JP6766974B2 - Sealant film for packaging materials, laminated film for packaging materials, and packaging bags using plant-derived polyethylene. - Google Patents

Description

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

Conventionally, packaging bags typified by, for example, refilling shampoos and rinses and pouches used as packaging materials for foods, etc., are composed of packaging materials composed of a sealant film and a base film, which are environmentally problematic and petroleum. In order to save depleted resources and reduce the amount of these petroleum resources used in packaging materials, polylactic acid-based resins as carbon-neutral materials, ethylene-α-olefin copolymers, and polymers having epoxy groups. There is a packaging bag (for example, Patent Document 1) containing a biodegradable resin composition containing a predetermined amount of each.

JP-A-2009-155516

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 with the above, there is a problem that the processability such as tear strength and heat seal strength is remarkably inferior, and the productivity cannot be improved.
Therefore, an object of the present invention is to use a polyethylene-based resin derived from a plant, which is a renewable resource, as a raw material to enable saving of petroleum resources and an environment-friendly sealant film for packaging materials by reducing carbon dioxide emissions. Another object of the present invention is to provide a laminated film for a packaging material and a packaging bag having excellent processability using these films.

The present invention comprises a single-layer film containing a plant-derived linear low-density polyethylene-based resin in which plant-derived ethylene and petroleum-derived α-olefin are copolymerized, and the plant-derived linear low-density polyethylene. The based resin is an ethylene-α-olefin copolymer having a biomass degree of less than 80 to 100% calculated from the measured value of radioactive carbon dating ^14C , and has a density of 0.910 to 0.925 g / cm ³ . The single layer containing the plant-derived linear low-density polyethylene-based resin having a melt flow rate of 0.5 to 4.0 g / 10 minutes is a plant-derived linear low-density polyethylene-based resin. Is a heat-sealing film for packaging materials, which comprises 5% by weight or more and 90% by weight or less.

The present invention also comprises a multi-layered film containing at least one layer containing a plant-derived linear low-density polyethylene-based resin in which a plant-derived ethylene and a petroleum-derived α-olefin are copolymerized, and the plant-derived film. The linear low-density polyethylene resin of No. 1 is an ethylene-α-olefin copolymer having a biomass degree of less than 80 to 100% calculated from the measured value of radioactive carbon dating 14C, and has a density of 0.910 to 0. The layer containing the plant-derived linear low-density polyethylene-based resin has physical properties of .925 g / cm3 and a melt flow rate of 0.5 to 4.0 g / 10 minutes, and the plant-derived linear low-density polyethylene-based resin is used. A heat-sealing film for packaging materials, which comprises 5% by weight or more and 90% by weight or less of a density polyethylene-based resin.

In the packaging material sealant film of the present invention, the α-olefin may be butene-1 or hexene-1 or a mixture thereof.

The present invention comprises at least a base film and the above-mentioned heat-sealing film for packaging materials, and the base film is for a packaging material in which the base film is any one of polypropylene-based resin, polyester-based resin, and polyamide-based resin. It may be a laminated film.

The present invention may be a container characterized by using the above-mentioned laminated film for packaging material.
The present invention may be a packaging bag characterized by using the above-mentioned laminated film for packaging material.
The present invention may be a lid material characterized by using the above-mentioned laminated film for packaging material.
The present invention may be a label characterized by using the above-mentioned laminated film for packaging material.
The present invention may be a laminated tube characterized by using the above-mentioned laminated film for a packaging material.
The present invention may be a container characterized by using the above-mentioned sealant film for packaging material.
The present invention may be a packaging bag characterized by using the above-mentioned sealant film for packaging material.

By mixing plant-derived polyethylene-based resin from a state in which the composition of the sealant film for packaging materials depends entirely on the resin composition derived from petroleum, the amount of petroleum resources used can be reduced and the sealant film for packaging materials can be manufactured. Carbon dioxide emissions can be suppressed. Therefore, it is possible to provide a sealant film for a packaging material having a reduced environmental load. Therefore, it is possible to provide a sealant film for a packaging material that saves petroleum resources and reduces the environmental load.

