Resin composition and molded article

Abstract

By combining a thermoplastic resin with a plant-derived biopolymer and making them compatible, we provide a resin composition with excellent mechanical properties, and a molded article made therefrom. [Solution] The resin composition according to the present invention contains (A) a thermoplastic resin, (B) bio-based polypropylene, and (C) a hydrogenated block copolymer, wherein (C) the hydrogenated block copolymer is a hydrogenated polymer satisfying the following conditions (a) to (c), and contains a polymer in which 50% or more of the structural units derived from butadiene are hydrogenated. (a) It is a copolymer of a conjugated diene compound containing butadiene and an aromatic vinyl compound. (b) Having two or more polymer blocks mainly composed of aromatic vinyl compounds. (c) The weight-average molecular weight is between 50,000 and 500,000.

Description

[Technical Field]

[0001] The present invention relates to resin 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 resin 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] Thermoplastic resins have superior toughness compared to thermosetting resins. Furthermore, while thermoplastic resins require high molding temperatures, they can be molded quickly, resulting in excellent productivity. They are also relatively easy to recycle as they can be remolded by heating. Therefore, they are used in applications such as housings for everyday goods and electrical appliances, building materials like rain gutters and window frames, and packaging materials like films and cushions.

[0006] On the other hand, biopolymers have been used in various applications to reduce the use of fossil resources, and if biopolymers can be blended with thermoplastic resins, it could help reduce the consumption of fossil resources. However, thermoplastic resins and biopolymers can be incompatible, and blending them can significantly impair the mechanical properties of the thermoplastic resin.

[0007] Some embodiments of the present invention provide a resin composition with excellent mechanical properties and a molded article made therefrom, by combining a thermoplastic resin and a plant-derived biopolymer and making them compatible. [Means for solving the problem]

[0008] 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.

[0009] One aspect of the resin composition according to the present invention is A resin composition comprising (A) a thermoplastic resin (excluding (B) bio-based polypropylene), (B) bio-based polypropylene, and (C) a hydrogenated block copolymer, The (C) hydrogenated block copolymer is a hydrogenated polymer that satisfies the following conditions (a) to (c), and contains a polymer in which 50 mol% or more of the structural units derived from butadiene are hydrogenated. (a) It is a copolymer of a conjugated diene compound containing butadiene and an aromatic vinyl compound. (b) Having two or more polymer blocks mainly composed of aromatic vinyl compounds. (c) The weight-average molecular weight is between 50,000 and 500,000.

[0010] One embodiment of the resin composition, The aforementioned component (A) may contain at least one selected from the group consisting of styrene resins and polyolefin resins.

[0011] In any aspect of the resin composition, when the constitutional ratios (molar ratios) of the structural unit represented by the following formula (1), the structural unit represented by the following formula (2), the structural unit represented by the following formula (3) and the structural unit represented by the following formula (4) of the component (C) are p, q, r and s respectively, the component (C) may satisfy the following formula (A). 0.50≦(p+(0.5×r)) / (p+q+(0.5×r)+s)≦0.98 ·····(A)

Chemical Formula

[0012] In any aspect of the resin 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 (C) may be 1 to 20 parts by mass.

[0013] In any aspect of the resin composition, a mass ratio (A / B) of the component (A) to the component (B) may be 85 / 15 to 15 / 85, and a mass ratio (B / C) of the component (B) to the component (C) 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 resin composition according to any of the above aspects.

[0015] One aspect of the blow molded article according to the present invention is obtained by blow molding the resin composition according to any of the above aspects.

[0016] One aspect of the extrusion molded article according to the present invention is obtained by extrusion molding the resin composition according to any of the above aspects.

Effects of the Invention

[0017] According to the resin composition of the present invention, a resin composition and a molded article excellent in mechanical properties can be obtained by combining a thermoplastic resin and a plant-derived biopolymer and compatibilizing the two. MODE FOR CARRYING OUT THE INVENTION

[0018] Hereinafter, preferred embodiments according to the present invention will be described in detail. It should be understood that the present invention is not limited to only the embodiments described below, and also includes various modifications implemented within a scope that does not alter the gist of the present invention.

[0019] In the present specification, a numerical range described using "X to Y" means that it includes the numerical value X as a lower limit and includes the numerical value Y as an upper limit.

