JP6432589B2 - Sealant film for packaging material, laminated film for packaging material, and packaging bag using plant-derived polyethylene - Google Patents

Description

  More specifically, the present invention relates to a sealant film for packaging material and a laminated film for packaging material containing the plant-derived polyethylene resin, and a packaging bag using these films.

  Conventionally, for example, packaging bags represented by refills such as shampoos and rinses, and pouches used as packaging materials for foods, etc. have been composed of packaging materials consisting of a sealant film and a base film, and have been In order to save depleted resources, etc., and to reduce the amount of petroleum resources used in packaging materials, a polylactic acid resin as a carbon neutral material, an ethylene-α-olefin copolymer and a polymer having an epoxy group There exists a packaging bag (for example, patent document 1) containing the biodegradable resin composition which contained each predetermined amount.

JP 2009-155516 A

However, in such a packaging bag, as described above, although the resin composition constituting the packaging bag contains a biodegradable resin other than the petroleum-derived raw material to reduce the ratio of the petroleum-derived raw material, the petroleum-based resin Compared to the above, there is a problem that the processability such as tear strength, heat seal strength and resin pressure during film formation is remarkably inferior, and the 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 be an environmentally friendly sealant film for packaging materials by reducing carbon dioxide emissions. It is another object of the present invention to provide a laminated film for packaging material and a packaging bag excellent in processability using these films.

  For this reason, the sealant film for a packaging material according to the invention of claim 1 is a film made of a polyethylene-based resin, which is obtained directly by a gas phase polymerization method of plant-derived ethylene and petroleum-derived α-olefin. A layer obtained by mixing a resin composition containing 5 to 90% by weight of a chain-like low-density plant-derived polyethylene resin and 10 to 95% by weight of a petroleum-derived polyethylene resin and a petroleum-derived polyethylene resin. A film having a multilayer structure in which the outer layer and the inner layer are made of petroleum-derived polyethylene resin is used as a heat-sealable film.

The sealant film for a packaging material according to claim 2 is the film according to claim 1, wherein the polyethylene-based resin has an ethylene-α having a biomass degree calculated from a measurement value of radiocarbon dating ¹⁴ C. -An olefin copolymer.

The invention according to claim 3 is the sealant film for packaging material according to claim 1 or 2, wherein the α-olefin is butene-1, hexene-1, or a mixture thereof, The plant-derived polyethylene resin having a density of 0.910 to 0.925 g / cm ³ and a melt flow rate of 0.5 to 4.0 g / 10 min have physical properties.

  The laminated film for packaging material according to the invention described in claim 4 is characterized in that the sealant film for packaging material according to any one of claims 1 to 3 is laminated with a base film.

  The packaging bag which concerns on invention of Claim 5 uses the laminated | multilayer film for packaging materials of Claim 4, It is characterized by the above-mentioned.

  According to invention of Claim 1, it is a film which consists of polyethylene-type resin, Comprising: The linear low density plant origin polyethylene obtained by the gas phase polymerization method of plant origin ethylene and petroleum origin alpha-olefin A layer obtained by mixing a resin composition containing 5 to 90% by weight of a resin and 10 to 95% by weight of a petroleum-derived polyethylene resin with a petroleum-derived polyethylene resin is used as an intermediate layer, and the outer layer and the inner layer are derived from petroleum. Since the film having a multilayer structure made of polyethylene resin is a heat-sealable film, the composition of the sealant film for packaging material made of polyethylene resin is completely dependent on the resin composition derived from petroleum. There is no difference in performance in petroleum-based resins from polyethylene-based resins derived from petroleum, and plant-derived plastics such as carbon-neutral sugarcane. By hybrid ethylene-based resin (substitution), as well as reduce the use of petroleum resources, it is possible to suppress carbon dioxide emissions during sealant film production and waste packaging. Therefore, it is possible to provide a sealant film for packaging material made of a polyethylene-based resin with reduced environmental load. Furthermore, the use ratio derived from petroleum of the polyethylene-type resin which comprises the sealant film for packaging materials can be reduced. In addition, by using a petroleum-derived polyethylene resin for the inner and outer layers constituting the sealant film for packaging material, the sealant film for packaging material can be produced with the characteristics of existing production processes. Accordingly, it is possible to provide a sealant film for a packaging material made of a polyethylene resin that saves petroleum resources and reduces environmental burden.

