CN113727853A - Polyethylene resin multilayer film, and vapor deposition film, laminate, and package using same - Google Patents

Abstract

A polyethylene resin multilayer film comprising at least: a laminate layer and a sealant layer comprising a polyethylene resin composition, the polyethylene resin composition constituting the sealant layer satisfying the following 1) to 3), and the sealant layer surface satisfying the following 4) and 5). 1) Comprising a density of 900kg/m³Above and 935kg/m³The following polyethylene resin. 2) Comprises particles comprising a polyethylene resin. 3) The content of the organic lubricant is 0.05 wt% or less. 4) The three-dimensional surface roughness SRa is 0.05-0.2 μm. 5) The maximum mountain height SRmax is 2-8 μm.

Description

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

Technical Field

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

Background

Vapor-deposited films having a vapor-deposited layer formed on a polyethylene resin film are widely used for packaging materials such as food packaging and clothes packaging, metallic yarns, labels, stickers, reflectors, and the like, and several polyethylene resin multilayer films have been proposed as substrates for vapor deposition.

For example, in patent document 1, the slidability is improved by using an inorganic anti-blocking agent having a particle diameter of 2 to 5 μm without adding an organic lubricant, but when a long film containing zeolite as an anti-blocking agent is wound up to form a film roll, the gas barrier property of the vapor-deposited film tends to be lowered.

Recently, the size of the vapor deposition machine has been increased, but when a polyethylene resin film having a long and wide size is vapor deposited by a large vapor deposition machine, if the tension is increased to improve the adhesion to the cooling drum, the film roll obtained by winding the vapor deposition film may have a portion where the roll is hardened due to unevenness in thickness, or the roll may easily be hardened in the core portion of the film roll, and thus the gas barrier property may be easily lowered.

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent application No. 2001-225409

Disclosure of Invention

Problems to be solved by the invention

Disclosed is a method for producing a semiconductor device, which comprises: a multilayer polyethylene resin film having excellent gas barrier properties over the entire length and width of the vapor-deposited film even when the vapor-deposited polyethylene resin film having a long and wide width is subjected to vapor deposition by a large-scale vapor deposition machine. Further, it is disclosed that the following objects are achieved: a vapor-deposited film using the polyethylene resin multilayer film.

Means for solving the problems

The present inventors have conducted intensive studies and, as a result, have found that: the above object can be achieved by controlling the protrusion height of the surface of a sealing layer formed of a polyethylene resin composition containing a polyethylene resin having a density within a specific range and particles of the polyethylene resin and the content of an organic lubricant, and the present invention has been achieved.

That is, the present invention is a polyethylene resin multilayer film comprising at least: a laminated layer and a sealing layer, wherein the polyethylene resin composition constituting the sealing layer satisfies the following 1 to 3), and the surface of the sealing layer satisfies the following 4) and 5).

1) Comprising a density of 900kg/m³Above and 935kg/m³The following polyethylene resin.

2) Comprises particles comprising a polyethylene resin.

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

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

5) The maximum mountain height SRmax is 2-8 μm.

Another embodiment is a polyethylene resin multilayer film comprising at least: a laminated layer and a sealing layer, wherein the polyethylene resin composition constituting the sealing layer satisfies the following 1 to 3), and the surface of the sealing layer satisfies the following 4) and 5).

1) The density is 900kg/m³Above and 935kg/m³The following.

2) Comprises particles comprising a polyethylene resin.

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

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

5) The maximum mountain height SRmax is 2-8 μm.

In this case, the viscosity average molecular weight of the polyethylene resin-containing particles used in the sealing layer is preferably 150 ten thousand or more.

In this case, the polyethylene resin-containing particles in the sealing layer preferably have an average particle diameter of 5 to 20 μm.

In this case, the polyethylene resin composition constituting the sealing layer preferably contains polyethylene resin particles in an amount of 0.4 to 2.0 wt%.

Further, in this case, the resin hardness of the polyethylene resin-containing particles is preferably D70 or less.

Further, in this case, it is preferable that the density of the polyethylene resin composition constituting the laminate layer is higher than the density of the polyethylene resin composition constituting the seal layer.

In this case, the content of the organic lubricant in the polyethylene resin composition constituting the sealing layer is preferably 0.02% by weight or less.

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

Further additionally, the present invention also includes: a laminate comprising a polyethylene resin multilayer film or a vapor-deposited film having a vapor-deposited layer deposited on the surface of the laminate layer thereof, and a base film comprising a thermoplastic resin composition; and a package comprising the laminate.

ADVANTAGEOUS EFFECTS OF INVENTION

The polyethylene resin multilayer film of the present invention has excellent gas barrier properties over the entire length and width of the resulting vapor-deposited film even when vapor-deposited by a large-scale vapor deposition machine at high speed. Further, the film before vapor deposition is excellent in handling properties and vapor deposition processability.

Detailed Description

The polyethylene resin multilayer film of the present invention comprises: a sealing layer comprising a polyethylene-based resin composition and a laminate layer comprising a polyethylene-based resin composition, and having an intermediate layer interposed between the aforementioned sealing layer and the aforementioned laminate layer as required.

(sealant layer comprising polyethylene resin composition)

The polyethylene resin composition of the sealing layer of the present invention mainly contains a polyethylene resin, and also contains particles containing a polyethylene resin. The polyethylene resin composition preferably contains the polyethylene resin in an amount of 50 wt% or more, more preferably 70 wt%, and still more preferably 90 wt% or more.

(polyethylene resin)

The polyethylene resin in the present invention is any of a homopolymer of an ethylene monomer, a copolymer of an ethylene monomer and an α -olefin, and a mixture thereof, and examples of the α -olefin include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, and the like.

The density of the polyethylene resin is preferably 900 to 935kg/m³More preferably 910 to 933kg/m³More preferably 910 to 930kg/m³Particularly preferably 915-928 kg/m³Particularly preferably 915-925 kg/m³. Density less than 900kg/m³The blocking resistance of the polyethylene resin (2) is liable to be lowered.

The density is 935kg/m³The following polyethylene resin has a heat sealing initiation temperature not excessively increased, can be easily processed for bag making, and has excellent transparency.

More importantly, the inventors have found that the use of a density of 935kg/m³In the case of the following polyethylene resin, since the three-dimensional surface roughness SRa of the surface of the sealing layer is easily 0.05 μm or more and the maximum mountain height SRmax is 2 μm or more by including the polyethylene resin particles, the slidability and the blocking resistance are easily obtained, and therefore wrinkles and projections are not easily generated at the time of vapor deposition processing, and thus a film having excellent vapor deposition processability is obtained. Particularly, the blocking resistance is stable without being easily changed in each of 4 measurements.

In addition, the used density was 900kg/m³In the case of the polyethylene resin described above, by controlling the content of the polyethylene resin-containing particles, the three-dimensional surface roughness SRa of the surface of the sealing layer can be easily controlled to 0.2 μm or less, the maximum peak height SRmax can be easily controlled to 8 μm or less, and the gas barrier properties can be easily improved.

The polyethylene resin preferably has a melt flow rate (hereinafter sometimes referred to as MFR) of about 2.5 to 4.5 g/min from the viewpoint of film-forming properties. MFR is herein determined according to ASTM D1893-67. Alternatively, the polyethylene resin is synthesized by a method known per se.

When a polyethylene resin having an MFR as low as 2.5g/10 min or less is used, it is observed that the blocking resistance tends to deteriorate or the heat-seal initiation temperature tends to increase, and therefore, attention must be paid to extrusion conditions. When a film is formed at a high speed by a large-size T-die film forming machine, the MFR is particularly preferably about 3 to 4g/10 min for film forming properties.

The polyethylene resin has a melting point of preferably 85 ℃ or higher, more preferably 100 ℃ or higher, and particularly preferably 110 ℃ or higher, from the viewpoint of heat resistance and the like.

The polyethylene resin may be a single type, but 2 or more types of polyethylene resins having different densities within the above density range may be blended. When 2 or more polyethylene resins having different densities are blended, the average density and blending ratio can be estimated by GPC measurement and density measurement. The pellets containing the polyethylene resin described below may be further blended.

As the Polyethylene resin used in the sealing layer, commercially available products may be used, and examples thereof include Ube-Maruzen Polyethylene co., UMERIT (registered trademark) 2040FC manufactured by ltd, 0540F, 3540FC, Sumitomo Chemical co., sumikanene (registered trademark) E FV402, E FV405 manufactured by ltd.

(pellets comprising polyethylene resin)

When the polyethylene resin composition constituting the sealing layer contains particles comprising a polyethylene resin, the average particle diameter of the particles comprising the polyethylene resin can be controlled, and the three-dimensional surface roughness SRa of the sealing layer surface of at least one surface layer can be set to 0.05 to 0.2 μm and the maximum mountain height SRmax can be set to 2 to 8 μm by using the polyethylene resin composition in combination with a polyethylene resin having a specific density.