It is a flow chart which shows an example of the production of polyethylene derived from sugar cane. FIG. 5 is a cross-sectional side view schematically showing a film made of a linear low-density polyethylene-based resin derived from sugar cane of the present invention. FIG. 5 is a cross-sectional side view schematically showing a single-layer film in which the resin composition of the present invention and a polyethylene-based resin derived from petroleum are mixed. FIG. 5 is a cross-sectional side view schematically showing a film having a multilayer structure in which the intermediate layer of the present invention 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 of the present invention is a layer in which a resin composition and a polyethylene-based resin derived from petroleum are mixed. It is sectional drawing which shows typically an example of the laminated film of this invention. It is a perspective view which shows the standing pouch as an example of the packaging bag formed by 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 such as laminated tubes used for foods and cosmetics, and packaging bags such as standing pouches that are widely used as packaging materials for refilling shampoos and conditioners. It is composed of film.

Some of these laminated films are made by laminating a sealant film used on the inner surface of the laminated film as a heat sealing material on the base film. As the material of the base film, for example, polyethylene resin or the like is used, and the sealant film is used. As the material of the above, for example, a linear low-density polyethylene-based resin is used as a laminate with an intermediate layer interposed therebetween.

As described above, polyethylene-based resin, which is a plastic resin, is often used as the material of the laminated film. Conventionally, this polyethylene-based resin is produced from petrochemical origin using petroleum as a starting material, for example. In the above-mentioned linear low-density polyethylene-based resin, ethylene obtained by refining crude oil and α-olefin as a copolymer species are mixed at a high temperature of 120 ° C. or higher in the gas phase in the presence of a metallocene catalyst. It is copolymerized with. The α-olefin is represented by the general formula R-CH = CH ₂ (in the formula, R is an alkyl group having 1 or more carbon atoms), such as propylene, 1-butene, 1-pentene, 1-hexene, 1-. Examples thereof 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, and is, for example, one type of group selected from a cyclopentadienyl group, a cyclopentadienyl group having a substituent (substituted cyclopentadienyl group), an indenyl group, and a substituted indenyl group. , A transition metal compound of Group 4 of the periodic table having a ligand in which one kind of group selected from a fluorenyl group and a substituted fluorenyl group has a ligand crosslinked by a cross-linking group can be mentioned, and as a typical example thereof, 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, diphenylmethylene (1-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-
Indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (2,7-di-t-butyl) A metallocene catalyst containing a dichloro compound such as -9-fluorenyl) zirconium dichloride and a metallocene compound exemplifying the dimethyl form, diethyl form, dihydro form, diphenyl form, dibenzyl form and the like of the metallocene compound as a main component is used. Further, the metallocene catalyst is, for example, one kind of group selected from 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 the substituted fluorenyl groups can be a transition metal compound of Group 4 of the periodic table having a ligand crosslinked by a bridging group, and a typical example thereof is diphenylmethylene (1-cyclopentadienyl). 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-cyclopentadienyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride, diphenylmethylene (1-indenyl) (9-fluorenyl) zirconium dichloride, diphenyl Dichloro compounds such as methylene (4-phenyl-1-indenyl) (9-fluorenyl) zirconium dichloride, diphenylmethylene (4-phenyl-1-indenyl) (2,7-di-t-butyl-9-fluorenyl) zirconium dichloride The main component of the metallocene compound is a metallocene compound such as a dimethyl compound, a diethyl compound, a dihydro compound, a diphenyl compound, or a dibenzyl compound.

However, with the desire to save depleted resources such as petroleum and the growing awareness of environmental issues such as global warming due to the increase in carbon dioxide emissions, the above-mentioned petroleum-derived polyethylene-based resins have been changed from the production of petroleum products to disposal. In the meantime, a large amount of fixed carbon dioxide contained in petroleum raw materials will be emitted, so the above intention cannot be met.

In light of these problems, in recent years, the development of technology for producing plastics from plants, which are carbon-neutral and renewable resources, has been progressing. Among them, polyethylene, which is the most produced among plastics, is biomass. The technology to produce sugar cane as a starting material has been established. (Edited by Processing Technology Study Group, Convertec 2009.9, P63-67) In addition, 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 sugarcane-derived polyethylene production, and FIG. 2 is a cross-sectional side view schematically showing a film made of a linear low-density polyethylene-based resin derived from sugarcane of the present invention.