According to the invention described in claim 2, since the polyethylene resin is an ethylene-α-olefin copolymer having a biomass degree calculated from the measured value of the radiocarbon dating ¹⁴ C, the sealant film for packaging material is used. The origin of the raw material of the polyethylene-based resin to be configured can be identified using the degree of biomass as an index, and the raw material can be confirmed from the time of manufacture of the sealant film for packaging material to the time of disposal. Therefore, it is possible to provide a sealant film for a packaging material made of a polyethylene resin that can be identified from the raw material.

According to the invention described in claim 3, the α-olefin is butene-1, hexene-1, or a mixture thereof, and the density of the linear low-density plant-derived polyethylene resin is 0.910 to 0. .925 g / cm ³ and a melt flow rate of 0.5 to 4.0 g / 10 min, so there is no difference in physical properties from petroleum-derived polyethylene resin. The raw material can be switched without impairing the processing suitability of the packaging material. Therefore, it is possible to provide a sealant film for a packaging material made of a polyethylene resin that is excellent in environmental load reduction and production efficiency.

  According to invention of Claim 4, the packaging which laminated | stacked the sealant film for packaging materials which consists of a polyethylene-type resin containing a plant origin polyethylene-type resin (in any one of Claim 1 thru | or 3) with the base film. Because it is a laminated film for materials, even in the sealant film used for heat sealing, the ratio of petroleum-derived polyethylene-based resin constituting the film that is the sealant film can be reduced, and the amount of petroleum resources used can be reduced. At the same time, it is possible to suppress carbon dioxide emissions during the production and disposal of the laminated film for packaging materials. Therefore, it is possible to provide a laminated film for a packaging material made of a polyethylene resin with reduced petroleum resources and reduced environmental burden.

  According to invention of Claim 5, the laminated | multilayer film for packaging materials which laminated | stacked the film (in any one of Claim 1 thru | or 3) which consists of a polyethylene-type resin containing a plant origin polyethylene-type resin with the base film. Since it is a packaging bag using (claim 4), the ratio of petroleum-derived use of polyethylene resin in the laminated film for packaging material constituting the packaging bag can be reduced, and the amount of petroleum resources used can be reduced. It is possible to reduce the carbon dioxide emission during the manufacture and disposal of the packaging bag. Accordingly, it is possible to provide a packaging bag made of a polyethylene-based resin with reduced oil resources and reduced environmental burden.

  Furthermore, it can reduce the ratio of petroleum-derived polyethylene resins that make up packaging bags that are widely used in the world as disposables, reduce the amount of petroleum resources used, and emit carbon dioxide during the production and disposal of packaging bags. The amount can be suppressed.

It is a flowchart which shows an example of polyethylene manufacture derived from sugarcane. It is a section side view showing typically the film which consists of a linear low density polyethylene system resin derived from sugar cane of the present invention. It is a section side view showing typically the film of the single layer composition which mixed the resin composition of the present invention, and petroleum origin polyethylene system resin. It is a cross-sectional side view which shows typically the film which consists of a multilayer structure which used the intermediate | middle layer of this invention as the resin composition. 1 is a cross-sectional side view schematically showing a film having a multilayer structure in which an intermediate layer of the present invention is a layer in which a resin composition and a petroleum-derived polyethylene resin are mixed. It is a section side view showing typically an example of a 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. Containers such as laminated tubes used for food and cosmetics, etc., and packaging bags such as standing pouches widely used as packaging materials for refilling shampoos and rinses, these containers and packaging bags are laminated. Consists of film.

  In this laminated film, there is one in which a base film is laminated with a sealant film used as an inner surface of the laminated film as a heat seal material. As a material of the base film, for example, a polyethylene resin is used, and a sealant film is used. For this material, for example, a linear low-density polyethylene resin is used as a laminate with an intermediate layer interposed therebetween.

