JP6662437B2 - Sealant film for packaging material using plant-derived polyethylene, laminated film for packaging material, and packaging bag - Google Patents

Description

  The present invention relates to a film made of a polyethylene resin, and more particularly, to a sealant film and a laminated film for a packaging material, in which the polyethylene resin contains a plant-derived polyethylene resin, and a packaging bag using these films.

  Conventionally, packaging bags represented by, for example, refills such as shampoos and rinses, and pouches used as packaging materials for foods and the like have been constituted by packaging materials composed of a sealant film and a base film, and have environmental problems and oil problems. In order to save depleted resources and reduce the amount of these petroleum resources used in packaging materials, ethylene-α-olefin copolymers and polymers having epoxy groups are added to polylactic acid resins as carbon-neutral materials. (For example, Patent Document 1).

JP 2009-155516 A

However, in such a packaging bag, as described above, although the ratio of the petroleum-derived material is reduced by including a biodegradable resin other than the petroleum-derived material in the resin composition constituting the packaging bag, Compared with the method described above, there is a problem that workability such as tear strength and heat seal strength is remarkably inferior, and productivity cannot be improved.
Accordingly, an object of the present invention is to use a plant-based polyethylene resin which is a renewable resource as a raw material, to save petroleum resources, and to reduce the amount of carbon dioxide emitted. Another object of the present invention is to provide a laminated film for packaging materials and a packaging bag excellent in processability using these films.

  Therefore, the sealant film for a packaging material according to the first aspect of the present invention is a film made of a polyethylene resin, and is a film obtained by a gas phase polymerization method of plant-derived ethylene and petroleum-derived α-olefin. A single-layer film made of a resin composition containing 5 to 90% by weight of a chain-like low-density plant-based polyethylene resin and 10 to 95% by weight of a petroleum-based polyethylene resin is a heat-sealing film. Features.

The sealant film for a packaging material according to the invention described in claim 2 is the film according to claim 1, wherein the polyethylene resin has a biomass degree calculated from a measured value of radiocarbon dating ¹⁴ C. -It is characterized by being an olefin copolymer.

The invention according to claim 3 is the sealant film for a packaging material according to claim 1 or 2, wherein the α-olefin is butene-1 or hexene-1 or a mixture thereof, and the density is 0.910 to 0. 925 g / cm ³ , and a melt flow rate having physical properties of 0.5 to 4.0 g / 10 minutes.

  According to a fourth aspect of the present invention, there is provided a laminated film for packaging material, wherein the sealant film for packaging material according to any one of the first to third aspects is laminated with a base film.

  According to a fifth aspect of the present invention, there is provided a packaging bag using the laminated film for a packaging material according to the fourth aspect.

  According to the invention of claim 1, a film made of a polyethylene resin, a linear low-density plant-derived polyethylene obtained by a gas phase polymerization method of plant-derived ethylene and petroleum-derived α-olefin. Since a single-layer film made of a resin composition containing 5 to 90% by weight of a resin-based resin and 10 to 95% by weight of a petroleum-derived polyethylene resin is used as a heat-sealing film, it is used for a packaging material made of a polyethylene resin. From the state in which the composition of the sealant film all depends on the petroleum-derived resin composition, this petroleum-derived polyethylene resin has no difference in performance from the petroleum-derived polyethylene resin, and is derived from plants such as carbon-neutral sugarcane. Mixing (substituting) polyethylene resin reduces the use of petroleum resources and sealant film for packaging materials. It is possible to suppress granulation and carbon dioxide emissions at the time of disposal. Therefore, it is possible to provide a sealant film for a packaging material made of a polyethylene resin with reduced environmental load. Further, the use ratio of the polyethylene-based resin constituting the sealant film for packaging materials derived from petroleum can be reduced. Therefore, it is possible to provide a sealant film for a packaging material made of a polyethylene resin, which saves petroleum resources and reduces an environmental load.

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 radiocarbon dating ¹⁴ C, the sealant film for a packaging material is used. The origin of the raw material of the constituent polyethylene resin can be identified by using the degree of biomass as an index, and the raw material derived from the production of the sealant film for a packaging material to the disposal can be confirmed. Therefore, it is possible to provide a sealant film for a packaging material made of a polyethylene-based resin, which can be identified from the raw material.

