JP6638758B2 - Film and packaging bag using plant-based polyethylene resin - Google Patents

Description

  The present invention relates to a film comprising a polyethylene-based resin composition, and more particularly, to at least one plant-based polyethylene 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-based resin composition containing a resin, and a packaging bag using the film.

  2. Description of the Related Art Conventionally, packaging bags represented by pouches and the like used as refills of shampoos and rinses and packaging materials of foods and the like are formed of a packaging material including a sealant film and a base film. In order to respond to environmental issues and to save depleted resources such as petroleum, ethylene-α is added to polylactic acid resin as a carbon-neutral material with the aim of reducing the amount of these petroleum resources used in packaging materials. There is known a packaging bag containing a biodegradable resin containing predetermined amounts of an olefin copolymer and a polymer having an epoxy group, respectively (for example, Patent Document 1).

JP 2009-155516 A

  However, such packaging bags, as described above, contain a biodegradable resin other than the petroleum-derived material in the resin composition constituting the packaging bag, and reduce the ratio of the petroleum-based material. In comparison with the above, there was a problem that the workability such as tensile strength, seal strength, and waist was remarkably inferior, and the productivity could not be improved.

  Therefore, 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 emission and the film. An object of the present invention is to provide a packaging bag excellent in processability.

  Another object of the present invention is to provide such a film by extrusion molding using 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 same achieve the above objects.
1. Either a single-layer film composed of the polyethylene resin composition, or a multi-layer film including at least one layer composed of the polyethylene resin composition, which is extruded by a T-die method, The above 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 the above item 1, wherein the plant-based 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 a petroleum-derived comonomer, wherein the petroleum-derived comonomer includes butene-1, hexene -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-based polyethylene resin is 5 to 90% by mass, the blending amount of the petroleum-based polyethylene resin is 10 to 95% by mass, and the following (A) or (B) 5. The film according to any one of the above items 1 to 4, having a configuration.
(A) Single-layer structure composed of the polyethylene-based resin composition. (B) Multi-layered structure having an intermediate layer composed of the polyethylene-based resin composition and an outer layer and an inner layer composed of a petroleum-derived polyethylene-based resin. A laminated film, wherein the film according to any one of 1 to 5 above is used as a sealant film and laminated with a base film.
7. A packaging bag using a laminated film obtained by laminating a film according to any one of the above 1 to 5 as a sealant film and a base film.
8. The packaging bag according to the above item 7, wherein the packaging bag is a refilling standing pouch.

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

  Since the film of the present invention contains a plant-based polyethylene resin selected from plant-derived HDPE or plant-derived LLDPE, there is no difference in performance from a film made of a petroleum-derived polyethylene resin, and the use of petroleum resources The amount can be reduced, and the amount of carbon dioxide emitted during film production and disposal can be suppressed.

  Therefore, it is possible to provide a film made of polyethylene resin with reduced environmental load. Moreover, since it is extruded by the T-die method, it is possible to provide a low-cost film having a uniform thickness.

  Further, by using a plant-derived polyethylene resin having an MFR of 2.4 to 8.0 g / 10 minutes as a plant-based polyethylene resin used in the film of the present invention, a uniform film can be formed at a high speed during extrusion molding by the T-die method. Can be manufactured.

Further, as the plant-derived LLDPE used in the film of the present invention, the density is 910 to 925 kg / m ³ , and plant-derived ethylene and plant- or petroleum-derived butene-1;
By using an ethylene-α-olefin copolymer with hexene-1 or a mixture thereof, the film has excellent tensile strength, seal strength and waist suitable for a packaging bag, for example, a refilling standing pouch, 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 Raw materials 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 enables identification of the origin of the raw material.

Further, in one embodiment of the present invention, the film of the present invention has a compounding amount of the plant-derived polyethylene resin of 5 to 90% by mass and a compounding amount of the petroleum-derived polyethylene resin of 10 to 95% based on the whole film. % By mass and has the following constitution (A) or (B):
(A) Single-layer structure composed of the polyethylene-based resin composition. (B) Multi-layered structure having an intermediate layer composed of the polyethylene-based resin composition and an outer layer and an inner layer composed of a petroleum-derived polyethylene-based resin.

