Resin compositions, molded articles, laminates, and laminated tubes

Abstract

The present invention provides a resin composition containing a polyolefin that includes biomass-derived ethylene, and which exhibits excellent heat seal strength and moldability in the resulting molded article. [Solution] A biomass-derived polyolefin (A) obtained by polymerizing monomer components mainly consisting of biomass-derived ethylene (x): 40-90% by mass, with a density of 0.90-0.93 g / cm³ 3 It contains linear low-density polyethylene (B): 25-50% by mass and modified polyolefin (C): 1-10% by mass, and the biomass content of the above polyolefin (A) is P bio The biomass content of the resin composition is 90% or more. bio A resin composition in which 50% or more of the above is present. P bio (%) = pMC / 105.5 × 100 (wherein pMC is radioactive carbon in polyolefin (A) or resin composition as determined in accordance with ASTM D6866) 14 (This indicates the C content.)

Description

Technical Field

[0001] The present disclosure relates to a resin composition, a molded body, a laminate, and a laminated tube.

Background Art

[0002] In recent years, due to the growing awareness of preventing global warming and reducing the use of petroleum, which is a depleting resource, replacement of conventional plastic materials derived from fossil fuels with carbon-neutral plant-derived plastic materials has been desired, and the utilization of biomass has attracted attention.

[0003] Biomass is an organic compound synthesized from carbon dioxide and water through photosynthesis, and is a so-called carbon-neutral renewable energy that can be converted back into carbon dioxide and water by utilizing it. Recently, the practical application of biomass plastics using such biomass as a raw material has been rapidly progressing, and attempts have also been made to produce various resins from biomass raw materials.

[0004] As resins derived from biomass, in 2011, Braskem began the production and sale of high-pressure low-density polyethylene (LDPE), linear low-density polyethylene (LLDPE), and high-density polyethylene (HDPE). Replacement from conventional fossil fuel-derived polyethylene using such biomass-derived LDPE, LLDPE, and HDPE has been studied (see, for example, Patent Documents 1 and 2).

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0006] According to the latest studies, resin compositions containing polyolefins (e.g., biomass-derived LDPE, LLDPE, HDPE, etc.) using biomass-derived ethylene tend to have lower heat seal strength than resin compositions containing polyolefins using conventional fossil fuel-derived ethylene. In order to improve the heat seal strength of resin compositions containing polyolefins using biomass-derived ethylene, increasing the blending amount of LLDPE, which is widely used as a material for improving heat seal strength, has been considered. However, if the blending amount of LLDPE is increased too much, the moldability tends to decrease. Therefore, the realization of a resin composition that contains polyolefins using biomass-derived ethylene and is excellent in both heat seal strength and moldability is awaited.

[0007] The problem to be solved by one embodiment of the present disclosure is to provide a resin composition that contains polyolefins containing biomass-derived ethylene and is excellent in both the heat seal strength and moldability of the resulting molded body. Another problem to be solved by one embodiment of the present disclosure is to provide a molded body, a laminate, and a laminated tube that contain polyolefins containing biomass-derived ethylene and are excellent in both heat seal strength and moldability.

Means for Solving the Problems

[0008] The means for solving the above problems include the following aspects. <1> Biomass-derived polyolefin (A) obtained by polymerizing a monomer component mainly composed of biomass-derived ethylene (x): 40 to 90% by mass, Linear low-density polyethylene (B) having a density of 0.90 to 0.93 g / cm 3 : 25 to 50% by mass, Modified polyolefin (C): 1 to 10% by mass (where the total of the above (A), (B), and (C) is 100% by mass), The biomass degree P of the polyolefin (A) calculated by the following method bio is 90% or more, The biomass degree P of the resin composition calculated by the following method bio is 50% or more, the resin composition; [Biomass degree P bio : Based on ASTM D6866, the radiocarbon 14 C content pMC in the polyolefin (A) or the resin composition is determined, and the obtained pMC is substituted into the following formula for determination. P bio (%) = pMC / 105.5 × 100] <2> The linear low-density polyethylene (B) has a biomass degree P bio calculated by the following method and is 80% or more, and the resin composition according to <1> containing biomass-derived linear low-density polyethylene; [Biomass degree P bio : Based on ASTM D6866, the radiocarbon 14 C content pMC in the linear low-density polyethylene (B) is determined, and the obtained pMC is substituted into the following formula for determination. P bio (%) = pMC / 105.5 × 100] <3> The content of the polyolefin (A) is 50 to 75% by mass, the content of the linear low-density polyethylene (B) is 25 to 45% by mass, the content of the modified polyolefin (C) is 3 to 7% by mass (however, the total of (A), (B) and (C) is 100% by mass), the resin composition according to <1> or <2>. <4> The density of the polyolefin (A) is 0.91 to 0.96 g / cm 3 and the resin composition according to any one of <1> to <3>. <5> A molded article containing the resin composition according to any one of <1> to <4>. <6> The molded article according to <5>, wherein the molded article is a tube. <7> A laminate comprising a layer containing the resin composition according to any one of <1> to <4>. <8> A laminated tube containing the laminate according to <7>.

