, durability, and economy, or preferably in the range of 2 to 4 in terms of optical density (OD value). .

The deposition material 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 the viewpoint of workability, glossiness, safety, cost, etc. It is preferably aluminum.

(Deposition processability)

When the winding state of a 500 m roll manufactured under a specific winding condition using a vapor deposition film is observed, it is preferable that wrinkles and projections do not occur, and it is particularly preferable that there is almost no flow wrinkle during winding.

(Oxygen permeability and water vapor permeability of vapor deposition film)

Even when the vapor-deposited film in which a gas barrier layer is provided on the surface of the laminate layer of the polyethylene-based resin multilayer film of the present invention is wound into a roll, there are protrusions due to particles made of the polyethylene-based resin on the surface of the sealing layer of the present invention, but the Since the particle size is controlled and the hardness of the particles made of the polyethylene-based resin is lower than that of the vapor deposition layer, defects are less likely to occur in the vapor deposition layer, and the gas barrier property is easily maintained. Oxygen permeability and water vapor permeability are performed by the method described below.

The oxygen permeability is preferably 100 mL/m2·d·MPa or less, more preferably 80 ml/m2·d·MPa or less, still more preferably 60 ml/m2·d·MPa or less, and 40 ml/m2·d·MPa or less. · MPa or less is particularly preferable.

The water vapor transmission rate is preferably 1.0 g/m 2 ·d or less, more preferably 0.5 g/m 2 ·d or less, and still more preferably 0.3 g/m 2 ·d or less.

(Deposition Glossiness)

The metallic luster of the vapor-deposited layer in the vapor-deposited film measured in accordance with JIS K5600-4-7 using a gloss meter (VG2000 type manufactured by Nippon Denshoku Kogyo Co., Ltd.) is preferably 700% or more, and more preferably 1000% or more desirable.

(heat sealing strength)

The lower limit of the heat-sealing strength at 160°C of a laminate obtained by laminating a biaxially oriented nylon film (15 µm) and a polyethylene-based resin multilayer film provided with a vapor deposition layer is preferably 30 N/15 mm, more preferably is 35 N/15 mm. If it is less than the above, a bag may become easy to tear after bag manufacture.

The upper limit of the heat-sealing strength at 160°C of a laminate obtained by laminating a biaxially oriented nylon film (15 µm) and a polyethylene-based resin film provided with a vapor deposition layer is preferably 70 N/15 mm, more preferably 65 N/15 mm. When the above is exceeded, it may become difficult to open a bag after bag manufacture. The measurement method is performed by the method described below.

(peel strength)

The lower limit of the peel strength of a laminate obtained by laminating a biaxially oriented nylon film (15 µm) and a polyethylene-based resin multilayer film provided with a vapor deposition layer is preferably 0.7 N/15 mm, more preferably 1.0 N/15 mm and more preferably 1.2 N/15 mm. If it is below the above, peeling occurs after the bag is manufactured, so that the bag is difficult to tear.

The upper limit of the peel strength of a laminate obtained by laminating a biaxially oriented nylon film (15 µm) and a polyethylene-based resin multilayer film provided with a vapor deposition layer is preferably 2.5 N/15 mm or more. If it is above-mentioned, the possibility of peeling after bag manufacture will become low, and it will become easy to open a bag. The measurement method is performed by the method described below.

The lower limit of the peel strength of a laminate in which a biaxially oriented nylon film (15 µm) and a polyethylene-based resin multilayer film provided with a vapor deposition layer are laminated is preferably 0.5 N/15 mm , more preferably 1.0 N/15 mm, and still more preferably 1.2 N/15 mm. If it is above-mentioned, peeling will generate|occur|produce after bag manufacture, and it is hard to tear a bag.

The upper limit of the peel strength of a laminate obtained by laminating a biaxially oriented nylon film (15 µm) and a polyethylene-based resin multilayer film provided with a vapor deposition layer is preferably 2.5 N/ 15 mm or more. If it is above-mentioned, the possibility of peeling after bag manufacture will become low, and it will become easy to open a bag. The measuring method is performed by the method described in an Example.

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 may exist to some extent are also filled, so that it is easy to maintain high gas barrier properties.

(Laminate)

It is also possible to use as a packaging film or a packaging sheet by the structure of the laminated body which laminated|stacked 1 or more types of other base films in addition to the polyethylene-type resin multilayer film of this invention.

