JP2008156604A - Thermoplastic resin composition for shock absorbing member and method of producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition for a shock absorbing member excellent in heat resistance and shock absorption, more specifically a thermoplastic resin composition for a shock absorbing member having sufficient heat resistance at ambient temperatures, and inflicting a low maximum load on an object so as to absorb big energy without breakdown even when receiving high speed impact. <P>SOLUTION: The thermoplastic resin composition for a shock absorbing member includes a thermoplastic resin (A), and a resin (B) having a reactive functional group wherein the deflection temperature under load at 0.45 MPa is not less than 45°C, and the maximum point load received by a cone is less than 20 kN and cracks not less than 5 cm are not generated when the cone having a mass of 193 kg is freely dropped from a drop height of 0.5 m onto a cylindrically molded test specimen of the composition having an outermost diameter of 50 mm, a thickness of 2 mm and a height of 150 mm. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition for an impact absorbing member that is excellent in heat resistance and impact absorbability. More specifically, an impact-absorbing member that has sufficient heat resistance at room temperature and absorbs a large amount of energy without causing damage when the maximum load applied to the object is low even when subjected to a heavy load or high-speed impact. The present invention relates to a thermoplastic resin composition.

  In recent years, from the viewpoint of pedestrian protection and occupant protection, development of shock absorbing parts has been progressing mainly in automobile interior and exterior applications. At present, many approaches from the shape side such as honeycomb-like structures and foams have been made, but there are few approaches from the material side and development is desired.

  Typical examples of shock absorbing materials include thermoplastic elastomers such as polyurethane, but their range of use is often limited due to their low heat resistance, and in recent years materials with excellent heat resistance and impact resistance due to polymer alloys Has been developed. Patent Documents 1 and 2 disclose a thermoplastic composition having excellent heat resistance and impact resistance composed of polyamide and ionomer. However, when the material is subjected to a heavy load and a high-speed impact, the maximum load applied to the object is high and the material itself is destroyed. Therefore, a material that is more excellent in shock absorption is desired at present. is there.

In Patent Document 3, in a resin composition containing a thermoplastic resin and a resin having a reactive functional group, one forms a continuous phase and the other forms a dispersed phase, or both form a continuous phase (both continuous phases). And the resin composition which was excellent in rigidity, impact resistance, and the external appearance after a deformation | transformation by having 300 nm or less microparticles | fine-particles in the continuous phase and a disperse phase or both continuous phases is disclosed. Further, Patent Document 4 discloses a resin composition and an impact absorbing member in which the elastic modulus decreases and becomes flexible as the tensile speed is increased. However, none of them has been subjected to a high degree of structural control in the dispersed phase, and the absorbency against a heavy load and a high speed impact has not been sufficient.
U.S. Pat. No. 3,845,163 Japanese Patent Laid-Open No. 51-151797 Japanese Patent Laying-Open No. 2005-187809 JP 2006-89701 A

  An object of the present invention is to provide a thermoplastic resin composition for an impact absorbing member that is excellent in heat resistance and impact absorbability. More specifically, an impact-absorbing member that has sufficient heat resistance at room temperature and absorbs a large amount of energy without causing damage when the maximum load applied to the object is low even when subjected to a heavy load or high-speed impact. It is an object of the present invention to provide a thermoplastic resin composition.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a screw length L and a screw diameter in a thermoplastic resin composition containing a thermoplastic resin (A) and a resin (B) having a reactive functional group. D ratio L / D ₀ of ₀ using a twin-screw extruder is 50 or more, the resin pressure, vent vacuum pressure, water content, by controlling the resin temperature was melt-kneaded, highly controlled structures in dispersed phase As a result, the present inventors have found that the above problems can be solved, and have completed the present invention.

