Resin composition and molded body

Abstract

A resin composition comprising a block copolymer (A), a block copolymer (B), a plasticizer (C), and a biomass-derived polyolefin resin (D), wherein the block copolymer (A) comprises polymer blocks (a1) and (a2), wherein the polymer blocks (a1) contain structural units derived from aromatic vinyl compounds, and the polymer blocks (a2) contain structural units derived from farnesene; the block copolymer (B) comprises polymer blocks (b1) and (b2), wherein the polymer blocks (b1) contain structural units derived from aromatic vinyl compounds, and the polymer blocks (b2) contain at least 30 mol% of structural units derived from isoprene; the biomass content of the resin composition is at least 37 wt%; and a molded article formed using the above resin composition.

Description

Technical Field

[0001] The present invention relates to a resin composition having a biocompatibility of a certain value or higher and to a molded article made using the above-mentioned resin composition. Background Technology

[0002] Thermoplastic resins are lightweight and possess excellent formability. Some thermoplastic resins also exhibit superior strength and heat resistance, making them widely used in various packaging materials, household appliances, machinery parts, automotive components, and industrial parts. Furthermore, due to rising environmental awareness, there is an increasing expectation for using biomass-derived raw materials in these components.

[0003] Examples of biomass-derived raw materials include, for instance, biomass-derived β-farnesene. Techniques have been disclosed for imparting various physical properties to block copolymers having polymer blocks comprising structural units derived from β-farnesene and polymer blocks comprising structural units derived from aromatic vinyl compounds (Patent Documents 1-5).

[0004] Existing technical documents

[0005] Patent documents

[0006] Patent Document 1: International Publication No. 2018 / 232200

[0007] Patent Document 2: Japanese Patent Application Publication No. 2019-52225

[0008] Patent Document 3: International Publication No. 2020 / 102074

[0009] Patent Document 4: Japanese Patent Application Publication No. 2018-24778

[0010] Patent Document 5: Japanese Patent Application Publication No. 2019-11472 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] Furthermore, it is required that components made from thermoplastic resins maintain their physical properties even when used in harsh environments. For example, if the hardness increases at low temperatures, it may cause breakage of the molded article; therefore, it is desirable to have components that can maintain their physical properties even when exposed to low temperatures. In addition, sometimes the appearance design of the above-mentioned components is sought, requiring that the resin composition containing thermoplastic resin also possess moldability that can impart a good appearance design. However, Patent Documents 1 to 5 do not explore techniques for imparting these physical properties to resin compositions.

[0013] Furthermore, while using biomass-derived raw materials can reduce the environmental burden, it is not easy to maintain physical properties at low temperatures and obtain excellent formability at the same time.

[0014] Therefore, the objective of this invention is to provide a molded article that reduces environmental impact, provides a molded article whose physical properties are not easily reduced even at low temperatures, a resin composition with excellent formability, and a molded article made using the above-mentioned resin composition.

[0015] Solution for solving the problem

[0016] As a result of in-depth research in order to solve the above-mentioned problems, the inventors conceived of the following invention and found that it can solve the above-mentioned problems.

[0017] That is, the present invention is as follows.

[0018] [1] A resin composition comprising a block copolymer (A), a block copolymer (B), a plasticizer (C), and a biomass-derived polyolefin resin (D),

[0019] The block copolymer (A) comprises polymer blocks (a1) and (a2), wherein polymer block (a1) contains structural units derived from aromatic vinyl compounds, and polymer block (a2) contains structural units derived from farnesene.

[0020] The block copolymer (B) comprises polymer block (b1) and polymer block (b2), wherein polymer block (b1) contains structural units derived from aromatic vinyl compounds, and polymer block (b2) contains more than 30 mol% structural units derived from isoprene.

[0021] The bioavailability of the resin composition is ≥37% by mass.

[0022] [2] A molded body made using the resin composition described in [1] above.

[0023] Invention Effects

[0024] According to the present invention, it is possible to provide molded articles that reduce environmental burden, provide molded articles whose physical properties are difficult to degrade even at low temperatures, resin compositions with excellent formability, and molded articles made using the above-described resin compositions. Attached Figure Description

[0025] Figure 1 This is a schematic diagram showing the measurement area of ​​the surface roughness in the sheets that underwent surface texturing processing in the embodiments and comparative examples. Detailed Implementation

[0026] Hereinafter, an example of an embodiment of the present invention will be described. The embodiments shown below are examples for detailing the technical concept of the present invention, and the present invention is not limited to the following description.

[0027] Furthermore, while this specification shows preferred embodiments, combinations of two or more preferred embodiments are also preferred. Regarding matters indicated by numerical ranges, when several numerical ranges exist, their lower and upper limits can be selectively combined to form preferred embodiments. When a numerical range of "XX to YY" is described, it means "XX or more and YY or less".

[0028] In addition, in this specification, "biocompatibility" refers to the proportion of biologically derived substances in the target material, as measured according to ASTM D6866-16. For example, "biocompatibility of resin composition" refers to the proportion of biologically derived raw materials in the resin composition, as measured according to ASTM D6866-16. "Biocompatibility of resin" refers to the proportion of biologically derived raw materials in the resin, as measured according to ASTM D6866-16.

[0029] <Resin Composition>

[0030] [Block copolymer (A)]

[0031] The resin composition of this embodiment, by containing a block copolymer (A), exhibits good softness, easily suppresses the decrease in physical properties at low temperatures, and demonstrates excellent formability.

[0032] The block copolymer (A) comprises polymer block (a1) and polymer block (a2), wherein the polymer block (a1) contains structural units derived from aromatic vinyl compounds and the polymer block (a2) contains structural units derived from farnesene.

[0033] Block copolymer (A) can be used alone or in combination of two or more.

[0034] (polymer block (a1))

[0035] The polymer block (a1) contains structural units derived from aromatic vinyl compounds. Examples of such aromatic vinyl compounds include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzene. These aromatic vinyl compounds can be used alone or in combination of two or more. Among these, styrene, α-methylstyrene, and 4-methylstyrene are preferred, and styrene is more preferred.

[0036] The polymer block (a1) may contain monomers other than aromatic vinyl compounds, such as structural units derived from monomers constituting the polymer block (a2) described later. The content of structural units derived from aromatic vinyl compounds in the polymer block (a1) is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass. The maximum content of structural units derived from aromatic vinyl compounds in the polymer block (a1) can be 100% by mass, 99% by mass, or 98% by mass.

[0037] Furthermore, the total content of polymer blocks (a1) in the block copolymer (A) is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, more preferably 5 to 50% by mass, even more preferably 10 to 40% by mass, and even more preferably 10 to 35% by mass. If the above content is 1% by mass or more, the resin composition readily exhibits excellent formability. Furthermore, if the above content is 65% by mass or less, sufficient softness and exhibiting tear strength and tensile properties are expected.

[0038] (polymer block (a2))

[0039] The polymer block (a2) contains structural units derived from farnesene.

[0040] The farnesene described above can be either α-farnesene or β-farnesene as shown in formula (1) below. From the viewpoint of ease of manufacturing the block copolymer (A), β-farnesene is preferred. It should be noted that α-farnesene and β-farnesene can be used in combination.

[0041] [Chemistry 1]

[0042]

[0043] The content of farnesene-derived structural units in the polymer block (a2) is preferably 1 to 100% by mass. By including farnesene-derived structural units in the polymer block (a2), good flexibility and excellent formability are achieved. From the above viewpoint, the content of farnesene-derived structural units in the polymer block (a2) is more preferably 10 to 100% by mass, more preferably 20 to 100% by mass, even more preferably 30 to 100% by mass, particularly preferably 50 to 100% by mass, and most preferably 100% by mass. That is, the polymer block (a2) is most preferably a polymer block composed solely of farnesene-derived structural units.

[0044] Furthermore, when farnesene is of biological origin, the use of conjugated diene compounds other than farnesene, such as butadiene and isoprene, derived from petroleum, can be suppressed, thereby reducing petroleum dependence and contributing to further reduction of environmental burden. Based on the above viewpoint, the content of farnesene-derived structural units in the polymer block (a2) is preferably 50–100% by mass, more preferably 60–100% by mass, even more preferably 70–100% by mass, even more preferably 80–100% by mass, and particularly preferably 90–100% by mass.

[0045] Furthermore, when the polymer block (a2) contains structural units derived from conjugated diene compounds other than farnesene (described later), the content of structural units derived from farnesene in the polymer block (a2) is more preferably 10% by mass or more, further preferably 20% by mass or more, even more preferably 30% by mass or more, particularly preferably 50% by mass or more, and most preferably 70% by mass or more.

[0046] When the structural unit constituting the polymer block (a2) is a β-farnesene unit, the bonding mode of β-farnesene can be 1,2-bonding, 1,13-bonding, or 3,13-bonding. Specifically, the 1,2-bonding and 3,13-bonding of β-farnesene are vinyl bonds. The content of this vinyl bond unit (hereinafter sometimes simply referred to as "vinyl bond amount") is preferably 1 to 35 mol%, more preferably 1 to 30 mol%, further preferably 1 to 25 mol%, and even more preferably 1 to 20 mol%.

[0047] Here, the vinyl bond amount is determined according to the method described in the examples and by... 1 The value was calculated by H-NMR measurement.

[0048] The polymer block (a2) may contain structural units derived from conjugated diene compounds other than farnesene.

[0049] Examples of conjugated diene compounds other than farnesene include isoprene, butadiene, 2,3-dimethyl-butadiene, 2-phenyl-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octtriene, geraniol, and chloroprene. These can be used alone or in combination of two or more. Among these, isoprene, butadiene, and geraniol are preferred, and isoprene and butadiene are more preferred.

[0050] When the polymer block (a2) contains structural units derived from conjugated diene compounds other than farnesene, the content of structural units derived from conjugated diene compounds other than farnesene is more preferably 90% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, particularly preferably 50% by mass or less, most preferably 30% by mass or less, and the lower limit can be 0% by mass.

[0051] The polymer block (a2) may contain structural units other than those derived from farnesene and those derived from conjugated diene compounds other than farnesene. The total content of structural units derived from farnesene and structural units derived from conjugated diene compounds other than farnesene in the polymer block (a2) is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass.

[0052] (polymer block (a3))

[0053] In the block copolymer (A), in addition to the aforementioned polymer blocks (a1) and polymer blocks (a2), there may also be a polymer block (a3), which contains structural units derived from conjugated diene compounds other than farnesene.