[0020] 1. Resin Composition A resin composition according to one embodiment of the present invention contains (A) a thermoplastic resin (also referred to as "component (A)" in the present specification), (B) a bio-based polypropylene (also referred to as "component (B)" in the present specification), and (C) a hydrogenated block copolymer (also referred to as "component (C)" in the present specification). Hereinafter, components that may be contained in the resin composition according to the present embodiment will be described.

[0021] 1.1. (A) Thermoplastic Resin The resin composition according to the present embodiment contains (A) a thermoplastic resin other than (B) bio-based polypropylene. There is no particular limitation on (A) the thermoplastic resin, and thermoplastic resins such as: acrylonitrile-styrene (AS) resin, acrylonitrile-butadiene-styrene (ABS) resin, acrylic resins, polyurethane, polymethyl methacrylate, polybutyl methacrylate, polyvinyl carbazole, polycarbonate, polyamide, polyacetal, polystyrene, polyvinyl chloride, polyvinyl acetate; polyester-based resins such as polyethylene terephthalate and polybutylene terephthalate; polyolefin-based resins such as polyolefin and cyclic polyolefin can be used.

[0022] (A) The thermoplastic resin preferably contains at least one selected from the group consisting of polystyrene, styrene-based resins such as AS resin and ABS resin, and polyolefin-based resins such as polyolefins and cyclic polyolefins.

[0023] (A) 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 resin 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).

[0024] (A) 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 the thermoplastic resin (A) having an MFR value within this range, resin compositions and molded articles with excellent mechanical properties can be obtained.

[0025] From the viewpoint of compatibility, the content of thermoplastic resin (A) in the resin 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 resin composition is 100% by mass. The content of thermoplastic resin (A) in the resin 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 resin composition is 100% by mass. The content of thermoplastic resin (A) in the resin 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.

[0026] 1.2.(B) Bio-based polypropylene (B) Bio-based polypropylene is polypropylene that uses plant-derived monomers or polypropylene that has a biomass allocation ratio according to the mass balance method (hereinafter referred to as "mass It is also called "balanced polypropylene." Examples of plants 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 propylene, which is the raw material for polypropylene, is produced from this bioethanol.

[0027] (B) When the bio-based polypropylene is a polypropylene synthesized using plant-derived monomers, it is preferably a propylene homopolymer and / 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. (B) The bio-based polypropylene may be a single bio-based polypropylene or a combination of multiple bio-based polypropylenes having different bio-basednesses.

[0028] From this viewpoint, when (B) bio-based polypropylene is polypropylene 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 resin composition according to this embodiment, it is preferable that the bio-basedness of (B) bio-based polypropylene be a reasonably high value.

[0029] (B) If the bio-based polypropylene is mass-balanced polypropylene, using mass-balanced bio-based polypropylene (B) 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.

[0030] (B) When the bio-based polypropylene is a mass-balance polypropylene, it is preferably a propylene homopolymer and / or a copolymer of propylene and α-olefin having a biomass allocation of 80% or more and 100% or less. The biomass allocation 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.

[0031] (B) The preferred MFR value of bio-based polypropylene 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 (B) bio-based polypropylene having an MFR value within this range, resin compositions and molded articles with excellent mechanical properties can be obtained.

[0032] Furthermore, (B) the density range of bio-based polypropylene is 0.90 to 0.91 (g / cm³). 3 It is within the range of ).

[0033] The content of (B) bio-based polypropylene in the resin 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 resin composition is 100% by mass, from the viewpoint of compatibility. The content of (B) bio-based polypropylene in the resin 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 resin composition is 100% by mass. The content of (B) bio-based polypropylene in the resin composition according to this embodiment is preferably 5% by mass or more and 90% by mass or less, and more preferably 10% by mass or more and 85% by mass or less. Particularly preferable is a concentration of 15% by mass or more and 80% by mass or less.

[0034] 1.3.(C) Hydrogenated block copolymer The resin composition according to this embodiment contains (C) a hydrogenated block copolymer. The (C) hydrogenated block copolymer is a hydrogenated polymer that satisfies the following conditions (a) to (c), and contains a polymer in which 50 mol% or more of the structural units derived from butadiene are hydrogenated. (a) It is a copolymer of a conjugated diene compound containing butadiene and an aromatic vinyl compound. (b) Having two or more polymer blocks mainly composed of aromatic vinyl compounds. (c) The weight-average molecular weight is between 50,000 and 500,000.