That is, the present invention
(1) A thermoplastic resin composition comprising a thermoplastic resin (A) and a resin (B) having a reactive functional group, the deflection temperature under load at 0.45 MPa is 45 ° C. or more, and the outermost diameter is 50 mm. In a cylindrical molded product with a thickness of 2 mm and a height of 150 mm, when a weight body with a mass of 193 kg is freely dropped from a drop height of 0.5 m, the maximum point load applied to the weight body is less than 20 kilonewtons, and more than 5 cm A thermoplastic resin composition for an impact absorbing member that does not generate cracks,
(2) In the morphology of the resin composition observed by transmission electron beam tomography, one of (A) or (B) forms a continuous phase, the other forms a dispersed phase, and the dispersed phase contains A three-dimensional connection structure Cs containing a continuous phase component is formed, and the proportion of the area of the connection structure Cs in the cross section of the dispersion phase Dp having an average particle diameter of 1000 nm or less is 10% or more. The thermoplastic resin composition for impact-absorbing members according to (1),
(3) In the tensile test, when the tensile elastic modulus is E (V1) and E (V2) at the tensile speeds V1 and V2, it is E (V1)> E (V2) when V1 <V2. The thermoplastic resin composition for impact absorbing members according to any one of (1) and (2),
(4) In the tensile test, when the tensile breaking elongation at the tensile speeds V1 and V2 is ε (V1) and ε (V2), ε (V1) <ε (V2) when V1 <V2. The thermoplastic resin composition for impact absorbing members according to any one of (1) to (3),
(5) A twin screw extruder having a ratio L / D _{0 of the} screw length L to the screw diameter D ₀ of 50 or more is used, and the screw of the twin screw extruder has a plurality of full flight zones and kneading zones. When the maximum resin pressure of the resin pressure in the kneading zone in the screw is Pkmax (MPa), and the minimum resin pressure of the resin pressure in the full flight zone in the screw is Pfmin (MPa),
Pkmax ≧ Pfmin + 0.3
The thermoplastic resin composition for an impact-absorbing member according to any one of (1) to (4), wherein the thermoplastic resin composition is produced by melt-kneading under a condition that satisfies the following conditions.
(6) Production is carried out by melt-kneading under a condition that the residence time from the supply of the raw material to the extrusion to the extrusion is from 1 minute to 30 minutes and the extrusion amount is 0.01 kg / h or more per 1 rpm of the screw rotation. The thermoplastic resin composition for impact absorbing members according to any one of (1) to (5),
(7) The thermoplastic resin composition for an impact-absorbing member according to any one of (1) to (6), wherein the screw of the twin-screw extruder is a co-rotating fully meshing type,
(8) The thermoplastic resin composition for an impact-absorbing member according to any one of (1) to (7), wherein the total length of the kneading zone is 5 to 50% of the screw length object,
(9) The heat for the impact absorbing member according to any one of (1) to (8), wherein each length Lk of the kneading zone satisfies Lk / D ₀ = 0.2 to 10 A plastic resin composition,
(10) Thermoplastic for impact-absorbing member according to any one of (1) to (9), wherein the pressure is reduced to a gauge pressure of -0.07 MPa or less in the vent vacuum zone and melt kneaded. Resin composition,
(11) The thermoplastic resin composition for impact-absorbing members according to any one of (1) to (9), wherein the thermoplastic resin composition according to any one of (1) to (9), which is manufactured by melt-kneading using a raw material having a moisture content of less than 5000 ppm,
(12) The thermoplastic resin composition for impact-absorbing members according to any one of (1) to (9), wherein the thermoplastic resin composition is produced by melt-kneading while controlling the maximum resin temperature at 180 ° C to 330 ° C,
(13) The thermoplastic resin (A) is at least one selected from polyamide resin, polyester resin, polyphenylene sulfide resin, styrene resin, polyphenylene oxide resin, and polycarbonate resin. 12) The thermoplastic resin composition for impact absorbing members according to any one of
(14) The heat for impact-absorbing member according to any one of (1) to (13), wherein the resin serving as a base of the resin (B) having a reactive functional group is a rubber polymer. A plastic resin composition,
(15) The reactive functional group of the resin (B) having the reactive functional group is at least one selected from an amino group, a carboxyl group, a carboxyl metal salt, an epoxy group, an acid anhydride group, and an oxazoline group. The thermoplastic resin composition for impact absorbing members according to any one of (1) to (14),
(16) A molded article comprising the thermoplastic resin composition for impact absorbing members according to any one of (1) to (15),
(17) The molded article according to (16), wherein the molded article is at least one selected from a film, a sheet, and a fiber.
(18) The molded article according to (16) or (17), wherein the molded article is at least one selected from automotive parts, building materials, sports equipment, and electrical / electronic parts,
(19) A twin screw extruder having a ratio L / D _{0 of the} screw length L to the screw diameter D ₀ of 50 or more is used, and the screw of the twin screw extruder has a plurality of full flight zones and kneading zones. When the maximum resin pressure of the resin pressure in the kneading zone in the screw is Pkmax (MPa), and the minimum resin pressure of the resin pressure in the full flight zone in the screw is Pfmin (MPa),
Pkmax ≧ Pfmin + 0.3
The method for producing a thermoplastic resin composition for an impact-absorbing member according to any one of (1) to (15), wherein the mixture is melt-kneaded under conditions that satisfy
(20) The present invention is characterized in that the residence time from the supply of the raw material to the extrusion to the twin screw extruder is from 1 minute to 30 minutes, and the amount of extrusion is melt-kneaded under the condition of 0.01 kg / h or more per 1 rpm of screw rotation (19) The method for producing a thermoplastic resin composition for an impact-absorbing member according to
(21) The method for producing a thermoplastic resin composition for an impact-absorbing member according to any one of (19) and (20), wherein the screw of the twin-screw extruder is a co-rotating fully meshing type ,
(22) The thermoplastic resin composition for an impact-absorbing member according to any one of (19) to (21), wherein the total length of the kneading zone is 5 to 50% of the screw length. Manufacturing method,
(23) The heat for the impact absorbing member according to any one of (19) to (22), wherein each length Lk of the kneading zone satisfies Lk / D ₀ = 0.2 to 10 Method for producing a plastic resin composition,
(24) Thermoplastic for impact-absorbing member according to any one of (19) to (23), wherein the pressure is reduced to a gauge pressure of −0.07 MPa or less in a vent vacuum zone and melt kneaded. Production method of resin composition,
(25) The method for producing a thermoplastic resin composition for an impact-absorbing member according to any one of (19) to (23), which is produced by melt-kneading using a raw material having a moisture content of less than 5000 ppm,
(26) The thermoplastic resin composition for an impact-absorbing member according to any one of (19) to (23), wherein the thermoplastic resin composition is manufactured by melt-kneading while controlling the maximum resin temperature at 180 ° C to 330 ° C. Production method,
Is to provide.

  From the present invention, an impact absorbing member that has sufficient heat resistance at normal temperature and absorbs large energy without causing breakage because the maximum load applied to the object is low even when subjected to a large load and high speed impact It becomes possible to provide a thermoplastic resin composition.

  Hereinafter, the present invention will be described in more detail.

  The thermoplastic resin composition for impact absorbing members of the present invention is a thermoplastic resin composition comprising a thermoplastic resin (A) and a resin (B) having a reactive functional group.

  The thermoplastic resin (A) used in the present invention is not particularly limited as long as it is a resin that can be molded by heating and melting. For example, polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polycarbonate resin, Polylactic acid resin, polyacetal resin, polysulfone resin, tetrafluoroethylene resin, polyetherimide resin, polyamideimide resin, polyimide resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, polyethylene Preferred examples include at least one thermoplastic resin selected from resins, polypropylene resins, styrene resins such as polystyrene resins and ABS resins, rubbery polymers, polyalkylene oxide resins and the like. Kill.

  Among the thermoplastic resins shown above, polyamide resins, polyester resins, polyphenylene sulfide resins, styrene resins, polyphenylene oxide resins, polycarbonate resins, and polylactic acid resins are preferably used, especially polyamide resins, polyester resins, Polyphenylene oxide resin is most preferably used because of the high reactivity of the end groups.

  In the present invention, the polyamide resin is a resin composed of a polymer having an amide bond, and is mainly composed of amino acid, lactam or diamine and dicarboxylic acid. Representative examples of the raw materials include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-caprolactam and ω-laurolactam, tetramethylenediamine, penta Methylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylene Diamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4 -Aminocyclohex Sil) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, aliphatic, alicyclic, aromatic Diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid Examples thereof include aliphatic, alicyclic, and aromatic dicarboxylic acids such as acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. In the present invention, polyamide homopolymers or copolymers derived from these raw materials are used individually or individually. It can be used in the form of a mixture.

