JP2020084161A - Resin film - Google Patents

Abstract

To provide a resin film having high rigidity and high hand tearability while maintaining biomass degree at high level.SOLUTION: A resin film has at least one layer formed from a resin composition containing polyolefin derived from biomass by polymerizing monomers mainly containing ethylene derived from biomass, and a polylactic acid resin, and content of the polylactic acid resin in the resin composition is 1 mass% or more.SELECTED DRAWING: None

Description

The present invention relates to a resin film containing a biomass-derived polyolefin. More specifically, the present invention relates to a resin film having at least one layer formed from a resin composition containing a polyolefin derived from biomass obtained by polymerizing a monomer containing ethylene derived from biomass and a polylactic acid resin.

In recent years, due to the increasing consideration for the environment, the use of biomass has been attracting attention in order to escape from fossil fuels, and biomass plastics using this as a raw material have been put into practical use. In particular, it is desired to reduce the amount of fossil fuel used by using a biomass-derived raw material for the production of polyethylene resin, which is in high demand, and a polyolefin resin film made from a biomass-derived ethylene-containing polymer as a raw material. Are known (for example, Patent Document 1 and Patent Document 2).

Patent No. 5862055 Patent No. 6350589

However, the polymer containing ethylene derived from biomass has a broader molecular weight distribution and compositional distribution than the conventional polymer containing ethylene derived from fossil fuels due to the influence of monomer purity. As described above, the resin film formed from the polymer containing ethylene derived from the biomass is derived from the fossil fuel-derived ethylene because the molecular weight distribution and the composition distribution are wider than those of the conventional polymer containing ethylene derived from the fossil fuel. There is a problem that the hand-cutting property and the rigidity are inferior to those of the ethylene polymer.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a resin film having high rigidity and high hand tearability while maintaining a high biomass level.

In order to solve the above problems, the resin film according to one embodiment of the present invention is a resin composition containing a biomass-derived polyolefin obtained by polymerizing a biomass-derived ethylene-based monomer and a polylactic acid-based resin. At least one layer formed is provided, and the content of the polylactic acid resin in the resin composition is 1% by mass or more.

A resin film according to one embodiment of the present invention includes an outer layer, an intermediate layer, and an inner layer, and the intermediate layer forms the above-described layers included in the resin film according to one embodiment of the present invention. The outer layer and the inner layer are formed from a resin composition containing a fossil fuel-derived polyolefin as a main component.

According to one aspect of the present invention, it is possible to provide a resin film having high rigidity and high hand tearability while maintaining a high degree of biomass.

<Resin film>
The resin film according to one embodiment of the present invention has at least one layer formed from a resin composition containing a biomass-derived polyolefin obtained by polymerizing a biomass-derived ethylene-based monomer and a polylactic acid resin. A layer is provided, and the content of the polylactic acid-based resin in the resin composition is 1% by mass or more.

According to the above configuration, it is possible to obtain a resin film having high rigidity and high hand tearability. In addition, the combined use of the biomass-derived polyolefin and the polylactic acid-based resin makes it possible to maintain the biomass degree of the resin film at a high level.

The hand tearability of the resin film means that the resin film can be successfully cut by applying a shear stress with a human hand. The rigidity of a resin film means the difficulty of being deformed by the force applied to the resin film. The biomass degree of the resin film is the ratio of the biomass-derived monomer contained in the entire polyolefin contained in the resin composition (mass %) and the proportion of the polylactic acid-based resin contained in the resin composition. (Mass %) means the total.

When the resin film formed from the resin composition is a single-layer resin film, the proportion of the biomass-derived component in the resin film can be increased. That is, there is an advantage that the biomass level can be maintained at a high level.

Further, the resin film according to one aspect of the present invention takes advantage of the high rigidity and high hand-cutting property provided by the above-mentioned configuration, for example, packaging products such as containers and bags, sheet molded products such as decorative sheets and trays, Laminated films, optical films, resin plates, various label materials, and resin films used as lid materials, as well as various applications such as standing pouches, sealant films used for laminated tubes, and the like, and particularly It can be suitably used as a sealant film for a standing pouch.

[Resin composition]
A resin composition for forming a resin film according to an aspect of the present invention contains a biomass-derived polyolefin obtained by polymerizing a biomass-derived ethylene-based monomer as a main component.

