JP6508319B2 - 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 for a packaging material, a laminated film for a packaging material, and a packaging bag using these films, wherein the polyethylene resin comprises a plant-derived polyethylene resin.

  Conventionally, packaging bags typified by, for example, refills such as shampoos and rinses and pouches used as packaging materials for foods and the like are made of a packaging material composed of a sealant film and a base film, and environmental problems and petroleum Etc. In order to reduce the consumption of these petroleum resources to packaging materials in response to the saving of depleted resources, polylactic acid based resin as a carbon neutral material, ethylene-α-olefin copolymer and polymer having epoxy group There is a packaging bag (for example, patent document 1) containing the biodegradable resin composition which each contained a 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 material to reduce the ratio of the petroleum-derived material, the petroleum-based resin Compared with the above, the processing aptitude such as the tear strength and the heat seal strength is remarkably inferior, and there is a problem that the productivity can not be improved.
Accordingly, an object of the present invention is to use a plant-based polyethylene resin as a renewable resource as a raw material to save petroleum resources, and to use an environmentally friendly sealant film for packaging materials by reducing carbon dioxide emissions. It is an object of the present invention to provide a laminated film for packaging material and a packaging bag which is excellent in processability using these films.

Therefore, the sealant film for a packaging material according to the invention described in claim 1 is a film made of a polyethylene-based resin, and the polyethylene-based resin has a biomass degree of 80 calculated from the measured value of radiocarbon dating ¹⁴ C. It is a resin composition containing plant origin polyethylene system resin which has 100%, and it is characterized by making the film by the above-mentioned resin composition into a heat sealable film.

The invention according to claim 2 is the sealant film for packaging material according to claim 1, which contains 5 to 90% by mole of the plant-derived polyethylene-based resin and 10 to 95% by mole of a petroleum-derived polyethylene-based resin. The resin composition is characterized by comprising the following (A) or (B) or (C).
(A) Single-layer structure in which the resin composition and the petroleum-derived polyethylene-based resin are mixed (B) A multilayer structure in which the intermediate layer is the resin composition and the outer layer and the inner layer are the petroleum-derived polyethylene-based resin C) A multilayer structure in which the intermediate layer is a layer in which the resin composition and the petroleum-derived polyethylene resin are mixed, and the outer layer and the inner layer are the petroleum-derived polyethylene resin

The laminated film for a packaging material according to the invention described in claim 3 is characterized in that the sealant film for a packaging material according to claim 1 or 2 is laminated with a base film.

  The packaging bag which concerns on invention of Claim 4 is characterized by using the laminated film for packaging materials of Claim 3. It is characterized by the above-mentioned.

According to the invention as set forth in claim 1, the polyethylene-based resin is a film made of a polyethylene-based resin, wherein the polyethylene-based resin is a plant-derived polyethylene-based resin having a biomass degree of 80 to 100% calculated from the measured value of radiocarbon dating ^14C. Since a resin composition containing a resin is used as a heat sealable film, the configuration of the sealant film for packaging material made of a polyethylene-based resin depends entirely on the petroleum-derived resin composition. In this petroleum-derived polyethylene resin, there is no difference in performance from the petroleum-derived polyethylene resin, and the amount of petroleum resources used is mixed (replaced) with plant-derived polyethylene resins such as carbon neutral sugar cane. While reducing the amount of carbon dioxide emissions during film production and disposal Therefore, the sealant film for packaging materials which consists of polyethylene-type resin which reduced the environmental impact can be provided.

  Furthermore, since there is no difference in physical properties from petroleum-derived polyethylene resins, the existing sealant film manufacturing process for packaging materials can be used, and the raw materials can be switched without impairing the processability of the packaging material. Therefore, the sealant film for packaging materials which consists of polyethylene-type resin which was excellent in reduction of environmental impact and production efficiency can be provided.

  Furthermore, the raw material origin of the polyethylene-based resin constituting the sealant film for packaging material can be identified by using the degree of biomass as an index, and the derived raw material can be confirmed from the time of production of the film to the time of disposal. Therefore, the sealant film for packaging materials which consists of a polyethylene-type resin which enabled identification derived from a raw material can be provided.

