Polymer composition and molded article

Abstract

The present invention provides a polymer composition having a desired degree of bio-basedness and excellent mechanical properties, and a molded article made therefrom. [Solution] The polymer composition according to the present invention is a polymer composition containing (A) a bio-based polyolefin and (B) a hydrogenated block copolymer, wherein (B) the hydrogenated block copolymer is a hydrogenated polymer satisfying the following conditions (a) to (d), and contains a polymer in which 50 mol% or more of the structural units derived from butadiene are hydrogenated. (a) The number of polymer blocks mainly composed of aromatic vinyl compounds is 0 or 1. (b) Having a polybutadiene block with a vinyl group content of 20% or less. (c) Having a polymer block mainly composed of a conjugated diene compound having a vinyl group content of more than 20%, wherein the content of the polymer block mainly composed of the conjugated diene compound is 85% by mass or less of the total mass of the (B) hydrogenated block copolymer. (d) The weight-average molecular weight is between 50,000 and 500,000.

Description

[Technical Field]

[0001] This invention relates to polymer compositions and molded articles. [Background technology]

[0002] In recent years, with growing awareness of global environmental issues, there has been a growing momentum to reduce plastic use and switch to materials that do not rely on fossil fuels, and such initiatives are spreading in various fields and applications. For example, from the perspective of reducing the use of fossil fuels, biopolymers made from plant-derived monomers are attracting attention as carbon-neutral materials.

[0003] As for compositions using biopolymers, compositions containing bio-based polyethylene (bioPE), styrene-based hydrogenated block copolymer, and acrylonitrile / styrene-based resin (AS-based resin) have been proposed (see, for example, Patent Document 1). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2024-059224 [Overview of the project] [Problems that the invention aims to solve]

[0005] Biopolymers have been used in various applications to reduce the use of fossil fuels, but biopolymers alone do not provide sufficient mechanical properties. Therefore, methods for modifying the mechanical properties of molded articles containing biopolymers are being investigated.

[0006] Some aspects of the present invention provide polymer compositions having a desired degree of biobase and excellent mechanical properties, and molded articles made therefrom. [Means for solving the problem]

[0007] The present invention has been made to solve at least some of the above-mentioned problems and can be realized in any of the following embodiments.

[0008] One embodiment of the polymer composition according to the present invention is: A polymer composition containing (A) a bio-based polyolefin and (B) a hydrogenated block copolymer, The (B) hydrogenated block copolymer is a hydrogenated polymer that satisfies the following conditions (a) to (d), and contains a polymer in which 50 mol% or more of the structural units derived from butadiene are hydrogenated. (a) The number of polymer blocks mainly composed of aromatic vinyl compounds is 0 or 1. (b) Having a polybutadiene block with a vinyl group content of 20% or less. (c) Having a polymer block mainly composed of a conjugated diene compound having a vinyl group content of more than 20%, wherein the content of the polymer block mainly composed of the conjugated diene compound is 85% by mass or less of the total mass of the (B) hydrogenated block copolymer. (d) The weight-average molecular weight is between 50,000 and 500,000.

[0009] In one embodiment of the polymer composition, The aforementioned component (B) may satisfy the following formula (A) when the constituent ratios of the structural units represented by formula (1), formula (2), formula (3), and formula (4) are p, q, r, and s, respectively. 0.50≦(p+(0.5×r)) / (p+q+(0.5×r)+s)≦0.98 ...(A) [ka]

[0010] In any embodiment of the polymer composition, (C) a thermoplastic resin (excluding the aforementioned (A) bio-based polyolefin) may be further contained.

[0011] In any embodiment of the polymer composition, The component (C) may contain at least one selected from the group consisting of acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, polyester-based resin and polyolefin-based resin.

[0012] In any embodiment of the polymer composition, When the total amount of the component (A), the component (B) and the component (C) is 100 parts by mass, the content of the component (B) may be 1 to 20 parts by mass.

[0013] In any embodiment of the polymer composition, The mass ratio (C / A) of the component (C) to the component (A) is 85 / 15 to 15 / 85, and the mass ratio (A / B) of the component (A) to the component (B) may be 99 / 1 to 50 / 50.

[0014] One aspect of the injection-molded article according to the present invention is obtained by injection-molding the polymer composition according to any one of the foregoing aspects.

[0015] One aspect of the blow-molded article according to the present invention is obtained by blow-molding the polymer composition according to any one of the foregoing aspects.

[0016] One aspect of the extrusion-molded article according to the present invention is obtained by extrusion-molding the polymer composition according to any one of the foregoing aspects.

Effects of the Invention

[0017] According to the polymer composition of the present invention, a polymer composition and a molded article having a desired bio-based content and excellent mechanical physical properties can be obtained.

Mode for Carrying Out the Invention

[0018] Preferred embodiments of the present invention will be described in detail below. It should be understood that the present invention is not limited to the embodiments described below, but also includes various modifications that do not alter the essence of the invention.

[0019] In this specification, a numerical range described using "X~Y" means that the numerical value X is included as the lower limit and the numerical value Y is included as the upper limit.

[0020] 1. Polymer composition A polymer composition according to one embodiment of the present invention contains (A) a bio-based polyolefin (hereinafter also referred to as "component (A)") and (B) a hydrogenated block copolymer (hereinafter also referred to as "component (B)"). The components that may be included in the polymer composition according to this embodiment will be described below.

[0021] 1.1.(A) Bio-based polyolefins The polymer composition according to this embodiment contains (A) a bio-based polyolefin. (A) A bio-based polyolefin refers to a polyolefin using plant-derived monomers or a polyolefin having a mass-balance biomass allocation ratio (hereinafter also referred to as "mass-balance polyolefin"). Examples of plants that can be used as raw materials for plant-derived monomers include corn, sugarcane, and cassava. First, the sugars obtained from these plants are fermented to produce bioethanol, and ethylene and propylene, which are raw materials for polyolefins, are produced from this bioethanol.