(Biomass-derived polyolefin)
The biomass-derived polyolefin may be a biomass-derived ethylene homopolymer or a copolymer with another monomer. The monomer, which is a raw material of the biomass-derived polyolefin, may further contain ethylene derived from fossil fuel and/or α-olefin derived from fossil fuel. Alternatively, the monomer that is a raw material of the biomass-derived polyolefin may further include a biomass-derived α-olefin. Examples of the α-olefin include C3-C20 α-olefins such as butene, hexene, and octene. The biomass-derived polyolefin is preferably a copolymer of biomass-derived ethylene and fossil fuel-derived α-olefin.

Biomass-derived polyolefin is a polyolefin obtained by polymerizing biomass-derived ethylene-based monomers, and "mainly biomass-derived ethylene" refers to the proportion (mass% ) Indicates that the most component is ethylene derived from biomass. The biomass-derived ethylene is, for example, ethylene produced by using ethanol extracted and purified from plants such as corn and sugar cane as a raw material. Since such biomass-derived ethylene is used as a raw material monomer, the polymerized polyolefin is “biomass-derived”. In addition, it is more preferable that the ethylene contained in the biomass-derived polyolefin is made of biomass-derived ethylene from the viewpoint of maintaining the biomass degree at a high level.

Biomass-derived polyolefin can be obtained, for example, by homopolymerization of ethylene by a high-pressure method, using a solid catalyst or a metallocene catalyst, and copolymerizing ethylene with an α-olefin comonomer such as butene, hexene, and octene. it can. Further, as the biomass-derived polyolefin, for example, a commercially available product such as plant-derived polyethylene manufactured by Braschem can be used.

The resin composition may contain two or more types of biomass-derived polyolefins having different compositions. When two or more types of biomass-derived polyolefins are included, "density of biomass-derived polyolefin" refers to a value calculated by a weighted average, and "MFR of biomass-derived polyolefin" is calculated by the logarithmic addition rule. Value.

Density of the polyolefin-derived biomass is not particularly limited, is preferably 0.900~0.932g / cm ^3, more preferably 0.910~0.925g / cm ^3. In this document, the density is a value measured according to the method defined in Method A of JIS K7112-1980 after performing the annealing described in JIS K6760-1995. When the density of the biomass-derived polyolefin is 0.900 g/cm ³ or more, there is an advantage that the antiblocking property is more excellent. Further, when the density of the polyolefin derived from biomass is 0.932 g/cm ³ or less, there is an advantage that the impact strength is excellent.

The melt flow rate (MFR) of the biomass-derived polyolefin is not particularly limited, but is preferably 0.1 to 10 g/10 minutes, more preferably 0.5 to 5 g/10 minutes. In this document, the melt flow rate of a polyolefin is a value measured by the method A under the conditions of a temperature of 190° C. and a load of 21.18 N according to the method defined in JIS K7210-1995. When the MFR of the biomass-derived polyolefin is 0.1 g/10 minutes or more, there is an advantage that the resin does not generate much heat during film formation. Further, when the MFR of the biomass-derived polyolefin is 10 g/10 minutes or less, there is an advantage that the bubble stability during the inflation film forming process is excellent.

(Polylactic acid resin)
The resin composition for forming the resin film according to one embodiment of the present invention contains a polylactic acid-based resin as a biomass-derived resin. The polylactic acid-based resin is a polylactic acid having a repeating unit derived from L lactic acid and/or a repeating unit derived from D lactic acid (hereinafter, simply referred to as polylactic acid), or this polylactic acid and another plant-derived polyester resin. It is a copolymer. The polylactic acid-based resin may contain other plant-derived polyester resin, if necessary. Other plant-derived monomers copolymerizable with lactic acid include hydroxycarboxylic acids such as glycolic acid, aliphatic polyhydric alcohols such as butanediol, and aliphatic polycarboxylic acids such as succinic acid. The polylactic acid resin is a method of directly dehydrating and polycondensing lactic acid and/or other plant-derived monomers, or ring-opening polymerization of a cyclic dimer of lactic acid and/or hydroxycarboxylic acid (eg, lactide, glycolide, ε-caprolactone). It can be manufactured by the method.

