JP2018154133A - Film and packaging bag using plant-derived polyethylene-based resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a film using a plant-derived polyethylene-based resin being a renewable resource as a raw material to enable oil-resource saving, as well as being environment-friendly by reducing carbon dioxide output, and also to provide a packaging bag using the film.SOLUTION: A film is a film having a single layer constitution including a polyethylene-based resin composition or a film having a multilayer constitution including at least one layer composed of a polyethylene-based resin composition, and formed through extrusion molding by a T-die method. The polyethylene-based resin composition includes a plant-derived polyethylene-based resin selected from a plant-derived high-density polyethylene or a plant-derived linear low-density polyethylene.SELECTED DRAWING: Figure 3

Description

  The present invention relates to a film comprising a polyethylene resin composition, and more specifically, at least one plant-derived polyethylene system selected from plant-derived high-density polyethylene (HDPE) or plant-derived linear low density (LLDPE). The present invention relates to a film made of a polyethylene resin composition containing a resin and a packaging bag using the film.

  2. Description of the Related Art Conventionally, packaging bags represented by refilling shampoos and rinses, pouches used as packaging materials for foods and the like are made of a packaging material composed of a sealant film and a base film. In order to cope with environmental problems and the saving of petroleum-depleted resources such as oil, ethylene-α is added to polylactic acid-based resin as a carbon-neutral material for the purpose of reducing the amount of petroleum resources used in packaging materials. A packaging bag containing a biodegradable resin containing a predetermined amount of an olefin copolymer and a polymer having an epoxy group (for example, Patent Document 1) is known.

JP 2009-155516 A

  However, as described above, such a packaging bag contains a biodegradable resin other than petroleum-derived raw materials in the resin composition constituting the packaging bag to reduce the ratio of petroleum-derived raw materials. Compared to the above, there is a problem that workability such as tensile strength, seal strength and waist is remarkably inferior, and productivity cannot be improved.

  Accordingly, an object of the present invention is to use a plant-derived polyethylene resin, which is a renewable resource, as a raw material, to save petroleum resources, and to use an environmentally friendly film by reducing carbon dioxide emissions and the film. The object is to provide a packaging bag having excellent processability.

  Another object of the present invention is to provide a film as described above by extrusion molding by a T-die method.

As a result of various studies, the present inventors have found that a film characterized by the following points and a packaging bag using the film achieve the above object.
1. It is a film having a single-layer structure composed of a polyethylene-based resin composition, or a film having a multilayer structure including at least one layer composed of the polyethylene-based resin composition, and is extruded by a T-die method, The above-mentioned film, wherein the polyethylene resin composition contains a plant-derived polyethylene resin selected from plant-derived HDPE or plant-derived LLDPE.
2. 2. The film according to 1 above, wherein the plant-derived polyethylene resin has a melt flow rate (MFR) of 2.4 to 8.0 g / 10 minutes.
3. The plant-derived LLDPE has a density of 910 to 925 kg / m ³ and is an ethylene-α-olefin copolymer of plant-derived ethylene and petroleum-derived comonomer, wherein the petroleum-derived comonomer comprises butene-1, hexene The film according to 1 or 2 above, which is -1, or a mixture thereof.
4). Characterized in that it has a biomass degree calculating from measurements of radiocarbon dating C ^14, the film according to any one of the above 1 to 3.
5. The blending amount of the plant-derived polyethylene resin is 5 to 90% by mass with respect to the entire film, the blending amount of the petroleum-derived polyethylene resin is 10 to 95% by mass, and the following (A) or (B) 5. The film according to any one of 1 to 4 above, which has a configuration.
(A) Single layer configuration made of the polyethylene resin composition (B) Multilayer configuration having an intermediate layer made of the polyethylene resin composition, and an outer layer and an inner layer made of petroleum-derived polyethylene resin. A laminated film, wherein the film according to any one of 1 to 5 is used as a sealant film and laminated with a base film.
7). A packaging bag formed by using a laminated film obtained by laminating the film according to any one of 1 to 5 as a sealant film and a base film.
8). 8. The packaging bag according to 7 above, wherein the packaging bag is a refilling standing pouch.

  Hereinafter, a polyethylene resin composition containing a plant-derived polyethylene resin selected from the above-mentioned plant-derived HDPE or plant-derived LLDPE is referred to as a “polyethylene resin composition of the present invention”.

  The film of the present invention includes a plant-derived polyethylene resin selected from plant-derived HDPE or plant-derived LLDPE, so that there is no difference in performance from a film made of petroleum-derived polyethylene resin, and the use of petroleum resources. In addition to reducing the amount, carbon dioxide emissions during film production and disposal can be suppressed.