[0022] (A) When the bio-based polyolefin is a polyolefin synthesized using plant-derived monomers, it is preferable that it be an ethylene homopolymer, a propylene homopolymer, a copolymer of ethylene and α-olefin, or a copolymer of propylene and α-olefin, having a bio-basedness of 80% or more and 100% or less as defined in ASTM D6866. (A) The bio-based polyolefin may be a single bio-based polyolefin or a combination of multiple bio-based polyolefins having different bio-basednesses.

[0023] From this viewpoint, when (A) the bio-based polyolefin is a polyolefin synthesized using plant-derived monomers, it is preferable that the bio-basedness as defined in ASTM D6866 be 80% or more, more preferably 85% to 100%, even more preferably 90% to 100%, and particularly preferably 95% to 100%. In view of the purpose of introducing a desired bio-basedness into the polymer composition according to this embodiment, it is preferable that the bio-basedness of (A) the bio-based polyolefin be a reasonably high value.

[0024] (A) If the bio-based polyolefin is a mass-balance type polyolefin, using the mass-balance type (A) bio-based polyolefin can reduce the use of fossil resources and contribute to the realization of a carbon-neutral society. Furthermore, it can expand the range of applications for recycled products and lead to a circular economy.

[0025] (A) When the bio-based polyolefin is a mass-balance polyolefin, it is preferable that it be an ethylene homopolymer, a propylene homopolymer, a copolymer of ethylene and α-olefin, or a copolymer of propylene and α-olefin, with a biomass allocation rate of 80% or more and 100% or less. The biomass allocation rate is preferably 80% or more, more preferably 85% or more and 100%, even more preferably 90% or more and 100%, and particularly preferably 95% or more and 100% or less.

[0026] As bio-based polyethylene, polyethylenes such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), and linear low-density polyethylene (LLDPE) can be suitably used.

[0027] (A) The preferred MFR value for bio-based polyolefins is 230°C and 21.2N load. Under these conditions, the MFR value is preferably 0.1 to 30, more preferably 0.2 to 15, even more preferably 0.5 to 10, and particularly preferably 1 to 5. By using (A) bio-based polyolefin having an MFR value in this range, polymer compositions and molded articles with excellent mechanical properties can be obtained.

[0028] The density range of bio-based polyethylene is 0.91 to 0.97 (g / cm³). 3 The density range for bio-based polypropylene is 0.90 to 0.91 (g / cm³). 3 It is within the range of ).

[0029] From the viewpoint of compatibility, the content of (A) bio-based polyolefin in the polymer composition according to this embodiment is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more, when the total mass of the polymer composition is 100% by mass. The content of (A) bio-based polyolefin in the polymer composition according to this embodiment is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less, when the total mass of the polymer composition is 100% by mass. The content of (A) bio-based polyolefin in the polymer composition according to this embodiment is preferably 5% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 85% by mass or less, and particularly preferably 15% by mass or more and 80% by mass or less.

[0030] 1.2.(B) Hydrogenated block copolymer The polymer composition according to this embodiment contains (B) hydrogenated block copolymer. (B) hydrogenated block copolymer is a hydrogenated polymer that satisfies the following conditions (a) to (d), and contains a polymer in which 50 mol% or more of the structural units derived from butadiene are hydrogenated. (a) The number of polymer blocks mainly composed of aromatic vinyl compounds is 0 or 1. (b) Having a polybutadiene block with a vinyl group content of 20% or less. (c) Having a polymer block mainly composed of a conjugated diene compound having a vinyl group content of more than 20%, wherein the content of the polymer block mainly composed of the conjugated diene compound is 85% by mass or less of the total mass of the (B) hydrogenated block copolymer. (d) The weight-average molecular weight is between 50,000 and 500,000.

[0031] (B) A hydrogenated block copolymer is a block copolymer having polymer block A mainly composed of aromatic vinyl compounds, polymer block B mainly composed of conjugated diene compounds with a vinyl group content of more than 20%, and polybutadiene block C with a vinyl group content of 20% or less. (B) A hydrogenated block copolymer has 0 or 1 polymer block A mainly composed of aromatic vinyl compounds. (B) A hydrogenated block copolymer has 1 or more polymer blocks B mainly composed of conjugated diene compounds with a vinyl group content of more than 20%. (B) A hydrogenated block copolymer has 1 or more polybutadiene blocks C with a vinyl group content of 20% or less.

[0032] (B) From the viewpoint of balancing the rigidity and impact strength of the molded article of the polymer composition, the hydrogenated block copolymer preferably contains 0 to 20% by mass of polymer block A mainly composed of aromatic vinyl compounds, more preferably 0 to 15% by mass, and particularly preferably 0 to 10% by mass.

[0033] (B) The hydrogenated block copolymer contains 85% by mass or less of polymer block B, mainly composed of a conjugated diene compound with a vinyl group content of more than 20%, preferably 40-85% by mass, more preferably 43-80% by mass, and particularly preferably 45-75% by mass, from the viewpoint of balancing the rigidity and impact strength of the molded article of the polymer composition.

[0034] (B) Hydrogenated block copolymers have a balance between the rigidity and impact strength of the molded polymer composition. From this viewpoint, it is preferable to contain 10 to 60% by mass of polybutadiene block C having a vinyl group content of 20% or less, more preferably 15 to 50% by mass, and particularly preferably 20 to 45% by mass.

[0035] "Vinyl group content" refers to the total percentage (on a mol% basis) of conjugated diene compound units incorporated in the polymer block before hydrogenation in the form of 1,2-linked, 3,4-linked, and 1,4-linked bonds, specifically those incorporated in the form of 1,2-linked and 3,4-linked bonds. The vinyl group content is as follows: 1This can be determined by 1H-NMR.

[0036] (B) The hydrogenated block copolymer contains a polymer in which 50 mol% or more of the structural units derived from butadiene are hydrogenated. By hydrogenating the structural units derived from butadiene, an olefin structure is formed, improving compatibility with (A) bio-based polyolefins.

