CN113767137B

CN113767137B - Polyethylene resin film

Info

Publication number: CN113767137B
Application number: CN202080030669.9A
Authority: CN
Inventors: 大木祐和; 西忠嗣
Original assignee: Toyobo Co Ltd
Current assignee: Toyobo Co Ltd
Priority date: 2019-04-26
Filing date: 2020-04-03
Publication date: 2023-12-22
Anticipated expiration: 2040-04-03
Also published as: KR20220004822A; CN113767137A; WO2020217931A1; TW202043359A; JPWO2020217931A1

Abstract

Providing: a polyethylene resin film which is excellent in heat sealability, blocking resistance and sliding properties, has little residue when the film is burned, and is excellent in appearance and scratch resistance. A polyethylene resin film comprising at least an A layer comprising a polyethylene resin composition, wherein the polyethylene resin composition constituting the A layer satisfies the following 1) to 3), and the surface of the A layer satisfies the following 4) and 5). 1) Comprising a density of 900kg/m ³ Above and 935kg/m ³ The following polyethylene resins. 2) Comprises particles comprising a polyethylene resin. 3) The content of the organic lubricant is 0.16 wt% or more. 4) The three-dimensional surface roughness SRa is 0.05-0.2 mu m. 5) The maximum protrusion height SRmax is 2 to 15 μm.

Description

Polyethylene resin film

Technical Field

The present invention relates to a polyethylene resin film, and a laminate and a package using the same.

Background

In recent years, packaging or containers using films for convenience, resource saving, environmental load reduction, and the like have been increasingly used in a wide range of fields. The film has advantages of light weight, easy disposal and low cost compared with conventional molded containers and molded articles.

The sealant film is generally laminated with a base film such as a biaxially stretched nylon film, a biaxially stretched ester film, or a biaxially stretched polypropylene film, which is inferior to the sealant film in low-temperature heat adhesiveness. When the film is stored in a roll form after lamination with these base material films, adhesion may occur between the sealant film and the base material film, and before bag making, the laminated film may not be easily unwound, or the sealant films that become the inner surfaces of the bags during bag making may adhere to each other, and food may not be easily filled.

Therefore, measures for preventing the adhesion of the sealant film to the substrate and the adhesion of the sealant films to each other by scattering powder such as starch on the surface of the sealant film are known.

However, this countermeasure causes not only contamination of the periphery of the thin film processing apparatus but also the following problems: the appearance of the packaged food is remarkably deteriorated, or the powder attached to the sealant film is directly mixed into the package together with the food, or the heat seal strength is lowered.

Therefore, a polyethylene resin film using inorganic fine powder or inorganic fine particles such as silica has been reported.

However, in this countermeasure, when the film surfaces including inorganic fine powder such as silica or inorganic particles added to the polyethylene resin film are rubbed against each other, scratches are likely to occur, and there are problems such as the problem that the inorganic fine powder or inorganic particles are likely to come off and scratches and foreign matter are likely to occur when the sealant film or a laminate of the sealant film and the base film is passed through a laminator, a bag making machine, or the like.

Further, report: a polyethylene resin film comprising organic crosslinked particles formed from a copolymer comprising an acrylic monomer and a styrene monomer as main components is used.

However, in this countermeasure, scratch easiness is not inferior to that of inorganic particles, but is not sufficient. In addition, there remains a problem of falling off of particles.

Further, in order to improve the blocking resistance of polyethylene resin films, it has been reported to add a low-density polyethylene resin or a high-density polyethylene resin to a linear low-density polyethylene resin (for example, refer to patent documents 1 and 2).

However, these measures have problems such as deterioration of mechanical strength characteristics such as tensile strength and transparency, and also poor blocking resistance.

And further, report: a polyethylene resin film comprising a high-density polyethylene resin and particles of a polyethylene resin having a high molecular weight.

However, this countermeasure has the following problems: the mechanical strength characteristics such as tear strength, heat sealability at low temperature and transparency are poor, and the particles containing polyethylene resin are added, but the blocking resistance and sliding property become unstable.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 10-120849

Patent document 2: japanese patent laid-open No. 10-87909

Disclosure of Invention

Problems to be solved by the invention

The purpose of the present invention is to provide: a polyethylene resin film which has excellent appearance, heat sealability, stable blocking resistance and stable sliding properties, and also has excellent scratch resistance. In addition, it is also an object to provide: laminate using the polyethylene resin film, and package.

Solution for solving the problem

The present inventors have conducted intensive studies and as a result found that: the present invention has been achieved to solve the above-mentioned problems by controlling the protrusion height and the organic lubricant content of the surface of a layer formed of a polyethylene resin composition containing polyethylene resin and particles containing polyethylene resin having a density in a specific range.

Specifically, the present invention is a polyethylene resin film comprising at least one layer A comprising a polyethylene resin composition, wherein the polyethylene resin composition constituting the layer A satisfies the following 1) to 3), and wherein at least one surface of the layer A satisfies the following 4) and 5).

1) Comprising a density of 900kg/m ³ Above and 935kg/m ³ The following polyethylene resins.

2) Comprises particles comprising a polyethylene resin.

3) The content of the organic lubricant is 0.16 wt% or more.

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

5) The maximum mountain height SRmax is 2-15 mu m.

In addition, another embodiment is a polyethylene resin film comprising at least one layer a comprising a polyethylene resin composition, wherein the polyethylene resin composition constituting the layer a satisfies the following 1) to 3), and wherein at least one surface of the layer a satisfies the following 4) and 5).

1) Density of 900kg/m ³ Above and 935kg/m ³ The following is given.

2) Comprises particles comprising a polyethylene resin.

3) The content of the organic lubricant is 0.16 wt% or more.

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

5) The maximum mountain height SRmax is 2-15 mu m.

In this case, the particles containing the polyethylene resin preferably have a resin hardness of D70 or less. The multilayer polyethylene resin film according to claim 1 or 2.

In this case, it is preferable that the particles containing the polyethylene resin have a viscosity average molecular weight of 150 ten thousand or more and a melting point peak temperature of 150 ℃ or less based on DSC.

Further, in this case, it is preferable that the average particle diameter of the particles containing the polyethylene resin is 5 to 15. Mu.m.

Further, in this case, it is preferable that the content of the particles containing the polyethylene resin in the polyethylene resin composition constituting the layer a is 0.2 to 2.0% by weight.

Further, in this case, it is preferable that the adhesion value between the surfaces of the A layers is 200mN/70mm or less.

Further, in this case, it is preferable that the change in haze after the surface of the layer a is attached to a An Tian precision mechanical vibration type abrasion tester and abraded 100 times under a load of 200g is 5% or less.

Further, in this case, a laminate is preferable, which comprises: the polyethylene resin film according to any one of the preceding claims, and a base film comprising the composition.

Further, in this case, a packaging bag containing the laminate is preferable.

ADVANTAGEOUS EFFECTS OF INVENTION

The present invention can provide: a polyethylene resin film which is excellent in appearance, heat sealability, stable blocking resistance and stable sliding properties, and particularly excellent in scratch resistance. In addition, it is possible to provide: a laminate using the polyethylene resin film, and a further package.

Detailed Description

(layer A comprising a polyethylene-based resin composition)

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

(polyethylene resin)

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

The polyethylene resin has a density in the range of more preferably 900 to 935kg/m ³ Further preferably 910 to 933kg/m ³ Particularly preferably 910 to 930kg/m ³ . Density of 935kg/m ³ The following polyethylene systemThe heat-sealing starting temperature of the resin is not high, the bag making processing is easy, and the transparency is excellent.