The base film is not particularly limited, but a polyolefin film such as polyethylene or polypropylene, a styrene-based resin film, a polyester film such as polyethylene terephthalate or polybutylene terephthalate, and a poly such as nylon 6 or nylon 6,6 A film of an amide or a stretched film thereof, a laminated film of a polyolefin film and a resin film having gas barrier properties such as a polyamide film or an ethylene-vinyl alcohol copolymer film, and, if necessary, a metal foil such as aluminum, or aluminum or A vapor-deposited film or paper on which silica or the like is deposited is appropriately selected and used according to the purpose of use of the laminate. It is also possible to use this base film by laminating|stacking not only one type but combining two or more types.

In that case, it is preferable to make a base film adjoin to the lamination layer side of a polyethylene-type resin multilayer film.

As a method of laminating|stacking a polyethylene-type resin multilayer film on the said base film, the method of dry lamination of a base film and a polyethylene-type resin multilayer film is employable. In that case, it can be set as the structure of a polyethylene-type resin multilayer film/adhesive layer/other base film. As the adhesive layer, when an anchor coat agent such as a urethane-based or isocyanate-based adhesive is used or a modified polyolefin such as an unsaturated carboxylic acid graft polyolefin is used as the adhesive resin, the adjacent layers can be firmly bonded.

The thickness of the laminate is not particularly limited, but when the laminate is used as a film such as a lid material, it is preferably 10 to 200 µm, and when used as a sheet for cups or trays, it is preferably 200 to 1000 µm. .

(packaging body)

After making the sealing layer surfaces of the sealant film of the laminated body face each other, or the sealing layer face of the sealant film layer of the laminated body and another substrate film, the laminate layer side around it so as to form the desired container shape. By heat sealing at least a part of the container can be manufactured. Further, by heat sealing the entire periphery, it is possible to manufacture a sealed bag-shaped container. Combining the molding process of the bag-shaped container with the filling process of the contents, that is, after heat-sealing the bottom and sides of the bag-shaped container, filling the contents, and then heat sealing the top, the package can be manufactured. Accordingly, this laminate can be used in an automatic packaging apparatus for solid, powder, or liquid materials such as snack foods.

In addition, after filling the contents into a container molded into a cup shape by vacuum molding or air pressure molding, a container obtained by injection molding or blow molding, or a container formed from a paper substrate, the laminate of the present invention is coated as a lid material, Also by heat-sealing, the container which packaged the content is obtained.

Example

The present invention will be described in more detail below by way of Examples and Comparative Examples, but the present invention is not particularly limited by the Examples below. In addition, the measurement value of each item in the detailed description and Examples of the present invention was measured by the following method.

<Hardness of polyethylene resin particles>

As the hardness of particles made of a polyethylene-based resin, a resin sheet prepared by melting particles made of a polyethylene-based resin was measured with a shore hardness tester D-type in accordance with ASTM D2240.

<Volume Average Particle Size>

The average particle diameter of the particles made of polyethylene resin before use was measured as follows. The particles are dispersed in ion-exchanged water stirred at a predetermined rotation speed (about 5000 rpm) using a high-speed stirrer, and the dispersion is added to isotone (physiologic saline) and further dispersed with an ultrasonic disperser, Coulter counter method was calculated as the volume average particle diameter by calculating the particle size distribution.

<Particle size distribution of polyethylene-based resin particles>

The weight ratio of the particles of each particle diameter of the particles made of polyethylene resin before use was calculated from the particle size distribution obtained by the Coulter counter method.

<Mohs hardness>

As inorganic particles, the Mohs hardness of the mineral before pulverization was calculated|required from a Mohs hardness table. Specifically, before grinding, the mineral was sequentially rubbed from a standard material having a small hardness, and the hardness of the measured object was determined by visually confirming whether or not scratches were generated on the measured object.

<Content in the resin composition of inorganic particles (weight %)>

The content of the inorganic particles in the resin composition was calculated from the amount added in the raw resin composition before processing. Moreover, even after film-forming, estimation is also possible by measuring the layer ratio by cross-sectional observation and the ash fraction after incineration.

<Melt flow rate: MFR (g/10 min)>

The melt flow rate of the polyethylene-based resin was measured at a temperature of 190°C in accordance with JIS-K7210.