The reason for this is presumed to be that, since the difference in molecular weight between the polyethylene resin particles and the polyethylene resin other than the polyethylene resin particles is very large, even when the polyethylene resin particles and the polyethylene resin particles are melt-mixed, the shape of the polyethylene resin particles is easily maintained in a film obtained by melt-mixing and extruding the polyethylene resin particles without mixing the molecules of the polyethylene resin particles with each other, and aggregation due to fusion, adhesion, or the like of the polyethylene resin particles is not easily caused, and therefore, protrusions having a particle diameter corresponding to the particle diameter can be formed on the surface of the sealing layer in the same manner as the inorganic particles.

In this case, the viscosity average molecular weight of the polyethylene resin-containing pellets is preferably 150 ten thousand or more, more preferably 160 ten thousand or more, and further preferably 170 ten thousand or more. Further, it is preferably 250 ten thousand or less, more preferably 240 ten thousand or less, and further preferably 230 ten thousand or less.

When the viscosity average molecular weight of the particles comprising the polyethylene resin is 150 ten thousand or more, even if the temperature during melt mixing is higher than the melting point peak, decomposition by heat or shear, fusion aggregation, or change in particle size and shape due to partial compatibility with the base resin is less likely to occur, and therefore, as in the case of using inorganic particles or organic crosslinked resin particles, protrusions are likely to form on the film surface, and not only functions as an antiblocking agent but also the effect on appearance such as transparency, mechanical strength of the film, or heat sealability is less likely to occur.

Further, it has been unexpectedly found that particles containing a polyethylene resin having a viscosity average molecular weight of 150 ten thousand or more have a property of being less likely to aggregate in the polyethylene resin, but are less likely to fall off from the polyethylene resin in the vicinity of the film surface, which is a feature that inorganic particles and organic crosslinked resin particles do not have.

Further, if the viscosity average molecular weight of the polyethylene resin-containing particles is 150 ten thousand or more, the polyethylene resin-containing particles themselves have self-lubricating properties, and the slip properties are more easily improved than those of conventional inorganic particles.

When the viscosity average molecular weight is 150 to 250 ten thousand, the average particle diameter is easily set to 5 to 20 μm, and when a film is formed by melt-mixing and extruding the sealing layer raw material, a suitable protrusion on the surface of the film tends to be easily formed.

The particles containing the polyethylene resin are softer than the inorganic particles as long as the particle diameter is in the range of 5 to 20 μm, and the protrusions do not easily penetrate through the deposition layer even when the deposition film is wound into a roll so that the particles containing the polyethylene resin strongly contact the deposition layer provided on the laminate layer side. Therefore, although cracks in the vapor deposition layer may slightly occur in a portion where the vapor deposition layer is pushed into the large projection, even if a recess is formed in the vapor deposition layer due to the projection, the vapor deposition layer is likely to remain in a portion other than the portion where the cracks occur.

The resin hardness of the polyethylene resin-containing particles is preferably D70 or less. If the hardness is 70 or less, the vapor deposited layer is less likely to be deficient and the gas barrier property is less likely to be lowered. The hardness is more preferably D68 or less.

Further, if the hardness of the particles containing the polyethylene resin is D60 or more, the slidability is improved, and the slidability is not easily deteriorated even when the particles are subjected to heat during vapor deposition.

The particles containing the polyethylene resin are homopolymers of an ethylene monomer, copolymers of an ethylene monomer and an α -olefin, and mixtures thereof, and examples of the α -olefin include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene.

In the present invention, the density of the polyethylene resin-containing pellets is preferably 930 to 950kg/m³More preferably 935 to 945kg/m³More preferably 937 to 942kg/m³. The density is less than 930kg/m³The pellets of (4) are soft, and the pellets are not easily maintained in shape during melt extrusion, and are liable to have reduced blocking resistance. In addition, the density is more than 950kg/m³The pellets comprising a polyethylene resin of (3) are hard and not only are the scratch resistance easily reduced, but also the affinity with the polyethylene resin to be the base is reduced, and therefore, there is a possibility that the falling-off resistance is reduced.

The average particle diameter of the polyethylene resin-containing particles is preferably 5 μm or more, more preferably 6 μm or more, and still more preferably 7 μm or more. 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.

By setting the average particle diameter of the polyethylene resin-containing particles to 5 μm or more, the sliding property and blocking resistance can be improved.

In addition, if the average particle size is 20 μm or less, the three-dimensional surface roughness SRa and the maximum protrusion height SRmax are not excessively increased, and the number of protrusions is increased as compared with the case where particles containing a polyethylene resin are added in the same weight, and therefore, sufficient slidability for vapor deposition processing is easily obtained.

Further, particles containing a polyethylene resin are less likely to be crushed or aggregated by extrusion kneading than softer inorganic particles such as talc and calcium carbonate, and therefore, the particle diameter is less likely to be changed, and the average particle diameter before and after extrusion can be easily controlled.

When the average particle diameter of the polyethylene resin-containing particles is in the range of 5 to 20 μm, the protrusions generated by the coarse particles are substantially eliminated, and the hardness of the protrusions per se on the film surface is lower than that of the inorganic particles, so that defects such as cracks in the vapor deposition layer provided on the other surface (laminate layer) are suppressed, and the reduction in gas barrier properties is further suppressed.

The polyethylene resin-containing particles preferably contain particles having a particle diameter of 30 μm or more in a proportion of 10% or less, and more preferably do not contain particles having a particle diameter of 30 μm or more. Thus, the maximum peak height of the surface of the sealing layer can be easily set to 8 μm or less.

The amount of the particles containing the polyethylene resin added to the polyethylene resin composition constituting the seal layer is preferably 0.4% by weight or more, more preferably 0.5% by weight or more, and still more preferably 0.6% by weight or more, based on the polyethylene resin composition constituting the seal layer. Further, it is preferably 2% by weight or less, more preferably 1.5% by weight or less, and further preferably 1.0% by weight or less.

When the content of the polyethylene resin-containing particles is 0.4 wt% or more, the number of particles is liable to decrease, and the maximum height of the surface of the sealing layer is liable to be set per a predetermined area (0.2 mm)²) The particle diameter is 2 μm or more, and the blocking resistance and the sliding property can be easily obtained. Further, if the content of the polyethylene resin-containing particles is 2 wt% or less, the number of protrusions on the surface of the sealing layer is not excessively increased, and the transparency and the low-temperature sealing property are easily excellent. Further, the screw load for extrusion is reduced and the high-speed film forming property is excellent.

The content of the organic lubricant in the polyethylene resin composition constituting the sealing layer is preferably 0.05 wt% or less. When the content of the organic lubricant is 0.05 wt% or less, the adhesion to the vapor-deposited 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 oleamide, erucamide, stearic acid amide, behenamide, ethylene bis-oleamide, and ethylene bis-erucamide, and polymer waxes.

The content of the organic lubricant in the seal layer is more preferably 0.03 wt% or less, still more preferably 0.02 wt% or less, particularly preferably 0.01 wt% or less, as long as the sliding property can be ensured, and most preferably 0 wt% (that is, the organic lubricant is not contained in the seal layer).

In addition to the particles containing the polyethylene resin, inorganic particles may be used in combination for the purpose of improving the slidability. Examples of the inorganic particles that can be used in combination include talc, calcium carbonate, silica, and diatomaceous earth, and the lower the mohs hardness, the more preferable the mohs hardness is, and the more preferable the mohs hardness is 3 or less.

From the viewpoint of sliding properties and gas barrier properties, it is particularly preferable that the inorganic particles used in combination have an average particle diameter smaller than that of the particles containing the polyethylene resin and 2 to 10 μm, and more preferably 3 to 6 μm. In this case, the inorganic particles are less expensive than the particles containing the polyethylene resin, have a small particle diameter, and have a shorter contact distance with the vapor-deposited layer than the particles containing the polyethylene resin, so that scratches on the vapor-deposited layer can be suppressed and the slidability can be improved.

From the viewpoint of gas barrier properties after the deposition layer is provided, the content of the inorganic particles in the polyethylene resin composition constituting the sealing layer is preferably 0.5% by weight or less, more preferably 0.4% by weight or less, further preferably 0.3% by weight or less, particularly preferably 0.2% by weight or less, and most preferably 0% by weight (that is, the sealing layer does not contain the inorganic particles).