As described above, a polyethylene resin, which is a plastic resin, is often used as the material of the laminated film. Conventionally, this polyethylene resin has been manufactured by petrochemical origin using petroleum as a starting material, for example, The above-mentioned linear low-density polyethylene-based resin is obtained by combining ethylene obtained by refining crude oil and α-olefin as a comonomer species with a high temperature such as 120 ° C. or higher in the gas phase in the presence of a metallocene catalyst. Copolymerized with The α-olefin is represented by general formula R—CH═CH ₂ (wherein R is an alkyl group having 1 or more carbon atoms), propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 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, One group selected from fluorenyl group and substituted fluorenyl group includes a transition metal compound belonging to Group 4 of the periodic table having a ligand bridged by a bridging group. A typical example thereof is diphenylmethylene (1 -Cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (3-methyl-1-cyclopentadienyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (1-cyclopentadienyl) (2,7 -Dimethyl-9-fluorenyl) zirconium dichloride, diphenyl Tylene (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-t-butyl-9-fluorenyl) zirconium dichloride and the like, and the dimethyl form of the above metallocene compound A metallocene catalyst containing a metallocene compound exemplified as a diethyl, dihydro, diphenyl, dibenzyl or the like as a main component is 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, along with the desire to conserve oil and other depleted resources, and with increasing awareness of environmental issues such as global warming due to an increase in carbon dioxide emissions, the use of petroleum-based polyethylene resins such as those mentioned above has resulted in the shift from the production of petrochemical products to disposal. In the meantime, the fixed carbon dioxide possessed by the petroleum raw material will be discharged in large quantities, so that the above-mentioned orientation cannot be met.

  In light of these problems, in recent years, the development of technology for producing plastics from plants that are carbon-neutral and renewable resources is progressing. A technology for producing sugarcane as a starting material has been established. (Processing Technology Research Group, Convertec 2009.9, P63-67) 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. Say.

  FIG. 1 is a flow chart showing an example of the production of sugarcane-derived polyethylene, and FIG. 2 is a cross-sectional side view schematically showing a film made of a sugarcane-derived linear low-density polyethylene resin of the present invention.

  As shown in FIG. 1, the sugar solution taken out from the sugarcane cut from the field and heated to concentrate and crystallize the crude sugar and the waste sugar-tight 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. In addition, plant-derived ethylene and polyethylene have been confirmed to be equivalent in quality to petroleum-derived ethylene and polyethylene.

  Therefore, the linear low-density polyethylene resin used for the film of the present invention is produced from ethylene derived from plants as a starting material as described above. As in the case of producing a chain low density polyethylene-based resin, it can be obtained by copolymerizing plant-derived ethylene and α-olefin by a gas phase polymerization method in the presence of a metallocene catalyst.

  In this invention, it uses for a laminated | multilayer film by manufacturing the film which forms the laminated | multilayer film which comprised the container and the packaging bag using the plant-derived linear low density polyethylene-type resin obtained as mentioned above. In resin compositions (such as linear low-density polyethylene resins), the use ratio of petroleum-derived resin compositions can be reduced to save petroleum resources and contribute to improving the environment by reducing carbon dioxide emissions. To do.

  In the present application, linear low density polyethylene derived from sugar cane obtained by the above gas phase polymerization method (not limited to sugar cane, but any other plant that can be a raw material for producing linear low density polyethylene resin). Using the resin composition 1 made of resin, a film F1 as shown in FIG. 2 can be obtained.

In addition, the above-mentioned linear low density polyethylene resin derived from sugar cane has a comonomer type of butene-1 (C4) and a density of 0.910 to 0.925 g, similar to the linear low density polyethylene resin derived from petroleum. / Cm ³ , melt flow rate (MFR) in the range of 0.5 to 4.0 g / 10 min, more preferably 0.7 to 3.5 g / 10 min. An α-olefin copolymer is used. Such a resin composition comprising a linear low-density polyethylene resin derived from sugar cane is contained in an appropriate ratio up to 90% by weight with respect to the linear low-density polyethylene resin derived from petroleum.