<Density>

The density of polyethylene-type resin was measured based on JISK7112.

<melting point>

The melting point of the polyethylene resin was measured using a differential scanning calorimeter (DSC) manufactured by SII at a sample amount of 10 mg and a temperature increase rate of 10°C/min. The melting endothermic peak temperature detected here was made into melting|fusing point.

<Filt pressure boosting (film forming processability)>

When the resin composition used for the sealing layer was discharged for 5 hours at a discharge amount of 1 kg/hour in a filtration area of 81π square millimeters using a Trauton tester at a resin temperature of 230°C on a Nathlon sintered filter with a filtration accuracy of 120 μm. The amount of pressure increase (ΔMPa) was used as the reference (Δ), and the following categories were classified into ◎, ○, △, and ×, respectively.

(double-circle): The pressure increase amount is 5% or less at the time of the extrusion start.

(circle): The amount of pressure increase is 10% or less at the time of the extrusion start.

(triangle|delta): The pressure increase amount is 20% or less at the time of the extrusion start.

x: The amount of pressure increase is 30% or less at the time of the extrusion start.

<Lip contamination (film forming processability)>

When the resin composition used for the sealing layer was extruded at 230°C using a strand die (2 holes with 5 mmφ) with an extruder for 5 hours at a discharge rate of 20 kg/hour, contamination of the lips was visually observed, and it was (Δ) and classified into ◎, ○, △, and × below.

(double-circle) : Lip contamination is hardly recognized.

(circle): A lip stain|pollution|contamination is seen to some extent.

(triangle|delta): Lip contamination can be confirmed clearly.

x: The lip stain|pollution|contamination grew and the stripe-shaped dent arose in the strand.

<Three-dimensional surface roughness SRa, maximum peak height SRmax>

In accordance with JIS B0601-1994, using a three-dimensional surface roughness meter (Surfcorder ET4000A manufactured by Kosaka Research Institute), from a film piece of 3 cm × 3 cm in width, arbitrarily measuring surface 1 mm × 0.2 mm, low-pass cutoff λs = 0.08 mm, 1000 micrometers length, 100 measurements were performed with 2 micrometers pitch.

Based on JIS B0601-1994, three-dimensional surface roughness SRa and maximum peak height SRmax of the sealing layer surface of a polyethylene-based resin multilayer film were calculated from the obtained cross-sectional curve using the three-dimensional surface roughness analysis program TDA-22.

In the said method, it measured by n=3, and calculated|required the average value of three-dimensional surface roughness SRa and maximum peak height SRmax.

<blocking resistance>

A polyethylene-based resin multilayer film having a size of 12 cm × 10 cm was superimposed on the surface of the sealing layer and the surface of the laminate layer, and 10 cm × 10 cm paper was placed as one set. sandwiched between the glass plates. 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 180° at a tensile rate of 200 mm/min was measured four times, and the The averaged value was evaluated based on the following criteria.

◎: 200 mN/25 mm or less

○: Greater than 200 mN/25 mm and less than 0.5 N/25 mm

△: Greater than 500 mN/25 mm and less than 1 N/25 mm

×: Larger than 1000 mN/25 mm

<Aluminum deposition processability>

In each of Examples and Comparative Examples, aluminum deposition was processed on the surface of the laminate layer of a polyethylene-based resin multilayer film having a width of 1 m × 1000 m ^{at an OD 3.0 and a vacuum degree of 10 -4} torr or less in a vacuum deposition apparatus with a width of 1 m or more, and wound up. The deposition processability was evaluated by slitting from one aluminum deposition film roll with the following tension and contact pressure.

Using a 40 μm aluminum vapor deposition film roll, a 500 mm wide 500 m roll was produced at a line speed of 50 m/min with a tension of 60 N/m and a contact pressure of 20 N/m using a general slitter. . The state of the obtained roll was observed, and aluminum vapor deposition processability was evaluated as follows.

◎: Wrinkles and projections did not occur during winding and after inspection.

○: Wrinkles and protrusions were observed during winding, but did not occur during rewinding inspection.

△: Wrinkles and protrusions were slightly generated in the inspection results.

x: Wrinkles and protrusions were generated

<Glossiness of the aluminum vapor deposition layer>

Using a gloss meter (VG2000 type manufactured by Nippon Denshoku Kogyo Co., Ltd.), according to JIS K5600-4-7, the incident angle and the measurement angle were 60°, and the metallic gloss of the aluminum vapor deposition layer in the aluminum vapor deposition film was measured. , was evaluated based on the following criteria.

