JP2023020914A - Resin composition and molded article of the same - Google Patents

Abstract

To provide a molded article in which energy absorption property thereof in high temperature and low temperature environments can be suppressed, and furthermore deformation amount of a member to impact can be suppressed.SOLUTION: A resin composition is provided, obtained by blending at least polyamide (A), polyphenylene ether (B), polyrotaxane (C) whose cyclic molecules are modified with a graft chain having a hydroxyl group at a terminal, a copolymer (D) composed of an aromatic vinyl-based monomer and conjugated diene and a fibrous filler (E), wherein with respect to 100 pts.wt. of the polyamide (A), the polyphenylene ether (B), the polyrotaxane (C) and the fibrous filler (E), 3 pts.wt. or more and 35 pts.wt. or less of the polyphenylene ether (B) and 0.1 pts.wt. or more and 10 pts.wt. or less of the polyrotaxane (C) are blended.SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a resin composition obtained by blending a polyamide, a polyphenylene ether, a polyrotaxane modified with a cyclic molecule, and a fibrous filler, and a molded article thereof.

Polyamide is a thermoplastic engineering plastic that is excellent in mechanical properties such as rigidity and toughness and in moldability. Polyamide resin reinforced with carbon fiber or glass fiber is lightweight, has excellent elastic modulus and mechanical strength, and has good heat resistance. used.

Many proposals have been made to add glass fibers for the purpose of improving the strength and rigidity of plastics (for example, Patent Document 1). However, as the strength and rigidity of the molded article are improved by adding high-strength, high-modulus fibers, there is a problem that toughness and impact resistance are lowered. Therefore, for the purpose of improving the toughness of fiber-reinforced plastics, fiber-reinforced polyamides to which a modified elastomer is added (for example, Patent Document 2) have been proposed. Further, Patent Document 3 proposes a method of greatly improving the toughness of polyamide by adding polyrotaxane to the resin composition described in Patent Document 3.

JP-A-6-100774 JP 2010-209247 A WO2018/043025

When applying resin compositions to structural materials for automobiles and the like, high mechanical properties that can replace conventional metal members, particularly both rigidity and toughness under usage environment, are required. However, the mechanical properties of resin compositions are highly dependent on temperature, and in low-temperature environments such as winter and cold regions (for example, about -30 ° C), the problem is that the toughness and impact resistance of the material tend to decrease. be. In addition, in order to function as a protective member even in the heat-generating environment of automobile batteries, the resin composition has rigidity and impact resistance even in a high-temperature environment (for example, about 80 ° C.), and the amount of member deformation due to impact is suppressed. It must be.

In the polyamide composition containing a fibrous filler disclosed in Patent Document 2, the addition of an elastomer improves the impact resistance and toughness, but has the problem of lowering the rigidity. Further, as shown in Patent Document 3, by adding polyrotaxane to a polyamide resin composition containing a fibrous filler, it was possible to obtain a resin composition having both rigidity and toughness. It was not possible to obtain a resin composition excellent in impact resistance and rigidity that can be used in a wide range of temperature environments up to high temperatures.

In view of the above, it is an object of the present invention to provide a resin composition that maintains rigidity at high temperatures while also having toughness at low temperatures and that achieves both rigidity and toughness in a wide range of temperature environments, and molded articles thereof.

In order to solve the above problems, the present invention has the following configurations.
(1) A copolymer comprising at least a polyamide (A), a polyphenylene ether (B), a polyrotaxane (C) whose cyclic molecule is modified with a graft chain having a terminal hydroxyl group, and an aromatic vinyl monomer and a conjugated diene A resin composition containing (D) and a fibrous filler (E), wherein the polyamide (A), the polyphenylene ether (B), the polyrotaxane (C), and the fibrous filler (E) are combined. A resin composition containing 3 to 35 parts by weight of the polyphenylene ether (B) and 0.1 to 10 parts by weight of the polyrotaxane (C) with respect to 100 parts by weight.
(2) The copolymer (D) consisting of an aromatic vinyl monomer and a conjugated diene is a block copolymer and a random copolymer consisting of an aromatic vinyl monomer and a conjugated diene, and these The resin composition according to item (1), which is at least one selected from hydrogenated substances.
(3) The resin composition was used to prepare and measure a test piece conforming to ISO 178:2010, and the bending elastic modulus at 80°C was 7 GPa or more and the bending maximum point strain was 4% or less, and -30°C. The resin composition according to item (1) or (2), which has a bending breaking strain at 4% or more.
(4) The resin composition according to any one of items (1) to (3), wherein the fibrous filler (E) is at least one selected from the group consisting of glass fibers and carbon fibers.
(5) A molded article made of the resin composition according to any one of items (1) to (4).
(6) A three-dimensional modeling material comprising the resin composition according to any one of items (1) to (4).
(7) The three-dimensional modeling material according to (6), wherein the three-dimensional modeling material is filament-shaped.
(8) The three-dimensional modeling material according to item (6), wherein the three-dimensional modeling material is in the form of powder.
(9) A modeled object obtained by modeling the three-dimensional modeling material according to any one of items (6) to (8).

The resin composition of the present invention is a resin composition having both rigidity and toughness in a wide temperature environment. With such a resin composition, it is possible to obtain a molded product capable of suppressing member deformation due to impact while improving energy absorption in high-temperature and low-temperature environments.

FIG. 1 is a diagram showing an energy absorbing member (EA member). FIG. 2 is a diagram showing a falling weight impact test. FIG. 3(A) is a load (F)-displacement (ΔH) curve obtained by a falling weight impact test. (B) is a graph obtained by integrating the F-ΔH curve and converting it into an energy absorption (EA)-ΔH curve. (C) is an explanatory diagram for calculating the deformed resin amount (ΔW) from the cross-sectional area of the EA member portion corresponding to ΔH. (D) is the EA-ΔW curve using the obtained ΔW.

The present invention will now be described in more detail.