Further important, the inventors have found that: the use density is 935kg/m ³ In the case of the polyethylene resin below, the three-dimensional surface roughness SRa of at least one surface of the a layer is easily set to 0.05 μm or more and the maximum mountain height SRmax is 2 μm or more by the particles containing the polyethylene resin, and the polyethylene resin film is easily obtained in slidability, blocking resistance and scratch resistance, so that wrinkles and protrusions are not easily generated in coating processing, printing processing and bag making processing, and transparency is easily maintained. In particular, the blocking resistance was stable with less variation in each of the 2 measurement values of the 4 measurement.

In addition, if a density of 900kg/m is used ³ The above polyethylene resin can easily control the three-dimensional surface roughness SRa of at least one surface of the a layer to 0.2 μm or less and the maximum mountain height SRmax to 15 μm or less by the particles containing the polyethylene resin, and can easily improve the transparency and the stiffness.

The blocking resistance was obtained by subjecting a sample obtained by stacking the surfaces of the A layers of the film to a pressing treatment in a hot press (model SA-303, manufactured by TESTER SANGYO Co., ltd.) at a temperature of 7cm by 7cm and a pressure of 18MPa for 15 minutes. The sample and the rod (diameter: 6 mm: aluminum) adhered during the pressing treatment were mounted on an Autograph (model: UA-3122, manufactured by Shimadzu corporation) so that the rod and the peeling surface became horizontal, the force at the time of peeling the adhered portion was measured 4 times at a speed (200 m/min) of the rod, and the average value was taken as an index, but it was confirmed that the use density was 935kg/m ³ In the case of the polyethylene resin described below, the measured values measured 4 times are not easy to change, and the heat seal start temperature is not easy to increase. The variation of each measurement value measured 4 times is preferably at the same level as in the case of using inorganic particles.

For the reason that the measured value of each measurement sample is not easily changed, it is assumed that: the density was 935kg/m ³ When the following polyethylene is melt-mixed with particles containing a polyethylene resin, the viscosity average of the particles containing a polyethylene resin is less likely to occurThe particles of the polyethylene resin are not likely to be entangled with molecular chains other than particles of the polyethylene resin, and the particle diameter is not likely to be changed, so that the protrusions on the surface are uniform.

Scratch resistance was determined by the amount of change in haze after abrasion 100 times under a load of 200g by a vibration type abrasion tester in which the surfaces of the a layers of the polyethylene resin film were attached to each other by a An Tian polishing machine. Haze was measured as follows: the haze of the center portion (the point for the end portion was located from the opposite side to the rubbing surface and the two end mark points having no influence on the haze measurement) of the film (width×length=50 mm×180 mm) before being mounted on the rubbing table was measured, and the haze at the same location was measured after rubbing, and the difference was obtained.

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

When a resin having an MFR of 2.5g/10 minutes or less is used, the viscosity average molecular weight of the particles containing the polyethylene resin is not easily reduced, and the change in particle diameter due to entanglement with molecular chains of the polyethylene resin other than the particles containing the polyethylene resin is not easily caused, as in the case of the description of the density, and therefore, attention must be paid to the extrusion conditions. When high-speed film formation is performed by a large-scale film forming machine, it is particularly preferable that the MFR is about 3 to 4g/10 minutes for film formability.

The melting point of the polyethylene resin is preferably 85℃or higher, more preferably 100℃or higher, 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 kinds of polyethylene resins having different densities in the above density range may be blended. When 2 or more polyethylene resins having different densities are blended, the average density and the blending ratio can be estimated from GPC measurement and density measurement.

The density is 900-935 kg/m ³ The polyethylene resin of (2) may be used according to the use thereofAnd (3) selecting: a high-pressure low-density polyethylene (LDPE) which is transparent and is excellent in softness, tear strength and tensile strength on average, a linear short-chain branched polyethylene (LLDPE) which is obtained by copolymerizing 1-butene/1-hexene-1-octene in a small amount and has a large amount of short molecular chains in the molecular chain, has excellent sealing performance and physical strength, and a metallocene catalyst linear short-chain branched polyethylene (LLDPE) which has a very sharp molecular weight distribution, is uniform in comonomer distribution and has excellent tear/tensile/puncture strength and pinhole resistance.

As the polyethylene resin used for the sealing layer, commercially available products may be used, and examples thereof include Ube-Maruzen Polyethylene co., ltd. UMERIT (registered trademark) 2040FC, 0540F, 3540FC, sumitomo Chemical co., ltd. SUMIKATHENE (registered trademark) E FV402, E FV405, and the like.

(particles comprising polyethylene resin)

The particles containing the polyethylene resin contained in the polyethylene resin composition constituting the layer a preferably have a viscosity average molecular weight of 150 ten thousand or more, more preferably 160 ten thousand or more, and still more preferably 170 ten thousand or more. Further, it is preferably 250 ten thousand or less, more preferably 240 ten thousand or less, and still more preferably 230 ten thousand or less.

If the viscosity average molecular weight of the particles containing the polyethylene resin is within this range, the average particle diameter of the particles containing the polyethylene resin can be controlled, and when the particles are used in combination with a polyethylene resin having a specific density, the three-dimensional surface roughness SRa of at least one surface of the a layer can be set to 0.05 to 0.2 μm and the maximum mountain height SRmax can be set to 2 to 15 μm.

The reason for this is presumed that since the difference between the molecular weight of the particles containing the polyethylene resin and the molecular weight of the polyethylene resin other than the particles containing the polyethylene resin is very large, the particles containing the polyethylene resin are also likely to maintain a nearly spherical shape in the film obtained by melt-mixing and extrusion of the molecules without sufficient mixing, and aggregation due to fusion, adhesion, or the like of the particles is also unlikely to occur, and therefore, protrusions with a controlled shape can be formed on the film surface.

If the viscosity average molecular weight of the particles containing a polyethylene resin is 150 ten thousand or more, the particles containing a polyethylene resin are less likely to be decomposed by heat or shear or to be fused together with each other under film forming conditions where the shear and draw ratio of a large extruder are high, and the particles containing a polyethylene resin are less likely to be fused together with each other, and the particles containing a polyethylene resin are less likely to be changed in particle diameter or shape due to the compatibility with the portions of the polyethylene resin other than the particles containing a polyethylene resin, so that the particles such as inorganic particles or organic crosslinked resin particles are likely to be formed into controlled projections, and the function as an anti-blocking agent is sufficient, and the effect on the appearance such as transparency, the mechanical strength of a film, or the heat sealing property is less likely to be exerted.

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 hardly aggregating in the polyethylene resin, but are hardly detached from the polyethylene resin in the vicinity of the film surface, which is not characteristic of inorganic particles or organic crosslinked resin particles.

When the viscosity average molecular weight is 150 to 250 ten thousand, the average particle diameter becomes easily 5 to 20. Mu.m, and when the sealant layer raw material is melt-mixed and extruded to form a film, the film tends to easily form appropriate surface protrusions.

Further, it is considered that if the viscosity average molecular weight of the particles containing the polyethylene resin is 150 ten thousand or more, the particles themselves have lubricity, which is advantageous for the improvement of blocking resistance and sliding properties, and the particles containing the polyethylene resin are soft, and therefore, scratch resistance is also improved.