In the above physical property evaluation, a density (d, unit: g / cm 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 min) is measured under a test load of 21.18 N under a test temperature of 190 ° C. according to JIS K 7210 (1995).

Furthermore, the said ethylene-alpha-olefin copolymer in which the biomass degree by radioactive carbon dating ^14C has 80-100% is used for the said linear low density polyethylene-type resin derived from sugarcane.

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

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, the graphite was attached to the tandem accelerator ¹⁴ C-AMS-only apparatus which is based on (manufactured by NEC ^{Corp.), 14} C ^counts, the ¹³ C concentration ^{(13 C} / 12 ^C), the ¹⁴ C concentration ⁽¹⁴ C / ¹² C) is measured, and from this measured value, ¹⁴ of the sample carbon relative to standard modern carbon is measured.
The ratio of C concentration is calculated. In this measurement, oxalic acid (HOxII) provided by the National Bureau of Standards (NIST) was used as a standard sample.

  In the present application, by forming a film composed of such a resin composition, from a state that depends on all petroleum-derived resin compositions, this petroleum-derived polyethylene resin has a performance in combination with petroleum-derived polyethylene resins. By hybridizing (substituting) plant-derived polyethylene resins such as sugarcane that have no difference, carbon dioxide emissions during film production and disposal can be suppressed.

Further, the resin composition 1 of the present invention has an ethylene-α- with a comonomer species of butene-1, a density of 0.910 to 0.920 g / cm ³ , and a melt flow rate of 0.70 to 1.30 g / 10 min. Since it is an olefin copolymer, there is no difference in physical properties from petroleum-derived polyethylene resin, so that an existing film manufacturing process can be used, and the raw material can be switched without impairing the processability of the packaging material.

Furthermore, since the resin composition 1 of the present invention is an ethylene-α-olefin copolymer having a biomass degree calculated from the measurement value of the radiocarbon dating ¹⁴ C, the origin of the polyethylene resin constituting the film is derived from This biomass degree can be used as an index to identify the raw material from the time of film production to the time of disposal.

  Next, in this application, it can be comprised by the following films with the resin composition 1 mentioned above and the petroleum origin polyethylene-type resin 2 mentioned later. 3 is a cross-sectional side view schematically showing a single-layer film in which a resin composition and a petroleum-derived polyethylene resin are mixed, and FIG. 4 schematically shows a film having a multilayer structure in which an intermediate layer is a resin composition. FIG. 5 is a sectional side view schematically showing a film having a multilayer structure in which an intermediate layer is a layer in which a resin composition and a petroleum-derived polyethylene resin are mixed.

  In this case, the resin composition 1 is 5 to 90% by weight, the petroleum-derived polyethylene resin 2 is 10 to 95% by weight, and the film is formed according to the following (A), (B) or (C). Configured. First, as shown in FIG. 3, the film F <b> 2 of (A) can have a single layer configuration in which a resin composition 1 and a petroleum-derived polyethylene resin 2 are mixed.

  As shown in FIG. 4, the film F <b> 3 (B) can have a multilayer structure in which the intermediate layer is the resin composition 1 and the outer layer and the inner layer are petroleum-derived polyethylene resins 2.

  Further, as shown in FIG. 5, as the film F <b> 4 of (C), the intermediate layer is a layer obtained by mixing the resin composition 1 and the petroleum-derived polyethylene resin 2, and the outer layer and the inner layer are the petroleum-derived polyethylene resin 2 and A multi-layer structure can also be used.

  By setting it as such a structure, the use ratio derived from petroleum of the polyethylene-type resin 2 which comprises the films F2-F4 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 films F3 to F4 as in (B) or (C), the films F3 to F4 are manufactured with the characteristics of existing manufacturing processes. Can do.

  Next, in this application, it can be set as the laminated film using the said films F1-F4. FIG. 6 is a sectional side view schematically showing an example of a laminated film, and FIG. 7 is a perspective view showing a standing pouch as an example of a packaging bag formed using the laminated film of the present invention.