◎: 1000% by weight or more

○: 700 wt% or more and less than 1000 wt%

△: 500 wt% or more and less than 700 wt%

×: less than 500% by weight

<Oxygen permeability of aluminum vapor deposition film>

A roll of 500 m was fabricated using an aluminum 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 600-650 roll hardness. Finally, in accordance with the JIS K7126-2A 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, a sealing layer, which is a non-evaporated surface, was mounted on the humidity control side.

<Water vapor permeability of aluminum vapor deposition 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 K7129B method, using a water vapor transmission rate measuring apparatus (PERMATRAN-W3/33 manufactured by MOCON), the water vapor transmission rate of the vapor deposition film was measured under conditions of a temperature of 40°C and a humidity of 90% by weight. When measuring water vapor permeability, a sealing layer, which is a non-evaporated surface, was mounted on the high-humidity side.

<Sealing strength after lamination>

After leaving the aluminum-deposited roll-shaped film under an environment of 40 ° C for 1 month, lamination was performed with Toyobo's biaxially stretched nylon film N1100 15 µm and the same as the measurement of vapor deposition adhesion strength, sealing temperature 150 ° C, sealing pressure 0.2 MPa, After heat-sealing with a sealing time of 1 second, it cut to 15 mm width, and the intensity|strength (unit; N/15 mm) of the sealing part was measured using the speed|rate of 200 m/min using an autograph.

<Peel strength of laminate film (adhesiveness of vapor deposition layer)>

TM569/CAT10L, which is 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 3 . Next, after bonding the vapor deposition surface of the vapor deposition film together on the said adhesive agent and setting it as a laminate film, it aged at 40 degreeC for 48 hours. Peeling strength between the vapor deposition layer and the laminate layer when peeled at 180° under the condition of a tensile rate of 200 mm/min after aging with a tensile tester (Autograph (registered trademark) AGS-J 100NJ, manufactured by Shimadzu Corporation). (unit: N/15 mm) was measured.

<After aging of peel strength (adhesiveness of vapor deposition layer) of laminate film>

After producing a 500 m roll using an aluminum vapor deposition film, it was left to stand in an environment of 30 degreeC for 1 month. Next, TM569/CAT10L, which is 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 . Then, on the said adhesive agent, after bonding the vapor deposition surface of the said vapor deposition film left to stand for one month and setting it as a laminate film, it aged at 40 degreeC for 48 hours. Peeling strength between the vapor deposition layer and the laminate layer when peeled at 180° under the condition of a tensile rate of 200 mm/min after aging with a tensile tester (Autograph (registered trademark) AGS-J 100NJ, manufactured by Shimadzu Corporation). (unit: N/15 mm) was measured.

Next, the present invention will be described in more detail by way of Examples and Comparative Examples, but the present invention is not limited to the following examples.

In Examples and Comparative Examples, the following raw materials were used.

(polyethylene resin)

(1) Sumitomo Chemical Co., Ltd. Exelene (registered trademark) FX307 (density: 890 kg/m3, MFR: 3.2 g/10 min, melting point: 83°C)

(2) Ube Maruzen Polyethylene Co., Ltd. Umerit (registered trademark) 0540F (metallocene-based linear low-density polyethylene, density 904 kg/m3, MFR 4.0 g/10 min, melting point 111°C)

(3) Sumitomo Chemical Co., Ltd. Sumikasen (registered trademark) E FV402 (metallocene catalyst-based LLDPE, density: 913 kg/m3, MFR: 3.8 g/10 min, melting point: 115°C)

(4) Umerit (registered trademark) 2040FC manufactured by Ube Maruzen Polyethylene Co., Ltd. (metallocene catalyst-based LLDPE, density: 919 kg/m3, MFR: 5.0 g/10 min, melting point: 117°C)

(5) Sumitomo Chemical Co., Ltd. Sumikasen (registered trademark) E FV405 (metallocene catalyst-based LLDPE, density: 923 kg/m3, MFR: 3.8 g/10 min, melting point: 118°C)

