Resin composition for biomass-containing resin molded articles, masterbatch composition for use therein, biomass-containing resin molded article using the same, and method for manufacturing the same.

Abstract

The present invention provides a resin composition for biomass-containing resin molded articles, a masterbatch composition, and a method for manufacturing biomass-containing resin molded articles, which enable high-filling of biomass materials while ensuring physical properties such as strength. [Solution] An environmentally friendly resin composition for biomass-containing resin molded articles, comprising a biomass material, a polyethylene resin, and a polyethylene-based compatibilizer, wherein the polyethylene-based compatibilizer is selected from (a) a modified ethylene copolymer modified with an unsaturated carboxylic acid and / or its anhydride and / or (b) a polar group-containing ethylene copolymer having a polar group-containing comonomer having ethylene and an unsaturated carboxylic acid and / or its anhydride.

Description

[Technical Field]

[0001] The present invention relates to a resin composition for biomass-containing resin molded articles that can be filled with biomass materials such as natural resource fillers, resource crops, unused biomass, or biomass derived from industrial waste, a masterbatch composition used therein, a biomass-containing resin molded article using the same, and a method for producing the same. [Background technology]

[0002] In recent years, with the growing interest in and need for a sustainable society and environmental preservation, there has been a demand for research and development of plastic products containing biomass materials, which are natural materials such as rice flour and starch (organic or inorganic materials derived from renewable organisms), as an alternative to conventional plastic products made entirely from fossil fuel-derived raw materials.

[0003] One area of ​​research on resin compositions for molding to manufacture such plastic products involves molding using a resin composition for biomass-containing resin molded articles, which is obtained by mixing biomass materials, such as starch, which are natural materials, with polyolefin resins. Biomass materials (biological resources) are originally produced by absorbing carbon dioxide from the atmosphere. Therefore, even when burned, they do not increase or decrease the concentration of carbon dioxide in the atmosphere, unlike when burning fossil fuels. They are carbon-neutral resources. Furthermore, it is attractive because it can be easily obtained and is relatively inexpensive by utilizing plants themselves or their unused parts, food itself or its surplus or unused parts, or food waste. For example, surplus agricultural products produced for food can be stored for a certain period, but those that have passed their expiration date must be discarded. In order to reduce waste or surplus stockpiles, alternative uses beyond food are being explored.

[0004] For example, as an effective use of surplus rice, the conventional method has been to mold polyolefin resin compositions into which rice has been blended with polyolefin resin (see, for example, Patent Documents 1 and 2). These materials are preferable from an environmental perspective because, by incorporating such biomass raw materials, they reduce the amount of thermoplastic resins produced from fossil fuels used and decrease carbon dioxide emissions during combustion (compared to olefin resins: approximately 20%). Furthermore, the applicant has disclosed combinations of biomass materials and resins for producing such biomass-containing resin molded articles (see Patent Document 3). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2005-330402 [Patent Document 2] Japanese Patent Publication No. 2007-169615 [Patent Document 3] Japanese Patent Publication No. 2022-12572 [Disclosure of the Invention] [Problems that the invention aims to solve]

[0006] In recent years, it has been recommended to increase the concentration of biomass material in resin compositions for biomass-containing resin molded articles. For example, certification standards have been established for biomass mass content of 10% or more, 20% or more, 40% or more, 50% or more, etc., requiring high concentrations of biomass material. However, biomass materials (biological resources) often contain polar groups, particularly on their surface, that are suitable for linking with functional groups such as hydroxyl groups, phenolic groups, mercapto groups, amino groups, carboxyl groups, and other double bonds of other compounds. On the other hand, ordinary polyolefin resins are nonpolar. Therefore, when attempting to create a biomass-containing resin molded product by mixing biomass material with ordinary polyolefin resin at a high packing ratio, there was a problem in that the biomass material and the polyolefin resin did not mix well, making it difficult to obtain a biomass-containing resin molded product with good properties.

[0007] Therefore, when manufacturing products using biomass as a material, reactivity and dispersibility are improved by performing a micronization treatment to eliminate the aggregated structure of the biomass during or before the process of reacting or compounding it with various reagents. However, further improvements are needed in terms of incorporating biomass materials at a high density while ensuring physical properties such as strength. The present invention aims to solve the above-mentioned problems and to provide a resin composition for use in biomass-containing resin molded articles that can contain biomass material in a high-filling capacity and can ensure strength and other properties even when a large amount of biomass material is mixed in, as well as a biomass-containing resin molded article using the same and its applications. [Means for solving the problem]

[0008] As a result of intensive studies to solve the above problems, the inventors of the present invention have found that, at least, an environmentally friendly resin composition for a biomass-containing resin molded body, which is characterized by containing a biomass material, a polyethylene resin, and a polyethylene-based compatibilizer. Preferably, the polyethylene-based compatibilizer is a compatibilizer selected from (a) a modified ethylene copolymer modified with an unsaturated carboxylic acid and / or its anhydride and / or (b) a polar group-containing ethylene copolymer having ethylene and a polar group-containing comonomer having an unsaturated carboxylic acid and / or its anhydride. More preferably, the polyethylene resin contained in the resin composition for the biomass-containing resin molded body is characterized in that there are two or more types including at least a first polyethylene resin and a second polyethylene resin. When using the resin composition for an environmentally friendly biomass-containing resin molded body, good mixing is possible, and as a result, a good biomass-containing resin molded body can be obtained, leading to the present invention.

[0009] That is, according to the first invention of the present application, an environmentally friendly resin composition for a biomass-containing resin molded body, which is characterized by containing at least a biomass material, a polyethylene resin, and a polyethylene-based compatibilizer, is provided. According to the second invention of the present application, the environmentally friendly resin composition for a biomass-containing resin molded body according to the first invention, wherein the polyethylene-based compatibilizer is a compatibilizer selected from (a) a modified ethylene copolymer modified with an unsaturated carboxylic acid and / or its anhydride and / or (b) a polar group-containing ethylene copolymer having ethylene and a polar group-containing comonomer having an unsaturated carboxylic acid and / or its anhydride, is provided. According to the third invention of the present application, the environmentally friendly resin composition for a biomass-containing resin molded body according to the first invention, wherein the polyethylene resin contained in the resin composition for the biomass-containing resin molded body is characterized in that there are two or more types including at least a first polyethylene resin and a second polyethylene resin, is provided. According to the fourth invention of the present application, there is provided a masterbatch composition for use in an environmentally friendly biomass-containing resin molded body, which is obtained by kneading at least a biomass material and a first polyethylene resin. According to the fifth invention of the present application, there is provided the masterbatch composition according to the fourth invention, wherein the first polyethylene resin contained in the masterbatch composition is a polyethylene-based resin having a melt flow rate (MFR) of 3.0 g / 10 min or more. According to the sixth invention of the present application, there is provided a method for producing an environmentally friendly biomass-containing resin molded body containing at least a biomass material and a polyethylene resin, characterized by molding using a resin composition obtained by mixing a masterbatch material obtained by kneading a biomass material and a first polyethylene resin, a polyethylene-based compatibilizer, and a second polyethylene resin. According to the seventh invention of the present application, there is provided the method for producing a biomass-containing resin molded body according to the sixth invention, wherein the first polyethylene resin contained in the masterbatch composition is a polyethylene-based resin having a melt flow rate (MFR) of 3.0 g / 10 min or more. According to the eighth invention of the present application, there is provided a biomass-containing resin film which is a molded body obtained by using the resin composition for a biomass-containing resin molded body according to any one of the first to third inventions, and wherein the molded body is a film.