First, as shown in FIG. 6, the laminated film 3 is laminated with the base film 5 using any one of the films F1 to F4 as the 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.

  By using such a configuration, also in the sealant film 4 used for heat sealing, the use ratio derived from petroleum of the polyethylene resin constituting each of the films F1 to F4 that are the sealant film 4 can be reduced. Along with saving resources, carbon dioxide emissions during production and disposal of the laminated film 3 can be suppressed.

  Using the laminated film 3 as described above, the two side sheets 7 and 8 made of the laminated film 3 are arranged so that the surfaces of the sealant films 4 face each other, and the sealant film 4 is at least on one side at the lower end of the laminated film 3. The bottom sheet 9 made of the laminated body is inserted into the center with the sealant film 4 faced as an outer surface, and is formed in a form having a gusset portion. In the vicinity, a notch portion of a substantially semicircular bottom sheet is provided, and the gusset portion is heat-sealed with a bottom-shaped bottom seal portion including a peripheral edge portion to form a bottom portion.

  Next, both side edge portions of the two side sheets 7 and 8 on the front and back sides are heat-sealed with side edge seal portions to form a body portion, and the upper end portion is left to serve as a filling port for contents. A pouch (packaging bag 6) formed in a standing pouch form as shown 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.

  By adopting such a configuration, it is possible to reduce the ratio of petroleum-based use of polyethylene-based resin in the laminated film 3 constituting the packaging bag 6, saving petroleum resources, and at the time of manufacturing and disposal of the packaging bag 6. Carbon dioxide emissions can be suppressed. In particular, since this packaging bag 6 is a refilling standing pouch, the ratio of petroleum-derived polyethylene resins constituting such packaging bags that are widely used as disposables is reduced, and carbon dioxide emissions are greatly suppressed. Can do.

  In addition to the packaging bag 6 exemplified by the above-described standing pouch, using the films F1 to F4 made of the resin composition 1 of the present invention and the laminated film 3 using these films F1 to F4, polyethylene-based Consists of a resin composition 1 using a resin, for example, a laminate tube containing contents such as foods, beverages, cosmetics, medicines, miscellaneous goods, containers including liquid paper containers, container lids, or containers In addition, the use ratio derived from petroleum can be further reduced, and the carbon dioxide emission can be greatly suppressed.

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

  Using a screw diameter 30 mmφ extruder, Brass Chem C4LL-LL118 (d = 0.916, MFR = 1.0 g / 10 min), a sugarcane-derived linear low-density polyethylene resin (resin composition 1), was 200. The resin composition was obtained by melt-kneading at ° C. Next, the film F1 shown in FIG. 1 having a thickness of 50 μm and excellent in appearance is stably formed by molding the resin composition under the processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm by a top-blown air-cooled inflation coextrusion film forming machine. A film could be formed, and the degree of biomass measured was about 88%. The comonomer species butene-1 (C4) contained in the sugarcane-derived linear low-density polyethylene-based resin is derived from petroleum, and its content is 1 to 15 mol% (the same applies hereinafter).

  On the other hand, as Comparative Example 1 of the film F1, using a petrochemically derived C4LL linear low-density polyethylene resin, in the same manner as in Example 1, the thickness was 50 μm under the processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm. And the degree of biomass was measured and found to be 0%.

上記結果から、サトウキビ（植物）由来直鎖状低密度ポリエチレン系樹脂（実施例１）は、石化由来直鎖状低密度ポリエチレン系樹脂（比較例１）に比べて、引張破断強度や引裂強さが強く、腰やシール強度は同等の強度を有し、弾性率が低く柔軟であることが分かる。このように、植物由来直鎖状低密度ポリエチレン系樹脂は、石化由来直鎖状低密度ポリエチレン系樹脂と比較して同等以上の物性を有し、石化由来直鎖状低密度ポリエチレン系樹脂の製造加工適性と遜色ないことが実証された。 The following physical property evaluation tests were conducted on the resin composition of Example 1, and the results obtained are described below.