[0054] The polymer block (a3) ​​is preferably a polymer block in which the content of structural units derived from farnesene is 0% or more but less than 1% by mass, and the content of structural units derived from conjugated diene compounds other than farnesene is 1 to 100% by mass.

[0055] The farneses that constitute structural units derived from farneses and the conjugated dienes that constitute structural units derived from conjugated dienes other than farneses can be listed as substances identical to the farneses that constitute structural units derived from farneses and the conjugated dienes that constitute structural units derived from conjugated dienes other than farneses.

[0056] As the structural units of conjugated diene compounds derived from conjugated diene compounds other than farnesene, isoprene, butadiene, and geraniol are preferred, and isoprene and butadiene are more preferred. They can be used alone or in combination of two or more.

[0057] The content of farnesene-derived structural units in the polymer block (a3) ​​is preferably 0% by mass.

[0058] The content of structural units derived from conjugated diene compounds other than farnesene in the polymer block (a3) ​​is more preferably 60 to 100% by mass, more preferably 80 to 100% by mass, even more preferably 90 to 100% by mass, and particularly preferably 100% by mass.

[0059] When the structural unit constituting the polymer block (a3) ​​is any one of isoprene unit, butadiene unit, or a mixture of isoprene and butadiene, the bonding forms for isoprene and butadiene are 1,2-bonded, 3,4-bonded, or 1,4-bonded in the case of isoprene, and 1,2-bonded or 1,4-bonded in the case of butadiene. The total content of 3,4-bonded units and 1,2-bonded units (hereinafter sometimes simply referred to as "vinyl bond content") is preferably 1 to 35 mol%, more preferably 1 to 30 mol%, further preferably 1 to 25 mol%, and even more preferably 1 to 20 mol%.

[0060] It should be noted that when the conjugated diene compound is only a butadiene unit, the above "vinyl bond amount" refers to the content of 1,2-bonded units.

[0061] Here, the vinyl bond amount is determined according to the method described in the examples and by... 1 The value was calculated by H-NMR measurement.

[0062] In addition, the polymer block (a3) ​​may contain structural units other than those derived from farnesene and those derived from conjugated diene compounds other than farnesene.

[0063] The total content of structural units derived from farnesene and structural units derived from conjugated diene compounds other than farnesene in the polymer block (a3) ​​is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass.

[0064] (bonding morphology)

[0065] The block copolymer (A) is a block copolymer containing at least one polymer block (a1) and one polymer block (a2).

[0066] The bonding morphology of polymer blocks (a1) and (a2) is not particularly limited and can be linear, branched, radial, or a combination of two or more of these. Among these, a linear bonding morphology is preferred.

[0067] As a linear bonding configuration, when polymer block (a1) is represented as A and polymer block (a2) as B, example (AB) can be shown. l A-(BA) m Or B-(AB) n The bonding patterns shown are as follows. It should be noted that l, m, and n each independently represent integers greater than 1.

[0068] When the block copolymer (A) contains at least one polymer block (a1) and one polymer block (a2), it is preferably a triblock copolymer having a block bonding morphology in the order of polymer block (a1), polymer block (a2), and polymer block (a1) and represented by ABA.

[0069] That is, the block copolymer (A) is preferably a triblock copolymer represented by ABA, which can be either unhydrogenated or hydrogenated. When the resin composition of the present invention is used for applications where heat resistance is of particular importance, the triblock copolymer is preferably hydrogenated.

[0070] When the block copolymer (A) comprises polymer blocks (a1), polymer blocks (a2), and polymer blocks (a3), the block copolymer (A) is preferably a block copolymer having at least one polymer block (a2) at each end. This block copolymer can be either unhydrogenated or hydrogenated. By having at least one polymer block (a2) present at the end of the polymer chain, the formability is improved. From this viewpoint, when the block copolymer (A) is linear, it is more preferable to have polymer blocks (a2) at both ends. Furthermore, when the block copolymer (A) is branched or radial, the number of polymer blocks (a2) present at the ends is preferably two or more, more preferably three or more.

[0071] Additionally, the block copolymer (A) can be a block copolymer comprising at least two polymer blocks (a1), at least one polymer block (a2), and at least one polymer block (a3). Alternatively, it can be a block copolymer comprising at least two polymer blocks (a1), at least one polymer block (a2), and at least one polymer block (a3), and having at least one polymer block (a2) at the end.

[0072] When the block copolymer (A) comprises polymer blocks (a1), polymer blocks (a2), and polymer blocks (a3), the bonding morphology of the multiple polymer blocks is not particularly limited and can be linear, branched, radial, or a combination of two or more of these. Among these, a linear bonding morphology is preferred.

[0073] When polymer block (a1) is designated as A, polymer block (a2) as B, and polymer block (a3) ​​as C, the block copolymer (A) preferably comprises a structure having blocks in the order of polymer block (a2), polymer block (a1), and polymer block (a3), i.e., the structure of BAC.

[0074] Specifically, the block copolymer (A) is preferably a tetrablock copolymer represented by BACA, a pentablock copolymer represented by BACAB, or a copolymer represented by BA-(CA). p -B、BA-(CAB) q B-(ACAB) r The copolymer represented by (p, q, r each independently represent an integer greater than 2), wherein, more preferably, is a pentablock copolymer represented by BACAB.

[0075] That is, the block copolymer (A) is preferably a pentablock copolymer represented by BACAB, which can be either unhydrogenated or hydrogenated. When the resin composition of the present invention is used for applications where heat resistance is of particular importance, the pentablock copolymer is preferably hydrogenated.

[0076] In this specification, when the same polymer blocks are bonded into a linear form using a divalent coupling agent, the bonded polymer blocks are considered as a single polymer block. Therefore, a polymer block that would strictly be described as AXA (where X represents a coupling agent residue) is generally referred to as A. In this specification, such polymer blocks containing coupling agent residues are treated as described above; therefore, for example, a block copolymer containing coupling agent residues and strictly speaking BACXCAB is described as BACAB, and is considered an example of a pentablock copolymer.

[0077] Furthermore, the two or more polymer blocks (a1) in the block copolymer (A) described above can be polymer blocks containing the same structural unit or polymer blocks containing different structural units. Similarly, when the block copolymer (A) has two or more polymer blocks (a2) or two or more polymer blocks (a3), each polymer block can be a polymer block containing the same structural unit or a polymer block containing different structural units. For example, in the two polymer blocks (a1) of the triblock copolymer represented by ABA, the types of aromatic vinyl compounds can be the same or different.

[0078] When the block copolymer (A) comprises polymer blocks (a1) and (a2) but not polymer block (a3), the mass ratio of polymer blocks (a1) to polymer blocks (a2) [(a1) / (a2)] is preferably 1 / 99 to 65 / 35, more preferably 5 / 95 to 60 / 40, even more preferably 5 / 95 to 50 / 50, even more preferably 10 / 90 to 40 / 60, and particularly preferably 10 / 90 to 35 / 65. Within the above ranges, a resin composition with excellent flexibility and superior formability can be obtained.

[0079] When the block copolymer (A) comprises polymer blocks (a1), (a2), and (a3), the mass ratio of polymer blocks (a1) to polymer blocks (a2) [(a1) / (a2)] is 1 / 99 to 70 / 30, preferably 5 / 95 to 60 / 40, more preferably 10 / 90 to 50 / 50, further preferably 20 / 80 to 40 / 60, and even more preferably 25 / 75 to 35 / 65. Within these ranges, a resin composition with excellent flexibility and superior formability can be obtained.

[0080] In the block copolymer (A), the mass ratio of polymer block (a1) to the total amount of polymer blocks (a2) and polymer blocks (a3) ​​[(a1) / ((a2)+(a3))] is preferably 1 / 99 to 70 / 30. The above mass ratio [(a1) / ((a2)+(a3))] is more preferably 1 / 99 to 60 / 40, even more preferably 10 / 90 to 40 / 60, even more preferably 10 / 90 to 30 / 70, and particularly preferably 15 / 85 to 25 / 75.

[0081] When the block copolymer (A) comprises polymer blocks (a1) and polymer blocks (a2) but does not contain a polymer block (a3), the total content of polymer blocks (a1) and polymer blocks (a2) in the block copolymer is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and even more preferably 100% by mass. The upper limit of the total content of polymer blocks (a1) and polymer blocks (a2) can be 100% by mass. As one embodiment of the block copolymer (A), examples include block copolymers comprising at least one polymer block (a1) and at least one polymer block (a2).

[0082] Furthermore, when the block copolymer (A) comprises polymer blocks (a1), polymer blocks (a2), and polymer blocks (a3), the total content of these polymer blocks (a1) to (a3) ​​in the block copolymer (A) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and even more preferably 100% by mass. The upper limit of the total content of polymer blocks (a1) to (a3) ​​can be 100% by mass. As one embodiment of the block copolymer (A), examples include block copolymers comprising at least one polymer block (a1), at least one polymer block (a2), and at least one polymer block (a3).

[0083] As an example of a more preferred method for block copolymer (A), from the viewpoints of suppressing formability, reducing physical properties at low temperatures, and improving tear strength and tensile properties,

[0084] • The block copolymer containing polymer block (a1) and polymer block (a2) is a hydrogenated block copolymer;

[0085] • The mass ratio of polymer block (a1) to polymer block (a2) [(a1) / (a2)] is 15 / 85 to 35 / 65;

[0086] • It comprises at least two of the aforementioned polymer blocks (a1) and at least one of the aforementioned polymer blocks (a2), and has blocks in the order of polymer blocks (a1), polymer blocks (a2), and polymer blocks (a1);

[0087] • The hydrogenation rate of carbon-carbon double bonds in the structural units derived from conjugated diene compounds in the block copolymer (A) is above 70 mol%.

[0088] As another example of a more preferred approach for block copolymer (A), from the viewpoints of suppressing formability, reducing physical properties at low temperatures, and improving tear strength and tensile properties,

[0089] • The block copolymer containing polymer blocks (a1), polymer blocks (a2) and polymer blocks (a3) ​​is a hydrogenated block copolymer;

[0090] • The mass ratio of polymer block (a1) to the total mass of polymer blocks (a2) and (a3) ​​[(a1) / ((a2)+(a3))] is 15 / 85 to 25 / 75;

[0091] • Contains at least two polymer blocks (a1), at least one polymer block (a2), and at least one polymer block (a3), and has at least one polymer block (a2) at the end;

[0092] • The hydrogenation rate of carbon-carbon double bonds in the structural units derived from conjugated diene compounds in the block copolymer (A) is above 70 mol%.