Advantages of the Invention

[0010] By selectively using a resin material optimal for mixing with the biomass material, the biomass-containing resin molded body and the material used therefor, which can be filled with the biomass material at a high concentration, can be obtained. In addition, since the biomass material is easily dissolved at the molecular level and finely and uniformly dispersed in the molten resin, the physical properties such as the strength of the biomass-containing resin molded body can be improved.

Embodiments for Carrying Out the Invention

[0011] The present invention is characterized by an environmentally friendly resin composition for biomass-containing resin molded articles, which contains a biomass material (P), a polyethylene resin, and a polyethylene-based compatibilizer. The present invention relates to a biomass-containing resin molded article containing a resin composition for forming a final molded article, preferably containing 10% by weight or more, more preferably 10 to 90% by weight of a biomass material (P), and a resin material of 10% to 90% by weight, wherein at least a portion of the resin material contains a specific polyethylene resin, preferably a metallocene-based polyethylene resin, more preferably a metallocene-based ethylene plastomer (A), and a polyethylene-based compatibilizer. The present invention also relates to a resin material used therein and a molded article obtained therefrom. The present invention will be described in detail below.

[0012] 1. Biomass material (P) Biomass materials refer to renewable organic or inorganic resources of biological origin, excluding fossil resources. Examples include carbohydrate resources such as sugarcane and sugar beets, starch resources such as rice, potatoes, and corn, oil and fat resources such as rapeseed, soybeans, and peanuts, resource crops selected from these sources, forestry resources such as forest residues, unused biomass selected from agricultural resources such as rice straw, rice husks, and wheat straw, livestock resources, food resources such as processing residues, industrial resources such as pulp wastewater, forestry resources such as sawmill residues and construction waste, and waste biomass selected from sewage sludge (definition from materials created by the Japan Organic Resources Association). In particular, plants themselves, unused parts of plants, plant residues, food itself, unused parts of food, and processing residues are easy to use as raw materials for biomass-containing resin molded products. Specifically, starch resources such as rice, potatoes, and corn are preferred. These biomass materials may be used in their original form, but preferably they are crushed or otherwise processed into a filler or powder form before being mixed with the resin material, or they can be used after being pre-mixed with other liquids or other masterbatch resins. Furthermore, thermoplasticized starch that has undergone processing such as thermoplasticization can also be used.

[0013] 2. Components of resin materials The biomass-containing resin molded article of the present invention is characterized in that the polyethylene resin material mixed with the biomass material contains, for example, at least a portion of any or a combination thereof of the polyethylene resins described in (1) to (5) below. (1) High-density polyethylene resin (2) Medium-density polyethylene resin (3) Linear low-density polyethylene resin (4) Metallocene-based low-density polyethylene resin (5) Low-density polyethylene resin by high-pressure radical polymerization Among these, (4) metallocene-based low-density polyethylene resin is preferred, and more preferably, among these, metallocene-based ethylene plastomer (4A) is included.

[0014] (1) High-density polyethylene resin High-density polyethylene resin is a homopolymer of ethylene or a copolymer of ethylene and α-olefin polymerized by catalytic polymerization, with a density of 0.950 g / cm³. 3 More than 0.970g / cm 3 The following molecular structure refers to linear polyethylene (hereinafter also called "HDPE"). The polymerization catalyst may be any of the following: metallocene catalyst, Ziegler catalyst, Phillips catalyst, etc., and the polymerization method may be any of ionic polymerization, slurry polymerization, solution polymerization, or gas-phase polymerization. The density is 0.950~0.970 g / cm³ 3 Preferably 0.950~0.966 g / cm³ 3 And more preferably, 0.950~0.960 g / cm³ 3 be. In this invention, the density of the polymer is measured according to JIS-K-6922-2. The melt flow rate (MFR) of high-density polyethylene is preferably 0.1 to 30 g / 10 min at 190°C. More preferably, it is 0.5 to 4.0 g / 10 min. In this invention, the melt flow rate (MFR) is the melt flow rate value measured according to JIS-K-7210. High-density polyethylene is specifically an ethylene homopolymer or an ethylene-α-olefin copolymer. In the latter, the proportion of α-olefin units copolymerized with ethylene is usually 0.05 to 2 mol%, preferably 0.05 to 1 mol%, and particularly preferably 0.1 to 1 mol%. The types of α-olefins are usually α-olefins having 3 to 8 carbon atoms, and specifically include propylene, butene-1, pentene-1, hexene-1, heptene-1, octen-1, and 4-methylpentene-1. A typical example of high-density polyethylene is "Novatec" manufactured by Nippon Polyethylene Co., Ltd. TM Examples of the "HD" series include the "HF562" and "HY443".