From the above results, the sugarcane (plant) -derived linear low density polyethylene resin (Example 1) is higher in tensile strength and tear strength than the fossilized linear low density polyethylene resin (Comparative Example 1). It is clear that the waist and the seal strength are equivalent, and the elastic modulus is low and flexible. Thus, the plant-derived linear low-density polyethylene resin has physical properties equivalent to or higher than those of the petrochemically-derived linear low-density polyethylene resin. It was proved that it was inferior to processability.

The tensile breaking strength (elongation) was measured using a Tensilon universal testing machine with reference to JIS-Z1702 at a test speed of 500 mm / min. N = 3 JIS-K7127 test piece type 5 (dumbbell piece: minimum parallel width 6 mm, distance between chucks 80 mm).
The elastic modulus (tensile) was measured using a Tensilon universal testing machine with reference to JIS-K7176 and a test speed of 1 mm / min. The strength was measured when the film was stretched by 1.5 mm. N = 3 JIS-K7127 test piece type 2 reference (strip: width 15 mm, distance between chucks 150 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 was measured by using a heat seal tester TP-701S, sealing one-side heating 1 kgf / cm ² × 1.0 s PET 12 μm on the evaluation sample, and using a Tensilon universal testing machine at a test speed of 300 mm / min. Width 15 mm N = 3 Performed at 140 ° C.

Using a screw diameter 30 mmφ extruder, Brass Chem C4LL-LL118 (d = 0.916, MF), which is a linear low density polyethylene resin (resin composition 1) derived from sugarcane
R = 1.0 g / 10 min) and 50 wt%, Ube Maruzen polyethylene LDPE-F120N (d = 0.920, MFR = 1.2 g / 10 min) which is a petroleum-derived linear low density polyethylene resin 2 50% by weight was melt-kneaded at 200 ° C. to obtain a resin composition. Next, the resin composition was formed into a film F2 shown in FIG. 3 having a thickness of 130 μm under processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm by an upper blown air-cooled inflation coextrusion film forming machine, and the biomass degree was measured. 44%.

  As a resin composition for the first layer and the third layer, Mitsui Chemicals C6LL-Evolution SP2020 (d = 0.916, MFR = 2.3 g / 10 min) was melted at 200 ° C. using a screw diameter 30 mmφ extruder. The resin composition was obtained by kneading. Similarly, as a resin composition for the second layer, using a screw diameter 30 mmφ extruder, Brass Chem C4LL-LL118 (d = 0.916, MFR = 1.0 g / 1.0), which is a linear low density polyethylene resin derived from sugarcane. 10 minutes) was melt-kneaded at 200 ° C. to obtain a resin composition. The layer ratio of the first layer: second layer: third layer was 1: 1: 1. Next, the resin composition was formed into a film F3 shown in FIG. 4 having a thickness of 130 μm under the processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm by a two-type three-layer top-blown air-cooled inflation co-extrusion film forming machine. Was about 29%.

  As a resin composition for the first layer and the third layer, Mitsui Chemicals C6LL-Evolution SP2020 (d = 0.916, MFR = 2.3 g / 10 min) was melted at 200 ° C. using a screw diameter 30 mmφ extruder. The resin composition was obtained by kneading. Similarly, as a resin composition for the second layer, using a screw diameter 30 mmφ extruder, Brass Chem C4LL-LL118 (d = 0.916, MFR = 1.0 g / 1.0), which is a linear low density polyethylene resin derived from sugarcane. 10 minutes) and 50 parts by weight of Ube Maruzen polyethylene LDPE-F120N (d = 0.920, MFR = 1.2 g / 10 minutes) were melt-kneaded at 200 ° C. to obtain a resin composition. The layer ratio of the first layer: second layer: third layer was 1: 2: 1. Subsequently, the resin composition was formed into a film F4 shown in FIG. 5 having a thickness of 130 μm under the processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm by a two-type three-layer top-blown air-cooled inflation coextrusion film forming machine. Was about 22%.