  Specific examples of particularly useful polyamide resins in the present invention include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polypentamethylene adipamide (nylon 56), polytetramethylene. Adipamide (nylon 46), polyhexamethylene sebamide (nylon 610), polypentamethylene sebacamide (nylon 510), polyhexamethylene dodecane (nylon 612), polyundecanamide (nylon 11), polydodecane Amide (nylon 12), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (nylon 66 / 6T), polyhexamethylene adipamide / Poly Xamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (nylon 66 / 6I / 6), 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), polyhexamethylene terephthalamide / poly pentamethylene terephthalamide copolymer (nylon 6T / 5T), and mixtures thereof or copolymers, and the like.

  Particularly preferable examples include polyamide 6, polyamide 66, polyamide 610, polyamide 11, polyamide 12, polyamide 6/66 copolymer, polyamide 6/12 copolymer and the like. Furthermore, it is also practically preferable to use these polyamide resins as a mixture depending on required properties such as moldability, heat resistance, toughness, and surface properties. Among these, polyamide 6, polyamide 66, polyamide 610, and polyamide 11 are suitable. Polyamide 12 is most preferred.

  The degree of polymerization of these polyamide resins is not particularly limited, and the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is preferably in the range of 1.5 to 7.0. A polyamide resin in the range of 1.8 to 6.0 is preferred. When the relative viscosity is less than 1.5, it is difficult to express the excellent impact absorption characteristic of the thermoplastic resin composition of the present invention. When the relative viscosity is more than 6.0, the thermoplastic resin composition Since melt viscosity increases remarkably and it becomes difficult to shape | mold a molded object, it is unpreferable.

  In the present invention, the polyester resin is a thermoplastic resin composed of a polymer having an ester bond in the main chain, and a dicarboxylic acid (or an ester-forming derivative thereof) and a diol (or an ester-forming derivative thereof). And a polymer or a copolymer obtained by a condensation reaction having as a main component thereof, or a mixture thereof.

  Examples of the dicarboxylic acid include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, and 4,4′-diphenyl ether dicarboxylic acid. Acid, aromatic dicarboxylic acid such as 5-sodiumsulfoisophthalic acid, adipic acid, sebacic acid, azelaic acid, aliphatic dicarboxylic acid such as dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. And alicyclic dicarboxylic acids and ester-forming derivatives thereof. The diol component is an aliphatic glycol having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol. , Cyclohexanedimethanol, cyclohexanediol and the like, or long-chain glycols having a molecular weight of 400 to 6000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol and the like, and ester-forming derivatives thereof.

  Preferred examples of these polymers or copolymers include polybutylene terephthalate, polybutylene (terephthalate / isophthalate), polybutylene (terephthalate / adipate), polybutylene (terephthalate / sebacate), polybutylene (terephthalate / decanedicarboxylate), Polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate / isophthalate), polyethylene (terephthalate / adipate), polyethylene (terephthalate / 5-sodium sulfoisophthalate), polybutylene (terephthalate / 5-sodium sulfoisophthalate), polyethylene Naphthalate, polycyclohexanedimethylene terephthalate, etc. Polybutylene terephthalate, polybutylene (terephthalate / adipate), polybutylene (terephthalate / decane dicarboxylate), polybutylene naphthalate, polyethylene terephthalate, polyethylene (terephthalate / adipate), polyethylene naphthalate, polycyclohexanedimethylene terephthalate, etc. Particularly preferred is polybutylene terephthalate (polybutylene terephthalate resin).

  The polybutylene terephthalate resin has an intrinsic viscosity measured in a 0.5% o-chlorophenol solution at 25 ° C. in the range of 0.35 to 2.00, more preferably 0.50 to 1.50. A range is preferred. Moreover, you may use together polybutylene terephthalate resin from which intrinsic viscosity differs, and it is preferable that intrinsic viscosity exists in the range of 0.35-2.00.

  Further, the polybutylene terephthalate resin is durable if the COOH end group amount obtained by potentiometric titration of the m-cresol solution with an alkaline solution is in the range of 1 to 50 eq / t (end group amount per ton of polymer). From the point of anisotropy suppressing effect, it can be preferably used.

  Specific examples of the polyphenylene oxide resin used in the present invention include poly (2,6-dimethyl-1,4-phenylene oxide), poly (2-methyl-6-ethyl-1,4-phenylene oxide), and poly (2,6-dimethyl-1,4-phenylene oxide). (2,6-diphenyl-1,4-phenylene oxide), poly (2-methyl-6-phenyl-1,4-phenylene oxide), poly (2,6-dichloro-1,4-phenylene oxide) and the like. And a copolymer such as a copolymer of 2,6-dimethylphenol and other phenols (for example, 2,3,6-trimethylphenol). Among them, poly (2,6-dimethyl-1,4-phenylene oxide) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and in particular, poly (2,6-dimethyl) -1,4-phenylene oxide) is preferred.

  The polyphenylene oxide resin preferably has a reduced viscosity measured in a 0.5 g / dl chloroform solution at 30 ° C. in the range of 0.15 to 0.70.

  The method for producing such a polyphenylene oxide resin is not particularly limited, and those obtained by a known method can be used. For example, it can be easily produced by oxidative polymerization using as a catalyst a complex of cuprous salt and amine by Hay described in US Pat. No. 3,306,874.

  In the present invention, the resin (B) having a reactive functional group is a resin having a reactive functional group in a molecular chain, and is obtained by introducing a reactive functional group into a base resin.

  The resin serving as the base of the resin (B) having a reactive functional group of the present invention is a thermoplastic resin different from the thermoplastic resin (A) described above, and is not particularly limited, but is preferably a polyamide resin or a polyester resin. , Polyphenylene sulfide resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, polyacetal resin, polysulfone resin, tetrafluoroethylene resin, polyetherimide resin, polyamideimide resin, polyimide resin, polyethersulfone resin, polyetherketone resin, From the above-mentioned thermoplastic resin from polythioetherketone resin, polyetheretherketone resin, polyethylene resin, polypropylene resin, styrene resin such as polystyrene resin and ABS resin, rubber polymer, polyalkylene oxide resin, etc. It is possible to use at least one resin selected to be different from the (A). Among them, the resin used as the base of the resin (B) having a reactive functional group is more preferably a polyethylene resin, a polypropylene resin, a styrene resin, or a rubbery polymer because of the ease of introduction of the reactive functional group, and further shock absorption. From the viewpoint of imparting properties, a rubbery polymer is more preferable.