[0093] (Polymer blocks composed of other monomers)

[0094] In addition to polymer blocks (a1), polymer blocks (a2) and polymer blocks (a3), the block copolymer (A) may contain polymer blocks composed of other monomers without impairing the effects of the present invention.

[0095] Other monomers mentioned include, for example, unsaturated hydrocarbon compounds such as propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, 1-undecene, 1-dodecene, 1-tetracene, 1-tetradecene, 1-pentadecadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecadecene, and 1-eicosene; and unsaturated compounds containing functional groups such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, acrylonitrile, methacrylonitrile, maleic acid, fumaric acid, crotonic acid, itaconic acid, 2-acryloylethanesulfonic acid, 2-methacryloylethanesulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, 2-methacrylamido-2-methylpropanesulfonic acid, vinyl sulfonic acid, vinyl acetate, and methyl vinyl ether. They can be used alone or in combination of two or more.

[0096] When the block copolymer (A) has other polymer blocks, its content is preferably 10% by mass or less, more preferably 5% by mass or less.

[0097] (Method for manufacturing block copolymer (A))

[0098] Block copolymer (A) can be suitably manufactured, for example, by an anionic polymerization process. Furthermore, when block copolymer (A) is a block copolymer containing polymer blocks (a1), polymer blocks (a2), and polymer blocks (a3), it can also be suitably manufactured by anionic polymerization. Moreover, when block copolymer (A) is a hydrogenated block copolymer, it can be suitably manufactured by a process of hydrogenating the carbon-carbon double bonds in the structural units derived from conjugated diene compounds in the aforementioned block copolymer.

[0099] <Polymerization Process>

[0100] Block copolymer (A) can be manufactured by solution polymerization or by the methods described in Japanese Patent Application Publication Nos. 2012-502135 and 2012-502136. Among these, solution polymerization is preferred, and known methods such as anionic polymerization, cationic polymerization, plasma polymerization, and free radical polymerization can be applied. Among these, anionic polymerization is preferred. As anionic polymerization, in the presence of a solvent, an anionic polymerization initiator, and a Lewis base as needed, a block copolymer can be obtained by sequentially adding, for example, an aromatic vinyl compound, farnesene, and optionally a conjugated diene compound other than farnesene.

[0101] Examples of anionic polymerization initiators include alkali metals such as lithium, sodium, and potassium; alkaline earth metals such as beryllium, magnesium, calcium, strontium, and barium; lanthanide rare earth metals such as lanthanum and neodymium; and compounds containing the aforementioned alkali metals, alkaline earth metals, and lanthanide rare earth metals. Among these, compounds containing alkali metals and alkaline earth metals are preferred, and organoalkali metal compounds are more preferred.

[0102] Examples of the aforementioned organoalkali metal compounds include, for instance, methyllithium, ethyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, hexyllithium, phenyllithium, lithium mesimilar, dilithium methane, dilithium naphthalene, 1,4-dilithium butane, 1,4-dilithium-2-ethylcyclohexane, and 1,3,5-trilithiumbenzene; sodium naphthalene, potassium naphthalene, etc. Among these, organolithium compounds are preferred, n-butyllithium and sec-butyllithium are more preferred, and sec-butyllithium is even more preferred. It should be noted that organoalkali metal compounds can react with secondary amines such as diisopropylamine, dibutylamine, dihexylamine, and dibenzylamine to be used as organoalkali metal amides.

[0103] The amount of organoalkali metal compounds used in the polymerization also varies depending on the molecular weight of the block copolymer (A), and is typically in the range of 0.01 to 3% by mass relative to the total amount of aromatic vinyl compounds, farnesene, and conjugated dienes other than farnesene.

[0104] As a solvent, there are no particular limitations as long as it does not adversely affect the anionic polymerization reaction. Examples include saturated aliphatic hydrocarbons such as n-pentane, isopentane, n-hexane, n-heptane, and isooctane; saturated alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclopentane; and aromatic hydrocarbons such as benzene, toluene, and xylene. One or more solvents can be used alone or in combination. There are no particular limitations on the amount of solvent used.

[0105] Lewis bases play a role in controlling the microstructure of structural units derived from farnesene and structural units derived from conjugated dienes other than farnesene. Examples of Lewis bases include, for instance, ether compounds such as dibutyl ether, diethyl ether, tetrahydrofuran, dioxane, and ethylene glycol diethyl ether; pyridine; tertiary amines such as N,N,N',N'-tetramethylethylenediamine and trimethylamine; alkali metal alkoxides such as potassium tert-butoxide; and phosphine compounds. When using a Lewis base, its amount is typically preferably in the range of 0.01 to 1000 molar equivalents relative to 1 mole of the anionic polymerization initiator.

[0106] The polymerization temperature is typically around -80 to 150°C, preferably 0 to 100°C, and more preferably 10 to 90°C. The polymerization reaction can be either batch or continuous. Block copolymers (A) can be produced by continuously or intermittently supplying monomers to the polymerization reaction solution in a specific range of amounts of aromatic vinyl compounds, farnesene, and optionally conjugated diene compounds other than farnesene, or by sequentially polymerizing monomers in a specific ratio in the polymerization reaction solution.

[0107] The polymerization reaction can be stopped by adding alcohols such as methanol or isopropanol as polymerization terminators. The block copolymer can be separated by injecting the obtained polymerization reaction solution into a poor solvent such as methanol to precipitate it, or by washing the polymerization reaction solution with water, separating it, and then drying it.

[0108] As an example of a preferred embodiment of the block copolymer (A), a structure having polymer blocks (a1), (a2), and (a1) in sequence can be cited. Therefore, it is preferable to obtain the block copolymer (A) by sequentially manufacturing polymer blocks (a1), (a2), and (a1). In addition, in the case of hydrides, it is more preferable to manufacture the hydrogenated block copolymer (A) by a method including a step of further hydrogenating the obtained block copolymer (A).

[0109] In the manufacture of block copolymer (A), from the point of view of efficient manufacturing, coupling agents can be used.

[0110] Examples of coupling agents mentioned above include, for instance, divinylbenzene; epoxidized 1,2-polybutadiene, epoxidized soybean oil, tetraglycidyl-1,3-diaminomethylcyclohexane, and other polycyclic epoxy compounds; halides such as tin tetrachloride, tetrachlorosilane, trichlorosilane, trichloromethylsilane, dichlorodimethylsilane, and dibromodimethylsilane; and methyl benzoate, ethyl benzoate, phenyl benzoate, diethyl oxalate, diethyl malonate, diethyl adipate, and diphthalate. Ester compounds such as methyl ester and dimethyl terephthalate; carbonate compounds such as dimethyl carbonate, diethyl carbonate, and diphenyl carbonate; alkoxysilane compounds such as diethoxydimethylsilane, trimethoxymethylsilane, triethoxymethylsilane, tetramethoxysilane, tetraethoxysilane, tetrabutoxysilane, tetra(2-ethylhexyloxy)silane, bis(triethoxysilyl)ethane, and 3-aminopropyltriethoxysilane; 2,4-toluene diisocyanate, etc.

[0111] <Hydrogenation Process>

[0112] A hydrogenated block copolymer (A) can also be prepared by subjecting the block copolymer (A) to a hydrogenation process of the block copolymer obtained by the aforementioned method. One preferred embodiment of the block copolymer (A) is a hydrogenated block copolymer (A).

[0113] Hydrogenation can be carried out using known methods. For example, in a solution obtained by dissolving the block copolymer (A) in a solvent that does not affect the hydrogenation reaction, a Ziegler catalyst, a nickel, platinum, palladium, ruthenium, or rhodium metal catalyst supported on carbon, silica, diatomaceous earth, etc., or an organometallic complex containing cobalt, nickel, palladium, rhodium, or ruthenium metals, etc., can be used as a hydrogenation catalyst, and the hydrogenation reaction can be carried out.

[0114] In the hydrogenation process, a hydrogenation catalyst can be added to the polymerization reaction solution containing the block copolymer obtained by the aforementioned method for manufacturing the block copolymer (A) to carry out the hydrogenation reaction. In this invention, the hydrogenation catalyst is preferably palladium on carbon, which is obtained by supporting palladium on carbon.

[0115] In the hydrogenation reaction, the hydrogen pressure is preferably 0.1 to 20 MPa, the reaction temperature is preferably 100 to 200 °C, and the reaction time is preferably 1 to 20 hours.

[0116] The hydrogenation rate of the carbon-carbon double bonds in the structural units derived from the conjugated diene compound in the block copolymer (A) is preferably 70 mol% or more. From the viewpoint of heat resistance and weather resistance, the hydrogenation rate of the carbon-carbon double bonds in the structural units derived from the conjugated diene compound is more preferably 70 to 98 mol%, more preferably 70 to 97 mol%, even more preferably 80 to 96 mol%, particularly preferably 85 to 96 mol%, and most preferably 87 to 96 mol%.

[0117] The hydrogenation rate can be determined by measuring the block copolymer (A) before hydrogenation and the block copolymer (A) after hydrogenation. 1 Calculated using H-NMR.

[0118] It should be noted that the hydrogenation rate mentioned above is the hydrogenation rate of all carbon-carbon double bonds in the structural units of the block copolymer (A) that originate from the conjugated diene compound.

[0119] Examples of carbon-carbon double bonds in structural units derived from conjugated diene compounds present in block copolymers (A) include, for example, carbon-carbon double bonds in structural units derived from conjugated diene compounds in polymer blocks (a2) and polymer blocks (a3).

[0120] It should be noted that, in this specification, the polymer blocks (a2) and (a3) ​​in the hydrogenated block copolymer (A) have been hydrogenated, but are referred to as "polymer block (a2)" and "polymer block (a3)" in the same manner as before hydrogenation.

[0121] In this embodiment, unmodified block copolymers can be used, or modified block copolymers can be used as follows.

[0122] In the case of modified block copolymers, the block copolymers can be further modified after the hydrogenation process. Examples of functional groups that can be introduced through modification include, for example, amino, alkoxysilyl, hydroxyl, epoxy, carboxyl, carbonyl, mercapto, isocyanate, and anhydride groups.

[0123] As a method for modifying block copolymers, one example is grafting the separated hydrogenated block copolymers with modifiers such as maleic anhydride.