(6) Umerit (registered trademark) 3540FC manufactured by Ube Maruzen Polyethylene Co., Ltd. (metallocene catalyst-based LLDPE, density: 931 kg/m3, MFR: 3.6 g/10 min, melting point: 123°C)

(7) Umerit (registered trademark) 4040FC manufactured by Ube Maruzen Polyethylene Co., Ltd. (density: 938 kg/m3, MFR: 3.5 g/10 min, melting point: 126°C)

(8) Ube Maruzen Polyethylene Co., Ltd. Umerit (registered trademark) 4540F (metallocene catalyst-based LLDPE, density: 944 kg/m3, MFR: 4.0 g/10 min, melting point: 128°C)

(Particles made of polyethylene-based resin)

(1) Mitsui Chemicals Co., Ltd. make, Mipelon PM200 (average particle size of 10 μm, melting point 136° C., viscosity average molecular weight of 1.8 million, the proportion of particles having a particle size exceeding 30 μm is 0%, resin hardness D65, density 940 kg/ ㎥, ultra-high molecular weight polyethylene particles)

(2) Mitsui Chemicals Co., Ltd. make, Mipelon XM221U (average particle diameter of 25 μm, melting point 136, viscosity average molecular weight of 2 million, ratio of particles having a particle size exceeding 30 μm is 25%, resin hardness D65, density 940 kg/m 3 , ultra-high molecular weight polyethylene particles)

(3) A mixture of PM200 manufactured by Mitsui Chemicals Co., Ltd. and XM221U manufactured by Mitsui Chemicals Co., Ltd. in a ratio of 3/1 (weight ratio), respectively (average particle diameters exceeding 12 μm and exceeding 30 μm had a volume ratio of 6.3%)

(inorganic particles)

(1) Maruo Calcium Co., Ltd. CUBE-50KAS (Mohs hardness 3, average particle diameter 5 µm, calcium carbonate particles)

(2) zeolite particles having a Mohs hardness of 5 and an average particle diameter of 5 μm obtained by pulverizing natural zeolite with a pin mill

(3) Diatomaceous earth particles having a Mohs hardness of 7 and an average particle diameter of 5 μm obtained by pulverizing diatomaceous earth with a pin mill

(Masterbatch)

(1) Mipelon PM200 was mixed with Sumitomo Chemical Co., Ltd. Sumikasen (registered trademark) E FV405 to prepare a masterbatch (1) containing 15 wt% of Mipelon PM200.

(2) A blend product (2) of Mipelon PM200 and Mipelon XM221U was mixed with Sumitomo Chemical Co., Ltd. Sumikasen (registered trademark) E FV405 to prepare a masterbatch (2) containing 15 wt% of the blend product.

(3) Mipelon XM221U was mixed with Sumitomo Chemical Co., Ltd. Sumikasen (registered trademark) E FV405 to prepare a masterbatch (3) containing 15% by weight of Mipelon XM221U.

(4) Sumitomo Chemical Co., Ltd. Sumikasen (registered trademark) E FV405 was mixed with Maruo Calcium Co., Ltd. CUBE-50KAS, and a masterbatch (4) containing 15% by weight of Maruo Calcium Co., Ltd. CUBE-50KAS was prepared.

(5) Sumitomo Chemical Co., Ltd. Sumitomo Chemical Co., Ltd. Sumikasen (registered trademark) E FV405, obtained by pulverizing natural zeolite with a pin mill, and mixing zeolite particles having Mohs hardness 5 and average particle diameter of 5 μm, masterbatch containing 15% by weight of zeolite particles (5) was prepared.

(6) Sumitomo Chemical Co., Ltd. Sumitomo Chemical Co., Ltd. Sumikasen (registered trademark) E FV405, obtained by pulverizing diatomaceous earth with a pin mill, and mixing diatomaceous earth particles having a Mohs hardness of 7 and an average particle diameter of 5 μm, a master batch containing 15 wt% of diatomaceous earth particles ( 6) was prepared.

(7) Sumitomo Chemical Co., Ltd. Sumikasen (registered trademark) E FV402 was mixed with erucic acid amide to prepare a masterbatch (7) containing 4 wt% of erucic acid amide.