  In the present invention, the rubbery polymer generally contains a polymer having a glass transition temperature lower than room temperature, and some of the intermolecular molecules are constrained by covalent bonds, ionic bonds, van der Waals forces, entanglement, etc. It is a polymer. Examples of rubber polymers include polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated products of the block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, and the like. Diene rubber, ethylene-propylene random copolymer and block copolymer, ethylene-butene random copolymer and block copolymer, ethylene and α-olefin copolymer, ethylene-acrylic acid, ethylene -Ethylene-unsaturated carboxylic acid copolymer such as methacrylic acid, ethylene-acrylic acid ester, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-methacrylic acid ester, part of unsaturated carboxylic acid is a metal salt A certain ethylene-acrylic acid-acrylic acid metal salt Acrylic elasticity such as ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer such as ethylene-methacrylic acid-methacrylic acid metal salt, acrylic ester-butadiene copolymer such as butyl acrylate-butadiene copolymer Polymers, copolymers of ethylene and fatty acid vinyl such as ethylene-vinyl acetate, ethylene-propylene non-conjugated diene terpolymers such as ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer Preferred examples include thermoplastic elastomers such as butylene-isoprene copolymer, chlorinated polyethylene, polyamide elastomer, and polyester elastomer.

  When a polyamide resin is used as the thermoplastic resin (A), among these, from the viewpoint of compatibility, ethylene-unsaturated carboxylic acid ester copolymer, ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer Coalescence is preferably used.

  The unsaturated carboxylic acid ester in the ethylene-unsaturated carboxylic acid ester copolymer is a (meth) acrylic acid ester, preferably an ester of (meth) acrylic acid and an alcohol. Specific examples of unsaturated carboxylic acid esters include (meth) acrylic acid such as methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylate-2-ethylhexyl, stearyl (meth) acrylate Examples include esters.

  The weight ratio of the ethylene component to the unsaturated carboxylic acid ester component in the copolymer is not particularly limited, but is preferably in the range of 90/10 to 10/90, more preferably 85/15 to 15/85.

  The number average molecular weight of the ethylene-unsaturated carboxylic acid ester copolymer is not particularly limited, but is preferably in the range of 1000 to 70000 from the viewpoint of fluidity and mechanical properties.

  Specific examples of the unsaturated carboxylic acid in the ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer include (meth) acrylic acid. Examples of unsaturated carboxylic acid metal salts include (meth) acrylic acid metal salts. Although the metal of unsaturated carboxylic acid metal salt is not specifically limited, Preferably, alkali metals, such as sodium, alkaline-earth metals, such as magnesium, zinc etc. are mentioned.

  The weight ratio of the unsaturated carboxylic acid component to the unsaturated carboxylic acid metal salt component in the ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer is not particularly limited, but preferably 95/5 to 5/95, More preferably, it is the range of 90/10-10/90.

  The number average molecular weight of the ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer is not particularly limited, but is preferably in the range of 1000 to 70000 from the viewpoint of fluidity and mechanical properties.

  The reactive functional group contained in the resin (B) having a reactive functional group is not particularly limited as long as it reacts with the functional group present in the thermoplastic resin (A), preferably an amino group, Examples thereof include at least one selected from a carboxyl group, a carboxyl metal salt, a hydroxyl group, an acid anhydride group, an epoxy group, an isocyanate group, a mercapto group, an oxazoline group, and a sulfonic acid group. Of these, amino groups, carboxyl groups, carboxyl metal salts, epoxy groups, acid anhydride groups, and oxazoline groups are more preferred because they are highly reactive and have few side reactions such as decomposition and crosslinking.

  When the acid anhydride group is introduced into the rubbery polymer, the method can be carried out by a generally known technique and is not particularly limited. For example, maleic anhydride, itaconic anhydride, endic acid anhydride, A method of copolymerizing acid anhydrides such as citraconic anhydride and 1-butene-3,4-dicarboxylic acid anhydride and a monomer that is a raw material of the rubber polymer, grafting the acid anhydride onto the rubber polymer Or the like can be used.

  In addition, when the epoxy group is introduced into the rubbery polymer, the method can be carried out by a generally known technique and is not particularly limited. For example, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, itacon A method of copolymerizing a vinyl monomer having an epoxy group, such as a glycidyl ester compound of an α, β-unsaturated acid such as glycidyl acid, with a monomer which is a raw material of a rubbery polymer, having the above functional group A method of polymerizing a rubbery polymer using a polymerization initiator or a chain transfer agent, a method of grafting an epoxy compound onto a rubbery polymer, or the like can be used.

  Further, when the oxazoline group is introduced into the rubbery polymer, the method can be carried out by a generally known technique and is not particularly limited. For example, 2-isopropenyl-oxazoline, 2-vinyl-oxazoline, 2 A method of copolymerizing a vinyl monomer having an oxazoline group such as -acryloyl-oxazoline or 2-styryl-oxazoline with a monomer which is a raw material of a rubbery polymer can be used.

  The number of functional groups per molecular chain in the resin (B) having a reactive functional group is not particularly limited, but usually 1 to 10 is preferable, and 1 to 5 in order to reduce side reactions such as crosslinking. Preferably. Moreover, although the molecule | numerator which does not have a functional group at all may be contained, it is so preferable that the ratio is small.

  Although there is no restriction | limiting in particular about the compounding ratio of the thermoplastic resin (A) and the resin (B) which has a reactive functional group in this invention, Resin which has the weight Aw of a thermoplastic resin (A) and a reactive functional group ( The ratio Aw / Bw of B) to the weight Bw is preferably in the range of 5/95 to 95/5, more preferably in the range of 10/90 to 90/10, and most preferably in the range of 15/85 to 85/15. . When Aw / Bw is lower than 5/95, the reaction between the resins (B) having reactive functional groups becomes remarkable, and there is a tendency that molding processing becomes difficult due to an increase in viscosity, and Aw / Bw is 95/5. If the ratio exceeds 1, the amount of the functional group that reacts with the thermoplastic resin (A) decreases, and the effect of improving the mechanical properties of the thermoplastic resin composition and the manifestation effect of unique viscoelastic behavior tend to be small, which is not preferable. .