[0037] (B) The hydrogenated block copolymer is preferably satisfied with the following formula (A) when the constituent ratios (molar ratios) of the structural units represented by the following formula (1), the following formula (2), the following formula (3), and the following formula (4) in the polymer are p, q, r, and s, respectively. 0.50≦(p+(0.5×r)) / (p+q+(0.5×r)+s)≦0.98 ...(A) [ka]

[0038] A value expressed as (p + (0.5 × r)) / (p + q + (0.5 × r) + s) in the above formula (A) (hereinafter also referred to as the "α value") being between 0.50 and 0.98 indicates that the (B) hydrogenated block copolymer is a highly saturated conjugated diene polymer. The α value is preferably 0.50 or higher, more preferably 0.60 or higher, and particularly preferably 0.70 or higher. The α value is preferably 0.97 or lower, more preferably 0.95 or lower, and particularly preferably 0.92 or lower. If the α value is less than 0.50, the amount of unsaturated bonds in the (B) hydrogenated block copolymer is high, which tends to make the quality of the (B) hydrogenated block copolymer unstable. On the other hand, if the α value exceeds 0.98, there is a tendency for the rigidity and impact strength of the molded article to decrease.

[0039] The α value represented by the above formula (A) corresponds to the hydrogenation rate of the (B) hydrogenated block copolymer. For example, if α is 0.50, the hydrogenation rate of the (B) hydrogenated block copolymer is 50%. The hydrogenation rate and α value of the (B) hydrogenated block copolymer can be controlled by adjusting the type and amount of hydrogenation catalyst, the time of the hydrogenation reaction, and the cumulative amount of hydrogen supplied. In this specification, the hydrogenation rate is 1 These values ​​were measured using an H-NMR spectrometer. In formula (A) above, when the constituent ratio of each structural unit of formulas (1) to (4) in the polymer is expressed in mol%, p, q, r, and s can each take values ​​from 0 to 100% (however, the sum of p, q, r, and s is 100% or less).

[0040] (B) Polymer block A, which constitutes the hydrogenated block copolymer and is mainly composed of aromatic vinyl compounds, is a polymer block containing 90% by mass or more of structural units derived from aromatic vinyl compounds. It is preferable that this is the case. Furthermore, polymer block B, which constitutes the hydrogenated block copolymer and is mainly composed of a conjugated diene compound having a vinyl group content of more than 20%, may be a polymer block consisting solely of structural units derived from the conjugated diene compound, or it may be a copolymer block of structural units derived from the conjugated diene compound and structural units derived from the aromatic vinyl compound. In the case of copolymer blocks, various copolymer block structures can be adopted, such as a uniform random structure or a tapered structure (where the monomer composition ratio changes along the chain).

[0041] (B) The hydrogenated block copolymer may be a combination of two or more block copolymers having different average molecular weights, or a combination of two or more block copolymers having different copolymerization ratios between structural units derived from a conjugated diene compound and structural units derived from an aromatic vinyl compound. (B) The hydrogenated block copolymer may optionally contain structural units derived from other polymerizable monomers other than structural units derived from a conjugated diene compound and structural units derived from an aromatic vinyl compound.

[0042] (B) Polymer block A, which constitutes the hydrogenated block copolymer and is mainly composed of aromatic vinyl compounds, can be formed using aromatic vinyl compounds. Examples of aromatic vinyl compounds include styrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, α-methylstyrene, 2,4-dimethylstyrene, 2,4-diisopropylstyrene, 4-tert-butylstyrene, 5-tert-butyl-2-methylstyrene, vinylethylbenzene, divinylbenzene, trivinylbenzene, divinylnaphthalene, tert-butoxystyrene, vinylbenzyldimethylamine, (4-vinylbenzyl)dimethylaminoethyl ether, N,N-dimethylaminoethylstyrene, N,N-dimethylaminomethylstyrene, 2-ethylstyrene, 3-ethylstyrene, 4-ethylstyrene, 2-tert-butylstyrene, 3-tert-butylstyrene, vinylxylene, vinylnaphthalene, vinylpyridine, diphenylethylene, and tertiary amino group-containing diphenylethylene (e.g., 1-(4-N,N-dimethylaminophenyl)-1-phenylethylene). Among these, styrene and α-methylstyrene, or both, are preferred as aromatic vinyl compounds. The aromatic vinyl compounds may be used individually or in combination of two or more.

[0043] (B) Polymer block B, which constitutes the hydrogenated block copolymer and is mainly composed of a conjugated diene compound having a vinyl group content of more than 20%, can be formed using 1,3-butadiene and optionally other conjugated diene compounds or aromatic vinyl compounds. Examples of other conjugated diene compounds include isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 1,3-hexadiene, 1,3-heptadiene, 2-phenyl-1,3-butadiene, 3-methyl-1,3-pentadiene, and 2-chloro-1,3-butadiene. Other conjugated diene compounds may be used individually or in combination of two or more. As aromatic vinyl compounds, the compounds exemplified above can be used, individually or in combination of two or more.

[0044] (B) In the hydrogenated block copolymer, it is preferable that 70 mass% or more of the entire constituent units of the polymer block B, which is mainly composed of a conjugated diene compound and has a vinyl group content of more than 20%, are constituent units derived from 1,3-butadiene.

[0045] The content of the aromatic vinyl compound in the polymer block B (aromatic vinyl content) is preferably 0 to 30 mass%, more preferably 0 to 25 mass%, and particularly preferably 0 to 20 mass%. The aromatic vinyl content in the polymer block B is 1 measurable by 1H-NMR.

[0046] (B) The polybutadiene constituting the hydrogenated block copolymer and having a vinyl group content of 20% or less Block C can be formed by using 1,3-butadiene.

[0047] (B) In the hydrogenated block copolymer, the mass ratio of the structural units derived from an aromatic vinyl compound to the structural units derived from a conjugated diene compound is preferably in the range of (structural units derived from an aromatic vinyl compound) / (structural units derived from a conjugated diene compound) = 0 / 100 to 25 / 75, more preferably 0 / 100 to 20 / 80, and particularly preferably 0 / 100 to 15 / 85. When the ratio of each structural unit is within the above range, the obtained polymer composition has a better balance between rigidity and impact strength.

