JP7205252B2 - Resin composition and molded article thereof - Google Patents

Description

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

Fiber reinforced plastics consist of thermosetting resins such as unsaturated polyester resins and epoxy resins, thermoplastic resins such as polyamides and polyphenylene sulfide (PPS), and fibrous fillers such as carbon fibers and glass fibers. Due to its light weight and excellent mechanical properties, it is widely used in sporting goods, aerospace and general industrial applications.

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 molded articles are improved with high-strength, high-modulus fibers, there has been a problem of lowering toughness and impact resistance. 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.

JP-A-6-100774 JP 2010-209247 A

However, with conventional techniques, it has not been possible to obtain a fiber-reinforced plastic material having toughness while maintaining high strength. SUMMARY OF THE INVENTION In view of the above, an object of the present invention is to provide a resin composition from which a molded article having an excellent balance of strength and toughness can be obtained.

In order to solve the above problems, the present invention has the following configurations.

A resin composition comprising a thermoplastic resin (A), a polyrotaxane (B) in which a cyclic molecule is modified with a graft chain having a reactive functional group at its end, and a fibrous filler (C), wherein 1 to 200 parts by weight of the fibrous filler (C) is included with respect to a total of 100 parts by weight of the thermoplastic resin (A) and the polyrotaxane (B), and the thermoplastic resin (A) is a styrene resin, poly Oxymethylene, polyamide, polyester, polyimide, polyamideimide, vinyl chloride, olefin resin, polyacrylate, polyphenylene ether, polycarbonate, polyethersulfone, polyetherimide, polyetherketone, polyetheretherketone, polyarylene sulfide, cellulose derivative , a liquid crystalline resin and a modified resin thereof, a resin composition, wherein the thermoplastic resin (A ) has an ionic strength of a and the ionic strength of the polyrotaxane (B) is b, the ionic strength ratio b/a is 1.1 or more, and the resin composition is used to meet ISO527-1:2012. A compliant test piece is molded, and the energy absorbed when the tensile properties of the test piece are measured at the melting start temperature of the polyrotaxane (B) + 15 ° C. is the absorption when the tensile properties of the test piece are measured at 23 ° C. A resin composition that is 1.2 times or more of the energy .

A molded article made of the above resin composition.

The resin composition of the present invention makes it possible to obtain a molded product having an excellent balance between strength and toughness.

The present invention will now be described in more detail.

The resin composition of the present invention comprises a thermoplastic resin (A), a polyrotaxane (B) in which a cyclic molecule is modified with a graft chain having a reactive functional group at its end, and a fibrous filler (C). . By blending the thermoplastic resin (A), strength and heat resistance can be improved. Moreover, toughness can be improved by blending polyrotaxane (B). Furthermore, by blending the fibrous filler (C), strength and dimensional stability can be greatly improved. By blending the thermoplastic resin (A), the polyrotaxane (B), and the fibrous filler (C), it is possible to improve the toughness while maintaining the strength.

The thermoplastic resin (A) is not particularly limited as long as it is a resin exhibiting thermoplasticity. Polyphenylene ether, polycarbonate, polyether sulfone, polyether imide, polyether ketone, polyether ether ketone, polyarylene sulfide, cellulose derivatives, liquid crystalline resins and modified resins thereof. You may contain 2 or more types of these.

Examples of styrene resins include PS (polystyrene), HIPS (high impact polystyrene), AS (acrylonitrile/styrene copolymer), AES (acrylonitrile/ethylene/propylene/non-conjugated diene rubber/styrene copolymer), ABS ( acrylonitrile/butadiene/styrene copolymer), MBS (methyl methacrylate/butadiene/styrene copolymer), and the like. Here, "/" indicates a copolymer, and the same applies hereinafter. You may contain 2 or more types of these. Among these, ABS is particularly preferred.

Specific examples of polyamides include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polypentamethylene adipamide (nylon 56), polytetramethylene adipamide (nylon 46 ), polyhexamethylene sebacamide (nylon 610), polyhexamethylenedodecanamide (nylon 612), polyundecaneamide (nylon 11), polydodecanamide (nylon 12), polycaproamide/polyhexamethyleneadipamide 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), polynonamethylene terephthalamide (nylon 9T ) and copolymers thereof. You may contain 2 or more types of these.

Although the degree of polymerization of the polyamide is not particularly limited, it is preferable that the relative viscosity is in the range of 1.5 to 7.0 when measured at 25 ° C. as a 98% concentrated sulfuric acid solution with a resin concentration of 0.01 g / ml. , 2.2 to 4.0 are more preferred.

Examples of olefin resins include polypropylene, polyethylene, ethylene/propylene copolymer, ethylene/1-butene copolymer, ethylene/propylene/non-conjugated diene copolymer, ethylene/ethyl acrylate copolymer, ethylene/ Glycidyl methacrylate copolymer, ethylene/vinyl acetate/glycidyl methacrylate copolymer, propylene-g-maleic anhydride copolymer, ethylene/propylene-g-maleic anhydride copolymer, methacrylic acid/methyl methacrylate/ Examples include glutaric anhydride copolymers. You may contain 2 or more types of these.

The polyester is preferably a polymer or copolymer having residues of a dicarboxylic acid or its ester-forming derivative and a diol or its ester-forming derivative as main structural units. Among others, polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate/terephthalate, polypropylene isophthalate/terephthalate, polybutylene isophthalate/terephthalate, Aromatic polyesters such as polyethylene terephthalate/naphthalate, polypropylene terephthalate/naphthalate, polybutylene terephthalate/naphthalate are particularly preferred, with polybutylene terephthalate being most preferred. You may contain 2 or more types of these. In these polyesters, the ratio of terephthalic acid residues to all dicarboxylic acid residues is preferably 30 mol % or more, more preferably 40 mol % or more.