According to the invention as set forth in claim 2, a resin composition comprising 5 to 90% by mole of a plant-derived polyethylene resin and 10 to 95% by mole of a petroleum-derived polyethylene resin is used as follows (A) ) Or (B) or (C)
(A) Single-layer configuration in which resin composition and petroleum-derived polyethylene-based resin are mixed (B) Multilayer configuration in which the intermediate layer is a resin composition and the outer layer and the inner layer are petroleum-derived polyethylene-based resin (C) intermediate layer The layer is a mixture of the resin composition and a petroleum-derived polyethylene-based resin, and the outer layer and the inner layer are composed of a petroleum-derived polyethylene-based resin in a multilayer structure. The use ratio of petroleum origin can be reduced, and the use of petroleum resources can be reduced, and carbon dioxide emissions at the time of 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 sealant film for a packaging material such as (B) or (C), a film can be produced with the characteristics of the existing production process. Therefore, it is possible to provide a sealant film for packaging material made of a polyethylene-based resin with reduced petroleum resources and reduced environmental impact.

According to the invention as set forth in claim 3, a laminate for packaging material in which a sealant film for packaging material (described in claim 1 or 2) comprising a polyethylene resin containing a plant-derived polyethylene resin is laminated on a substrate film Since it is a film, the sealant film used for heat sealing can also reduce the petroleum-derived use ratio of the polyethylene resin constituting the film which is the sealant film, and reduce the amount of petroleum resources used and package It is possible to suppress carbon dioxide emissions at the time of production and disposal of laminated films for materials. Therefore, the laminated film for packaging materials which consists of polyethylene-type resin which saved the petroleum resource and reduced the environmental impact can be provided.

  According to the invention described in claim 4, a laminate for a packaging material in which a sealant film for a packaging material (described in claim 1 or 2) made of a polyethylene-based resin containing a plant-derived polyethylene-based resin is laminated with a substrate film Since it is a packaging bag using a film (claim 3), it is possible to reduce the petroleum-derived use ratio of polyethylene resin in the laminated film for packaging material that constitutes the packaging bag, and the amount of petroleum resources used And reduce carbon dioxide emissions during the manufacture and disposal of packaging bags. Therefore, it is possible to provide a packaging bag made of a polyethylene-based resin with reduced petroleum resources and reduced environmental impact.

  Furthermore, it is possible to reduce the petroleum-derived use ratio of polyethylene-based resins that make up many packaging bags widely used in the world as disposables, reduce the amount of petroleum resources used, and emit carbon dioxide when manufacturing and disposing of packaging bags. The amount can be reduced. Therefore, it is possible to provide a packaging bag made of a polyethylene-based resin with reduced petroleum resources and reduced environmental impact.

It is a flow figure showing an example of polyethylene production derived from sugarcane. It is a cross-sectional side view which shows typically the film which consists of a linear low density polyethylene-type resin derived from the sugarcane of this invention. It is a cross-sectional side view which shows typically the film of the single layer structure which mixed the resin composition of this invention, and petroleum-derived polyethylene-type resin. It is a cross-sectional side view which shows typically the film which consists of a multilayer structure which made the intermediate | middle layer of this invention the resin composition. It is a cross-sectional side view which shows typically the film which consists of a multilayer structure which made the intermediate | middle layer of this invention the layer which mixed resin composition and petroleum origin polyethylene-type resin. BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional side view which shows typically an example of the laminated | multilayer film of this 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.

  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 in a container exemplified by a laminated tube used for food and cosmetics, and a packaging pouch exemplified by a standing pouch widely adopted as a packaging material for refilling shampoo and rinse. It is made of film.

  This laminate film includes a substrate film on which a sealant film used as a heat seal material is laminated on the inner surface of the laminate film, and as a material of the substrate film, for example, a polyethylene resin is used For the material of (1), for example, a linear low density polyethylene-based resin is used as a laminate with an intermediate layer interposed therebetween.