  Therefore, the petroleum-derived use ratio of the polyethylene resin constituting the film can be reduced, the use amount of petroleum resources can be reduced, and the amount of carbon dioxide emitted during film production and disposal can be suppressed.

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

  Therefore, it is possible to provide a film made of a polyethylene-based resin, which saves petroleum resources and reduces environmental load.

  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 resin in which petroleum resources are saved and the environmental burden is reduced.

  Further, the film of the present invention containing a plant-derived polyethylene resin as a sealant film, a packaging bag using a laminated film laminated with a base film, the petroleum-derived polyethylene resin in the laminated film constituting the 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. Therefore, it is possible to provide a packaging bag made of polyethylene resin, which saves petroleum resources and reduces environmental load.

  Further, the packaging bag of the present invention may be a refilling standing pouch, and can reduce the use ratio of polyethylene-based resin, which constitutes a large number of packaging bags that are widely used as disposables, derived from petroleum, and the amount of petroleum resources used. And the amount of carbon dioxide emitted during the production and disposal of the packaging bag can be suppressed. Therefore, it is possible to provide a packaging bag made of polyethylene resin, which saves petroleum resources and reduces environmental load.

It is a flowchart which shows an example of manufacture of the polyethylene derived from a sugarcane. BRIEF DESCRIPTION OF THE DRAWINGS It is sectional side view which shows typically the film of the single layer structure which consists of a polyethylene resin composition of this invention. FIG. 2 is a cross-sectional side view schematically showing a film having a multilayer structure having an intermediate layer made of the polyethylene resin composition of the present invention, and an outer layer and an inner layer made of a petroleum-derived polyethylene resin. It is sectional side view which shows an example of the laminated film of this invention typically. It is a perspective view which shows the standing pouch as an example of the packaging bag formed using the laminated film of this invention.

Hereinafter, the best mode for carrying out the present invention will be described with reference to the drawings.
Containers exemplified by laminated tubes and the like used in foods and cosmetics, and packaging bags exemplified by standing pouches widely used as refills for shampoos and rinses are made of laminated films.

  As the laminated film, there is a laminated film in which a sealant film serving as an inner surface of the laminated film is laminated on a base film. For example, a polyethylene resin or the like is used as a material of the base film. Further, in order to construct a sealant film, for example, a linear low-density or high-density polyethylene sandwiching an intermediate layer is used as a laminate.

  As described above, a polyethylene resin, which is a plastic resin, is often used as a material of the laminated film. However, these polyethylene resins are manufactured using petroleum as a starting material. Low-density polyethylene is obtained by copolymerizing ethylene obtained by refining crude oil and an α-olefin that is a comonomer at a high temperature such as 120 ° C. or higher in the gas phase in the presence of a metallocene catalyst. .

The α-olefin is propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene represented by the general formula R—CH ＝ CH ₂ (where 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, octadecene, and the like.

  The metallocene catalyst is not particularly limited. For example, a cyclopentadienyl group, one group selected from a cyclopentadienyl group having a substituent (substituted cyclopentadienyl group), an indenyl group, and a substituted indenyl group may be used. , A fluorenyl group, or a substituted fluorenyl group, a transition metal compound of Group 4 of the periodic table having a ligand cross-linked by a cross-linking group.

  Representative 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-dienyl 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.

Further, the metallocene catalyst includes, for example, a cyclopentadienyl group, a cyclopentadienyl group having a substituent (substituted cyclopentadienyl group), an indenyl group, a substituted indenyl group, and a fluorenyl group. One type of group selected from substituted fluorenyl groups is a transition metal compound of Group 4 of the periodic table having a ligand cross-linked by a cross-linking group, and a typical example 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-cy 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, dichloromethylene 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 such as a diphenyl or dibenzyl compound.