The polyethylene resin film of the present invention preferably contains organic crosslinked resin particles in the sealing layer within a range that does not interfere with the effect of adding particles containing a polyethylene resin, such as suppression of the decrease in gas barrier properties after vapor deposition, scratch resistance, prevention of die lip build-up, and prevention of particle detachment. The crosslinked organic particles herein mean organic crosslinked particles represented by polymethyl acrylate resin, and the ratio of the amount of the crosslinked organic particles in the entire polyethylene resin multilayer film of the present invention is preferably 0.2 wt% or less, more preferably 0.1 wt% or less, and still more preferably 0 wt% (that is, the sealing layer does not contain the organic crosslinked resin particles).

(polyethylene resin composition)

The density of the polyethylene resin composition constituting the sealing layer is preferably 900 to 935kg/m³More preferably 910 to 933kg/m³More preferably 910 to 930kg/m³Particularly preferably 915-928 kg/m³Particularly preferably 915-925 kg/m³. Density less than 900kg/m³The blocking resistance of the polyethylene resin (2) is liable to be lowered.

The density is 935kg/m³The following polyethylene resin composition has a low heat sealing initiation temperature, is easy to form a bag, and has excellent transparency. It is further important to use a density of 940kg/m³In the case of the following polyethylene resin, stable blocking resistance or stable slidability of the polyethylene resin multilayer film can be easily obtained, and wrinkles or projections are less likely to occur during vapor deposition processing, resulting in a film having excellent vapor deposition processability.

The polyethylene resin composition preferably has a melt flow rate (hereinafter sometimes referred to as MFR) of about 2.5 to 4.5 g/min from the viewpoint of film-forming properties. MFR is herein determined according to ASTM D1893-67. Or the polyethylene resin is synthesized by a method known per se.

(laminated layer)

The polyethylene resin composition constituting the laminate layer is a homopolymer of an ethylene monomer, a copolymer of an ethylene monomer and an α -olefin, or a mixture thereof, and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, or the like can be used as the α -olefin.

On the other hand, the density of the polyethylene resin used in the laminate layer may be selected from a range different from that of the sealant layer, and specifically, it is preferably 910 to 950kg/m³From the viewpoint of reducing bleeding of low-molecular-weight components, 920 to 950kg/m is more preferable³More preferably 925 to 940kg/m³Particularly preferably 930 to 935kg/m³. When the density is outside the above range, the metallic luster (hereinafter, simply referred to as "luster") of the deposition layer may be reduced, or curling may occur in the film. In addition, the density of the polyethylene used in the laminate layer is preferably higher than the density of the polyethylene used in the seal layer, and the density of the polyethylene used in the laminate layer is more preferably higher than the density of the polyethylene used in the seal layer by 10kg/m³The above.

The Melt Flow Rate (MFR) of the polyethylene resin used in the laminate layer is preferably 1 to 10g/10 min, more preferably 2 to 8g/10 min, and still more preferably 3.5 to 6g/10 min. If the MFR is less than 1g/10 min, the extrudability of the resin in the production of a film may be poor, resulting in poor film-forming properties. Further, if the MFR exceeds 10g/10 min, the blocking resistance of the film may be lowered.

The melting point of the polyethylene resin used for the laminate layer is preferably 110 ℃ or higher, more preferably 115 ℃ or higher, and still more preferably 120 ℃ or higher. If the melting point is less than 110 ℃, the surface of the laminated layer is softened when the vapor deposition layer is formed, and the glossiness of the vapor deposition layer may be reduced. The upper limit of the melting point of the polyethylene resin is not particularly limited, and is, for example, 140 ℃ or lower, preferably 130 ℃ or lower. When the melting point is 140 ℃ or lower, the film-forming property of the film is excellent. When there are 2 or more melting point peaks, the highest temperature is defined as the melting point.

The polyethylene resin used for the laminate layer is preferably polyethylene (metallocene catalyst polyethylene) polymerized by a metallocene catalyst. The metallocene catalyst-based polyethylene has a narrower molecular weight distribution than a polyethylene produced by another production method such as a polyethylene polymerized by a ziegler-natta catalyst, and therefore, the bleeding of low molecular weight components can be reduced. The polyethylene resin is defined as the sealing layer.

The content ratio of the polyethylene resin-containing particles and the inorganic particles in the polyethylene resin composition constituting the laminate layer is preferably 0.1 wt% or less, respectively. When the content of the particles containing the polyethylene resin and the inorganic particles is 0.1 wt% or less, the surface of the laminate layer tends to be flat, and the vapor-deposited layer provided thereon has a dense structure, so that the oxygen permeability/water vapor permeability tends to be small. The content of the polyethylene resin-containing particles and the inorganic particles in the polyethylene resin composition constituting the laminate layer is more preferably 0.05 wt% or less, and still more preferably 0 wt% from the viewpoint of the gas barrier property after the deposition layer is formed.

Specific examples of the particles include polyethylene resins and inorganic particles similar to those described in the sealing layer.

The crosslinked organic particles are preferably contained in the polyethylene resin composition constituting the laminate layer within a range that does not interfere with the effects of suppressing the reduction in gas barrier properties after vapor deposition, scratch resistance, prevention of die lip build-up, and prevention of particle shedding. The crosslinked organic particles herein mean organic crosslinked particles represented by polymethyl acrylate resins 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.

The content of the organic lubricant in the polyethylene resin composition constituting the laminate layer is preferably 0.02% by weight or less, and more preferably 0% by weight. When the content of the organic lubricant is 0.02 wt% or less, the adhesion to the vapor-deposited 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 oleamide, erucamide, stearic acid amide, behenamide, ethylene bis-oleamide, and ethylene bis-erucamide, and polymer waxes.

The density of the polyethylene resin composition constituting the laminate layer may be selected from a range different from that of the sealant layer, and specifically, it is preferably 910 to 950kg/m³From the viewpoint of reducing bleeding of low-molecular-weight components, 920 to 950kg/m is more preferable³More preferably 925 to 940kg/m³Particularly preferably 930 to 935kg/m³. When the density is outside the above range, the metallic luster (hereinafter, simply referred to as "luster") of the deposition layer may be reduced, or curling may occur in the film.

The density of the polyethylene resin composition constituting the laminate layer is preferably higher than the density of the polyethylene resin composition constituting the seal layer, and the density of the polyethylene resin composition constituting the laminate layer is more preferably higher than the density of the polyethylene resin composition constituting the seal layer by 10kg/m³The above.

(intermediate layer)

The polyethylene resin multilayer film of the present invention may have an intermediate layer, preferably 1 or more intermediate layers, between the laminate layer and the sealant layer, as required. The resin used in the intermediate layer is not particularly limited, and a polyethylene resin is preferred.

The polyethylene resin composition constituting the intermediate layer is a homopolymer of an ethylene monomer, a copolymer of an ethylene monomer and an α -olefin, or a mixture thereof, and propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, or the like can be used as the α -olefin.

The density of the polyethylene resin used in the intermediate layer is preferably 940kg/m³The amount of the surfactant is preferably 900 to 940kg/m³More preferably 910 to 930kg/m³. The MFR, melting point, and the like of the polyethylene resin of the intermediate layer can be set within the same ranges as those of the seal layer.

The Melt Flow Rate (MFR) of the polyethylene resin used in the intermediate layer is preferably 1 to 10g/10 min, more preferably 2 to 8g/10 min, and still more preferably 3.5 to 6g/10 min. If the MFR is less than 1g/10 min, the extrudability of the resin in the production of a film may be poor, resulting in poor film-forming properties. When the MFR exceeds 10g/10 min, the film-forming properties in the multilayer structure are sometimes deteriorated.

The melting point of the polyethylene resin used in the intermediate layer is preferably 110 ℃ or higher, more preferably 115 ℃ or higher, and still more preferably 120 ℃ or higher. If the melting point is less than 110 ℃, the surface of the laminated layer is softened when the vapor deposition layer is formed, and the glossiness of the vapor deposition layer may be reduced. The upper limit of the melting point of the polyethylene resin is not particularly limited, and is, for example, 140 ℃ or lower, preferably 130 ℃ or lower. When the melting point is 140 ℃ or lower, the film-forming property of the film is excellent. When there are 2 or more melting point peaks, the highest temperature is defined as the melting point.

The content of the organic lubricant and the content of the inorganic particles in the polyethylene resin composition constituting the intermediate layer are preferably less than 0.1% by weight, respectively. Specific examples of the organic lubricant and the inorganic particles include those similar to those in the sealing layer. In addition, the content ratios of the organic lubricant and the inorganic particles in the intermediate layer are more preferably 0.05 wt% or less, and still more preferably 0 wt%, respectively (the organic lubricant and the inorganic particles are not contained in the intermediate layer).

The density of the polyethylene resin composition constituting the intermediate layer is preferably 940kg/m³The amount of the surfactant is preferably 900 to 940kg/m³More preferably 910 to 930kg/m³。

(thickness of polyethylene resin multilayer film)

The thickness of the polyethylene resin multilayer film is preferably in the range of 6 to 100. mu.m.