As described above, a polyethylene-based resin which is a plastic resin is often used as the material of the laminated film, but conventionally, this polyethylene-based resin is manufactured from petrochemicals using petroleum as a starting material, for example The linear low density polyethylene-based resin described above is a high temperature such as 120.degree. C. or higher in the gas phase in the presence of a metallocene catalyst and ethylene obtained by crude oil purification and the like and .alpha.-olefin as a comonomer species. Copolymerized with The α-olefin is represented by the 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- Heptene, 1-octene, 1-nonene, 1-decene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, octadecene and the like can be exemplified. The metallocene catalyst is not particularly limited, and, for example, one kind of group selected from a cyclopentadienyl group, a substituted cyclopentadienyl group (substituted cyclopentadienyl group), an indenyl group and a substituted indenyl group And a transition metal compound of Group 4 of the periodic table having a ligand in which one type of group selected from a fluorenyl group and a substituted fluorenyl group is crosslinked by a crosslinking group, and 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 Thiylene (1-cyclopentadienyl) (2,7-di-tert-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 The metallocene catalyst which has as a main component the metallocene compound which illustrates a diethyl body, a dihydro body, a diphenyl body, a dibenzyl body etc. is used. Moreover, the metallocene catalyst includes, for example, one kind of group selected from a cyclopentadienyl group, a substituted cyclopentadienyl group (substituted cyclopentadienyl group), an indenyl group and a substituted indenyl group, a fluorenyl group, A transition metal compound of Group 4 of the periodic table having a ligand in which one type of group selected from substituted fluorenyl groups is cross-linked by a cross-linking group can be mentioned, and a representative example thereof is diphenylmethylene (1-cyclopentadiphenyl). 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- Ropentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (9-fluorenyl ) Dichloro bodies such as zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride and dimethyl, diethyl or dihydro bodies of the above metallocene compounds A metallocene compound having a diphenyl compound, a dibenzyl compound and the like as an example is a main component.

  However, with an increasing awareness of environmental problems such as global warming due to an increase in carbon dioxide emissions, as well as saving resources such as oil and other depleted resources, polyethylene-based resins derived from petroleum as described above have been changed from manufacturing petrochemical products to disposal. In the meantime, the fixed carbon dioxide possessed by petroleum raw materials is discharged in large quantities, so the above intention can not be met.

  Based on these problems, in recent years, development of technology to produce plastics from plants that are carbon neutral and renewable resources is in progress, and among them, polyethylene, which is the most produced in plastics, is a biomass Technology was established to produce sugarcane as a starting material. Note that carbon neutral means that carbon dioxide absorption during plant growth and carbon dioxide emissions during combustion are approximately the same. Say.

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

As shown in FIG. 1, the sugar solution from which the sugarcane harvested from the field has been removed is removed by heating and concentration to crystallize crude sugar and crystallized waste sugar by means of a centrifugal separator. The waste molasses is then diluted with water to an appropriate concentration and fermented by yeast to produce ethanol. Then, this bioethanol is heated, and ethylene obtained by the intramolecular dehydration reaction in the presence of a catalyst is polymerized by a polymerization catalyst to obtain polyethylene. Plant-derived ethylene and polyethylene have been confirmed to have the same quality as petroleum-derived ethylene and polyethylene.

  Then, although the linear low density polyethylene resin used for the film of this invention is produced from ethylene which made the above-mentioned starting materials a plant origin, as this production method, it is direct from ethylene derived from petroleum. As in the case of producing a linear low density polyethylene-based resin, it can be obtained by copolymerizing plant-derived ethylene and an α-olefin by gas phase polymerization in the presence of a metallocene catalyst.

  In this invention, it is used for a laminated film by manufacturing the film which forms the laminated film which comprised the container and the packaging bag using the linear low density polyethylene type resin of plant origin obtained as mentioned above In resin compositions (such as linear low density polyethylene resins), the use ratio of petroleum-derived resin composition can be reduced to save oil resources and contribute to environmental improvement by reducing carbon dioxide emissions. It is

  In the present application, a linear low density polyethylene-based material derived from sugar cane (not limited to sugarcane and may be any plant as a raw material for producing a linear low density polyethylene-based resin) obtained by the above gas phase polymerization method It can be set as the film F1 as shown in FIG. 2 using the resin composition 1 which consists of resin.