The resin composition of the present invention comprises at least a polyamide (A), a polyphenylene ether (B), and a polyrotaxane (C) in which a cyclic molecule is modified with a graft chain having a terminal hydroxyl group (hereinafter sometimes referred to as polyrotaxane (C). ), a copolymer (D) comprising an aromatic vinyl monomer and a conjugated diene, and a fibrous filler (E). The strength and heat resistance can be improved by blending the polyamide (A). By blending the polyphenylene ether (B), strength and rigidity at high temperatures can be improved. By blending the polyrotaxane (C), it is possible to improve the toughness while maintaining the rigidity at low temperatures. In addition, impact resistance can be improved by blending a copolymer (D) comprising an aromatic vinyl-based monomer and a conjugated diene. Furthermore, by blending the fibrous filler (E), strength and dimensional stability can be greatly improved. Therefore, by blending a polyamide (A), a polyphenylene ether (B), a polyrotaxane (C), a copolymer (D) composed of an aromatic vinyl monomer and a conjugated diene, and a fibrous filler (E), , the toughness can be improved while maintaining the rigidity in a wide range of temperature environments from low to high temperatures.

The polyamide (A) in the resin composition of the present invention contains residues of amino acids, lactams or diamines and dicarboxylic acids as main constituents. Representative examples of raw materials thereof include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and para-aminomethylbenzoic acid; lactams such as ε-caprolactam and ω-laurolactam; methylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4-/2,4,4-trimethylhexamethylenediamine, 5 - aliphatic diamines such as methylnonamethylenediamine, aromatic diamines such as meta-xylylenediamine and para-xylylenediamine, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1- Amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis(4-aminocyclohexyl)methane, bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane , bis(aminopropyl)piperazine, aminoethylpiperazine and other alicyclic diamines, adipic acid, suberic acid, azelaic acid, sebacic acid, dodecanedioic acid and other aliphatic dicarboxylic acids, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid acids, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, aromatic dicarboxylic acids such as hexahydroisophthalic acid, 1,4-cyclohexane alicyclic dicarboxylic acids such as dicarboxylic acids, 1,3-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, and 1,3-cyclopentanedicarboxylic acid; In the present invention, two or more polyamide homopolymers or copolymers derived from these raw materials may be blended.

Specific examples of polyamide (A) include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polytetramethylene adipamide (nylon 46), polytetramethylene sebacamide (nylon 410), polypentamethylene adipamide (nylon 56), polypentamethylene sebacamide (nylon 510), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612), polydecamethylene adipamide Pamide (nylon 106), polydecamethylene sebacamide (nylon 1010), polydecamethylenedodecanamide (nylon 1012), polyundecaneamide (nylon 11), polydodecanamide (nylon 12), polycaproamide/polyhexa Methylene Adipamide Copolymer (Nylon 6/66), Polycaproamide/Polyhexamethylene Terephthalamide Copolymer (Nylon 6/6T), Polyhexamethylene Adipamide/Polyhexamethylene Terephthalamide Copolymer (Nylon 66/6T), Poly Hexamethylene adipamide/polyhexamethylene isophthalamide copolymer (nylon 66/6I), polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer (nylon 6T/6I), polyhexamethylene terephthalamide/polydodecanamide copolymer (nylon 6T/12), polyhexamethylene adipamide/polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer (nylon 66/6T/6I), polyxylylene adipamide (nylon XD6), polyxylylene sebacamide (nylon XD10), polyhexamethylene terephthalamide/polypentamethylene terephthalamide copolymer (nylon 6T/5T), polyhexamethylene terephthalamide/poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T/M5T), polypentamethylene Terephthalamide/polydecamethylene terephthalamide copolymer (nylon 5T/10T), polynonamethylene terephthalamide (nylon 9T), polydecamethylene terephthalamide (nylon 10T), polydodecamethylene terephthalamide (nylon 12T) and copolymers thereof Amalgamation etc. are mentioned. You may mix|blend 2 or more types of these. Here, "/" indicates a copolymer, and the same applies hereinafter.

In the resin composition of the present invention, the polyamide (A) preferably has a melting point of 150°C or higher and lower than 300°C. If the melting point is 150° C. or higher, the heat resistance can be improved. On the other hand, if the melting point is less than 300° C., the processing temperature during production of the resin composition can be moderately suppressed, and thermal decomposition of the polyrotaxane (C) can be suppressed.

Here, the melting point of the polyamide in the present invention is measured by using a differential scanning calorimeter, in an inert gas atmosphere, the temperature of the polyamide is lowered from the molten state to 30 ° C. at a temperature lowering rate of 20 ° C./min, and then 20 ° C./min. is defined as the temperature of the endothermic peak that appears when the temperature is raised to the melting point + 40°C at a heating rate of . However, when two or more endothermic peaks are detected, the temperature of the endothermic peak with the highest peak intensity is taken as the melting point.

Specific examples of polyamides having a melting point of 150° C. or more and less than 300° C. include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polypentamethylene adipamide (nylon 56), poly Tetramethylene adipamide (nylon 46), polyhexamethylene sebacamide (nylon 610), polyhexamethylenedodecanamide (nylon 612), polyundecaneamide (nylon 11), polydodecanamide (nylon 12), polycaproamide /polyhexamethylene adipamide copolymer (nylon 6/66), polycaproamide/polyhexamethylene terephthalamide copolymer (nylon 6/6T), polyhexamethylene adipamide/polyhexamethylene isophthalamide copolymer (nylon 66/6I ), polyhexamethylene terephthalamide/polyhexamethylene isophthalamide copolymer (nylon 6T/6I), polyhexamethylene terephthalamide/polydodecanamide copolymer (nylon 6T/12), polyhexamethylene adipamide/polyhexamethylene terephthalamide /polyhexamethylene isophthalamide copolymer (nylon 66/6T/6I), polyxylylene adipamide (nylon XD6), polyhexamethylene terephthalamide/poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T/M5T), Examples include polynonamethylene terephthalamide (nylon 9T) and copolymers thereof. You may mix|blend 2 or more types of these.

The degree of polymerization of the polyamide (A) is not particularly limited, but the relative viscosity measured at 25° C. in a 98% concentrated sulfuric acid solution having a resin concentration of 0.01 g/ml is in the range of 1.5 to 5.0. is preferred. If the relative viscosity is 1.5 or more, the toughness and rigidity of the resulting molded article can be further improved. 2.0 or more is more preferable. On the other hand, when the relative viscosity is 5.0 or less, the moldability is excellent due to the excellent fluidity.