The thickness of the sealing layer is preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 7 μm or more. A thickness of the sealing layer of 3 μm or more is particularly preferable because the sliding property and blocking resistance are stable. When the particle diameter is 7 μm or more, the effect of the particles containing the polyethylene resin can be sufficiently obtained, and the effect of the blocking resistance and the sliding property can be easily obtained 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.

The thickness of the laminate layer is preferably 3 μm or more, more preferably 5 μm or more, and particularly preferably 7 μm or more. A laminate layer having a thickness of 3 μm or more is particularly preferable because the blocking resistance and the gloss at the time of vapor deposition are stabilized. When the thickness is 3 μm or more, the smoothness of the laminate layer is easily maintained, and when a vapor deposition layer is provided, the gas barrier property is easily exhibited.

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

(method for producing polyethylene resin multilayer film)

The process for producing the polyethylene resin multilayer film of the present invention preferably comprises, for example, the following steps: a step of mixing and melt-kneading pellets containing a polyethylene resin and a polyethylene resin having a density in a specific range other than the pellets containing the polyethylene resin; a step of melt-extruding the polyethylene resin composition after melt-kneading to form a sealing layer containing the molten polyethylene resin composition; a step of forming a laminate layer containing the molten polyethylene resin composition in the same manner; a step of forming an intermediate layer containing a molten polyethylene resin composition in the same manner; a step of merging the sealant layer, the intermediate layer, and the laminate layer and extruding a 3-layer laminated sheet of a molten polyethylene resin composition; and a step of cooling and solidifying the 3-layer molten polyethylene resin composition laminated sheet.

(sealing layer raw material mixing step)

When the polyethylene resin other than the polyethylene resin-containing pellets is mixed with the pellets, the polyethylene resin may be uniformly mixed, and when a master batch is used, a method of mixing the polyethylene resin-containing pellets and the polyethylene resin may be performed by using a ribbon mixer, a henschel mixer, a tumbler mixer, or the like. In the case of directly adding the polyethylene resin-containing particles, the polyethylene resin-containing particles may be attached to the polyethylene resin with an additive, or may be directly added to the extruder by side feeding or the like.

The method of mixing the polyethylene resin particles with the polyethylene resin other than the polyethylene resin particles at a high concentration to obtain the master batch, and mixing the obtained master batch with the polyethylene resin other than the polyethylene resin particles in a small amount to use is also excellent in dispersibility and is simple. However, when pellets containing a polyethylene resin are directly mixed with a linear low-density polyethylene, a homopolymer of ethylene, or a copolymer of ethylene and an α -olefin without using a master batch, dispersibility is obtained depending on the method of addition, and therefore, in order to reduce costs, direct addition by a side-feeding system or the like which merges at the inlet of an extruder is preferable. The laminate layer and the intermediate layer may be formed by changing the raw materials in the same manner.

(sealing layer raw Material melt kneading Process)

First, as a film material, polyethylene resin particles other than polyethylene resin particles and polyethylene resin particles are dried or hot air dried as necessary so that the moisture percentage is less than 1000 ppm. Subsequently, the respective raw materials were measured and mixed, and supplied to an extruder to be melt-kneaded.

The lower limit of the melt mixing temperature of the polyethylene resin composition is preferably 200 ℃, more preferably 210 ℃, and still more preferably 220 ℃. If the amount is less than the above range, the discharge may become unstable. The upper limit of the melting temperature of the resin is preferably 260 ℃. If the amount exceeds the above range, the decomposition of the resin proceeds and recombination proceeds, and as a result, the amount of a cross-linked organic substance, a foreign substance such as a so-called gel, is increased. When the antioxidant is contained in the polyethylene resin composition, melt extrusion at a higher temperature is possible, but the temperature is preferably 270 ℃ or lower. The laminate layer and the intermediate layer may be formed by changing the raw materials in the same manner.

The melting point of the polyethylene resin-containing pellets used in the present invention is about 150 ℃ or lower, and the pellets are mixed with a polyethylene resin other than the polyethylene resin-containing pellets, and the melting point of the pellets is far lower than the temperature at the time of melt kneading, but surprisingly, in a polyethylene resin film obtained by extrusion from a T die and a cooling step without dispersing the polyethylene resin other than the polyethylene resin-containing pellets at a molecular level, the polyethylene resin-containing pellets are present in the polyethylene resin other than the polyethylene resin-containing pellets substantially in a state in which the particle diameter and shape before addition are maintained.

(sealing layer filtration)

In the melt kneading step, high-precision filtration may be performed to remove foreign matters contained in the polyethylene resin composition after melting. The filter medium used for the high-precision filtration of the molten resin is not particularly limited, and in the case of a filter medium of a stainless steel sintered body, the removal performance of aggregates containing Si, Ti, Sb, Ge, and Cu as main components derived from additives such as a catalyst is excellent in addition to foreign matters such as gel, and is suitable. The filtration accuracy is preferably 200 μm or less. The term "filtration accuracy" as used herein refers to a nominal filtration accuracy and refers to the ability to capture particles having a size of not less than 60 to 98% of the nominal filtration accuracy (here, not less than 200 μm). The laminate layer and the intermediate layer may be formed by changing the raw materials in the same manner.

(seal layer Filter pressure boosting)

The amount of pressure increase in the step of melt-kneading the polyethylene resin composition is preferably small. The laminate layer and the intermediate layer may be formed by changing the raw materials in the same manner.

The method of measuring the amount of increased pressure was performed by the method described in examples.

(melt lamination Process)

As a specific method of laminating the sealing layer and the laminated layer, if necessary, the intermediate layer, a general multilayering apparatus (multilayer feed block, static mixer, multilayer manifold, etc.) may be used. For example, the following methods can be used: and a method of laminating 2 or 3 layers of the molten polyethylene resin composition fed from different flow paths by two or three extruders, a static mixer, a manifold die, or the like.

(melt extrusion Process)

Next, the 3-layer polyethylene resin composition laminated sheet after melting is melt-extruded from, for example, a T-die, cast onto a cooling roll, and cooled and solidified to obtain an unstretched sheet. As a specific method therefor, casting onto a chill roll is preferable.

Since the particles containing the polyethylene resin used in the present invention are originally hydrophobic resins, the hydrophobicity of the particle surfaces is not changed even after the melt kneading and extrusion steps, and it is extremely difficult to cause the deposition of a thermally deteriorated substance, so-called a build-up, in the lip of the T-die, which is visible in the inorganic particles having the surfaces subjected to the hydrophobic treatment.

A method of melt-extruding a 3-layer polyethylene resin composition laminate sheet after melting into a film by a T-die method or inflation method is exemplified, but the T-die method is particularly preferable from the viewpoint of productivity since the melting temperature of the polyethylene resin composition can be increased.

(die lip contamination)

Preferably, the contamination of the die lip of the T-die is small when the 3-layer polyethylene resin composition laminated sheet is melt-extruded from the T-die by the T-die method. The method for measuring the die lip contamination was performed by the following method.

(Cooling solidification Process)

For example, it is preferable that a 3-layer polyethylene resin composition laminate sheet melt-extruded from a T die is cast onto a cooling roll and cooled. The lower limit of the cooling roll temperature is preferably 10 ℃. When the temperature is 10 ℃, the crystallization-inhibiting effect is sufficient and no problems such as dew condensation occur, and the like, are preferable. The upper limit of the cooling roll temperature is preferably 70 ℃ or lower. If the temperature is 70 ℃ or lower, crystallization is not likely to proceed, and transparency is not likely to deteriorate, so that it is preferable. When the temperature of the cooling roller is set to the above range, it is preferable to reduce the humidity of the environment in the vicinity of the cooling roller in order to prevent condensation.

During casting, the resin having a high temperature contacts the surface, and therefore, the temperature of the surface of the cooling roll rises. In general, the cooling roll is cooled by flowing cooling water through a pipe inside, but it is necessary to reduce the temperature difference in the width direction of the surface of the cooling roll so as to ensure a sufficient amount of cooling water, to design the arrangement of the pipe, and to perform maintenance so that deposits do not adhere to the pipe.

(characteristics of polyethylene resin multilayer film)

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

(three-dimensional surface roughness SRa)

The three-dimensional surface roughness (SRa) of the sealant layer of the polyethylene resin multilayer film of the present invention is preferably 0.05 μm or more. When the SRa is 0.05 μm or more, the slidability and blocking resistance are excellent. SRa is more preferably 0.07 μm or more, particularly preferably 0.1 μm or more.