[0035] (C) A hydrogenated block copolymer is a block copolymer having polymer block A mainly composed of an aromatic vinyl compound and polymer block B mainly composed of a conjugated diene compound containing butadiene. (C) A hydrogenated block copolymer has two or more polymer blocks A mainly composed of an aromatic vinyl compound. (C) A hydrogenated block copolymer has one or more polymer blocks B mainly composed of a conjugated diene compound.

[0036] (C) From the viewpoint of balancing the rigidity and impact strength of the molded article of the resin composition, the hydrogenated block copolymer preferably contains 3 to 70% by mass of polymer block A mainly composed of aromatic vinyl compounds, more preferably 4 to 65% by mass, and particularly preferably 5 to 60% by mass.

[0037] (C) From the viewpoint of balancing the rigidity and impact strength of the molded article of the resin composition, the hydrogenated block copolymer preferably contains 30 to 97% by mass of polymer block B mainly composed of a conjugated diene compound containing butadiene, more preferably 35 to 96% by mass, and particularly preferably 40 to 95% by mass.

[0038] (C) 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 (B) bio-based polypropylene.

[0039] (C) The hydrogenated block copolymer preferably satisfies 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]

[0040] The value expressed by (p + (0.5 × r)) / (p + q + (0.5 × r) + s) in the above formula (A) (hereinafter also referred to as the "α value") being 0.50 to 0.98 indicates that (C) the hydrogenated block copolymer is a highly saturated conjugated diene polymer. The α value is preferably 0 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 (C) hydrogenated block copolymer is high, which tends to make the quality of the (C) 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.

[0041] The α value represented by the above formula (A) corresponds to the hydrogenation rate of the (C) hydrogenated block copolymer. For example, if α is 0.50, the hydrogenation rate of the (C) hydrogenated block copolymer is 50%. The hydrogenation rate and α value of the (C) 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 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).

[0042] (C) The polymer block A, which mainly consists of an aromatic vinyl compound and constitutes the hydrogenated block copolymer, is preferably a polymer block containing 90% by mass or more of structural units derived from the aromatic vinyl compound. Furthermore, the polymer block B, which mainly consists of a conjugated diene compound containing butadiene and constitutes the hydrogenated block copolymer, 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).

[0043] (C) 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 of structural units derived from aromatic vinyl compounds and structural units derived from conjugated diene compounds. (C) The hydrogenated block copolymer may optionally contain structural units derived from other polymerizable monomers other than structural units derived from aromatic vinyl compounds and structural units derived from conjugated diene compounds.

[0044] (C) Polymer block A, which mainly consists of aromatic vinyl compounds constituting the hydrogenated block copolymer, 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.

[0045] (C) Polymer block B, which mainly consists of a conjugated diene compound containing butadiene that constitutes the hydrogenated block copolymer, contains 1,3-butadiene and optionally other conjugated diene compounds and aromatic compounds. It can be formed using a vinyl compound. 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.

[0046] (C) Polymer block B, which mainly consists of a conjugated diene compound containing butadiene that constitutes the hydrogenated block copolymer, preferably has 70% by mass or more of the constituent units of polymer block B derived from 1,3-butadiene.

[0047] The aromatic vinyl compound content (aromatic vinyl content) in polymer block B is preferably 0 to 30% by mass, more preferably 0 to 25% by mass, and particularly preferably 0 to 20% by mass. 1 It can be measured by 1H-NMR.

[0048] The content of 1,2-vinyl bonds (1,2-vinyl content) in the conjugated diene compound in polymer block B is preferably 60% or more, preferably 65% ​​or more, and particularly preferably 70% or more. A 1,2-vinyl content within the above range is preferable because it results in good mechanical properties for the resulting resin composition and molded article. Note that the 1,2-vinyl content is... 1 This can be measured using 1H-NMR.

[0049] (C) The hydrogenated block copolymer preferably has a mass ratio of structural units derived from aromatic vinyl compounds to structural units derived from conjugated diene compounds in the range of structural units derived from aromatic vinyl compounds / structural units derived from conjugated diene compounds = 3 / 97 to 70 / 30, more preferably in the range of 4 / 96 to 65 / 35, and particularly preferably in the range of 5 / 95 to 60 / 40. When the ratio of each structural unit is within the above range, the molded article of the resulting resin composition has a better balance of rigidity and impact strength.