  Accordingly, it is possible to provide a film made of a polyethylene resin with reduced environmental burden. Moreover, since it is extrusion-molded by the T-die method, it is possible to provide a film having a uniform thickness and a low cost.

  Moreover, as a plant-derived polyethylene resin used in the film of the present invention, a resin having an MFR of 2.4 to 8.0 g / 10 min can be used to produce a homogeneous film at the time of extrusion molding by the T-die method. Can be manufactured.

The plant-derived LLDPE used in the film of the present invention has a density of 910 to 925 kg / m ³ , plant-derived ethylene, and plant-derived or petroleum-derived butene-1.
By using an ethylene-α-olefin copolymer with hexene-1 or a mixture thereof, the film has a suitable tensile strength, sealing strength and waist as a packaging bag, for example a standing pouch for refilling, and has excellent processing Show aptitude.

The film of the present invention has a biomass degree to calculate from the measured value of radiocarbon dating C ^14, a raw material derived from a polyethylene-based resin constituting the film can be identified by the biomass degree index, the film The raw material can be confirmed from the time of manufacture to the time of disposal.

  Therefore, it is possible to provide a film made of a polyethylene-based resin that can be identified from the raw material.

Furthermore, in one embodiment of the present invention, the film of the present invention has a blending amount of the plant-derived polyethylene resin of 5 to 90% by mass and a blending amount of the petroleum-derived polyethylene resin with respect to the whole film of 10 to 95. And has the following constitution (A) or (B):
(A) Single-layer structure which consists of said polyethylene-type resin composition (B) The multilayer structure which has the intermediate | middle layer which consists of said polyethylene-type resin composition, and the outer layer and inner layer which consist of petroleum origin polyethylene-type resin.

  Therefore, the ratio of petroleum-derived polyethylene-based resins constituting the film can be reduced, the amount of petroleum resources used can be reduced, and carbon dioxide emissions during film production and disposal can be suppressed.

  In addition, by using a petroleum-derived polyethylene resin for the inner and outer layers constituting the film as in (B), the film can be produced with the characteristics of existing production processes.

  Therefore, it is possible to provide a film made of a polyethylene-based resin with reduced petroleum resources and reduced environmental burden.

  In addition, the film of the present invention containing a plant-derived polyethylene resin is used as a sealant film, and the laminated film laminated with the base film reduces the amount of petroleum resources used and emits carbon dioxide during production and disposal of the laminated film. The amount can be suppressed. Therefore, it is possible to provide a laminated film made of a polyethylene-based resin with reduced petroleum resources and reduced environmental burden.

  Moreover, the packaging bag which uses the film of this invention containing a plant origin polyethylene-type resin as a sealant film, and uses the lamination film laminated | stacked with the base film is a petroleum origin of the polyethylene-type resin in the lamination film which comprises a packaging bag. The use ratio can be reduced, the amount of petroleum resources used can be reduced, and the amount of carbon dioxide emitted during the production and disposal of the packaging bag can be suppressed. Accordingly, it is possible to provide a packaging bag made of a polyethylene-based resin with reduced oil resources and reduced environmental burden.

  Furthermore, the packaging bag of the present invention may be a refilling standing pouch, which can reduce the ratio of petroleum-derived use of polyethylene-based resin that constitutes a packaging bag that is widely available in the world as a disposable, and the amount of petroleum resources used. In addition, the amount of carbon dioxide emitted during the manufacture and disposal of the packaging bag can be reduced. Accordingly, it is possible to provide a packaging bag made of a polyethylene-based resin with reduced oil resources and reduced environmental burden.

It is a flowchart which shows an example of polyethylene manufacture derived from sugarcane. It is a cross-sectional side view which shows typically the film of the single layer structure which consists of a polyethylene-type resin composition of this invention. It is a sectional side view showing typically the film which consists of a multilayer structure which has the intermediate layer which consists of a polyethylene system resin composition of the present invention, and the outer layer and inner layer which consist of petroleum origin polyethylene system resin. It is a section side view showing typically an example of the lamination film of the present invention. It is a perspective view which shows the standing pouch as an example of the packaging bag formed using the laminated | multilayer film of this invention.

The best mode for carrying out the present invention will be described below with reference to the drawings.
Packaging bags exemplified by containers such as laminated tubes used for foods and cosmetics, and standing pouches widely used as packaging materials for refilling shampoos and rinses are composed of laminated films.