The three-dimensional surface roughness (SRa) of the sealant layer of the polyethylene resin multilayer film of the present invention is preferably 0.2 μm or less. When the SRa is 0.2 μm or less, the transparency is not easily lowered. SRa is more preferably 0.18 μm or less, particularly preferably 0.16 μm or less. The measurement method was performed by the method described in examples.

(maximum mountain height SRmax)

The maximum mountain height SRmax of the seal layer of the polyethylene resin multilayer film of the present invention is preferably 2 μm or more. If the maximum mountain height SRmax is 2 μm or more, the slidability and the blocking resistance are easily obtained. SRmax is more preferably 3 μm or more, and further preferably 4 μm or more.

The maximum mountain height SRmax of the seal layer of the polyethylene resin multilayer film of the present invention is preferably 8 μm or less. When the maximum height SRmax is 8 μm or less, it is preferable that the gas barrier property is not easily lowered even after a deposition layer is formed on the laminate layer and then the laminate layer is wound into a film roll, and appearance defects such as glitter are not caused. SRmax is more preferably 7 μm or less, still more preferably 6 μm or less, and particularly preferably 5 μm or less. The measurement method was performed by the method described in examples.

(blocking Strength)

The film roll comprising the multilayer film for a vapor deposition substrate of the present invention is excellent in blocking resistance and also excellent in slidability, and therefore, the film is easily unwound, the vapor deposition process can be smoothly performed, and wrinkles and projections are less likely to occur in the obtained vapor deposition film.

The lower limit of the blocking strength of the polyethylene resin multilayer film is preferably 0mN/20mm, and the most preferably 0mN/20mm, and the upper limit of the blocking strength is preferably 200mN/20mm or less, more preferably 150mN/20mm, and further preferably 100mN/20 mm. If the amount exceeds the above range, the resolution may be deteriorated. The measurement method was performed by the method described in examples.

(vapor deposition layer)

When a vapor-deposited layer is provided on the surface of the laminate layer of the polyethylene resin multilayer film of the present invention, it is effective in reducing the oxygen permeability/water vapor permeability. For providing the vapor deposition layer, a method of depositing an inorganic vapor deposition material is, for example, a continuous or batch vacuum deposition machine, and examples thereof include electrothermal heating, sputtering, ion plating, and ion beam deposition. The thickness of the deposited layer of the deposited film obtained in this way is preferably in the range of 500 to 1200 angstrom or in the range of 2 to 4 in terms of optical density (OD value) from the viewpoints of adhesiveness, durability and economy.

The evaporation material is preferably a metal. The metal is not particularly limited, and examples thereof include aluminum, gold, silver, copper, zinc, nickel, chromium, titanium, selenium, germanium, tin, and the like, and aluminum is preferable from the viewpoints of workability, glossiness, safety, cost, and the like.

(vapor deposition processability)

When observing the winding state of a 500 m-ply roll produced using a vapor deposition film under specific winding conditions, it is preferable that wrinkles and projections are not generated, and it is particularly preferable that flow wrinkles during winding are not substantially generated.

(oxygen permeability/Water vapor permeability of vapor deposition film)

The vapor-deposited film having the gas barrier layer provided on the surface of the laminate layer of the polyethylene resin multilayer film of the present invention has projections of the polyethylene resin-containing particles derived from the surface of the sealing layer of the present invention even when wound into a roll, but the particle diameter thereof is controlled, and the hardness of the polyethylene resin-containing particles is lower than that of the vapor-deposited layer, so that defects are less likely to occur in the vapor-deposited layer, and the gas barrier properties are easily maintained. The oxygen permeability/water vapor permeability were measured by the following methods.

The oxygen permeability is preferably 100ml/m²d.MPa or less, more preferably 80ml/m²d.MPa or less, more preferably 60ml/m²d.MPa or less, particularly preferably 40ml/m²d.MPa or less.

The water vapor transmission rate is preferably 1.0g/m²D or less, more preferably 0.5g/m²D is less than or equal to, more preferably 0.3g/m²D is as follows.

(deposition gloss)

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 (model VG2000, manufactured by Nippon Denshoku industries Co., Ltd.), is preferably 700% or more, more preferably 1000% or more.

(Heat seal Strength)

The lower limit of the heat seal strength at 160 ℃ of the laminate comprising the biaxially stretched nylon film (15 μm) and the polyethylene resin multilayer film provided with a vapor deposition layer laminated thereon is preferably 30N/15mm, more preferably 35N/15 mm. If the amount is less than the above, the bag may be easily broken after the bag is produced.

The upper limit of the heat seal strength at 160 ℃ of the laminate comprising the biaxially stretched nylon film (15 μm) and the polyethylene resin film provided with a vapor deposition layer laminated thereon is preferably 70N/15mm, more preferably 65N/15 mm. If the amount exceeds the above range, the bag may not be easily opened after the bag is produced. The measurement method was performed by the method described below.

(Peel Strength)

The lower limit of the peel strength of a laminate obtained by laminating a biaxially stretched nylon film (15 μm) and a polyethylene resin multilayer film provided with a vapor-deposited layer is preferably 0.7N/15mm, more preferably 1.0N/15mm, and still more preferably 1.2N/15 mm. If the amount is less than the above range, delamination occurs after the bag is produced, and the bag is less likely to break.

The upper limit of the peel strength of the laminate comprising the biaxially stretched nylon film (15 μm) and the polyethylene resin multilayer film having a vapor-deposited layer is preferably higher, and more preferably 2.5N/15mm or more. If the amount is more than the above, the possibility of delamination after the bag is produced becomes low, and the bag becomes easy to open. The measurement method was performed by the method described below.

The lower limit of the peel strength immediately after the laminate comprising the biaxially stretched nylon film (15 μm) and the polyethylene resin multilayer film provided with a vapor deposition layer is left to stand in an environment at 30 ℃ for 1 month is preferably 0.5N/15mm, more preferably 1.0N/15mm, and still more preferably 1.2N/15 mm. If the amount is more than the above, delamination occurs after the bag is manufactured, and the bag is not easily broken.

The upper limit of the peel strength of a laminate comprising a biaxially stretched nylon film (15 μm) and a polyethylene resin multilayer film having a vapor-deposited layer laminated thereon immediately after being left to stand at 30 ℃ for 1 month is preferably 2.5N/15mm or more. If the amount is more than the above, the possibility of delamination after the bag is produced becomes low, and the bag becomes easy to open. The measurement method was performed by the method described in examples.

Further, if another film such as a polyethylene terephthalate film or a polyamide film is laminated on the vapor deposition layer, a crack of the vapor deposition layer which may be slightly present is also blocked, and thus it is easy to maintain a high gas barrier property.

(laminated body)

The polyethylene resin multilayer film of the present invention may be used as a packaging film or a packaging sheet, with a laminate comprising at least 1 other base film laminated thereon.

The base film is not particularly limited, and can be suitably selected and used according to the purpose of use of the laminate: polyolefin films such as polyethylene and polypropylene, films of styrene resins, films of polyesters such as polyethylene terephthalate and polybutylene terephthalate, films of polyamides such as nylon 6 and nylon 6, or stretched films thereof, laminated films of polyolefin films and polyamide films, resin films having gas barrier properties such as ethylene-vinyl alcohol copolymer films, and if necessary, metal foils such as aluminum, vapor-deposited films such as aluminum and silica, and paper. The base film may be used alone of 1 type, or may be used in combination of 2 or more types.

In this case, it is preferable to arrange the base films adjacent to each other on the laminate side of the polyethylene resin multilayer film.

As a method for laminating a polyethylene resin multilayer film on the base film, the following method can be adopted: the base film and the polyethylene resin multilayer film are dry-laminated. In this case, a polyethylene resin multilayer film, an adhesive layer, and another base film can be formed. When an anchor coating agent such as a urethane-based or isocyanate-based adhesive or a modified polyolefin such as an unsaturated carboxylic acid-grafted polyolefin is used as the adhesive resin for the adhesive layer, the adjacent layers can be firmly bonded.

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

(packaging body)

The container can be produced by facing the sealing layer surfaces of the sealant films of the laminate with each other or facing the sealing layer surface of the sealant film layer of the laminate with another base film, and then heat-sealing at least a part of the periphery of the laminate from the laminate side so as to have a desired container shape. And the entire periphery is heat-sealed, whereby a sealed pouch container can be manufactured. When the molding process of the pouch container is combined with the filling process of the contents, the contents are filled after the bottom and side portions of the pouch container are heat-sealed, and then the upper portion is heat-sealed, whereby a package can be manufactured. Therefore, the laminate can be used for an automatic packaging device for solid, powder, or liquid materials such as snacks.