  However, with the desire to conserve depleted resources such as petroleum and the growing awareness of environmental issues such as global warming due to increased carbon dioxide emissions, petroleum-based polyethylene resins such as those described above must be discarded from the production of petrochemical products to disposal. In this period, a large amount of carbon dioxide immobilized in the petroleum feedstock is discharged, so that the above intention cannot be met.

Under these circumstances, in recent years, the technology for producing plastics from plants that are carbon-neutral and renewable resources has been developed, and among them, polyethylene, which is most frequently used in plastics, has been replaced with biomass-based plastics. A technology for producing sugarcane as a starting material has been established (edited by Processing Technology Research Group, Convertec 2009. 9, P63-67).
Note that carbon neutral means that the amount of carbon dioxide absorbed during plant growth and the amount of carbon dioxide emitted during combustion are substantially the same.

  FIG. 1 is a flowchart showing an example of producing polyethylene derived from sugarcane. FIG. 2 is a cross-sectional side view schematically showing a film made of a polyethylene-based resin composition containing a sugarcane-derived polyethylene-based resin of the present invention.

  As shown in FIG. 1, a sugar solution taken out from a sugarcane harvested from a field is heated and concentrated to crystallize a crude sugar crystallized from waste sugar, using a centrifuge. The waste molasses is then diluted with water to the appropriate concentration and fermented with yeast to produce ethanol. Then, the bioethanol is heated and ethylene obtained by an intramolecular dehydration reaction in the presence of a catalyst is polymerized by 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-based polyethylene resin used for the film of the present invention is LLDPE or HDPE generated from ethylene using the above-mentioned starting material as a plant-derived material. These can be produced in the same manner as when a polyethylene-based resin is produced from petroleum-derived ethylene. That is, plant-derived LLDPE can be produced by copolymerizing plant-derived ethylene and an α-olefin by a gas phase polymerization method in the presence of a metallocene catalyst. In addition, by polymerizing the above-mentioned plant-derived ethylene at a medium pressure or a low pressure in the presence of a Ziegler catalyst or a Phillips catalyst, HDPE with few branches can be produced.

In the present invention, by producing a film forming a laminated film constituting a packaging bag using the plant-based polyethylene resin obtained as described above, in the resin composition used for the laminated film, petroleum-derived By reducing the ratio of resin used, petroleum resources can be saved and at the same time, the carbon dioxide emission can be reduced to contribute to environmental improvement.
The method for producing this film is not particularly limited, and it can be produced by a conventionally known method.

  In the present invention, it is preferable to manufacture by extrusion molding, and it is possible to form a film with a uniform thickness, and it is possible to perform high-speed cooling and high-speed film formation and to be excellent in productivity. Production is particularly preferred.

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

Next, for example, by using a die such as a T die, the molten resin composition is extruded into a sheet, and the obtained sheet is rapidly cooled and solidified by a rotating cooling drum or the like, whereby a film can be produced. .
As the melt extruder, a single-screw extruder, a twin-screw extruder, a vent extruder, a tandem extruder or the like can be used according to the purpose.

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

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

In addition, the above-mentioned sugarcane-derived HDPE can have various physical properties with a density of 941 to 965 kg / m ³ and a melt flow rate (MFR) of 2.4 to 8.0 g / 10 minutes.

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

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

  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 up to 90% by mass, more preferably in an amount of 5 to 90% by mass. In one embodiment of the present invention, the polyethylene resin composition contains 5-90% by mass of plant-derived LLDPE or HDPE and 10-95% by mass of a petroleum-derived polyethylene resin.

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, a resin derived from a plant (biomass) and a resin derived from petroleum have no difference in physical properties such as molecular weight, mechanical properties, and thermal properties. Therefore, in order to distinguish them, a biomass degree is generally used.

In this biomass, the carbon of the petroleum-derived resin does not contain C ¹⁴ (radioactive carbon 14, half-life 5730 years), so the concentration of C ¹⁴ was measured by accelerator mass spectrometry, , As an index of the content ratio of the plant-derived resin. Therefore, in the case of a film using a plant-derived resin, a biomass degree corresponding to the content of the plant-derived resin can be obtained by measuring the biomass degree of the film.