[0124] Furthermore, the block copolymer can also be modified before the hydrogenation process. Specific methods include adding coupling agents such as tin tetrachloride, tetrachlorosilane, dichlorodimethylsilane, dimethyldiethoxysilane, tetramethoxysilane, tetraethoxysilane, 3-aminopropyltriethoxysilane, tetraglycidyl-1,3-diaminomethylcyclohexane, and 2,4-toluene diisocyanate, or polymerization terminator modifiers such as 4,4'-bis(diethylamino)benzophenone and N-vinylpyrrolidone, or other modifiers described in Japanese Patent Application Publication No. 2011-132298, before adding the polymerization terminator.

[0125] The functional group can be introduced at the polymerization end of the block copolymer or at the side chain. Furthermore, there can be one type of functional group or a combination of two or more. The preferred molar equivalent of the modifier relative to the anionic polymerization initiator is 0.01 to 10 molar equivalents per mole.

[0126] (peak molecular weight)

[0127] From the viewpoint of mechanical strength, the peak molecular weight (Mp) of the block copolymer (A) is preferably 4,000 to 1,000,000, more preferably 9,000 to 800,000, even more preferably 30,000 to 700,000, even more preferably 50,000 to 600,000, and particularly preferably 100,000 to 500,000.

[0128] The molecular weight distribution (Mw / Mn) of the block copolymer (A) is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and even more preferably 1 to 2. If the molecular weight distribution is within the aforementioned range, the viscosity deviation of the block copolymer (A) is small and it is easy to process.

[0129] It should be noted that the peak molecular weight (Mp) and molecular weight distribution (Mw / Mn) in this specification are values ​​measured using the methods described in the examples below.

[0130] From the viewpoint of formability, the peak molecular weight of the polymer block (a1) is preferably 2,000 to 100,000, more preferably 4,000 to 80,000, even more preferably 5,000 to 70,000, and even more preferably 6,000 to 65,000.

[0131] [Block copolymer (B)]

[0132] The resin composition of this embodiment, by containing a block copolymer (B), can suppress the decrease in physical properties at low temperatures and exhibit excellent formability.

[0133] Block copolymer (B) comprises polymer blocks (b1) containing structural units derived from aromatic vinyl compounds and polymer blocks (b2) containing more than 30 mol% structural units derived from isoprene. Block copolymer (B) does not contain polymer blocks containing structural units derived from farnesene. Furthermore, block copolymer (A) differs from block copolymer (B).

[0134] Block copolymers (B) can be used alone or in combination of two or more.

[0135] (polymer block (b1))

[0136] The polymer block (b1) contains structural units derived from aromatic vinyl compounds. Examples of such aromatic vinyl compounds include styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 4-propylstyrene, 4-tert-butylstyrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 2,4,6-trimethylstyrene, 2-ethyl-4-benzylmethylstyrene, 4-(phenylbutyl)styrene, 1-vinylnaphthalene, 2-vinylnaphthalene, vinylanthracene, N,N-diethyl-4-aminoethylstyrene, vinylpyridine, 4-methoxystyrene, monochlorostyrene, dichlorostyrene, and divinylbenzene. These aromatic vinyl compounds can be used alone or in combination of two or more. Styrene, α-methylstyrene, and 4-methylstyrene are preferred, with styrene being more preferred.

[0137] The polymer block (b1) may contain structural units derived from monomers other than aromatic vinyl compounds.

[0138] As monomers other than aromatic vinyl compounds, examples include at least one selected from butadiene, isoprene, 2,3-dimethylbutadiene, 1,3-pentadiene, 1,3-hexadiene, isobutene, methyl methacrylate, methyl vinyl ether, β-pinene, 8,9-p-menthene, dipentene, methylene norbornene, 2-methylenetetrahydrofuran, etc.

[0139] From a mechanical property point of view, the content of structural units derived from aromatic vinyl compounds in the polymer block (b1) is preferably 60% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 100% by mass. The upper limit of the content of structural units derived from aromatic vinyl compounds in the polymer block (b1) can be 100% by mass, 99% by mass, or 98% by mass.

[0140] Furthermore, the total content of polymer blocks (b1) in the block copolymer (B) is preferably 1 to 65% by mass, more preferably 5 to 60% by mass, more preferably 5 to 50% by mass, and even more preferably 10 to 40% by mass. If the above content is 1% by mass or more, the resin composition readily exhibits excellent formability. Furthermore, if the above content is 65% by mass or less, sufficient softness and exhibiting tear strength and tensile properties are expected.

[0141] (polymer block (b2))

[0142] The polymer block (b2) contains at least 30 mol% isoprene-derived structural units. If the content of isoprene-derived structural units in the polymer block (b2) is less than 30 mol%, it is difficult to suppress the decrease in physical properties at low temperatures and exhibit excellent formability. The content of isoprene-derived structural units in the polymer block (b2) is preferably 40 mol% or more, more preferably 45 mol% or more, even more preferably 50 mol% or more, and can also be set to 100 mol%. The upper limit of isoprene-derived structural units can be 100 mol%, 99 mol%, or 98 mol%.

[0143] In the polymer block (b2), in addition to structural units derived from isoprene, structural units derived from conjugated diene compounds other than isoprene may be contained.

[0144] As a conjugated diene compound other than isoprene, at least one can be selected from butadiene, hexadiene, 2,3-dimethyl-1,3-butadiene, 2-phenyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 1,3-octadiene, 1,3-cyclohexadiene, 2-methyl-1,3-octadiene, 1,3,7-octtriene, geraniol, and chloroprene. Butadiene is preferred.

[0145] When butadiene and isoprene are used in combination, their mixing ratio [isoprene / butadiene] (mass ratio) is not particularly limited, but is preferably 35 / 65 to 95 / 5, more preferably 40 / 60 to 90 / 10, further preferably 40 / 60 to 70 / 30, and particularly preferably 45 / 55 to 65 / 35. It should be noted that if the mixing ratio [isoprene / butadiene] is expressed as a molar ratio, it is preferably 30 / 70 to 95 / 5, more preferably 35 / 90 to 90 / 10, further preferably 40 / 60 to 70 / 30, and particularly preferably 45 / 55 to 55 / 45.

[0146] When the structural unit constituting the polymer block (b2) is either an isoprene unit or a mixture of isoprene and butadiene units, the bonding forms for isoprene and butadiene can be 1,2-bonded or 1,4-bonded in the case of butadiene, and 1,2-bonded, 3,4-bonded or 1,4-bonded in the case of isoprene.

[0147] In the block copolymer (B), the total content of 3,4-bonded units and 1,2-bonded units in the polymer block (b2) (hereinafter sometimes simply referred to as "vinyl bond content") is preferably 1 to 35 mol%, more preferably 1 to 30 mol%, further preferably 1 to 25 mol%, even more preferably 1 to 20 mol%, and can be 1 to 15 mol%, or 1 to 10 mol%. If it is within the above range, it is suitable for suppressing the decrease in physical properties at low temperatures.

[0148] Here, the vinyl bond amount is determined according to the method described in the examples and by... 1 The value was calculated by H-NMR measurement.

[0149] In addition, the polymer block (b2) may contain structural units other than those derived from isoprene and those derived from conjugated diene compounds other than isoprene.

[0150] The total content of structural units derived from isoprene and structural units derived from conjugated diene compounds other than isoprene in the polymer block (b2) is preferably 60% by mass or more, more preferably 80% by mass or more, and even more preferably 100% by mass.

[0151] (Bonding method)

[0152] The block copolymer (B) is a block copolymer containing at least one polymer block (b1) and one polymer block (b2).

[0153] The bonding mode of polymer blocks (b1) and polymer blocks (b2) is not particularly limited and can be linear, branched, radial, or a combination of two or more of them. Among them, it is preferred that the blocks are bonded in a linear manner.

[0154] As a linear bonding method, when polymer block (b1) is represented by A and polymer block (b2) by B, it can be exemplified as (AB). l A-(BA) m Or B-(AB) n The bonding method shown, etc. It should be noted that the aforementioned l, m, and n each independently represent integers greater than 1.

[0155] When the block copolymer (B) contains at least one polymer block (b1) and one polymer block (b2), it is preferably a triblock copolymer as shown in ABA, in which the blocks are bonded in sequence having polymer blocks (b1), polymer blocks (b2), and polymer blocks (b1).

[0156] Specifically, the block copolymer (B) is preferably a triblock copolymer as shown in ABA, and the triblock copolymer can be either unhydrogenated or hydrogenated. When the resin composition of the present invention is used in applications where heat resistance is of particular importance, the triblock copolymer is preferably hydrogenated.

[0157] Furthermore, in a block copolymer (B), two or more polymer blocks (b1) can each be a polymer block containing the same structural unit or a polymer block containing different structural units. Similarly, when a block copolymer (B) has two or more polymer blocks (b2), each polymer block can be a polymer block containing the same structural unit or a polymer block containing different structural units. For example, in the triblock copolymer shown in ABA, the two polymer blocks (b1) can each contain the same or different types of aromatic vinyl compounds.

[0158] In the block copolymer (B), the mass ratio of polymer block (b1) to polymer block (b2) [(b1) / (b2)] is preferably 1 / 99 to 65 / 35, more preferably 5 / 95 to 60 / 40, even more preferably 5 / 95 to 50 / 50, even more preferably 10 / 90 to 40 / 60, and particularly preferably 15 / 85 to 35 / 65. Within the above range, it is suitable for suppressing the decrease in physical properties at low temperatures.

[0159] In addition to polymer blocks (b1) and polymer blocks (b2), the block copolymer (B) may contain polymer blocks composed of other monomers without impairing the effects of the present invention.

[0160] On the other hand, from the viewpoint of better realizing the effects of the present invention, the total content of polymer blocks (b1) and polymer blocks (b2) in the block copolymer (B) is preferably 80% by mass or more, more preferably 90% by mass or more, further preferably 95% by mass or more, and even more preferably 100% by mass. As one embodiment of the block copolymer (B), examples include block copolymers containing at least one polymer block (b1) and at least one polymer block (b2).

[0161] (Method for manufacturing block copolymer (B))

[0162] Block copolymer (B) can be manufactured by the same manufacturing method as the aforementioned block copolymer (A), and their suitability is also the same.

[0163] For example, a block copolymer (B) can be suitably manufactured by a process of polymerizing polymer blocks (b1) and (b2) using anionic polymerization. Furthermore, in the case where the block copolymer (B) is a hydrogenated block copolymer, it can be suitably manufactured by a process of hydrogenating the carbon-carbon double bonds in the structural units of the block copolymer (B) derived from the conjugated diene compound.