Further, a container in which the content is packaged can be obtained by filling the content in a container formed into a cup shape by vacuum forming or pressure forming, a container formed by injection molding or blow molding, a container formed of a paper base material, or the like, and then covering the container with the laminate of the present invention as a lid material and heat-sealing the lid material.

Examples

The present invention will be described in further detail below with reference to examples and comparative examples, but the present invention is not particularly limited by the following examples. The measurement values of the respective items in the detailed description and examples of the present invention are measured by the following methods.

< hardness of polyethylene resin particles >

As the hardness of the particles containing the polyethylene resin, a resin sheet obtained by melting the particles containing the polyethylene resin was measured by shore D durometer according to ASTM D2240.

< volume average particle diameter >

The average particle diameter of the pellets formed from the polyethylene resin before use was measured as follows. The particles were dispersed in ion-exchanged water stirred at a predetermined rotation speed (about 5000rpm) using a high-speed stirrer, the dispersion was added to isotonicity (physiological saline), further dispersed in an ultrasonic disperser, and the particle size distribution was determined by the coulter counter method and calculated as the volume average particle size.

< particle size distribution of particles comprising polyethylene resin >

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

Hardness in Mohs

The mohs hardness of the mineral before pulverization as the inorganic particles was determined from the mohs hardness table. Specifically, the mineral before pulverization is rubbed in order from a standard substance having a low hardness to visually confirm whether or not a scratch is caused on the measurement object, and the hardness of the measurement object is determined.

< content (wt%) of inorganic particles in the resin composition >

The content of the inorganic particles in the resin composition is calculated from the amount added in the raw material resin composition before processing. After the film was formed, the layer ratio and the ash content after incineration were measured and estimated.

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

The melt flow rate of the polyethylene resin was measured at 190 ℃ in accordance with JIS-K7210.

< Density >

The density of the polyethylene resin was measured according to JIS K7112.

< melting Point >

The melting points of the polyethylene resins were as follows: the measurement was carried out by a Differential Scanning Calorimeter (DSC) manufactured by SII (Standard institute of Electrical and electronics Engineers) at a sample amount of 10mg and a temperature rise rate of 10 ℃ per minute. The melting endothermic peak temperature detected here was taken as the melting point.

< Filter Booster (film-making processability) >

A resin composition used in a sealing layer was discharged at a filtration area of 81 pi square mm at a discharge rate of 1 kg/hr using a Trouton tester at a resin temperature of 230 ℃ in a Naslon sintered filter having a filtration accuracy of 120 μm, and the pressure increase (Δ MPa) was defined as a reference (Δ) in the following X, Y, Δ and Δ.

Very good: the amount of pressure increase is 5% or less of the amount at the start of extrusion.

O: the amount of pressure increase is 10% or less of the amount at the start of extrusion.

And (delta): the amount of pressure increase is 20% or less of the amount at the start of extrusion.

X: the amount of pressure increase is 30% or less of the amount at the start of extrusion.

< die lip contamination (film forming processability) >)

The resin composition used for the sealant layer was visually observed for contamination of the die lip at the time of extrusion at 230 ℃ for 5 hours in an extruder using a strand die (5 mm. phi., 2 holes) at a discharge rate of 20 kg/hour, and was classified as "excellent", "good", and "bad" as a reference (delta).

Very good: die lip contamination was essentially not identified.

O: die lip contamination was slightly visible.

And (delta): die lip contamination can be clearly identified.

X: die lip contamination grows and strip-like dents are produced in the strand.

< three-dimensional surface roughness SRa, maximum mountain height SRmax >

According to JIS B0601-1994, 100 measurements were carried out using a three-dimensional surface roughness meter (Surfcorder ET4000A manufactured by Kosaka Laboratory Ltd.) with a low-domain cutoff λ s of 0.08mm, a length of 1000 μm, and a pitch of 2 μm for an arbitrary 1mm × 0.2mm portion of the measurement surface of a 3cm × 3cm square film sheet.

From the obtained cross-sectional line, the three-dimensional surface roughness SRa and the maximum peak height SRmax of the surface of the sealing layer of the multilayer polyethylene resin film were calculated in accordance with JIS B0601-1994 using the three-dimensional surface roughness analysis program TDA-22.

In the above method, the average value of the three-dimensional surface roughness SRa and the maximum mountain height SRmax is determined by measuring n to 3.

< blocking resistance >

After a polyethylene resin multilayer film having a size of 12cm × 10cm was laminated on the surface of the sealing layer and the surface of the laminate layer, 10cm × 10cm of paper was placed thereon as 1 set, and the laminate having 5 sets of layers was sandwiched between glass plates having a thickness of 5 mm. A load of 50kg was applied to the glass plate, and the plate was left at 40 ℃ for 48 hours. After returning to room temperature, the laminate was cut into a width of 25 mm. The peel strength (in N/25mm) of the cut laminate was measured 4 times at a tensile rate of 200 mm/min at 180 ℃ by AUTOGRAPH (registered trademark) manufactured by Shimadzu Corporation, and the average value was evaluated according to the following criteria.

Very good: 200mN/25mm or less

O: more than 200mN/25mm and less than 0.5N/25mm

And (delta): more than 500mN/25mm and 1N/25mm or less

X: greater than 1000mN/25mm

< aluminum vapor deposition processability >

In each of examples and comparative examples, the vacuum deposition apparatus having a width of 1m or more had an OD3.0 and a vacuum degree of 10^-4the aluminum deposition processing was performed on the surface of the laminate layer of a polyethylene resin multilayer film having a width of 1m × 1000m set to torr or less, and the vapor deposition processability was evaluated by slitting from the aluminum deposition film roll after winding under the following tension and contact pressure.

A500 mm wide 500 m-ply roll was produced by using a 40 μm aluminum vapor deposition film roll and using a general slitter at a linear speed of 50 m/min under a tension of 60N/m and a contact pressure of 20N/m. The state of the obtained coil was observed, and the aluminum deposition processability was evaluated as follows.

Very good: no wrinkles or bulges during coiling and after the test article

O: the material with wrinkles or protrusions was visible during winding, but the test article did not appear after unwinding

And (delta): slight wrinkles and bulges occur in the results of the test articles

X: wrinkles and bulges occur

< gloss of aluminum vapor deposition layer >

The metallic gloss of the aluminum deposited layer in the aluminum deposited film was measured by a gloss meter (model VG2000, manufactured by Nippon Denshoku industries Co., Ltd.) with an incident angle and a measurement angle of 60 degrees in accordance with JIS K5600-4-7, and evaluated according to the following criteria.

Very good: more than 1000 wt%

O: 700% by weight or more and less than 1000% by weight

And (delta): 500% by weight or more and less than 700% by weight

X: less than 500% by weight

< oxygen permeability of aluminum vapor deposition film >

A500 m-strand roll was prepared by depositing a film on aluminum. Then, the roll hardness was measured at 2cm intervals in the width direction of a 500 m-ply roll by a PARO tester manufactured by Proceq. Then, a sample is taken out from a portion where the coil hardness is 600 to 650. Finally, the oxygen permeability of the sample was measured by an oxygen permeability measuring apparatus (OX-TRAN 2/21 manufactured by MOCON) at 23 ℃ and 65% humidity according to JIS K7126-2A. In the measurement of the oxygen permeability, a sealing layer as a non-vapor-deposited surface was attached to the humidity control side.

< Water vapor Transmission Rate of aluminum vapor deposition film >

A500 m-ply roll was prepared by using a vapor-deposited film. Subsequently, the roll hardness was measured at 2cm intervals in the width direction of a 500 m-ply roll by a PARO tester manufactured by Proceq. Then, a sample is taken out from a portion where the coil hardness is 600 to 650. Finally, the vapor transmission rate of the vapor deposition film was measured by a vapor transmission rate measuring apparatus (PERMATRAN-W3/33, MOCON) according to JIS K7129B under conditions of a temperature of 40 ℃ and a humidity of 90% by weight. In the measurement of the water vapor transmission rate, a sealing layer as a non-vapor-deposited surface was attached to the high humidity side.

< sealing Strength after lamination >

After the rolled aluminum vapor-deposited film was left to stand at 40 ℃ for 1 month, it was laminated on a biaxially stretched nylon film N110015 μm manufactured by TOYOBO CO., LTD., in the same manner as in the measurement of vapor deposition adhesion strength, heat-sealed at a sealing temperature of 150 ℃ and a sealing pressure of 0.2MPa for a sealing time of 1 second, cut into a width of 15mm, and the strength (unit; N/15mm) of the sealed portion was measured at a speed of 200 m/min by AUTOGRAPH.