The polylactic acid-based resin has low compatibility with the polyolefin contained as a main component in the resin composition. The melting point of the polylactic acid resin is about 140°C to 180°C. Therefore, the polylactic acid resin can be dispersed in the resin composition at a temperature at which the above-mentioned biomass-derived polyolefin can be suitably melt-kneaded. Therefore, by using the resin composition, it is possible to form a layer including a continuous phase containing a biomass-derived polyolefin as a main component and a dispersed phase containing a polylactic acid resin as a main component. In addition, since polylactic acid-based resin is harder and more brittle than polyolefin, for example, when shear stress is applied by human hands, a continuous phase composed of biomass-derived polyolefin and polylactic acid-based resin The force can be suitably concentrated on the interface formed between the resin and the dispersed phase, and this can be used as an opportunity to impart suitable hand-cutting properties to the resin film. Further, it is possible to improve the hand tearability, but by dispersing the polylactic acid-based resin in at least one polyolefin layer (continuous phase) that constitutes the resin film, the resin film is made to have a higher degree of durability than the resin film made of the polyolefin. High rigidity (in other words, difficulty of deformation) can be imparted. Furthermore, since the resin film can resist the force applied to bend the resin film due to its appropriate rigidity, it can be suitably used as a sealant film for a standing pouch, for example.

The content of the polylactic acid-based resin contained in the layer formed from the resin composition is 1% by weight or more, preferably 15% by weight or less, and more preferably 11% by weight or less. When the content of the polylactic acid-based resin contained in the layer formed from the resin composition is 1% by weight or more, it is possible to improve the rigidity of the resin film including the layer and to impart the hand tearability. .. As a commercial product, a polylactic acid-based resin manufactured by Nature Works or Unitika can be used.

The melt flow rate (MFR) of the polylactic acid resin is not particularly limited, but is preferably 0.1 to 10 g/10 minutes. In this document, the melt flow rate of a polylactic acid-based resin is a value measured under the conditions of a temperature of 190° C. and a load of 21.18 N by the method specified in ASTM D1238. When the MFR of the polylactic acid-based resin is 0.1 g/10 minutes or more, there is an advantage that the resin generates less heat during film forming. Further, when the MFR of the polylactic acid-based resin is 10 g/10 min or less, there is an advantage that the bubble stability during the inflation film forming process is excellent.

(Polyolefin derived from fossil fuel)
The resin composition for forming the resin film according to one aspect is mainly composed of fossil fuel-derived ethylene, to the extent that the biomass-derived polyolefin and the degree of biomass dependent on the polylactic acid-based resin do not become excessively low. A polyolefin may be included.

A homopolymer or copolymer mainly composed of fossil fuel-derived ethylene is a polyolefin obtained by polymerizing a monomer mainly composed of ethylene (fossil fuel-derived ethylene) obtained from fossil fuel such as crude oil, It is also called a fossil fuel-derived polyolefin. “Mainly ethylene derived from fossil fuel” means that ethylene is derived from fossil fuel as a component having the largest proportion (mass %) among the monomers which are raw materials of the homopolymer or the copolymer. In the case of a copolymer, examples of the comonomer include α-olefin derived from fossil fuel. Examples of the α-olefin include C3-C20 α-olefins such as butene, hexene, and octene.

Fossil fuel-derived polyolefin can be obtained, for example, by homopolymerization of ethylene by a high-pressure method, or by copolymerizing ethylene and a comonomer such as butene, hexene, or octene using a solid catalyst or a metallocene catalyst. Moreover, a commercial item can also be used.

When the layer formed from the resin composition contains a fossil fuel-derived polyolefin, the “density of the polyolefin” contained in the resin composition refers to a value calculated by a weighted average, and “MFR” refers to a value calculated by the logarithmic addition rule. When the homopolymer or copolymer mainly composed of ethylene derived from two or more fossil fuels is included, the “density of the homopolymer or copolymer mainly composed of ethylene derived from fossil fuel” is a weighted average. "MFR of homopolymer or copolymer mainly composed of ethylene derived from fossil fuel" refers to a value calculated by the logarithmic addition rule. In the present specification, when simply described as “polyolefin”, unless otherwise specified, “polyolefin” may include both “biomass-derived polyolefin” and “fossil fuel-derived polyolefin”. ..

The density of the homopolymer or copolymer mainly composed of fossil fuel-derived ethylene is not particularly limited, but is preferably 0.910 to 0.932 g/cm ³ , and 0.913 to 0.930 g/cm ^{3. 3} is more preferable. When the density of the homopolymer or copolymer mainly composed of fossil fuel-derived ethylene is 0.910/cm ³ or more, there is an advantage that the antiblocking property is more excellent. Further, when the density of the homopolymer or copolymer mainly composed of fossil fuel-derived ethylene is 0.932 g/cm ³ or less, there is an advantage that the impact strength is excellent.