The resin hardness of the particles containing the polyethylene resin is preferably D70 or less. If the hardness is 70 or less, the laminated layers of the film, for example, the vapor deposition layer, are less likely to suffer from defects, and the gas barrier properties are less likely to be degraded. 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 even when subjected to heat during film processing, the slidability is not easily deteriorated.

Examples of the α -olefin include propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene.

The density of the particles containing the polyethylene resin is preferably in the range of 930 to 950kg/m ³ More preferably 935 to 945kg/m ³ More preferably 937 to 942kg/m ³ . Density of less than 930kg/m ³ The pellets comprising the polyethylene resin are soft and are not easy to maintain the shape of the pellets during melt extrusion, and the blocking resistance is easy to be reduced. In addition, the density is greater than 950kg/m ³ The particles comprising the polyethylene resin tend to be hard, and not only tend to be less resistant to scratches, but also tend to have a lower affinity for the polyethylene resin to be the base, and therefore have a lower resistance to falling off.

The average particle diameter of the particles containing the polyethylene resin contained in the polyethylene resin composition constituting the layer a 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 17 μm or less, particularly preferably 15 μm or less.

It is preferable that the composition does not contain particles having a particle diameter of 30 μm or more. Even if the average particle diameter is 20 μm or less, when particles having a particle diameter of 30 μm or more are contained in a predetermined amount of 10% or more, the maximum peak height of the film surface becomes easily more than 15 μm, and thus flickering, which will be described later, occurs if the film surface is visually observed.

Further, particles of 30 μm or more are not preferable in that they have the same appearance as those of gel-like particles and have a reduced quality.

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

Further, if the average particle diameter is 20 μm or less, the three-dimensional surface roughness SRa and the maximum protrusion height SRmax of at least one surface of the a layer do not excessively increase, and the number of protrusions increases as compared with the case of adding particles containing a polyethylene resin of the same weight, so that sufficient slidability, blocking resistance, and scratch resistance to film processing are easily obtained.

Further, since the average particle diameter of the particles containing the polyethylene resin is less likely to change in the crushing and aggregation caused by kneading at the time of extrusion than that of the relatively soft inorganic particles such as talc and calcium carbonate, and the average particle diameter (before and after extrusion) is easily controlled so that the average particle diameter of the particles containing the polyethylene resin is in the range of 5 to 20 μm, the projections due to the coarse particles substantially disappear, and the hardness of the projections themselves is lower than that of the inorganic particles, adverse effects on the other surface of the layer a or the coating layer other than the layer a are suppressed.

The content of the particles containing the polyethylene resin in the polyethylene resin composition constituting the layer a is preferably 0.2% by weight or more, more preferably 0.3% by weight or more, and still more preferably 0.4% by weight or more, based on the polyethylene resin composition. Further, it is preferably 2.0% by weight or less, more preferably 1.5% by weight or less, and still more preferably 1.0% by weight or less. If the amount of the particles containing the polyethylene resin added is 0.2 wt% or more, it becomes easy to make the maximum mountain height of at least one surface of the A layer to be 0.2mm per a predetermined area ² ) When the particle size is 2 μm or more, blocking resistance and sliding property can be easily obtained. In addition, if the amount of the particles containing the polyethylene resin is 2.0 wt% or less, the protrusions on the surface of the layer a do not excessively increase, and the transparency and low-temperature sealability are also easily improved.

The polyethylene resin composition constituting the layer a contains an organic lubricant. The slidability and anti-blocking effect of the film are improved, and the operability of the film is improved. The reason for this is considered that the organic lubricant bleeds out and is present on the film surface, thereby exhibiting the lubricant effect and the release effect. Further, it is preferable that the organic lubricant has a melting point of normal temperature or higher.

Examples of the organic lubricant include fatty acid amides and fatty acid esters. Specifically, oleamide, erucamide, behenamide, ethylenebisoleamide, hexamethylenebisoleamide, ethylenebisstearamide, and the like. These may be used alone, but a combination of 2 or more kinds is preferable because the slidability and anti-blocking effect can be maintained even in a severe environment.

The lower limit of the content of the organic lubricant in the polyethylene resin composition constituting the layer a is preferably 0.16 wt% or more, preferably 0.18 wt%, more preferably 0.19 wt%, and particularly preferably 0.21 wt%. If it is 0.16% by weight or more, the sliding property is easily stabilized immediately after film formation. The upper limit is preferably 0.3 wt%, more preferably 0.25 wt%. If the amount is 0.3% by weight or less, excessive sliding is not performed, and whitening with time is not easy.

When the inorganic particles are contained in the layer a, the average particle diameter is preferably sufficiently smaller than the average particle diameter of the particles containing the polyethylene resin. The average particle diameter of the inorganic particles is preferably 50% or less of the average particle diameter of the particles containing the polyethylene resin, and coarse particles 2 times or more the average particle diameter are not contained.

The content of the inorganic particles in the polyethylene resin composition constituting the layer a is preferably 0.20 wt% or less, more preferably 0.10 wt% or less, still more preferably 0.05 wt% or less, and most preferably 0 wt%. By setting the content of the inorganic particles to 0.20 wt% or less, not only is the residue at the time of incineration reduced, but also effects similar to those obtained when only particles containing a polyethylene resin are added, such as scratch resistance and no falling of the particles, are easily obtained.

Even when inorganic particles are added, if the particle size is 500ppm or less and residues at the time of film burning are added, the amount of burned residues can be extremely reduced when burning the film as compared with conventional films containing inorganic particles.

The inorganic particles herein are inorganic substances such as silica, talc, calcium carbonate, diatomaceous earth, zeolite, etc., which are usually used as antiblocking agents.

When the crosslinked organic particles are contained in the layer a, the average particle diameter is preferably sufficiently smaller than the average particle diameter of the particles containing the polyethylene resin. The crosslinked organic particles preferably have an average particle diameter of 50% or less of the average particle diameter of the particles containing the polyethylene resin and are substantially free of coarse particles having an average particle diameter of 2 times or more.

From the viewpoint of suppressing the accumulation of the mold and the cost, the content of the crosslinked organic particles in the polyethylene resin composition constituting the layer a is preferably equal to or less than the amount of the particles containing the polyethylene resin.

In the polyethylene resin composition constituting the layer a, it is most preferable that the polyethylene resin composition does not contain crosslinked organic particles in order to obtain the effect of adding particles containing a polyethylene resin such as scratch resistance and particle falling-off, as in the case of inorganic particles.

The crosslinked organic particles herein are organic crosslinked particles represented by polymethyl acrylate resin and the like.

(polyethylene resin composition)

The polyethylene resin composition constituting the layer A preferably has a density in the range of 900 to 935kg/m ³ More preferably 910 to 933kg/m ³ Further preferably 910 to 930kg/m ³ Particularly preferably 915 to 928kg/m ³ Particularly preferably 915 to 925kg/m ³ . Density of less than 900kg/m ³ The blocking resistance of the polyethylene resin is liable to be lowered.

Density of 935kg/m ³ The polyethylene resin composition below has a low heat seal initiation temperature, is easy to manufacture into bags, and has excellent transparency. Further important, the inventors have found that: with a use density of 940kg/m ³ In the case of the polyethylene resin below, the polyethylene resin multilayer film is easy to obtain stable blocking resistance or stable sliding properties, and the scratch resistance is extremely excellent by the synergistic effect of the organic lubricant contained in the polyethylene resin composition constituting the layer a and the surface protrusions generated by the particles of the polyethylene resin.