[0164] One preferred embodiment of the block copolymer (B) is a hydrogenated block copolymer (B).

[0165] The hydrogenation rate of the carbon-carbon double bonds in the structural units derived from the conjugated diene compound in the block copolymer (B) is preferably 70 mol% or more. From the viewpoint of heat resistance and weather resistance, the hydrogenation rate of the carbon-carbon double bonds in the structural units derived from the conjugated diene compound is more preferably 70 to 99.5 mol%, more preferably 75 to 99.5 mol%, even more preferably 80 to 99.5 mol%, particularly preferably 85 to 99.5 mol%, and most preferably 87 to 99.5 mol%.

[0166] The hydrogenation rate can be determined by measuring the block copolymer (B) before hydrogenation and the block copolymer (B) after hydrogenation. 1 Calculated using H-NMR.

[0167] It should be noted that the above hydrogenation rate is the hydrogenation rate of all carbon-carbon double bonds in the structural units of the block copolymer (B) that originate from the conjugated diene compound.

[0168] Carbon-carbon double bonds in structural units derived from conjugated diene compounds present in block copolymers (B) can be exemplified by carbon-carbon double bonds in structural units derived from conjugated diene compounds in polymer blocks (b2).

[0169] It should be noted that in this specification, the polymer blocks (b2) in the hydrogenated block copolymer (B) have been hydrogenated, but they are referred to as "polymer blocks (b2)" in the same way as before hydrogenation.

[0170] Examples of hydrogenated block copolymers (B) include, for instance, SEPS (styrene-ethylene-propylene-styrene block copolymer), a hydrogenated form of styrene-isoprene-styrene triblock copolymer (SIS), and SEEPS (styrene-ethylene-ethylene-propylene-styrene block copolymer), a hydrogenated form of styrene-isoprene / butadiene-styrene triblock copolymer (SIBS), as preferred embodiments.

[0171] (peak molecular weight)

[0172] From a formability point of view, the peak molecular weight (Mp) of the block copolymer (B) is preferably 4,000 to 1,000,000, more preferably 9,000 to 800,000, further preferably 30,000 to 700,000, even more preferably 50,000 to 600,000, particularly preferably 75,000 to 500,000, and may also be 100,000 to 500,000.

[0173] The molecular weight distribution (Mw / Mn) of the block copolymer (B) is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and even more preferably 1 to 2. If the molecular weight distribution is within the aforementioned range, the viscosity deviation of the block copolymer (B) is small and it is easy to process.

[0174] From the viewpoint of formability, the peak molecular weight of the polymer block (b1) is preferably 2,000 to 100,000, more preferably 4,000 to 80,000, even more preferably 5,000 to 70,000, and even more preferably 5,000 to 50,000.

[0175] [Plasticizer (C)]

[0176] From the viewpoint of formability and flowability, the resin composition of this embodiment contains a plasticizer (C).

[0177] Examples of plasticizers (C) include, for instance, oil-based softeners such as process oils, mineral oils, and white oils from alkane, cycloalkane, and aromatic families; phthalic acid derivatives such as dioctyl phthalate and dibutyl phthalate; liquid copolymers of ethylene and α-olefins; liquid paraffin; polybutene; low molecular weight polyisobutylene; liquid polybutadiene, liquid polyisoprene, liquid polyisoprene / butadiene copolymer, liquid styrene / butadiene copolymer, liquid styrene / isoprene copolymer, and other liquid polydienes, as well as their hydrides or modified forms. Plasticizers (C) can be used alone or in combination of two or more.

[0178] From the viewpoint of compatibility with block copolymers (A) and (B), the preferred plasticizers are alkane-based and cycloalkane-based process oils; liquid copolymer oligomers of ethylene and α-olefins; liquid paraffin; and low molecular weight polyisobutylene, more preferably alkane-based and cycloalkane-based process oils, and even more preferably alkane-based process oils.

[0179] [Polyolefin resin (D)]

[0180] From the viewpoint of reducing environmental burden, the resin composition of this embodiment contains a polyolefin resin (D) derived from biomass.

[0181] By using the polyolefin resin (D) together with the aforementioned block copolymer (A) containing structural units of bio-derived farnesene, dependence on petroleum can be effectively reduced. From this viewpoint, the polyolefin resin (D) is preferably a biomass-derived polyethylene resin or a polypropylene resin, more preferably a biomass-derived polyethylene resin, and even more preferably a biomass-derived low-density polyethylene (LDPE).

[0182] These polyolefin resins (D) can be used alone or in combination of two or more.

[0183] The bioavailability of the polyolefin resin (D) is preferably 70% by mass or more, more preferably 80% by mass or more, and even more preferably 90% by mass or more.

[0184] From the viewpoint of compatibility, formability and flowability with block copolymers (A) and (B), the melt flow rate of the polyolefin resin (D) at a temperature of 190°C and a load of 21 N is preferably 0.1 to 100 (g / 10 min), more preferably 0.5 to 70 (g / 10 min), further preferably 1 to 50 (g / 10 min), even more preferably 1.5 to 40 (g / 10 min), particularly preferably 2 to 35 (g / 10 min), and most preferably 5 to 35 (g / 10 min).

[0185] [Polyolefin resins (E)]

[0186] The resin composition of this embodiment may contain polyolefin resins (E) other than the above-described biomass-derived polyolefin resins (D).

[0187] There are no particular limitations on the polyolefin resin (E), and existing well-known olefin polymers can be used. Examples include homopolymers of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 3-methyl-1-butene, 4-methyl-1-pentene, etc.; and homopolymers of ethylene with propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, 1-hexene, 1-heptene, 6-methyl-1-heptene, isooctene, isooctadiene, decadiene, etc., with 3 to 20 carbon atoms. These include copolymers formed from α-olefins, namely ethylene-α-olefin copolymers; ethylene-propylene-diene copolymers (EPDM); ethylene-vinyl acetate copolymers; ethylene-acrylic acid copolymers, ethylene-methacrylic acid copolymers, and other ethylene-unsaturated carboxylic acid copolymers; and polyolefin elastomers containing polyolefins such as polypropylene and polyethylene as hard segments and ethylene-propylene copolymer rubber (EPM) and ethylene-propylene-diene copolymer rubber (EPDM) as soft segments. These polyolefin resins (E) can be used alone or in combination of two or more.

[0188] Among these polyolefin resins (E), polypropylene is preferred from the viewpoint of compatibility with block copolymers (A) and (B) and mechanical strength. Specifically, it is preferred to select at least one of homopolymer polypropylene, block polypropylene, and atactic polypropylene.

[0189] When the polyolefin resin (E) is polypropylene, from the viewpoint of compatibility with block copolymer (A) and block copolymer (B), formability and flowability, the melt flow rate of polypropylene under the conditions of temperature 230°C and load 21N is preferably 0.1 to 100 (g / 10 min), more preferably 0.5 to 80 (g / 10 min), further preferably 1 to 70 (g / 10 min), and even more preferably 10 to 60 (g / 10 min).

[0190] [content]

[0191] One preferred embodiment of the resin composition in this embodiment is:

[0192] It contains block copolymer (A) and block copolymer (B) with a mass ratio [(A) / (B)] of 99 / 1 to 1 / 99.

[0193] Relative to the total content of block copolymer (A) and block copolymer (B) in 100 parts by weight, it comprises:

[0194] Plasticizer (C) 1-350 parts by weight

[0195] 1-200 parts by weight of biomass-derived polyolefin resin (D).

[0196] The mass ratio of block copolymer (A) to block copolymer (B) [(A) / (B)] is preferably 99 / 1 to 1 / 99, more preferably 95 / 5 to 20 / 80, further preferably 95 / 5 to 30 / 70, even more preferably 90 / 10 to 40 / 60, particularly preferably 90 / 10 to 50 / 50, and most preferably 85 / 15 to 55 / 45. When this mass ratio is within the above range, it is possible to produce a resin composition that provides reduced environmental impact, suppression of low-temperature property degradation, and superior moldability.

[0197] In addition, relative to the total content of block copolymer (A) and block copolymer (B) of 100 parts by mass, the content of plasticizer (C) is preferably 1 to 350 parts by mass, more preferably 5 to 300 parts by mass, even more preferably 10 to 200 parts by mass, and even more preferably 20 to 100 parts by mass.

[0198] Furthermore, relative to the total content of 100 parts by mass of block copolymer (A) and block copolymer (B), the content of biomass-derived polyolefin resin (D) is preferably 1 to 200 parts by mass, more preferably 5 to 150 parts by mass, even more preferably 10 to 150 parts by mass, and even more preferably 20 to 90 parts by mass. If the content of biomass-derived polyolefin resin (D) is within the above-mentioned range, biocompatibility can be improved, and it is easier to achieve suppression of property degradation at low temperatures and excellent formability.

[0199] Furthermore, when the resin composition of this embodiment includes a polyolefin resin (E) other than a biomass-derived polyolefin resin (D), the content of the polyolefin resin (E) is preferably 1 to 100 parts by mass relative to 100 parts by mass of the total content of the block copolymer (A) and the block copolymer (B), more preferably 1 to 50 parts by mass, even more preferably 1 to 45 parts by mass, and even more preferably 5 to 25 parts by mass.

[0200] In addition, as a preferred embodiment of this invention, the following embodiments can be listed:

[0201] A resin composition comprising a block copolymer (A) and a block copolymer (B) in a mass ratio [(A) / (B)] preferably 99 / 1 to 65 / 35, more preferably 90 / 10 to 70 / 30.

[0202] Relative to the total content of block copolymer (A) and block copolymer (B) in 100 parts by weight, it comprises:

[0203] The plasticizer (C) is preferably 10 to 60 parts by weight, more preferably 20 to 45 parts by weight;

[0204] Preferably, 5 to 50 parts by weight, more preferably 10 to 40 parts by weight, are biomass-derived polyolefin resins (D);

[0205] Preferably, it is a polyolefin resin (E) other than a biomass-derived polyolefin resin (D), which is 1 to 45 parts by weight, more preferably 5 to 25 parts by weight.

[0206] Furthermore, as a preferred embodiment of this invention, the following embodiments can be listed:

[0207] A resin composition comprising a block copolymer (A) and a block copolymer (B) in a mass ratio [(A) / (B)] of 70 / 30 to 50 / 50, more preferably 65 / 35 to 55 / 45.