The polyester may also contain one or more residues selected from hydroxycarboxylic acids or their ester-forming derivatives and lactones. Hydroxycarboxylic acids include, for example, glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, o-hydroxybenzoic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy- 2-naphthoic acid and the like. Lactones include, for example, caprolactone, valerolactone, propiolactone, undecalactone, 1,5-oxepan-2-one and the like. Examples of polymers or copolymers having these residues as structural units include fatty acids such as polyglycolic acid, polylactic acid, polyglycolic acid/lactic acid, polyhydroxybutyric acid/β-hydroxybutyric acid/β-hydroxyvaleric acid, and the like. family polyester resins.

Although the melting point of the polyester is not particularly limited, it is preferably 120° C. or higher, more preferably 220° C. or higher, from the viewpoint of heat resistance. Although the upper limit is not particularly limited, it is preferably 300° C. or lower, more preferably 280° C. or lower. In addition, the melting point of the polyester was measured by using a differential scanning calorimeter (DSC), and the temperature of the polyester was lowered from the molten state to 30°C at a cooling rate of 20°C/min in an inert gas atmosphere, and then 20°C/min. It is defined as the temperature of the endothermic peak that appears when the temperature is increased at the rate of temperature increase. It is preferable to raise the temperature up to +40°C of the melting point.

Although the amount of carboxyl terminal groups in the polyester is not particularly limited, it is preferably 50 eq/t or less, more preferably 10 eq/t or less, from the viewpoints of fluidity, hydrolysis resistance and heat resistance. The lower limit is 0 eq/t. Incidentally, the amount of carboxyl terminal groups of the polyester was obtained by dissolving the polyester resin in an o-cresol/chloroform (2/1, vol/vol) solvent, and then using 1% bromophenol blue as an indicator to obtain a 0.05 mol/L ethanolic solution. It is a value measured by titration with potassium hydroxide.

The intrinsic viscosity of the polyester is not particularly limited as long as melt-kneading is possible, but from the standpoint of moldability, the intrinsic viscosity of a 0.5% by weight o-chlorophenol solution measured at 25° C. is 0.5%. It is preferably in the range of 36 to 1.60 dl/g, more preferably in the range of 0.50 to 1.25 dl/g, and even more preferably in the range of 0.7 to 1.0 dl/g. .

The molecular weight of the polyester is not particularly limited, but from the viewpoint of heat resistance, the weight average molecular weight (Mw) is preferably in the range of 50,000 to 500,000, more preferably in the range of 150,000 to 250,000. In the present invention, the weight average molecular weight (Mw) of polyester is a relative value to the molecular weight of standard polymethyl methacrylate measured by gel permeation chromatography (GPC).

The method for producing the polyester is not particularly limited, and examples thereof include known polycondensation methods and ring-opening polymerization methods. Either batch polymerization or continuous polymerization may be used, and both transesterification reaction and direct polymerization reaction may be applied.

Polycarbonates can be obtained by a phosgene method in which phosgene is blown into a bifunctional phenolic compound in the presence of caustic alkali and a solvent, an ester exchange method in which a bifunctional phenolic compound and diethyl carbonate are transesterified in the presence of a catalyst, and the like. . Polycarbonates include aromatic homopolycarbonates, aromatic copolycarbonates, and the like. The viscosity-average molecular weight of these aromatic polycarbonates is preferably in the range of 10,000 to 100,000.

Examples of bifunctional phenol compounds include 2,2'-bis(4-hydroxyphenyl)propane, 2,2'-bis(4-hydroxy-3,5-dimethylphenyl)propane, bis(4-hydroxyphenyl) ) methane, 1,1′-bis(4-hydroxyphenyl)ethane, 2,2′-bis(4-hydroxyphenyl)butane, 2,2′-bis(4-hydroxy-3,5-diphenyl)butane, 2,2'-bis(4-hydroxy-3,5-dipropylphenyl)propane, 1,1'-bis(4-hydroxyphenyl)cyclohexane, 1-phenyl-1,1'-bis(4-hydroxyphenyl) ) ethane and the like. You may use 2 or more types of these.

Polyarylene sulfides include, for example, polyphenylene sulfide (PPS), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers and block copolymers thereof. You may use 2 or more types of these.

Polyarylene sulfide is described in JP-B-45-3368, a method for obtaining a polymer with a relatively small molecular weight, JP-B-52-12240 and JP-A-61-7332. It can be produced by a generally known method such as a method for obtaining a polymer having a large target molecular weight. The obtained polyarylene sulfide is subjected to cross-linking/high molecular weight by heating, heat treatment under inert gas atmosphere such as nitrogen or under reduced pressure, washing with organic solvent, hot water, acid aqueous solution, etc., acid anhydride, amine, isocyanate. Of course, it is also possible to use it after performing various treatments such as activation with a functional group-containing compound such as a functional group-containing disulfide compound.

As a specific method for cross-linking/high molecular weight polyarylene sulfide by heating, in an oxidizing gas atmosphere such as air or oxygen, or in a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. can be exemplified by heating in a heating vessel at a predetermined temperature until a desired melt viscosity is obtained. The heat treatment temperature is preferably in the range of 200 to 270° C., and the heat treatment time is preferably in the range of 2 to 50 hours. From the viewpoint of efficient and uniform heat treatment, it is preferable to heat in a rotary or stirring blade-equipped heating vessel. As a specific method for heat-treating polyarylene sulfide in an inert gas atmosphere such as nitrogen or under reduced pressure, heating is performed in an inert gas atmosphere such as nitrogen or under reduced pressure (preferably 7,000 Nm ⁻² or less). A method of heat treatment under conditions of a treatment temperature of 200 to 270° C. and a heat treatment time of 2 to 50 hours can be exemplified. From the viewpoint of efficient and uniform heat treatment, it is more preferable to heat in a rotary or stirring blade-equipped heating vessel. When the polyarylene sulfide is washed with an organic solvent, N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like are preferably used as the organic solvent. As a method of washing with an organic solvent, for example, there is a method of immersing the polyarylene sulfide resin in an organic solvent, and if necessary, it is possible to appropriately stir or heat the resin. The washing temperature is preferably normal temperature to 150°C. The polyarylene sulfide that has been washed with an organic solvent is preferably washed several times with water or warm water to remove the remaining organic solvent. When the polyarylene sulfide is treated with hot water, the water used is preferably distilled or deionized water. The operation of hydrothermal treatment is usually carried out by adding a predetermined amount of polyarylene sulfide to a predetermined amount of water, heating and stirring under normal pressure or in a pressure vessel. The ratio of the polyarylene sulfide resin to water is preferably a bath ratio of 200 g or less of polyarylene sulfide per 1 liter of water. Specific methods for acid-treating polyarylene sulfide include, for example, immersing polyarylene sulfide resin in acid or an aqueous solution of acid, and if necessary, stirring or heating is also possible. As the acid, acetic acid and hydrochloric acid are preferably used. The acid-treated polyarylene sulfide is preferably washed several times with water or warm water to remove residual acids or salts. The water used for washing is preferably distilled or deionized water.