In addition, the linear low density polyethylene-based resin derived from sugar cane has, as the petroleum-derived linear low density polyethylene-based resin, the comonomer type is butene-1 (C4) and the density is 910 to 925 kg / m ³ , Melt flow rate (MFR) in the range of 0.5 to 4.0 g / 10 min,
More preferably, each physical property can be set to 0.7 to 3.5 g / 10 min, and the ethylene-α-olefin copolymer is used. Such a resin composition comprising a linear low density polyethylene-based resin derived from sugar cane is contained in an appropriate ratio in an upper limit of 90 mol% with respect to a petroleum-derived linear low density polyethylene-based resin.

In addition, in the said physical-property evaluation, it measured according to JISK6760 (1981) using the sheet | seat of thickness 1mm obtained by press-molding at 150 degreeC as a density (d, unit: kg / m < ³ >) It is. Moreover, melt flow rate (MFR, unit: g / 10 minutes) is measured according to JIS K 7210 (1995) at a test temperature of 190 ° C. under a test load of 21.18 N.

Furthermore, in the above-mentioned polyethylene-based resin derived from sugar cane, a linear low density polyethylene-based resin having a biomass degree of 80 to 100%, for example, a biomass degree of 87%, according to radioactive carbon dating ¹⁴ C; A low density polyethylene resin having a% biomass degree is used.

Here, resin compositions derived from plants (biomass) and petroleum do not cause differences in physical properties such as molecular weight, mechanical properties and thermal properties. Therefore, in order to distinguish them, the degree of biomass is generally used. In this degree of biomass, carbon of petroleum-derived resin composition does not contain ¹⁴ C (radioactive carbon 14, half-life 5730), so the concentration of this ¹⁴ C is measured by accelerator mass spectrometry, and resin The composition is used as an indicator of the content ratio of the plant-derived resin composition. Therefore, if it is a film using the resin composition derived from plants, when the biomass degree of the film is measured, the biomass degree according to content of a plant origin resin composition will arise.

In the measurement of the degree of biomass, a sample to be measured is burned to generate carbon dioxide, and carbon dioxide purified in a vacuum line is reduced with hydrogen using iron as a catalyst to generate 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 Measure C / ¹² C) and calculate the ratio of ¹⁴ C concentration of sample carbon to standard modern carbon from this measurement value. In this measurement, oxalic acid (HOxII) provided by the National Institute of Standards (NIST) was used as a standard sample.

  In the present application, by making a film composed of such a resin composition, it is possible to use this petroleum-derived polyethylene-based resin and the petroleum-derived polyethylene-based resin in terms of performance from the state entirely dependent on the petroleum-derived resin composition. By mixing (substituting) a plant-based polyethylene-based resin such as sugar cane which has no difference, carbon dioxide emissions at the time of film production and disposal can be suppressed.

Further, the resin composition 1 of the present invention is an ethylene-α-olefin copolymer in which comonomer type is butene-1, density is 910 to 920 kg / m ³ and melt flow rate is 0.70 to 1.30 g / 10 min. Therefore, since there is no difference in physical properties from the petroleum-derived polyethylene resin, the existing film manufacturing process can be used, and the raw materials 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 radiocarbon dating ¹⁴ C, the raw material origin of the polyethylene resin constituting the film is This biomass degree can be identified as an index, and the raw material from the time of film production to the time of disposal can be confirmed.

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

  In this case, 5 to 90% by mole of the resin composition 1 and 10 to 95% by mole of the petroleum-derived polyethylene resin 2 in the following manner (A) or (B) or (C) Configured. First, as the film F2 of (A), as shown in FIG. 3, it is possible to have a single layer configuration in which the resin composition 1 and the petroleum-derived polyethylene-based resin 2 are mixed.

  In addition, as the film F3 of (B), as shown in FIG. 4, the intermediate layer may be a resin composition 1, and the outer layer and the inner layer may be a petroleum-derived polyethylene resin 2 in a multilayer structure.

  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 the petroleum-derived polyethylene resin 2 and It is also possible to have a multi-layered configuration.

  With such a configuration, the petroleum-derived use ratio of the polyethylene resin 2 constituting the films F2 to F4 can be reduced, and carbon dioxide emissions at the time of film production and disposal can be suppressed. In addition, by using the petroleum-derived polyethylene-based resin 2 in the inner and outer layers constituting the films F3 to F4 such as (B) or (C), the films F3 to F4 are manufactured with the characteristics of the existing manufacturing process. Can.