The MFR of a homopolymer or copolymer mainly composed of fossil fuel-derived ethylene is not particularly limited, but is preferably 0.1 to 10 g/10 minutes, and is 0.5 to 5 g/10 minutes. Is more preferable. Further, it is more preferable that it is lower than the MFR of the biomass-derived polyolefin from the viewpoint of surface property expression. When the MFR of the homopolymer or copolymer mainly composed of fossil fuel-derived ethylene is 0.1 g/10 min or more, there is an advantage that the resin does not generate much heat during film forming. Further, when the MFR of the homopolymer or copolymer mainly composed of fossil fuel-derived ethylene is 10 g/10 min or less, there is an advantage that the bubble stability during the inflation film forming process is excellent.

The content of the fossil fuel-derived polyolefin contained in the resin composition is less than 50% by weight, preferably 30% by weight or less, and more preferably 10% by weight or less. It is preferable that the content of the fossil fuel-derived polyolefin contained in the resin composition is smaller in the range of less than 50% by weight in order to maintain the proportion of the biomass-derived component at a high level. Further, in the present specification, when the content of the fossil fuel-derived polyolefin contained in the resin composition is less than 50% by weight, the resin composition contains a biomass-derived polyolefin as a main component. Can be defined as

(Additive)
In one aspect of the present invention, the resin composition for forming the resin film may include an anti-blocking agent and an eye-candy inhibitor as additives.

When the ethylene copolymer obtained by polymerization has a wide molecular weight distribution, the low molecular weight component contained in the biomass-derived polyolefin deteriorates the anti-blocking property of the resin film. Therefore, it is preferable to improve the anti-blocking agent by adding the anti-blocking agent.

As anti-blocking agents, cross-linked resin beads such as polystyrene and polymethylmethacrylate, silica, clay, talc, diatomaceous earth, feldspar, kaolin, zeolite, kaolinite, wollastonite, sericite, amorphous aluminosilicate, amorphous calcium A silicate etc. are mentioned. In particular, in order to develop the anti-blocking property of the biomass-derived polyolefin, crosslinked resin beads of polymethylmethacrylate, amorphous aluminosilicate, and a mixture thereof are preferable from the viewpoint of film forming processing stability.

The amount of the anti-blocking agent contained in the layer formed from the resin composition is not particularly limited, but is preferably 0.01 to 5% by mass, more preferably 0.05 to 3% by mass.

In the biomass-derived polyolefin, when the ethylene copolymer obtained by the polymerization has a wide composition distribution, a component having a low amount and a large amount of comonomer is likely to cause a burnishing during film forming. For this reason, it is preferable to prevent the occurrence of mesiness by blending a mesiness inhibitor.

The anti-meyer agent can be used for the purpose of suppressing poor processing stability due to heat-deteriorated products mainly of low molecular weight components of polyolefin derived from biomass. Examples include phenol-based heat stabilizers, phosphorus-based heat stabilizers, and combined phenol-phosphorus stabilizers for suppressing thermal deterioration. Further, for the purpose of preventing adhesion to the die lip during extrusion molding, a fluorine-based composition, a silicon-based composition and the like can be mentioned. As the anti-meyer agent, a fluorine-based composition such as a fluororesin is particularly preferable from the viewpoint of processing stability.

The amount of the anti-meyer agent contained in the layer formed from the resin composition is not particularly limited, but is preferably 0 to 5% by mass, and more preferably 0.01 to 3% by mass.

In addition, various additives may be added to the resin composition for forming the layer as long as the characteristics thereof are not impaired. Examples of the additive include an antioxidant, a plasticizer, an ultraviolet stabilizer, an anti-coloring agent, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a thread friction reducing agent, a slip agent, and a releasing agent. Examples include mold agents, ion exchange agents, and color pigments. The amount of these additives can be added so as to be, for example, 0 to 10 mass% with respect to the entire layer.

(Multilayer film)
The resin film according to one aspect may be a single-layer film that includes at least one layer formed from a resin composition containing a biomass-derived polyolefin and a polylactic acid resin, and does not include other layers. However, it may be a multilayer film containing only one layer and one or more layers not corresponding to the above layer, or a multilayer film containing two or more layers and not including any layer not corresponding to the above layer. It may be present or may be a multilayer film containing two or more layers and one or more layers not corresponding to the above layers. In one example, the resin film of the present invention may be a multilayer film consisting of three layers, an inner layer, an intermediate layer and an outer layer, of which the middle layer is formed from a resin composition containing a biomass-derived polyolefin and a polylactic acid-based resin. Can be Further, when the resin film is a multilayer film, the inner layer, and the outer layer is formed from a resin composition containing the above-mentioned fossil fuel-derived polyolefin as a main component, in the range that does not impair the manufacturing processability, the biomass described above. It may contain a polyolefin derived from it. The content of the fossil fuel-derived polyolefin contained in the resin composition for forming the inner layer and the outer layer is 50% by weight or more, more preferably 70% by weight or more, and 90% by weight or more. Is more preferable. When the content of the fossil fuel-derived polyolefin contained in the resin composition is 50% by weight or more, the resin composition can be defined as a resin composition containing the fossil fuel-derived polyolefin as a main component.