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

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

In the present invention, it is used as a laminated film by producing a film for forming a laminated film constituting a container or a packaging bag by using the plant-derived linear low-density polyethylene resin obtained as described above. In resin compositions (linear low-density polyethylene-based resins, etc.), the ratio of petroleum-derived resin compositions used can be reduced to save petroleum resources and contribute to environmental improvement by reducing carbon dioxide emissions. Is what you do.

In the present application, a linear low-density polyethylene-based material derived from sugar cane obtained by the above-mentioned vapor phase polymerization method (not limited to sugar cane, as long as it is a plant used as a raw material for producing a linear low-density polyethylene-based resin). A resin composition 1 made of a resin can be used to obtain a film F1 as shown in FIG.

Further, the linear low-density polyethylene-based resin derived from sugar cane has a copolymer type of butene-1 (C4) and a density of 0.910 to 0.925 g, similarly to the linear low-density polyethylene-based resin derived from petroleum. It can have various physical properties such as / cm ³ and a melt flow rate (MFR) in the range of 0.5 to 4.0 g / 10 minutes, more preferably 0.7 to 3.5 g / 10 minutes, and its ethylene-. An α-olefin copolymer is used. A resin composition made of such a linear low-density polyethylene-based resin derived from sugar cane is contained in an appropriate ratio up to 90% by weight with respect to the linear low-density polyethylene-based resin derived from petroleum.

In the above physical property evaluation, 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. Is. The melt flow rate (MFR, unit: g / 10 minutes) was measured at a test load of 21.18 N under the condition of a test temperature of 190 ° C. according to JIS K 7210 (1995).

Further, as the linear low-density polyethylene-based resin derived from sugar cane, the ethylene-α-olefin copolymer having a biomass degree of 80 to 100% by radiocarbon dating ^14C is used.

Here, the plant (biomass) -derived and petroleum-derived resin compositions do not have any difference in physical properties such as molecular weight, mechanical properties, and thermal properties. Therefore, in order to distinguish between them, the degree of biomass is generally used. At this biomass degree, the carbon of the petroleum-derived resin composition does not contain ¹⁴ C (radiocarbon 14, half-life 5730 years), so the concentration of this ¹⁴ C was measured by accelerator mass spectrometry and the resin. It is used as an index of the content ratio of the plant-derived resin composition in the composition. Therefore, in the case of a film using a plant-derived resin composition, when the biomass degree of the film is measured, the biomass degree is generated according to the content of the plant-derived resin composition.

In this measurement of biomass degree, the sample to be measured is burned to generate carbon dioxide, and the carbon dioxide purified in the vacuum line is reduced with hydrogen using iron as a catalyst to produce graphite. Then, this graphite was mounted on a ¹⁴ C-AMS dedicated device (manufactured by NEC) based on a tandem accelerator, and ¹⁴ C count, ¹³ C concentration ( ¹³ C / ¹² C), and ¹⁴ C concentration ( ^14). C / ¹² C) is measured, and the ratio of the ¹⁴ C concentration of sample carbon to standard modern carbon is calculated from this measured value. For this measurement, oxalic acid (HOxII) provided by the National Institute of Standards and Standards (NIST) was used as a standard sample.

In the present application, by forming a film composed of such a resin composition, the polyethylene-based resin derived from petroleum can be compared with the polyethylene-based resin derived from petroleum in terms of performance from the state of being completely dependent on the resin composition derived from petroleum. By mixing (replacement) a polyethylene-based resin derived from a plant such as sugar cane that has no difference, it is possible to suppress carbon dioxide emissions during film production and disposal.

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

Further, 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 radiocarbon dating ^14C , it is derived from the raw material of the polyethylene-based resin constituting the film. , This degree of biomass can be used as an index for identification, and the raw materials derived from the time of film production to the time of disposal can be confirmed.

Next, in the present application, the above-mentioned resin composition 1 and the petroleum-derived polyethylene-based resin 2 described later can be formed into the following film. FIG. 3 is a cross-sectional side view schematically showing a film having a single-layer structure in which a resin composition and a polyethylene-based resin derived from petroleum are mixed, and FIG. 4 is a schematic view of a film having a multilayer structure with an intermediate layer as 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 polyethylene-based resin derived from petroleum 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 as described in (A), (B) or (C) below. Configured. First, as the film F2 of (A), as shown in FIG. 3, a single-layer structure in which the resin composition 1 and the polyethylene-based resin 2 derived from petroleum are mixed can be formed.