A two-component curable urethane adhesive is used using a biaxially stretched nylon film (ONy, Toyobo Harden N-1102) as the base film 5 and a film F4 of Example 4 having a thickness of 25 μm as the outer layer. When the adhesive is applied to the ONy surface at about 4 g / m ² and the corona-treated surface of polyethylene is bonded by a dry lamination method, a laminated film 3 shown in FIG. 6 having a two-layer structure is obtained, and this biomass degree is measured. About 18%.

  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.

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, A film F4 of Example 4 was formed by laminating the aluminum vapor-deposited surface of a polyethylene 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 of was laminated by a dry lamination method to obtain a laminated film 3 having a three-layer structure. And when this laminated film 3 was used, the refilling standing pouch (packaging bag 6) with the spout part which provided the opening cut line with the laser was created, and the biomass degree was measured, it was about 17%.

  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.

  Only the bottom material in the refilling standing pouch with the spout part of Example 6 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. Therefore, as the bottom material of the standing pouch of the present invention, either the laminated film 3 containing the same plant origin as the trunk portion or the petroleum-derived film may be used.

  In the same manner as in Example 1, using a 30 mmφ screw diameter extruder, Brass Chem C4LL-LL318 (d = 0.918, MFR = 2.7 g), which is a sugarcane-derived linear low-density polyethylene resin (resin composition 1). / 10 minutes) was melt-kneaded at 200 ° C. to obtain a resin composition. Next, the resin composition is molded by 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, thereby forming a film having a thickness of 120 μm (1 type, 3 layers) and having an excellent appearance. It was about 88% when the biomass degree was measured.

  In the same manner as in Example 1, using a 30 mmφ screw diameter extruder, Brass Chem C4LL-LL318 (d = 0.918, MFR = 2.7 g), which is a sugarcane-derived linear low-density polyethylene resin (resin composition 1). / 10 minutes) and Mitsui Chemicals C6LL-Evolu SP2020 (d = 0.918, MFR = 3.8 g / 10 minutes) at 7: 3 at 200 ° C. and extruded, and extruded by a T-die cast film forming machine. By molding the resin composition under the processing conditions of a temperature of 220 ° C. and a rotational speed of 45 rpm, a film having a thickness of 120 μm (1 type, 3 layers) and having a stable and excellent appearance can be formed. About 59%.

  As described in detail above, the films F1 to F4 made of the polyethylene resin of this example are made of the resin composition 1 containing a linear low-density plant-derived polyethylene resin obtained by a gas phase polymerization method. It is. The films F <b> 1 to F <b> 4 are used as sealant films to form a laminated film 3 laminated with the base film 5, and the packaging bag 6 is made of the laminated film 3.

  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 or container made of the film.

DESCRIPTION OF SYMBOLS 1 Resin composition 2 Petroleum origin polyethylene-type resin 3 Laminated | multilayer film 4 Sealant film 5 Base film 6 Packaging bag 7,8 Side sheet 9 Bottom sheet F1-F4 film

Claims (4)

A film made of polyethylene resin,
5 to 90% by weight of linear low-density plant-derived polyethylene resin obtained by vapor phase polymerization method of plant-derived ethylene and petroleum-derived α-olefin, and 10 to 95% by weight of petroleum-derived polyethylene resin. And a layer mixed with
The α-olefin is butene-1 or hexene-1 or a mixture thereof;
The linear low-density plant-derived polyethylene resin has physical properties of 0.910 to 0.925 g / cm ³ and a melt flow rate of 0.5 to 4.0 g / 10 min.
A sealant film for a packaging material, wherein a film having a multilayer structure in which an outer layer and an inner layer are made of petroleum-derived polyethylene resin is used as a heat-sealable film. The sealant film for a packaging material according to claim 1, wherein the polyethylene-based resin is an ethylene-α-olefin copolymer having a biomass degree calculated from a measurement value of radiocarbon dating ^14C . A laminated film for packaging material, wherein the sealant film for packaging material according to claim 1 or 2 is laminated with a base film. A packaging bag comprising the laminated film for packaging material according to claim 3 .

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