The blending amount of the polyamide (A) in the resin composition of the present invention is 10 parts per 100 parts by weight in total of the polyamide (A), the polyphenylene ether (B), the polyrotaxane (C), and the fibrous filler (E). It is preferable that the amount is not less than 95.9 parts by weight and not more than 95.9 parts by weight. In addition, when the amount of the polyamide (A) blended is 10 parts by weight or more, a molded article having good strength and heat resistance can be obtained. The blending amount of the polyamide (A) is more preferably 20 parts by weight or more, further preferably 30 parts by weight or more. On the other hand, by setting the blending amount of the polyamide (A) to 95.9 parts by weight or less, the effect of blending the polyphenylene ether (B) and the polyrotaxane (C) is sufficiently exhibited, and the rigidity and toughness at low and high temperatures are improved. An excellent molded product can be obtained. 80 parts by weight or less is more preferable, and 70 parts by weight or less is even more preferable.

As the polyphenylene ether (B) used in the present invention, a homopolymer or a copolymer having the following general formula [1] as a repeating unit and the structural unit having the general formula [1] can be used.

(Wherein R ₁ , R ₂ , R ₃ , R ₄ are monovalent residues selected from alkyl groups of 1 to 4 carbons, aryl groups, halogens, and hydrogen.)

Specific examples of homopolymers of polyphenylene ether (B) include poly(2,6-dimethyl-1,4-phenylene) ether, poly(2-methyl-6-ethyl-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene oxide), poly(2-methyl-6-phenyl-1,4-phenylene oxide), poly(2,6-dichloro-1,4-phenylene oxide), poly (2,6-diethyl-1,4-phenylene) ether, poly(2-ethyl-6-n-propyl-1,4-phenylene) ether, poly(2,6-di-n-propyl-1,4 -phenylene) ether, poly(2-methyl-6-n-butyl-1,4-phenylene) ether, poly(2-ethyl-6-isopropyl-1,4-phenylene) ether, poly(2-methyl-6 -chloroethyl-1,4-phenylene)ether, poly(2-methyl-6-hydroxyethyl-1,4-phenylene)ether and other homopolymers. Among them, poly(2,6-dimethyl-1,4-phenylene) ether is most preferably used.

The polyphenylene ether copolymers include copolymers of 2,6-dimethylphenol and 2,3,6-trimethylphenol, copolymers of 2,6-dimethylphenol and o-cresol, and 2,6- Examples thereof include copolymers of dimethylphenol, 2,3,6-trimethylphenol, and o-cresol, including polyphenylene ether copolymers having formula [1] as a main structural unit. Here, the term "constituted as a main structural unit" means that the structural unit represented by formula [1] accounts for 50 mol% or more of all structural units.

The polyphenylene ether (B) also includes those obtained by grafting a styrene-based polymer or other polymer to the above polyphenylene ether homopolymer or copolymer.

Polyphenylene ether (B) preferably has a reduced viscosity in the range of 0.15 to 0.70 measured at 30° C. in a 0.5 g/dl chloroform solution.

The glass transition temperature of the polyphenylene ether (B) obtained when the temperature is raised at 20°C/min in an inert gas atmosphere using a differential scanning calorimeter is preferably 80°C or higher and lower than 250°C. If the glass transition temperature is 80° C. or higher, heat resistance can be improved. On the other hand, if the glass transition temperature is less than 250°C, compatibility with the polyamide (A) is improved, and strength, elastic modulus and toughness can be improved.

The amount of polyphenylene ether (B) in the resin composition of the present invention is, with respect to a total of 100 parts by weight of polyamide (A), polyphenylene ether (B), polyrotaxane (C), and fibrous filler (E), It is 3 parts by weight or more and 35 parts by weight or less. If the amount of polyphenylene ether (B) to be blended is less than 3 parts by weight, a molded article having good rigidity at high temperatures cannot be obtained. The blending amount of the polyphenylene ether (B) is preferably 5 parts by weight or more, more preferably 7 parts by weight or more. On the other hand, if the blending amount of the polyphenylene ether (B) exceeds 35 parts by weight, a molded article having excellent low-temperature toughness cannot be obtained. The blending amount of the polyphenylene ether (B) is preferably 30 parts by weight or less, more preferably 18 parts by weight or less, and even more preferably 15 parts by weight or less.

The resin composition of the present invention contains a polyrotaxane (C) in which a cyclic molecule is modified with a graft chain having a terminal hydroxyl group. Rotaxanes are described, for example, in Harada, A.; , Li, J.; & Kamachi, M.; , Nature 356, 325-327, it generally refers to a molecule having a shape in which a cyclic molecule is pierced through a linear molecule having bulky blocking groups at both ends. Polyrotaxanes are those in which a plurality of cyclic molecules are penetrated by a single linear molecule.

The polyrotaxane (C) consists of a linear molecule and a plurality of cyclic molecules, has a structure in which the linear molecule penetrates through openings of the plurality of cyclic molecules, and has cyclic molecules at both ends of the linear molecule. It has a bulky blocking group so that it does not detach from the linear molecule. In the polyrotaxane (C), the cyclic molecule can move freely on the straight-chain molecule, but has a structure that prevents it from escaping from the straight-chain molecule due to the blocking group. In other words, linear molecules and cyclic molecules have structures that maintain their shape through mechanical bonds rather than chemical bonds. Such polyrotaxane (C) is effective in relieving external stress and internal residual stress due to the high mobility of the cyclic molecules. Furthermore, by blending the polyrotaxane (C) in which the cyclic molecule is modified with a graft chain having a hydroxyl group at the end, it is possible to spread the same effect to the resin composition.

The linear molecule is not particularly limited as long as it penetrates through the opening of the cyclic molecule and has a functional group capable of reacting with the blocking group. Linear molecules preferably used include polyalkylene glycols such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol; hydroxyl-terminated polyolefins such as polyethylene diol and polypropylene diol; polyesters such as polycaprolactone diol, polylactic acid, polyethylene adipate, polybutylene adipate, polyethylene terephthalate and polybutylene terephthalate; terminal functional polysiloxanes such as silanol-terminated polydimethylsiloxane Amino-terminated chain polymers such as amino-terminated polyethylene glycol, amino-terminated polypropylene glycol, and amino-terminated polybutadiene; trifunctional or higher polyfunctional chain polymers having three or more of the above functional groups in one molecule Examples include polymers. Among them, polyethylene glycol and/or amino-terminated polyethylene glycol are preferably used because polyrotaxane synthesis is easy.