[0015] (2) Medium-density polyethylene resin The medium-density polyethylene resin (2) of the present invention is specifically an ethylene-α-olefin copolymer having a medium density and linear molecular structure, obtained by copolymerizing ethylene and an α-olefin having 3 to 18 carbon atoms by catalytic polymerization (hereinafter also referred to as "MDPE"). Here, examples of α-olefins having 3 to 18 carbon atoms include propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, and 1-octadecene. Among these, those having 4 to 12 carbon atoms are preferred, and those having 4 to 10 carbon atoms, such as 1-butene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, and 1-decene, are particularly preferred. In addition, the content of α-olefin in the ethylene-α-olefin copolymer is preferably 3 to 24% by weight, more preferably 5 to 20% by weight, and still more preferably 7 to 15% by weight. Furthermore, the linear medium density polyethylene in the present invention preferably satisfies the following characteristics. The density is 0.930 g / cm 3 or more to 0.950 g / cm 3 less than, preferably 0.930 g / cm 3 or more to 0.940 g / cm 3 or less, still more preferably 0.930 g / cm 3 ultra to 0.938 g / cm 3 or less. The melt flow rate (MFR) is 0.1 to 20 g / 10 min, preferably 0.3 to 15 g / 10 min, and more preferably 0.5 to 10 g / 10 min. As the linear medium density polyethylene, it is preferably copolymerized in the presence of a Kaminsky-type catalyst, a so-called metallocene catalyst, rather than copolymerized in the presence of a Ziegler-Natta type catalyst, a Phillips type catalyst, etc. The ethylene-α-olefin copolymer by the Kaminsky-type catalyst uses, for example, a metallocene catalyst, particularly a metallocene-alumoxane catalyst, described in JP-A Nos. 58-19309, 59-95292, 60-35005, 60-35006, 60-35007, 60-35008, 60-35009, 61-130314, 3-163088, European Patent Publication No. 420436, U.S. Patent No. 5055438, and International Publication WO91 / 04257, etc., or uses, for example, a catalyst composed of a metallocene compound and a compound that reacts with the compound to form a stable anion described in International Publication WO92 / ., and can be produced by a polymerization method such as a gas phase method, a slurry method, a solution method, a high-pressure ionic polymerization method, etc. In particular, polymers polymerized using a catalyst in which a tetravalent transition metal compound such as titanium, zirconium, nickel, palladium, hafnium, or platinum is used as a metallocene compound, with a mono-, di-, or tri-cyclopentadienyl ring or a substituted cyclopentadienyl ring as a ligand, are used, and polymers polymerized using a catalyst in which a transition metal compound with a hafnium compound as the central metal is used as the metallocene compound are preferred. More preferably, ethylene-α-olefin copolymers produced with special catalyst species, such as those described in Japanese Patent No. 3539801, are preferred. As the linear medium-density polyethylene, an ethylene-α-olefin copolymer having the following physical properties is preferred. Molecular weight distribution (Mw / Mn) is 1.8-3.5 The molecular weight distribution (Mw / Mn) is determined from the weight-average molecular weight (Mw) and number-average molecular weight (Mn) obtained by gel permeation chromatography (GPC). Examples of linear medium-density polyethylene (2) include "NC596A," a medium-density resin in the "Harmolex" (trademark) series, which has recently been manufactured and sold by the applicant (Nippon Polyethylene Co., Ltd.) and polymerized with a metallocene catalyst in the medium-density range. Such copolymers have a narrower molecular weight distribution than polymers obtained with conventional Ziegler-Natta type catalysts, and are polyethylene resins that possess strength and high rigidity over a wide temperature range.

[0016] (3) Linear low-density polyethylene resin Linear low-density polyethylene resin (hereinafter referred to as "LLDPE") is specifically obtained by copolymerizing ethylene and α-olefins having 3 to 18 carbon atoms by catalytic polymerization, with a density of 0.900 g / cm³. 3 More than 0.930g / cm 3 This is an ethylene-α-olefin copolymer having a low density and a linear molecular structure with a density less than 100%, excluding the linear low-density polyethylene resin produced by metallocene catalysts as described in (4) below. In other words, it refers to ethylene-α-olefin copolymers with a broad molecular weight distribution, polymerized using heterogeneous catalysts, within the broad category of linear low-density polyethylene. Specifically, it can be arbitrarily selected from known linear low-density polyethylenes with a broad molecular weight distribution, such as those copolymerized in the presence of heterogeneous catalysts like Ziegler-Natta or Phillips catalysts. Here, examples of α-olefins having 3 to 18 carbon atoms include propylene, 1-butene, 3-methyl-1-butene, 1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, 1-decene, and 1-octadecene. Among these, those having 4 to 12 carbon atoms are preferred, and those having 4 to 10 carbon atoms, such as 1-butene, 1-hexene, 4-methyl-1-hexene, 1-heptene, 1-octene, and 1-decene, are particularly preferred. Furthermore, the α-olefin content in the ethylene-α-olefin copolymer is preferably 3 to 24% by weight, more preferably 5 to 20% by weight, and even more preferably 7 to 15% by weight. Furthermore, linear low-density polyethylene preferably satisfies the following characteristics. The density is 0.900-0.930 g / cm³. 3 It is less than 0.905 to 0.924 g / cm³, preferably 0.905 to 0.924 g / cm³. 3 That is the case. The melt flow rate (MFR) is preferably 0.1 to 20 g / 10 min, more preferably 0.3 to 15 g / 10 min, and more preferably 0.5 to 10 g / 10 min. If the MFR is too low, the resin pressure tends to increase, resulting in poor processability. On the other hand, if the MFR is too high, processability such as bubble stability during molding tends to be poor. Examples of linear low-density polyethylene (3) used in the present invention include "Novatec LL" (registered trademark) and "Novatec C6" (registered trademark) manufactured by Nippon Polyethylene Co., Ltd.

[0017] (4) Metallocene-based low-density polyethylene resin Metallocene-based low-density polyethylene resin (hereinafter referred to as "mLL") is a metallocene-based ethylene-α-olefin copolymer resin, that is, an ethylene-α-olefin copolymer resin produced using a metallocene catalyst, with a generally linear molecular structure and a density of 0.930 g / cm³. 3 It has a low density of less than 100%, and is characterized by a narrow molecular weight distribution, which is derived from polymerization using metallocene-based catalysts, which are homogeneous catalysts with uniformly distributed catalytic activity. In this technical field, particularly in the low-density sector, the properties of resins differ depending on the polymerization method and catalyst type. Therefore, identifying the type of resin by polymerization method and catalyst type is a common technical practice, and this definition is clear. Metallocene-based low-density polyethylene (mLL) is often referred to separately from general linear low-density polyethylene (LLDPE) obtained by heterogeneous catalysts such as other Ziegler-based catalysts. The types of α-olefins copolymerized with ethylene are typically α-olefins having 3 to 12 carbon atoms, specifically including propylene, butene-1, pentene-1, hexene-1, heptene-1, octene-1, and 4-methylpentene-1. Among these α-olefins, those having 3 to 8 carbon atoms are preferred. One type of α-olefin may be used, or two or more types may be used in combination as desired. For example, copolymers of ternary or higher systems containing C3 propylene and C6 hexene can also be preferably used. The melt flow rate (MFR) of metallocene-based low-density polyethylene resin, measured in accordance with JIS K7210, is 0.05 to 20 g / 10 min, preferably 0.1 to 10 g / 10 min, and more preferably 0.5 to 5 g / 10 min. If the MFR is too high, the punching impact strength tends to decrease, which is undesirable. Conversely, if the MFR is too low, the resin pressure during molding increases, causing resin heat generation or increasing the extrusion load, which tends to worsen processability. Note that the MFR in this invention is the value at 190°C and a load of 21.18 N. The density of the metallocene-based low-density polyethylene resin of the present invention, as measured in accordance with JIS K7112, is 0.870 g / cm³. 3 More than 0.930g / cm3 It is less than 0.870 to 0.920 g / cm³. 3 More preferably 0.870 to 0.910 g / cm³ 3 That is the case. The metallocene-based low-density polyethylene resin of the present invention preferably has one or more melting points below 110°C, preferably below 100°C, and more preferably below 90°C, as measured in accordance with JIS K6922-2. Having melting points in this temperature range is preferable because it contains low-crystallinity components that impart flexibility and punching impact strength when compounded. In this invention, the melting point refers to the temperature at the peak of the melting peak measured in accordance with JIS K6922-2 (hereinafter also referred to as the melting peak temperature). Commercially available metallocene polyethylene resins can be used for this purpose. For example, typical options include the "Kernel®" series or the "Harmolex®" series manufactured by Nippon Polyethylene Co., Ltd. Examples include "NF444A," "NF366A," and "NC564A."