The polyethylene resin composition preferably has a melt flow rate (hereinafter, may be referred to as mfr) of about 2.5 to 4.5 g/min from the viewpoint of film forming property and the like. The MFR is determined here according to ASTM D1893-67.

(multilayer constitution)

The polyethylene resin film of the present invention may be formed in a plurality of layers. In the case of multiple layers, other layers than the layer a may be provided, such as 1 layer or 2 layers or more.

As a specific method of such multilayering, a general multilayering apparatus (a multilayering head, a static mixer, a multilayering manifold, etc.) can be used.

For example, the following methods and the like can be used: the thermoplastic resin feed head, static mixer, multi-manifold die, etc. fed from different flow paths by two or more extruders are laminated in a plurality of layers. In addition, the multilayered device may be introduced into the welding line from the extruder to the T die by using only one extruder.

In the case of the 3-layer structure, the other layers are respectively an intermediate layer (B layer) and a laminated layer (C layer), and may be composed in this order. The outermost layers at this time are layer a and layer C, respectively.

Examples of the polyethylene resin used for the intermediate layer (layer B) and the laminate layer (layer C) include ethylene/α -olefin copolymers and polyethylene obtained by mixing 1 or 2 or more kinds of polyethylene obtained by a high-pressure method. The ethylene/α -olefin copolymer is a copolymer of ethylene and an α -olefin having 4 to 18 carbon atoms, and examples of the α -olefin include 1-butene, 1-hexene, 4-methyl-1-pentene, 1-octene, and 1-decene.

Films obtained from these polyethylene resins have excellent heat seal strength, hot tack, impurity sealability, and impact resistance, and the polyethylene resins may be used by mixing other resins such as ethylene/vinyl acetate copolymer and ethylene/acrylic acid ester copolymer within a range that does not interfere with these characteristics.

In this case, the polyethylene resin used for the intermediate layer (layer B) and the laminate layer (layer C) may be the same or different. In addition, particles containing a polyethylene resin may be added or may not be added, but if large-sized particles such as coarse particles are present in the laminate layer, delamination is likely to occur, and therefore, it is preferable not to add the particles.

In this case, the average density of the polyethylene resin composition constituting each layer of the film is preferably a layer of a.ltoreq.intermediate layer (B layer). Ltoreq.laminated layer (C layer). The organic lubricant to be compounded is not likely to migrate to a layer having a high density, and is therefore effective for maintaining the slidability of the laminated a layer and maintaining the lamination strength with time.

In this case, the lower limit of the density of the polyethylene resin composition constituting the intermediate layer (layer B) is preferably 900kg/m ³ More preferably 920kg/m ³ Further preferably 930kg/m ³ . If the stiffness is lower than the above, the stiffness is weak and the processing may be difficult.

The upper limit of the density of the intermediate layer (layer B) is preferably 960kg/m ³ More preferably 940kg/m ³ Further preferably 935kg/m ³ 。

The polyethylene resin composition constituting the intermediate layer (B layer) of the polyethylene resin film of the invention may contain the above-mentioned organic lubricant, and the lower limit of the organic lubricant is preferably 100ppm. If it is lower than the above, the sliding property may deteriorate.

The upper limit of the organic lubricant in the polyethylene resin composition constituting the intermediate layer is preferably 2000ppm, more preferably 1500ppm. If the amount exceeds the above, excessive slip may cause winding displacement or whitening with time.

The intermediate layer (B layer) of the film of the present invention may be blended to such an extent that the quality of the recovered resin is not impaired.

In the present invention, the surface of the laminated layer (C layer) of the polyethylene resin film described above is preferably subjected to active ray treatment such as corona treatment. The lamination strength is improved by this countermeasure.

In the case where the polyethylene resin film of the present invention has 2 layers, the layer a may be a sealing layer, and the other layer may be a laminate layer (layer C).

(three-dimensional surface roughness SRa)

The three-dimensional surface roughness SRa of the sealing layer of the multilayer polyethylene resin 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 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 sealing layer of the multilayer polyethylene resin 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 as described in examples.

(maximum protrusion height SRmax)

The maximum protrusion height of at least one surface of the A layer of the polyethylene resin film of the present invention is required to be 2 μm or more and 15 μm or less. If the maximum protrusion height SRmax exceeds 15 μm, an appearance defect occurs, which is not preferable. The measurement method was performed as described in examples.

(Heat seal initiation temperature)

The upper limit of the heat-seal initiation temperature of the polyethylene resin film in which the laminate of the biaxially stretched nylon film (15 μm) and the polyethylene resin film is laminated is preferably 140 ℃, more preferably 130 ℃. If the above-mentioned amount exceeds, the sealing process may become difficult.

(attaining heat seal Strength)

The lower limit of the heat seal strength at 150℃of the polyethylene resin film in which the laminate of the biaxially stretched nylon film (15 μm) and the polyethylene resin film is laminated is preferably 30N/15mm, more preferably 35N/15mm. If it is lower than the above, the bag sometimes becomes easily ruptured after the bag is manufactured.

The upper limit of the heat seal strength at 150℃of the polyethylene resin film in which the laminate of the biaxially stretched nylon film (15 μm) and the polyethylene resin film is laminated is preferably substantially the same as the break strength of the nylon after lamination. When the strength was equal to the breaking strength of nylon, the lamination strength was sufficiently high, and the peel strength of the seal interface was sufficiently high. The measurement method was performed as described in examples.

(blocking Strength)

The lower the blocking strength of the polyethylene resin film of the laminate of biaxially stretched nylon film (15 μm) and the polyethylene resin film is, the more preferably 200mN/70mm or less, and even more preferably 150mN/70mm. If the content exceeds the above, the powder-free property, the opening property of the bag product, and the like cannot be sufficiently obtained. The measurement method was performed as described in examples.

(coefficient of friction)

The lower limit of the static friction coefficient of the polyethylene resin film in which the laminate of the biaxially stretched nylon film (15 μm) and the polyethylene resin film is laminated is preferably 0.05, more preferably 0.08. If the thickness is less than the above, the film may slip excessively during winding, which may cause winding displacement.

The upper limit of the static friction coefficient after lamination is preferably 0.70, more preferably 0.5. If the content exceeds the above, the opening property after the bag is produced and the filling property of the content is poor, and the loss during processing may increase.

The measurement method was performed as described in examples.

(haze)

The lower limit of the haze of the polyethylene resin film of the invention is preferably 3%, more preferably 4%, and still more preferably 5%. If the content is less than the above, the anti-blocking agent may not be sufficiently present on the surface, and may cause blocking.

The upper limit of the haze is preferably 18%, more preferably 16%, and further preferably 13%. If the content exceeds the above, visual recognition of the content may become difficult. The measurement method was performed as described in examples.

(flicker sense)

The polyethylene resin film of the present invention preferably has little or no perceived flicker, or has fine flicker but is uniform and is not particularly noticeable. The measurement method was performed as described in examples.

Conventionally, inorganic particles having an average particle diameter of about 10 μm have been added to so-called powder-free films having blocking resistance even when starch or the like is not scattered on the film surface, but in many cases, when coarse particles are included, flickering feeling and transparency tend to be poor.

(scratch resistance)

The laminate having the biaxially stretched nylon film (15 μm) and the polyethylene resin film laminated thereon is rubbed so that the polyethylene resin film surfaces overlap each other, and the change in haze is also preferably 3% or less, more preferably 2% or less, still more preferably 1% or less, and particularly preferably 0.5% or less. The measurement method was performed as described in examples.