Further, as the film F3 of (B), as shown in FIG. 4, a multilayer structure may be formed in which the intermediate layer is the resin composition 1 and the outer layer and the inner layer 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 in which the resin composition 1 and the petroleum-derived polyethylene-based resin 2 are mixed, and the outer layer and the inner layer are the petroleum-derived polyethylene-based resin 2. It is also possible to have a multi-layered structure.

With such a configuration, the proportion of the polyethylene-based 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 petroleum-derived polyethylene-based resin 2 for the inner and outer layers constituting the films F3 to F4 such as (B) or (C), the films F3 to F4 can be produced with the characteristics of the existing manufacturing process. Can be done.

Next, in the present application, a laminated film using the above 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 by 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 by using any of the films F1 to F4 as the sealant film 4.

The base film 5 includes, for example, a polyethylene resin, a polypropylene resin, a cyclic polyolefin resin, a polystyrene resin, an acrylonitrile-styrene copolymer (AS resin), and an acrylonitrile-butadiene-styrene copolymer (ABS resin). ), Polyvinyl chloride resin, fluororesin, poly (meth) acrylic resin, polycarbonate resin, polyethylene terephthalate, polyester resin such as polyethylene naphthalate, polyamide resin such as various nylons, polyimide resin, polyamide Use various resin films or sheets such as imide resin, polyarylphthalate resin, silicone resin, polysulfone resin, polyphenylene sulfide resin, polyether sulfone resin, polyurethane resin, acetal resin, cellulose resin, etc. Can be done.

With such a configuration, even in the sealant film 4 used for heat sealing, the ratio of the polyethylene-based resins constituting the films F1 to F4 of the sealant film 4 derived from petroleum can be reduced, and petroleum can be used. In addition to saving resources, it is possible to suppress carbon dioxide emissions during the production and disposal of the laminated film 3.

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

Next, both side edge portions of the two front and back side surface sheets 7 and 8 are heat-sealed with the side edge seal portion to form a body portion, and the upper end portion is left as a filling port for the contents. A pouch (packaging bag 6) made in the standing pouch format as shown is formed. The upper seal portion provided at the filling port at the upper end is filled with the contents from this portion and then heat-sealed by, for example, a degassing seal. Although not shown, a spout portion having a cut line for opening may be formed by a laser on the upper part of the body portion or the like.

With such a configuration, it is possible to reduce the ratio of the polyethylene-based resin used in the laminated film 3 constituting the packaging bag 6 derived from petroleum, which saves petroleum resources and at the time of manufacturing and disposing of the packaging bag 6. It is possible to suppress carbon dioxide emissions. In particular, since the packaging bag 6 is a standing pouch for refilling, the ratio of the polyethylene-based resin constituting such a packaging bag, which is widely used as a disposable bag, derived from petroleum is reduced, and carbon dioxide emissions are greatly suppressed. Can be done.

In addition to the packaging bag 6 exemplified in the above-mentioned standing pouch, 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 are used in addition to the polyethylene-based film. A container composed of a resin composition 1 using a resin, for example, a laminated tube for accommodating contents such as food and drink, cosmetics, chemicals, miscellaneous goods, a liquid paper container, a container lid material, or a container. It is possible to further reduce the usage ratio of petroleum-derived materials and greatly reduce carbon dioxide emissions.

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

Using an extruder with a screw diameter of 30 mmφ, 200 braskem C4LL-LL118 (d = 0.916, MFR = 1.0 g / 10 minutes), which is a linear low-density polyethylene resin derived from sugar cane (resin composition 1). The resin composition was obtained by melt-kneading at ° C. Next, the resin composition was formed by a top-blown air-cooled inflation coextrusion film forming machine under processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm to obtain a stable film F1 having a thickness of 50 μm and an excellent appearance. A film could be formed, and the biomass degree was measured to be about 88%. The comonomer species butene-1 (C4) contained in the sugar cane-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, a petrified C4LL linear low-density polyethylene resin was used, and the thickness was 50 μm under the processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm in the same manner as in Example 1. When it was molded into the film and the biomass degree was measured, it was 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 carried out on the resin composition of Example 1, and the results obtained are described below.