According to the invention described in claim 3, the α-olefin is butene-1 or hexene-1 or a mixture thereof, the density is 0.910 to 0.925 g / cm ³ , and the melt flow rate is 0.5 to 4. Since it has physical properties of 0.0 g / 10 min, there is no difference in physical properties from petroleum-based polyethylene resin, so that the existing film manufacturing process can be used and the raw material can be switched without impairing the processing suitability of the packaging material. Can be. Therefore, it is possible to provide a sealant film for a packaging material made of a polyethylene-based resin which is excellent in reduction of environmental load and production efficiency.

  According to the invention as set forth in claim 4, packaging in which a sealant film for a packaging material (described in any one of claims 1 to 3) made of a polyethylene resin containing a plant-derived polyethylene resin is laminated with a base film. Since it is a laminated film for materials, even in a sealant film used for heat sealing, it is possible to reduce the petroleum-derived usage ratio of the polyethylene resin constituting the film which is the sealant film, thereby reducing the amount of petroleum resources used. At the same time, the amount of carbon dioxide emitted during production and disposal of the laminated film for packaging material can be suppressed. Therefore, it is possible to provide a laminated film for a packaging material made of a polyethylene resin, which saves petroleum resources and reduces the environmental burden.

  According to the invention as set forth in claim 5, a film made of a polyethylene-based resin containing a plant-derived polyethylene-based resin (in any one of claims 1 to 3) is laminated with a base film and a laminated film for a packaging material. Since it is a packaging bag using (claim 4), it is possible to reduce the petroleum-derived use ratio of the polyethylene resin in the laminated film for packaging material constituting the packaging bag, and to reduce the amount of petroleum resources used. In addition to the reduction, it is possible to suppress the amount of carbon dioxide emitted during the production and disposal of the packaging bag. Therefore, it is possible to provide a packaging bag made of polyethylene resin, which saves petroleum resources and reduces environmental load.

  In addition, the ratio of petroleum-based polyethylene resin used in packaging bags, which are widely used as disposables in the world, can be reduced, reducing the use of petroleum resources and reducing carbon dioxide emissions during the production and disposal of packaging bags. The amount can be suppressed.

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 | membrane which consists of a linear low density polyethylene system resin derived from a sugarcane of this invention. FIG. 1 is a cross-sectional side view schematically showing a single-layer film in which a resin composition of the present invention and a petroleum-based polyethylene resin are mixed. It is sectional side view which shows typically the film which has the multilayer structure which used the intermediate | middle layer of this invention as a resin composition. FIG. 1 is a cross-sectional side view schematically illustrating 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 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. These containers and packaging bags are laminated on containers exemplified by laminated tubes used for food and cosmetics, and packaging bags exemplified by standing pouches widely used as packaging materials for refilling shampoos and rinses. It is composed of film.

  In this laminated film, there is a base film, in which a sealant film to be used on the inner surface of the laminated film as a heat sealing material is laminated, and as a material of the base film, for example, a polyethylene resin or the like is used, and a sealant film is used. For example, a linear low-density polyethylene-based resin with an intermediate layer interposed therebetween is used as a laminate.

As described above, as the material of the laminated film, a polyethylene resin, which is a plastic resin, is often used.However, conventionally, this polyethylene resin has been produced from petrochemical origin using petroleum as a starting material. The above-mentioned linear low-density polyethylene-based resin is obtained by converting ethylene obtained by refining crude oil and an α-olefin as a comonomer species into a gas phase in the presence of a metallocene catalyst at a high temperature of 120 ° C. or higher. Are copolymerized. 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 substituted cyclopentadienyl group (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. -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) Dichloro bodies such as -indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride and dimethyl bodies of the above metallocene compounds A metallocene catalyst containing a metallocene compound as a main component, for example, an isomer, diethyl, dihydro, diphenyl, dibenzyl, etc. is 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 increasing awareness of environmental issues such as global warming due to increased carbon dioxide emissions, the petroleum-based polyethylene resin described above has been used in the production and disposal of petrochemical products. Until that time, a large amount of the immobilized carbon dioxide of the petroleum feedstock will be discharged, so that the above-mentioned intention cannot be met.

  In view of these problems, in recent years, technology for producing plastics from plants that are carbon-neutral and renewable resources has been developed, and among them, polyethylene, which is the most produced among plastics, is The technology to produce sugar cane as a starting material has been established. (Edited by 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 approximately 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 the sugarcane-derived linear low-density polyethylene resin of the present invention.

  As shown in FIG. 1, a sugar solution taken out of a sugarcane harvested from a field is heated and concentrated to separate crystallized crude sugar and waste sugar by 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. In addition, ethylene and polyethylene derived from plants have been confirmed to have the same quality as ethylene and polyethylene derived from petroleum.