In the past, inorganic particles having an average particle diameter of about 10 μm were sometimes added to so-called powder-free films having blocking resistance even when starch or the like was not scattered on the film surface, but the inorganic particles were far harder than the polyethylene resin, so that even if a sufficient organic lubricant was present on the film surface, the scratch resistance was easily poor.

(Young's modulus)

The lower limit of Young's Modulus (MD) of the polyethylene resin film of the invention is preferably 60MPa, more preferably 70MPa. If the stiffness is lower than the above, the stiffness is too low and the processing may be difficult. The upper limit of Young's Modulus (MD) is preferably 600MPa, more preferably 500MPa.

The lower limit of Young's modulus (TD) of the polyethylene resin film of the invention is preferably 60MPa, more preferably 70MPa. If the stiffness is lower than the above, the stiffness is too low and the processing may be difficult. The upper limit of Young's modulus (TD) is preferably 600MPa, more preferably 500MPa.

(laminate)

The multilayer film of the present invention may be used as a packaging film or a packaging sheet, which is a laminate of at least 1 other base film further laminated on the multilayer film of the present invention.

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

In this case, the base film is preferably adjacent to the laminated layer 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 multilayer polyethylene resin film, an adhesive layer, and another base film may 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 layer, the adjacent layers can be firmly bonded.

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

(packaging body)

The sealing layer surfaces of the sealing film of the laminate are made to face each other or the sealing layer surfaces of the sealing film layers of the laminate are made to face other base films, and thereafter, at least a part of the periphery thereof is heat-sealed from the laminate layer side so as to have a desired container shape, whereby a container can be produced. But also heat-seals all around, so that a sealed pouch container can be manufactured. When the molding process of the bag-like container is combined with the filling process of the content, that is, the bottom and side portions of the bag-like container are heat-sealed and then the content is filled, and then the upper portion is heat-sealed, the package can be manufactured. Therefore, the laminate can be used in an automatic packaging apparatus for solid, powder, or liquid materials such as snack foods.

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

Examples

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. The measurement values of the respective items in the detailed description and examples of the present invention were measured by the following methods.

Hereinafter, embodiments of the present invention will be described in detail.

(1) Method for measuring particles containing polyethylene resin

The pellets containing the polyethylene resin were measured for various physical properties of the raw material resin before processing.

Even after the film was formed, the film was completely dissolved in decane to form particles, and then the particles containing the polyethylene resin were separated by a method such as separating a portion having a high molecular weight by GPC.

(2) Viscosity average molecular weight of particles comprising polyethylene-based resin

Measured according to ASTM-D4020.

(3) Average particle diameter of particles comprising polyethylene resin

The average particle diameter of the particles formed of the polyethylene resin before use was measured as follows.

The particles were dispersed in ion-exchanged water stirred at a predetermined rotational speed (about 5000 rpm) using a high-speed stirrer, the dispersion was added to isotonic (physiological saline), and the particles were further dispersed in an ultrasonic disperser, and then the particle size distribution was obtained by the coulter counter method, and calculated as the average particle size.

(4) Particle size distribution of particles comprising polyethylene-based resin

The ratio of particles having a particle diameter of 30 μm or more in the particles formed of the polyethylene resin before use is calculated from the particle size distribution obtained by the Coulter counter method.

(5) Melting point of particles comprising polyethylene-based resin

The melting point of the pellets formed from the polyethylene resin before use was determined as follows: the measurement was performed by a SII Differential Scanning Calorimeter (DSC) at a sample amount of 10mg and a heating rate of 10 ℃/min. The melting endotherm temperature detected here was taken as the melting point.

(6) Density, MFR, melting point of polyethylene resin other than particles containing polyethylene resin

The raw materials before film formation were measured by the following methods.

The polyethylene resin forming the layer containing the particles of the polyethylene resin may be measured in the same manner as the solution obtained in the above (1) after filtration, by confirming the entire layer with an electron microscope or the like if it is a single layer, confirming the layer constitution with an electron microscope or the like if it is a laminate, and then cutting the surface at a thickness lower than the surface layer. In the case of cutting out from the laminate, the laminate may be laminated on a PET film or the like, and then the surface layer may be cut off by a razor or the like.

(Density)

According to JIS-K7112, measured according to the density gradient tube method.

(melt flow Rate: MFR) (g/10 min)

Measured at a temperature of 190℃according to JIS-K7210.

(melting point)

The measurement was performed by a SII Differential Scanning Calorimeter (DSC) at a sample amount of 10mg and a heating rate of 10 ℃/min. The melting endotherm temperature detected here was taken as the melting point.

(7) Content of inorganic particles in resin composition (wt%)

The content of the inorganic particles in the resin composition is calculated from the addition amount in the raw resin composition before processing.

Even after the film was formed, the film was dissolved at a temperature at which decane was completely dissolved, and inorganic particles were separated and measured by a method such as filtration of the residue using a filter having a filtration accuracy of 1 to 2 μm.

(8) Amount of residue after film incineration (ppm)

The film was measured with a precision balance for about 30g up to position 1 (rounded off at position 2) after the decimal point. The crucible was previously baked at 700℃for 1 hour, and then air-dried in a glass drier until room temperature was reached, and the weight of the crucible was measured. Then, a film was put in a crucible, burned in an electric furnace at 700 ℃ for 2 hours, after the heater was removed, the temperature was lowered to about 100 ℃, and then the crucible was transferred to a glass drier, and after air-drying for 30 minutes until room temperature was reached, the difference in weight of the crucible before and after the burning was divided by the weight of the film, and the amount of residue was calculated.

(9) Filter boost (film processing)

The resin composition used in the sealing layer of comparative example 1 was discharged at a resin temperature of 230℃for 5 hours at a discharge amount of 1 kg/hour to 81 pi square millimeters of the filtration area in the Naston sintered filter with a filtration accuracy of 120. Mu.m using a Trauton tester, and the pressure increase (DeltaMPa) at this time was classified into the following "excellent", "DeltaO", "X", respectively.

And (3) the following materials: the pressure increase was 5% or less at the start of extrusion.

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

Delta: the pressure increase was 15% or less at the start of extrusion.

X: the pressure increase was 20% or less at the start of extrusion.

(10) Die lip contamination (film forming processability)

The resin composition used in the sealing layer was extruded at 230℃for 5 hours using a strand die (5 mm. Phi., 2 holes) in an extruder at a discharge amount of 20 kg/hour, and the contamination of the die lip at this time was visually observed and classified into the following excellent materials (DeltaA), deltaA and X.

And (3) the following materials: die lip contamination was substantially undetectable.

O: die lip contamination was slightly visible.

Delta: die lip contamination can be clearly confirmed.

X: lip contaminants grow and streak-like depressions are created in the strand.

(11) Three-dimensional surface roughness SRa

According to JIS B0601-1994, 100 strips of film were measured with a low-area cut λs=0.08 mm, a length of 1000 μm, and a pitch of 2 μm at a position of 1mm×0.2mm on an arbitrary measurement surface of a film sheet from 3cm×3cm square, using a contact surface roughness (Ministry of Kogyo ET al, model ET 4000A).

Based on the obtained cross-sectional curve, the three-dimensional surface roughness SRa of the seal layer surface of the polyethylene resin multi-layer film was 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 SRx is determined by measuring n=3.

(12) Maximum protrusion height SRmax

The maximum protrusion height SRmax was calculated according to JIS B0601-1994 using the three-dimensional surface roughness analysis program TDA-22 from the obtained cross-sectional curve.