The number average molecular weight of the straight-chain molecule is preferably 2,000 or more, and the rigidity can be further improved. 10,000 or more is more preferable. On the other hand, 100,000 or less is preferable, and compatibility with polyamide (A) and polyphenylene ether (B) can be improved, and the phase separation structure can be refined, so toughness can be further improved. . 50,000 or less is more preferable. Here, the number average molecular weight of the linear molecule is measured by gel permeation chromatography using hexafluoroisopropanol as a solvent and Shodex HFIP-806M (2 columns) + HFIP-LG as columns, polymethyl methacrylate. Refers to the conversion value.

The blocking group is not particularly limited as long as it is capable of binding to the terminal functional group of the straight-chain molecule and is sufficiently bulky to prevent the cyclic molecule from leaving the straight-chain molecule. Blocking groups preferably used include a dinitrophenyl group, a cyclodextrin group, an adamantyl group, a trityl group, a fluoresceinyl group, a pyrenyl group, an anthracenyl group, a main chain of a polymer having a number average molecular weight of 1,000 to 1,000,000, or A side chain and the like can be mentioned. You may have 2 or more types of these.

The cyclic molecule is not particularly limited as long as a linear molecule can pass through the opening. Preferred cyclic molecules include cyclodextrins, crown ethers, cryptands, macrocyclic amines, calixarenes, cyclophanes and the like. Cyclodextrins are compounds in which multiple glucoses are cyclically linked by α-1,4-bonds. α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin are more preferably used.

The polyrotaxane (C) is characterized in that the cyclic molecule is modified with a graft chain having a terminal hydroxyl group. By modifying the cyclic molecule with a hydroxyl group-terminated graft chain, the compatibility with the polyamide (A) and the polyphenylene ether (B) and the affinity with the interface of the fibrous filler (E) are improved. As a result, toughness can be improved while maintaining the rigidity of the resin composition, and rigidity and toughness can be improved in a well-balanced manner.

The graft chain is preferably made of polyester. Aliphatic polyesters are more preferable in terms of compatibility with polyamide (A) and polyphenylene ether (B) and solubility in organic solvents. Aliphatic polyesters include polylactic acid, polyglycolic acid, poly-3-hydroxybutyrate, poly-4-hydroxybutyrate, poly(3-hydroxybutyrate/3-hydroxyvalerate), poly(ε-caprolactone), and the like. mentioned. Among them, poly(ε-caprolactone) is more preferable from the viewpoint of compatibility with the polyamide (A). Polyrotaxane (C) can be obtained by the following method. For example, by grafting poly(ε-caprolactone) onto cyclodextrins, a polyrotaxane in which the ends of grafted chains are modified with hydroxyl groups can be obtained.

The hydroxyl group concentration at the end of the graft chain of polyrotaxane (C) in the resin composition of the present invention is preferably 2×10 ⁻⁵ mol/g or more and 5×10 ⁻³ mol/g or less. Compatibility with the polyamide (A) and the polyphenylene ether (B) can be improved by adjusting the hydroxyl group concentration to 2×10 ⁻⁵ mol/g or more. As a result, the toughness can be further improved while maintaining the rigidity of the resin composition, and the rigidity and toughness can be improved in a well-balanced manner. More preferably, the hydroxyl group concentration is 3×10 ⁻⁵ mol/g or more. On the other hand, by setting the hydroxyl group concentration to 5×10 ⁻³ mol/g or less, it is possible to suppress aggregation due to the association of hydroxyl groups of the polyrotaxane (C) and excessive chemical cross-linking with the polyamide (A). It is possible to further improve the toughness by suppressing the generation of substances and gels. More preferably, the hydroxyl group concentration is 2×10 ⁻³ mol/g or less.

Here, the hydroxyl group concentration at the end of the graft chain of the polyrotaxane (C) can be determined by titration. An absolutely dry sample is prepared by drying polyrotaxane (C) for 10 hours or more using an 80° C. vacuum dryer. A large excess of succinic anhydride is added to a solution prepared by dissolving 1.0 g of the absolute dry sample in 50 ml of toluene, and the mixture is heated at 90° C. for 6 hours under nitrogen flow. After concentrating with an evaporator until the polymer concentration reaches about 50%, the polymer solution is added to a large excess of methanol solution and the precipitate is collected. The obtained precipitate is dried in a vacuum dryer at 80° C. for 8 hours to obtain a polymer. A hydroxyl group concentration can be determined by titrating a solution obtained by dissolving 0.2 g of the obtained polymer in 25 ml of benzyl alcohol with an ethanol solution of potassium hydroxide having a concentration of 0.02 mol/L.

The weight average molecular weight of the polyrotaxane (C) in the resin composition of the present invention is preferably 100,000 or more, and can further improve the strength and toughness. On the other hand, the weight average molecular weight of the polyrotaxane (C) is preferably 1,000,000 or less, which improves the compatibility with the polyamide (A) and the polyphenylene ether (B), and can further improve the toughness. Here, the weight average molecular weight of the polyrotaxane (C) is measured by gel permeation chromatography using hexafluoroisopropanol as a solvent and Shodex HFIP-806M (2 columns) + HFIP-LG as columns. Refers to the methacrylate conversion value.

The amount of the polyrotaxane (C) in the resin composition is 0.1 with respect to a total of 100 parts by weight of the polyamide (A), the polyphenylene ether (B), the polyrotaxane (C), and the fibrous filler (E). It is not less than 10 parts by weight and not more than 10 parts by weight. If the amount of the polyrotaxane (C) is less than 0.1 parts by weight, the stress relaxation effect of the polyrotaxane (C) is not sufficiently exhibited, and the effect of improving the toughness of the molded article cannot be obtained. The blending amount of the polyrotaxane (C) is preferably 0.3 parts by weight or more, more preferably 1 part by weight or more. On the other hand, when the amount of the polyrotaxane (C) exceeds 10 parts by weight, the amounts of the polyamide (A) and the polyphenylene ether (B) are relatively decreased, and the rigidity and heat resistance of the obtained molded article are lowered. . 7 parts by weight or less is preferable, and 5 parts by weight or less is more preferable.