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

  In the present invention, by using a plant-derived linear low-density polyethylene-based resin obtained as described above to produce a film that forms a laminated film that constitutes a container or a packaging bag, is used as a laminated film Reduce the use ratio of petroleum-derived resin compositions in resin compositions (such as linear low-density polyethylene resins), thereby conserving petroleum resources and contributing to an improved environment by reducing carbon dioxide emissions. Is what you do.

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

The 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, similarly to the linear low-density polyethylene resin derived from petroleum. / Cm ³ , and a 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. The resin composition comprising such a sugarcane-derived linear low-density polyethylene resin is appropriately contained in an upper limit of 90% by weight based on the petroleum-derived linear low-density polyethylene resin.

In the evaluation of the above physical properties, the 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 minutes) was measured at a test temperature of 190 ° C. and a test load of 21.18 N according to JIS K 7210 (1995).

Furthermore, the above-mentioned ethylene-α-olefin copolymer having a biomass degree by radiocarbon dating ¹⁴ C of 80 to 100% is used as the sugarcane-derived linear low-density polyethylene resin.

Here, a resin composition derived from a plant (biomass) and a petroleum-derived resin composition 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 degree, since carbon of the resin composition derived from petroleum does not contain ¹⁴ C (radioactive carbon 14, half-life 5730 years), the concentration of ¹⁴ C was measured by accelerator mass spectrometry, In the composition, it is used as an index of the content ratio of the plant-derived resin composition. Therefore, in the case of a film using a plant-derived resin composition, when the biomass degree of the film is measured, a biomass degree corresponding to the content of the plant-derived resin composition is generated.

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, this graphite was mounted on a ¹⁴ C-AMS dedicated device (manufactured by NEC Corporation) based on a tandem accelerator to count ¹⁴ C, ¹³ C concentration ( ¹³ C / ¹² C), and ¹⁴ C concentration ( ¹⁴ C). C / ¹² C) is measured, and the ratio of the ¹⁴ C 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 application, by making a film composed of such a resin composition, from the state that all depends on the petroleum-derived resin composition, to this petroleum-based polyethylene resin, the petroleum-derived polyethylene resin and performance By mixing (substituting) a plant-based polyethylene resin such as sugarcane with no difference, it is possible to suppress carbon dioxide emission during film production and disposal.

In addition, the resin composition 1 of the present invention has 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 a petroleum-based 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 measured value of the radiocarbon dating ¹⁴ C, the resin composition 1 is derived from the raw material of the polyethylene resin constituting the film. The biomass degree can be identified using the index as an index, and the source material from the time of film production to the time of disposal can be confirmed.

  Next, in the present application, the above-described resin composition 1 and a petroleum-derived polyethylene-based resin 2 described below can be formed into the following film. FIG. 3 is a cross-sectional side view schematically showing a single-layer film in which a resin composition and a petroleum-based polyethylene resin are mixed, and FIG. 4 is a schematic view of a film having a multilayer structure in which an intermediate layer is a resin composition. FIG. 5 is a cross-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-based resin are mixed.

  In this case, 5 to 90% by weight of the resin composition 1 and 10 to 95% by weight of the petroleum-derived polyethylene-based resin 2 are used to form a film according to the following (A), (B) or (C). Configured. First, as shown in FIG. 3, the film F2 of (A) can have a single-layer structure in which the resin composition 1 and a petroleum-based polyethylene resin 2 are mixed.

  Further, as shown in FIG. 4, the film F3 of (B) may have a multilayer structure in which the intermediate layer is the resin composition 1 and the outer and inner layers are the petroleum-derived polyethylene-based resin 2.

  Further, as the film F4 of (C), as shown in FIG. 5, 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 formed of the petroleum-derived polyethylene resin 2. A multi-layer configuration can also be used.

  With such a configuration, the use ratio of the polyethylene resin 2 constituting the films F2 to F4 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 resin 2 for the inner and outer layers constituting the films F3 to F4 as in (B) or (C), the films F3 to F4 can be manufactured with the characteristics of the existing manufacturing process. Can be.

  Next, in the present application, a laminated film using the films F1 to F4 can be obtained. FIG. 6 is a cross-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 formed by laminating any one of the films F1 to F4 as a sealant film 4 and a base film 5.

  In addition, 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 and 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, in the sealant film 4 used for heat sealing, the use ratio of the polyethylene-based resin constituting each of the films F1 to F4 as the sealant film 4 can be reduced due to petroleum. Along with saving resources, it is possible to suppress the amount of carbon dioxide emitted during production and disposal of the laminated film 3.