In the above method, the average value of the maximum protrusion height SRmax is obtained by measuring n=3.

(13) Heat seal initiation temperature (. Degree. C.)

On the corona surface of a nylon film (Toyo spun biaxially stretched nylon film: N1100, 15 μm), toyo-Morton, ltd. Dry lamination adhesive (TM 569, CAT-10L) was applied so that the solid content became 3g/m ² After the solvent was volatilized and removed in an oven at 80 ℃, the corona surface of the polyethylene resin film and the coated surface of the adhesive were sandwiched and laminated on a temperature control roller at 60 ℃. The laminated film was cured at 40℃for 2 days. The laminated sample thus produced was heat-sealed at a sealing pressure of 0.1MPa, a sealing time of 0.5 seconds and a sealing temperature of 90 to 160℃at a pitch of 10mm wide. The heat-sealed sample was cut into strips so that the heat-sealed width became 15mm, and the strips were attached to an Autograph (model: UA-3122 manufactured by Shimadzu corporation), the maximum value of the strength of peeling the sealing surface at a speed of 200 mm/min was measured at n number 3, and the heat-sealing strength and heat-sealing temperature at each temperature were plotted. The heat-seal temperature was read from the graph obtained by connecting the plots with a straight line to be 4.9N/15mm, and used as the heat-seal start temperature.

(14) Reaching the heat sealing strength (N/15 mm)

On the corona surface of a nylon film (Toyo spun biaxially stretched nylon film: N1100, 15 μm), toyo-Morton, ltd. Dry lamination adhesive (TM 569, CAT-10L) was applied so that the solid content became 3g/m ² Volatilizing the solvent in an oven at 80 DEG CAfter removal, the corona surface of the polyethylene resin film and the coated surface of the adhesive were sandwiched and laminated on a temperature control roller at 60 ℃. The laminated film was cured at 40℃for 2 days. The laminated sample thus produced was heat-sealed at a sealing pressure of 0.1MPa, a sealing time of 0.5 seconds and a sealing temperature of 120 to 190℃at a pitch of 10 mm. The heat-sealed sample was cut into strips so that the heat-sealed width became 15mm, and the strips were attached to an Autograph (model: UA-3122 manufactured by Shimadzu corporation), the maximum value of the strength of peeling the sealing surface at a speed of 200 mm/min was measured by n number 3, and the heat-sealed strength having the highest average value was regarded as the reaching seal strength.

(15) Adhesion Strength (mN/70 mm)

A laminated film with a nylon film (Toyo-spun biaxially oriented nylon film: N1100, 15 μm) was produced as follows.

On the corona surface of the nylon film, toyo-Morton, ltd. Dry lamination adhesive (TM 569, CAT-10L) was applied so that the solid content became 3g/m ² After the solvent was volatilized and removed in an oven at 80 ℃, the corona surface of the polyethylene resin film and the coated surface of the adhesive were sandwiched and laminated on a temperature control roller at 60 ℃. The laminated film was cured at 40℃for 2 days.

A sample (10 cm. Times.15 cm) having the surfaces of the layers A overlapped with each other was placed on a hot press (model SA-303, manufactured by TESTER SANGYO Co.) so that one end of an aluminum plate (2 mm thick) having a size of 7 cm. Times.7 cm was aligned at a position 1cm inside in the longitudinal direction (15 cm) at the center of the sample width (10 cm), and was subjected to a press treatment at a temperature of 50℃under a gauge pressure of 18MPa for 15 minutes.

The specimen bonded by the pressure treatment and a rod (diameter: 6 mm: aluminum) were mounted on an Autograph (model: UA-3122 manufactured by Shimadzu corporation), and the force at which the rod peeled off the bonded portion was measured at a speed (200 m/min).

In this case, the precondition is that the bar and the peeling surface are horizontal. For the same sample, 4 determinations were performed, expressed as an average.

(16) Coefficient of static friction

On the corona surface of the nylon film, toyo-Morton, ltd. Dry lamination adhesive (TM 569, CAT-10L) was applied so that the solid content became 3g/m ² After the solvent was volatilized and removed in an oven at 80 ℃, the corona surface of the polyethylene resin film and the coated surface of the adhesive were sandwiched and laminated on a temperature control roller at 60 ℃. The laminated film was cured at 40℃for 2 days. The coefficient of static friction between the polyethylene resin film faces of the laminated film obtained was measured in accordance with JIS-K-7125 under an atmosphere of 65% RH at 23 ℃.

(17) Haze degree

Only the polyethylene resin film was measured according to JIS-K-7105 using a direct-reading haze meter manufactured by Toyo Seisakusho Co., ltd.

Haze (%) = [ Td (diffuse transmittance%)/Tt (total light transmittance%) ×100

(18) Flicker sense

Only the polyethylene resin film was visually observed, and the flicker was classified into the following excellent, O, delta, and X.

And (3) the following materials: no substantial bright spots are perceived.

O: there is a fine bright spot but it is uniform and not particularly noticeable.

Delta: some of the spots were bright, and a foreign body sensation was felt.

X: the whole surface has bright spots, and the transparency is impaired.

(19) Scratch resistance (mechanical evaluation)

The scratch resistance was determined by a change in haze after 40 times of rubbing under a load of 200g by attaching sealing surfaces of a film to a An Tian precision vibration type friction tester (friction tester type II flat friction material 20X 20mm test piece table flat sliding arc length 100 mm) so that surfaces of polyethylene resin particles face each other. Haze was measured as follows: the haze of the center portion of the film (width×length=30 mm×180mm, 50×50mm for a flat friction material) before the film was attached to the friction plate was measured, and the haze at the same position was measured before and after the friction to determine the difference.

(20) Scratch resistance (visual evaluation)

On the corona surface of the nylon film, toyo-Morton, ltd. Dry lamination adhesive (TM 569, CAT-10L) was applied so that the solid content became 3g/m ² After the solvent was volatilized and removed in an oven at 80 ℃, the corona surface of the polyethylene resin film and the coated surface of the adhesive were sandwiched and laminated on a temperature control roller at 60 ℃. The laminated film was cured at 40℃for 2 days. The polyethylene resin film surfaces of the laminated films were laminated with each other, and were rubbed with a finger 10 times, and the ease of scratching was visually classified into excellent, good, [ delta ] and X as described below.

And (3) the following materials: substantially without scratches.

O: with fine streak-like scratches but without whitening.

Delta: fine striped dense and partially whitened is seen.

X: the rubbed area is substantially whitened.

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) Ube-Maruzen Polyethylene Co., ltd. UMERIT (registered trademark) 0540F (metallocene linear low density polyethylene, density 904 kg/m) ³ MFR4.0g/10 min, melting point 111 ℃)

(2) Sumitomo Chemical Co., ltd. SUMIKATHENTE (registered trademark) EFV402 (metallocene catalyst LLDPE, density: 913 kg/m) ³ MFR:3.8g/10 min, melting point: 115 ℃ C.)

(3) Sumitomo Chemical Co., ltd. SUMIKATHENTE (registered trademark) EFV405 (metallocene catalyst LLDPE, density: 923 kg/m) ³ MFR:3.8g/10 min, melting point: 118 ℃ C.)