(Example 1)

[Composition for sealing layer]

A composition for a sealing layer was prepared using a composition in which 90 wt% of Umerit (registered trademark) 2040FC manufactured by Ube Maruzen Polyethylene Co., Ltd. and 4 wt% of the masterbatch (1) were mixed. In 100% by weight of the composition for the sealing layer, 0.6% by weight of polyethylene particles is contained, but an organic lubricant was not added to the composition for the sealing layer.

[Composition for Laminate Layer]

A composition for a laminate layer was prepared using only Umerit (registered trademark) 3540FC manufactured by Ube Maruzen Polyethylene. In addition, inorganic particles and organic lubricants were not added to the composition for a laminate layer.

[Composition for Intermediate Layer]

A composition for an intermediate layer was prepared using only Umerit (registered trademark) 2040FC manufactured by Ube Maruzen Polyethylene. 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 the laminate layer, the composition for the intermediate layer, and the composition for the sealing layer, the composition for the laminate layer, the composition for the intermediate layer, and the composition for the sealing layer are in order, and the thickness ratio of the laminate layer, the intermediate layer, and the sealing layer is 1 : Melt-extrusion was carried out at 240 degreeC so that it might become 2:1. After that, corona discharge treatment was performed on the surface of the laminate layer. Then, it wound up with the roll at the speed|rate of 150 m/min, and obtained the polyethylene-type resin multilayer film whose thickness is 40 micrometers and the wet tension of the treated surface is 45 mN/m.

Next, the roll of the obtained polyethylene-based resin multilayer film is set in a vacuum vapor deposition machine, and aluminum deposition is performed on the corona-treated surface of the polyethylene-based resin multilayer film at a vacuum degree of ^{10 −4 torr or less, and the aluminum deposition layer is wound with a roll.} A vapor deposition film provided with The thickness of the deposition layer was adjusted so that the aluminum deposition layer had an optical density (OD value) of 3. Aluminum has a Mohs hardness of 2.75.

Table 1 shows the evaluation results of this polyethylene-based resin multilayer film. The three-dimensional surface roughness SRa was 0.10 μm, and the maximum height SRmax was 4.9 μm.

In the vapor deposition film of Example 1, even in locations with high winding hardness (where the hardness measured by a paro tester is 600 to 650), an increase in perforation of the deposited layer due to transfer of inorganic particles (surface layer and winding hardness with a high-brightness LED light) Investigation of the defect condition compared with a location with a low value) was very small, and the gas barrier property was excellent.

In addition, the vapor deposition film of Example 1 exhibited a value equivalent to the oxygen gas barrier properties of a polyethylene-based resin multilayer film in which aluminum was deposited on a biaxially oriented nylon film.

Moreover, the laminated film of Example 1 was excellent in blocking resistance, and the vapor deposition film of Example 1 was excellent in vapor 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)

In the sealing layer, a polyethylene-based resin multilayer film and vapor deposition were carried out in the same manner as in Example 1 except that 92 wt% of Umerit (registered trademark) 2040FC manufactured by Ube Maruzen Polyethylene Co., Ltd. and 8 wt% of the masterbatch (1) were mixed. got a film.

It was excellent in sliding property and blocking resistance than Example 1, and it was also excellent in gas barrier property, glossiness, adhesiveness, and low temperature heat sealing property.

(Example 3)

In the sealing layer, a polyethylene-based resin multilayer film and vapor deposition were carried out in the same manner as in Example 1 except that 94 wt% of Umerit (registered trademark) 2040FC manufactured by Ube Maruzen Polyethylene Co., Ltd. and 6 wt% of the masterbatch (2) were mixed. got a film.

Also in Example 3, it was excellent in gas barrier property, blocking resistance, vapor deposition processability, glossiness, adhesiveness, and low temperature heat sealing property.

(Example 4)

In the sealing layer, 94% by weight of Umerit (registered trademark) 2040FC manufactured by Ube Maruzen Polyethylene Co., Ltd., 4% by weight of masterbatch (1), and 2% by weight of masterbatch (4) were mixed in the same manner as in Example 1 Thus, a polyethylene-based resin multilayer film and a vapor deposition film were obtained.

Also in Example 4, it was excellent in gas barrier property, blocking resistance, vapor deposition processability, glossiness, adhesiveness, and low temperature heat sealing property.

(Example 5)

In the sealing layer, a polyethylene-based resin multilayer film and vapor deposition were carried out in the same manner as in Example 1 except that 96 wt% of Umerit (registered trademark) 0540F manufactured by Ube Maruzen Polyethylene Co., Ltd. and 4 wt% of the masterbatch (1) were mixed. got a film.