The resin composition of the present invention contains a copolymer (D) comprising an aromatic vinyl monomer and a conjugated diene. The copolymer (D) comprising an aromatic vinyl monomer and a conjugated diene includes block copolymers and random copolymers comprising an aromatic vinyl monomer and a conjugated diene, and hydrogenated copolymers thereof. It is preferably at least one selected from substances. When the copolymer (D) composed of the aromatic vinyl monomer and the conjugated diene is not blended, the compatibility between the polyamide (A) and the polyphenylene ether (B) deteriorates, resulting in a molded product with excellent rigidity and toughness. can't get

Examples of aromatic vinyl monomers include styrene, α-methylstyrene, vinyltoluene, p-methylstyrene, pt-butylstyrene, o-ethylstyrene and o,p-dichlorostyrene. Conjugated dienes include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3-hexadiene, 4,5 -diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like. Among these, block copolymers obtained from styrene and 1,3-butadiene, block copolymers obtained from styrene and isoprene, and hydrogenated products thereof are preferred.

At least one copolymer selected from the block copolymer and random copolymer comprising the aromatic vinyl monomer and the conjugated diene, and hydrogenated products thereof, may be acid-modified, Acid modification includes a method of reacting a compound having a carboxyl group or an acid anhydride group in the presence of a radical generator.

When blending at least one copolymer selected from block copolymers and random copolymers composed of the aromatic vinyl monomer and conjugated diene, and hydrogenated products thereof, the blending amount is Polyamide (A), polyphenylene ether (B), polyrotaxane (C), and fibrous filler (E) total amount of 100 parts by weight, preferably in the range of 1 to 20 parts by weight, preferably in the range of 1 to 10 parts by weight is more preferred. When the amount is 1 part by weight or more, the resulting resin composition tends to have improved impact resistance, and when the amount is 20 parts by weight or less, the heat resistance tends to be maintained.

The resin composition of the present invention contains a fibrous filler (E). By containing the fibrous filler (E), it is possible to obtain a molded product excellent in dimensional stability in addition to mechanical properties such as strength and rigidity.

Any filler having a fibrous shape can be used as the fibrous filler (E). Specifically, glass fiber; polyacrylonitrile (PAN)-based and pitch-based carbon fiber; stainless steel fiber, aluminum fiber, brass fiber and other metal fibers; polyester fiber, aromatic polyamide fiber and other organic fibers; gypsum fiber, ceramic fibrous or whisker-like fillers such as fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, silicon nitride whisker, wollastonite, alumina silicate; nickel , glass fibers coated with one or more metals selected from the group consisting of copper, cobalt, silver, aluminum, iron and alloys thereof. You may contain 2 or more types of these.

Among the fibrous fillers, fibrous fillers selected from glass fiber, carbon fiber, stainless fiber, aluminum fiber and aromatic polyamide fiber are preferably used from the viewpoint of further improving the strength, rigidity and surface appearance of the molded product. be done. Furthermore, at least one fibrous filler selected from glass fiber and carbon fiber is particularly preferably used in terms of obtaining a resin composition having an excellent balance between the mechanical properties of molded articles such as rigidity and strength and the fluidity of the resin composition. be done.

The fibrous filler (E) may have a surface coated with a coupling agent, a sizing agent, or the like. By attaching a coupling agent or a sizing agent, the wettability of the polyamide (A) and the handleability of the fibrous filler (E) can be improved. Examples of coupling agents include amino-based, epoxy-based, chlorine-based, mercapto-based, and cationic silane coupling agents. An amino-based silane-based coupling agent can be used particularly preferably. Examples of sizing agents include sizing agents containing compounds selected from carboxylic acid compounds, maleic anhydride compounds, urethane compounds, acrylic compounds, epoxy compounds, phenol compounds, and derivatives thereof.

The content of the fibrous filler (E) in the resin composition of the present invention is based on a total of 100 parts by weight of the polyamide (A), the polyphenylene ether (B), the polyrotaxane (C), and the fibrous filler (E). , 1 part by weight or more and 60 parts by weight or less. By setting the content of the fibrous filler (E) to 1 part by weight or more, the mechanical properties and dimensional stability of the molded product are improved. The content of the fibrous filler (E) is more preferably 10 parts by weight or more, and even more preferably 20 parts by weight or more. On the other hand, by setting the content of the fibrous filler (E) to 60 parts by weight or less, it is possible to suppress deterioration of the appearance of the molded product due to the fibrous filler (E) protruding from the surface of the molded product. The content of the fibrous filler (E) is more preferably 55 parts by weight or less, even more preferably 50 parts by weight or less.

When the resin composition of the present invention is used to mold a test piece conforming to ISO178:2010, and the flexural properties of the test piece are measured by a method conforming to ISO178:2010, It is preferable that the bending elastic modulus at -30°C is 7 GPa or more, the bending maximum point strain is 4% or less, and the bending breaking strain at -30°C is 4% or more. The bending elastic modulus at 80° C. is more preferably 8 GPa or more, and even more preferably 9 GPa or more. The upper limit of the bending elastic modulus at 80° C. is preferably 14 GPa or less. Further, the bending maximum strain at 80° C. is more preferably 3% or less, and even more preferably 2% or less. The lower limit of the bending maximum point strain at 80° C. is preferably 1.5% or more. When the bending elastic modulus at 80° C. is 7 GPa or more and 14 GPa or less and the bending maximum point strain is 1.5% or more and 4% or less, the member deformation amount can be suppressed when impact is applied to the molded product at high temperature, It is preferable because it can function as a protective member. Also, the bending elastic strain at -30°C is preferably 6% or less. When the bending breaking strain at −30° C. is 4% or more and 6% or less, brittle fracture does not occur when an impact is applied to the molded article at low temperatures, and energy absorption can be maintained, which is preferable. The bending maximum strain at −30° C. is more preferably 4.5% or more, more preferably 5% or more.