The melt viscosity of polyarylene sulfide is preferably 80 Pa·s or less, more preferably 20 Pa·s or less at 310° C. and a shear rate of 1000/sec. Although the lower limit of the melt viscosity is not particularly limited, it is preferably 5 Pa·s or more. Also, two or more polyarylene sulfides having different melt viscosities may be used in combination. The melt viscosity can be measured using a capillograph (manufactured by Toyo Seiki Co., Ltd.) under the conditions of a die length of 10 mm and a die hole diameter of 0.5 to 1.0 mm.

Examples of cellulose derivatives include cellulose acetate, cellulose acetate butyrate, and ethyl cellulose. You may contain 2 or more types of these.

Among these thermoplastic resins, resins selected from polyamides, styrenic resins, polycarbonates, polyesters, polyarylene sulfides, etc. are excellent in moldability due to their excellent affinity with the fibrous filler (C). , is preferable because it can further improve the mechanical properties and surface appearance of the molded product. Among these, nylon 6, nylon 66, nylon 610, nylon 9T, ABS (acrylonitrile/butadiene/styrene copolymer), polycarbonate, polybutylene terephthalate, polyphenylene sulfide and the like can be used more preferably.

The melting point of the thermoplastic resin (A) is preferably 150°C or higher and lower than 300°C. If the melting point is 150°C or higher, the heat resistance of the resin composition 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 (B) can be suppressed.

Here, the melting point of the thermoplastic resin (A) is measured by using a differential scanning calorimeter to lower the temperature of the thermoplastic resin (A) from the molten state to 30°C at a rate of 20°C/min in an inert gas atmosphere. After that, it is defined as the temperature of the endothermic peak that appears when the temperature is raised at a rate of 20° C./min. It is preferable to raise the temperature up to +40°C of the melting point. 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.

The resin composition of the present invention contains polyrotaxane (B) in which a cyclic molecule is modified with a graft chain having a reactive functional group at its terminal. A rotaxane is generally a straight-chain molecule having bulky blocking groups at both ends, as described, for example, in Harada, A., Li, J. & Kamachi, M., Nature 356, 325-327. It refers to a molecule with a shape that is penetrated by a molecule. Polyrotaxanes are those in which a plurality of cyclic molecules are penetrated by a single linear molecule.

The polyrotaxane is composed of a linear molecule and a plurality of cyclic molecules, and has a structure in which the linear molecule penetrates through the openings of the plurality of cyclic molecules, and the cyclic molecules are linear molecules at both ends of the linear molecule. It has a bulky blocking group so as not to detach from. In the polyrotaxane, 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 a polyrotaxane is effective in relieving external stress and internal residual stress due to the high mobility of the cyclic molecules. Furthermore, by blending the polyrotaxane in which the cyclic molecule is modified with a graft chain having a specific functional group at the end, in the thermoplastic resin (A), it is possible to spread the same effect to the thermoplastic resin (A). Become.

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; Polyfunctional chains having three or more functional groups in one molecule that can react with the blocking groups and the like 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 molecules is preferably 2,000 or more, and can improve the strength. More preferably, the number average molecular weight is 10,000 or more. On the other hand, the number average molecular weight is preferably 100,000 or less, which can improve the compatibility with the thermoplastic resin (A) and can refine the phase separation structure, so that the toughness can be further improved. can. More preferably, the number average molecular weight is 50,000 or less. 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 use 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. A compound selected from α-cyclodextrin, β-cyclodextrin and γ-cyclodextrin is more preferably used.

In the polyrotaxane (B), the cyclic molecule is modified with a graft chain having a reactive functional group at its terminal. By modifying the cyclic molecule with a graft chain having a reactive functional group, the compatibility between the polyrotaxane (B) and the thermoplastic resin (A) and the affinity with the interface of the fibrous filler (C) are improved. Become. As a result, toughness can be improved while maintaining strength of the thermoplastic resin (A), and strength and toughness can be improved in a well-balanced manner.

In general, by blending the fibrous filler (C) with the thermoplastic resin (A), a resin composition having high strength can be obtained. However, although such a resin composition has high strength, it has a problem of low toughness. On the other hand, by blending an elastomer into the thermoplastic resin (A), a resin composition having high toughness can be obtained. However, although such a resin composition has high toughness and ductile fracture, it has a problem of low strength. In other words, it has not been possible to obtain a fiber-reinforced plastic material with high tenacity while maintaining high strength with conventional techniques. According to the resin composition of the present invention, it is possible to obtain a fiber-reinforced plastic material having high toughness in spite of having high strength.

The reactive functional group at the end of the graft chain is not particularly limited. At least one or more groups selected from and the like can be mentioned.

The graft chain is preferably made of polyester. Aliphatic polyesters are more preferable in terms of compatibility with the thermoplastic resin (A) 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 thermoplastic resin (A).