The thickness of the resin film of the present invention may be appropriately set depending on the application, but may be, for example, 5 to 500 μm. The thickness of each layer may be appropriately set depending on the application, but may be, for example, 1 to 490 μm. When the resin film has a three-layer structure, the ratio of the inner layer, the intermediate layer, and the outer layer may be appropriately set according to the application, but is, for example, 1 to 98%: 1 to 98%: 1 to 98%. obtain.

In addition, when the resin film is a multi-layer film, the anti-blocking agent and the eye-dropping agent described above may be contained in the outer layer and the inner layer forming the multi-layer film.

Further, various additives may be added to the outer layer and the inner layer constituting the multilayer film, as long as the characteristics are not impaired. Examples of the additive include an antioxidant, a plasticizer, an ultraviolet stabilizer, an anti-coloring agent, a matting agent, a deodorant, a flame retardant, a weathering agent, an antistatic agent, a thread friction reducing agent, a slip agent, and a releasing agent. Examples include mold agents, ion exchange agents, and color pigments. The amount of these additives can be added to each layer to be, for example, 0 to 10% by mass.

[Method for producing resin film]
The method for producing the resin film of the present invention is not particularly limited, and for example, it can be produced by a conventionally known method. The resin film of the present invention is preferably extruded, and more preferably extruded by a T-die method or an inflation method. The method for preparing the resin composition to be subjected to extrusion molding is not limited as long as it can melt-knead the biomass-derived polyolefin and the polylactic acid-based resin, but the melt-kneaded the biomass-derived polyolefin and the polylactic acid-based resin. The method of preparing the masterbatch in advance and melt-kneading the masterbatch and the biomass-derived polyolefin is more preferable from the viewpoint that the decrease in transparency of the resin film can be prevented.

The resin film of the present invention can be suitably used as a sealant film, and may be used as a laminate in which a base film is laminated on one surface thereof. As the base film, any resin film or sheet can be used depending on the application of the laminate. For example, when the laminate is applied as a refill pouch, it is preferable that it has excellent mechanical properties such as tensile strength, flexural strength, and impact strength, and that it has excellent printability, and that it is used as a base film for such a laminate. For example, a biaxially stretched nylon film, a biaxially stretched polyester film such as a biaxially stretched polyethylene terephthalate film, a biaxially stretched polypropylene film, or the like can be preferably used, and synthetic paper or the like can also be used. These may be used alone or in combination of two or more.

The resin film of the present invention and the substrate film can be bonded to each other by, for example, an extrusion laminating method (so-called sandwich laminating method) via an adhesive layer. In this case, as the adhesive layer, a polyolefin-based heat-adhesive resin, for example, LDPE, ethylene-methacrylic acid copolymer, ethylene-acrylic acid copolymer, a simple substance such as an ionomer, or an adhesive property such as a hard resin to these. A resin blended with an improver can be used.

It is also possible to laminate by extrusion-coating the polyolefin or composition constituting the resin film of the present invention on the substrate film.

Furthermore, it is also possible to bond them by a dry laminating method via an adhesive. Examples of the adhesive to be used include a two-component curing type polyurethane adhesive for dry lamination.

A barrier layer may be provided between the resin film of the present invention and the base film.

Examples of the barrier layer include a metal foil such as aluminum foil, a metal film such as aluminum, a metal oxide such as aluminum oxide, and an inorganic oxide such as silicon oxide, and a base film such as a biaxially stretched polyethylene terephthalate film. Vapor-deposited film, polyacrylonitrile film, ethylene-vinyl alcohol copolymer film and the like can be used.

The base film and the barrier layer can be bonded by, for example, the extrusion laminating method or the dry laminating method, as in the case of the above-mentioned base film and the sealant.

The resin film of the present invention and the barrier layer can be adhered by, for example, the extrusion laminating method or the dry laminating method as in the above. Alternatively, the barrier layer may be laminated by extrusion coating the polyolefin or composition constituting the resin film of the present invention.