Advantages of the Invention

[0009] According to one embodiment of the present disclosure, a resin composition comprising a polyolefin containing biomass-derived ethylene is provided, which exhibits excellent heat seal strength and moldability, and its applications. According to one embodiment of the present disclosure, a molded article, a laminate, and a laminated tube comprising a polyolefin containing biomass-derived ethylene are provided, which exhibit excellent heat seal strength and moldability. [Modes for carrying out the invention]

[0010] In this disclosure, unless otherwise specified, the expressions "XX or greater and YY or less" and "XX to YY" that represent a numerical range mean a numerical range that includes the lower and upper limits. Furthermore, when numerical ranges are listed in steps, the upper and lower limits of each numerical range can be combined in any way. Furthermore, the phrase "A and / or B" is a concept that includes cases A, cases B, and cases both A and B. In this specification, the "~" symbol indicating a numerical range means that the units listed before or after it refer to the same unit unless otherwise specified. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In this disclosure, density is a value measured according to a method compliant with ASTM D1505. The details of this disclosure are described below.

[0011] (Resin composition) The resin composition relating to this disclosure comprises a biomass-derived polyolefin (A) obtained by polymerizing a monomer mainly composed of biomass-derived ethylene (x): 40-90% by mass, and a density of 0.90-0.93 g / cm³. 3 The biomass P of the polyolefin (A) is calculated by the following method and comprises linear low-density polyethylene (B): 25-50% by mass and modified polyolefin (C): 1-10% by mass (provided that the sum of (A), (B), and (C) is 100% by mass).bio The biomass content of the resin composition is 90% or more, and is calculated using the following formula: bio However, the percentage is over 50%. Biomass content P bio : Radioactive carbon in the polyolefin (A) or the resin composition in accordance with ASTM D6866 14 The C content pMC is determined, and the result is calculated by substituting the obtained pMC into the following formula. P bio (%) = pMC / 105.5 × 100 The resin composition according to this disclosure, having the above configuration, exhibits high melt tension, which facilitates the stabilization of the molten resin during molding and results in excellent moldability. Furthermore, it increases the resin strength, resulting in excellent heat seal strength for the resulting molded article.

[0012] From the viewpoint of obtaining a molded article that is excellent in both heat seal strength and moldability, the biomass content P of the resin composition according to this disclosure is calculated by the following formula. bio The biomass content of the resin composition is 50% or more, preferably 55% or more, more preferably 60% or more, and even more preferably 70% or more. bio There is no particular upper limit to the value, but it is preferably 100% or less, and more preferably 98% or less.

[0013] The above "Biomass Degree P" bio (Biomass-derived carbon concentration) is radiocarbon (in accordance with ASTM D6866) 14 C) Obtained by the measurement method 14 This is the value of the C content. Carbon dioxide in the atmosphere 14 Because it contains a certain percentage (105.5 pMC) of carbon, plants that take in carbon dioxide from the atmosphere to grow, such as corn, 14 It is also known that the carbon content is around 105.5 pMC. 14 It is also known that it contains almost no carbon (C).

[0014] Therefore, of the total carbon atoms contained in polyolefin (A) or resin composition14 By measuring the proportion of C, the proportion of carbon derived from biomass can be calculated. In this disclosure, biomass degree P bio (i.e., the content of biomass-derived carbon) is defined in accordance with ASTM D6866 as radioactive carbon in polyolefin (A) or resin compositions. 14 The C content pMC is determined, and the result can be calculated by substituting the obtained pMC into the following formula. pMC stands for Percent Modern Carbon. P bio (%) = pMC / 105.5 × 100

[0015] Biomass content P of the resin composition relating to this disclosure bio This can be adjusted by the content of biomass-derived monomer components (for example, biomass-derived ethylene(x) described later) in the resin composition. The following describes in detail each component included in the resin composition relating to this disclosure.

[0016] <Biomass-derived polyolefin (A)> Biomass-derived polyolefin (A) (hereinafter also simply referred to as "polyolefin (A)") is a polyolefin obtained by polymerizing monomer components mainly consisting of biomass-derived ethylene (x) (hereinafter also simply referred to as "ethylene (x)"). The polyolefin (A) described above may be a homopolymer of ethylene (x), or a copolymer of ethylene (x) and other monomers other than ethylene (x). Furthermore, the polyolefin (A) may be biodegradable.

[0017] "Mainly composed of biomass-derived ethylene(x)" means that among the monomer components that are raw materials for polyolefin (A), the component that accounts for the largest proportion (mass%) is biomass-derived ethylene(x). Preferably, the content of structural units derived from biomass-derived ethylene(x) exceeds 50% by mass, more preferably 52% by mass or more, and even more preferably 55% by mass or more, relative to the total structural units of polyolefin (A). Furthermore, there is no particular upper limit to the content, but it can be, for example, 100% by mass or less. Moreover, biomass-derived polyolefin (A) only needs to contain at least a portion of biomass-derived raw materials (for example, the aforementioned ethylene(x)) as raw materials, and not all of the raw materials need to be biomass-derived.

[0018] Preferably, the ethylene(x) is ethylene produced from ethanol extracted and purified from plants such as corn or sugarcane. Since the resin composition according to this disclosure uses such biomass-derived ethylene(x) as a raw material monomer, the polyolefin obtained by polymerizing ethylene(x) is "biomass-derived". Furthermore, it is more preferable that the ethylene component contained in the polyolefin (A) consists of biomass-derived ethylene(x) from the viewpoint of maintaining a high level of biomass content (biomass-derived carbon concentration).