  This laminated film includes a base film that is laminated with a sealant film that becomes the inner surface of the laminated film. As the material of the base film, for example, a polyethylene resin or the like is used. In order to form a sealant film, for example, a linear low density or high density polyethylene with an intermediate layer interposed therebetween is used as a laminate.

  In this way, polyethylene-based resins, which are plastic resins, are often used as the material of the laminated film, but these polyethylene-based resins are manufactured using petroleum as a starting material. Low-density polyethylene is a copolymer of ethylene obtained by refining crude oil and α-olefin, which is a comonomer species, in the presence of a metallocene catalyst at a high temperature such as 120 ° C. or higher in the gas phase. .

The α-olefin is a propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene represented by the general formula R—CH═CH ₂ (wherein R is an alkyl group having 1 or more carbon atoms). Examples include heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene and octadecene.

  The metallocene catalyst is not particularly limited. For example, a cyclopentadienyl group, a substituted cyclopentadienyl group (substituted cyclopentadienyl group), an indenyl group, a substituted indenyl group, , A transition metal compound belonging to Group 4 of the periodic table having a ligand in which one group selected from a fluorenyl group and a substituted fluorenyl group has been crosslinked by a crosslinking group.

  Typical examples are diphenylmethylene (1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclohexane). Pentadienyl) (2,7-dimethyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1 -Indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (2,7-di Dimethyl body t- butyl-9-fluorenyl) zirconium dichloride dichloro body and the metallocene compounds such as diethyl body, dihydro derivative, diphenyl body, metallocene catalyst comprising as a main component a metallocene compound to illustrate the dibenzyl and the like are used.

The metallocene catalyst is, for example, a cyclopentadienyl group, a substituted cyclopentadienyl group (substituted cyclopentadienyl group), an indenyl group, a substituted indenyl group, a fluorenyl group, One group selected from substituted fluorenyl groups is a transition metal compound of Group 4 of the periodic table having a ligand bridged by a bridging group, and a typical example thereof is diphenylmethylene (1-cyclopentadiene). Enyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7-dimethyl-9 -Fluorenyl) zirconium dichloride, diphenylmethylene (1-si Lopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (9-fluorenyl) ) Zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride and the like, and dimethyl, diethyl and dihydro forms of the above metallocene compounds, The main component is a metallocene compound that exemplifies diphenyl, dibenzyl and the like.

  However, with the desire to conserve oil and other depleted resources and the growing awareness of environmental issues such as global warming due to an increase in carbon dioxide emissions, polyethylene-based resins derived from petroleum as described above are discarded from the production of petrochemical products. In the meantime, the fixed carbon dioxide possessed by the petroleum raw material is exhausted in large quantities, so that the above-mentioned orientation cannot be met.

Therefore, in recent years, development of technology for producing plastics from plants, which are carbon neutral and renewable resources, has progressed. Among them, polyethylene, which is most frequently used in plastics, is the biomass type. Technology for producing sugarcane as a starting material has been established (Edited by Processing Technology Study Group, Convertec 2009.9, P63-67).
Carbon neutral means that the amount of carbon dioxide absorbed during plant growth is substantially the same as the amount of carbon dioxide emitted during combustion.

  FIG. 1 is a flow diagram showing an example of the production of sugarcane-derived polyethylene. FIG. 2 is a cross-sectional side view schematically showing a film made of a polyethylene resin composition containing a sugarcane-derived polyethylene resin of the present invention.

  As shown in FIG. 1, crude sugar obtained by heating and concentrating sugar solution taken from sugarcane cut from a field and crystallized from waste sugar are separated by a centrifuge. The waste molasses is then diluted with water to an appropriate concentration and fermented with yeast to produce ethanol. Then, this bioethanol is heated to polymerize ethylene obtained by an intramolecular dehydration reaction in the presence of a catalyst with a polymerization catalyst to obtain polyethylene. It has been confirmed that plant-derived ethylene and polyethylene have the same quality as petroleum-derived ethylene and polyethylene.

  Therefore, the plant-derived polyethylene resin used in the film of the present invention is LLDPE or HDPE produced from ethylene using the above starting material as a plant. These can be produced in the same manner as when a polyethylene resin is produced from petroleum-derived ethylene. That is, plant-derived LLDPE can be produced by copolymerizing plant-derived ethylene and α-olefin by a gas phase polymerization method in the presence of a metallocene catalyst. Moreover, HDPE with few branches can be produced by polymerizing the above plant-derived ethylene in the presence of a Ziegler catalyst or a Philips catalyst at medium or low pressure.