Also in Example 5, it was excellent in gas barrier property, blocking resistance, vapor deposition processability, glossiness, adhesiveness, and low temperature heat sealing property.

(Example 6)

In the sealing layer, in the same manner as in Example 1, except that 95% by weight of Umerit (registered trademark) 2040FC manufactured by Ube Maruzen Polyethylene Co., Ltd., 4% by weight of masterbatch (1), and 1% by weight of masterbatch (7) were mixed. Thus, a polyethylene-based resin multilayer film and a vapor deposition film were obtained.

In Example 6, although a slight decrease was seen in the laminate strength after aging, the slidability was good and the gas barrier property, blocking resistance, vapor deposition processability, glossiness and low temperature heat sealing property were excellent.

(Example 7)

The polyethylene-based resin multilayer film obtained in Example 1 was subjected to aluminum vapor deposition under the following conditions to obtain an aluminum vapor deposition film.

The roll of the obtained polyethylene-based resin multilayer film is set in a vacuum vapor deposition machine, and aluminum deposition is performed on the corona-treated surface of the polyethylene-based resin multilayer film at a vacuum degree of ^{10 -4 torr or less, and wound up into a roll, provided with an aluminum deposition layer.} A vapor deposition film was obtained. The thickness of the aluminum deposition layer was adjusted so that the optical density (OD value) was 3.2. Aluminum has a Mohs hardness of 2.75.

Also in Example 7, it was excellent in gas barrier property, blocking resistance, vapor deposition processability, glossiness, adhesiveness, and low temperature heat sealing property, and was excellent in gas barrier property and adhesiveness than Example 1.

(Comparative Example 1)

In the sealing layer, a polyethylene-based resin multilayer film, vapor deposition was carried out in the same manner as in Example 1 except that 90 wt% of Umerit (registered trademark) 2040FC manufactured by Ube Maruzen Polyethylene Co., Ltd. and 10 wt% of masterbatch (5) were mixed. got a film.

In Comparative Example 1, the three-dimensional surface roughness SRa and the maximum height SRmax were equal to or less than Example 1, but a significant decrease in the gas barrier properties of the vapor-deposited film in a portion having a roll hardness of 600 or more and 650 or less was confirmed.

(Comparative Example 2)

In the sealing layer, a polyethylene-based resin multilayer film, vapor deposition was carried out in the same manner as in Example 1 except that 90 wt% of Umerit (registered trademark) 2040FC manufactured by Ube Maruzen Polyethylene Co., Ltd. and 10 wt% of the masterbatch (6) were mixed. got a film.

In Comparative Example 2, the three-dimensional surface roughness SRa and the maximum height SRmax were equal to or less than those of Example 1, but a significant decrease in the gas barrier properties of the vapor-deposited film in a portion having a roll hardness of 600 or more and 650 or less was confirmed.

(Comparative Example 3)

In the sealing layer, in the same manner as in Example 1, except that 93.3% by weight of Umerit (registered trademark) 2040FC 2040FC manufactured by Ube Maruzen Polyethylene Co., Ltd. and 6.7% by weight of the masterbatch 3 were mixed, a polyethylene-based resin multilayer film, vapor deposition got a film.

In the comparative example 3, the oxygen gas barrier property of the vapor deposition film of the part whose roll hardness is 600 or more and 650 or less was slightly reduced in glossiness. Moreover, wrinkles at the time of vapor deposition also generate|occur|produced.

(Comparative Example 4)

In the sealing layer, in the same manner as in Example 1, except that 91 wt% of Umerit (registered trademark) 2040FC manufactured by Ube Maruzen Polyethylene Co., Ltd., 4 wt% of masterbatch (1) and 5 wt% of masterbatch (7) were mixed. Thus, a polyethylene-based resin multilayer film and a vapor deposition film were obtained.

In Comparative Example 4, although the slidability was excellent, the adhesion (including aging) of the vapor deposition layer was extremely deteriorated.

(Comparative Example 5)

In the sealing layer, a polyethylene-based resin multilayer film and a vapor deposition film were obtained in the same manner as in Example 1 except that 96% by weight of Sumitomo Chemical Co., Ltd. Exelene (registered trademark) FX307 and 4% by weight of the masterbatch (1) were mixed.