From the above results, the linear low-density polyethylene-based resin derived from sugar cane (plant) (Example 1) has a tensile breaking strength and tear strength as compared with the petrified linear low-density polyethylene-based resin (Comparative Example 1). It can be seen that the strength is strong, the waist and seal strength are the same, the elastic modulus is low, and the material is flexible. As described above, the plant-derived linear low-density polyethylene-based resin has the same or better physical properties as the petrification-derived linear low-density polyethylene-based resin, and the petrification-derived linear low-density polyethylene-based resin can be produced. It was proved to be comparable to processing suitability.

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

Using an extruder with a screw diameter of 30 mmφ, 50 brasschem C4LL-LL118 (d = 0.916, MFR = 1.0 g / 10 minutes), which is a linear low-density polyethylene resin derived from sugar cane (resin composition 1). 50% by weight and 50% by weight of Ube Maruzen polyethylene LDPE-F120N (d = 0.920, MFR = 1.2g / 10 minutes), which is a petroleum-derived linear low-density polyethylene resin 2, are melt-kneaded at 200 ° C. A resin composition was obtained. Next, the resin composition was molded into the film F2 shown in FIG. 3 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 top-blown air-cooled inflation coextrusion film forming machine, and the biomass degree was measured. It was 44%.

Mitsui Chemicals C6LL-Evolu SP2020 (d = 0.916, MFR = 2.3 g / 10 minutes) was melted at 200 ° C. using a screw diameter 30 mmφ extruder as the resin composition for the first layer and the third layer. The mixture was kneaded to obtain a resin composition. Similarly, as the resin composition for the second layer, using an extruder having a screw diameter of 30 mmφ, Braskem's C4LL-LL118 (d = 0.916, MFR = 1.0 g /), which is a linear low-density polyethylene resin derived from sugar cane. 10 minutes) was melt-kneaded at 200 ° C. 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 was formed into a film F3 having a thickness of 130 μm as shown in FIG. 4 under processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm by a two-kind three-layer top-blown air-cooled inflation coextrusion film forming machine, and the degree of biomass thereof. Was measured and was about 29%.

Mitsui Chemicals C6LL-Evolu SP2020 (d = 0.916, MFR = 2.3 g / 10 minutes) was melted at 200 ° C. using a screw diameter 30 mmφ extruder as the resin composition for the first layer and the third layer. The mixture was kneaded to obtain a resin composition. Similarly, as the resin composition for the second layer, using a screw diameter 30 mmφ extruder, Brasschem's C4LL-LL118 (d = 0.916, MFR = 1.0 g /), which is a linear low-density polyethylene-based resin derived from sugar cane. 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 layer ratio of the first layer: the second layer: the third layer was 1: 2: 1. Next, the resin composition was formed into a film F4 having a thickness of 130 μm as shown in FIG. 5 under processing conditions of an extrusion temperature of 200 ° C. and a rotation speed of 60 rpm by a two-kind three-layer top-blown air-cooled inflation coextrusion film forming machine. Was measured and was about 22%.

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

Then, using this laminated film 3, a refillable standing pouch (packaging bag 6) with a spout portion provided with a cut line for opening is created by a laser, and the contents are put in the refillable standing pouch and the mouth portion. Leakage, tipping, buckling, and breakage of the torso were observed in the sealed product, but no evidence was observed. Furthermore, a drop test was conducted 5 times from a height of 1 m, but no bag breakage or leakage was observed.

A biaxially stretched nylon film (ONy, Toyo Boseki Harden N-1102) as a base film 5 having a thickness of 25 μm on the outer layer, and a 12 μm-thick VMPET (metal-deposited film) having aluminum vapor-deposited on one side of the intermediate layer. The film F4 of Example 4 was laminated with an aluminum-deposited surface of (a polyethylene terephthalate film on which aluminum was vapor-deposited), and further coated with a two-component curable urethane-based adhesive at about 4 g / m ^{2 on} the polyethylene terephthalate surface of VMPET. Was bonded to the corona-treated surface of the above by a dry lamination method to obtain a laminated film 3 having a three-layer structure. Then, using this laminated film 3, a refillable standing pouch (packaging bag 6) with a spout portion provided with a cut line for opening was prepared by a laser, and the biomass degree was measured and found to be about 17%.