In the present invention, by producing a film that forms a laminated film comprising a packaging bag using the plant-derived polyethylene resin obtained as described above, in the resin composition used for the laminated film, petroleum-derived By reducing the resin usage ratio, it is possible to save petroleum resources and contribute to improving the environment by reducing carbon dioxide emissions.
The manufacturing method of this film is not specifically limited, It can manufacture by a conventionally well-known method.

  In the present invention, it is preferable to produce by extrusion molding, and it is possible to form a film with a uniform thickness, to enable high-speed cooling and high-speed film formation, and excellent productivity. It is particularly preferred to produce.

In the present invention, production of a film by extrusion molding can be performed, for example, as follows. That is, a resin composition used for a film is dried, and a melting extruder heated to a temperature of the melting point + 70 ° C. (Tm + 70) from the melting point (Tm) of the resin in the resin composition,
The dried resin composition is supplied and melted.

Next, a film can be produced by extruding the molten resin composition into a sheet shape by a die such as a T die, and rapidly solidifying the obtained sheet material with a rotating cooling drum or the like. .
As the melt extruder, a single screw extruder, a twin screw extruder, a vent extruder, a tandem extruder, or the like can be used depending on the purpose.

  In the present invention, a film F1 as shown in FIG. 2 is used by using a resin composition 1 containing LLDPE or HDPE derived from the above-mentioned sugarcane (which is not limited to sugarcane but may be a plant that is a raw material for producing a polyethylene resin). It can be.

The sugarcane-derived LLDPE has a density of 910 to 925 kg / m ³ and a melt flow rate (MFR) in the range of 2.4 to 8.0 g / 10 min. Alternatively, it may be an ethylene-α-olefin copolymer with a petroleum-derived comonomer, and the comonomer may be any α-olefin such as butene-1, hexene-1, or a mixture thereof.

The sugar cane-derived HDPE can have physical properties of a density of 941 to 965 kg / m ³ and a melt flow rate (MFR) of 2.4 to 8.0 g / 10 min.

In the above physical property evaluation, the density (d, unit: kg / m ³ ) was measured according to JIS K 6760 (1981) using a 1 mm thick sheet obtained by press molding at 150 ° C. It is.

The melt flow rate (MFR, unit: g / 10 minutes) is measured according to JIS K 7210 (1995) at a test temperature of 190 ° C. and a test load of 21.18 N.

  In a preferred embodiment, the polyethylene resin composition constituting the film of the present invention contains the plant-derived LLDPE or HDPE in an amount of up to 90% by mass, more preferably in an amount of 5 to 90% by mass. Moreover, 1 aspect of this invention WHEREIN: The said polyethylene-type resin composition contains 5-90 mass% of plant origin LLDPE or HDPE, and 10-95 mass% of petroleum origin polyethylene resins.

Further, the polyethylene resin from the sugarcane, biomass degree of radiocarbon dating C ¹⁴ is a polyethylene-based resin is used having a 80% to 100%.

  Here, plant (biomass) -derived and petroleum-derived resins do not cause differences in physical properties such as molecular weight, mechanical properties, and thermal properties. Therefore, in order to distinguish these, the biomass degree is generally used.

In this biomass, carbon of petroleum-derived resin does not contain C ¹⁴ (radiocarbon 14, half-life 5730 years). Therefore, the concentration of C ¹⁴ is measured by accelerator mass spectrometry, and the resin composition contains It is used as an index of the content ratio of plant-derived resin. Therefore, if it is a film using plant-derived resin, the biomass degree according to content of plant-derived resin is obtained by measuring the biomass degree of the film.

The biomass degree is measured by burning a sample to be measured to generate carbon dioxide, reducing carbon dioxide purified by a vacuum line with hydrogen using iron as a catalyst, and generating graphite. Then, this graphite is mounted on a C ¹⁴ -AMS dedicated device (manufactured by NEC) based on a tandem accelerator, and C ¹⁴ count, C ¹³ concentration (C ¹³ / C ¹² ), C ¹⁴ concentration (C was measured in ¹⁴ / C ^12), calculates the ratio of the C ¹⁴ concentration of the sample carbon to standard modern carbon from the measurement value.

In this measurement, oxalic acid (HOXII) provided by the National Bureau of Standards (NIST) was used as a standard sample.

  In the present invention, since a film made of such a resin composition is used to make all of the resin derived from petroleum, this petroleum-derived polyethylene resin does not differ in performance from petroleum-derived polyethylene resin. The carbon dioxide emission at the time of film manufacture and disposal can be suppressed by hybridizing (substituting) plant-derived polyethylene resins.