  The thermoplastic resin composition of the present invention drops a weight body of 193 kg in a cylindrical molded product having a deflection temperature under load of 0.45 MPa at 45 ° C. or more and an outermost diameter of 50 mm, a thickness of 2 mm, and a height of 150 mm. It is characterized in that the maximum point load applied to the weight body is less than 20 kilonewtons when a free fall is made from a height of 0.5 m, and no cracks of 5 cm or more are generated.

  The deflection temperature under load at 0.45 MPa is a sample in which a JIS-1 strip test piece obtained by injection molding is conditioned for 48 hours under conditions of 23 ° C. and 50% RH. For example, an HDT tester manufactured by Toyo Seiki Co., Ltd. Using S3-MH, a load of 0.45 MPa is applied and the measurement is performed according to ISO75-1,2.

  A cylindrical molded product having an outermost diameter of 50 mm, a thickness of 2 mm, and a height of 150 mm is produced as follows. First, the dried thermoplastic resin composition is put into a single screw extruder, and a round bar having a diameter of 50 mm is produced by extrusion molding. Next, the round bar is cut into a length of 150 mm, and finally a lathe is used to cut out the thermoplastic resin composition therein to a thickness of 2 mm. Here, the outermost diameter is 1 in FIG. 1, the thickness is 2 in FIG. 1, and the height is 3 in FIG.

  In the present invention, in a state where the circle of the cylindrical molded product is standing on the horizontal base, the drop height is 0 so that the weight (weight) having a mass of 193 kg contacts the circle of the cylindrical molded product in parallel. . Test with 5m free fall. At that time, the speed immediately before contact with the cylindrical molded product is as high as 11.3 km / h. The thermoplastic resin composition of the present invention has a remarkable non-viscoelastic property that it becomes more flexible as it deforms at higher speeds. Therefore, when the test is performed, the maximum point given to the weight body as compared with the conventional material Since the load is as low as less than 20 kilonewtons, and the molded product itself does not generate cracks of 5 cm or more, there is no major breakage and it is excellent for use as an impact absorbing member.

  In the thermoplastic resin composition of the present invention, the structure is observed by transmission electron beam tomography (TEMT). TEMT is a microscopy method that visualizes the internal structure of a material on the nanometer scale by applying a computed tomography method (CT method) to transmission electron microscopy (TEM). Utilizing that TEM is a technique for obtaining a transmission image of a sample with respect to an electron beam, the sample is inclined with respect to the electron beam, a large number of transmission images are taken, and a series of these inclined transmission images are reconstructed by the CT method This is a technique for obtaining a three-dimensional image.

  An experimental technique for obtaining a three-dimensional image by TEMT is not particularly limited, but a representative example is given. Similar to the preparation of a sample for observation by a two-dimensional TEM, a sliced product (sample) of a thermoplastic resin composition is prepared by a known technique, and the sample is dyed or dyed with an appropriate staining agent. create. The sample is subjected to a three-dimensional electron microscope (for example, JEM-2200FS manufactured by JEOL). For example, the sample is tilted in steps of 1 ° within a tilt angle range of −60 ° to + 60 °, and a transmission image is displayed. Photograph and obtain 121 inclined transmission images. Before photographing an image, gold particles having a diameter of about 10 nm are placed on the surface of the sample, and the movement along with the inclination of the gold particles is tracked to correct the tilt axis of the transmitted image. Three-dimensional data is reconstructed from a series of inclined transmission images with respect to the inclination axis to obtain a three-dimensional transmission image.

  In the thermoplastic resin composition of the present invention, one of the thermoplastic resin (A) or the resin (B) having a reactive functional group forms a continuous phase and the other forms a dispersed phase. The resin constituting the continuous phase is either a thermoplastic resin (A) or a resin (B) having a reactive functional group, and is not particularly limited. However, if heat resistance is required, the continuous phase is a thermoplastic resin. It is preferable to be composed of (A).

  In the thermoplastic resin composition of the present invention, it is preferable that a three-dimensional connection structure Cs including a continuous phase component is formed in the dispersed phase. The three-dimensional connection structure here is a connection structure that is confirmed by a three-dimensional transmission image obtained by TEMT, and is not particularly limited as long as it is a structure in which particles are not three-dimensionally connected but three-dimensionally connected. There are no column shapes, T shapes, cross shapes, network shapes, and the like.

  In the thermoplastic resin composition of the present invention, the proportion of the area of the connecting structure Cs in the cross section of the dispersed phase Dp having an average particle diameter of 1000 nm or less in the dispersed phase is preferably 10% or more. The average particle diameter here can be calculated by image analysis of a transmission image at an inclination angle of 0 ° in TEMT. For image analysis, image analysis software such as “Scion Image” manufactured by Scion Corporation is used to calculate the average value of the diameter and minor axis of the dispersed phase present in the transmission image. The average particle diameter is calculated as the average value of the diameters.

  In the thermoplastic resin composition of the present invention, the three-dimensional connection structure Cs including the continuous phase component in the dispersed phase is formed as follows. That is, when producing the thermoplastic resin composition of the present invention, one of the thermoplastic resin (A) and the resin (B) having a reactive functional group forms a continuous phase and the other forms a dispersed phase. Resin (A) and resin (B) having a reactive functional group react at the interface between the continuous phase and the dispersed phase. As the reaction at the interface proceeds, the amount of reactant increases, and the reactant generated at the interface is drawn into the dispersed phase. As the reaction further proceeds, the amount of reactants drawn into the dispersed phase increases, and the reactants are connected to each other to form a three-dimensional connection structure in the dispersed phase. Moreover, since the reaction product produced by the reaction at the interface acts as a surfactant, the dispersed phase becomes finer, and coalescence and coarsening of the dispersed phase are prevented to stabilize the dispersed state. In this way, the reaction between the thermoplastic resin (A) and the resin (B) having a reactive functional group proceeds to form a three-dimensional connection structure Cs containing a continuous phase component in the dispersed phase, and an average particle size. When the proportion of the area of the connecting structure Cs in the cross section of the dispersed phase Dp with a thickness of 1000 nm or less is 10% or more, the impact absorbability with respect to a heavy load and a high speed impact, which is the effect of the present invention, is remarkably exhibited. .