In the measurement of the degree of biomass, carbon dioxide is generated by burning a sample to be measured, and carbon dioxide purified in a vacuum line is reduced with hydrogen using iron as a catalyst to generate graphite. Then, the graphite wearing the tandem accelerator based the C ¹⁴ AMS-only device (manufactured by NEC Corporation), the count of C ^14, the concentration (C ¹³ / C ¹²⁾ of the C ^13, the concentration of C ¹⁴ (C ¹⁴ / C ¹² ) is measured, and the ratio of the C ¹⁴ concentration of the sample carbon to the standard modern carbon is calculated from the measured value.

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

  In the present invention, by using a film made of such a resin composition, the petroleum-derived polyethylene-based resin is completely converted from petroleum-derived resin to sugar-cane having no difference in performance from the petroleum-derived polyethylene-based resin. By mixing (substituting) such a plant-based polyethylene resin, the amount of carbon dioxide emitted during film production and disposal can be suppressed.

In the present invention, as the plant-derived polyethylene resin contained in the polyethylene resin composition 1, the comonomer species is butene-1, hexene-1, or a mixture thereof, and the density is 910 to 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 the petroleum-based polyethylene resin in the existing film production process. Therefore, the raw material can be switched without impairing the processing suitability 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 In addition, it is possible to confirm the raw materials from the time of film production to the time of disposal.

  The MFR of the plant-derived LLDPE or the plant-derived HDPE constituting the film of the present invention is preferably 2.4 to 8.0 g / 10 minutes. And in order to show a high biomass degree and to obtain good tensile strength and seal strength as a packaging bag, the MFR is more preferably 2.5 to 3.0 g / 10 min. Further, in order to exhibit a high biomass degree and to produce a film having a uniform thickness at a high speed by extrusion molding by the T-die method, the MFR is more preferably greater than 4.0, for example, 4 It is about 0.1 to 8.0 g / 10 minutes.

  Next, in the present invention, the above-mentioned resin composition 1 and the petroleum-derived polyethylene-based resin 2 described below can form the following film.

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

  First, as shown in FIG. 2, the film (A) (A) can have a single-layer structure composed 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.

Further, 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 a petroleum-derived polyethylene resin. Can be. Here, the polyethylene-based resin composition 1 of the present invention contains the plant-based polyethylene resin at a concentration such that the blending amount of the plant-based polyethylene resin with respect to the entire film is 5 to 90% by mass.

  With such a configuration, the use ratio of the polyethylene resin constituting the film derived from petroleum can be reduced, and the amount of carbon dioxide emitted during film production and disposal can be suppressed. In addition, by using the petroleum-derived polyethylene-based 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 co-extrusion molding.

Next, in the present invention, a laminated film using the films F1 and F2 can be obtained. 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 formed by laminating any one of the films F <b> 1 and F <b> 2 as a sealant film 4 and a base film 5.

  As the base film 5, for example, a polyethylene resin, a polypropylene resin, a cyclic polyolefin resin, a polystyrene resin, an acrylonitrile-styrene copolymer (AS resin), an acrylonitrile-butadiene-styrene copolymer (ABS resin) ), Polyvinyl chloride resin, fluorine resin, poly (meth) acrylic resin, polycarbonate resin, polyester resin such as polyethylene terephthalate, polyethylene naphthalate, polyamide resin such as various nylons, polyimide resin, polyamide Various types of imide resin, polyaryl phthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone 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, and to save the petroleum resources, Carbon dioxide emission during the production and disposal of the product 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 were arranged to face each other, and the sealant film 4 was laminated on at least one side at the lower end of the laminated film 3. The bottom sheet made of the laminated body is inserted in a form having a gusset portion by being folded in the center with the sealant film 4 as the outer surface, and is formed in a form having a gusset portion. A cutout portion of the semicircular bottom sheet is provided, and the gusset portion is heat-sealed with a ship-bottom bottom seal portion including a peripheral portion to form a bottom portion.