In either case, the adhesion strength between the layers can be increased by applying an anchor coating agent on the laminated surface in advance or by performing pretreatment such as corona treatment.

The present invention is not limited to the above-described embodiments, and various modifications can be made within the scope of the claims, and the embodiments obtained by appropriately combining the technical means disclosed in the different embodiments. Is also included in the technical scope of the present invention.

An embodiment of the present invention will be described below.

<Evaluation method of resin film>
First, the evaluation method of the resin film in the following examples and comparative examples will be described.

[Evaluation of hand-cutability]
The evaluation of the hand tearability of the resin film is that when the resin film is cut in the film forming direction (MD direction) and the direction orthogonal to it (TD direction), and when tearing by hand from the cut, the resistance is low and the hand tearability is good. Those that were judged to be good were evaluated, and those that were judged to have a large resistance when tearing in the TD direction by hand and poor hand tearability were evaluated to be “poor”.

[Evaluation of rigidity]
The rigidity of the resin film is evaluated as "good" when the resin film is judged to be difficult to stretch when pulled by hand in the film forming direction (MD direction), and easily stretched when pulled by hand in the MD direction. What was judged to be was evaluated as "poor".

<Manufacture of resin film>
A method for manufacturing the resin films of Examples and Comparative Examples will be described.

<Example 1>
Copolymer of biomass-derived ethylene and fossil fuel-derived butene-1 and fossil fuel-derived hexene-1 (BRHCHEM SLH118 (hereinafter referred to as BLL-1), MFR (190°C) = 1 g/10 minutes , Density=0.916 g/cm ³ ) 98% by weight, and polylactic acid (PLA, 4032D manufactured by Nature Works Co., Ltd. (hereinafter, referred to as PLA-1)) 2% by weight were mixed by a pellet mixer to obtain a resin composition. (1) was produced.

Subsequently, the resin composition (1) was supplied to an intermediate layer extruder having a diameter of 50 mm, and was supplied to an inflation film molding machine manufactured by Sumitomo Heavy Industries Modern Co., Ltd. equipped with a three-layer annular die having a die diameter of 100 mm. A tubular film extruded from a three-layer annular die (only the annular die for forming the intermediate layer of the three-layer annular die) under the conditions of a die temperature of 200° C., a folding width of 280 mm, and a take-up speed of 5 m/min. By inflation molding, a single-layer (only the intermediate layer) resin film having a total thickness of 100 μm was manufactured. Table 1 shows the evaluation results of the resin film of Example 1.

<Example 2>
A single layer (intermediate layer) was prepared from the resin composition prepared in the same manner as in Example 1 except that the mixing ratio of BLL-1 and PLA-1 in the resin composition (1) was changed to 95% by weight:5% by weight. Example 2) was produced. Table 1 shows the evaluation results of the resin film of Example 2.

<Example 3>
A single layer (intermediate layer) was prepared from the resin composition prepared in the same manner as in Example 1 except that the mixing ratio of BLL-1 and PLA-1 in the resin composition (1) was changed to 90% by weight: 10% by weight. Of the resin film of Example 3 which is (only). Table 1 shows the evaluation results of the resin film of Example 3.

<Example 4>
The resin composition NatureWorks Ltd. polylactic acid from PLA-1 used in (1) Ingeo TM 4043D resin composition except for changing the ^{(hereinafter,} PLA-2 hereinafter) was prepared in the same manner as in Example 1 A resin film of Example 4 having a single layer (only the intermediate layer) was produced from. Table 1 shows the evaluation results of the resin film of Example 4.

<Example 5>
Resin composition (1) NatureWorks Ltd. polylactic acid from PLA-1 used in Ingeo TM 4060D resin composition except for changing the ^{(hereinafter,} PLA-3 hereinafter) was prepared in the same manner as in Example 1 A resin film of Example 5 which is a single layer (only the intermediate layer) was produced from. Table 1 shows the evaluation results of the resin film of Example 5.

<Example 6>
In the same manner as in Example 1 except that the polylactic acid used in the resin composition (1) was changed from PLA-1 to Terramac (registered trademark) TP-4000 (hereinafter referred to as PLA-4) manufactured by Unitika. A resin film of Example 6 which is a single layer (only the intermediate layer) was produced from the produced resin composition. Table 1 shows the evaluation results of the resin film of Example 6.