[0019] Other monomers besides ethylene(x) include α-olefins derived from fossil fuels and α-olefins other than ethylene derived from biomass. These other monomers may be used individually or in combination of two or more. Examples of α-olefins derived from fossil fuels and biomass (excluding ethylene derived from biomass) include α-olefins with 3 to 20 carbon atoms, such as butene, hexene, and octene. The polyolefin (A) is preferably a copolymer of biomass-derived ethylene (x) and fossil fuel-derived α-olefin.

[0020] Polyolefins (A), in addition to those mentioned above, also include olefins produced by the biomass balance approach, which involves using plant and animal waste oils as bionaphtha, mixing it with petroleum-derived naphtha, and cracking the mixture to obtain olefins. Examples of olefins produced by the biomass balance approach include biomass-derived ethylene (x) and α-olefins such as propylene.

[0021] From the viewpoint of excellent moldability of the resulting molded article, polyolefin (A) is preferably a homopolymer of ethylene (x), and more preferably a low-density polyethylene derived from biomass.

[0022] From the viewpoint of the moldability of the resulting molded article, the content of structural units derived from biomass-derived ethylene(x) is 50% to 100% by mass relative to the total mass (100% by mass) of the resin composition, preferably 60% to 99% by mass, and more preferably 70% to 98% by mass.

[0023] Polyolefin (A) may be obtained by synthesis or as a commercially available product. For example, polyolefin (A) can be obtained by homopolymerization of ethylene by high-pressure method, or by copolymerization of ethylene with α-olefin comonomers such as butene, hexene, and octene using a solid catalyst or metallocene catalyst. Alternatively, commercially available polyolefin (A), such as plant-derived polyethylene from Braschem, can be used.

[0024] The resin composition may contain two or more biomass-derived polyolefins (A) with different compositions. When two or more polyolefins (A) are included, "density of polyolefin (A)" refers to a value calculated using a weighted average, and "MFR of polyolefin (A)" refers to a value calculated using the logarithmic addition rule.

[0025] <<density>> The density of polyolefin (A) is not particularly limited, but is preferably 0.91 to 0.96 g / cm³. 3 More preferably 0.91 g / cm³3 ~0.93g / cm 3 That is the case. The density of polyolefin (A) is a value measured according to the method compliant with ASTM D1505. The density of polyolefin (A) is 0.91 g / cm³. 3 In the above case, there is the advantage of superior antiblocking properties. Also, the density of polyolefin (A) is 0.96 g / cm³. 3 In the following cases, it has the advantage of superior impact resistance.

[0026] The melt flow rate (MFR) of polyolefin (A) is not particularly limited, but is preferably 0.1 g / 10 min to 10 g / 10 min, and more preferably 0.3 g / 10 min to 8 g / 10 min. In this disclosure, the MFR of polyolefin (A) is a value measured under conditions of 190°C and a 2.16 kg load in accordance with ASTM D1238. When the MFR of polyolefin (A) is 0.1 g / 10 min or higher, there is the advantage that the resin generates less heat during film formation. Furthermore, when the MFR of polyolefin (A) is 10 g / 10 min or lower, the resulting molded article exhibits excellent heat seal strength and moldability.

[0027] From the viewpoint of improving the biomass content, the polyolefin (A) content is 40 to 90% by mass, preferably 50 to 85% by mass, more preferably 55 to 80% by mass, and even more preferably 50 to 75% by mass (provided that the total of (A), (B), and (C) is 100% by mass). Polyolefin (A) may be used alone or in combination of two or more types.

[0028] The polymerization method for polyolefin (A) is not particularly limited and can be carried out by conventionally known methods. The polymerization temperature and polymerization pressure are preferably adjusted as appropriate depending on the polymerization method and polymerization apparatus. The polymerization apparatus is also not particularly limited and can be conventionally known apparatus.

[0029] <Linear low-density polyethylene (B)> The resin composition relating to this disclosure has a density of 0.90 to 0.93 g / cm³. 3 The resin composition contains linear low-density polyethylene (B) (hereinafter also simply referred to as "linear low-density polyethylene (B)"). The inclusion of the above-mentioned specific linear low-density polyethylene (B) in the resin composition improves the heat seal strength. Linear low-density polyethylene (B) may be a copolymer containing ethylene and propylene and small amounts of α-olefins having 3 to 20 carbon atoms, such as 1-butene, 1-hexene, and 1-octene.

[0030] The density of linear low-density polyethylene (B) is 0.90–0.93 g / cm³. 3 The concentration is preferably 0.905 g / cm³. 3 ~0.925g / cm 3 The density is measured according to the method compliant with ASTM D1505.

[0031] Linear low-density polyethylene (B) may be derived from biomass or fossil fuels. The biomass content P of linear low-density polyethylene (B) is calculated by the following method. bio Preferably, it contains linear low-density polyethylene derived from biomass, with a biomass content of 80% or more. bio It is more preferable to include biomass-derived linear low-density polyethylene in which P is 85% or more. bio This refers to the biomass content P in the above polyolefin (A). bio It is synonymous with [the above]. Biomass content P in the above linear low-density polyethylene (B) bio This refers to the radioactive carbon in the above linear low-density polyethylene (B) in accordance with ASTM D6866. 14 The C content pMC is determined, and the result can be calculated by substituting the obtained pMC into the following formula. P bio (%) = pMC / 105.5 × 100 Linear low-density polyethylene (B) is the biomass of P bioWhen containing biomass-derived linear low-density polyethylene (B) which is 80% or more (preferably 85% or more), the content of biomass-derived linear low-density polyethylene in linear low-density polyethylene (B) is preferably more than 50% by mass and 100% by mass or less, more preferably 80-100% by mass, and even more preferably 95-100% by mass.