  Next, the side edges of the two side sheets on the front and back are heat-sealed with side edge seals to form a body, and the upper end is left as a filling port for the contents, as shown in FIG. A pouch (packing bag) formed in a standing pouch format is formed. The upper sealing portion provided at the filling port at the upper end is filled with the content from this portion, and then heat-sealed by, for example, a degassing seal to seal. Although not shown, a spout may be formed at the upper portion of the body by providing a break line for opening with a laser.

With such a configuration, the use ratio of the petroleum-based polyethylene resin in the laminated film 3 constituting the packaging bag 6 can be reduced, and the petroleum resources can be saved and the production and disposal of the packaging bag 6 can be reduced. Carbon dioxide emissions can be reduced. In particular, since the packaging bag 6 is a standing pouch for refilling, it is possible to reduce the usage ratio of petroleum-based polyethylene resin constituting such a disposable packaging bag and to significantly suppress carbon dioxide emissions. it can.

  In addition, other than the packaging bags 6 exemplified by the above-mentioned standing pouches, using the films F1 and F2 made of the polyethylene resin composition 1 of the present invention and the laminated film 3 using these films F1 and F2, Can be used to form containers such as laminated tubes, liquid paper containers, etc., containing containers such as food, beverages, cosmetics, medicines, and miscellaneous goods, container lids, or container labels. And the amount of carbon dioxide emission can be greatly suppressed.

  Next, an example of a film constituted by using the polyethylene resin composition 1 of the present invention will be described.

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

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

  On the other hand, as Comparative Example 1, using C6LL-Evolu SP2040 (d = 0.918, MFR = 3.8 g / 10 min) 100% manufactured by Prime Polymer Co., Ltd. derived from petrochemical, in the same manner as in Example 1, The mixture 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 measured biomass degree was 0%.

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

  As described above, the film of the present invention composed of a polyethylene-based resin composition containing plant-derived LLDPE has physical properties equivalent to those of a film composed only of petrochemical-derived LLDPE, and exhibits good tensile strength, suitability for production processing and seal strength. Was.

[Test method]
The tensile breaking strength (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 with a loop length of 60 mm, a sample width of 15 mm, N = 3, and a crushing distance of 17 mm (scale 3).
The sealing strength was measured by using a heat seal tester TP-701S, placing PET 12 μm on the evaluation sample, sealing at 180 ° C. × 1 kgf / cm ² × 1.0 second, cutting out a 15 mm wide strip-shaped sample, and testing the Tensilon universal test. Test speed 300mm / min.N
= 3.

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

[Example 3]
In the same manner as in Example 1, a sugarcane-derived HDPE, Braschem SHC7260 (d = 0.959, MFR = 7.2 g / 10 min) was kneaded and melted at 200 ° C. using a 30 mmφ screw extruder. Was obtained. Next, a T-die casting film forming machine was used to mold the resin composition under the processing conditions of an extrusion temperature of 220 ° C. and a rotation speed of 45 rpm, whereby a 120 μm-thick film F1 shown in FIG. 2 could be formed. The measured biomass degree was about 95%. This film had a beautiful appearance with a uniform thickness, and was excellent in tensile strength, suitability for production processing and seal strength.

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

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

[Example 5]
As a resin for the first layer (inner layer) and a resin for the third layer (outer layer), Mitsui Chemicals C6LL-Evolu SP2020 (d = 0.916, MFR = 2.3 g / 10 min) was used using a screw diameter of 30 mm extruder. The mixture was melt-kneaded at 200 ° C. to prepare a petroleum-derived polyethylene resin. Similarly, as a resin for the second layer (middle layer), C4LL-LL118 (d = 0.916, MFR = 1.0 g / 10 min), which is LLDPE derived from sugar cane, using a screw extruder with a screw diameter of 30 mm, is 200. The mixture was melted and kneaded at ℃ to obtain the polyethylene resin composition of the present invention. The ratio of the thickness of the first layer: the second layer: the third layer was 1: 1: 1. Next, the resin composition was formed into a 130 μm-thick film F2 shown in FIG. 3 by a T-die casting co-extrusion film forming machine under an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm.
The measured biomass degree was about 29%. This film had a beautiful appearance with a uniform thickness, and was excellent in tensile strength, suitability for production processing and seal strength.