[0018] (4A) Furthermore, among the metallocene-based low-density polyethylene resins, resins with physical properties within the range referred to as metallocene-based ethylene plastomer (A) are particularly preferred. Metallocene-based ethylene plastomer (A) is specifically a type of copolymer of ethylene and α-olefin (ethylene-α-olefin copolymer) obtained by a metallocene catalyst. It is an ethylene-based resin that possesses properties known as metallocene-based plastomers, including a density in the ultra-low density region, which is relatively low even within low densities, a uniform polymer distribution indicated by a narrow molecular weight distribution (Mw / Mn) derived from the polymerization method using a metallocene catalyst, which has uniform catalytic active sites, and plastomer-like properties. Commercially available metallocene-based ethylene plastomers can be used, and typical examples include those from the "Kernel (registered trademark)" series manufactured by Nippon Polyethylene Co., Ltd., such as "KF260T," "KF360T," and "KS340T." The metallocene-based ethylene plastomer (A) is a copolymer of ethylene obtained by a metallocene catalyst and an α-olefin having 3 to 12 carbon atoms, more preferably 4 to 12 carbon atoms. Examples of α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-octadecene, and 1-eicosene. Copolymers of two or more α-olefins, such as a ternary or higher copolymer containing C3 propylene and C6 hexene, can also be preferably used. Furthermore, the ethylene-α-olefin copolymer of the present invention preferably has the following properties (a-1) to (a-3).

[0019] (a-1) Density The density of the metallocene-based ethylene plastomer (4A) used in this invention is 0.880 to 0.920 g / cm³. 3 The concentration is preferably 0.885 to 0.915 g / cm³. 3 More preferably 0.890 to 0.910 g / cm³ 3 If the density is too low, it tends to become sticky and the blocking properties will be poor. Here, the density is measured according to Method D (density gradient tube method) of "Plastics - Method for measuring density and specific gravity of non-foamed plastics" in JIS K7112-1999.

[0020] (a-2) Meltflow rate (MFR) The preferred MFR for metallocene-based ethylene plastomer (4A) is 0.5 to 8.0 g / 10 min, preferably 0.7 to 4.0 g / 10 min, and more preferably 1.0 to 3.5 g / 10 min. If the MFR is too low, the resin pressure increases during molding, making it difficult to extrude and prone to foaming due to excessive heat generation of the resin. In addition, dispersibility with other components such as biomass materials and polypropylene tends to be poor, and the appearance tends to deteriorate. On the other hand, if the MFR is too high, the mechanical strength tends to decrease. Here, MFR is a value measured in accordance with JIS K7210-1999, "Plastics - Test methods for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastic plastics," under test conditions of 190°C and a load of 21.18 N (2.16 kg).

[0021] (a-3)Mw / Mn The ratio of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) (Mw / Mn) of the ethylene-α-olefin copolymer used in the present invention is 1.5 to 3.5, preferably 1.8 to 3.3, and more preferably 2.1 to 3. This range is preferable for ensuring the processability and impact strength of the biomass-containing resin molded article.

[0022] Here, the Mw / Mn of an ethylene-α-olefin copolymer refers to the value obtained by the following method (hereinafter sometimes referred to as the "method for measuring molecular weight distribution"). Mw / Mn is defined as the ratio (Mw / Mn) of the weight-average molecular weight (Mw) and the number-average molecular weight (Mn) measured by gel permeation chromatography (GPC).

[0023] Equipment: Waters GPC 150C type detector: MIRAN 1A infrared spectrophotometer (measurement wavelength, 3.42 μm) Columns: Showa Denko AD806M / S (3 pieces) [The column was calibrated by measuring monodisperse polystyrene (A500, A2500, F1, F2, F4, F10, F20, F40, F288, each 0.5 mg / ml solution) manufactured by Tosoh Corporation, and approximating the logarithm of the elution volume and molecular weight with a quadratic equation. Furthermore, the molecular weight of the samples was converted to polyethylene equivalent using the viscosity formulas for polystyrene and polyethylene. Here, the coefficients in the viscosity formula for polystyrene are α = 0.723 and logK = -3.967, while for polyethylene they are α = 0.707 and logK = -3.407.] Measurement temperature: 140℃ Injection amount: 0.2ml Concentration: 20mg / 10mL Solvent: Orthodichlorobenzene Flow rate: 1.0ml / min

[0024] The metallocene-based ethylene plastomer of the present invention is obtained by a metallocene catalyst. The metallocene catalyst is a catalyst comprising a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, a co-catalyst, an organometallic compound if necessary, and a support, each of which is a catalytic component.

[0025] Here, in a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, the cyclopentadienyl skeleton is a cyclopentadienyl group, a substituted cyclopentadienyl group, etc. The substituted cyclopentadienyl group has at least one substituent selected from hydrocarbon groups having 1 to 30 carbon atoms, silyl groups, silyl-substituted alkyl groups, silyl-substituted aryl groups, cyano groups, cyanoalkyl groups, cyanoaryl groups, halogen groups, haloalkyl groups, halosilyl groups, etc. The substituted cyclopentadienyl group may have two or more substituents, and these substituents may bond to each other to form a ring, forming an indenyl ring, a fluorenyl ring, an azlenyl ring, or a hydrogenated version thereof. The ring formed by the bonding of substituents may further have substituents on each other.