[0048] (B) Examples of the hydrogenated block copolymer include A-(B-C) n , A-(C-B) n , A-(B-C-B) n , A-(C-B-C) n , (B-C-B) n , (C-B-C) n , (B-C) n , A-(B-C) n X, A-(C-B) n X, A-(B-C-B) n X, A-(C-B-C) n X, (B-C-B)n X, (CBC) n X, (CB) n X, (BC) n X is an example. Here, A represents a polymer block mainly composed of aromatic vinyl compounds, B represents a polymer block mainly composed of conjugated diene compounds with a vinyl group content of more than 20%, and C represents a polybutadiene block C with a vinyl group content of 20% or less. Also, n represents any integer from 1 to 6. X represents a coupling agent residue.

[0049] (B) For hydrogenated block copolymers, the weight-average molecular weight (Mw) in polystyrene terms, measured using gel permeation chromatography (GPC), is preferably 50,000 to 500,000 from the viewpoint of obtaining molded articles with excellent rigidity and impact strength. (B) The weight-average molecular weight (Mw) of hydrogenated block copolymers is preferably 70,000 or more, and more preferably 80,000 or more. (B) The weight-average molecular weight (Mw) of hydrogenated block copolymers is preferably 450,000 or less, and more preferably 400,000 or less. (B) The weight-average molecular weight (Mw) of hydrogenated block copolymers is preferably 70,000 to 450,000, and more preferably 80,000 to 400,000. Note that the weight-average molecular weight of hydrogenated block copolymers is the value obtained from all peaks of the GPC curve measured by GPC before hydrogenation.

[0050] (B) The preferred MFR value of the hydrogenated block copolymer is preferably 0.1 to 30, more preferably 0.2 to 15, even more preferably 0.5 to 10, and particularly preferably 1 to 5, under conditions of 230°C and a 21.2N load. By using the (B) hydrogenated block copolymer having an MFR value within this range, polymer compositions and molded articles with excellent mechanical properties can be obtained.

[0051] The block copolymer before hydrogenation can be obtained, for example, by living anionic polymerization of a conjugated diene compound and, if necessary, an aromatic vinyl compound in an inert organic solvent such as an aliphatic hydrocarbon solvent such as pentane, hexane, heptane, or octane; an alicyclic hydrocarbon solvent such as cyclopentane, methylcyclopentane, cyclohexane, or methylcyclohexane; or an aromatic hydrocarbon solvent such as benzene, xylene, toluene, or ethylbenzene, using an organoalkali metal compound as a polymerization initiator. The (B) hydrogenated block copolymer can be easily obtained by hydrogenating the obtained block copolymer.

[0052] Examples of organoalkali metal compounds used as polymerization initiators include organolithium compounds and organosodium compounds. Among these, organolithium compounds such as n-butyllithium, sec-butyllithium, and tert-butyllithium are preferred. The amount of organoalkali metal compound used is not particularly limited, but usually 0.02 to 15 parts by mass, preferably 0.03 to 5 parts by mass, is used per 100 parts by mass of monomer.

[0053] The polymerization temperature is typically -10 to 150°C, preferably 0 to 120°C. The atmosphere of the polymerization system. It is preferable to replace the solvent with an inert gas such as nitrogen gas. The polymerization pressure should be within a range sufficient to maintain the monomer and solvent in the liquid phase, and is not particularly limited. There are no particular limitations on the method of introducing the monomer into the polymerization system, but examples include a single, continuous, intermittent, or a combination thereof.

[0054] (B) Hydrogenated block copolymers can be obtained by partially or selectively hydrogenating the block copolymer obtained as described above. There are no particular restrictions on the hydrogenation method or reaction conditions, and it is usually carried out at 20 to 150°C, under a hydrogen pressure of 0.1 to 10 MPa, and in the presence of a hydrogenation catalyst.

[0055] The hydrogenation rate can be arbitrarily selected by changing the amount of hydrogenation catalyst, the hydrogen pressure during the hydrogenation reaction, or the reaction time. As hydrogenation catalysts, compounds containing any of the metals of Group Ib, IVb, Vb, VIb, VIIb, or VIII of the periodic table can usually be used, such as compounds containing Ti, V, Co, Ni, Zr, Ru, Rh, Pd, Hf, Re, or Pt atoms. Specifically, examples include metallocene-type compounds with Ti, Zr, Hf, Co, Ni, Pd, Pt, Ru, Rh, Re, etc. as the central metal; supported heterogeneous catalysts in which metals such as Pd, Ni, Pt, Rh, Ru are supported on carriers such as carbon, silica, alumina, or diatomaceous earth; homogeneous Ziegler-type catalysts combining organic salts or acetylacetone salts of metal elements such as Ni and Co with reducing agents such as organoaluminum; organometallic compounds or complexes such as Ru and Rh; and fullerenes or carbon nanotubes that have absorbed hydrogen. Among these, metallocene compounds containing any of Ti, Zr, Hf, Co, or Ni are preferred because they can undergo hydrogenation in a homogeneous system in an inert organic solvent. Furthermore, metallocene compounds containing any of Ti, Zr, or Hf are preferred. In particular, hydrogenation catalysts obtained by reacting titanocene compounds with alkyllithium are preferred because they are inexpensive and industrially particularly useful catalysts. The hydrogenation catalysts can be used individually or in combination of two or more.

[0056] After hydrogenation, catalyst residue is removed as needed, or a phenolic or amine-based antioxidant is added, and then the (B) hydrogenated block copolymer is isolated. The (B) hydrogenated block copolymer can be isolated by, for example, adding acetone or alcohol to the hydrogenated block copolymer solution and allowing it to precipitate, or by adding the hydrogenated block copolymer solution to hot water with stirring and removing the solvent by distillation.

[0057] From the viewpoint of compatibility, the content of (B) hydrogenated block copolymer in the polymer composition according to this embodiment is preferably 1% by mass or more, more preferably 3% by mass or more, and particularly preferably 5% by mass or more, when the total mass of the polymer composition is 100% by mass. The content of (B) hydrogenated block copolymer in the polymer composition according to this embodiment is preferably 30% by mass or less, more preferably 25% by mass or less, and particularly preferably 20% by mass or less, when the total mass of the polymer composition is 100% by mass. The content of (B) hydrogenated block copolymer in the polymer composition according to this embodiment is preferably 1% by mass or more and 30% by mass or less, more preferably 3% by mass or more and 25% by mass or less, and particularly preferably 5% by mass or more and 20% by mass or less.