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

  Next, the resin composition was formed into a 130 μm-thick film F2 shown in FIG. 3 by a T-die casting co-extrusion film forming machine under an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm. The measured biomass degree was about 22%. This film had a beautiful appearance with a uniform thickness, and was excellent in tensile strength, suitability for production processing and seal strength.

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

  Then, using this laminated film 3, a refilling standing pouch (packing bag 6) with a spout portion provided with a break line for opening with a laser is prepared, and the contents are put into the refilling standing pouch and the opening is formed. With respect to what was sealed, leakage of contents, overturning, buckling, and breakage of the trunk were observed, but were not recognized. Further, a drop test was performed 5 times from a height of 1 m, but no bag breakage or leakage was observed.

Example 8
A biaxially stretched nylon film (ONy, Toyobo Haden N-1102) as the base film 5 having a thickness of 25 μm in the outer layer, and a 12 μm thick VMPET (metal-deposited film) in which the intermediate layer is aluminum-evaporated on one side, A polyethylene terephthalate film (which is obtained by vapor-depositing aluminum on a polyethylene terephthalate film), and a two-part curable urethane-based adhesive was applied to the polyethylene terephthalate surface of VMPET at about 4 g / m ² . The corona-treated surface was bonded by a dry lamination method to obtain a three-layer laminated film.

Using this laminated film, a refilling standing pouch (packing bag 6) with a spout provided with a break line for opening was formed with a laser.
The measured biomass degree was about 62%.
The contents were put in the prepared refilling standing pouch, and the mouth was sealed. Leakage of the contents, overturning, buckling, and breaking 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, or the like was observed.

[Example 9]
Only the bottom material of the refilling standing pouch with the spout in Example 8 was used in a refilling standing pouch made using a petroleum-derived film made of stretched polyamide (ONY) / LLDPE (linear low-density polyethylene). With respect to the one in which the material was put and the mouth was sealed, leakage of the contents, overturning, buckling, and breaking 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, or the like was observed.
Therefore, as the bottom material of the standing pouch of the present invention, either a laminated film containing the same plant-derived material as the trunk or a petroleum-derived film may be used.

  As described in detail above, 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. In addition, these films are used as a sealant film, a laminated film laminated with a base film, and a packaging bag is made of the 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-derived polyethylene resin 3 Laminated film 4 Sealant film 5 Base film 6 Packaging bag 7, 8 Side sheet 9 Bottom sheet F1-F2 film

Claims (6)

A sealant film having a multilayer structure including at least one layer made of a polyethylene-based resin composition,
The polyethylene-based resin composition includes a plant-derived high-density polyethylene having a density of 941 to 965 kg / m ³ and a melt flow rate of 2.4 to 8.0 g / 10 minutes,
Plant-derived high density polyethylene has a biomass degree 80% to 100% of calculated from measurements of radiocarbon dating C ^14,
The above-mentioned sealant film, wherein the compounding amount of the plant-based polyethylene resin is 5 to 90% by mass and the compounding amount of the petroleum-based polyethylene resin is 10 to 95% by mass with respect to the whole film.   The sealant film according to claim 1, wherein the polyethylene-based resin composition includes a plant-derived high-density polyethylene and a plant-derived linear low-density polyethylene. The plant-derived linear low-density polyethylene has a density of 910 to 925 kg / m ³ , and is an ethylene-α-olefin copolymer of plant-derived ethylene and a petroleum-derived comonomer. The sealant film according to claim 2, which is butene-1, hexene-1, or a mixture thereof. A laminated film, wherein the sealant film according to any one of claims 1 to 3 is laminated on a base film. A packaging bag comprising a laminated film obtained by laminating the sealant film according to any one of claims 1 to 3 with a base film. The packaging bag according to claim 5 , wherein the packaging bag is a refilling standing pouch.

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