[0050] (C) The hydrogenated block copolymer is not particularly limited, but examples include block copolymers having the block structure shown in the following general formulas (5) to (8). A-(BA) n ...(5) B-(AB)m ...(6) A-(BAB) n ...(7) (AB) m X ···(8) Here, A represents a polymer block mainly composed of aromatic vinyl compounds, and B represents a polymer block mainly composed of conjugated diene compounds containing butadiene. Also, n represents any integer from 1 to 6, and m represents any integer from 2 to 6. X represents a coupling agent residue.

[0051] The above general formulas (5) to (7) are linear hydrogenated block copolymers, and the above general formula (8) is a branched hydrogenated block copolymer with the B portion as the binding center; both can be suitably used.

[0052] (C) For hydrogenated block copolymers, the weight-average molecular weight (Mw) in polystyrene terms, measured using gel permeation chromatography (GPC), is 50,000 to 500,000, from the viewpoint of obtaining molded articles with excellent rigidity and impact strength. (C) The weight-average molecular weight (Mw) of hydrogenated block copolymers is preferably 70,000 or more, and more preferably 80,000 or more. (C) Weight-average molecular weight of hydrogenated block copolymers The molecular weight (Mw) is preferably 450,000 or less, and more preferably 400,000 or less. The weight-average molecular weight (Mw) of the (C) hydrogenated block copolymer is preferably 70,000 or more and 450,000 or less, and more preferably 80,000 or more and 400,000 or less. The weight-average molecular weight of the (C) hydrogenated block copolymer is the value obtained from all peaks of the GPC curve measured by GPC before hydrogenation.

[0053] (C) 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 a (C) hydrogenated block copolymer having an MFR value within this range, resin compositions and molded articles with excellent mechanical properties can be obtained.

[0054] The block copolymer before hydrogenation can be obtained, for example, by living anionic polymerization of an aromatic vinyl compound and a conjugated diene 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. Furthermore, the obtained block copolymer can be easily obtained by hydrogenation to obtain a (C) hydrogenated block copolymer.

[0055] 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.

[0056] The polymerization temperature is typically -10 to 150°C, preferably 0 to 120°C. The polymerization system atmosphere is preferably replaced with an inert gas such as nitrogen gas. The polymerization pressure is not particularly limited, and should be within a range sufficient to maintain the monomer and solvent in the liquid phase. The method of introducing the monomer into the polymerization system is not particularly limited, but examples include a single, continuous, intermittent, or a combination thereof.

[0057] (C) 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.

[0058] 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, titanocene compounds and alkyllithium compounds are preferred. Hydrogenated catalysts obtained by reacting with are preferred because they are inexpensive and particularly useful industrially. Hydrogenated catalysts can be used individually or in combination of two or more.

[0059] After hydrogenation, catalyst residue is removed as needed, or a phenolic or amine-based antioxidant is added, and then the (C) hydrogenated block copolymer is isolated. The (C) 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.

[0060] From the viewpoint of compatibility, the content of (C) hydrogenated block copolymer in the resin 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 resin composition is 100% by mass. The content of (C) hydrogenated block copolymer in the resin 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 resin composition is 100% by mass. The content of (C) hydrogenated block copolymer in the resin 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.

[0061] 1.4. Other ingredients The resin 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.

[0062] 1.5. Content ratio of each component In the resin composition according to this embodiment, when the total amount of components (A), (B), and (C) is 100 parts by mass, the content of component (C) 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 (C) is within the above range, components (A) and (B) become more compatible, which may result in a resin composition and molded article with excellent mechanical properties.

[0063] In the resin composition according to this embodiment, the mass ratio (A / B) of component (A) to component (B) 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 (A / B) is within the above range, a resin composition and molded article with excellent mechanical properties are easily obtained.

[0064] In the resin composition according to this embodiment, the mass ratio (B / C) of component (B) to component (C) is preferably 99 / 1 to 50 / 50, more preferably 95 / 5 to 60 / 40, and particularly preferably 90 / 10 to 70 / 30. When the mass ratio (B / C) is within the above range, it is easy to obtain a resin composition and molded article that maintains compatibility and has excellent mechanical properties.

[0065] 1.6. Method for producing resin compositions The method for producing the resin composition according to this embodiment is not particularly limited as long as it can sufficiently knead components (A), (B), (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 may be used in which some of the components are kneaded first, and then the remaining components are added and kneaded. It is also possible to adopt a different method. For example, typical mixing conditions for a laboplast mill include a mixing temperature of 150-250°C, a rotation speed of 40-80 rpm, and a mixing time of 5-60 minutes.