(4) Sumitomo Chemical Co., ltd. SUMIKATHENTE (registered trademark) EFV407 (metallocene catalyst)LLDPE and density of the agent: 930kg/m ³ MFR:3.2g/10 min, melting point: 124 degree C

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

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

(particles comprising polyethylene resin)

(1) Mitsui Chemicals, inc. MIPELON PM200 (average particle size 10 μm, melting point 136 ℃, density 940 kg/m) ³ Particles having a viscosity average molecular weight of 180 ten thousand and a particle diameter exceeding 30 μm have a ratio of 0%, a resin hardness D65, and ultra-high molecular weight polyethylene particles

(2) Mitsui Chemicals, inc. MIPELON XM221U (average particle size 25 μm, melting point 136, density 940 kg/m) ³ Particles having a viscosity average molecular weight of 200 ten thousand and a particle diameter exceeding 30 μm were 25%, resin hardness D65, and ultra-high molecular weight polyethylene particles

(inorganic particles)

(1) Grefco.Inc., manufactured and used as Dicalite WF (diatomaceous earth, which was processed to an average particle size of 5 μm by a needle mill pulverizer)

(2) Shin-Etsu Silicon Co., ltd. Manufactured by KMP-130-10 (spherical silica particles, average particle diameter 10 μm) was used as 15% MB based on FV402 manufactured by Ltd. Manufactured by Sumitomo Chemical Co., ltd.

(masterbatch)

(1) A masterbatch (1) containing MIPELON PM200 15 wt% was prepared by mixing MIPELON PM200 with an EFV405 manufactured by SUMIKATHENE (registered trademark) of Sumitomo Chemical co.

(2) A masterbatch (2) containing 15 wt% of MIPELON XM221U was prepared by mixing MIPELON XM221U with EFV405 manufactured by SUMIKATHENE (registered trademark) by Sumitomo Chemical Co., ltd.

(3) A master batch (3) containing 20 wt% of grefco.inc., dicalite WF was prepared by mixing grefco.inc., ltd., majora sumikave (registered trademark) EFV405 with Sumitomo Chemical co., ltd.

(4) A masterbatch (4) containing Shin-Etsu Silicon Co.Ltd.manufactured by SUMIKATHENE (registered trademark) EFV405 was prepared by mixing Shin-Etsu Silicon Co.manufactured by Ltd.manufactured by KMP-130-10, and then mixing the mixture with the masterbatch.

(5) Erucamide was mixed with EFV402 manufactured by SUMIKATHENTE (registered trademark) by Sumitomo Chemical Co., ltd to prepare a master batch (5) containing 4 wt% erucamide.

(6) Ethylene bis-oleamide was mixed with EFV402 manufactured by SUMIKATHENE (registered trademark) by Sumitomo Chemical Co., ltd to prepare a master batch (6) containing 2 wt% of ethylene bis-oleamide.

Example 1

[ composition for sealing layer ]

Ube-Maruzen Polyethylene Co., ltd. UMERIT (registered trademark) 0540F was mixed so as to be 86.25 wt%, master batch (1) was 4 wt%, master batch (5) was 1.25 wt%, and master batch (6) was 8.5 wt%, to obtain a composition, and the obtained composition was used to prepare a composition for a sealing layer.

[ composition for laminate layer ]

A composition for a laminate layer was prepared using only Sumitomo Chemical co., ltd.

[ composition for intermediate layer ]

Sumitomo Chemical Co., ltd., FV402 was 99.4 wt%, a master batch (5) was 0.5 wt%, and a master batch (6) was 0.1 wt% were mixed to obtain a composition, and the obtained composition was used to prepare a composition for an intermediate layer.

Using an extruder having a T die, the thickness ratio of the laminate layer, the intermediate layer, and the sealing layer was 8:34:8, the composition for a laminate layer, the composition for an intermediate layer and the composition for a sealing layer were melt-extruded at 240 ℃. After that, corona discharge treatment is performed on the laminate layer surface. Then, the resultant was wound around a roll at a speed of 150 m/min to obtain a polyethylene resin multilayer film having a thickness of 50. Mu.m, and a wet tension of the treated surface of 45 mN/m.

Example 2

In the sealing layer, sumitomo Chemical Co., ltd. SUMIKATHENE FV402 (registered trademark) 86 wt%, masterbatch (1) 4 wt%, masterbatch (5) 1.50 wt%, and masterbatch (6) 8.5 wt% were mixed,

a polyethylene resin multilayer film and a vapor deposition film were obtained in the same manner as in example 1 except that only Sumitomo Chemical co., ltd. SUMIKATHENE (registered trademark) E FV405 was used as the laminated layer.

Example 3

A polyethylene resin multilayer film and a vapor deposition film were obtained in the same manner as in example 1, except that Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, 87.75 wt%, master batch (1) 4 wt%, master batch (5) 1.25 wt%, and master batch (6) 7 wt% were mixed in the sealing layer, and Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV402, which was used as a sealing layer, was Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, which was used as a sealing layer, and sumikatine (registered trademark) E FV407, which was used as a laminated layer, was used as a Sumitomo chemical co., ltd. Sumikatine (registered trademark) E FV 407.

Example 4

A polyethylene resin multilayer film and a vapor deposition film were obtained in the same manner as in example 1, except that Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, 84.75 wt%, master batch (1) 8 wt%, master batch (5) 1.25 wt%, and master batch (6) 6 wt% were mixed in the sealing layer, and Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV402 was changed to Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, and only Sumitomo chemical co., ltd. Sumikatine (registered trademark) E FV407 was changed to the laminate layer in the intermediate layer.

Example 5

In the sealing layer, ube-Maruzen Polyethylene Co., ltd. UMERIT (registered trademark) 3540F 86.75 wt%, masterbatch (1) 4 wt%, masterbatch (5) 1.75 wt%, and masterbatch (6) 7.5 wt% were mixed,

in the intermediate layer, sumitomo Chemical co., ltd. SUMIKATHENTE (registered trademark) E FV402 manufactured by SUMIKATHENTE is changed to Ube-Maruzen Polyethylene co., UMERIT (registered trademark) 3540F manufactured by Ltd,

a polyethylene resin multilayer film and a vapor deposition film were obtained in the same manner as in example 1 except that only Ube-Maruzen Polyethylene co., ltd, manufactured by UMERIT (registered trademark) 3540F was used as the laminated layer.

Example 6

A polyethylene-based resin multilayer film and a vapor deposition film were obtained in the same manner as in example 1 except that Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, 86.75 wt%, master batch (1) 4 wt%, master batch (3) 0.5 wt%, master batch (5) 1.25 wt%, and master batch (6) 7.5 wt% were mixed in the sealing layer, sumitomo chemical co., ltd. Sumikatine (registered trademark) E FV402 was Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, and sumikatine (registered trademark) E FV405, respectively, in the intermediate layer.

Example 7

A polyethylene-based resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, 87.25 wt%, master batch (1) 4 wt%, master batch (5) 1.25 wt%, and master batch (6) 7.5 wt% were mixed in the sealing layer, sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV402 was changed to Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, and Sumitomo chemical co., ltd. Sumikatine (registered trademark) E FV407 were changed to the laminate layer.

The polyethylene resin films obtained in examples 1 to 7 were also excellent in scratch resistance, low-temperature heat sealability, blocking resistance, slidability, and appearance because they contained substantially no inorganic particles having a particle size larger than the particles containing the polyethylene resin.

In addition, the residue generated during film burning is very small, and the film forming processability such as accumulated materials, filter boosting and the like is basically avoided.