< peeling Strength (adhesion of vapor deposition layer) of laminated film >

On a nylon film (TOYOBO CO., LTD., manufactured by "N1100") having a thickness of 15 μm, 3g/m in terms of solid content³TM569/CAT10L was applied to the thickness of (A) of (B) of (D). Then, a deposition surface of a deposition film was bonded to the adhesive to form a laminate film, and the laminate film was cured at 40 ℃ for 48 hours. The cured product was subjected to 180 ℃ peeling at a stretching speed of 200 mm/min in a tensile tester (AUTOGRAPH (registered trademark) AGS-J100 NJ manufactured by Shimadzu Corporation), and the peel strength (in N/15mm) between the vapor-deposited layer and the laminate layer was measured.

< peeling Strength (adhesion of vapor deposition layer) of laminated film with time >

A500 m-strand roll was prepared by depositing a thin film on aluminum, and the roll was left to stand at 30 ℃ for 1 month. Then, a nylon film (TOYOBO CO., LTD., manufactured by "N1100") having a thickness of 15 μm was coated on the surface of the substrate so as to obtain a solid content of 3g/m²TM569/CAT10L was applied to the thickness of (A) of (B) of (D). Then, the deposition surface of the deposited film left alone for 1 month was bonded to the adhesive to form a laminated film, which was then cured at 40 ℃ for 48 hours. The cured product was subjected to 180 ℃ peeling at a stretching speed of 200 mm/min in a tensile tester (AUTOGRAPH (registered trademark) AGS-J100 NJ manufactured by Shimadzu Corporation), and the peel strength (in N/15mm) between the vapor-deposited layer and the laminate layer was measured.

Next, the present invention will be described in further detail with reference to 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) EXCELLEN (registered trademark) FX307 (density: 890 kg/m) manufactured by Sumitomo Chemical Co., Ltd³MFR: 3.2g/10 min, melting point: 83 degree centigrade)

(2) Ube-Maruzen Polyethylene Co., Ltd, UMERIT (registered trademark) 0540F (metallocene-based linear low-density Polyethylene, density 904 kg/m)³MFR4.0g/10 min, mp 111 ℃ C.)

(3) SUMIKATHENE (registered trademark) EFV402 (metallocene catalyst LLDPE, density: 913 kg/m), manufactured by Sumitomo Chemical Co., Ltd³MFR: 3.8g/10 min, melting point: 115 ℃ C.)

(4) Ube-Maruzen Polyethylene Co., Ltd., UMERIT (registered trademark) 2040FC (metallocene catalyst-based LLDPE, density: 919 kg/m)³MFR: 5.0g/10 min, melting Point: 117 deg.C)

(5) SUMIKATHENE (registered trademark) EFV405 (metallocene catalyst LLDPE, density: 923 kg/m), manufactured by Sumitomo Chemical Co., Ltd³MFR: 3.8g/10 min, melting point: 118 deg.C)

(6) Ube-Maruzen Polyethylene Co., Ltd., UMERIT (registered trademark) 3540FC (metallocene catalyst LLDPE, density: 931 kg/m)³MFR: 3.6g/10 min, melting point: 123 ℃ C.)

(7) Ube-Maruzen Polyethylene Co., Ltd., UMERIT (registered trademark) 4040FC (density: 938 kg/m)³MFR: 3.5g/10 min, melting point: 126 deg.C)

(8) Ube-Maruzen Polyethylene Co., Ltd., UMERIT (registered trademark) 4540F (metallocene catalyst LLDPE, density: 944 kg/m)³MFR: 4.0g/10 min, melting point: 128 degree C)

(pellets comprising polyethylene resin)

(1) MIPELON PM200 (average particle diameter 10 μm, melting point 136 ℃, viscosity average molecular weight 180 ten thousand, particle diameter over 30 μm ratio of 0%, resin hardness D65, density 940kg/m, manufactured by Mitsui Chemicals, Inc.)³Ultra high molecular weight polyethylene particles

(2) MIPELON XM221U (average particle size 25 μm, melting point 136, viscosity average molecular weight 200 ten thousand, ratio of particle size of more than 30 μm 25%, resin hardness D65, density 940kg/m, manufactured by Mitsui Chemicals, Inc.)³Ultra high molecular weight polyethylene particles

(3) Each of PM200 manufactured by Mitsui Chemicals, Inc. and XM221U manufactured by Mitsui Chemicals, Inc. was mixed at 3/1 (weight ratio) (the volume ratio of particles having an average particle diameter of 12 μm and particles having a particle diameter of more than 30 μm was 6.3%)

(inorganic particles)

(1) CUBE-50KAS manufactured by Maruo Calcium Co., Ltd. (Mohs hardness of 3, average particle diameter of 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

(Master batch)

(1) MIPELON PM200 was mixed with SUMIKATHENE (registered trademark) EFV405 manufactured by Sumitomo Chemical co., ltd. to prepare a master batch (1) containing 15 wt% of MIPELON PM 200.

(2) A blend (2) of MIPELON PM200 and MIPELON XM221U was mixed in Sumitomo Chemical co., ltd, sumikanene (registered trademark) EFV405 to prepare a master batch (2) containing 15 wt% of the blend.

(3) MIPELON XM221U was mixed with sumikanene (registered trademark) EFV405 manufactured by Sumitomo Chemical co., ltd. to prepare a master batch (3) containing 15 wt% of MIPELON XM 221U.

(4) A master batch (4) containing 15% by weight of Maruo Calcium Co., Ltd., CUBE-50KAS, manufactured by Ltd., was prepared by mixing Maruo Calcium Co., Ltd., SUMIKATHENE (registered trademark) EFV405 manufactured by Ltd.

(5) Zeolite particles having a mohs hardness of 5 μm and an average particle size of 5 μm, which were obtained by pulverizing natural zeolite with a pin mill, were mixed with Sumitomo Chemical co., ltd.

(6) Diatomaceous earth particles having a mohs hardness of 7 and an average particle diameter of 5 μm, which were obtained by pulverizing diatomaceous earth with a pin mill, were mixed with Sumitomo Chemical co., ltd, product sumikanene (registered trademark) EFV405 to prepare a master batch (6) containing 15 wt% of the diatomaceous earth particles.

(7) Erucamide was mixed with Sumitomo Chemical co., ltd. sumikanene (registered trademark) EFV402 to prepare a master batch (7) containing 4 wt% of erucamide.

(example 1)

[ composition for sealing layer ]

A composition for a sealant layer was prepared by using a composition obtained by mixing Ube-Maruzen Polyethylene co., ltd. manufactured UMERIT (registered trademark) 2040FC 90 wt% and masterbatch (1)4 wt%. The sealing layer composition contained 0.6 wt% of polyethylene particles in 100 wt%, but the organic lubricant was not added to the sealing layer composition.

[ composition for laminated layer ]

A laminate layer composition was prepared using only Ube-Maruzen Polyethylene co., ltd. manufactured umeritt (registered trademark) 3540 FC. The laminate layer composition does not contain inorganic particles and an organic lubricant.

[ composition for intermediate layer ]

An intermediate layer composition was prepared using only Ube-Maruzen Polyethylene co., ltd. product umirit (registered trademark) 2040 FC. The composition for the intermediate layer does not contain inorganic particles and an organic lubricant.

The composition for a laminate layer, the composition for an intermediate layer, and the composition for a sealing layer were extruded using an extruder having a T-die so as to be in the order of the composition for a laminate layer, the composition for an intermediate layer, and the composition for a sealing layer, and the thickness ratio of the laminate layer, the intermediate layer, and the sealing layer was 1: 2: mode 1, melt extrusion was performed at 240 ℃. After that, the surface of the laminate was subjected to corona discharge treatment. Then, the film was wound up into a roll at a speed of 150 m/min to obtain a polyethylene resin multilayer film having a thickness of 40 μm and a wet tension of the treated surface of 45 mN/m.

Then, the obtained roll of the polyethylene resin multilayer film was mounted on a vacuum evaporator at10^-4Aluminum deposition was performed on the corona-treated surface of the polyethylene resin multilayer film at a vacuum degree of torr or less, and the film was wound into a roll to obtain a deposited film having an aluminum deposited layer. The thickness of the aluminum deposition layer was adjusted so that the optical density (OD value) of the aluminum deposition layer became 3. The Mohs hardness of aluminum is 2.75.

The evaluation results of the polyethylene resin multilayer film are shown in table 1. The three-dimensional surface roughness SRa was 0.10 μm and the maximum height SRmax was 4.9. mu.m.

The vapor deposition film of example 1 had a very small increase in the number of holes in the vapor deposition layer due to transfer of the inorganic particles at a portion having a high winding hardness (at a portion having a hardness of 600 to 650 as measured by a PARO tester) (in a high-luminance LED lamp, the lack of the inorganic particles was observed as compared with a portion having a low surface layer and low winding hardness), and was excellent in gas barrier properties.