The amount of polyrotaxane (B) in the resin composition of the present invention is 0.1 parts by weight or more and 20 parts by weight or less with respect to a total of 100 parts by weight of thermoplastic resin (A) and polyrotaxane (B). preferable. When the amount of the polyrotaxane (B) is 0.1 part by weight or more, the stress relaxation effect of the polyrotaxane (B) is sufficiently exhibited, and the toughness of the molded product is improved. The blending amount of the polyrotaxane (B) is preferably 0.5 parts by weight or more. On the other hand, when the blending amount of the polyrotaxane (B) is 20 parts by weight or less, the strength and heat resistance of the resulting molded article can be maintained. The blending amount of the polyrotaxane (B) is preferably 15 parts by weight or less, more preferably 10 parts by weight or less.

In the polyrotaxane (B), the functional group concentration at the end of the graft chain is preferably 2×10 ⁻⁵ mol/g or more and 5×10 ⁻⁴ mol/g or less. Compatibility with the thermoplastic resin (A) can be improved by setting the functional group concentration to 2×10 ⁻⁵ mol/g or more. As a result, the toughness can be further improved while maintaining the strength of the thermoplastic resin (A), and the strength and toughness can be improved in a well-balanced manner. The functional group concentration is more preferably 3×10 ⁻⁵ mol/g or more. On the other hand, by setting the functional group concentration to 5×10 ⁻⁴ mol/g or less, aggregation due to association of the functional groups of the polyrotaxane (B) and excessive chemical cross-linking with the thermoplastic resin (A) can be suppressed. It is possible to suppress the generation of aggregates and gels and further improve the toughness. The functional group concentration is more preferably 1×10 ⁻⁴ mol/g or less.

Here, the functional group concentration at the end of the graft chain of the polyrotaxane (B) can be determined by titration. For example, when the functional group at the end of the graft chain is a carboxyl group, the carboxyl group concentration can be obtained by the following method. An absolutely dry sample is prepared by drying the polyrotaxane (B) for 10 hours or more using an 80° C. vacuum dryer. A solution obtained by dissolving 0.2 g of an absolutely dry sample in 25 ml of benzyl alcohol is titrated with an ethanol solution of potassium hydroxide having a concentration of 0.02 mol/L to determine the carboxyl group concentration. For other functional groups, it is possible to calculate the functional group concentration by a known method.

The functional group at the end of the graft chain can be imparted, for example, by reacting the polyrotaxane in which the cyclic molecule is modified with the graft chain and an introduced compound having the desired functional group and capable of reacting with the end of the graft chain. . In this case, the functional group concentration at the end of the graft chain can be adjusted within a desired range, for example, by adjusting the charging ratio of the polyrotaxane whose cyclic molecule is modified by the graft chain and the introduced compound.

The weight average molecular weight of the polyrotaxane (B) is preferably 100,000 or more, and can further improve strength and toughness. On the other hand, the weight-average molecular weight of the polyrotaxane (B) is preferably 1,000,000 or less, which improves the compatibility with the thermoplastic resin (A) and further improves the toughness. Here, the weight average molecular weight of the polyrotaxane (B) 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 resin composition of the present invention contains a fibrous filler (C). By containing the fibrous filler (C), it is possible to obtain a molded article 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 (C). 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.

A fibrous filler (C) having a coupling agent, a sizing agent, or the like attached to its surface may also be used. By attaching a coupling agent or a sizing agent, the wettability of the thermoplastic resin (A) and the handleability of the fibrous filler (C) 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 (C) in the resin composition of the present invention is 1 to 200 parts by weight with respect to a total of 100 parts by weight of the thermoplastic resin (A) and the polyrotaxane (B). If the content of the fibrous filler (C) is less than 1 part by weight, the effect of improving the mechanical properties and dimensional stability of the molded product cannot be obtained. The content of the fibrous filler (C) is more preferably 10 parts by weight or more, and even more preferably 20 parts by weight or more. On the other hand, when the content of the fibrous filler (C) exceeds 200 parts by weight, the fibrous filler (C) floats on the surface of the molded product, making it impossible to obtain a molded product with excellent surface appearance. The content of the fibrous filler (C) is more preferably 175 parts by weight or less, even more preferably 150 parts by weight or less.

The resin composition of the present invention localizes the polyrotaxane (B) at the interface between the thermoplastic resin (A) and the fibrous filler (C), so that the thermoplastic resin (A) and the fibrous filler (C) The stress relaxation effect of the polyrotaxane (B) can be sufficiently exhibited without impairing the interface strength with C), and the strength and toughness can be improved in a well-balanced manner.

As a method for localizing the polyrotaxane (B) at the interface between the thermoplastic resin (A) and the fibrous filler (C), for example, a fibrous filler having a compound having a high affinity for the polyrotaxane (B) adhered to the surface A method of using the material (C), a method of directly treating the surface of the fibrous filler (C) with the polyrotaxane (B), and the like.

When the ionic strength derived from the thermoplastic resin (A) at the interface between the thermoplastic resin (A) and the fibrous filler (C) of the present invention is a, and the ionic strength derived from the polyrotaxane (B) is b, ions The intensity ratio b/a is preferably 1.1 or more. When the ionic strength ratio b/a is 1.1 or more, the polyrotaxane (B) concentration at the interface is high, and the strength and toughness can be further improved. The ionic strength ratio b/a is more preferably 1.10 or more, more preferably 1.2 or more, and still more preferably 1.3 or more. Also, the ionic strength ratio b/a is preferably 10 or less. Here, the ion intensity ratio b/a is obtained by TOF-SIMS (time-of-flight secondary ion mass spectrometry).