[0066] 2. Molded body A molded article according to one embodiment of the present invention is a molded article obtained from the above-described resin composition. The molded article according to this embodiment is obtained by molding the above-described resin composition using a known injection molding machine, blow molding machine, extrusion molding machine, etc.

[0067] Examples of the molded article according to the present embodiment include injection-molded articles, blow-molded articles, and extrusion-molded articles, and specific examples include food containers, caps, medical instruments, medical containers, automobile parts, electrical parts, solar cell encapsulants, films, fibers, and sheets.

[0068] 3. Examples Hereinafter, specific examples of the present invention will be described, but the present invention is not limited to these examples. Unless otherwise specified, "%" in the following Production Examples, Examples and Comparative Examples is based on mass.

[0069] 3.1. Method for measuring physical properties For polymers (C-1) to (C-3), the measurement methods for each physical property value are as follows.

[0070] (1) 1,2-vinyl content Calculated from a 1 H-NMR spectrum at 500 MHz for the polymer before hydrogenation.

[0071] (2) Hydrogenation rate Calculated from a 1 H-NMR spectrum at 100 MHz using ethylene tetrachloride as a solvent.

[0072] (3) Weight average molecular weight Determined in terms of polystyrene equivalent using gel permeation chromatography (GPC, column: GMHHR-H, manufactured by Tosoh Corporation).

[0073] (4) Melt flow rate (MFR) Determined by measurement at 230°C under a load of 21.2 N in accordance with the test method described in "JIS K7210-1".

[0074] 3.2. Production of (C) Hydrogenated Block Copolymer 3.2.1. Production of Block Copolymer (C-1) 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, and 92.9 mmol of n-butyllithium was added at a polymerization initiation temperature of 30°C to carry out adiabatic polymerization. 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 further adiabatic polymerization was carried out. 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 1,2-vinyl content of 71%. Furthermore, the weight-average molecular weight of the above block copolymer was 100,000.

[0075] 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 mixture was heated with a predetermined amount of water while maintaining a hydrogen pressure of 1.0 MPa. The reaction was carried out by supplying hydrogen until the primary integrated value was reached. After the predetermined hydrogen integrated 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 a block copolymer (C-1) in which the hydrogenation rate of structural units derived from butadiene was 98 mol%. Various physical properties of the obtained block copolymer (C-1) are shown in Table 1 below.

[0076] 3.2.2. Production of Block Copolymer (C-2) In a nitrogen-purged autoclave reactor with a volume of 50 liters, 25,000 g of cyclohexane, 500 g of styrene, and 500 g of tetrahydrofuran were charged, and 77.4 mmol of n-butyllithium was added at a polymerization initiation temperature of 45°C to carry out adiabatic polymerization. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10°C, and 2,750 g of 1,3-butadiene and 1,250 g of styrene were added, and further adiabatic polymerization was carried out. After the polymerization conversion rate reached 99% or more, 500 g of styrene was added and adiabatic polymerization was carried out. The above block copolymer was a block copolymer having polymer block A consisting of structural units derived from styrene, and polymer block B containing structural units derived from 1,3-butadiene and styrene, with a 1,2-vinyl content of 73%. Furthermore, the weight-average molecular weight of the above block copolymer was 120,000.

[0077] 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, 11.07 mmol of tetrachlorosilane was added to the reaction vessel and stirred, then 0.96 g of diethylaluminum chloride and 2.14 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 a block copolymer (C-2) in which the hydrogenation rate of structural units derived from butadiene was 98 mol%. Various physical properties of the obtained block copolymer (C-2) are shown in Table 1 below.

[0078] 3.2.3. Production of Block Copolymer (C-3) In a nitrogen-purged autoclave reactor with a volume of 50 liters, 25,000 g of cyclohexane, 250 g of styrene, and 500 g of tetrahydrofuran were charged, and 26.8 mmol of n-butyllithium was added at a polymerization initiation temperature of 45°C to carry out adiabatic polymerization. After the polymerization conversion rate reached 99% or more, the reaction solution was cooled to 10°C, and 4,250 g of 1,3-butadiene and 250 g of styrene were added, and further adiabatic polymerization was carried out. After the polymerization conversion rate reached 99% or more, 250 g of styrene was added and adiabatic polymerization was carried out. The above block copolymer was a block copolymer having polymer block A consisting of structural units derived from styrene, and polymer block B containing structural units derived from 1,3-butadiene and styrene, with a 1,2-vinyl content of 78%. Furthermore, the weight-average molecular weight of the above block copolymer was 330,000.