Comparative example 1

In the sealing layer, sumitomo Chemical co., ltd. SUMIKATHENTE (registered trademark) EFV 405.25 wt%, masterbatch (3) 2.5 wt%, masterbatch (4) 8 wt%, masterbatch (5) 1.25 wt%, and masterbatch (6) 6 wt% were mixed. A polyethylene resin multilayer film and a vapor deposition film were obtained in the same manner as in example 1 except that Sumitomo chemical co., ltd. SUMIKATHENE (registered trademark) E FV402 was changed to Sumitomo Chemical co., ltd. SUMIKATHENE (registered trademark) E FV405, and only Sumitomo Chemical co., ltd. SUMIKATHENE (registered trademark) E FV405 was changed to the laminate layer in the intermediate layer.

The film obtained in comparative example 1 was excellent in blocking resistance and sliding property, but slightly flickering was observed, and the inorganic residue after incineration was large, and the scratch resistance was particularly poor, and the film-forming processability was also slightly poor.

Comparative example 2

A polyethylene-based resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, 90.25 wt%, master batch (3) 2.5 wt%, master batch (5) 1.25 wt%, and master batch (6) 6 wt% of each of the sealing layers were mixed, and Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV402, which was denoted by the intermediate layer, was denoted by the intermediate layer as Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, and only Sumitomo chemical co., ltd. Sumikatine (registered trademark) E FV405 was denoted by the laminate layer.

The film obtained in comparative example 2 had less residue and excellent flicker, but had poor blocking resistance, scratch resistance and sliding properties.

Comparative example 3

A polyethylene-based resin multilayer film and a vapor deposition film were obtained in the same manner as in example 1 except that Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, 1 wt% of master batch (1), 2.5 wt% of master batch (3), 1.25 wt% of master batch (5), and 7.5 wt% of master batch (6) were mixed in the sealing layer, sumitomo chemical co., ltd. Sumikatine (registered trademark) E FV402 was changed to Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, and the laminate layer was changed to Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV 405.

The film obtained in comparative example 3 had little residue and slightly excellent scratch resistance, but had few protrusions and poor blocking resistance.

Comparative example 4

In the sealing layer, ube-Maruzen Polyethylene Co., ltd. UMERIT (registered trademark) 4540F 87.25 wt%, masterbatch (1) 4 wt%, masterbatch (5) 1.25 wt%, and masterbatch (6) 7.5 wt% were mixed,

in the intermediate layer, sumitomo Chemical co., ltd. SUMIKATHENTE (registered trademark) E FV402 manufactured by SUMIKATHENTE is changed to Ube-Maruzen Polyethylene co., UMERIT (registered trademark) 4540F manufactured by Ltd,

a polyethylene resin multilayer film and a vapor deposition film were obtained in the same manner as in example 1 except that only Ube-Maruzen Polyethylene co., ltd, manufactured by UMERIT (registered trademark) 4540F was used as the laminated layer.

The film obtained in comparative example 4 had less residue and also had excellent scratch resistance, but the resin density was high, which resulted in unstable surface protrusions of polyethylene particles, insufficient blocking resistance and sliding properties, and large fluctuation.

Comparative example 5

A polyethylene-based resin multilayer film and a vapor-deposited film were obtained in the same manner as in example 1, except that Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, 87.25 wt%, master batch (2) 4 wt%, master batch (5) 1.25 wt%, and master batch (6) 7.5 wt% were mixed in the sealing layer, sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV402 was changed to Sumitomo Chemical co., ltd. Sumikatine (registered trademark) E FV405, and Sumitomo chemical co., ltd. Sumikatine (registered trademark) E FV407 were changed to the laminate layer.

The film obtained in comparative example 5 had little residue and excellent scratch resistance, but even if the amount of the additive was large, the protrusion density was low and the blocking resistance and the flicker feeling were poor due to the large particle size.

Comparative example 6

In the sealing layer, a polyethylene resin multilayer film and a vapor deposition film were obtained in the same manner as in example 1, except that a composition was obtained by mixing Ube-Maruzen Polyethylene Co., ltd. UMERIT (registered trademark) 0540F of 86.25 wt%, master batch (1) of 4 wt%, master batch (5) of 1.25 wt%, and master batch (6) of 5.0 wt% of the sealing layer, and the obtained composition was used to prepare a composition for sealing layer.

Comparative example 7

A polyethylene resin multilayer film and a vapor deposition film were obtained in the same manner as in example 2, except that Sumitomo Chemical co., ltd. Company, SUMIKATHENE (registered trademark) E FV402 95.90 wt%, master batch (1) 4 wt%, master batch (5) 1.25 wt%, and master batch (6) 5.0 wt% were mixed in the sealing layer to obtain a composition, and the obtained composition was used to prepare a sealing layer composition.

The results are shown in tables 1 and 2.

TABLE 1

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TABLE 2

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The polyethylene resin film of the present invention has been described above with reference to several examples, but the present invention is not limited to the configurations described in the above examples, and the configurations described in the respective examples may be appropriately combined and the configurations may be appropriately modified within a range not departing from the gist thereof.

Industrial applicability

The polyethylene resin film of the present invention is excellent in characteristics, and therefore can be suitably used for a wide range of applications such as food packaging.

Claims

1. A polyethylene resin film comprising at least an A layer comprising a polyethylene resin composition, wherein the polyethylene resin composition constituting the A layer satisfies the following 1) to 3), and wherein at least one surface of the A layer satisfies the following 4) and 5),

1) Comprising a density of 900kg/m ³ Above and 935kg/m ³ The following polyethylene-based resin was used as a resin,

2) Contains particles containing a polyethylene resin, the particles having an average particle diameter of 5 to 20 [ mu ] m and not containing particles having a particle diameter of 30 [ mu ] m or more, the content of the particles being 0.2 to 2.0% by mass relative to the polyethylene resin composition,

3) The content of the organic lubricant is 0.16 wt% or more,

4) The three-dimensional surface roughness SRa is 0.05-0.2 mu m,

5) The maximum mountain height SRmax is 2-15 mu m.

2. A polyethylene resin film comprising at least one layer A comprising a polyethylene resin composition, wherein the polyethylene resin composition constituting the layer A satisfies the following 1) to 3), and wherein at least one surface of the layer A satisfies the following 4) and 5),

1) Density of 900kg/m ³ Above and 935kg/m ³ In the following the procedure is described,

3) The content of the organic lubricant is 0.16 wt% or more,

4) The three-dimensional surface roughness SRa is 0.05-0.2 mu m,

5) The maximum mountain height SRmax is 2-15 mu m.

3. The polyethylene-base resin film according to claim 1 or 2, wherein the particles comprising the polyethylene-base resin have a resin hardness of D70 or less.

4. The polyethylene resin film according to any one of claims 1 to 3, wherein the particles comprising the polyethylene resin have a viscosity average molecular weight of 150 ten thousand or more.

5. The polyethylene resin film according to any one of claims 1 to 4, wherein the average particle diameter of the particles of the polyethylene resin is 5 to 15. Mu.m.

6. The polyethylene-base resin film according to any one of claims 1 to 5, wherein the adhesion value between the A-layer surface layers is 200mN/70mm or less.

7. The polyethylene resin film according to any one of claims 1 to 6, wherein the a-layer surface layers are attached to each other in a An Tian precision mechanical vibration type abrasion tester, and the change in haze after abrasion 100 times under a load of 200g is 3% or less.

8. A laminate, comprising: the polyethylene resin film according to any one of claims 1 to 7, and a base film comprising a thermoplastic resin composition.

9. A package comprising the laminate of claim 8.