[0032] The melt flow rate (MFR) of linear low-density polyethylene (B), measured under conditions of 190°C and a 2.16 kg load in accordance with ASTM D1238, is preferably 0.1 to 5 g / 10 min, and more preferably 0.2 to 3 g / 10 min.

[0033] The content of linear low-density polyethylene (B) is 25 to 50% by mass, preferably 25 to 45% by mass, more preferably 30 to 45% by mass, and even more preferably 30 to 40% by mass (provided that the total of (A), (B), and (C) is 100% by mass). Linear low-density polyethylene (B) may be used alone or in combination of two or more types. Linear low-density polyethylene (B) can be produced by any conventionally known method, for example, by a high-pressure method or a low-pressure method using a titanium-based catalyst, a vanadium-based catalyst, a metallocene catalyst, etc. Furthermore, commercially available resins can also be used directly to produce linear low-density polyethylene (B).

[0034] <Modified polyolefin (C)> The resin composition relating to this disclosure includes modified polyolefin (C). Modified polyolefin (C) is a modified polyolefin obtained by modifying at least a portion of an unmodified polyolefin, and is preferably a modified polyolefin obtained by graft modification with at least one compound (y) selected from the group consisting of unsaturated carboxylic acids and their derivatives.

[0035] <<Unmodified Polyolefin>> The above-mentioned unmodified polyolefin is not particularly limited as long as it is a polyolefin obtained by polymerizing monomer components containing olefins derived from fossil fuels, but preferably it is an ethylene homopolymer and a copolymer of ethylene and an α-olefin having 3 to 20 carbon atoms, more preferably an ethylene homopolymer and a copolymer of ethylene and an α-olefin having 3 to 10 carbon atoms, and even more preferably an ethylene homopolymer and a copolymer of ethylene and an α-olefin having 2 to 8 carbon atoms. The unmodified polyolefin may be used alone or in combination of two or more types.

[0036] Examples of the above-mentioned α-olefins having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, 1-decene, and 4-methyl-1-pentene, and these may be used individually or in combination of two or more.

[0037] The density of the unmodified polyolefin is preferably 0.860 to 0.960 g / cm³. 3 , more preferably 0.865~0.955 g / cm³ 3 More preferably 0.870 to 0.950 g / cm³ 3 That is the case. Furthermore, the melt flow rate (MFR) of unmodified polyolefins, measured under ASTM D1238 conditions of 190°C and a 2.16 kg load, is preferably 0.01 to 100 g / 10 min, more preferably 0.05 to 50 g / 10 min, and even more preferably 0.1 to 10 g / 10 min. If the density and MFR of unmodified polyolefins are within this range, the density and MFR of modified polyolefins (C) will be similar, making them easier to handle.

[0038] There are no particular restrictions on the method for producing unmodified polyolefins; they can be produced by any conventionally known method, such as a high-pressure method or a low-pressure method using a titanium-based catalyst, a vanadium-based catalyst, or a metallocene catalyst. Furthermore, the unmodified polyolefin may be in the form of either a resin or an elastomer, and both isotactic and syndiotactic structures can be used. There are also no particular restrictions on stereoregularity. Unmodified polyolefins can also be used as commercially available resins.

[0039] <<Compound(y)>> Examples of at least one compound (y) selected from the group consisting of unsaturated carboxylic acids and their derivatives for use in graft modification of unmodified polyolefins include unsaturated compounds having one or more carboxyl groups, and unsaturated compounds having one or more anhydrous carboxyl groups and their derivatives. Examples of unsaturated groups in the above-mentioned unsaturated compounds include vinyl groups, vinylene groups, and unsaturated cyclic hydrocarbon groups. Specific examples of such unsaturated compounds include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornenedicarboxylic acid, and bicyclo[2,2,1]hepto-2-ene-5,6-dicarboxylic acid, or their acid anhydrides or derivatives thereof (e.g., acid halides, amides, imides, esters, etc.).

[0040] Specific examples of compound (y) include malenyl chloride, maleylimide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citraconate, dimethyl tetrahydrophthalate, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid dimethyl, hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, glycidyl (meth)acrylate, aminoethyl methacrylate, and aminopropyl methacrylate. Furthermore, compound (y) can be used alone or in combination of two or more types. Among these, preferred compound (y) is maleic anhydride, (meth)acrylic acid, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride, hydroxyethyl (meth)acrylate, glycidyl methacrylate, and aminopropyl methacrylate. Dicarboxylic acid anhydrides such as maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, and bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride are more preferred, and maleic anhydride is particularly preferred.

[0041] As a method for introducing compound (y) into an unmodified polyolefin, well-known methods can be employed. For example, methods such as graft copolymerization of compound (y) into the main chain of an unmodified polyolefin, or radical copolymerization of the olefin and compound (y), can be cited.