[0208] Relative to the total content of block copolymer (A) and block copolymer (B) in 100 parts by weight, it comprises:

[0209] 50 to 150 parts by weight, more preferably 60 to 100 parts by weight of plasticizer (C);

[0210] 50 to 150 parts by weight, preferably 70 to 90 parts by weight, of a biomass-derived polyolefin resin (D);

[0211] Preferably, it is a polyolefin resin (E) other than a biomass-derived polyolefin resin (D), which is 1 to 45 parts by weight, more preferably 5 to 25 parts by weight.

[0212] The total content of (A) to (E) in the resin composition of this embodiment is not particularly limited as long as the effects of the present invention can be obtained. On the other hand, in embodiments where environmental reduction is particularly important, the total content of (A) to (E) in the resin composition of this embodiment is preferably 85 to 100% by mass, more preferably 90 to 100% by mass, and even more preferably 95 to 100% by mass.

[0213] [additive]

[0214] In the resin composition of this embodiment, other additives and inorganic fillers besides the substances described above may be added without impairing the effects of the present invention.

[0215] Other additives include heat-resistant aging agents, antioxidants, light stabilizers, antistatic agents, mold release agents, flame retardants, foaming agents, pigments, dyes, and whitening agents. These additives can be used alone or in combination of two or more.

[0216] The content of other additives in the resin composition is preferably 15% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less. The content of other additives in the resin composition may, for example, be 0.01% by mass or more.

[0217] Specific examples of inorganic fillers include talc, calcium carbonate, silica, glass fiber, carbon fiber, mica, kaolin, and titanium dioxide. Among these, talc, calcium carbonate, and silica are preferred, and calcium carbonate and silica are particularly preferred. The content of the inorganic filler is not particularly limited, but from the viewpoint of balancing mechanical properties and reducing environmental impact, it is preferably 70% by mass or less in the resin composition, more preferably 50% by mass or less, further preferably 30% by mass or less, and most preferably 25% by mass or less. For example, the content of the inorganic filler in the resin composition can be set to 0.01% by mass or more.

[0218] Furthermore, in this embodiment, the content of polyester elastomer containing structural units derived from biomass in the resin composition is preferably 5% by mass or less, more preferably 1% by mass or less, and even more preferably 0% by mass. From the viewpoint of more easily suppressing the degradation of physical properties at low temperatures and obtaining better formability, it is one of the preferred embodiments that the resin composition of this embodiment does not contain polyester elastomer containing structural units derived from biomass.

[0219] [Method for manufacturing the resin composition]

[0220] The method for manufacturing the resin composition of this embodiment is not particularly limited, but examples include: pre-blending the above-described (A) to (D) and, as needed, the above-described (E), and further, other additives and inorganic fillers, and then performing melt mixing after blending. Melt mixing can be performed using a single-screw extruder, a multi-screw extruder, a Banbury mixer, heated rollers, various kneaders, etc. Alternatively, examples include: supplying the above-described (A) to (D) and, as needed, the above-described (E), and further, other additives and inorganic fillers from their respective feed ports and performing melt mixing.

[0221] In addition, pre-mixing methods include using mixers such as Henschel mixers, high-speed agitators, V-type mixers, belt mixers, rotary drum mixers, and conical mixers. The temperature during melt mixing can preferably be selected arbitrarily within the range of 150°C to 300°C.

[0222] [Biometrics]

[0223] The biomass of the resin composition in this embodiment is 37% by mass or more, preferably 40% by mass or more, and can be set to 44% by mass or more, or 46% by mass or more. Furthermore, the upper limit of biomass can be, for example, 98% by mass. The aforementioned biomass is an indicator of the petroleum dependence of the resin composition; by setting the biomass within the above range, petroleum dependence can be reduced.

[0224] The above biomass (mass%) is calculated based on the mass ratio of block copolymer (A) and polyolefin resin (D), the biomass of each component, and using the following formula.

[0225] Biological density (mass%) = (MA × XA / 100) + (MD × XD / 100)

[0226] In the above formula, MA represents the mass ratio (mass%) of the block copolymer (A) to the total mass of the resin composition, and MD represents the mass ratio (mass%) of the polyolefin resin (D) to the total mass of the resin composition. XA (mass%) represents the bioavailability of the block copolymer (A), and XD (mass%) represents the bioavailability of the polyolefin resin (D).

[0227] Surface roughness

[0228] As one of the preferred embodiments of the resin composition in this embodiment, the six-point standard deviation of the maximum height roughness Rz, measured according to JIS B 0601-2001, when the resin composition is surface-textured by injection molding, is preferably 12 or less.

[0229] The maximum height roughness Rz is the sum of the maximum mountain height and the maximum valley depth in the reference length along the average line direction of the roughness curve.

[0230] In this specification, a sample is prepared by injection molding to perform surface texturing on a resin composition. For this sample, the maximum height roughness Rz is measured at six locations according to JIS B 0601-2001. Figure 1 ), calculate the standard deviation. The smaller the standard deviation, the more uniform the surface texture transfer.

[0231] If the standard deviation is 12 or less, the surface texture can be considered to be uniformly transferred, resulting in excellent formability. Various conditions can be considered for the standard deviation to be 12 or less, and it is important that the resin composition of this embodiment contains a block copolymer (B). It can be considered that by including a block copolymer (B) in the resin composition, there is a tendency for tanδ to increase near the injection molding temperature (described later), resulting in uniform transfer of the surface texture. The standard deviation of the resin composition of this embodiment can also be set to 10 or less.

[0232] In this specification, the maximum height roughness Rz is a value measured using the method described in the embodiments described later.

[0233] [hardness]

[0234] The resin composition of this embodiment does not easily degrade in physical properties even at low temperatures. Therefore, the resin composition of this embodiment can maintain good hardness even at low temperatures.

[0235] As one of the preferred embodiments of the resin composition of this embodiment, it is preferable to satisfy the following formula (1).

[0236] [(Hardness at -16℃ / Hardness at 23℃) × 100 ≤ 120] (1)

[0237] In the above formula (1), "23℃ hardness" means the hardness measured at an atmosphere temperature of 23℃ using the Type A hardness tester method of JIS K 6253-2:2012.

[0238] Additionally, "-16℃ hardness" indicates the hardness measured at an ambient temperature of -16℃ using the Type A hardness tester method according to JIS K 6253-2:2012.

[0239] As a condition for satisfying the above formula (1), various conditions can be considered, and it is important that the resin composition of this embodiment contains a block copolymer (B).

[0240] Regarding hardness, more specifically, it is a value measured using the method described in the examples below.

[0241] <molded body>

[0242] The molded articles of the present invention are made using the resin composition of the present invention.

[0243] The shape of the molded body can be any shape that can be manufactured using the resin composition of the present invention. It can be molded into various shapes such as granules, films, sheets, plates, pipes, tubes, rods, and granules. The manufacturing method of the molded body is not particularly limited, and it can be formed by various conventional molding methods, such as injection molding, blow molding, compression molding, extrusion molding, calendering, etc.

[0244] The resin composition of this embodiment has excellent formability, and is therefore suitable for injection molding or extrusion molding, especially for injection molding of surface-textured parts with good appearance design.

[0245] <Applications>

[0246] It is expected that the environmental impact of the resin composition of the present invention will be reduced, and the formability will be excellent. In addition, the physical properties of the molded articles will not easily decrease even at low temperatures, and thus, the softness, weather resistance and rubber elasticity are excellent. Therefore, the resin composition and molded articles of the present invention can be suitable for use as molded articles such as sheets, films, tubes, hoses, and belts. Specifically, it can be applied to various vibration damping and shock absorption components such as anti-vibration rubber, pads, sheets, rubber pads, shock absorbers, linings, and fixing rubber; shoes such as sports shoes and fashionable sandals; components of household appliances such as televisions, audio equipment, vacuum cleaners, and refrigerators; building materials such as sealing fillers for door and window frames; interior and exterior trim components of automobiles such as bumper parts, body panels, weatherstripping, wheel rim gaskets, dashboards, and airbag covers; handles of golf clubs, tennis rackets, ski poles, bicycles, motorcycles, fishing gear, and equipment used in water sports and fitness; handles of tools and power tools such as hammers, screwdrivers, pliers, and wrenches; handles of water-related items such as kitchen utensils, toothbrushes, interdental brushes, razors, and bathtub handrails; handles of stationery such as pens and scissors; and gear shift levers and auxiliary knobs. Handles used in automotive interior and exterior trim such as knobs; bag handles; anti-slip materials for gloves, kitchen mats, etc.; toys; tires such as car tires, bicycle tires, and motorcycle tires, etc.

[0247] In addition, it can also be used for food packaging materials such as food preservation film; medical devices such as infusion bags, syringes, and catheters; and plugs and bottle cap liners for storing food, beverages, and medicines.

[0248] Example

[0249] The present invention will now be specifically described through examples and comparative examples, but the invention is not limited thereto. It should be noted that β-farnesene (purity: 97.6% by mass, biological concentration (ASTM D6866-16): 99%, Amyris, manufactured by Inco-Polyteide Co., Ltd.) is obtained by utilizing... The molecular sieve is purified and distilled under a nitrogen atmosphere to remove hydrocarbon impurities such as gingerene, bisabolene, farnesene epoxide, farnesol isomer, E,E-farnesol, squalene, ergosterol and various dimers of farnesene, so that it can be used for the following polymerization.

[0250] The components used in the examples and comparative examples are shown below.

[0251] <Block copolymer (A)>

[0252] The block copolymers (A-1) to (A-3) of Manufacturing Examples 1, 7, and 8 described later.

[0253] <Block copolymer (B)>

[0254] The block copolymers (B-1) to (B-5) of Manufacturing Examples 2 to 6 described later.

[0255] <Block copolymer (B')>

[0256] Block copolymer (B'-1)

[0257] SEBS, styrene-ethylene-butene-styrene block copolymer, vinyl bond content: 37 mol% (Product name: G1654, manufactured by Kraton Polymers).

[0258] Block copolymer (B'-2)

[0259] SEBS, styrene-ethylene-butene-styrene block copolymer (product name: G1642, vinyl bond content: 73 mol%, manufactured by Kraton Polymers).

[0260] Block copolymer (B'-3)

[0261] SEBS, styrene-ethylene-butene-styrene block copolymer (product name: G1651, vinyl bond content: 37 mol%, manufactured by Kraton Polymers)

[0262] <Plasticizer (C)>

[0263] Alkane-based process oil (Product name: Daiana Proces PW-90, manufactured by Idemitsu Kosan Co., Ltd.)