[0026] In a transition metal compound of Group IV of the periodic table containing a ligand having a cyclopentadienyl skeleton, examples of the transition metal include zirconium, titanium, and hafnium, with zirconium and hafnium being particularly preferred. The transition metal compound usually has two ligands having a cyclopentadienyl skeleton, and it is preferable that each ligand having a cyclopentadienyl skeleton is bonded to each other by a bridging group. The bridging group may be an alkylene group, silylene group, dialkylsilylene group, diarylsilylene group, etc., having 1 to 4 carbon atoms. Examples include substituted germylene groups such as substituted silylene groups, dialkylgermylene groups, and diarylgermylene groups. Preferably, it is a substituted silylene group.

[0027] In transition metal compounds of Group IV of the periodic table, typical ligands other than those having a cyclopentadienyl skeleton include hydrogen, hydrocarbon groups having 1 to 20 carbon atoms (alkyl groups, alkenyl groups, aryl groups, alkylaryl groups, aralkyl groups, polyenyl groups, etc.), halogens, metaalkyl groups, and metaaryl groups.

[0028] The transition metal compounds of Group IV of the periodic table containing the ligand having the cyclopentadienyl skeleton described above can be used as a catalyst component, either individually or as a mixture of two or more.

[0029] Co-catalysts are those that can effectively utilize the transition metal compounds of Group IV of the periodic table as polymerization catalysts, or that can balance the ionic charge of the catalytically activated state. Examples of co-catalysts include benzene-soluble aluminoxanes and benzene-insoluble organoaluminum oxy compounds, ion-exchangeable layered silicates, boron compounds, ionic compounds consisting of cations containing or not containing active hydrogen groups and non-coordinating anions, lanthanide salts such as lanthanum oxide, tin oxide, and phenoxy compounds containing fluoro groups.

[0030] Transition metal compounds of Group IV of the periodic table containing ligands having a cyclopentadienyl skeleton may be used by being supported on an inorganic or organic compound. The support is preferably a porous oxide of an inorganic or organic compound, and specifically includes ion-exchange layered silicates such as montmorillonite, SiO2, Al2O3, MgO, ZrO2, TiO2, B2O3, CaO, ZnO, BaO, ThO2, etc., or mixtures thereof.

[0031] Further organometallic compounds that may be used as needed include organoaluminum compounds, organomagnesium compounds, and organozinc compounds. Of these, organoaluminum compounds are preferred.

[0032] In particular, among low-density ethylene-α-olefin copolymers (metallocene-based ethylene plastomers), it is preferable that they have the following physical properties (a-4). It is presumed that this is preferable because the relatively high content of vinyl and vinylidene in the molecule allows for favorable mixing with biomass material (P). An example of such copolymer is "Kernel®," manufactured by Nippon Polyethylene Co., Ltd., which is produced by high-pressure ionic polymerization using a homogeneous metallocene catalyst. (a-4) The total number of vinyl and vinylidene double bonds (V) in the copolymer is 0.10 (bonds / total 1000C) or more (however, the number of vinyl and vinylidene is the number per 1000 carbon atoms in the main chain and side chains as measured by NMR). Furthermore, the total number of vinyl and vinylidene molecules (V) in the ethylene-α-olefin copolymer is preferably 0.10 (molecules / total1000C) or more, more preferably 0.12 or more, even more preferably 0.17 or more, and particularly preferably 0.2 or more. There is no particular upper limit to the number (V), but it is preferably 5.0 or less, even more preferably 3.0 or less, and particularly preferably 1.5 or less from the viewpoint of the thermal stability of the resin. The individual amounts of vinyl and vinylidene are not particularly limited, but for example, the amounts of vinyl and vinylidene are preferably 0.05 or more each.

[0033] Here, the number of vinyl and vinylidene atoms can be measured by 1H-NMR. The number of vinyl and vinylidene atoms in the polymer is measured by 1H-NMR and determined as the number per 1000 carbon atoms in the main chain and side chains combined. Specifically, the number of vinyl atoms per 1000 carbon atoms is calculated from the peak area derived from saturated alkyl chains appearing between 0.4 and 2.8 ppm of chemical shift and the peak area derived from vinyl around 4.9 ppm. The number of vinylidene atoms is calculated using the characteristic peak around 4.7 ppm. Furthermore, the number of vinyl and vinylidene molecules can be adjusted by manufacturing conditions such as the polymerization temperature during polymerization, or by using a diene compound as a comonomer.

[0034] (5) Low-density polyethylene resin by high-pressure radical polymerization High-pressure radical polymerization low-density polyethylene resin is a low-density polyethylene resin with numerous branched structures obtained by polymerizing ethylene monomers using a high-pressure radical polymerization method. The density is 0.910 g / cm³. 3 More than 0.930g / cm 3 It is less than 0.915 to 0.930 g / cm³. 3 More preferably, 0.918 to 0.925 g / cm³ 3 Here, the density is a value measured in accordance with Method D (density gradient tube method) of "Plastics - Method for measuring density and specific gravity of non-foamed plastics" in JIS K7112-1999. The melt flow rate (MFR) is preferably 0.5 to 20 g / 10 min, more preferably 0.7 to 10 g / 10 min, and more preferably 0.7 to 5 g / 10 min. Here, the MFR is the value measured in accordance with JIS K7210-1999 "Plastics - Test method for melt mass flow rate (MFR) and melt volume flow rate (MVR) of thermoplastic plastics" under test conditions: 190°C and a load of 21.18 N (2.16 kg). Furthermore, the shape of the high-pressure low-density polyethylene is not limited and may be in pellet or powder form. The high-pressure low-density polyethylene used in this invention can be appropriately selected from commercially available products. Examples of commercially available products include "Novatec LD" (trademark name) manufactured by Nippon Polyethylene Co., Ltd.

[0035] The content of polyethylene-based resin in the resin material is 10% by weight or more, preferably 20% by weight or more, more preferably 50% by weight or more, with an upper limit of 100% by weight or less, and when other resins are mixed, it is preferably 90% by weight or less, and more preferably 80% by weight or less. In particular, the polyethylene resin of the present invention may use not only a monomer component derived from petroleum, but also biomass polyethylene polymerized from so-called biomass-derived ethylene or α-olefin. By using polyethylene resin polymerized with monomer components derived from biomass, the biomass content of the biomass-containing resin molded product can be increased, making it easier to meet biomass standards.