TOF-SIMS (time-of-flight secondary ion mass spectrometry) is a method of irradiating the sample surface with pulsed ions (primary ions) and analyzing the mass spectrum obtained from the secondary ions emitted from the sample surface. It is an analysis method for identifying organic substances and inorganic substances that are present in the material, and the vertical axis is the relative ionic strength derived from each component with respect to the component derived from the fibrous filler (C), and the horizontal axis is the number of cycles, which is an index in the depth direction. In the positive secondary ion profile, the ionic strength derived from the thermoplastic resin (A) at the interface calculated from the profile shape of each ion species is a, the ionic strength derived from the polyrotaxane (B) is b, and the ionic strength ratio b / a Calculate

For the resin composition of the present invention, the resin composition is used to mold a test piece conforming to ISO527-1:2012, and the tensile properties of the test piece are measured by a method conforming to ISO527-1:2012. In , it is preferable that the absorbed energy indicated by the area of the stress-strain curve until breakage is 24 J or more. When the absorbed energy is 24 J or more, the balance between strength and toughness is excellent, and the impact resistance of the molded product can be improved, which is preferable. The absorbed energy is more preferably 25 J or more, and even more preferably 30 J or more. The absorbed energy is the energy (area calculated from the stress-strain curve from the start of the test to the fracture) calculated using analysis software: TRAPEZIUM X. The resin composition of the present invention uses the resin composition to mold a test piece conforming to ISO178:2010, and when the bending properties of the test piece are measured by a method conforming to ISO178:2010, the elastic modulus is preferably 3.5 GPa or more. The elastic modulus is more preferably 5 GPa or more, and more preferably 6 GPa or more. Also, the elastic modulus is preferably 100 GPa or less. If the flexural modulus is less than 3.5 GPa, bending or deformation may occur when molding a large-sized molded product, which is not preferable.

The resin composition of the present invention is molded into a test piece conforming to ISO527-1:2012, and the absorbed energy when measuring the tensile properties of the test piece at a temperature of +15 ° C. from the melting start temperature of polyrotaxane (B) is , 1.2 times or more of the absorbed energy when the tensile properties are measured at 23°C. When the absorbed energy is 1.2 times or more, the balance between strength and toughness at high temperatures is excellent, and the impact resistance of the molded product can be improved, which is preferable. The absorbed energy is more preferably 1.25 times or more, more preferably 1.3 times or more.

The melting initiation temperature of the polyrotaxane (B) is obtained when the temperature of the polyrotaxane (B) 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. was the start temperature of the endothermic peak appearing at .

The resin composition of the present invention has high rigidity and an excellent balance between strength and toughness. In general, the higher the rigidity and strength, the harder and more brittle the material becomes, resulting in a decrease in toughness. In addition, the higher the toughness, the softer the material and the lower the strength. Therefore, it has been difficult to improve both properties in a well-balanced manner with conventionally known techniques.

The resin composition of the present invention can contain an elastomer within a range that does not impair the object of the present invention. Examples of elastomers include natural rubbers, silicone rubbers, fluororubbers, thermoplastic elastomers, core-shell rubbers, ionomers, and the like. Among these, from the viewpoint of compatibility with the thermoplastic resin (A), elastomers selected from thermoplastic elastomers and core-shell rubbers are preferable, and thermoplastic elastomers are more preferably used. When a thermoplastic elastomer is used as the elastomer, the thermoplastic elastomer is also calculated as the thermoplastic resin (A) in calculating the content ratio of each component in the resin composition.

A thermoplastic elastomer generally refers to a polymer whose glass transition temperature is lower than room temperature and whose molecules are partially constrained by ionic bonds, van der Waals forces, entanglement of molecular chains, or the like. For example, polybutadiene, polyisoprene, random copolymers and block copolymers of styrene-butadiene, hydrogenated products of said polymers, styrene-ethylene-butylene-styrene block copolymers, hydrogenated products of said polymers, styrene- Diene rubbers such as isoprene-butylene-styrene block copolymers, hydrogenated products of said polymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, ethylene-propylene random copolymers and block copolymers , random copolymers and block copolymers of ethylene-butene, copolymers of ethylene and α-olefins, ethylene-unsaturated carboxylic acid ester copolymers such as ethylene-acrylic acid esters and ethylene-methacrylic acid esters, Acrylic elastic polymers such as acrylate-butadiene copolymers and butyl acrylate-butadiene copolymers, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethylene-propylene-ethylidenenorbornene copolymers , ethylene-propylene non-conjugated diene terpolymers such as ethylene-propylene-hexadiene copolymers, butylene-isoprene copolymers, chlorinated polyethylene, polyamide elastomers, polyester elastomers and the like.

Core-shell rubber refers to a multi-layer structure comprising at least one layer made of rubber and one or more layers made of a different polymer. The number of layers constituting the multilayer structure may be 2 or more, and may be 3 or more or 4 or more, but it is preferable to have at least one core layer having rubber elasticity inside. . The type of rubber constituting the core layer of the multilayer structure is not particularly limited. Examples include rubber obtained by polymerizing components selected from components. The type of different polymer that constitutes the layers other than the rubber layer of the multilayer structure is not particularly limited as long as it is a polymer having thermoplasticity, but a polymer having a higher glass transition temperature than the rubber layer is used. preferable. Examples of thermoplastic polymers include unsaturated carboxylic acid alkyl ester units, unsaturated carboxylic acid units, unsaturated glycidyl group-containing units, unsaturated acid anhydride units, aliphatic vinyl units, aromatic vinyl units, cyan Examples include polymers containing units selected from vinylized units, maleimide units, unsaturated dicarboxylic acid units and other vinyl units.

The elastomer may be modified with reactive functional groups. Examples of reactive functional groups include at least one group selected from amino groups, carboxyl groups, hydroxyl groups, acid anhydride groups, glycidyl groups, isocyanate groups, isothiocyanate groups, mercapto groups, oxazoline groups, sulfonic acid groups, and the like. is mentioned. Among these, groups selected from amino groups, carboxyl groups, glycidyl groups, acid anhydride groups and isocyanate groups are preferably used from the viewpoint of ease of functional group introduction and reactivity, and glycidyl groups, acid anhydride groups and isocyanate groups. A group selected from is more preferably used. When introducing a functional group into an elastomer, the method is not particularly limited. and a method of grafting an acid anhydride onto a thermoplastic elastomer.