Moreover, in this invention, as plant origin polyethylene-type resin contained in the polyethylene-type resin composition 1, a comonomer seed | species is butene-1, hexene-1, or these mixtures, Comprising: A density is 910-925 kg / m < ³ >, A plant-derived ethylene-α-olefin copolymer (LLDPE) having a melt flow rate of 2.4 to 8.0 g / 10 min, or a density of 941 to 965 kg / m ³ and a melt flow rate of 2.4 to 8 By using HDPE of 0.0 g / 10 min, it is possible to produce a film having no physical difference from petroleum-derived polyethylene resin in an existing film production process. Therefore, the raw material can be switched without impairing the processability of the packaging material.

Further, the resin composition 1 of the present invention has a biomass degree to calculate from the measured value of radiocarbon dating C ^14, a raw material derived from a polyethylene-based resin constituting the film can be identified by the biomass degree index The origin material from the time of manufacture of a film to the time of disposal can be confirmed.

  The MFR of plant-derived LLDPE or plant-derived HDPE constituting the film of the present invention is preferably 2.4 to 8.0 g / 10 min. And in order to show a high degree of biomass and to obtain favorable tensile strength and seal strength as a packaging bag, the MFR is more preferably 2.5 to 3.0 g / 10 min. In order to produce a film having a high degree of biomass and a uniform film thickness at high speed by extrusion molding by the T-die method, the MFR is more preferably larger than 4.0, for example, 4 About 1 to 8.0 g / 10 minutes.

  Next, in this invention, it can be set as the following film structures with the resin composition 1 mentioned above and the petroleum origin polyethylene-type resin 2 mentioned later.

  That is, the following (A) or so that the blending amount of the plant-derived polyethylene resin is 5 to 90% by mass and the blending amount of the petroleum-derived polyethylene resin is 10 to 95% by mass with respect to the entire film. A film can be comprised in the way of (B).

  First, as shown in FIG. 2, the film F <b> 1 (A) can have a single-layer configuration made of the polyethylene resin composition 1 of the present invention. Here, the polyethylene resin composition 1 of the present invention contains 5 to 90% by mass of a plant-derived polyethylene resin and 10 to 95% by mass of a petroleum-derived polyethylene resin.

Moreover, as shown in FIG. 3, the film F2 of (B) has a multilayer structure having an intermediate layer made of the polyethylene resin composition 1 of the present invention, and an outer layer and an inner layer made of petroleum-derived polyethylene resin. Can do. Here, the polyethylene resin composition 1 of the present invention contains the plant-derived polyethylene resin at a concentration such that the blending amount of the plant-derived polyethylene resin with respect to the entire film is 5 to 90% by mass.

  By setting it as such a structure, the use ratio derived from petroleum of the polyethylene-type resin which comprises a film can be reduced, and the carbon dioxide emission amount at the time of film manufacture and disposal can be suppressed. In addition, by using the petroleum-derived polyethylene resin 2 for the inner and outer layers constituting the film F2 as in (B), the film F2 can be manufactured with the characteristics of the existing manufacturing process. These multilayer films can be produced by coextrusion molding.

Next, in this invention, it can be set as the laminated film using the said films F1-F2. FIG. 4 is a cross-sectional side view schematically showing an example of a laminated film, and FIG. 5 is a perspective view showing a standing pouch as an example of a packaging bag formed using the laminated film of the present invention.
As shown in FIG. 4, the laminated film 3 is laminated with the base film 5 using any one of the films F <b> 1 to F <b> 2 as a sealant film 4.

  Examples of the base film 5 include polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), and acrylonitrile-butadiene-styrene copolymer (ABS resin). ), Polyvinyl chloride resins, fluorine resins, poly (meth) acrylic resins, polycarbonate resins, polyester resins such as polyethylene terephthalate and polyethylene naphthalate, polyamide resins such as various nylons, polyimide resins, polyamides Imido resin, polyaryl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyurethane resin, acetal resin, cellulose resin, etc. It may be used fat film or sheet.

  With such a configuration, it is possible to reduce the use ratio of the petroleum-derived polyethylene resin constituting each of the films F1 to F2 of the sealant film 4 used for heat sealing. Carbon dioxide emissions during production and disposal can be suppressed.

  Using the laminated film 3 as described above, the sealant films 4 of the two side sheets made of the laminated film 3 are arranged to face each other, and the sealant film 4 is laminated on at least one side of the lower end portion of the laminated film 3. A bottom sheet made of a laminate is inserted into the center with the sealant film 4 facing outside, and is formed into a form having a gusset portion. A semicircular bottom sheet cutout is provided, and the gusset portion is heat-sealed by a bottom-shaped bottom seal portion including a peripheral portion to form a bottom portion.