[0079] 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, 12.3 mmol of tetrachlorosilane was added to the reaction vessel and stirred, then 1.12 g of diethylaluminum chloride and 2.50 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 (C-3) in which the hydrogenation rate of structural units derived from butadiene was 98 mol%. Various physical properties of the obtained block copolymer (C-3) are shown in Table 1 below.

[0080] [Table 1]

[0081] 3.3. Manufacture of resin compositions and molded articles (A) Thermoplastic resin, (B) Bio-based polypropylene, and (C) Hydrogenated block copolymer 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. Resin pellets were obtained by the strand-cut method.

[0082] Furthermore, while the resin composition containing (C) hydrogenated block copolymer could be stranded without any problems, the resin compositions of Comparative Examples 1 to 3, which were made only from (A) thermoplastic resin and (B) bio-based polypropylene without containing (C) hydrogenated block copolymer, all exhibited surging phenomena, regardless of whether the polypropylene was bio-based or petroleum-based, and could not be stably stranded, requiring constant assistance from workers.

[0083] 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.

[0084] 3.4. Characterization of Resin 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.

[0085] (2) Drop 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.

[0086] (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.

[0087] (4) Biopolymer ratio The mass fraction of the biopolymer in the entire resin composition was calculated.

[0088] (5) Hayes For 1 mm thick test specimens, haze (%) was measured in accordance with ASTM D-1003.

[0089] 3.5. Evaluation Results Tables 2 and 3 below show the compound composition and the results of the property evaluation of the resin composition.

[0090] [Table 2]

[0091] [Table 3]

[0092] 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) Thermoplastic resin> • PS: Manufactured by Toyo Styrene Co., Ltd., product name "Toyo Styrofoam GP G200C", polystyrene resin • ABS: Manufactured by Techno UMG, product name "Techno ABS 130G30", ABS resin • Petroleum-based PP: Manufactured by Nippon Polypropylene Co., Ltd., product name "Novatec PP MA3", polypropylene homopolymer • Petroleum-based PE: Manufactured by Nippon Polyethylene Co., Ltd., product name "Novatec LL UJ990", linear low-density polyethylene <(B) Biopolypropylene> • Bio-PP: Manufactured by Kyokuto Trading Co., Ltd., product name "M-VERA PPH6000"

[0093] As shown in Examples 1 to 10 of Table 2 above, the resin composition containing (A) thermoplastic resin, (B) biopolypropylene, and (C) hydrogenated block copolymer exhibited impact resistance and bending properties comparable to those of Comparative Example 4, which used petroleum-based polypropylene. Furthermore, compared to Comparative Examples 1 to 3, which did not use (C) hydrogenated block copolymer, a significant improvement in impact resistance was observed while maintaining bending properties.

[0094] As shown in Examples 11-17 of Table 3 above, the resin composition containing (A) thermoplastic resin, (B) biopolypropylene, and (C) hydrogenated block copolymer exhibited impact resistance and transparency comparable to Comparative Example 8, which used petroleum-based polypropylene. Furthermore, a significant improvement in impact resistance was observed compared to Comparative Examples 5-7, which did not use (C) hydrogenated block copolymer.

[0095] 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 resin composition comprising (A) a thermoplastic resin (excluding (B) bio-based polypropylene), (B) bio-based polypropylene, and (C) a hydrogenated block copolymer, The resin composition wherein the (C) hydrogenated block copolymer is a hydrogenated polymer satisfying the following conditions (a) to (c), and contains a polymer in which 50 mol% or more of the structural units derived from butadiene are hydrogenated. (a) It is a copolymer of a conjugated diene compound containing butadiene and an aromatic vinyl compound. (b) Having two or more polymer blocks mainly composed of aromatic vinyl compounds. (c) The weight-average molecular weight is 50,000 or more and 500,000 or less.

2. The resin composition according to claim 1, wherein the component (A) contains at least one selected from the group consisting of styrene resins and polyolefin resins.

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

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

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

6. An injection-molded article of the resin composition according to any one of claims 1 to 5.

7. A blow-molded article of the resin composition according to any one of claims 1 to 5.

8. An extruded article of the resin composition according to any one of claims 1 to 5.

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