  Using the laminated film 3 as described above, the two side sheets 7 and 8 made of the laminated film 3 are arranged such that the surfaces of the sealant films 4 are opposed to each other. A bottom sheet 9 made of the laminated body is inserted into the center with the sealant film 4 as the outer surface by being mountain-folded at the center, and is formed in a form having a gusset portion. In the vicinity, a cutout portion of a substantially semicircular bottom sheet is provided, and the gusset portion is heat-sealed with a ship-bottom bottom seal portion including a peripheral edge to form a bottom portion.

  Next, the side edges of the two side sheets 7, 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 as a filling port for contents. A pouch (packing bag 6) formed in a standing pouch format as shown is formed. The upper seal 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 or the like. Although not shown, a spout may be formed at the upper part of the body, for example, with a break line for opening by laser.

  By adopting such a configuration, the use ratio of the polyethylene-based resin derived from petroleum in the laminated film 3 constituting the packaging bag 6 can be reduced, and while saving petroleum resources, 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 petroleum-derived use ratio of the polyethylene resin constituting such a packaging bag which is widely used as disposable bags, and to greatly reduce carbon dioxide emissions. Can be.

  In addition, using a film F1 to F4 made of the resin composition 1 of the present invention or a laminated film 3 using these films F1 to F4, in addition to the packaging bag 6 exemplified in the above-mentioned standing pouch, a polyethylene-based resin For example, a container including a laminating tube, a liquid paper container, or the like, which contains contents such as food and drink, cosmetics, medicines, and miscellaneous goods, which is made of the resin composition 1 using a resin, a lid material of the container, or a container And the like, so that the use ratio derived from petroleum can be further reduced, and the carbon dioxide emission can be greatly suppressed.

  Next, an example of a film constituted using the plant-derived polyethylene resin (resin composition 1) of the present invention will be described.

  Using a screw diameter 30 mmφ extruder, C4LL-LL118 (d = 0.916, MFR = 1.0 g / 10 min), which is a sugarcane-derived linear low-density polyethylene-based resin (resin composition 1), was added for 200 times. The mixture was melted and kneaded at a temperature of ℃ ° C. to obtain a resin composition. Next, by using a top blow air-cooled inflation co-extrusion film-forming machine, the resin composition was molded under the processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm to obtain a film F1 shown in FIG. A film could be formed, and its biomass degree was measured to be about 88%. In addition, the butene-1 (C4) comonomer species contained in the sugarcane-derived linear low-density polyethylene 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 petrochemical-derived C4LL linear low-density polyethylene resin, in the same manner as in Example 1, an extrusion temperature of 200 ° C. and a processing speed of 60 rpm and a thickness of 50 μm were used. And the biomass degree was measured 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 performed on the resin composition of Example 1, and the obtained results are described below.

From the above results, the sugarcane (plant) -derived linear low-density polyethylene-based resin (Example 1) has a higher tensile breaking strength and tear strength than the petrochemical-derived linear low-density polyethylene-based resin (Comparative Example 1). It is clear that the waist and seal strength are equivalent, the elastic modulus is low and the waist is flexible. As described above, the plant-derived linear low-density polyethylene-based resin has properties equal to or higher than those of the petrified-derived linear low-density polyethylene-based resin, It proved to be comparable to processing suitability.

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 at a test speed of 1 mm / min. Using a Tensilon universal testing machine according to JIS-K7176. The strength at the time of elongation of 1.5 mm was measured. N = 3 Reference was made to JIS-K7127 test piece type 2 (strip: width 15 mm, distance between chucks 150 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 determined by using a heat seal tester TP-701S, placing a single-sided heating of 1 kgf / cm ² × 1.0 s PET 12 μm on the evaluation sample and sealing the same, and testing with a Tensilon universal testing machine at a test speed of 300 mm / min. The test was performed at a width of 15 mm N = 3 140 ° C.

  Using a screw diameter 30 mmφ extruder, C4LL-LL118 (d = 0.916, MFR = 1.0 g / 10 min), which is a sugarcane-derived linear low-density polyethylene-based resin (resin composition 1), was added to 50 parts. Wt% and 50 wt% of 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, is melt-kneaded at 200 ° C. A resin composition was obtained. Next, the resin composition was molded into a film F2 having a thickness of 130 μm as shown in FIG. 3 under the processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm by a top-blowing air-cooled inflation co-extrusion film-forming machine. It was 44%.