The method of setting the flexural modulus and maximum bending strain at 80°C and the bending breaking strain at -30°C to the above values is not particularly limited as long as such a resin composition can be obtained. Polyamide (A), polyphenylene ether (B), polyrotaxane (C), and fibrous filler It may be 1 to 20 parts by weight with respect to the total 100 parts by weight of the material (E).

The resin composition of the present invention further improves the affinity between the polyamide (A) and the polyrotaxane (C), thereby improving toughness while maintaining rigidity. and at least one alkoxysilyl group. By using such a silane coupling agent, a functional group reactive with an amino group reacts with the amino group at the end of the polyamide (A), and the alkoxysilyl group modifies the cyclic molecule of the polyrotaxane (C) graft chain end. By reacting with the hydroxyl groups of, a copolymer of polyamide (A) and polyrotaxane (C) is formed, and toughness can be improved while maintaining rigidity in a wide range of temperature environments from low to high temperatures.

Examples of the functional group reactive with the amino group of the silane coupling agent include isocyanate group, glycidyl group, carboxyl group, acid anhydride, acyl halide group, aldehyde group and ketone group. From the viewpoint of reactivity, it is preferably at least one selected from isocyanate groups, glycidyl groups, acid anhydrides, and acyl halide groups.

Examples of the isocyanate group include an aliphatic isocyanate group, an aromatic isocyanate group, a blocked isocyanate group, and the like, and any of these may be used.

The blocked isocyanate group is a functional group in which the isocyanate group is protected by reaction with a blocking agent and is temporarily inactivated. A compound having a plurality of blocked isocyanate groups is a blocked isocyanate compound. The blocking agent can be dissociated by heating to a predetermined temperature. As such a blocked isocyanate compound, an addition reaction product of an isocyanate compound and a blocking agent is used. Examples of the isocyanate compound that can react with the blocking agent include the compounds exemplified as the isocyanate compound. Examples of blocked isocyanate compounds include isocyanurate, biuret, and adduct. Two or more of the blocked isocyanate compounds may be used in combination, if necessary.

Examples of the blocking agent include phenolic blocking agents such as phenol, cresol, xylenol, chlorophenol and ethylphenol; lactam blocking agents such as ε-caprolactam, δ-valerolactam, γ-butyrolactam and β-propiolactam. active methylene-based blocking agents such as ethyl acetoacetate and acetylacetone; methanol, ethanol, propanol, butanol, amyl alcohol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, propylene glycol monomethyl ether, Alcohol-based blocking agents such as benzyl ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate, and ethyl lactate; Blocking agents; mercaptan blocking agents such as butyl mercaptan, hexyl mercaptan, t-butyl mercaptan, thiophenol, methylthiophenol and ethylthiophenol; acid amide blocking agents such as acetamide and benzamide; imide-based blocking agents; amine-based blocking agents such as xylidine, aniline, butylamine and dibutylamine; imidazole-based blocking agents such as imidazole and 2-ethylimidazole; and imine-based blocking agents such as methyleneimine and propyleneimine. The blocking agents may be used alone or in combination of two or more.

Examples of the alkoxy group of the alkoxysilyl group of the silane coupling agent include a methoxy group, an ethoxy group, a propioxy group, and a butoxy group. A methoxy group or an ethoxy group is preferred from the viewpoint of reactivity. Moreover, the alkoxysilyl group may be any of a monoalkoxysilyl group, a dialkoxysilyl group, and a trialkoxysilyl group.

The amount of the silane coupling agent is 0.05 to 2 parts by weight with respect to 100 parts by weight of the total amount of polyamide (A), polyphenylene ether (B), polyrotaxane (C), and fibrous filler (E). is preferred, and a range of 0.05 to 1 part by weight is more preferred. When the amount is 0.05 parts by weight or more, the resulting resin composition tends to have improved impact resistance, and when the amount is 2 parts by weight or less, the polyamide (A) and the polyrotaxane (C) are excessively crosslinked. can be suppressed, and a decrease in the breaking strength of the material can be suppressed.

The method for producing the resin composition of the present invention is not particularly limited, but examples include a method of kneading raw materials in a molten state, a method of mixing them in a solution state, and the like. From the viewpoint of improving reactivity, a method of kneading in a molten state is preferred. Melt-kneading devices for kneading in a molten state include, for example, a single-screw extruder; a multi-screw extruder such as a twin-screw extruder and a four-screw extruder; mentioned. From the viewpoint of productivity, an extruder capable of continuous production is preferred, and from the viewpoint of improvement in kneadability, reactivity and productivity, a twin-screw extruder is more preferred.

An example of producing the resin composition of the present invention using a twin-screw extruder will be described below. From the viewpoint of suppressing thermal deterioration of the polyrotaxane (C) and further improving toughness, the maximum resin temperature in the melt-kneading step is preferably 300° C. or less. On the other hand, the minimum resin temperature is preferably at least the melting point of polyamide (A). Here, the maximum resin temperature refers to the highest temperature among temperatures measured by resin thermometers evenly installed at a plurality of locations of the extruder.

Further, the ratio of the extrusion amount of the resin composition to the screw rotation speed in the melt-kneading step is 0.01 kg per screw rotation speed 1 rpm from the viewpoint of further suppressing thermal deterioration of the polyamide (A) and the polyrotaxane (C). /h or more is preferable, and 0.05 kg/h or more is more preferable. Here, the extrusion rate refers to the weight (kg) of the resin composition extruded from the extruder per hour. Further, the extrusion rate per 1 rpm of screw rotation speed is a value obtained by dividing the extrusion rate by the screw rotation speed.

The resin composition thus obtained can be molded by a known method to obtain various molded articles such as sheets and films. Examples of molding methods include injection molding, injection compression molding, extrusion molding, compression molding, blow molding, and press molding.

In addition, the resin composition of the present invention can be used as a three-dimensional modeling material by molding into filaments, particles, pellets, or the like.

For example, by molding the resin composition of the present invention by commonly known extrusion molding, a Fused Deposition Molding (FDM) three-dimensional modeling filament can be obtained. The thickness of the filament may be freely adjusted to suit the three-dimensional modeling apparatus used, and generally filaments with a diameter of 1.5 to 2.0 mm are preferably used.

A model can be obtained by using filaments, particles, or pellets as the three-dimensional modeling material and modeling with a three-dimensional modeling apparatus.