The resin composition of the present invention may further contain non-fibrous fillers, various additives, and the like, as long as the objects of the present invention are not impaired.

Non-fibrous fillers include, for example, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, non-swelling silicates such as calcium silicate; Li-type fluorine Swellable layered silicates such as teniolite, Na-type fluoroteniolite, Na-type tetrasilicon fluoromica, swelling mica of Li-type tetrasilicon fluoromica; silicon oxide, magnesium oxide, alumina, silica, diatomaceous earth, zirconium oxide, titanium oxide, metal oxides such as iron oxide, zinc oxide, calcium oxide, tin oxide and antimony oxide; metal carbonates such as calcium carbonate, magnesium carbonate, zinc carbonate, barium carbonate, dolomite and hydrotalcite; metal sulfates; metal hydroxides such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide, and basic magnesium carbonate; smectite clay minerals such as montmorillonite, beidellite, nontronite, saponite, hectorite, and sauconite; various clay minerals such as halloysite, kanemite, kenyaite, zirconium phosphate and titanium phosphate; glass beads, glass flakes, ceramic beads, boron nitride, aluminum nitride, silicon carbide, calcium phosphate, carbon black and graphite; In the swelling layered silicate, exchangeable cations existing between layers may be exchanged with organic onium ions. Organic onium ions include, for example, ammonium ions, phosphonium ions, and sulfonium ions.

Specific examples of various additives include heat stabilizers; coupling agents such as isocyanate-based compounds, organic silane-based compounds, organic titanate-based compounds, organic borane-based compounds, and epoxy compounds; polyalkylene oxide oligomer-based compounds, thioether-based compounds. plasticizers such as ester compounds and organic phosphorus compounds; crystal nucleating agents such as organic phosphorus compounds and polyether ether ketone; metal soaps such as montanic acid waxes, lithium stearate and aluminum stearate; Release agents such as polycondensates of sebacic acid and silicone compounds; Anti-coloring agents such as hypophosphite; Lubricants such as carboxylic acid amide waxes, UV inhibitors, colorants, flame retardants, foaming agents, etc. be able to. When these additives are contained, the content is preferably 10 parts by weight or less with respect to 100 parts by weight of the thermoplastic resin (A) in order to fully utilize the characteristics of the thermoplastic resin (A), and 1 part by weight The following are more preferred.

Thermal stabilizers include N,N'-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis[methylene-3-(3',5'-di-t-butyl -4'-Hydroxyphenyl)propionate]methane and other phenol compounds, phosphorus compounds, mercaptobenzimidazole compounds, dithiocarbamic acid compounds, sulfur compounds such as organic thioacid compounds, N,N'-di-2 -naphthyl-p-phenylenediamine, 4,4'-bis(α,α-dimethylbenzyl)diphenylamine and other amine compounds. You may contain 2 or more types of these.

As the coupling agent, an isocyanate compound having two or more isocyanate groups or blocked isocyanate groups in one molecule is preferably used. includes, for example, aliphatic polyisocyanates, aromatic polyisocyanates, alicyclic polyisocyanates, and the like. Examples of aliphatic polyisocyanates include tetramethylene diisocyanate, hexamethylene diisocyanate, methylene diisocyanate, and trimethylhexamethylene diisocyanate. Examples of aromatic polyisocyanates include 4,4-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, naphthalene-1,5-diisocyanate, o-xylylene diisocyanate, m-xylylene diisocyanate, Examples include isocyanate and 2,4-tolylene dimer. Alicyclic polyisocyanates include, for example, bicycloheptane triisocyanate, 4,4-methylenebis(cyclohexylisocyanate), and isophorone diisocyanate. From the viewpoint of reactivity, 4,4-diphenylmethane diisocyanate is preferred. The high-molecular isocyanate compound is a compound in which the end of the high-molecular chain is modified with an isocyanate group by a low-molecular-weight isocyanate compound. The polymer used for the main chain is not particularly limited as long as the terminal has a functional group that reacts with isocyanate. Polymer compounds preferably used include polyolefin resins such as polyethylene glycol, polypropylene glycol, polyvinyl methyl ether polyethylene, polypropylene, and copolymers with other olefin monomers, polyester resins, polyvinyl chloride resins, polystyrene, and Polystyrene resins such as acrylonitrile-styrene copolymer resins, acrylic resins such as polymethyl methacrylate, (meth)acrylic acid ester copolymers, and acrylonitrile-methyl acrylate copolymers, polyurethane resins, vinyl chloride-vinyl acetate copolymers and derivatives or modified products thereof, polyisobutylene, polytetrahydrofuran, acrylonitrile-butadiene-styrene copolymer (ABS resin), polyamides such as nylon, polyimides, polyisoprene, polydienes such as polybutadiene, polydimethylsiloxane, etc. polysiloxanes, polysulfones, polyimines, polyacetic anhydrides, polyureas, polysulfides, polyphosphazenes, polyketones, polyphenylenes, polyhaloolefins, and derivatives thereof. From the viewpoint of compatibility with the polyamide (A), polyamides such as nylon or polyester resins are more preferable, and aliphatic polyamides and aliphatic polyester resins are more preferable. The above isocyanate compounds may be used in combination of two or more, if necessary.

A blocked isocyanate group is a functional group in which the isocyanate group is protected and temporarily deactivated by reaction with a blocking agent. 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 blocking agents 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 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, benzyl alcohol-based blocking agents such as ether, methyl glycolate, butyl glycolate, diacetone alcohol, methyl lactate, and ethyl lactate; 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; imides such as succinimide and maleic imide system blocking agents; amine blocking agents such as xylidine, aniline, butylamine and dibutylamine; imidazole blocking agents such as imidazole and 2-ethylimidazole; and imine blocking agents such as methyleneimine and propyleneimine. The blocking agents may be used alone or in combination of two or more.