[0042] When obtaining a modified polyolefin (C) by graft copolymerization, it is preferable to graft copolymerize the unmodified polyolefin that will form the graft main chain with the above compound (y), and optionally other ethylenically unsaturated monomers, in the presence of a radical initiator.

[0043] The method for grafting compound (y) onto the main chain of the unmodified polyolefin is not particularly limited, and conventionally known graft polymerization methods such as solution methods and melt kneading methods can be employed. For example, one method involves dissolving the unmodified polyolefin in an organic solvent, then adding compound (y) and, if necessary, a radical initiator such as an organic peroxide to the resulting solution, and reacting it at a temperature of typically 60 to 350°C, preferably 80 to 190°C, for 0.5 to 15 hours, preferably 1 to 10 hours. Alternatively, one method involves using an extruder or the like to add the unmodified polyolefin, compound (y), and, if necessary, a radical initiator such as an organic peroxide, in a solvent-free environment, and reacting it at a temperature typically above the melting point of the unmodified polyolefin, preferably 120 to 350°C, for 0.5 to 10 minutes.

[0044] <<Properties of Modified Polyolefin (C)>> The content (graft amount) of structural units derived from compound (y) in the modified polyolefin (C) is, for example, when compound (y) is at least one compound selected from the group consisting of maleic anhydride and its derivatives, preferably 0.01% to 5.0% by mass, more preferably 0.05% to 4.0% by mass, and even more preferably 0.1% to 3.0% by mass, in terms of structural units derived from maleic anhydride. The same applies when compound (y) is another compound. If the amount of graft exceeds the above range, it becomes uneconomical, while if the amount of graft in modified polyolefin (C) is less than the above range, the adhesive strength tends to be low.

[0045] In modified polyolefin (C), the content ratio of ethylene-derived structural units in all structural units excluding those derived from compound (y) is preferably 80 mol% to 100 mol%, more preferably 85 mol% to 100 mol%, and even more preferably 95 mol% to 100 mol%. When the content ratio of ethylene-derived structural units is within the above range, it is superior from the viewpoint of moldability.

[0046] According to ASTM D1238 for modified polyolefin (C), the melt flow rate (MFR) measured under conditions of 190°C and a load of 2.16 kg is preferably 0.01 g / 10 min to 500 g / 10 min, and more preferably 0.05 g / 10 min to 100 g / 10 min. When the MFR of modified polyolefin (C) falls within the above range, it exhibits good moldability and excellent adhesive strength. In a method of measuring adhesive strength by hot press molding, for example, by sandwiching a 100 μm thick adhesive layer between substrates and performing a peel test, there is a tendency for higher adhesive strength at lower MFRs and with longer molecular chains.

[0047] The density of the modified polyolefin (C) is preferably 0.90 to 0.99 g / cm³. 3 More preferably 0.95 to 0.98 g / cm³ 3 That is the case.

[0048] The content of modified polyolefin (C) is 1 to 10% by mass, preferably 2 to 8% by mass, and more preferably 3 to 7% by mass (provided that the total of (A), (B), and (C) is 100% by mass).

[0049] [Other ingredients] The resin compositions relating to this disclosure may further contain components other than polyolefin (A), linear low-density polyethylene (B), and modified polyolefin (C) (hereinafter also referred to as "other components"), to the extent that they do not impair the purpose of this disclosure. Other components may include additives such as commonly used antioxidants, weather stabilizers, antistatic agents, antifogging agents, antiblocking agents, lubricants, nucleating agents, and pigments, or other polymers or rubbers other than polyolefin (A), linear low-density polyethylene (B), and modified polyolefin (C), as needed.

[0050] [Composition of the resin composition] From the viewpoint of making it easy to prepare a resin composition having a high biomass content and having excellent heat seal strength and moldability of the resulting molded article, the resin composition according to this disclosure preferably has a polyolefin (A) content of 50 to 85% by mass (more preferably 55 to 80% by mass, and even more preferably 50 to 75% by mass), a linear low-density polyethylene (B) content of 25 to 45% by mass (more preferably 30 to 45% by mass, and even more preferably 30 to 40% by mass), and a modified polyolefin (C) content of 2 to 8% by mass (more preferably 3 to 7% by mass).

[0051] From the viewpoint of facilitating the preparation of a resin composition having a high biomass content and providing excellent heat seal strength and moldability of the resulting molded article, it is preferable that the resin composition according to this disclosure has a content of 50 to 75% by mass of polyolefin (A), a content of 25 to 45% by mass of linear low-density polyethylene (B), and a content of 3 to 7% by mass of modified polyolefin (C), when the total of the above components (A), (B), and (C) is 100% by mass.

[0052] There are no particular limitations on the method for producing the resin composition according to this disclosure, and various known methods can be used. For example, the resin composition can be prepared by dry blending the above components (A), (B), and (C) and other components as needed using a Henschel mixer, tumbler blender, V-blender, etc., by melt-kneading after dry blending using a single-screw extruder, multi-screw extruder, Banbury mixer, etc., and by stirring and mixing in the presence of a solvent.