  The proportion of the area of the connected structure Cs in the cross section of the dispersed phase Dp having an average particle diameter of 1000 nm or less is preferably 10% or more, but for the more remarkable expression of the unique viscoelastic behavior, preferably the average The proportion of the area of the connected structure Cs in the cross section of the dispersed phase Dp having a particle size of 800 nm or less, more preferably 500 nm or less is preferably 15% or more, more preferably 20% or more. The cross section of the disperse phase Dp here refers to a cross section in a transmission image at an inclination angle of 0 ° in TEMT. The method for calculating the ratio of the area of the connected structure Cs in the cross section of the dispersed phase Dp is not particularly limited, but an appropriate staining agent is used as the staining agent, and either the dispersed phase or the continuous phase is dyed and transmitted. By giving color contrast to the dispersed and continuous phases in the image, the dispersed and continuous phases can be distinguished. Therefore, the connected structure Cs including the continuous phase component can be similarly given a color contrast with the dispersed phase. The portion of the cross section of Dp in the dispersed phase that is different in color from the dispersed phase Dp can be defined as the cross section of the connection structure Cs including the continuous phase component, and the cross sectional area of the connection structure Cs including the continuous phase component is dispersed. The value divided by the cross-sectional area of the phase Dp is the ratio of the area of the connection structure Cs in the cross section of the dispersed phase Dp. The area calculation method is not particularly limited, but can be calculated using image analysis software such as the image analysis software “Scion Image” manufactured by Scion Corporation.

  In the tensile test, the thermoplastic resin composition of the present invention has E (V1)> E when V1 <V2 when the tensile elastic modulus is E (V1) and E (V2) at the tensile speeds V1 and V2. (V2) is preferred. The tensile test in this case is performed according to a method specified in the standard. The tensile elastic modulus indicates the gradient of the initial straight line portion of the stress-strain curve.

  Further, in the tensile test, the thermoplastic resin composition of the present invention has a tensile elongation at break of ε (V1) and ε (V2) at the tensile speeds V1 and V2, and ε (V1) when V1 <V2. ) <Ε (V2). The tensile elongation at break indicates the elongation at the moment of fracture. The above relational expression is preferably established for all V1 and V2 within the range of the tensile speed of 10 mm / min to 500 mm / min, and more preferably any V1 within the range of 1 mm / min to 1000 mm / min. , V2 is preferably established.

  As a method for producing the thermoplastic resin composition of the present invention, production in a molten state, production in a solution state, and the like can be used, but production in a molten state can be preferably used from the viewpoint of improving the reactivity. For production in a molten state, melt kneading with an extruder, melt kneading with a kneader, or the like can be used. From the viewpoint of productivity, melt kneading with an extruder that can be continuously produced can be preferably used. For melt kneading by an extruder, one or more extruders such as a single screw extruder, a twin screw extruder, a multi screw extruder such as a four screw extruder, and a twin screw single screw compound extruder can be used. From the viewpoint of improvement in productivity, reactivity, and productivity, a multi-screw extruder such as a twin-screw extruder or a four-screw extruder can be preferably used, and a method by melt kneading using a twin-screw extruder is most preferable.

When producing a thermoplastic resin composition according to the present invention, when a twin screw extruder is used, there is no particular limitation, but the value of L / D ₀ is 50 or more from the viewpoint of improving kneadability and reactivity. More preferably, it is more preferably in the range of 60 to 200, particularly 80 to 200. L / D ₀ is a value obtained by dividing the screw length L by the screw diameter D. The screw length is the length from the upstream end of the screw segment at the position (feed port) where the screw base material is supplied to the screw tip. Here, the raw material refers to the present invention such as thermoplastic resin (A), resin (B) having a reactive functional group, fillers added as other components, thermoplastic resins, rubbers, various additives, and the like. All the components necessary for obtaining the thermoplastic resin composition are shown. Here, the screw of the twin screw extruder is configured by combining screw segments having different lengths and shape characteristics such as full flight and kneading disc. In the extruder, the side to which raw materials are supplied may be referred to as upstream, and the side from which molten resin is discharged may be referred to as downstream.

When an extruder having a sampling valve or the like is used for sampling from the middle of the extruder, the screw length L is “upstream of the screw segment at the position (feed port) where the raw material of the screw is supplied. It can be considered that it is the same as that kneaded by a normal extruder equal to the “length from the end portion to the sampling location” and having a screw diameter D ₀ equal to the screw diameter of an extruder having a sampling valve or the like. The sampling location here refers to a position on the screw shaft on the upstream side closest to the port through which the resin in the cylinder is discharged.

  In addition, when producing a thermoplastic resin composition according to the present invention, when a twin screw extruder is used, the screw of the twin screw extruder has a plurality of full flight zones and knees in terms of improving kneadability and reactivity. It is preferable to have a bonding zone. The full flight zone is composed of one or more full flights, and the kneading zone is composed of one or more kneading discs.

  When producing a thermoplastic resin composition in the present invention, when a twin screw extruder is used, the resin in the kneading zone that is the maximum of the resin pressures indicated by the resin pressure gauges installed in the kneading zones at a plurality of locations. When the pressure is Pkmax (MPa), and the resin pressure in the full flight zone that is the minimum among the resin pressures indicated by the resin pressure gauges installed in a plurality of full flight zones is Pfmin (MPa), the value of Pkmax is ( It is preferable to produce the thermoplastic resin composition of the present invention under conditions of Pfmin + 0.3) or more, more preferably conditions of (Pfmin + 0.4) or more, and further production under conditions of (Pfmin + 0.5) or more. preferable.

  A kneading zone composed of one or more kneading discs is more excellent in kneadability and reactivity of the molten resin than a full flight zone composed of one or more full flights. By filling the kneading zone with the molten resin, the kneading property and the reactivity are drastically improved. As an index indicating the state of filling of the molten resin, there is a value of the resin pressure, and the larger the resin pressure, the more standard the molten resin is filled. That is, in the production of the thermoplastic resin composition of the present invention, when a twin screw extruder is used, the reaction is effectively performed by increasing the resin pressure in the kneading zone within a certain range from the resin pressure in the full flight zone. This makes it possible to promote the formation of a three-dimensional connection structure Cs containing a continuous phase component in the dispersed phase, and to make a specific viscoelastic behavior remarkably manifest.