The resin composition of the present invention, its molded article, and its three-dimensional molded article can be used for various purposes such as automobile parts, electrical and electronic parts, building materials, various containers, daily necessities, household goods, and sanitary goods, taking advantage of their excellent properties. can be used. In particular, it is particularly preferably used for automotive exterior parts requiring toughness and strength, automotive electronic parts, automotive underhood parts, automotive gear parts; and electrical and electronic parts such as housings, connectors, and reflectors. Specifically, automotive engine peripheral parts such as engine covers, air intake pipes, timing belt covers, intake manifolds, filler caps, throttle bodies, cooling fans; cooling fans, radiator tank tops and bases, cylinder head covers, oil pans, Automotive underhood parts such as brake piping, fuel piping tubes, waste gas system parts; automotive gear parts such as gears, actuators, bearing retainers, bearing cages, chain guides, chain tensioners; shift lever brackets, steering lock brackets, key cylinders , door inner handles, door handle cowls, interior mirror brackets, air conditioner switches, instrument panels, console boxes, glove boxes, steering wheels, trims; front fenders, rear fenders, fuel lids, door panels, cylinder head covers, door mirrors Automobile exterior parts such as stays, tailgate panels, license garnishes, roof rails, engine mount brackets, rear garnishes, rear spoilers, trunk lids, rocker moldings, moldings, lamp housings, front grilles, mudguards, side bumpers; air intake manifolds, intercoolers Intake and exhaust system parts such as inlets, exhaust pipe covers, inner bushes, bearing retainers, engine mounts, engine head covers, resonators, and throttle bodies; Engines such as chain covers, thermostat housings, outlet pipes, radiator tanks, alternators, and delivery pipes Cooling water system parts; Automotive electrical parts such as connectors, wire harness connectors, motor parts, lamp sockets, sensor in-vehicle switches, combination switches; SMT compatible connectors, sockets, card connectors, jacks, power supply parts, switches, sensors, condenser base plates , relays, resistors, fuse holders, coil bobbins, housings for ICs and LEDs, and reflectors.

Furthermore, the resin composition of the present invention, its molded article, and its three-dimensional structure can be suitably used as an energy absorbing member for vehicles, which requires high energy absorption performance, impact safety performance, and weight reduction of the member. The resin composition of the present invention has high energy absorption efficiency, and the shape of the energy absorption member is not particularly limited, and any shape can be adopted according to the place where it is used. Taking advantage of such properties, it is preferably used for automobile bumper beams, members installed together with side sills, underhoods, and parts installed inside door panels, for example.

EXAMPLES The present invention will be described below with reference to examples, but the present invention is not limited by these examples. In order to obtain the resin composition of each example, the following raw materials were used.

<Polyamide>
(A-1): Polyamide 6 resin (“Amilan” (registered trademark) manufactured by Toray Industries, Inc.) was used. ηr is 2.70, the melting point is 225° C., and the amide group concentration is 6.2×10 ⁻² mmol/g.

<Polyphenylene ether>
(B-1): A polyphenylene ether resin (“Iupiace” (registered trademark) PX-100F manufactured by Mitsubishi Engineering-Plastics Co., Ltd.) was used. The glass transition temperature is 205°C.

<Polyrotaxane>
(C-1): Polyrotaxane (“Celm” (registered trademark) superpolymer SH3400P manufactured by ASM Co., Ltd.) was used. The terminal group ^of the graft chain that modifies the cyclic molecule of this polyrotaxane is a hydroxyl group. 000, the overall weight average molecular weight is 654,000. Here, the weight-average molecular weight of the polyrotaxane is a value in terms of polymethyl methacrylate measured by gel permeation chromatography using hexafluoroisopropanol as a solvent and ShoDex HFIP-806M (2 columns) + HFIP-LG as columns. is. The melting initiation temperature of the polyrotaxane (C-1) was 35°C. Here, the melting initiation temperature of the polyrotaxane is the initiation temperature of the endothermic peak that appears when the temperature is raised from 23° C. to 120° C. at a rate of 20° C./min in an inert gas atmosphere using a differential scanning calorimeter. is.

<Copolymer Composed of Aromatic Vinyl Monomer and Conjugated Diene>
(D-1): A hydrogenated styrene-butadiene-styrene copolymer (Kraton FG1924 manufactured by Kraton Polymer Japan Co., Ltd.) was used.

(D-2): A polystyrene resin (HF77 manufactured by PS Japan Co., Ltd.) was used.

(D-3): Maleic anhydride-modified polystyrene (DYLARK D332 manufactured by NOVA Chemical Co., Ltd.) was used.

<Fibrous filler>
(E-1): Glass fiber (T-249 manufactured by Nippon Electric Glass Co., Ltd.) was used.

<Silane coupling agent>
(F-1): 3-isocyanatopropyltriethoxysilane (silane coupling agent KBE-9007N manufactured by Shin-Etsu Chemical Co., Ltd.) with a molecular weight of 247.4 g/mol.

<Evaluation method>
The evaluation method in each example and comparative example will be described. Unless otherwise specified, the number of evaluation n was set to n=5 and the average value was obtained.

(1) Flexural modulus After drying the pellets obtained in each example and comparative example under reduced pressure at 80 ° C. for 12 hours, using an injection molding machine (SE75DUZ-C250 manufactured by Sumitomo Heavy Industries), cylinder temperature: 250 ° C., A multi-purpose test piece conforming to ISO178:2010 was produced by injection molding under conditions of mold temperature: 80°C. A bending test piece obtained from this multi-purpose test piece is subjected to a bending test using a precision universal testing machine AG-50kNX (manufactured by Shimadzu Corporation) at a crosshead speed of 2 mm / min according to ISO178:2010 to determine the bending elastic modulus. rice field. The measurement was carried out at a temperature of 80° C., and after the test piece was attached to the tester, it was carried out when the desired temperature was reached.

(2) Maximum Bending Point Strain In the bending test described above, the maximum bending point strain was obtained.

(3) Bending Breaking Strain In the bending test described above, the test was conducted at a measurement temperature of −30° C. to obtain the bending breaking strain.