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 (B) and further improving toughness, the maximum resin temperature in the melt-kneading step is preferably 300° C. or less. On the other hand, the maximum resin temperature is preferably at least the melting point of the thermoplastic resin (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.

In addition, the ratio of the extrusion amount of the resin composition to the screw rotation speed in the melt-kneading step is 0 per 1 rpm of the screw rotation speed, from the viewpoint of further suppressing thermal deterioration of the thermoplastic resin (A) and the polyrotaxane (B). 01 kg/h or more is preferable, and 0.05 kg/h or more is more preferable. On the other hand, from the viewpoint of further promoting the reaction between the thermoplastic resin (A) and the polyrotaxane (B), the extrusion rate is preferably 1 kg/h or less per 1 rpm of screw rotation. 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.

The resin composition of the present invention and its molded article can be used for various purposes such as automobile parts, electrical/electronic parts, building materials, various containers, daily necessities, household goods and sanitary goods, taking advantage of their excellent properties. 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 and molded articles thereof of the present invention can be suitably used for sports applications, taking advantage of the excellent properties of high impact resistance and non-destructive properties, such as golf clubs, shafts, grips, golf balls, and the like. Related goods; Sports racket related goods such as tennis rackets, badminton rackets, and their guts; Masks for American football, baseball, softball, etc., body protective equipment for sports such as helmets, chest pads, elbow pads, knee pads, etc., sportswear, etc. Wear-related goods; shoe-related goods such as the soles of sports shoes; fishing tackle-related goods such as fishing rods and fishing lines; summer sports-related goods such as surfing; winter sports-related goods such as skis and snowboards; other indoor and outdoor sports-related goods etc. is preferably used.

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.

<Thermoplastic resin>
(A-1): Nylon 6 resin (“Amilan” (registered trademark) manufactured by Toray Industries, Inc.), η _r =2.70, melting point 225° C., amide group concentration 10.5 mmol/g.
Here, the relative viscosity η _r was measured at 25° C. with a 0.01 g/ml solution of 98% concentrated sulfuric acid. In addition, the melting point is measured by using a differential scanning calorimeter, in an inert gas atmosphere, the polyamide is cooled from the molten state to 30 ° C. at a temperature decrease rate of 20 ° C./min, and then 265 ° C. at a temperature increase rate of 20 ° C./min. The temperature of the endothermic peak that appears when the temperature is raised to However, when two or more endothermic peaks were detected, the temperature of the endothermic peak with the highest peak intensity was taken as the melting point. Further, the amide group concentration was calculated from the structural formula of the structural unit by the following formula (1).
Amide group concentration (mol/g)=(number of amide groups in structural unit/molecular weight of structural unit) (1).

(A-2): Polybutylene terephthalate resin ("Toraycon" (registered trademark) manufactured by Toray Industries, Inc.), η = 0.85 dl/g (measured with o-chlorophenol solution at 25°C), melting point 223°C.
Here, the intrinsic viscosity η was measured at 25° C. with an o-chlorophenol solution adjusted to 0.5% by weight. Using a differential scanning calorimeter, the melting point of polybutylene terephthalate was lowered from the molten state to 30°C at a rate of 20°C/min in an inert gas atmosphere, and then 263°C at a rate of 20°C/min. The temperature of the endothermic peak that appears when the temperature is raised to However, when two or more endothermic peaks were detected, the temperature of the endothermic peak with the highest peak intensity was taken as the melting point.

(A-3): Nylon 66 resin (“Amilan” (registered trademark) manufactured by Toray Industries, Inc.), η _r =2.78, melting point 260° C., amide group concentration 8.84 mmol/g.

<Polyrotaxane>
(B-1): Polyrotaxane (“Celm” (registered trademark) superpolymer SH3400P manufactured by Advanced Soft Materials Co., Ltd.) was used. The terminal group of the graft chain that modifies the cyclic molecule of this ^polyrotaxane is a hydroxyl group. 50,000 and the overall weight average molecular weight is 700,000. Here, the weight-average molecular weight of 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 (B-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.

<Fibrous filler>
(C-1): Glass fiber (T-251H manufactured by Nippon Electric Glass Co., Ltd.) was used.
(C-2): Glass fiber (T-249 manufactured by Nippon Electric Glass Co., Ltd.) was used.

(Reference example)
"Serum" super polymer SH3400P 6 parts by weight, "Neoperex" G-25 (manufactured by Kao Corporation: anionic surfactant; sodium dodecylbenzenesulfonate) 3 parts by weight, "KBE-903" (Shin-Etsu Chemical Co., Ltd.) A glass fiber having an E glass composition and an average diameter of 10 μm was immersed in a dispersion obtained by dispersing 0.6 parts by weight of γ-aminopropylethoxysilane) in 100 parts by weight of water. Thereafter, the glass fibers were extracted from the dispersion and dried at 130° C. for 6 hours to obtain surface-treated glass fibers. The content of "Cerum" superpolymer SH3400P (B-1) in the surface-treated glass fiber was 0.5% by weight. The surface-treated glass fiber was cut into 3 mm lengths to obtain (C-3) surface-treated glass fiber.