  There are no particular restrictions on how to increase the resin pressure in the kneading zone, but there is an effect of accumulating the reverse screw zone and the molten resin between the kneading zones and downstream of the kneading zone, which has the effect of pushing the molten resin upstream. For example, a method of introducing a seal ring zone having a gap can be preferably used. The reverse screw zone and the seal ring zone are composed of one or more reverse screws and one or more seal rings, which can be combined.

For example, when introducing reverse screw zones between kneading zones or downstream of the kneading zones, assuming that the length of each reverse screw zone is Lr, all the reverse screw zones have Lr / D ₀ = 0. A length of 1 to 10 is preferable from the viewpoints of kneading properties and reactivity. The length Lr / _{D 0} of the reverse screw zone, and more preferably 0.2 to 8, more preferably from 0.3 to 6. The length Lr of the reverse screw zone is defined as a perpendicular line from the upstream end portion of the most upstream reverse screw constituting the reverse screw zone to the screw shaft center line, and from the downstream end portion of the most downstream reverse screw to the screw shaft center. The distance between the perpendicular to the line.

  Moreover, when producing a thermoplastic resin composition in the present invention, when a twin-screw extruder is used, the extrusion amount of the thermoplastic resin composition is preferably 0.01 kg / h or more per 1 rpm of the screw. Preferably, it is 0.05 kg / h to 1 kg / h, more preferably 0.08 to 0.5 kg / h, and most preferably 0.1 to 0.3 kg / h. The extrusion amount is an extrusion rate of the thermoplastic resin composition discharged from the extruder, and is a weight (kg) extruded per hour.

  In addition, the preferable numerical range regarding the extrusion amount in the said twin-screw extruder is based on the extrusion amount of a twin-screw extruder with a screw diameter of 37 mm. When the screw diameters are significantly different, for example when using a twin screw extruder with a diameter of less than 30 mm or more than 50 mm, the extrusion rate is preferably 2. It can be read as an increase / decrease according to the fifth power law or the third power law, more preferably according to the 2.5 power law.

  For example, when a twin screw extruder having a screw diameter of 20 mm is used, assuming that the extrusion amount conforms to the 2.5th power rule of the screw diameter ratio before and after the scale down, the extrusion amount of the thermoplastic resin composition is the number of screw rotations. Preferably, 0.002 kg / h or more per 1 rpm, more preferably 0.01 to 0.2 kg / h, still more preferably 0.017 to 0.11 kg / h, most preferably 0.02 to 0.06 kg / h. h.

  Further, when a twin screw extruder having a screw diameter of 100 mm is used, assuming that the extrusion amount conforms to the 2.5th power rule of the screw diameter ratio before and after the scale-up, the extrusion amount of the thermoplastic resin composition is per 1 rpm of the screw. It is preferably 0.12 kg / h or more, more preferably 0.6 to 12 kg / h, still more preferably 0.96 to 6 kg / h, and most preferably 1.2 to 3.6 kg / h.

  Moreover, there is no restriction | limiting in particular as a rotational speed of a screw, Usually, 10 rpm or more, Preferably it is 15 rpm or more, More preferably, it is 20 rpm or more. The extrusion rate is not particularly limited, but is usually 0.1 kg / h or more, preferably 0.15 kg / h or more, and more preferably 0.2 kg / h or more.

  Moreover, when producing a thermoplastic resin composition in the present invention, when using a twin screw extruder, the residence time in the twin screw extruder of the thermoplastic resin composition is preferably 1 to 30 minutes, More preferably, it is 1.5 to 28 minutes, More preferably, it is 2 to 25 minutes. The residence time is an average of the residence time from when the raw material is supplied to the twin screw extruder until it is discharged, and is a steady melt kneading in which the uncolored thermoplastic resin composition is adjusted to a predetermined extrusion amount. In the state, from the position of the screw base to which the raw material is supplied, together with the raw material, usually about 1 g of the colorant is added, and from the time when the colorant is added, the thermoplastic resin composition is extruded from the discharge port of the extruder, The time until the point at which the degree of coloring by the colorant on the extrudate is maximized is taken.

  In addition, when a twin screw extruder is used when producing the thermoplastic resin composition in the present invention, the screw of the twin screw extruder is not particularly limited, and is a complete mesh type, an incomplete mesh type, a non-mesh type. However, from the viewpoint of kneadability and reactivity, a completely meshing screw is preferable. Further, the direction of rotation of the screw may be either the same direction or a different direction, but from the viewpoint of kneadability and reactivity, the same direction is preferable. When a twin screw extruder is used in the present invention, the screw is most preferably a co-rotating fully meshing type.

  In addition, when a twin screw extruder is used in the present invention, the screw configuration of the twin screw extruder is a combination of full flight and / or kneading disks, which is effective for a molten thermoplastic resin composition. A screw configuration that imparts a shear field to is preferred. Therefore, as described above, it is preferable that the screw of the twin-screw extruder has a plurality of kneading zones composed of one or more kneading disks in the longitudinal direction, and the total of these kneading zones The length is preferably in the range of 5 to 50%, more preferably 10 to 40%, and still more preferably 15 to 30% of the total length of the screw.

Moreover, when using the twin screw extruder in the present invention, when the length of each kneading zone in the screw of the twin screw extruder is Lk, all kneading zones have Lk / D ₀ = 0.2 to A length of 10 is preferable from the viewpoints of kneading properties and reactivity. The length Lk / _{D 0} of each kneading zone is more preferably 0.3 to 9, more preferably from 0.5 to 8. The length Lk of the kneading zone is determined by the perpendicular line from the upstream end of the most upstream kneading disk constituting the kneading zone to the screw shaft center line and the screw from the downstream end of the most downstream kneading disk. The distance between the vertical line to the axis center line.

  Moreover, when using a twin-screw extruder by this invention, it is preferable that the kneading zone of a twin-screw extruder is arrange | positioned over the whole region, without uneven distribution in the specific position in a screw.