The vapor-deposited film of example 1 had a value equivalent to the oxygen barrier property of a polyethylene resin multilayer film obtained by vapor-depositing aluminum on a biaxially stretched nylon film.

Further, 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. The laminated film produced using the vapor deposition film of example 1 was excellent in adhesion and low-temperature heat sealability.

(example 2)

A Polyethylene resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that 8 wt% of the master batch (1) was mixed with 2040FC 92 wt% of UMERIT (registered trademark) manufactured by Ube-Maruzen Polyethylene co.

The composition was excellent in slidability and blocking resistance as compared with example 1, and also excellent in gas barrier properties, gloss, adhesion, and low-temperature heat sealability.

(example 3)

A Polyethylene resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that UMERIT (registered trademark) 2040FC 94 wt%, manufactured by ltd, was mixed with 6 wt% of the master batch (2) in the seal layer.

In example 3, the gas barrier properties, blocking resistance, vapor deposition processability, gloss, adhesion, and low temperature heat sealing properties are also excellent.

(example 4)

A Polyethylene resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that UMERIT (registered trademark) 2040FC 94 wt%, manufactured by Ube-Maruzen Polyethylene co., ltd., was mixed with 4 wt% of the master batch (1) and 2 wt% of the master batch (4) in the seal layer.

In example 4, the gas barrier properties, blocking resistance, vapor deposition processability, gloss, adhesion, and low temperature heat sealing properties are also excellent.

(example 5)

A Polyethylene resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that 96 wt% of UMERIT (registered trademark) 0540F manufactured by ltd. was mixed with 4 wt% of the master batch (1) in the seal layer.

In example 5, the gas barrier properties, blocking resistance, vapor deposition processability, gloss, adhesion, and low temperature heat sealing properties are also excellent.

(example 6)

A Polyethylene resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that umber (registered trademark) 2040FC 95 wt%, manufactured by Ube-Maruzen Polyethylene co., ltd., was mixed with 4 wt% of the master batch (1) and 1 wt% of the master batch (7).

In example 6, although the lamination strength after the lapse of time was slightly lowered, the sliding property was good, and the gas barrier property, the blocking resistance, the vapor deposition processability, the gloss and the low-temperature heat sealability were excellent.

(example 7)

The polyethylene resin multilayer film obtained in example 1 was subjected to aluminum vapor deposition processing under the following conditions to obtain an aluminum vapor deposited film.

The obtained polyethylene resin multilayer film roll was mounted on a vacuum evaporator at10^-4Aluminum deposition was performed on the corona-treated surface of the polyethylene resin multilayer film at a vacuum degree of torr or less, and the film was wound into a roll to obtain a deposited film having an aluminum deposited layer. The thickness of the aluminum deposition layer was adjusted so that the optical density (OD value) of the aluminum deposition layer became 3.2. The Mohs hardness of aluminum is 2.75.

In example 7, the gas barrier property, blocking resistance, vapor deposition processability, gloss, adhesion, and low temperature heat sealing property were also excellent, and the gas barrier property and adhesion were excellent compared with example 1.

Comparative example 1

A Polyethylene resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that 20 wt% of UMERIT (registered trademark) 2040FC 90 wt%, manufactured by ltd, was mixed with 10 wt% of the master batch (5) in the seal layer.

In comparative example 1, the three-dimensional surface roughness SRa and the maximum height SRmax were equal to or less than those of example 1, but it was confirmed that the gas barrier property of the vapor-deposited film in the portion having the roll hardness of 600 or more and 650 or less was significantly lowered.

Comparative example 2

A Polyethylene resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that 20 wt% of UMERIT (registered trademark) 2040FC 90 wt%, manufactured by ltd, was mixed with 10 wt% of the master batch (6) in the seal layer.

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 it was confirmed that the gas barrier property of the vapor-deposited film in the portion having the roll hardness of 600 or more and 650 or less was significantly lowered.

Comparative example 3

A Polyethylene resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that UMERIT (registered trademark) 2040FC 93.3 wt% manufactured by Ube-Maruzen Polyethylene co.

In comparative example 3, the vapor deposited film having a portion of the coil hardness of 600 to 650 showed a slight decrease in oxygen barrier property and gloss. In addition, wrinkles also occur at the time of vapor deposition.

Comparative example 4

A Polyethylene resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that UMERIT (registered trademark) 2040FC 91 wt%, manufactured by Ube-Maruzen Polyethylene co., ltd., was mixed with 4 wt% of the master batch (1) and 5 wt% of the master batch (7).

In comparative example 4, the slidability was excellent, but the adhesion (including with time) of the deposition layer was extremely lowered.

Comparative example 5

A polyethylene resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that 4 wt% of the master batch (1) was mixed with 4 wt% of EXCELLEN (registered trademark) FX 30796 wt% manufactured by ltd.

In comparative example 5, the gloss was inferior to that in example 1. Further, blocking resistance and vapor deposition processability are poor.

Comparative example 6

A Polyethylene resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that in the sealing layer, Ube-Maruzen Polyethylene co., ltd. manufactured UMERIT (registered trademark) 4540F 96 wt% was mixed with the masterbatch (1)4 wt%, and in the lamination layer, Ube-Maruzen Polyethylene co., ltd. manufactured UMERIT (registered trademark) 4540F was used alone, and in the intermediate layer, Ube-Maruzen Polyethylene co., ltd. manufactured UMERIT (registered trademark) 4040FC was used alone.

In comparative example 6, since the resin density was higher than that in example 1, the low-temperature sealability was not only poor, but also the particle size of the polyethylene resin after film formation was fluctuated, and wrinkles were sometimes introduced during the vapor deposition process. In addition, the blocking resistance sometimes fluctuates.

The structures and various physical properties of examples and comparative examples are shown in tables 1 and 2.

[ Table 1]

[ Table 2]

Claims (13)

1. A polyethylene resin multilayer film comprising at least: a laminate layer and a sealant layer comprising a polyethylene resin composition, the polyethylene resin composition constituting the sealant layer satisfying the following 1) to 3), and the sealant layer surface satisfying the following 4) and 5),

1) comprising a density of 900kg/m³Above and 935kg/m³The following polyethylene-based resin is used,

2) comprising a particle comprising a polyethylene-based resin,

3) the content of the organic lubricant is 0.05 wt% or less,

4) the three-dimensional surface roughness SRa is 0.05 to 0.2 μm,

5) the maximum mountain height SRmax is 2-8 μm.

2. A polyethylene resin multilayer film comprising at least: a laminate layer and a sealant layer comprising a polyethylene resin composition, the polyethylene resin composition constituting the sealant layer satisfying the following 1) to 3), and the sealant layer surface satisfying the following 4) and 5),

1) the density is 900kg/m³Above and 935kg/m³In the following, the following description is given,

2) comprising a particle comprising a polyethylene-based resin,

3) the content of the organic lubricant is 0.05 wt% or less,

4) the three-dimensional surface roughness SRa is 0.05 to 0.2 μm,

5) the maximum mountain height SRmax is 2-8 μm.

3. The polyethylene resin multilayer film according to claim 1 or 2, wherein the polyethylene resin-containing particles used in the seal layer have a viscosity average molecular weight of 150 ten thousand or more.

4. The multilayer polyethylene resin film according to any one of claims 1 to 3, wherein the polyethylene resin-containing particles in the sealing layer have an average particle diameter of 5 to 20 μm.

5. The multilayer polyethylene resin film according to any one of claims 1 to 4, wherein the polyethylene resin composition constituting the sealing layer contains polyethylene resin particles in an amount of 0.4 to 2.0 wt%.

6. The multilayer polyethylene resin film according to any one of claims 1 to 5, wherein the polyethylene resin-containing particles have a resin hardness of D70 or less.

7. The polyethylene multilayer film according to any one of claims 1 to 6, wherein the density of the polyethylene resin composition used in the laminate layer is higher than the density of the polyethylene resin used in the seal layer.

8. The multilayer polyethylene resin film according to any one of claims 1 to 7, wherein the content of the organic lubricant in the polyethylene resin composition constituting the laminate layer is 0.02% by weight or less.

9. The multilayer polyethylene resin film according to any one of claims 1 to 8, wherein the content of the inorganic particles in the polyethylene resin composition constituting the sealant layer is 0.4% by weight or less.

10. A vapor-deposited film comprising the polyethylene resin multilayer film according to any one of claims 1 to 9 and a vapor-deposited layer provided on a surface of a laminate layer of the film.

11. A laminate, comprising: the polyethylene resin multilayer film according to any one of claims 1 to 9, and a base film comprising the thermoplastic resin composition.

12. A laminate, comprising: the vapor-deposited film according to claim 10, and a substrate film comprising the thermoplastic resin composition.

13. A package comprising the laminate of claim 11 or 12.