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

  As a resin composition for the first and third layers, a Mitsui Chemicals C6LL-Evolu SP2020 (d = 0.916, MFR = 2.3 g / 10 min) was melted at 200 ° C. using a 30 mmφ screw extruder. The mixture was kneaded to obtain a resin composition. Similarly, as a resin composition for the second layer, using a screw diameter of 30 mmφ extruder, C4LL-LL118 (d = 0.916, MFR = 1.0 g /), which is a sugarcane-derived linear low-density polyethylene resin, is used. 10 minutes) 50 parts by weight 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 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 F4 shown in FIG. 5 by a two-type three-layer top-blowing air-cooled inflation co-extrusion film forming machine under the processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm. Was about 22%.

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 F4 of Example 4, a two-component curable urethane-based adhesive was used. Then, about 4 g / m ² of the adhesive was applied to the ONy surface, and the corona-treated surface of polyethylene was adhered by a dry lamination method to obtain a laminated film 3 having a two-layer structure as shown in FIG. 6. , About 18%.

  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.

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) was laminated on the aluminum-deposited surface, and a two-part curable urethane-based adhesive was applied to the polyethylene terephthalate surface of VMPET at about 4 g / m ² to obtain a film F4 of Example 4. Was laminated by a dry lamination method to obtain a laminated film 3 having a three-layer structure. Using this laminated film 3, a refillable standing pouch (packing bag 6) with a spout provided with a break line for opening with a laser was prepared, and the degree of biomass was about 17%.

  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.

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

  Similarly to Example 1, using a 30 mm diameter screw extruder, C4LL-LL318 (d = 0.918, MFR = 2.7 g), which is a sugarcane-derived linear low-density polyethylene resin (resin composition 1), was used. / 10 min) at 200 ° C. to obtain a resin composition. Next, a T-die casting film forming machine is used to form a resin composition under the processing conditions of an extrusion temperature of 220 ° C. and a rotation speed of 45 rpm to form a film having a stable and excellent appearance with a thickness of 120 μm (one type and three layers). The biomass degree was measured to be about 88%.

  Similarly to Example 1, using a screw diameter of 30 mmφ extruder, C4LL-LL318 (d = 0.918, MFR = 2.7 g), a sugarcane-derived linear low-density polyethylene-based resin (resin composition 1), was used. / 10 min) and Mitsui Chemicals C6LL-Evolu SP 2020 (d = 0.918, MFR = 3.8 g / 10 min) were kneaded and melted at 7: 3 at 200 ° C. and extruded by a T-die casting film forming machine. By molding the resin composition under the processing conditions of a temperature of 220 ° C. and a rotation speed of 45 rpm, a film having a stable and excellent appearance having a thickness of 120 μm (one type and three layers) 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 the linear low-density plant-derived polyethylene resin obtained by the gas phase polymerization method. It is. These films F1 to F4 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 a container made of the film.

DESCRIPTION OF SYMBOLS 1 Resin composition 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-F4 film

Claims (4)

At least a base film, a laminated film for a packaging material comprising a heat-sealing film,
The heat-sealable film is made of a film of a single-layer structure according to the linear low density polyethylene resin derived from plants in which the plant-derived ethylene and petroleum-derived α- olefin copolymerized by gas phase polymerization,
The plant-derived linear low-density polyethylene resin is an ethylene-α-olefin copolymer having a biomass degree calculated from radiocarbon dating ¹⁴ C and a melt flow rate of 80 to less than 100%. There laminated film for packaging material characterized by having physical properties of 0.70~1.30g / 10 min. At least a base film, a laminated film for a packaging material comprising a heat-sealing film,
The heat-sealing film is a multi-layer film including at least one layer of a plant-derived linear low-density polyethylene resin in which plant-derived ethylene and petroleum-derived α-olefin are copolymerized by a gas phase polymerization method. Become
The plant-derived linear low-density polyethylene resin is an ethylene-α-olefin copolymer having a biomass degree calculated from the measured value of radiocarbon dating ¹⁴ C of 80 to less than 100%. Laminated film for packaging materials. The α-olefin is butene-1 or hexene-1 or a mixture thereof, and the plant-derived linear low-density polyethylene resin has a density of 0.910 to 0.925 g / cm ³ and a melt flow The laminated film for packaging materials according to claim 2, wherein the rate has a physical property of 0.5 to 4.0 g / 10 minutes. A packaging bag comprising the laminated film for packaging material according to claim 1.

Images