[0264] <Polyolefin Resins (D)>

[0265] Polyethylene: Bio-based LDPE polyethylene (Product name: SPB608, manufactured by Braskem, melt flow rate 30g / 10min (190℃, 21N), biocompatibility (ASTM D6866-16): 95% by mass)

[0266] <Polyolefin Resins (E)>

[0267] Polypropylene (E-1): Homopolymer polypropylene (Product name: J107G, manufactured by Polymer Corporation, MFR: 30g / 10 minutes (230℃, 21N))

[0268] Polypropylene (E-2): Block polypropylene (Product name: J707, manufactured by Polymer Corporation, MFR: 30g / 10 minutes (230℃, 21N))

[0269] Antioxidants

[0270] Hindered phenolic antioxidant (Product name: ADEKA AO-60, manufactured by ADEKA Corporation)

[0271] Details of the determination methods for the block copolymers (A) and (B) obtained in the manufacturing example are shown below.

[0272] (1) Determination of molecular weight distribution and peak molecular weight (Mp), etc.

[0273] The peak molecular weight (Mp) and molecular weight distribution (Mw / Mn) of block copolymers (A) and (B) and styrene blocks were determined by GPC (gel permeation chromatography) in the form of molecular weight converted from standard polystyrene. The peak molecular weight (Mp) was determined from the peak position of the molecular weight distribution. The measuring apparatus and conditions are shown below.

[0274] • Device: Tosoh Corporation, GPC device "HLC-8320GPC"

[0275] • Separation column: Tosoh Corporation, column "TSKgelSuperHZ4000"

[0276] • Eluent: Tetrahydrofuran

[0277] • Elution buffer flow rate: 0.7 mL / min

[0278] • Sample concentration: 5 mg / 10 mL

[0279] Column temperature: 40℃

[0280] (2) Method for determining hydrogenation rate

[0281] Block copolymers (A) and (B) before hydrogenation, as well as those after hydrogenation, were dissolved in CDCl3 and subjected to... 1 H-NMR determination [Apparatus "ADVANCE 400 Nano Bay" (Bruker Corporation), measurement temperature: 30°C]. The hydrogenation rate of carbon-carbon double bonds in the structural units derived from conjugated diene compounds in the unhydrogenated block copolymers (A) and (B) was calculated using the following formula based on the proton peaks of the carbon-carbon double bonds appearing at 4.5–6.0 ppm in the obtained spectra.

[0282] Hydrogenation rate (mol%) = {1 - (number of moles of carbon-carbon double bonds per mole of hydrogenated block copolymer (A) and block copolymer (B)) / (number of moles of carbon-carbon double bonds per mole of unhydrogenated block copolymer (A) and block copolymer (B))} × 100

[0283] (3) Vinyl bond content of block copolymer (A) and block copolymer (B)

[0284] In addition, details of the method for determining the vinyl bonding amount of the block copolymer (A) and block copolymer (B) obtained in the manufacturing example are shown below.

[0285] The unhydrogenated block copolymers (A) and (B) were dissolved in CDCl3 and subjected to... 1 H-NMR determination [Apparatus: "ADVANCE 400Nano bay" (manufactured by Bruker), measurement temperature: 30℃].

[0286] For the block copolymer (A), the amount of vinyl bonds was calculated based on the ratio of the peak areas corresponding to 1,2-bonds and 3,13-bonds in the β-farnesene structural unit to the total peak area of ​​the structural units derived from β-farnesene (Manufacturing Examples 1 and 7). It should be noted that the amount of vinyl bonds in Manufacturing Example 8 refers to the sum of the amounts of vinyl bonds in polymer block (a2) and polymer block (a3), calculated relative to the total peak areas of the structural units derived from β-farnesene (polymer block (a2)) and the structural units derived from butadiene (polymer block (a3)), corresponding to the peak areas corresponding to 1,2-bonds and 3,13-bonds in the β-farnesene structural unit and the peak areas corresponding to 1,2-bonds in the butadiene structural unit.

[0287] For the block copolymer (B), the amount of vinyl bonding is calculated based on the ratio of the peak area corresponding to the 3,4-bonded units and 1,2-bonded units in the isoprene structural unit and the 1,2-bonded units in the butadiene structural unit to the total peak area relative to the structural units derived from isoprene (manufacturing examples 3, 5) or structural units derived from butadiene and isoprene (manufacturing examples 2, 4, 6).

[0288] <Block copolymer (A)>

[0289] [Manufacturing Example 1]

[0290] Block copolymer (A-1)

[0291] 50.0 kg of cyclohexane as a solvent and 0.0155 kg of sec-butyllithium (10.5% by mass cyclohexane solution) as an anionic polymerization initiator were added to a pressure-resistant container that had been purged with nitrogen and dried. After heating to 50°C, 1.32 kg of styrene (1) was added and polymerization was carried out for 1 hour. Then, 6.18 kg of β-farnesene was added and polymerization was carried out for 2 hours. Finally, 1.32 kg of styrene (2) was added and polymerization was carried out for 1 hour to obtain a reaction solution containing polystyrene-poly(β-farnesene)-polystyrene triblock copolymer.

[0292] Palladium on carbon (palladium loading: 5% by mass relative to the block copolymer) was added as a hydrogenation catalyst to the above reaction solution, and the reaction was carried out for 10 hours at a hydrogen pressure of 2 MPa and a temperature of 150°C. After natural cooling and pressure release, the hydrogenation catalyst was removed by filtration, the filtrate was concentrated, and then vacuum dried to obtain the hydride of polystyrene-poly(β-farnesene)-polystyrene triblock copolymer (block copolymer (A-1)).

[0293] The biocompatibility of the resulting block copolymer (A-1) was 68% by mass, as measured according to ASTM D6866-16.

[0294] In addition, the above-mentioned physical properties were measured for the block copolymer (A-1). The results are shown in Table 1.

[0295] <Block copolymer (B)>

[0296] [Manufacturing Example 2]

[0297] Block copolymer (B-1)

[0298] 50.0 kg of cyclohexane as a solvent and 0.0531 kg of sec-butyllithium (10.5% by mass cyclohexane solution) as an anionic polymerization initiator were added to a pressure-resistant container that had been purged with nitrogen and dried. After heating to 50°C, 1.41 kg of styrene (1) was added and polymerization was carried out for 1 hour. A mixture of 3.44 kg of isoprene and 2.66 kg of butadiene was added and polymerization was carried out for 2 hours. Then, 1.41 kg of styrene (2) was added and polymerization was carried out for 1 hour to obtain a reaction solution containing polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer.

[0299] Palladium on carbon (palladium loading: 5% by mass) as a hydrogenation catalyst was added to the above reaction solution, relative to the above block copolymer, and the reaction was carried out for 10 hours at a hydrogen pressure of 2 MPa and a temperature of 150°C. After natural cooling and pressure release, the hydrogenation catalyst was removed by filtration, the filtrate was concentrated, and then vacuum dried to obtain the hydrogenated polystyrene-poly(isoprene / butadiene)-polystyrene triblock copolymer (block copolymer (B-1)).

[0300] In addition, the above-mentioned physical properties were measured for the block copolymer (B-1). The results are shown in Table 1.

[0301] [Manufacturing Examples 3-6]

[0302] Block copolymers (B-2) to (B-5)

[0303] The raw materials and their amounts are set as shown in Table 1. Otherwise, the block copolymers (B-2) to (B-5) are manufactured according to the same steps as in Manufacturing Example 2.

[0304] The above-mentioned physical properties were determined for the obtained block copolymers (B-2) to (B-5). The results are shown in Table 1.

[0305] <Block copolymer (A)>

[0306] [Manufacturing Example 7]

[0307] Block copolymer (A-2)

[0308] The raw materials and their amounts are shown in Table 1. Otherwise, the block copolymer (A-2) is manufactured following the same steps as in Manufacturing Example 1.

[0309] The biocompatibility of the resulting block copolymer (A-2), as measured according to ASTM D6866-16, was 80% by mass.

[0310] In addition, the above-mentioned physical properties were measured for the block copolymer (A-2). The results are shown in Table 1.

[0311] [Manufacturing Example 8]

[0312] Block copolymer (A-3)

[0313] 50.0 kg of cyclohexane as a solvent, 0.1905 kg of sec-butyllithium (10.5% by mass cyclohexane solution) as an anionic polymerization initiator, and 0.4007 kg of tetrahydrofuran as a Lewis base were added to a pressure-resistant container that had been purged with nitrogen and dried. After heating to 50°C, 6.34 kg of β-farnesene was added, and polymerization was carried out for 2 hours. Then, 2.50 kg of styrene was added, and polymerization was carried out for 1 hour. Next, 3.66 kg of butadiene was added, and polymerization was carried out for 1 hour. Then, 0.0202 kg of dichlorodimethylsilane as a coupling agent was added to the polymerization reaction solution, and the reaction was carried out for 1 hour, thereby obtaining a reaction solution containing a poly(β-farnesene)-polystyrene-polybutadiene-polystyrene-poly(β-farnesene) pentablock copolymer.

[0314] Palladium on carbon (palladium loading: 5% by mass relative to the above block copolymer) was added to the reaction solution as a hydrogenation catalyst, and the reaction was carried out for 10 hours at a hydrogen pressure of 2 MPa and a temperature of 150°C. After natural cooling and pressure release, the palladium on carbon was removed by filtration, the filtrate was concentrated, and then vacuum dried to obtain the hydride of poly(β-farnesene)-polystyrene-polybutadiene-polystyrene-poly(β-farnesene) pentablock copolymer (block copolymer (A-3)).

[0315] The biocompatibility of the resulting block copolymer (A-3), as measured according to ASTM D6866-16, was 48% by mass.

[0316] In addition, the above-mentioned physical properties were measured for the block copolymer (P-2). The results are shown in Table 1.

[0317] [Table 1]

[0318]

[0319] It should be noted that the statements in Table 1 are as follows.

[0320] [(a1) / (a2)+(a3)] or [(b1) / (b2)]:

[0321] [(a1) / (a2)+(a3)] represents the mass ratio of the content of polymer block (a1) to the content of polymer block (a2) (and polymer block (a3)).

[0322] [(b1) / (b2)] represents the mass ratio of the content of polymer block (b1) to the content of polymer block (b2).

[0323] Polymer backbone:

[0324] St-F-St indicates a polystyrene-poly(β-farnesene)-polystyrene triblock copolymer.