[0058] 1.3.(C) Thermoplastic resin The polymer composition according to this embodiment may contain (C) a thermoplastic resin (hereinafter also referred to as "component (C)") other than (A) a bio-based polyolefin. There are no particular limitations on the thermoplastic resin (C), and examples include acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylic resin, polyurethane, polymethyl methacrylate, polybutyl methacrylate, polyvinylcarbazole, polycarbonate, polyamide, polyacetal, polystyrene, polyvinyl chloride, polyvinyl acetate; and polyester-based resins such as polyethylene terephthalate and polybutylene terephthalate. Resins; Thermoplastic resins such as polyolefins and cyclic polyolefins can be used.

[0059] Among these, (C) the thermoplastic resin preferably contains at least one selected from the group consisting of acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, polyester resin, and polyolefin resin.

[0060] (C) The weight-average molecular weight (Mw) of the thermoplastic resin is preferably 0.5 million to 1 million, more preferably 10,000 to 900,000, and particularly preferably 20,000 to 800,000, from the viewpoint of improving the mechanical properties of the polymer composition and molded article. In this specification, "weight-average molecular weight" refers to the weight-average molecular weight on a polystyrene basis measured by gel permeation chromatography (GPC).

[0061] (C) The preferred MFR value of the thermoplastic resin is preferably 0.1 to 30, more preferably 0.2 to 15, even more preferably 0.5 to 10, and particularly preferably 1 to 5, under conditions of 230°C and a 21.2N load. By using (C) thermoplastic resin having an MFR value within this range, polymer compositions and molded articles with excellent mechanical properties can be obtained.

[0062] From the viewpoint of compatibility, the content of (C) thermoplastic resin in the polymer composition according to this embodiment is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15% by mass or more, when the total mass of the polymer composition is 100% by mass. The content of (C) thermoplastic resin in the polymer composition according to this embodiment is preferably 90% by mass or less, more preferably 85% by mass or less, and particularly preferably 80% by mass or less, when the total mass of the polymer composition is 100% by mass. The content of (C) thermoplastic resin in the polymer composition according to this embodiment is preferably 5% by mass or more and 90% by mass or less, more preferably 10% by mass or more and 85% by mass or less, and particularly preferably 15% by mass or more and 80% by mass or less.

[0063] 1.4. Other ingredients The polymer composition according to this embodiment may contain various additives in addition to the above-mentioned components, as needed. Examples of such additives include fillers, foaming nucleating agents, lubricants, antioxidants, heat stabilizers, weathering agents, and spreading oils.

[0064] 1.5. Content ratio of each component When the polymer composition according to this embodiment contains component (C), if the total amount of components (A), (B), and (C) is 100 parts by mass, the content of component (B) is preferably 1 to 20 parts by mass, more preferably 5 to 20 parts by mass, even more preferably 5 to 15 parts by mass, and particularly preferably 5 to 10 parts by mass. When the content of component (B) is within the above range, components (A) and (C) become more compatible, which may result in polymer compositions and molded articles with excellent mechanical properties.

[0065] When the polymer composition according to this embodiment contains component (C), the mass ratio (C / A) of component (C) to component (A) is preferably 85 / 15 to 15 / 85, more preferably 80 / 20 to 20 / 80, and particularly preferably 75 / 25 to 25 / 75. When the mass ratio (C / A) is within the above range, polymer compositions and molded articles with excellent mechanical properties are easily obtained.

[0066] In the polymer composition according to this embodiment, the mass ratio (A / B) of component (A) to component (B) is preferably 99 / 1 to 50 / 50, and preferably 95 / 5 to 60 / 40. More preferably, the ratio is 90 / 10 to 70 / 30. When the mass ratio (A / B) is within the above range, polymer compositions and molded articles with good mechanical properties are easily obtained while maintaining compatibility.

[0067] 1.6. Method for producing polymer compositions The method for producing the polymer composition according to this embodiment is not particularly limited as long as it can sufficiently knead component (A), component (B), and optionally component (C) and other components. For example, a method can be used in which a closed-type kneader (roll mill, laboplast mill, Banbury mixer, pressure kneader, etc.), a single-screw extruder, a twin-screw extruder, or a continuous kneader is heated and then kneaded while applying appropriate shear stress. In addition, when kneading, each component may be kneaded all at once, or a multi-stage divided kneading method can be employed in which some of the components are kneaded first, and then the remaining components are added and kneaded. For example, typical kneading conditions for a laboplast mill are a kneading temperature of 150 to 250°C, a rotation speed of 40 to 80 rpm, and a kneading time of 5 to 60 minutes.

[0068] 2. Molded body A molded article according to one embodiment of the present invention is a molded article obtained from the polymer composition described above. The molded article according to this embodiment is obtained by molding the polymer composition described above using a known injection molding machine, blow molding machine, or extrusion molding machine.

[0069] Examples of molded articles according to this embodiment include injection-molded articles, blow-molded articles, and extruded articles. Specifically, examples include food containers, caps, medical devices and medical containers, automobile parts, electrical components, solar cell encapsulants, films, fibers, and sheets.

[0070] 3. Examples The following describes specific examples of the present invention, but the present invention is not limited to these examples. In the following manufacturing examples, examples, and comparative examples, "%" refers to mass unless otherwise specified.

[0071] 3.1. Physical property measurement method For polymers (B-1) to (B-6), the methods for measuring each physical property are as follows.

[0072] (1) Vinyl group content In polymers before hydrogenation, 500 MHz, 1 It was calculated from the H-NMR spectrum.

[0073] (2) Hydrogenation rate Using ethylene tetrachloride as the solvent, at 100 MHz, 1 It was calculated from the H-NMR spectrum.

[0074] (3) Coupling rate The waveforms obtained from measurements using gel permeation chromatography (GPC, column: Tosoh Corporation, GMHHR-H) were calculated by waveform separation.

[0075] (4) Weight average molecular weight The results were obtained using gel permeation chromatography (GPC, column: Tosoh Corporation, GMHHR-H) and expressed in polystyrene equivalent.

[0076] (5) Melt Flow Rate (MFR) The results were obtained by measuring at 230°C and under a load of 21.2N, in accordance with the test method described in "JIS K7210-1".