In Comparative Example 5, the glossiness was inferior to that of Example 1. Moreover, blocking resistance and vapor deposition processability were also inferior.

(Comparative Example 6)

In the sealing layer, 96% by weight of Umerit (registered trademark) 4540F manufactured by Ube Maruzen Polyethylene Co., Ltd. and 4% by weight of the masterbatch (1) were mixed, and in the laminate layer, Umerit (registered trademark) manufactured by Ube Maruzen Polyethylene Co., Ltd. A polyethylene-based resin multilayer film and a vapor deposition film were obtained in the same manner as in Example 1 except that only 4540F (trademark) was used and only Umerit (registered trademark) 4040FC manufactured by Ube Maruzen Polyethylene Co., Ltd. was changed for the intermediate layer.

In Comparative Example 6, since the resin density was higher than that of Example 1, not only the low-temperature sealability was inferior, but also the size of the particles of the polyethylene-based resin after film formation was varied, and wrinkles were generated during vapor deposition. . Moreover, it turned out that a dispersion|variation also arises also in blocking resistance.

The structures and various physical properties of Examples and Comparative Examples are shown in Tables 1 and 2.

Claims (13)

It has at least a laminate layer and a sealing layer made of a polyethylene-based resin composition, and the polyethylene-based resin composition constituting the sealing layer satisfies 1) to 3) below, and the sealing layer surface satisfies 4) and 5) below Polyethylene-based resin multilayer film.
1) A polyethylene-based resin having a density of 900 kg/m 3 or more and 935 kg/m 3 or less is included.
2) It contains the particle|grains which consist of polyethylene-type resin.
3) The content of the organic lubricant is 0.05% by weight or less.
4) Three-dimensional surface roughness SRa is 0.05-0.2 ㎛.
5) The maximum peak height SRmax is 2-8 μm. It has at least a laminate layer and a sealing layer made of a polyethylene-based resin composition, and the polyethylene-based resin composition constituting the sealing layer satisfies 1) to 3) below, and the sealing layer surface satisfies 4) and 5) below Polyethylene-based resin multilayer film.
1) The density is 900 kg/m3 or more and 935 kg/m3 or less.
2) It contains the particle|grains which consist of polyethylene-type resin.
3) The content of the organic lubricant is 0.05% by weight or less.
4) Three-dimensional surface roughness SRa is 0.05-0.2 ㎛.
5) The maximum peak height SRmax is 2-8 μm. 3. The method of claim 1 or 2,
A polyethylene-based resin multilayer film having a viscosity average molecular weight of 1.5 million or more of particles made of a polyethylene-based resin used for the sealing layer. 4. The method according to any one of claims 1 to 3,
A polyethylene-based resin multilayer film having an average particle diameter of 5 to 20 μm of particles made of a polyethylene-based resin in the sealing layer. 5. The method according to any one of claims 1 to 4,
A polyethylene-based resin multilayer film having a content of particles made of a polyethylene-based resin in the polyethylene-based resin composition constituting the sealing layer is 0.4 to 2.0% by weight. 6. The method according to any one of claims 1 to 5,
A polyethylene-based resin multilayer film in which the resin hardness of the particles made of the polyethylene-based resin is D70 or less. 7. The method according to any one of claims 1 to 6,
A polyethylene-based multilayer film in which the density of the polyethylene-based resin composition used for the laminate layer is higher than that of the polyethylene-based resin used for the sealing layer. 8. The method according to any one of claims 1 to 7,
A polyethylene-based resin multilayer film having an organic lubricant content of 0.02 wt% or less in the polyethylene-based resin composition constituting the laminate layer. 9. The method according to any one of claims 1 to 8,
A polyethylene-based resin multilayer film having an inorganic particle content of 0.4 wt% or less in the polyethylene-based resin composition constituting the sealing layer. The vapor deposition film in which the vapor deposition layer was provided in the laminate layer surface of the polyethylene-type resin multilayer film in any one of Claims 1-9. The laminated body which has a base film which consists of the polyethylene-type resin multilayer film in any one of Claims 1-9, and a thermoplastic resin composition. The laminated body which has the base film which consists of the vapor deposition film of Claim 10, and a thermoplastic resin composition. A package comprising the laminate according to claim 11 or 12.