[0036] A preferred feature of the biomass-containing resin molded article resin composition of the present invention is that the polyethylene resin contained in the biomass-containing resin molded article resin composition comprises at least two types of polyethylene resin, including a first polyethylene resin and a second polyethylene resin. Furthermore, one feature is a masterbatch composition for use in an environmentally friendly biomass-containing resin molded article, characterized by being made by kneading at least a biomass material with a first polyethylene resin. Furthermore, a method for producing an environmentally friendly biomass-containing resin molded article comprising at least a biomass material and polyethylene resin, One method for producing a biomass-containing resin molded article is to mold it using a resin composition obtained by mixing a masterbatch material, which is obtained by kneading a biomass material and a first polyethylene resin, with a polyethylene compatibilizer and a second polyethylene resin. Furthermore, examples include a masterbatch composition characterized in that the first polyethylene resin contained in the masterbatch composition is a polyethylene-based resin with an MFR of 3.0 g / 10 min or more, or a method for producing a biomass-containing resin molded article. These features are particularly preferable when applied to a biomass-containing resin film, which is a molded article obtained using a resin composition for biomass-containing resin molded articles, and in which the molded article is a film.

[0037] (6) Other resins: Propylene resins (B) The resin material used in the biomass-containing resin molded article of the present invention may contain other resins in addition to the polyethylene-based resin described above, such as other polyethylene-based resins and propylene-based resins (B). In particular, biomass polyethylene or biomass polypropylene polymerized using so-called biomass-derived ethylene or propylene may be used. Preferred propylene resins (B) include propylene homopolymers and random copolymers of propylene and ethylene and / or butene obtained by a metallocene catalyst. Specifically, these include propylene homopolymers, propylene-ethylene random copolymers, propylene-butene random copolymers, and propylene-ethylene-butene ternary random copolymers. Of these, propylene-ethylene random copolymers are preferred. Furthermore, the propylene-based resin (B) described above may also have comonomer components other than ethylene and butene copolymerized with propylene. Examples of comonomers include α-olefins having 5 to 20 carbon atoms. Examples of α-olefins having 5 to 20 carbon atoms include hexene-1 and octene-1. The propylene resin used in the present invention preferably has the following properties (b-1) to (b-3), and more preferably has (b-4) if necessary.

[0038] (b-1) Propylene units, ethylene units and / or butene units The propylene resin used in the present invention must contain 85 to 100 mol%, preferably 90 to 99.5 mol%, more preferably 92 to 98.5 mol%, of propylene units, and 0 to 15 mol%, preferably 0.5 to 10 mol%, more preferably 1.5 to 8 mol%, of ethylene units and / or butene units. Here, the propylene units and ethylene and / or butene units are values ​​measured by Fourier transform infrared analysis.

[0039] (b-2)Mw / Mn The propylene resin used in this invention has an Mw / Mn ratio of 5 or less, preferably 2 to 4, more preferably 2.3 to 3.5, and particularly preferably 2.6 to 3.3. If the Mw / Mn ratio is less than 2, moldability may deteriorate, and if it is greater than 5, the transparency and balance of mechanical properties of the resulting molded product may deteriorate, and the impact strength may weaken. Here, Mw / Mn is defined as the ratio (Mw / Mn) of the weight-average molecular weight (Mw) to the number-average molecular weight (Mn) measured by GPC. The measurement of Mw / Mn is performed using the same method as described above. However, the coefficients in the viscosity formula for polypropylene were set to α = 0.707 and logK = -3.616.

[0040] (b-3) Amount of soluble matter at temperatures below 40°C measured by the temperature-reduced elution fractionation (TREF) method. The propylene resin used in this invention has a soluble content of 4% by weight or less, preferably 3% by weight or less, and more preferably 1.5% by weight or less, as measured by the temperature-reduced elution fractionation (TREF) method at temperatures below 40°C. If the soluble content at temperatures below 40°C is greater than 4% by weight, bleeding from the molded product is more likely to occur, and smoke generation during molding is more likely to occur. In addition, there is a risk that the affinity with starch-based substances will be poor. Soluble components below 40°C include so-called low-crystalline components such as oligomers (components with low molecular weight), atactic polypropylene (components with low stereoregularity), and components with extremely high comonomer content. Here, components with low stereoregularity, such as atactic polypropylene, and low-crystalline components with extremely high comonomer content can be soluble even if they have high molecular weights.

[0041] Here, the method for determining the soluble content using the thermal elution fractionation (TREF) method is specifically carried out according to the following procedure. The sample is dissolved in orthodichlorobenzene at 140°C to obtain a solution. This solution is then introduced into a 140°C TREF column under the following conditions, cooled to 100°C at a rate of 8°C / min, and then cooled to 40°C at a rate of 4°C / min, and held for 10 minutes. Subsequently, orthodichlorobenzene, the solvent, is flowed through the column at a flow rate of 1 mL / min to elute the components dissolved in orthodichlorobenzene at 40°C in the TREF column for 10 minutes. Then, the column is linearly heated to 140°C at a heating rate of 100°C / hour to obtain the elution curve. Column size: 4.3mmφ × 150mm Column packing material: 100 μm surface-inert treated glass beads Solvent: Orthodichlorobenzene Sample concentration: 5 mg / mL Sample injection volume: 0.2 mL Solvent flow rate: 1 mL / min Detector: Wavelength-fixed infrared detector, FOXBORO MIRAN 1A Measurement wavelength: 3.42μm From the elution curve obtained according to the above conditions, calculate the percentage (by weight) of the total amount of components eluted at 40°C.

[0042] (b-4) Melting point (Tp) The propylene resins preferably used in the present invention have a melting point (Tp) measured by differential scanning calorimeter (DSC) that is preferably 110 to 150°C, more preferably 115 to 145°C, and even more preferably 120 to 140°C. If Tp is higher than 150°C, it becomes necessary to set a higher molding temperature, and molding the starch-containing resin composition at a high temperature can cause the starch to discolor and emit odors, potentially impairing moldability and product quality. Here, Tp is a value measured by a differential scanning calorimeter (DSC). Using a Seiko differential scanning calorimeter, approximately 5 mg of the sample was taken, held at 200°C for 5 minutes, and then cooled to 40°C at a rate of 10°C / min. Subsequently, Tp was obtained from the heat of fusion curve obtained when the sample was melted at a heating rate of 10°C / min. In other words, Tp was defined as the maximum peak temperature of the heat of fusion curve.

[0043] The preferred propylene resin (B) is obtained by a metallocene catalyst. The metallocene catalyst is a catalyst containing a transition metal compound of Group IV of the periodic table with a ligand having a cyclopentadienyl skeleton, a co-catalyst, an organometallic compound if necessary, and a support, and the catalyst components can be those described above.

[0044] The propylene resin (B) used in this invention may be a mixture of two or more types. Furthermore, commercially available propylene resins can be used; for example, they can be selected from the WINTEC series manufactured by Nippon Polypropylene Co., Ltd.