[0077] 3.2.(B) Production of hydrogenated block copolymers 3.2.1. Production of Block Copolymer (B-1) In a nitrogen-purged autoclave reactor with a volume of 50 liters, 25,000 g of cyclohexane, 2,000 g of 1,3-butadiene, and 8.75 g of tetrahydrofuran were charged, and 60.1 mmol of n-butyllithium was added at a polymerization initiation temperature of 65°C to carry out adiabatic polymerization. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 45°C, and 2,000 g of 1,3-butadiene, 500 g of styrene, and 187.5 g of tetrahydrofuran were added, and further adiabatic polymerization was carried out. After the polymerization conversion rate reached 99% or more, 500 g of styrene was added to carry out polymerization. The above block copolymer was a block copolymer having polymer block C containing structural units derived from 1,3-butadiene and having a vinyl group content of 15%, polymer block B containing structural units derived from 1,3-butadiene and styrene and having a vinyl group content of 45%, and polymer block A consisting of structural units derived from styrene. Furthermore, the weight-average molecular weight of the above block copolymer was 160,000.

[0078] Next, the reaction mixture was heated to over 80°C, hydrogen was introduced into the system, and the reaction was allowed to proceed for 1 hour. After that, 7.3 mmol of tetrachlorosilane was added to the reaction vessel and stirred, then 1.39 g of diethylaluminum chloride and 3.11 g of bis(cyclopentadienyl)titanium furfuryl oxychloride were added, and the reaction was carried out by supplying hydrogen while maintaining a hydrogen pressure of 1.0 MPa until the predetermined hydrogen integration value was reached. After the predetermined hydrogen integration value was reached, the reaction solution was brought to 60°C and atmospheric pressure, withdrawn from the reaction vessel, and stirred into water to remove the solvent by steam distillation, thereby obtaining block copolymer (B-1) in which the hydrogenation rate of structural units derived from butadiene was 98%. Various physical properties of the obtained block copolymer (B-1) are shown in Table 1 below.

[0079] 3.2.2. Production of Block Copolymer (B-2) In a nitrogen-purged autoclave reactor with a volume of 50 liters, 25,000 g of cyclohexane, 1,750 g of 1,3-butadiene, and 8.75 g of tetrahydrofuran were charged, and 56.5 mmol of n-butyllithium was added at a polymerization initiation temperature of 65°C to carry out adiabatic polymerization. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 45°C, and 2,500 g of 1,3-butadiene and 125 g of tetrahydrofuran were added, and further adiabatic polymerization was carried out. After the polymerization conversion rate reached 99% or more, 750 g of styrene was added to carry out polymerization. The above block copolymer was a block copolymer having polymer block C containing structural units derived from 1,3-butadiene and having a vinyl group content of 15%, polymer block B containing structural units derived from 1,3-butadiene and having a vinyl group content of 40%, and polymer block A consisting of structural units derived from styrene. Furthermore, the weight-average molecular weight of the above block copolymer was 170,000.

[0080] Next, the reaction mixture was heated to over 80°C, hydrogen was introduced into the system, and the reaction was carried out for 1 hour. After that, 6.57 mmol of tetrachlorosilane was added to the reaction vessel and stirred, then 1.48 g of diethylaluminum chloride and 3.31 g of bis(cyclopentadienyl)titanium furfuryl oxychloride were added, and the reaction was carried out by supplying hydrogen while maintaining a hydrogen pressure of 1.0 MPa until the predetermined hydrogen integration value was reached. After the predetermined hydrogen integration value was reached, the reaction solution was brought to 60°C and atmospheric pressure, withdrawn from the reaction vessel, and stirred into water to remove the solvent by steam distillation, thereby obtaining block copolymer (B-2) in which the hydrogenation rate of structural units derived from butadiene was 98%. Various physical properties of the obtained block copolymer (B-2) are shown in Table 1 below.

[0081] 3.2.3. Production of Block Copolymer (B-3) 25,000 g of cyclohexane, 1,350 g of 1,3-butadiene, and 7.5 g of tetrahydrofuran were charged into a nitrogen-purged autoclave reactor with an internal volume of 50 liters, and polymerization was carried out. At a starting temperature of 65°C, 63.8 mmol of n-butyllithium was added, and adiabatic polymerization was carried out. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 20°C, and 3650 g of 1,3-butadiene and 437.5 g of tetrahydrofuran were added, and further adiabatic polymerization was carried out. After the polymerization conversion rate reached 99% or more, 26.1 mmol of methyldichlorosilane was added, and further adiabatic polymerization was carried out. The above block copolymer was a block copolymer having polymer block C containing structural units derived from 1,3-butadiene and a vinyl group content of 14%, and polymer block B containing structural units derived from 1,3-butadiene and a vinyl group content of 74%. Furthermore, the weight-average molecular weight of the above block copolymer was 290,000.

[0082] Next, the reaction mixture was heated to over 80°C, hydrogen was introduced into the system, and the reaction was allowed to proceed for 1 hour. Then, 1.74 g of diethylaluminum chloride, 3.89 g of bis(cyclopentadienyl)titanium furfuryl oxychloride, and 16.2 mmol of n-butyllithium were added to the reaction vessel, and hydrogen was supplied while maintaining a hydrogen pressure of 1.0 MPa until the predetermined hydrogen integration value was reached. After the predetermined hydrogen integration value was reached, the reaction solution was brought to 60°C at atmospheric pressure, withdrawn from the reaction vessel, and stirred into water to remove the solvent by steam distillation, thereby obtaining a block copolymer (B-3) in which the hydrogenation rate of structural units derived from butadiene was 98%. Various physical properties of the obtained block copolymer (B-3) are shown in Table 1 below.