  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 the 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 laminates any one of the films F1 to F4 as the sealant film 4 with the base film 5.

  In addition, as base film 5, for example, polyethylene resin, polypropylene resin, cyclic polyolefin resin, polystyrene resin, acrylonitrile-styrene copolymer (AS resin), 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, various polyamide resins such as nylon, polyimide resin, polyamide 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, also in the sealant film 4 used for heat sealing, it is possible to reduce the petroleum-derived use ratio of the polyethylene-based resin that constitutes each of the films F1 to F4 that is the sealant film 4 Along with saving of resources, carbon dioxide emissions at the time of production and disposal of the laminated film 3 can be suppressed.

  The sealant film 4 of the two side sheets 7 and 8 made of the laminated film 3 is disposed opposite to each other using the laminated film 3 as described above, and the sealant film 4 is provided on at least one side of the lower end of the laminated film 3 Bottom sheet 9 made of laminated laminate is inserted into the center by mountain folding with the surface of sealant film 4 as the outer surface, and is formed in a form having a gusset portion, both lower ends of mountain folding bottom sheet 9 In the vicinity, a substantially semi-circular bottom sheet cutout portion is provided, and the gusset portion is heat-sealed by the bottom seal portion including the peripheral portion to form the bottom portion.

  Next, the side edges of the two side sheets 7, 8 on the front and back are heat sealed with the side edge seal portions to form a body, leaving the upper end as the filling port for the contents, as shown in FIG. A pouch (packaging bag 6) is formed which is made into a standing pouch type as shown. The upper seal portion provided at the filling port at the upper end portion is formed by heat sealing with a degassing seal or the like after the content is filled from this portion. In addition, although not shown in the drawings, it is also possible to form a spout portion provided with a slit for opening by laser on the upper portion of the body portion or the like.

  With such a configuration, it is possible to reduce the petroleum-derived use ratio of the polyethylene resin in the laminated film 3 constituting the packaging bag 6, and at the time of manufacturing and discarding the packaging bag 6 along with saving of petroleum resources. CO2 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-based resin that constitutes such packaging bags that are disseminated as disposables, and to greatly suppress carbon dioxide emissions. Can.

In addition, using the films F1 to F4 made of the resin composition 1 of the present invention, and the laminated films 3 using these films F1 to F4, polyethylene can be used other than the packaging pouch 6 exemplified in the above-mentioned standing pouch. A container comprising a resin composition 1 using a resin, for example, a laminate tube for containing contents such as food and drink, cosmetics, medicines, sundries, etc., a container including a liquid paper container, a lid of the container, or a container While being able to comprise the label etc. of, and reducing the use ratio derived from petroleum further, a carbon dioxide emission can be suppressed large.

  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 of 30 mmφ extruder, the Braschem C4LL-LL118 (d = 0. 916, MFR = 1.0 g / 10 min), which is a sugarcane-derived linear low density polyethylene resin (resin composition 1) The mixture was melt-kneaded at ° C to obtain a resin composition. Next, the resin composition is molded with a top-blowing air-cooling inflation co-extrusion film-forming machine under the processing conditions of an extrusion temperature of 200 ° C. and a rotation number of 60 rpm to obtain a 50 μm thick film F1 shown in FIG. It was possible to form a film, and its biomass degree was about 88% when measured. The comonomer species butene-1 (C4) contained in the sugarcane-derived linear low density polyethylene resin is petroleum-derived, and the content thereof is 1 to 15 mol% (the same applies hereinafter).

  On the other hand, as Comparative Example 1 of the above-mentioned film F1, using a petrification-derived C4LL linear low density polyethylene resin, in the same manner as in Example 1, 50 μm thickness under processing conditions of an extrusion temperature of 200 ° C. and a rotation number of 60 rpm. It was molded into a film of 0% and the degree of biomass 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 tensile breaking strength and tear strength compared to the petrification-derived linear low density polyethylene-based resin (Comparative Example 1) It can be seen that the waist and seal strength have similar strength, low elastic modulus and flexibility. Thus, the plant-derived linear low density polyethylene-based resin has physical properties equal to or higher than those of the petrification-derived linear low density polyethylene-based resin, and the production of the petrification-derived linear low density polyethylene-based resin It proved to be comparable with processing aptitude.