[0045] (4) Compatibilizer (D) The present invention's resin composition for biomass-containing resin molded articles is characterized by the addition of a compatibilizer (D) in addition to the biomass material (P) and polyethylene resin material. The addition of the compatibilizer improves the affinity between the resin component and the biomass material. The compatibilizer (D) is selected from (a) a modified ethylene copolymer modified with an unsaturated carboxylic acid and / or its anhydride and / or (b) an ethylene copolymer containing polar groups and a polar group-containing comonomer having an unsaturated carboxylic acid and / or its anhydride.

[0046] Examples of saturated carboxylic acids include succinic anhydride, succinic acid, phthalic anhydride, phthalic acid, tetrahydrophthalic anhydride, and adipic anhydride. Examples of unsaturated carboxylic acids include maleic anhydride, maleic acid, nadic anhydride, itaconic anhydride, itaconic acid, citraconic anhydride, citraconic acid, crotonic acid, isocrotonic acid, mesaconic acid, angelic acid, sorbic acid, and acrylic acid. Derivatives of saturated or unsaturated carboxylic acids can include metal salts, amides, imides, and esters of saturated or unsaturated carboxylic acids.

[0047] Furthermore, examples of thermoplastic resins modified with unsaturated carboxylic acids or their derivatives include low-density polyethylene, ethylene-α-olefin copolymer, high-density polyethylene, polypropylene, propylene block copolymer, and propylene random copolymer.

[0048] These are obtained by heating and mixing a thermoplastic resin, an unsaturated carboxylic acid or its derivative, and a radical generator in or without a solvent. The amount of unsaturated carboxylic acid or its derivative added is preferably 0.1 to 15% by weight, particularly preferably 1 to 10% by weight. As the compatibilizer used in the present invention, modified polyethylene modified with an unsaturated carboxylic acid or its derivative that is odorless and has low acidity is preferred.

[0049] (b) A polar group-containing ethylene copolymer (ethylene-unsaturated carboxylic acid ester copolymer resin) having ethylene and a polar group-containing comonomer having an unsaturated carboxylic acid and / or its anhydride. Ethylene-unsaturated carboxylic acid ester copolymer resins include copolymers of ethylene and α,β-unsaturated carboxylic acid esters, such as ethylene-(meth)acrylic acid or its alkyl ester copolymers, including ethylene-methyl acrylate copolymer, ethylene-ethyl acrylate copolymer, ethylene-butyl acrylate copolymer, ethylene-methyl methacrylate copolymer, and ethylene-ethyl methacrylate copolymer; binary copolymers or polypolymers, such as ethylene-maleic anhydride-vinyl acetate copolymer, ethylene-maleic anhydride-methyl acrylate copolymer, and ethylene-maleic anhydride-ethyl acrylate copolymer, or metal salts thereof.

[0050] The content of the compatibilizer (D) in the biomass-containing resin composition is preferably 1% by weight or more, more preferably 3% by weight or more, particularly preferably 5% by weight or more, preferably 20% by weight or less, even more preferably 15% by weight or less, and particularly preferably 10% by weight or less, relative to the total resin composition for forming the molded article.

[0051] (5) Other ingredients The resin material for the biomass-containing resin molded article of the present invention may contain various additives, such as nucleating agents, heat-resistant stabilizers, antioxidants, weather-resistant stabilizers, antistatic agents, slip agents, anti-blocking agents, anti-fogging agents, colorants, fillers, elastomers, wood-based materials, etc., to the extent that the objectives of the present invention are not impaired.

[0052] (6) The ratio of each ingredient The biomass-containing resin molded article of the present invention is a biomass-containing resin molded article that contains 10% by weight or more of biomass material relative to the total amount of the compound, preferably 20% by weight or more, more preferably 40% by weight or more, particularly 50% by weight or more, and even more preferably 60% by weight or more, relative to the total amount of the compound. The upper limit of the biomass material content is 90% by weight or less, more preferably 80% by weight or less, relative to the total amount of the compound. As the biomass content increases, the rank according to biomass certification standards rises, and the original purpose of reducing the amount of thermoplastic resin used from fossil fuels or reducing carbon dioxide emissions during combustion is diminished. On the other hand, as the biomass content increases, the moldability of biomass-containing resin molded products deteriorates, and the balance of strength and other properties of products using the compound is easily disrupted, so adjustments are necessary as appropriate depending on the application. Biomass-containing resin molded articles are obtained by mixing biomass material and resin material. The resin material is present in an amount of 90% by weight or less, preferably 80% by weight or less, more preferably 60% by weight or less, particularly 50% by weight or less, and even more preferably 40% by weight or less, relative to the total amount of the compound. It contains 10% by weight or more, preferably 20% by weight or more. In the resin material for biomass-containing resin molded articles of the present invention, when a mixture of metallocene-based ethylene plastomer (A) and propylene-based resin (B) is used, the mixing ratio of metallocene-based ethylene plastomer (A) and propylene-based resin (B) is 90 to 30 parts by weight of metallocene-based ethylene plastomer, preferably 85 to 40 parts by weight, more preferably 80 to 55 parts by weight, and 10 to 70 parts by weight of propylene-based resin, preferably 15 to 60 parts by weight, more preferably 20 to 40 parts by weight. Mixing these materials improves dirt impact strength and other properties. The amount of compatibilizer added is 0 to 30 parts by weight, preferably 0 to 20 parts by weight, and more preferably 0.2 to 10 parts by weight, per 100 parts by weight of the total amount of resin material.

[0053] 2. Biomass-containing resin molded body The biomass-containing resin molded article of the present invention is obtained by mixing the above-mentioned biomass material (P), metallocene-based ethylene plastomer (A), other resins as needed, and, as needed, a compatibilizer (D) and other additives in the above-mentioned proportions using a Henschel mixer, V-blender, ribbon blender, tumbler blender, etc., and then kneading with a kneader such as a single-screw extruder, multi-screw extruder, kneader, or Banbury mixer.

[0054] Furthermore, the combustion heat of the biomass-containing resin molded article of the present invention is preferably less than 9,000 kcal / kg, more preferably less than 8,700 kcal / kg. A combustion heat of less than 9,000 kcal / kg is preferable because it can better prevent deterioration of the waste incinerator.

[0055] The biomass-containing resin molded article of the present invention can be molded into biomass plastic articles such as films and containers by known methods. Examples of methods for molding include inflation molding, T-die molding, hollow molding, and injection molding. In particular, films obtained using biomass-containing resin molded products can be used for garbage bags, shopping bags, fertilizer bags, and the like. [Examples]

[0056] The following describes specific examples of the present invention, but the present invention is not limited to these examples. The physical property measurement methods and raw materials used in each example and comparative example are as follows.