[0325] St-(Bd / Ip)-St represents polystyrene-poly(butadiene / isoprene)-polystyrene triblock copolymer.

[0326] St-Ip-St indicates a polystyrene-poly(isoprene)-polystyrene triblock copolymer.

[0327] F-St-Bd-St-F represents a poly(β-farnesene)-polystyrene-polybutadiene-polystyrene-poly(β-farnesene) pentablock copolymer.

[0328] [Examples 1-11][Comparative Examples 1-4]

[0329] Premix each component according to the proportions shown in Tables 2 and 3.

[0330] Next, using a twin-screw extruder (Coperion ZSK26Mc; number of barrels: 14), the premixed composition was fed into the hopper at a barrel temperature of 200°C and a screw speed of 300 rpm. Then, it was melt-blended and extruded into filaments for cutting to produce granules of the resin composition.

[0331] <Measurement and Evaluation>

[0332] The resin compositions obtained in the above examples and comparative examples were used to perform the following measurements and evaluations. The results are shown in Tables 2 and 3.

[0333] (1) Biocompatibility of the resin composition

[0334] Based on the mass ratio of the block copolymer (A) and polyolefin resin (D) used in the above examples and comparative examples, and the bioavailability of each component, the bioavailability (mass %) of the resin composition was calculated using the following formula.

[0335] Biological density (mass%) = (MA × XA / 100) + (MD × XD / 100)

[0336] In the above formula, MA represents the mass ratio (mass%) of the block copolymer (A) relative to the total mass of the resin composition, and MD represents the mass ratio (mass%) of the polyolefin resin (D) relative to the total mass of the resin composition. XA (mass%) represents the bioavailability of the block copolymer (A), and XD (mass%) represents the bioavailability of the polyolefin resin (D).

[0337] (2) Hardness

[0338] (2-1) Preparation of sheets of resin composition

[0339] Using an injection molding machine “EC75SX” (manufactured by Toshiba Machine Co., Ltd.), under the conditions of barrel temperature of 210°C, mold temperature of 40°C and injection pressure of 80MPa, the granules of the resin compositions obtained in each example were injection molded to produce injection sheets with a length of 110mm, a width of 110mm and a thickness of 2mm.

[0340] (2-2) Hardness determination

[0341] Using a punching tool based on JIS K 6251:2010, dumbbell-shaped test pieces (2 mm) were obtained from the above injection sheet.

[0342] The three test pieces were overlapped, and the hardness of the 6mm thick piece was measured using the indenter of a type A hardness tester in a constant temperature bath at room temperature of 23℃ and -16℃, in accordance with JIS K 6253-3:2012.

[0343] The INDEX is calculated using the values ​​measured at room temperature (23°C) and in a constant temperature bath at -16°C, according to the following formula.

[0344] (Hardness at -16℃ / Hardness at 23℃) × 100 ≤ 120

[0345] (3) Surface roughness

[0346] In a mold with dimensions of 100mm×35mm×5mm and a single-sided surface textured finish (average maximum height roughness of 34μm), the resin composition granules obtained in each example were injection molded at a barrel temperature of 210°C and a mold temperature of 40°C to produce surface-textured sheets.

[0347] For the surface texture (undulation) of the above-mentioned sheet, a Surfcorder SE1700α (manufactured by Kosaka Research Institute Co., Ltd.) was used, and the following measurement conditions were applied according to JIS B 0601-2001. Figure 1 The surface roughness was measured at the six locations shown, and the standard deviation was calculated. The smaller the standard deviation, the more uniform the surface texture transfer.

[0348] (Measurement conditions)

[0349] • Stylus R: 2μm

[0350] • Conveying speed: 0.500mm / s

[0351] Cutoff value: λc = 0.800 mm

[0352] • Measurement length: 4.000 mm

[0353] • Filter: GAUSS (ASME)

[0354] (4) Determination of tanδ

[0355] Cut a disc-shaped test piece with a diameter of 8 mm and a thickness of 2 mm from the sheet prepared in (2-1) above. For this test piece, perform dynamic viscoelasticity measurements using an ARES-G2 rheometer (manufactured by TA Instruments) under the following conditions, and calculate tanδ at 150°C and 180°C.

[0356] (Apparatus and conditions for measuring dynamic viscoelasticity)

[0357] Parallel plate: 8mm in diameter

[0358] • Vibration mode: Torsional vibration

[0359] • Deformation: 0.1%

[0360] • Frequency: 1Hz

[0361] • Measurement temperature: 200℃~40℃ (rapid cooling)

[0362] Cooling rate: 46℃ / minute

[0363] [Table 2]

[0364]

[0365] [Table 3]

[0366] Table 3

[0367]

[0368] It should be noted that the statements in Tables 2 to 4 are as follows.

[0369] • “Parts” refers to the mass parts of the resin composition.

[0370] • "%" refers to the percentage by mass in the resin composition.

[0371] According to Table 2, the comparison between Examples 1-2 and Comparative Example 1, Examples 3-4 and Comparative Example 2, and Examples 5-7 and Comparative Examples 3 and 4 shows that the resin compositions and molded articles of the examples do not have excessively high hardness even at low temperatures, and the hardness change at low temperatures is also minimal. Furthermore, the above comparisons show that the standard deviation of the surface roughness of the resin compositions and molded articles of the examples is small, and the surface texture is well transferred.

[0372] Furthermore, according to Table 3, the resin compositions and molded articles of Examples 8 to 11 showed little change in hardness even at low temperatures, and the surface texture was well transferred.

[0373] Therefore, as can be seen from the embodiments, it is possible to obtain resin compositions and molded articles that have reduced environmental burden, do not easily degrade physical properties at low temperatures, and have excellent formability.

[0374] Industrial utilization

[0375] It is expected that the environmental impact of the resin composition of the present invention will be reduced, and the formability will be excellent. In addition, the physical properties of the molded article will not easily decrease at low temperatures, and thus, the softness, weather resistance and rubber elasticity are all excellent. Therefore, the resin composition and molded article of the present invention can be suitable for use as molded articles such as sheets, films, tubes, hoses, and belts.

[0376] Explanation of reference numerals in the attached figures

[0377] G: Gate.

Claims

1. A resin composition comprising a block copolymer (A), a block copolymer (B), a plasticizer (C), and a biomass-derived polyolefin resin (D), The block copolymer (A) comprises polymer block (a1) and polymer block (a2), wherein polymer block (a1) contains structural units derived from aromatic vinyl compounds, and polymer block (a2) contains 50-100% by mass structural units derived from farnesene. The block copolymer (B) comprises polymer block (b1) and polymer block (b2), wherein polymer block (b1) contains structural units derived from aromatic vinyl compounds, and polymer block (b2) contains more than 30 mol% structural units derived from isoprene. The aromatic vinyl compound in the polymer block (b1) is styrene, and the content of the aromatic vinyl compound in the polymer block (b1) is 60% by mass or more. The structural units constituting the polymer block (b2) are either structural units derived from isoprene or structural units derived from a mixture of isoprene and butadiene. The biocompatibility of the resin composition is above 37% by mass. The biomass-derived polyolefin resin (D) has a biomass content of 70% by mass or higher. The biometrics is an indicator of the proportion of biologically derived substances in the target material, as measured according to ASTM D6866-16. The resin composition comprises the block copolymer (A) and the block copolymer (B) in a mass ratio of 99 / 1 to 1 / 99 [(A) / (B)], Relative to the total content of the block copolymer (A) and the block copolymer (B) in 100 parts by mass, It comprises 1 to 350 parts by weight of the plasticizer (C) and 1 to 200 parts by weight of the biomass-derived polyolefin resin (D).

2. The resin composition according to claim 1, wherein, The hydrogenation rate of the carbon-carbon double bonds in the structural units derived from the conjugated diene compound in the block copolymer (A) is above 70 mol%.

3. The resin composition according to claim 1 or 2, wherein, The aromatic vinyl compound in the polymer block (a1) is styrene.

4. The resin composition according to claim 1 or 2, wherein, The content of polymer blocks (a1) in the block copolymer (A) is 1-65% by mass.

5. The resin composition according to claim 1 or 2, wherein, The peak molecular weight of the block copolymer (A), determined by gel permeation chromatography and converted to standard polystyrene, is 50,000 to 600,000.

6. The resin composition according to claim 1 or 2, wherein, The hydrogenation rate of the carbon-carbon double bonds in the structural units derived from conjugated diene compounds in the block copolymer (B) is above 70 mol%.

7. The resin composition according to claim 1 or 2, wherein, The content of polymer blocks (b1) in the block copolymer (B) is 1-65% by mass.

8. The resin composition according to claim 1 or 2, wherein, The peak molecular weight of the block copolymer (B), determined by gel permeation chromatography and converted to standard polystyrene, is 50,000 to 600,000.

9. The resin composition according to claim 1 or 2, wherein, The vinyl bond content of the block copolymer (B) is 1 to 35 mol.

10. The resin composition according to claim 1 or 2, wherein, The plasticizer (C) is process oil.

11. The resin composition according to claim 1 or 2, wherein, The block copolymer (A) and the block copolymer (B) contain a mass ratio [(A) / (B)] of 95 / 5 to 20 / 80. Relative to the total content of the block copolymer (A) and the block copolymer (B) in 100 parts by mass, It comprises 5 to 350 parts by weight of the plasticizer (C) and 1 to 150 parts by weight of the biomass-derived polyolefin resin (D).

12. The resin composition according to claim 1 or 2, wherein, Relative to the total content of the block copolymer (A) and the block copolymer (B) in 100 parts by mass, It also contains 1 to 100 parts by weight of a polyolefin resin (E) other than the biomass-derived polyolefin resin (D).

13. The resin composition according to claim 12, wherein, The polyolefin resin (E) is polypropylene.

14. The resin composition according to claim 1 or 2, wherein, When surface finishing is performed by injection molding, the standard deviation of the maximum height roughness Rz measured according to JIS B0601-2001 at 6 points shall be less than 12.

15. The resin composition according to claim 1 or 2, which satisfies the following formula (1), [(Hardness at -16℃ / Hardness at 23℃) × 100 ≤ 120] (1) In the above formula (1), The 23℃ hardness was measured using the Type A hardness tester method according to JIS K 6253-2:2012 at an ambient temperature of 23℃. The -16℃ hardness was measured using the Type A hardness tester method according to JIS K 6253-2:2012 at an ambient temperature of -16℃.

16. A molded article made using the resin composition according to any one of claims 1 to 15.

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