(4) Energy absorbing member (Fig. 1)
An energy absorbing member (EA member) 1 having the shape shown in FIG. 1 was produced by injection molding using the resin compositions obtained in each example and comparative example. The EA member 1 includes a hollow, substantially conical energy absorbing portion 2 (height: 117 mm) having a spherical outer surface at the top, and a bottom plate portion 3 (length: 80 mm × 80 mm in width), a fixing hole 4 provided in the bottom plate portion 3 for fixing the EA member 1 to another member, and a rib 5 provided in the hollow portion of the energy absorbing portion 2, and the energy absorbing portion It is assumed that an impact load such as a collision load is input from the top side of 2.

(5) Falling weight impact test (Fig. 2)
As shown in FIG. 2, the EA member 1 obtained by the above-described method (4) is fixed or left stationary on a pedestal 11 of a falling weight impact tester, and a striker 12 (tip A falling weight impact test was performed by dropping a flat plate) at a drop height of 0.75 m, and the load and the amount of displacement (load-displacement curve: illustrated in FIG. 3(A)) were measured. The EA member used in the test was previously subjected to water absorption treatment (at 60° C. and 95% RH for 24 hours). Measurements are carried out under the conditions of -30°C, 23°C, and 80°C. In the measurement at -30°C, the temperature of the EA member is adjusted to -40°C in advance, and after it is attached to the tester, it reaches the desired temperature. implemented at a later stage.

(6) Energy absorption (EA) efficiency (Fig. 3)
As shown in FIG. 3, after obtaining the load (F)-displacement (ΔH) curve (illustrated in FIG. 3 (A)) by the falling weight test, the F-ΔH curve is integrated to obtain the energy absorption amount Convert to (EA)-ΔH curve (illustrated in FIG. 3(B)), further calculate the volume from the cross-sectional area of the EA member portion corresponding to ΔH, multiply the volume by the specific gravity, and the deformation corresponding to the amount of displacement The resin amount (ΔW) was calculated (Fig. 3 (C)), thereby obtaining an EA-ΔW curve (Fig. 3 (D)), and calculating the slope of this curve by the least squares method to obtain the EA efficiency (J / g).

(Examples 1 to 11, Comparative Examples 1 to 9)
Each raw material was blended with the composition shown in Table 1, preblended, and a twin-screw extruder (TEX30α manufactured by Japan Steel Works, Ltd.) set to cylinder temperature: 250 ° C. and screw rotation speed: 150 rpm, extruded gut. pelletized. Table 1 shows the results of evaluation by the above method using the obtained pellets.

A comparison of the flexural modulus, maximum flexural strain, and flexural breaking strain between Examples and Comparative Examples revealed that polyamide, polyphenylene ether, polyrotaxane, a copolymer consisting of an aromatic vinyl monomer and a conjugated diene, and It was found that by blending a predetermined amount of fibrous filler, the rigidity at 80° C. is superior to the case where polyphenylene ether is not blended (Comparative Examples 1 and 2). It was also found that the toughness at −30° C. is superior to the cases where no polyrotaxane is blended (Comparative Examples 1 and 4). In addition, it was found that high-temperature rigidity and low-temperature toughness are well-balanced and excellent compared to the case where a copolymer composed of an aromatic vinyl monomer and a conjugated diene is not blended (Comparative Examples 1 to 8). Further, in the examples, when the blending amount of polyphenylene ether is less than the lower limit of the predetermined amount (Comparative Examples 1, 2, 3) or exceeds the upper limit (Comparative Example 9), the blending amount of polyrotaxane is the lower limit of the predetermined amount It was found that high-temperature stiffness and low-temperature toughness are well-balanced when compared to cases of lower than (Comparative Examples 1 and 4) or higher than the upper limit (Comparative Example 5).

From the comparison of EA efficiency between Examples and Comparative Examples, by blending a predetermined amount of polyphenylene ether, polyrotaxane, a copolymer consisting of an aromatic vinyl monomer and a conjugated diene, and a fibrous filler into a polyamide, , When polyphenylene ether is not blended (Comparative Examples 1 and 2), When polyrotaxane is not blended (Comparative Examples 1 and 4), When a copolymer composed of an aromatic vinyl monomer and a conjugated diene is not blended (Comparative Examples 1 to 8), or when the amount of polyphenylene ether is less than the lower limit of the predetermined amount (Comparative Examples 1, 2, 3) or exceeds the upper limit (Comparative Example 9), the amount of polyrotaxane is less than the predetermined amount It was found that the energy absorption is superior at -30° C. to 80° C. as compared with the case where the lower limit of is lower (Comparative Examples 1 and 4) or the case where the upper limit is exceeded (Comparative Example 5).

1 Energy absorbing member (EA member)
2 Energy absorbing part 3 Bottom plate part 4 Fixing hole 5 Rib 11 Pedestal of falling weight impact tester 12 Striker

Claims (9)

At least a polyamide (A), a polyphenylene ether (B), a polyrotaxane (C) having a cyclic molecule modified with a hydroxyl-terminated graft chain, and a copolymer (D) comprising an aromatic vinyl monomer and a conjugated diene. and a fibrous filler (E), wherein the polyamide (A), polyphenylene ether (B), polyrotaxane (C), and fibrous filler (E) total 100 parts by weight 3 to 35 parts by weight of the polyphenylene ether (B) and 0.1 to 10 parts by weight of the polyrotaxane (C). The copolymer (D) consisting of an aromatic vinyl-based monomer and a conjugated diene is a block copolymer and a random copolymer consisting of an aromatic vinyl-based monomer and a conjugated diene, and hydrogenation of these 2. The resin composition according to claim 1, which is at least one selected from the group consisting of: Using the resin composition, a test piece conforming to ISO 178:2010 was prepared and measured. 3. The resin composition according to claim 1, which has a breaking strain of 4% or more. 4. The resin composition according to claim 3, wherein said fibrous filler (E) is at least one selected from the group consisting of glass fibers and carbon fibers. A molded article made of the resin composition according to claim 1 or 2. A three-dimensional modeling material comprising the resin composition according to claim 1 or 2. The three-dimensional fabrication material according to claim 6, wherein the three-dimensional fabrication material is filament-shaped. The three-dimensional modeling material according to claim 6, wherein the three-dimensional modeling material is in powder form. A modeled object obtained by modeling the three-dimensional modeling material according to claim 6 .

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