[0057] 1. Methods for measuring the physical properties of resins (1) Melt flow rate (MFR): In accordance with JIS K-7210, temperature 190°C, load Measurements were taken under a pressure of 21.18 N. For polypropylene resins, the measurement temperature was set to 2 It was done at 30℃. (2) Density: Measured in accordance with JIS K-7112. (3) Melting point: Measured using a differential scanning calorimeter.

[0058] 2.Materials used <Biomass raw materials> Biomass raw material-1: We used biomass raw materials derived from food waste that were dried and pulverized. Biomass raw material - 2: Uses biomass raw materials derived from wood. <Polyethylene resin> PE-1 Harmolex, manufactured by Japan Polyethylene Co., Ltd. TM NC566A (density 0.918g / cm 3 (MFR 3.8g / 10 mins) PE-2 Harmolex, manufactured by Japan Polyethylene Co., Ltd. TM NW564N PE-3 Harmolex, manufactured by Japan Polyethylene Co., Ltd. TM NF464A (density 0.918g / cm 3 (MFR 2.0g / 10 mins) PE-4 Kernel manufactured by Japan Polyethylene Co., Ltd. TM KF270 (density 0.907g / cm 3 (MFR 2.0g / 10 mins) <Polyethylene-based compatibilizer> Compatibility agent-1: Rexpearl, manufactured by Nippon Polyethylene Co., Ltd. TM ET ET720X Compatibility Agent-2: Rexpearl, manufactured by Japan Polyethylene Co., Ltd. TM ET ET530H Compatibilizer-3, manufactured by Nippon Polyethylene Co., Ltd., graft polymerization type A Compatibilizer-1 and compatibilizer-2 are (b) terpolymers such as ethylene-maleic anhydride-ethyl acrylate copolymer, and compatibilizer-3 is (a) a graft polymerization type modified ethylene copolymer modified with an unsaturated carboxylic acid and / or its anhydride.

[0059] 3. Manufacturing method <Masterbatch> Biomass raw materials and PE-1 or PE-2 were mixed in a twin-screw blender, and a masterbatch was granulated. <Film molding> The granulated masterbatch, PE-3 or PE-4, and a compatibilizer were dry-blended, and a film was formed under the following conditions. Molding machine: Inflation molding machine (extruder 50mmφ, die 75mmφ) Molding temperature: 170℃ Blow ratio: 2.0

[0060] 4. Evaluation Method <Film Evaluation Method> (1) Nominal strain at tensile failure The measurements were taken using the following equipment and conditions, referencing JIS K7127. MD represents the flow direction (Machine Direction), and TD represents the value in the transverse direction (Transverse Direction). Equipment: Tensilon Universal Tester, Model RTC-1210A (manufactured by Orientec Co., Ltd.) Test speed: 500 mm / min Measurement environment: temperature 23℃, humidity 50% (2) Elmendorf tear strength Measurements were taken using the following equipment and conditions, referencing JIS K7128-2. Equipment: Digital Elmendorf tear tester, model SA (manufactured by Toyo Seiki Seisakusho Co., Ltd.) Measurement environment: temperature 23℃, humidity 50% (3) Film Impact Measurements were taken using the following equipment and under the following conditions. Equipment: Film impact tester (manufactured by Toyo Seiki Seisakusho Co., Ltd.) Impact sphere: In Examples 1, 2, 3 and Comparative Example 1, a 1-inch (aluminum) impact sphere was used; in Examples 4, 5, 6 and Comparative Example 2, a 1 / 2-inch (brass) impact sphere was used. Measurement environment: temperature 23℃, humidity 50% (4) Dirt Drop Impact Measurements were taken using the following equipment and conditions, referencing JIS K7124. Equipment: Dirt Impact Tester, Type A (dedicated type), Model IM-302 (manufactured by Tester Sangyo Co., Ltd.) Measurement method: Method A Measurement environment: temperature 23℃, humidity 50%

[0061] 5. Examples, Comparative Examples and Results The compositions and results of embodiments and comparative examples of the present invention are described below.

[0062] [Table 1]

[0063] [Table 2] [Industrial applicability]

[0064] The biomass-containing resin molded articles of the present invention, which incorporate biomass materials, enable the effective utilization of biomass materials and, due to the reduced content of petroleum-derived components, have great potential for future use from an environmental perspective. Furthermore, the biomass-containing resin molded articles obtained by filling them with a high concentration of biomass materials together with specific resin materials are compounds that have improved strength and other properties, which were concerns in conventional proposals. Therefore, they can be effectively used for applications such as garbage bags and shopping bags that meet biomass standards and contain heavy items.

Claims

1. An environmentally friendly resin composition for biomass-containing resin molded articles, characterized by containing at least a biomass material, a polyethylene resin, and a polyethylene-based compatibilizer.

2. The environmentally friendly resin composition for biomass-containing resin molded articles according to claim 1, wherein the polyethylene-based compatibilizer is a compatibilizer selected from (a) a modified ethylene copolymer modified with an unsaturated carboxylic acid and / or its anhydride and / or (b) a polar group-containing ethylene copolymer having a polar group-containing comonomer having an unsaturated carboxylic acid and / or its anhydride.

3. The environmentally friendly resin composition for biomass-containing resin molded articles according to claim 1, characterized in that the polyethylene resin contained in the resin composition for biomass-containing resin molded articles comprises at least two types, including a first polyethylene resin and a second polyethylene resin.

4. A masterbatch composition for use in an environmentally friendly biomass-containing resin molded article, characterized by being obtained by kneading at least a biomass material with a first polyethylene resin.

5. The masterbatch composition according to claim 4, characterized in that the first polyethylene resin contained in the masterbatch composition is a polyethylene-based resin with an MFR of 3.0 g / 10 min or more.

6. A method for producing an environmentally friendly biomass-containing resin molded article, comprising at least a biomass material and a polyethylene resin, A method for producing a biomass-containing resin molded article, characterized by molding it using a resin composition obtained by mixing a masterbatch material obtained by kneading a biomass material and a first polyethylene resin, a polyethylene compatibilizer, and a second polyethylene resin.

7. A method for producing a biomass-containing resin molded article according to claim 6, characterized in that the first polyethylene resin contained in the masterbatch composition is a polyethylene-based resin with an MFR of 3.0 g / 10 min or more.

8. A biomass-containing resin film obtained using a resin composition for biomass-containing resin molded articles according to any one of claims 1 to 3, characterized in that the molded article is a film.

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