  Next, both side edge portions of the two front and back side sheets are heat-sealed with side edge seal portions to form a body portion, and the upper end portion is left as a filling port for contents, as shown in FIG. A pouch (packaging bag) formed in a standing pouch form is formed. And the upper seal part provided in the filling port of the upper end part is sealed by heat sealing with, for example, a degassing seal after filling the contents from this part. In addition, although not shown in figure, you may form the spout part which provided the cut line for opening in the upper part of a trunk | drum with a laser.

With such a configuration, the use ratio of the polyethylene-derived resin derived from petroleum in the laminated film 3 constituting the packaging bag 6 can be reduced, and at the time of manufacturing and disposal of the packaging bag 6 as well as saving petroleum resources. Carbon dioxide emissions can be suppressed. In particular, since this packaging bag 6 is a refilling standing pouch, it is possible to reduce the use ratio of petroleum-derived polyethylene resin that constitutes such a disposable packaging bag and to greatly suppress carbon dioxide emissions. it can.

  In addition to the packaging bag 6 exemplified by the above-described standing pouch, using the films F1 to F2 made of the polyethylene resin composition 1 of the present invention and the laminated film 3 using these films F1 to F2, It is possible to configure containers such as laminated tubes, liquid paper containers, etc. that contain contents such as food, drinks, cosmetics, medicines, miscellaneous goods, container lids, container labels, etc. As well as reducing the carbon dioxide emission, the carbon dioxide emission can be greatly suppressed.

  Next, the Example of the film comprised using the polyethylene-type resin composition 1 of this invention is demonstrated.

[Example 1]
Using a screw diameter 30 mmφ extruder, C4LL-LL318 (d = 0.918, MFR = 2.7 g / 10 min) manufactured by Brasschem, which is LLDPE derived from sugar cane, is melt-kneaded at 200 ° C., and the polyethylene resin of the present invention A composition was obtained.

  Next, the film F1 shown in FIG. 2 having a thickness of 120 μm could be formed by molding the resin composition with a T die cast film forming machine under the processing conditions of an extrusion temperature of 220 ° C. and a rotation speed of 45 rpm. The degree of biomass was measured and was about 88%. Moreover, this film had a uniform appearance and a beautiful appearance. The comonomer species butene-1 (C4) contained in the sugarcane-derived LLDPE is derived from petroleum, and its content is 1 to 15 mol% (the same applies hereinafter).

  On the other hand, as Comparative Example 1, using C6LL-Evolue SP2040 (d = 0.918, MFR = 3.8 g / 10 min) 100% manufactured by Prime Polymer Co., Ltd. derived from petrochemicals, as in Example 1, It was melt-kneaded at 200 ° C. and formed into a 120 μm-thick film under the processing conditions of an extrusion temperature of 220 ° C. and a rotation speed of 45 rpm. The degree of biomass was measured and found to be 0%.

  The following physical property evaluation tests were conducted on the resin compositions of Example 1 and Comparative Example 1, and the results obtained are described below.

  As described above, the film of the present invention made of a polyethylene resin composition containing plant-derived LLDPE has the same physical properties as a film made only of petrified LLDPE, and exhibits good tensile strength, manufacturing processability and seal strength. It was.

[Test method]
The tensile strength at break (elongation) was measured using a Tensilon universal testing machine with reference to JIS-Z1702.
Test speed 500 mm / min. N = 3 JIS-K7127 test piece type 5 (dumbbell piece: minimum parallel width 6 mm, distance between chucks 80 mm).
The waist was measured using a loop stiffness tester at a loop length of 60 mm, a sample width of 15 mm, N = 3, and a crushing distance of 17 mm (scale 3).
The seal strength is a heat seal tester TP-701S, PET 12 μm is placed on the evaluation sample, sealed at 180 ° C. × 1 kgf / cm ² × 1.0 second, a strip sample having a width of 15 mm is cut out, and Tensilon Universal Test Machine test speed 300mm / min.N
= 3.

[Example 2]
In the same manner as in Example 1, using a 30 mm diameter screw extruder, Brass Chem C4LL-LL318 (d = 0.918, MFR = 2.7 g / 10 min) which is LLDPE derived from sugar cane and C6LL- from Prime Polymer Co., Ltd. Evolue SP2040 (d = 0.918, MF
R = 3.8 g / 10 min) was kneaded and melted at a mass ratio of 7: 3 at 200 ° C. to obtain a polyethylene resin composition of the present invention. Next, the film F1 shown in FIG. 2 having a thickness of 120 μm could be formed by molding the resin composition with a T die cast film forming machine under the processing conditions of an extrusion temperature of 220 ° C. and a rotation speed of 45 rpm.
The degree of biomass was measured and was about 59%. Moreover, this film had a beautiful appearance with a uniform film thickness, and was excellent in tensile strength, suitability for production and seal strength.