[0053] <Molded body> The molded article relating to this disclosure includes the resin composition relating to this disclosure described above. The molded article is not particularly limited and examples include extruded articles and injection molded articles. The method for manufacturing the molded article is not particularly limited; for example, conventionally known manufacturing methods can be used, such as extrusion molding, compression molding, injection molding, 3D printing, and microwave heat molding. Among these molding methods, extrusion molding is preferred, as molded articles can be suitably manufactured by extrusion molding. There are no particular restrictions on the shape of the molded body; it can be made into any desired shape depending on the purpose. Examples include flat plates, films, tubes (cylindrical shapes), bottles, etc.

[0054] <Laminate> The laminate according to this disclosure comprises a layer containing the resin composition according to this disclosure (hereinafter also referred to as "adhesive layer (I)"). Since the laminate comprises a layer containing the resin composition, it has excellent heat seal strength and moldability. Furthermore, if the laminate includes a layer (II) described later, it also has excellent adhesion to layer (II). The laminate preferably further comprises the adhesive layer (I) and a layer (II) containing at least one polymer selected from the group consisting of polyamide, ethylene-vinyl acetate copolymer saponified (EVOH), and polyester, in which case it is preferable that the layer (II) and the adhesive layer (I) are laminated in contact with each other.

[0055] The polyamide included in layer (II) is not particularly limited and includes, for example, nylon 6, nylon 66, nylon 610, nylon 12, nylon 11, MXD nylon, amorphous nylon, copolymerized nylon, etc.

[0056] The ethylene-vinyl alcohol copolymer saponified product (EVOH) contained in layer (II) is preferably obtained by saponifying an ethylene-vinyl acetate copolymer having an ethylene content of preferably 15 to 60 mol%, more preferably 20 to 50 mol%. The degree of saponification of the ethylene-vinyl alcohol copolymer saponified product (EVOH) is preferably 90-100%, and more preferably 95-100%.

[0057] The polyester included in layer (II) is not particularly limited and includes, for example, polylactic acid, polyethylene terephthalate, polybutylene terephthalate, and polyethylene naphthenate, as well as mixtures of these resins or aromatic polyesters, such as liquid crystal polymers.

[0058] From the viewpoint of having excellent heat seal strength and moldability, layer (II) is preferably a layer (II) containing polyamide, ethylene vinyl acetate copolymer saponified (EVOH), or polyester, more preferably a layer (II) containing polyamide or ethylene vinyl acetate copolymer saponified (EVOH), and even more preferably a layer (II) containing ethylene vinyl acetate copolymer saponified (EVOH) (EVOH layer (II)).

[0059] From the viewpoint of having excellent heat seal strength, when the laminate comprises an adhesive layer (I) and an EVOH layer (II), the interlayer adhesive strength (peel strength) between the adhesive layer (I) and the EVOH layer (II) when peeled at a peeling speed of 300 mm / min is preferably 1 N / 15 mm or more and less than 5 N / 15 mm, and more preferably 5 N / 15 mm or more. The adhesive strength is determined by the measurement method described in the examples below.

[0060] From the viewpoint of having excellent heat seal strength and moldability, it is preferable that the laminate further comprises a base layer (III) made of polyethylene. When the laminate comprises a base layer (III) made of polyethylene, it is preferable that the adhesive layer (I) and the base layer (III) are laminated in contact with each other.

[0061] The polyethylene contained in the base layer (III) is not particularly limited, and any known polyethylene can be used.

[0062] Examples of the layer configurations of the laminate according to this disclosure include a two-layer structure of layer (II) / adhesive layer (I), a three-layer structure of layer (II) / adhesive layer (I) / layer (II), a three-layer structure of base material layer (III) / adhesive layer (I) / layer (II), a three-layer structure of adhesive layer (I) / layer (II) / adhesive layer (I), and a five-layer structure of base material layer (III) / adhesive layer (I) / layer (II) / adhesive layer (I) / base material layer (III). Among these, from the viewpoint of excellent barrier properties of the laminate, the laminate is preferably a three-layer structure of layer (II) / adhesive layer (I) / layer (II), a three-layer structure of base material layer (III) / adhesive layer (I) / layer (II), and a three-layer structure of adhesive layer (I) / layer (II) / adhesive layer (I), with the three-layer structure of base material layer (III) / adhesive layer (I) / layer (II) being more preferable.

[0063] From the viewpoint of having excellent heat seal strength and moldability, the thickness of the adhesive layer (I) is preferably 10 μm to 100 μm, more preferably 20 μm to 80 μm, and even more preferably 30 μm to 60 μm. From the viewpoint of having excellent heat seal strength and moldability, when the laminate has a three-layer structure, the thickness of the laminate is preferably 200 μm to 1000 μm, more preferably 200 μm to 850 μm, and even more preferably 200 μm to 500 μm. When the laminate has a five-layer structure, the thickness of the laminate is preferably 0.1 μm to 50 μm, and more preferably 1 μm to 20 μm.

[0064] Furthermore, the laminate relating to this disclosure may include other layers besides the adhesive layer (I), layer (II), and substrate layer (III) as long as they do not impair the effects of this disclosure. Other layers include, for example, layers made of metals such as aluminum, iron, copper, tin, and nickel, or layers made of alloys containing at least one of these metals as the main component, and regrind layers. The regrind layer is a layer made by crushing burrs (unnecessary parts) generated when forming the laminate, recovered laminate material (scrap), and defective products generated during molding, or, if necessary, by melting and kneading the crushed material in an extruder or the like (regrinding). Such other layers can also be used in place of the base layer (III) described above.