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 strip: minimum parallel width 6 mm, distance between chucks 80 mm).
The modulus of elasticity (tensile) was measured using a Tensilon universal tester in accordance with JIS-K7176, at a test speed of 1 mm / min. The strength was measured at an elongation of 1.5 mm, and 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 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 seal strength was measured using a heat seal tester TP-701S with one side heating 1 kgf / cm ² × 1.0 s PET 12 μm placed on the evaluation sample and sealed, and the test speed 300 mm / min. It carried out by width 15 mm N = 3 140 degreeC.

  Using a screw diameter of 30 mmφ extruder, 50 of Braschem C4LL-LL118 (d = 0. 916, MFR = 1.0 g / 10 min), which is a sugarcane-derived linear low density polyethylene resin (resin composition 1) Melt-knead at 200 ° C. with 50 mol% of mol% and Ube Maruzen polyethylene LDPE-F 120 N (d = 0.920, MFR = 1.2 g / 10 min) which is petroleum-derived linear low density polyethylene resin 2; A resin composition was obtained. Next, the resin composition is 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 number of 60 rpm by a top blowing air-cooling inflation coextrusion film forming machine, and its biomass degree is measured. It was 44%.

  Melt Mitsui Chemicals C6LL-Evolue SP 2020 (d = 0.916, MFR = 2.3 g / 10 min) at 200 ° C as a resin composition for the first layer and the third layer using an extruder with a screw diameter of 30 mmφ 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, Brass Chem C4LL-LL118 (d = 0. 916, MFR = 1.0 g / m) which is a linear low density polyethylene resin derived from sugar cane The mixture was melt-kneaded at 200 ° C. for 10 minutes to obtain a resin composition. The layer ratio of the first layer: the second layer: the third layer was 1: 1: 1. Next, the resin composition is formed into a film F3 shown in FIG. 4 having a thickness of 130 μm under processing conditions of an extrusion temperature of 200 ° C. and a rotation number of 60 rpm by two types and three layers of upper blowing air cooling inflation coextrusion film forming machine Was about 29%.

  Melt Mitsui Chemicals C6LL-Evolue SP 2020 (d = 0.916, MFR = 2.3 g / 10 min) at 200 ° C as a resin composition for the first layer and the third layer using an extruder with a screw diameter of 30 mmφ 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, Brass Chem C4LL-LL118 (d = 0. 916, MFR = 1.0 g / m) which is a linear low density polyethylene resin derived from sugar cane A resin composition was obtained by melt-kneading, at 200 ° C., 50 parts by weight of 10 minutes and 50 parts by weight of Ube Maruzen Polyethylene LDPE-F 120 N (d = 0.920, MFR = 1.2 g / 10 min). The layer ratio of the first layer: the second layer: the third layer was 1: 2: 1. Next, the resin composition is formed into a film F4 shown in FIG. 5 having a thickness of 130 μm under processing conditions of an extrusion temperature of 200 ° C. and a rotation number of 60 rpm by a two-kind three-layer upper blowing air cooling inflation coextrusion film forming machine. Was about 22%.

Using a two-component curable urethane adhesive using a biaxially stretched nylon film (ONy, Toyobo Harden N-1102) as the base film 5 and a film F4 of Example 4 in the outer layer with a thickness of 25 μm Then, about 4 g / m ² of the adhesive is applied to the ONy surface, and the corona-treated surface of polyethylene is bonded by the dry lamination method to obtain the laminated film 3 shown in FIG. , About 18%.

  Then, using this laminated film 3, create a standing pouch (packing bag 6) for refilling with a spout portion provided with a slit for opening by laser using a laminated film, insert the contents into this refilling standing pouch, and open the mouth The leaked contents, overturning, buckling, and breakage of the trunk of the sealed product were observed but not observed. Furthermore, the drop test was conducted 5 times from a height of 1 m, but no bag breakage or leakage was observed at all.

A biaxially stretched nylon film (ONy, Toyobo Harden 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) aluminum-deposited on one side in the intermediate layer, A film F4 of Example 4 is laminated with an aluminum vapor-deposited surface of a polyethylene terephthalate film), and further coated with about 4 g / m ² of a two-component curable urethane adhesive on a polyethylene terephthalate surface of VMPET. The laminate was bonded to the corona-treated surface by the dry lamination method to obtain a laminated film 3 having a three-layer structure. And using this laminated film 3, it was about 17% when a standing pouch (packing bag 6) for refilling with a spout with a slit for opening was provided with a laser and the degree of biomass was measured.