[Example 3]
In the same manner as in Example 1, using a 30 mm diameter screw extruder, Brass Chem SHC7260 (d = 0.959, MFR = 7.2 g / 10 min), which is HDPE derived from sugar cane, was kneaded and melted at 200 ° C. A polyethylene resin composition was obtained. Next, the film F1 shown in FIG. 2 having a thickness of 120 μm could be formed by molding the resin composition with a T die cast film forming machine under the processing conditions of an extrusion temperature of 220 ° C. and a rotation speed of 45 rpm. The degree of biomass was measured and was about 95%. Moreover, this film had a beautiful appearance with a uniform film thickness, and was excellent in tensile strength, suitability for production and seal strength.

[Example 4]
As in Example 1, using a 30 mmφ screw diameter extruder, 50% by mass of Brass Chem C4LL-LL118 (d = 0.916, MFR = 1.0 g / 10 min), which is LLDPE derived from sugar cane, derived from petroleum 50 parts by mass of Ube Maruzen polyethylene LDPE-F120N (d = 0.920, MFR = 1.2 g / 10 min) which is LLDPE was melt-kneaded at 200 ° C. to obtain a polyethylene resin composition of the present invention.

  Next, the resin composition was formed into a film F1 shown in FIG. 2 having a thickness of 130 μm by a T die cast film forming machine under processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm. The degree of biomass was measured and was about 44%. Moreover, this film had a beautiful appearance with a uniform film thickness, and was excellent in tensile strength, suitability for production and seal strength.

[Example 5]
As the resin for the first layer (inner layer) and the third layer (outer layer), Mitsui Chemicals C6LL-Evolution SP2020 (d = 0.916, MFR = 2.3 g / 10 min) was used using a screw diameter 30 mmφ extruder. Melt-kneading was performed at 200 ° C. to prepare a petroleum-derived polyethylene resin. Similarly, as the resin for the second layer (intermediate layer), using a 30 mmφ screw diameter extruder, Brass Chem C4LL-LL118 (d = 0.916, MFR = 1.0 g / 10 min), which is LLDPE derived from sugarcane, is 200. The polyethylene-based resin composition of the present invention was obtained by melt-kneading at ° C. The layer thickness ratio of the first layer: second layer: third layer was 1: 1: 1. Subsequently, the resin composition was formed into a film F2 shown in FIG. 3 having a thickness of 130 μm by a T die cast coextrusion film forming machine under processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm.
The degree of biomass was measured and was about 29%. Moreover, this film had a beautiful appearance with a uniform film thickness, and was excellent in tensile strength, suitability for production and seal strength.

[Example 6]
As the resin composition for the first layer (inner layer) and the third layer (outer layer), Mitsui Chemicals C6LL-Evolution SP2020 (d = 0.916, MFR) using an extruder with a screw diameter of 30 mm.
= 2.3 g / 10 min) was melt-kneaded at 200 ° C. to prepare a petroleum-derived polyethylene resin. Similarly, as a resin composition for the second layer (intermediate layer), a brass diameter C4LL-LL118 (d = 0.916), which is LLDPE derived from sugar cane, using a screw diameter 30 mmφ extruder.
, MFR = 1.0 g / 10 min) 50% by mass, Ube Maruzen polyethylene LDPE-F120
N (d = 0.920, MFR = 1.2 g / 10 min) 50 mass% was melt-kneaded at 200 ° C. to obtain a polyethylene resin composition of the present invention. The layer thickness ratio of the first layer: second layer: third layer was 1: 2: 1.

  Subsequently, the resin composition was formed into a film F2 shown in FIG. 3 having a thickness of 130 μm by a T die cast coextrusion film forming machine under processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm. When this biomass degree was measured, it was about 22%. Moreover, this film had a beautiful appearance with a uniform film thickness, and was excellent in tensile strength, suitability for production and seal strength.

[Example 7]
Using a two-component curable urethane adhesive with a biaxially stretched nylon film (ONy, Toyobo Harden N-1102) as a base film 5 having a thickness of 25 μm as an outer layer, and the film of Example 1, About 4 g / m ² of the adhesive was applied to the ONy surface, and the corona-treated surface of polyethylene was bonded by a dry lamination method to obtain a laminated film 3 shown in FIG. 4 having a two-layer structure.
When this biomass degree was measured, it was about 70%.