[0065] Each of the layers constituting the laminate relating to this disclosure may contain known additives such as fillers, stabilizers, lubricants, antistatic agents, flame retardants, and foaming agents, to the extent that they do not impair the purpose relating to this disclosure.

[0066] The method for manufacturing the laminate according to this disclosure is not particularly limited, and known methods such as co-extrusion molding, press molding, and extrusion lamination molding can be used. Among these, co-extrusion molding is preferred as the method for manufacturing the laminate in terms of interlayer adhesion. Examples of co-extrusion molding methods include the T-die method using a flat die and the inflation method using a circular die. The flat die may be either a single-manifold or multi-manifold type using a black box. There are no particular restrictions on the die used in the inflation method, and known dies can be used.

[0067] [Application] The resin compositions, molded articles containing the resin compositions (e.g., films, tubes, and bottles), laminates comprising layers containing the resin compositions, and laminated films, laminated tubes, and laminated bottles containing the laminates described herein can be suitably used in packaging products such as food containers and bags, cosmetic containers, sheets, and packaging products, and pharmaceutical containers, sheets, and packaging products. They can also be suitably used in various applications such as optical films, resin plates, various label materials, lid materials, and laminated tubes. From the viewpoint of having excellent heat-sealing properties, the above-mentioned laminate is preferably a laminated tube. [Examples]

[0068] The present disclosure will be described in more detail below based on examples, but the present disclosure is not limited to these examples.

[0069] [Methods for measuring physical properties] In the examples and comparative examples, the physical properties (density, melt flow rate, and melt tension) were measured by the following method.

[0070] <Density (g / cm 3 )> Density was measured in accordance with ASTM D1505.

[0071] <Melt Flow Rate (MFR) (g / 10 min)> The melt flow rate (MFR) was measured in accordance with ASTM D1238 at a temperature of 190°C and a load of 2160g.

[0072] [Materials used] The polyolefins used in the examples and comparative examples are listed below. Bio-LDPE-1, Bio-LDPE-2, and Bio-LLDPE-1 were commercially available products. LLDPE-1 and MAH-PE-1 were both prepared by polymerization according to conventional methods. Biomass content P bio This shows the value calculated using the formula described above.

[0073] <Biomass-derived polyolefin (A)> • BioLDPE-1: Low-density polyethylene derived from biomass (manufactured by Braskem SA, biomass degree P bio : 95% (according to ASTM D6866), Density: 0.92 g / cm³ 3 (MFR: 7.7g / 10 mins) • BioLDPE-2: Low-density polyethylene derived from biomass (manufactured by Braskem SA, biomass degree P) bio : 95% (according to ASTM D6866), Density: 0.92 g / cm³ 3 , MFR:0.3g / 10min)

[0074] <Linear low-density polyethylene (B)> • LLDPE-1: Linear low-density polyethylene derived from fossil fuels (density: 0.90 g / cm³) 3 MFR: 1.3g / 10 mins) · Bio LLDPE-1: Linear low-density polyethylene derived from biomass (manufactured by Braskem SA, biomass degree P bio : 87% (according to ASTM D6866), Density: 0.92 g / cm³ 3 (MFR: 0.9g / 10 mins)

[0075] <Modified polyolefin (C): Maleic anhydride-modified polyethylene> MAH-PE-1: Fossil fuel-derived maleic anhydride-modified high-density polyethylene, maleic anhydride graft amount: 2.4% by mass, density: 0.97 g / cm³ 3 (MFR: 5g / 10 minutes)

[0076] [Example 1] <Preparation of resin composition> A mixture of bio-LDPE-1 (40% by mass) and bio-LDPE-2 (25% by mass) as biomass-derived polyolefins (A), LLDPE-1 (30% by mass) as linear low-density polyethylene (LLDPE) (B), and MAH-PE-1 (5% by mass) as a modified polyolefin (C) was kneaded and granulated in a 65 mmφ single-screw extruder set to 220°C to obtain resin composition pellets. The resulting resin composition had a density of 0.92 g / cm³, as shown in Table 1. 3 The MFR was 2.0 g / 10 min, the melt tension was 26 mN, and the biomass content was P bio The figure was 65%.

[0077] <Manufacturing of laminates> A laminate (film) consisting of three layers, in which a PE (polyethylene) layer (III) formed from linear low-density polyethylene (LLDPE) (manufactured by Prime Polymer Co., Ltd., model number: Ultzex ​​2021L), an adhesive layer (I) formed from the resin composition obtained above, and an EVOH layer (II) formed from ethylene-vinyl alcohol copolymer (manufactured by Kuraray Co., Ltd., model number: EVAL F101A) are laminated in this order, was manufactured under the following molding conditions.

[0078] <<Forming conditions for laminated structures>> Layer structure: PE layer (III) / adhesive layer (I) / EVOH layer (II) Layer thickness: PE layer (III) 160 μm Adhesive layer (I) 40μm EVOH layer (II) 40μm T-die molding machine: PE layer (III) 40mmφ extruder, set temperature 220℃ Adhesive layer (I): 30mm diameter extruder, set temperature: 220℃ EVOH layer (II), 30mmφ extruder, set temperature: 220℃ Molding speed: 5m / min

[0079] <Adhesive strength (N / 15mm)> The adhesive strength of the laminate (3-layer film) obtained above was measured by cutting a 15 mm wide sample from the laminate and measuring the interlayer adhesive strength (peel strength) between the adhesive layer (I) and the EVOH layer (II) using a tensile testing machine (Intesco Corporation, model number: "IM-20ST") in a constant temperature chamber at 23°C. The peel test was performed using the T-peel method, with a peeling speed of 300 mm / min. This measurement was performed five times, and the average of the obtained values ​​was taken as the adhesive strength (EVOH adhesive strength) of the laminate. The adhesive strength was evaluated according to the following evaluation criteria. The results are shown in Table 1.