[0083] 3.2.4. Production of Block Copolymer (B-4) In a nitrogen-purged autoclave reactor with a volume of 50 liters, 25,000 g of cyclohexane, 1,400 g of 1,3-butadiene, and 7.5 g of tetrahydrofuran were charged, and 59.8 mmol of n-butyllithium was added at a polymerization initiation temperature of 65°C to carry out adiabatic polymerization. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 35°C, and 3,600 g of 1,3-butadiene and 150 g of tetrahydrofuran were added, and further adiabatic polymerization was carried out. After the polymerization conversion rate reached 99% or more, 24.5 mmol of methyldichlorosilane was added, and further adiabatic polymerization was carried out. The above block copolymer was a block polymer having polymer block C containing structural units derived from 1,3-butadiene and a vinyl group content of 15%, and polymer block B containing structural units derived from 1,3-butadiene and a vinyl group content of 55%. Furthermore, the weight-average molecular weight of the above block copolymer was 320,000.

[0084] Next, the reaction mixture was heated to over 80°C, hydrogen was introduced into the system, and the reaction was allowed to proceed for 1 hour. Then, 1.74 g of diethylaluminum chloride, 3.89 g of bis(cyclopentadienyl)titanium furfuryl oxychloride, and 17.1 mmol of n-butyllithium were added to the reaction vessel, and hydrogen was supplied while maintaining a hydrogen pressure of 1.0 MPa until the predetermined hydrogen integration value was reached. After the predetermined hydrogen integration value was reached, the reaction solution was brought to 60°C at atmospheric pressure, withdrawn from the reaction vessel, and stirred into water to remove the solvent by steam distillation, thereby obtaining a block copolymer (B-4) with a hydrogenation rate of 98% of the structural units derived from butadiene. Various physical properties of the obtained block copolymer (B-4) are shown in Table 1 below.

[0085] 3.2.5. Production of Block Copolymer (B-5) In a nitrogen-purged autoclave reactor with a volume of 50 liters, 25,000 g of cyclohexane, 2,000 g of styrene, and 500 g of tetrahydrofuran were charged. At a polymerization initiation temperature of 30°C, 92.9 mmol of n-butyllithium was added, and adiabatic polymerization was carried out. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10°C, and 2,250 g of 1,3-butadiene was added, and further adiabatic polymerization was carried out. After the polymerization conversion rate reached 99% or more, 750 g of styrene was added, and adiabatic polymerization was carried out further. The above block copolymer was a block copolymer having polymer block A containing structural units derived from styrene, and polymer block B containing structural units derived from 1,3-butadiene and having a vinyl group content of 71%. Furthermore, the weight-average molecular weight of the above block copolymer was 100,000.

[0086] Next, the reaction mixture was heated to over 80°C, hydrogen was introduced into the system, and the reaction was allowed to proceed for 1 hour. After that, 13.89 mmol of tetrachlorosilane was added to the reaction vessel and stirred, then 0.78 g of diethylaluminum chloride and 1.75 g of bis(cyclopentadienyl)titanium furfuryl oxychloride were added, and the reaction was carried out by supplying hydrogen while maintaining a hydrogen pressure of 1.0 MPa until the predetermined hydrogen integration value was reached. After the predetermined hydrogen integration value was reached, the reaction solution was brought to 60°C at atmospheric pressure, withdrawn from the reaction vessel, and stirred into water to remove the solvent by steam distillation, thereby obtaining a block copolymer (B-5) in which the hydrogenation rate of structural units derived from butadiene was 98%. Various physical properties of the obtained block copolymer (B-5) are shown in Table 1 below.

[0087] 3.2.6. Production of Block Copolymer (B-6) In a nitrogen-purged autoclave reactor with a volume of 50 liters, 25,000 g of cyclohexane, 500 g of 1,3-butadiene, and 8.75 g of tetrahydrofuran were charged, and 45.7 mmol of n-butyllithium was added at a polymerization initiation temperature of 65°C to carry out adiabatic polymerization. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 45°C, and 4,350 g of 1,3-butadiene and 187.5 g of tetrahydrofuran were added, and further adiabatic polymerization was carried out. After the polymerization conversion rate reached 99% or more, 150 g of styrene was added and polymerization was carried out. The above block copolymer was a block copolymer having polymer block C containing structural units derived from 1,3-butadiene and having a vinyl group content of 16%, polymer block B containing structural units derived from 1,3-butadiene and having a vinyl group content of 45%, and polymer block A consisting of structural units derived from styrene. Furthermore, the weight-average molecular weight of the above block copolymer was 220,000.

[0088] Next, the reaction mixture was heated to over 80°C, hydrogen was introduced into the system, and the reaction was carried out for 1 hour. After that, 3.6 mmol of tetrachlorosilane was added to the reaction vessel and stirred, then 1.68 g of diethylaluminum chloride and 3.78 g of bis(cyclopentadienyl)titanium furfuryl oxychloride were added, and the reaction was carried out by supplying hydrogen while maintaining a hydrogen pressure of 1.0 MPa until the predetermined hydrogen integration value was reached. After the predetermined hydrogen integration value was reached, the reaction solution was brought to 60°C and atmospheric pressure, withdrawn from the reaction vessel, and added to water with stirring to remove the solvent by steam distillation, thereby obtaining a block copolymer (B-6) in which the hydrogenation rate of structural units derived from butadiene was 98%. Various physical properties of the obtained block copolymer (B-6) are shown in Table 1 below.

[0089] [Table 1]

[0090] 3.3. Manufacture of polymer compositions and molded articles (A) Bio-based polyolefin, (B) Hydrogenated block copolymer, and (C) Thermoplastic resin were dry-blended at room temperature in pellet form according to the composition ratios shown in Table 2 or Table 3 below. The mixture was then melt-kneaded in a twin-screw extruder (manufactured by Japan Steel Works, Ltd., model "TEX-30αII", screw diameter 30 mm, L / D=36). The cylinder temperature was 220°C. Polymer pellets were obtained by the strand-cut method.

[0091] Furthermore, while polymer compositions containing (B) hydrogenated block copolymer could be stranded without any problems, compositions without (B) hydrogenated block copolymer, consisting only of (A) bio-based polyolefin and (C) thermoplastic resin, regardless of whether the polyolefin was bio-based or petroleum-based, all exhibited surging phenomena, making it impossible to stably strand them, and requiring constant assistance from workers.