<Example 7>
The resin composition (1) used in Example 1 was prepared and used as the intermediate layer composition.

Subsequently, as an inner layer composition, a fossil fuel-derived ethylene-hexene-1 copolymer (Sumikasen (registered trademark) EFV104 (hereinafter referred to as OLL-1) manufactured by Sumitomo Chemical Co., Ltd.), MFR (190° C.)= 1 g/10 min, density=0.915 g/cm ³ ) was charged into the inner layer extruder having a caliber of 40 mm, and as the intermediate layer composition, the resin composition (1) was charged into the intermediate layer extruder having a caliber of 50 mm to form the outer layer. Fossil fuel-derived ethylene-hexene-1 copolymer (Sumitomo Chemical Co., Ltd. Sumikasen EFV101 (hereinafter referred to as OLL-2)), MFR (190°C) = 1.5 g/10 minutes, density = 0.923 g/cm ³ ) was charged into an outer layer extruder having a caliber of 40 mm and supplied to an inflation film molding machine manufactured by Placo Co., Ltd. equipped with a three-layer annular die having a die diameter of 100 mm. The inner layer composition and the outer layer composition were laminated on both surfaces of the resin composition (1) such that the inner surface side of the tubular film extruded from the annular die was the inner layer and the outer surface side was the outer layer, and the die temperature was 200° C. and the folding width was 280 mm. Inflation molding was performed at a take-up speed of 10 m/min to produce a resin film having a total thickness of 100 μm and an inner layer/intermediate layer/outer layer thickness ratio of 35%/30%/35%. Table 2 shows the evaluation results of the resin film of Example 7.

<Example 8>
A resin film of Example 8 was produced in the same manner as in Example 7 except that the mixing ratio of BLL-1 and PLA-1 in the resin composition (1) was changed to 95% by weight:5% by weight. Table 2 shows the evaluation results of the resin film of Example 8.

<Example 9>
A resin film of Example 9 was produced in the same manner as in Example 7 except that the mixing ratio of BLL-1 and PLA-1 in the resin composition (1) was changed to 90% by weight: 10% by weight. Table 2 shows the evaluation results of the resin film of Example 9.

<Example 10>
A resin film of Example 10 was produced in the same manner as in Example 7, except that the polylactic acid used in the resin composition (1) was changed from PLA-1 to PLA-2. Table 2 shows the evaluation results of the resin film of Example 10.

<Example 11>
A resin film of Example 11 was produced in the same manner as in Example 7, except that the polylactic acid used in the resin composition (1) was changed from PLA-1 to PLA-3. Table 2 shows the evaluation results of the resin film of Example 11.

<Example 12>
A resin film of Example 12 was produced in the same manner as in Example 7, except that the polylactic acid used in the resin composition (1) was changed from PLA-1 to PLA-4. Table 2 shows the evaluation results of the resin film of Example 12.

<Example 13>
Copolymer of biomass-derived ethylene and fossil fuel-derived butene-1 and fossil fuel-derived hexene-1 (BRHCHEM SLH118 (hereinafter referred to as BLL-1), MFR (190°C) = 1 g/10 minutes , Density=0.916 g/cm ³ ) 49% by weight, and fossil fuel-derived ethylene-hexene-1 copolymer (Sumikasen (registered trademark) EFV104 manufactured by Sumitomo Chemical Co., Ltd. (hereinafter referred to as OLL-1)) , MFR (190° C.)=1 g/10 minutes, density=0.915 g/cm ³ ) 49% by weight, and polylactic acid-based resin (PLA, 4032D manufactured by Nature Works (hereinafter referred to as PLA-1)) 2 mass % Was mixed with a pellet mixer to prepare a resin composition (2).

Subsequently, a fossil fuel-derived ethylene-hexene-1 copolymer (Sumikasen (registered trademark) EFV104 (hereinafter referred to as OLL-1) manufactured by Sumitomo Chemical Co., Ltd.) as an inner layer composition, MFR (190° C.)=1 g /10 min, density=0.915 g/cm ³ ) was charged into the inner layer extruder having a caliber of 40 mm, and the resin composition (2) was charged as an intermediate layer composition into the intermediate layer extruder having a caliber of 50 mm to form the outer layer composition. As fossil fuel-derived ethylene-hexene-1 copolymer (Sumitomo Chemical Co., Ltd. Sumikasen EFV101 (hereinafter referred to as OLL-2)), MFR (190° C.)=1.5 g/10 min, density=0. 923 g/cm ³ ) was charged into an outer layer extruder having a caliber of 40 mm and supplied to an inflation film molding machine manufactured by Sumitomo Heavy Industries Modern Co., Ltd. equipped with a three-layer annular die having a die diameter of 100 mm. The inner layer composition and the outer layer composition were laminated on both surfaces of the intermediate layer composition so that the inner surface side of the tubular film extruded from the annular die was the inner layer and the outer surface side was the outer layer, and the die temperature was 200° C., the folding width was 280 mm, and the take-up By inflation molding at a speed of 10 m/min, a resin film having a total thickness of 100 μm and an inner layer/intermediate layer/outer layer thickness ratio of 35%/30%/35% was produced. Table 3 shows the evaluation results of the resin film of Example 13.