Leakage, tipping, buckling, and breakage of the torso were observed in the prepared refillable standing pouch with the contents sealed in the mouth, but no findings were observed. Furthermore, a drop test was conducted 5 times from a height of 1 m, but no bag breakage or leakage was observed.

Only the bottom material of the refillable standing pouch with the spout of Example 6 is contained in the refillable standing pouch prepared by using a petroleum-derived film made of stretched polyamide (ONY) / LLDPE (linear low density polyethylene). Leakage, tipping, buckling, and breakage of the torso were observed in the case where an object was put in and the mouth was sealed, but none was observed. Furthermore, a drop test was conducted 5 times from a height of 1 m, but no bag breakage or leakage was 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 body portion or the petroleum-derived film may be used.

Similar to Example 1, using an extruder with a screw diameter of 30 mmφ, Braskem C4LL-LL318 (d = 0.918, MFR = 2.7 g), which is a linear low-density polyethylene resin derived from sugar cane (resin composition 1). / 10 min) 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 processing conditions of an extrusion temperature of 220 ° C. and a rotation speed of 45 rpm to form a stable film having a thickness of 120 μm (3 layers of 1 type) and having an excellent appearance. When the biomass degree was measured, it was about 88%.

Similar to Example 1, using an extruder with a screw diameter of 30 mmφ, Braskem C4LL-LL318 (d = 0.918, MFR = 2.7 g), which is a linear low-density polyethylene resin derived from sugar cane (resin composition 1). / 10 min) and Mitsui Chemicals C6LL-Evolu SP2020 (d = 0.918, MFR = 3.8 g / 10 min) are kneaded and melted at 7: 3 at 200 ° C. 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 rotation speed of 45 rpm, a stable film having a thickness of 120 μm (3 layers of 1 type) and having an excellent appearance can be formed, and the degree of biomass thereof is measured. , About 59%.

As described in detail above, the films F1 to F4 made of the polyethylene-based resin of this example are made of the resin composition 1 containing the linear low-density plant-derived polyethylene-based resin obtained by the vapor phase polymerization method. Is. Further, these films F1 to F4 are used as a sealant film, and the laminated film 3 is 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.

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 to F4 film

Claims (11)

It consists of a single-layer film containing a plant-derived linear low-density polyethylene-based resin in which plant-derived ethylene and petroleum-derived α-olefin are copolymerized.
The plant-derived linear low-density polyethylene-based resin is an ethylene-α-olefin copolymer having a biomass degree of less than 80 to 100% calculated from the measured value of radiocarbon dating ^14C , and has a density of 0. .910-0.925 g / cm ³ , melt flow rate 0.7-3.5 g / 10 minutes,
The single layer containing the plant-derived linear low-density polyethylene-based resin contains 5% by weight or more and 90% by weight or less of the plant-derived linear low-density polyethylene-based resin, and has a heat-sealing property for packaging materials. the film. It is composed of a multi-layered film containing at least one layer containing a plant-derived linear low-density polyethylene-based resin obtained by copolymerizing plant-derived ethylene and petroleum-derived α-olefin.
The plant-derived linear low-density polyethylene-based resin is an ethylene-α-olefin copolymer having a biomass degree of less than 80 to 100% calculated from the measured value of radiocarbon dating ^14C , and has a density of 0. .910-0.925 g / cm ³ , melt flow rate 0.7-3.5 g / 10 minutes,
The layer containing the plant-derived linear low-density polyethylene-based resin contains 5% by weight or more and 90% by weight or less of the plant-derived linear low-density polyethylene-based resin, and is a heat-sealing film for packaging materials. .. The heat-sealable film for a packaging material according to claim 1 or 2, wherein the α-olefin is butene-1, hexene-1, or a mixture thereof. At least, it comprises a base film and the heat-sealing film for packaging material according to any one of claims 1 to 3.
A laminated film for a packaging material in which the base film is any one of polypropylene-based resin, polyester-based resin, and polyamide-based resin. A container using the laminated film for packaging material according to claim 4. A packaging bag using the laminated film for packaging material according to claim 4. A lid material using the laminated film for packaging material according to claim 4. A label according to claim 4, wherein the laminated film for a packaging material is used. A laminated tube using the laminated film for a packaging material according to claim 4. A container using the heat-sealing film for packaging material according to any one of claims 1 to 3. A packaging bag comprising the heat-sealing film for packaging material according to any one of claims 1 to 3.

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