  The contents were put in the prepared refilling standing pouch and the mouth was sealed. Leakage of the contents, overturning, buckling, and breakage of the trunk were observed, but were not observed. Furthermore, a drop test was conducted 5 times from a height of 1 m, but no bag breakage or leakage was observed at all.

  Contents of only the bottom material in the stand-up pouch for refilling with a spout in the above Example 6 is a stand-up pouch for refilling made using a petroleum-derived film consisting of stretched polyamide (ONY) / LLDPE (linear low density polyethylene) In the case where the object was put in and the mouth was sealed, leakage of the contents, overturning, buckling, and breakage of the trunk were observed, but not observed. Furthermore, a drop test was conducted 5 times from a height of 1 m, but no bag breakage or leakage was observed at all. Therefore, as the bottom material of the standing pouch of the present invention, either a laminated film 3 containing the same plant origin as the trunk or a petroleum-derived film may be used.

  Similarly to Example 1, using a screw diameter of 30 mmφ extruder, Brass Chem C4LL-LL 318 (d = 0. 918, MFR = 2.7 g), which is a linear low density polyethylene resin derived from sugar cane (resin composition 1) 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 processing conditions of an extrusion temperature of 220 ° C. and a rotation number of 45 rpm to form a film having a thickness of 120 μm (one kind three layers) with excellent appearance. The degree of biomass was about 88% when measured.

  Similarly to Example 1, using a screw diameter of 30 mmφ extruder, Brass Chem C4LL-LL 318 (d = 0. 918, MFR = 2.7 g), which is a linear low density polyethylene resin derived from sugar cane (resin composition 1) / 10 minutes) and Mitsui Chemicals C6LL-Evolue SP 2020 (d = 0. 918, MFR = 3.8 g / 10 min) by kneading at 200 ° C. at 7: 3 and extruding with a T die cast film forming machine By molding the resin composition under processing conditions of a temperature of 220 ° C. and a rotational speed of 45 rpm, it is possible to form a stable film with a thickness of 120 μm (one type and three layers) and an excellent appearance. , About 59%.

  As described in detail above, the films F1 to F4 made of the polyethylene-based resin of this example consist of the resin composition 1 containing the linear low density plant-derived polyethylene-based resin obtained by the gas phase polymerization method It is. Moreover, while making these films F1-F4 into a sealant film and making it the laminated | multilayer film 3 laminated | stacked with the base film 5, the packaging bag 6 consists of this laminated | multilayer film 3. FIG.

  In addition, this invention is applicable to all products using polyethylene-type resin, such as a film which consists of polyethylene-type resin, and a packaging bag and a container comprised with this film.

Reference Signs List 1 resin composition 2 petroleum-derived polyethylene-based resin 3 laminated film 4 sealant film 5 base film 6 packaging bag 7, 8 side sheet 9 bottom sheet F1 to F4 film

Claims (3)

A film made of polyethylene resin,
The polyethylene resin state, and are a resin composition containing a plant-derived polyethylene resin having 80% to 100% biomass degree be calculated from measurements of radiocarbon dating ¹⁴ C,
And 5 to 90 mol% of the plant-derived polyethylene resin, using said resin composition comprising a petroleum-derived polyethylene resin 10-95 mol%, composed of the following (A) or (B) or (C) A sealant film for packaging material, characterized in that the resulting film is a heat sealable film.
(A) Single-layer structure in which the resin composition and the petroleum-derived polyethylene-based resin are mixed (B) A multilayer structure in which the intermediate layer is the resin composition and the outer layer and the inner layer are the petroleum-derived polyethylene-based resin C) A multilayer structure in which the intermediate layer is a layer in which the resin composition and the petroleum-derived polyethylene resin are mixed, and the outer layer and the inner layer are the petroleum-derived polyethylene resin A laminated film for packaging material, wherein the film according to claim 1 is laminated with a substrate film. A packaging bag comprising the laminated film for packaging material according to claim 2 .

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