<Example 14>
An Example was carried out in the same manner as in Example 13 except that the mixing ratio of BLL-1, OLL-1 and PLA-1 in the resin composition (2) was changed to 73% by weight:25% by weight:2% by weight. 14 resin films were produced. Table 3 shows the evaluation results of the resin film of Example 14.

<Example 15>
An Example was carried out in the same manner as in Example 13 except that the mixing ratio of BLL-1, OLL-1 and PLA-1 in the resin composition (2) was changed to 88% by weight:10% by weight:2% by weight. Fifteen resin films were produced. Table 3 shows the evaluation results of the resin film of Example 15.

<Example 16>
An Example was carried out in the same manner as in Example 13 except that the mixing ratio of BLL-1, OLL-1 and PLA-1 in the resin composition (2) was changed to 95% by weight: 3% by weight: 2% by weight. Sixteen resin films were produced. Table 3 shows the evaluation results of the resin film of Example 16.

<Comparative Example 1>
As Comparative Example 1, instead of the resin composition (1), a copolymer of ethylene derived from biomass, butene-1 derived from fossil fuel and hexene-1 derived from fossil fuel (SLH118 manufactured by Braschem Co., Ltd. (hereinafter, referred to as BLL- 1), MFR (190° C.)=1 g/10 min, and density=0.916 g/cm ³ ) were fed to an intermediate layer extruder having a caliber of 50 mm, and the total thickness was the same as in Example 1. Of 100 μm was produced as a single-layer resin film. Table 4 shows the evaluation results of the resin film of Comparative Example 1.

<Comparative example 2>
As Comparative Example 2, instead of the resin composition (1), a copolymer of ethylene derived from biomass and butene-1 derived from fossil fuel and hexene-1 derived from fossil fuel (SLH118 manufactured by Braschem Co., Ltd. (hereinafter, BLL- 1), MFR (190° C.)=1 g/10 min, density=0.916 g/cm ³ ) was used as the intermediate layer composition and fed to an intermediate layer extruder having a diameter of 50 mm. A resin film having a total thickness of 100 μm and an inner layer/intermediate layer/outer layer thickness ratio of 35%/30%/35% was produced in the same manner as in. Table 4 shows the evaluation results of the resin film of Comparative Example 2.

<Comparative example 3>
As Comparative Example 3, a copolymer of ethylene derived from biomass, butene-1 derived from fossil fuel, and hexene-1 derived from fossil fuel (SLH118 manufactured by Braskem (hereinafter, referred to as BLL-1), MFR (190°C)). =1 g/10 min, density=0.916 g/cm ³ ) 50% by weight, and fossil fuel-derived ethylene-hexene-1 copolymer (Sumikasen (registered trademark) EFV104 manufactured by Sumitomo Chemical Co., Ltd. (hereinafter, referred to as OLL -1), MFR (190° C.)=1 g/10 minutes, and density=0.915 g/cm ³ )50 wt% by mixing with a pellet mixer to prepare a resin composition. Resin having a total thickness of 100 μm and a thickness ratio of inner layer/intermediate layer/outer layer of 35%/30%/35% in the same manner as in Example 13 except that was used instead of the resin composition (2). A film was produced. Table 4 shows the evaluation results of the resin film of Comparative Example 3.

Claims (2)

At least one layer formed from a resin composition containing a biomass-derived polyolefin obtained by polymerizing a biomass-derived ethylene-based monomer and a polylactic acid-based resin;
A resin film in which the content of the polylactic acid resin in the resin composition is 1% by mass or more. An outer layer, a middle layer, and an inner layer,
The intermediate layer is formed from a resin composition for forming the layer provided in the resin film according to claim 1,
The outer layer and the inner layer are resin films formed from a resin composition containing a fossil fuel-derived polyolefin as a main component.