[0080] (Evaluation Criteria) A: The adhesive strength is 5N / 15mm or higher. B: The adhesive strength is 1 N / 15 mm or more, and less than 5 N / 15 mm. C: The adhesive strength is less than 1 N / 15 mm.

[0081] <Manufacturing of heat seal strength measurement samples> A single-layer film was prepared using the resin composition obtained above under the following molding conditions.

[0082] <<Conditions for forming single-layer films>> Layer thickness: 100 μm T-die molding machine: 30mm diameter extruder, set temperature 220℃ Molding speed: 5m / min

[0083] <Heat seal strength (N / 15mm)> Two single-layer films of the resin composition manufactured as described above were stacked and heat-sealed using a heat sealing machine (Tester Industries Co., Ltd., model number: TP-701-A·B) at 170°C, 0.2 MPa pressure, and for 3 seconds to prepare samples for heat seal strength measurement. Heat seal strength was measured by cutting a 15 mm wide sample from the heat seal strength measurement sample and measuring the interlayer adhesion strength (heat seal strength) between single-layer films of the resin composition using a tensile testing machine (Intesco Corporation, model number: "IM-20ST") in a constant temperature chamber at 23°C. The peeling speed was set to 300 mm / min. This measurement was performed five times, and the average of the obtained values ​​was taken as the heat seal strength (HS strength) of the resin composition and evaluated according to the following evaluation criteria. The results are shown in Table 1.

[0084] (Evaluation Criteria) A: The heat seal strength is 30N / 15mm or higher. B: The heat seal strength is 25N / 15mm or more, and less than 30N / 15mm. C: Heat seal strength is less than 25N / 15mm.

[0085] <Melting Tension (Moldability)> The melt tension was measured using a Capillograph 1D manufactured by Toyo Seiki Seisakusho Co., Ltd. Pellets of the above resin composition were placed in a cylinder with a diameter of 9.55 mm and a length of 350 mm, and melted at 230°C. The molten resin was extruded at 15 mm / min, and the filament exiting from a capillary with a nozzle diameter of 2.095 mm and a length of 8 mm, attached to the bottom of the cylinder, was wound at room temperature. The tension at a winding speed of 15 m / min was measured and defined as the melt tension (unit: mN), and evaluated according to the following evaluation criteria. A higher melt tension value indicates better moldability.

[0086] (Evaluation Criteria) A: The melt tension is 30 mN or more. B: The melt tension is 20 mN or more, and less than 30 mN. C: The melt tension is less than 20 mN.

[0087] [Examples 2 and 3, and Comparative Examples 1-3] A resin composition was prepared in the same manner as in Example 1, except that the formulation was changed as shown in Table 1, and its MFR, density, and melt tension were measured. Using the obtained resin composition, a laminate and a single-layer film were manufactured in the same manner as in Example 1, and the adhesive strength and heat seal strength of the obtained single-layer film were measured. The results are shown in Table 1.

[0088] [Table 1]

[0089] In Table 1, "-" indicates that the ingredient is not present.

[0090] As shown in Table 1, laminates comprising layers formed from the resin compositions of Examples 1 to 3 of this disclosure exhibit superior heat seal strength and moldability compared to molded articles formed from the resin compositions of Comparative Examples 1 to 3.

[0091] Both Example 1, which contains LLDPE derived from fossil fuels, and Example 3, which contains LLDPE derived from biomass, exhibit superior heat seal strength and moldability compared to Comparative Examples 1-3. Furthermore, Example 2, which contains 40% by mass of biomass-derived LLDPE, also shows superior heat seal strength and moldability compared to Comparative Examples 1-3. Additionally, Example 3, which contains 30% by mass of biomass-derived LLDPE, exhibits heat seal strength and moldability equivalent to or better than Example 1, which contains 30% by mass of fossil fuel-derived LLDPE.

Claims

[Claim 1] A biomass-derived polyolefin (A) obtained by polymerizing monomer components mainly consisting of biomass-derived ethylene (x): 40 to 90% by mass, Density of 0.90–0.93 g / cm³ ３ Linear low-density polyethylene (B): 25-50% by mass, Modified polyolefin (C): 1 to 10% by mass, and (provided that the sum of (A), (B), and (C) is 100% by mass), The biomass content P of the polyolefin (A) calculated by the method described below ｂｉｏ The percentage is over 90%, The biomass content P of the resin composition calculated by the method described below ｂｉｏ However, the resin composition is 50% or more; [Biomass degree P] ｂｉｏ : Radioactive carbon in the polyolefin (A) or the resin composition in accordance with ASTM D6866 １４ Determine the C content pMC, and then substitute the obtained pMC into the following formula to calculate the result. P ｂｉｏ (%)=pMC / 105.5×100]

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