[0092] Next, various test specimens were molded using an injection molding machine (Nissei Plastic Industrial Co., Ltd., model "FNX110III Hybrid Type", clamping pressure: 110 tons, cylinder temperature: 230°C, mold temperature: 40°C). Prior to injection molding, pre-drying was performed at 90°C for 2 hours. After injection molding each test specimen, it was cured for 24 hours in a constant temperature room at 23°C and 50% humidity, and then various properties were evaluated.

[0093] 3.4. Characterization of Polymer Compositions (1) Charpy impact test The test specimens obtained above were subjected to a notched version in a 23°C constant temperature chamber with a sample size of 10, in accordance with ISO 179.

[0094] (2) Dropping weight impact test The fracture mode of the test specimens obtained above was determined in accordance with ISO 6603-2 using a drop weight impact testing machine manufactured by Toyo Seiki Seisakusho.

[0095] (3) Bending test The specimens obtained above were subjected to a tensile and compression test using a Minebea TG-5kN machine, in accordance with ISO 178, at a compression speed of 2 mm / min, in a constant temperature room at 23°C, with a sample size of 4.

[0096] (4) Biopolymer ratio The mass fraction of the biopolymer in the entire composition was calculated.

[0097] (5) Hayes For 1 mm thick test specimens, haze (%) was measured in accordance with ASTM D-1003.

[0098] 3.5. Evaluation Results Tables 2 and 3 below show the composition and characteristics evaluation results of the compositions.

[0099] [Table 2]

[0100] [Table 3]

[0101] In Tables 2 and 3 above, the values ​​for each component in the composition represent parts by mass. The following products were used for each material shown in Tables 2 and 3. <(A) Bio-based polyolefin> • Bio-PE: Manufactured by Braschem, product name "SGF4950" • Bio-PP: Manufactured by Kyokuto Trading Co., Ltd., product name "M-VERA PPH6000" <(C) Thermoplastic resin> • AS: Manufactured by Techno UMG Co., Ltd., product name "Sunlex SAN-C", AS resin • ABS: Manufactured by Techno UMG, product name "Techno ABS 130G30", ABS resin • PET: Manufactured by Unitika Corporation, product name "NES-2040", polyethylene terephthalate • Petroleum-based PE: Manufactured by Nippon Polyethylene Co., Ltd., product name "Novatec LL UJ990", linear low-density polyethylene • Petroleum-based PP: Manufactured by Nippon Polypropylene Co., Ltd., product name "Novatec PP MA3", polypropylene homopolymer

[0102] As shown in Examples 1 to 13 of Table 2 above, the polymer composition containing (A) bio-based polyolefin, (B) hydrogenated block copolymer, and (C) thermoplastic resin exhibited impact resistance and bending properties comparable to those of Comparative Example 4, which used petroleum-based polyethylene. Furthermore, compared to Comparative Examples 1 to 3, which did not use (B) hydrogenated block copolymer, a significant improvement in impact resistance was observed while maintaining bending properties.

[0103] As shown in Examples 14-20 of Table 3 above, polymer compositions containing (A) bio-based polyolefin, (B) hydrogenated block copolymer, and (C) thermoplastic resin exhibited impact resistance and transparency comparable to Comparative Example 16, which used petroleum-based polyolefin. Furthermore, compared to Comparative Examples 9-15, which did not use (B) hydrogenated block copolymer, a significant improvement in impact resistance was observed.

[0104] Furthermore, as shown in Examples 21-27 of Table 3 above, polymer compositions containing (A) bio-based polyolefin and (B) hydrogenated block copolymer also exhibited impact resistance and transparency comparable to Comparative Example 16, which used petroleum-based polyolefin.

[0105] The present invention is not limited to the embodiments described above, and various modifications are possible. The present invention encompasses configurations that are substantially identical to those described in the embodiments (for example, configurations with the same function, method, and result, or configurations with the same purpose and effect). The present invention also encompasses configurations in which non-essential parts of the configurations described in the embodiments are replaced with other configurations. Furthermore, the present invention also encompasses configurations that produce the same effects or achieve the same purpose as the configurations described in the embodiments. Furthermore, the present invention also encompasses configurations that add known technology to the configurations described in the embodiments.

Claims

1. A polymer composition containing (A) a bio-based polyolefin and (B) a hydrogenated block copolymer, The (B) hydrogenated block copolymer is a hydrogenated polymer that satisfies the following conditions (a) to (d), and is a polymer composition containing a polymer in which 50 mol% or more of the structural units derived from butadiene are hydrogenated. (a) The number of polymer blocks mainly composed of aromatic vinyl compounds is 0 or 1. (b) Having a polybutadiene block with a vinyl group content of 20% or less. (c) Having a polymer block mainly composed of a conjugated diene compound having a vinyl group content of more than 20%, wherein the content of the polymer block mainly composed of the conjugated diene compound is 85% by mass or less of the total mass of the hydrogenated block copolymer (B). (d) The weight-average molecular weight is 50,000 or more and 500,000 or less.

2. The polymer composition according to claim 1, wherein when the constituent ratios of the structural units represented by the following formula (1), the following formula (2), the following formula (3), and the following formula (4) of component (B) are p, q, r, and s, respectively, the following formula (A) is satisfied. 0.50≦(p+(0.5×r)) / (p+q+(0.5×r)+s)≦0.98 .....(A) 【Chemistry 1】

3. (C) The polymer composition according to claim 1, further comprising a thermoplastic resin (excluding the bio-based polyolefin described in (A) above).

4. The polymer composition according to claim 3, wherein component (C) contains at least one selected from the group consisting of acrylonitrile-styrene resin, acrylonitrile-butadiene-styrene resin, polyester resin, and polyolefin resin.

5. The polymer composition according to claim 3, wherein when the total amount of component (A), component (B), and component (C) is 100 parts by mass, the content of component (B) is 1 to 20 parts by mass.

6. The polymer composition according to claim 3, wherein the mass ratio (C / A) of component (C) to component (A) is 85 / 15 to 15 / 85, and the mass ratio (A / B) of component (A) to component (B) is 99 / 1 to 50 / 50.

7. An injection-molded article of a polymer composition according to any one of claims 1 to 6.

8. A blow-molded article of a polymer composition according to any one of claims 1 to 6.

9. An extruded article of a polymer composition according to any one of claims 1 to 6.

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