  Then, using this laminated film 3, a refilling standing pouch (packaging bag 6) with a spout part provided with an opening cut line with a laser is created, and the contents are put into this refilling standing pouch and the mouth part As for the sealed product, leakage of contents, falling, buckling, and bending of the trunk were observed, but were not recognized. Further, a drop test was performed five times from a height of 1 m, but no bag breakage, leakage, etc. were observed.

[Example 8]
Biaxially stretched nylon film (ONy, Toyobo Harden N-1102) as the base film 5 with a thickness of 25 μm on the outer layer, and VMPET (metal vapor deposition film) with a thickness of 12 μm aluminum deposited on one side of the intermediate layer, The film of Example 1 was formed by laminating the aluminum vapor-deposited surface of aluminum terephthalate film) and applying about 4 g / m ² of a two-component curable urethane adhesive to the polyethylene terephthalate surface of VMPET. The corona-treated surface was bonded by a dry lamination method to obtain a laminated film having a three-layer structure.

And using this laminated film, the standing pouch for refilling (packaging bag 6) with the spout part which provided the opening cut line with the laser was created.
When the degree of biomass was measured, it was about 62%.
In the prepared refillable standing pouch, the contents were sealed and the mouth was sealed. Leakage, overturning, buckling and bending of the torso were observed, but were not recognized. Further, a drop test was conducted five times from a height of 1 m, but no bag breakage, leakage, etc. were observed.

[Example 9]
Only the bottom material in the refilling standing pouch with the spout part of Example 8 described above is contained in the refilling standing pouch made using a petroleum-derived film made of stretched polyamide (ONY) / LLDPE (linear low density polyethylene). When the object was put in and the mouth was sealed, leakage of the contents, falling, buckling, and bending of the trunk were observed, but were not recognized.
Further, a drop test was conducted five times from a height of 1 m, but no bag breakage, leakage, etc. were observed.
Accordingly, the bottom material of the standing pouch of the present invention may be either a laminated film containing the same plant as the trunk or a petroleum-derived film.

  As described above in detail, the film made of the polyethylene resin of the present invention is made of the resin composition 1 containing plant-derived LLDPE or HDPE obtained by a gas phase polymerization method. Moreover, while using these films as a sealant film and a laminated film laminated with a base film, the packaging bag is made of this laminated film.

  The present invention can be applied to any product using a polyethylene resin such as a film made of a polyethylene resin and a packaging bag made of the film.

DESCRIPTION OF SYMBOLS 1 Polyethylene resin composition of this invention 2 Petroleum origin polyethylene resin 3 Laminated | multilayer film 4 Sealant film 5 Base film 6 Packaging bag 7, 8 Side sheet 9 Bottom sheet F1-F2 film

Claims (8)

It is a film having a single layer structure composed of a polyethylene resin composition, or a film having a multilayer structure including at least one layer composed of the polyethylene resin composition,
The film according to claim 1, wherein the polyethylene resin composition comprises a plant-derived polyethylene resin selected from plant-derived high-density polyethylene or plant-derived linear low-density polyethylene.   The film according to claim 1, wherein the plant-derived polyethylene resin has a melt flow rate of 2.4 to less than 4.1 g / 10 minutes. The plant-derived linear low-density polyethylene is
The density is 910-925 kg / m ³ ;
An ethylene-α-olefin copolymer of plant-derived ethylene and petroleum-derived comonomer, wherein the petroleum-derived comonomer is butene-1, hexene-1, or a mixture thereof. 3. The film according to 1 or 2. Characterized in that it has a biomass degree calculating from measurements of radiocarbon dating C ^14, the film according to any one of claims 1 to 3. The blending amount of the plant-derived polyethylene resin is 5 to 90% by mass with respect to the entire film, the blending amount of the petroleum-derived polyethylene resin is 10 to 95% by mass, and the following (A) or (B) It has a structure, The film of any one of Claims 1-4 characterized by the above-mentioned.
(A) Single layer configuration comprising the polyethylene resin composition (B) Multilayer configuration having an intermediate layer comprising the polyethylene resin composition, and an outer layer and an inner layer comprising a petroleum-derived polyethylene resin   A laminated film, wherein the film according to any one of claims 1 to 5 is used as a sealant film and laminated with a base film.   A packaging bag formed by using a laminated film in which the film according to any one of claims 1 to 5 is used as a sealant film and laminated with a base film.   The packaging bag according to claim 7, wherein the packaging bag is a refilling standing pouch.

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