<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) Ionic strength ratio 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, Ltd.), shown in Tables 1 and 2 Type 1A multi-purpose test specimens conforming to ISO 527-1:2012 were prepared by injection molding under molding conditions. About this multi-purpose test piece, TOF. Using SIMS 5, the primary ions are Bi ₃ ⁺⁺ , the etching ions are Ar cluster ions (Ar-GCIB), and the secondary ion polarity is positive. The fibrous filler (C) on the surface of the cleaved surface was subjected to depth profile measurement by GCIB-TOF-SIMS. The profile shape of each ion species in the positive secondary ion profile when the vertical axis is the relative ion intensity derived from each component with respect to the component derived from the fibrous filler (C), and the horizontal axis is the number of cycles as an index in the depth direction. The ionic strength ratio b/a was calculated, with the ionic strength derived from the thermoplastic resin (A) at the interface calculated from the above as a, and the ionic strength derived from the polyrotaxane (B) as b. Here, the ionic species derived from the thermoplastic resin (A-1) is C ₆ H ₁₂ NO ⁺ , the ionic species derived from the thermoplastic resin (A-2) is C ₁₂ H ₁₃ O ₄ ⁺ , and the thermoplastic resin (A- 3) C ₁₂ H ₂₃ N ₂ O ₂ ⁺ as the ionic species derived from 3), C ₃ H ₅ O ₂ ⁺ as the ionic species derived from the polyrotaxane (B-1), fibrous fillers (C-1), (C-2 ), and the ion species derived from (C-3) was ( ₂₇ Al ⁺ ). When the ionic strength b derived from the polyrotaxane (B) is less than 1.0×10 ⁻³ , this value is extremely small and the ionic strength derived from the polyrotaxane (B) is not accurately detected. , the ionic strength b derived from the polyrotaxane (B), and the ionic strength ratio b/a are also taken as reference values.

(2) Strength (tensile strength)
After drying the pellets obtained in each example and comparative example under reduced pressure at 80 ° C. for 12 hours, injection molding is performed using an injection molding machine (SE75DUZ-C250 manufactured by Sumitomo Heavy Industries, Ltd.) under the molding conditions shown in Tables 1 and 2. Thus, a type 1A multipurpose test piece conforming to ISO527-1:2012 was produced. The tensile test piece obtained from this multi-purpose test piece is subjected to a tensile test according to ISO527-1:2012 using a precision universal testing machine AG-20kNX (manufactured by Shimadzu Corporation) at a tensile speed of 5 mm / min and a gauge distance of 75 mm. to determine the tensile strength.

(3) Toughness (tensile elongation at break)
The tensile elongation at break was determined in the tensile test described above.

(4) Absorbed Energy In the tensile test described above, the area calculated from the stress-strain curve from the start of the test to the fracture was calculated using analysis software: TRAPEZIUM X (manufactured by Shimadzu Corporation).

(5) Rigidity (flexural modulus)
After drying the pellets obtained in each example and comparative example under reduced pressure at 80 ° C. for 12 hours, injection molding is performed using an injection molding machine (SE75DUZ-C250 manufactured by Sumitomo Heavy Industries, Ltd.) under the conditions shown in Tables 1 and 2. A multi-purpose test piece conforming to ISO178:2010 was produced. A bending test piece obtained from this multipurpose test piece was subjected to a bending test using a precision universal testing machine (AG-20kNX (manufactured by Shimadzu Corporation) at a crosshead speed of 2 mm / min according to ISO178:2010, and the bending elastic modulus was measured. asked.

(6) Strength (tensile strength at melting start temperature of polyrotaxane (B-1) + 15°C)
The tensile strength was determined by conducting the same tensile test as in (2) above except that the measurement temperature was 50°C.

(7) Toughness (tensile elongation at break at the melting start temperature of polyrotaxane (B-1) + 15 ° C.)
The tensile elongation at break was obtained by conducting the same tensile test as in (2) above except that the measurement temperature was 50°C.

(8) Absorbed energy (absorbed energy at the melting start temperature of polyrotaxane (B-1) + 15 ° C.)
The test was performed in the same manner as the tensile test in (2) above except that the measurement temperature was 50 ° C., and the area calculated from the stress-strain curve from the start of the test to the break was analyzed using Trapezium X (manufactured by Shimadzu Corporation). calculated using

(Examples 1 to 7, Comparative Examples 1 to 8)
The thermoplastic resin (A) and polyrotaxane (B) were blended so as to have the compositions shown in Tables 1 and 2, preblended, and set to the extrusion conditions shown in Tables 1 and 2. A twin screw extruder (Japan The thermoplastic resin (A) and polyrotaxane (B) were supplied from the main feeder, the fibrous filler (C) was supplied from the side feeder, and the extruded gut was pelletized using TEX30α manufactured by Steel Works. Tables 1 and 2 show the results of evaluation by the above method using the obtained pellets. The ionic strength b of the polyrotaxane detected in Comparative Examples 2 and 4 to 8 is smaller than 1.0×10 ⁻³ , and the ionic strength derived from the polyrotaxane is not detected, so it is used as a reference value.

Claims (3)

A resin composition comprising a thermoplastic resin (A), a polyrotaxane (B) in which a cyclic molecule is modified with a graft chain having a reactive functional group at its end, and a fibrous filler (C), wherein 1 to 200 parts by weight of the fibrous filler (C) is included with respect to a total of 100 parts by weight of the thermoplastic resin (A) and the polyrotaxane (B), and the thermoplastic resin (A) is a styrene resin, poly Oxymethylene, polyamide, polyester, polyimide, polyamideimide, vinyl chloride, olefin resin, polyacrylate, polyphenylene ether, polycarbonate, polyethersulfone, polyetherimide, polyetherketone, polyetheretherketone, polyarylene sulfide, cellulose derivative , a liquid crystalline resin and a modified resin thereof, a resin composition, wherein the thermoplastic resin (A ) has an ionic strength of a and the ionic strength of the polyrotaxane (B) is b, the ionic strength ratio b/a is 1.1 or more, and the resin composition is used to meet ISO527-1:2012. A compliant test piece is molded, and the energy absorbed when the tensile properties of the test piece are measured at the melting start temperature of the polyrotaxane (B) + 15 ° C. is the absorption when the tensile properties of the test piece are measured at 23 ° C. A resin composition that is 1.2 times or more of the energy . 2. The resin composition according to claim 1, wherein said fibrous filler (C) 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 .