When a twin screw extruder is used in the present invention, in order to remove reaction by-products or heat-degraded substances, a vent vacuum zone is provided and the pressure is reduced to a gauge pressure of −0.07 MPa or less and melt-kneaded. Preferably, the pressure is reduced to a gauge pressure of −0.08 MPa or less, and melt kneading is more preferable. Here, the gauge pressure indicates the pressure when the atmospheric pressure is zero, and the lower the pressure, the higher the degree of vacuum and the higher the ability to remove volatile components. When the gauge pressure in the vent vacuum zone exceeds −0.07 MPa, that is, when the degree of vacuum is low, the volatile components cannot be sufficiently removed, impurities remain in the thermoplastic resin composition, and impact absorption decreases. Therefore, it is not preferable. By sufficiently removing volatile components in the vent vacuum zone, it becomes possible to reduce the amount of impurities in the thermoplastic resin composition, and the impact absorption is remarkably imparted. There is no restriction | limiting in particular in the number of vent vacuum zones, It is preferable to install one or more. Also, there is no particular restriction on the position of the vent vacuum zone, but it is possible to effectively remove the volatile components by installing at least one at a position L / D ₀ = 0 to 10 before the sampling position. This is preferable.

  When a twin screw extruder is used in the present invention, it is preferable to melt and knead using a raw material having a moisture content of less than 5000 ppm, and it is more preferable to melt and knead using a raw material having a moisture content of less than 1000 ppm. The moisture content here is measured according to ISO15512. If a raw material with a moisture content exceeding 5000 ppm is used, the reaction in the extruder is suppressed by the water contained in the raw material, the kneadability is impaired, and the impact absorption of the produced thermoplastic resin composition is reduced. It is not preferable. Further, when the thermoplastic resin (A) is a polyester resin, hydrolysis further proceeds in the extruder, and the impact absorbability of the produced thermoplastic resin composition is greatly reduced, which is not preferable.

  When a twin screw extruder is used in the present invention, the maximum resin temperature is preferably controlled at 180 ° C. to 330 ° C. and melt kneaded, and more preferably 200 ° C. to 310 ° C. The maximum resin temperature here indicates the highest temperature measured by resin thermometers installed evenly at a plurality of locations in the extruder. When the maximum resin temperature is less than 180 ° C., the reactivity between the polymers is low, and when it exceeds 330 ° C., the thermal absorption of the polymer proceeds and the impact absorption decreases, so the maximum resin temperature is 180 ° C. It is preferable to perform melt kneading while controlling at a temperature of from C to 330C.

  When a twin-screw extruder is used in the present invention, it is preferable to introduce an inert gas from the raw material charging part and melt knead to suppress thermal deterioration. Nitrogen gas is preferred as the inert gas.

  In the thermoplastic resin composition of this invention, you may add other components other than said (A) and (B) as needed in the range which does not impair the characteristic. Examples of other components include fillers, thermoplastic resins, rubbers, and various additives.

  For example, a filler may be used as necessary to improve strength, dimensional stability, and the like. The filler may be fibrous or non-fibrous, or a combination of fibrous filler and non-fibrous filler may be used.

  Examples of the filler include glass fiber, glass milled fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone-kow fiber, metal Fibrous fillers such as fibers, wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate and other silicates, alumina, silicon oxide, magnesium oxide, zirconium oxide, Metal compounds such as titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, hydroxides such as magnesium hydroxide, calcium hydroxide and aluminum hydroxide, Rasubizu, ceramic beads, non-fibrous fillers such as boron nitride and silicon carbide and the like, which may be hollow, it is also possible to further combination of these fillers 2 or more. In addition, these fibrous and / or non-fibrous fillers are pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, an epoxy compound, This is preferable in terms of obtaining superior mechanical properties.

  In order to improve strength, dimensional stability and the like, when such a filler is used, the amount of the filler is not particularly limited, but it is preferably 30 to 400 parts by weight based on 100 parts by weight of the thermoplastic resin composition.

  Furthermore, in the thermoplastic resin composition of the present invention, other rubbers and various additives can be blended as necessary within the range not impairing the characteristics.

  Such rubbers include, for example, polybutadiene, polyisoprene, styrene-butadiene random copolymers and block copolymers, hydrogenated block copolymers, acrylonitrile-butadiene copolymers, butadiene-isoprene copolymers, and the like. Diene rubber, ethylene-propylene random copolymer and block copolymer, ethylene-butene random copolymer and block copolymer, ethylene and α-olefin copolymer, ethylene-acrylic acid, ethylene -Ethylene-unsaturated carboxylic acid copolymer such as methacrylic acid, ethylene-acrylic acid ester, ethylene-unsaturated carboxylic acid ester copolymer such as ethylene-methacrylic acid ester, part of unsaturated carboxylic acid is a metal salt A ethylene-acrylic acid-acrylic acid metal , Ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymer such as ethylene-methacrylic acid-methacrylic acid metal salt, acrylic ester-butadiene copolymer such as butyl acrylate-butadiene copolymer Ethylene-propylene non-conjugated diene terpolymers such as elastic polymers, ethylene-fatty acid vinyl copolymers such as ethylene-vinyl acetate, ethylene-propylene-ethylidene norbornene copolymers, ethylene-propylene-hexadiene copolymers Preferred examples thereof include thermoplastic elastomers such as coalescence, butylene-isoprene copolymer, chlorinated polyethylene, polyamide elastomer, and polyester elastomer, and modified products thereof. Two or more kinds of such rubbers can be used in combination. When such rubbers are used, the blending amount thereof is not particularly limited, but is preferably blended by 1 to 400 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.

  The various additives that can be added to the thermoplastic resin composition of the present invention are preferably crystal nucleating agents, anti-coloring agents, antioxidants such as hindered phenols and hindered amines, ethylene bisstearylamide and higher fatty acids. Examples include release agents such as esters, plasticizers, heat stabilizers, lubricants, ultraviolet light inhibitors, colorants, flame retardants, and foaming agents.

  These rubbers and various additives can be blended at any stage for producing the thermoplastic resin composition of the present invention. For example, the thermoplastic resin composition of the present invention can be blended with a twin screw extruder. When manufacturing, the method of adding at the time of compounding the resin, the method of adding the resin by a method such as side feed during melt kneading, the method of adding the resin after melt kneading in advance, and the thermoplastic A method of adding the remaining resin to one resin constituting the resin composition, melt-kneading, and the like is mentioned.

  When the thermoplastic resin composition of the present invention is produced by a twin-screw extruder, a supercritical fluid can also be introduced from the viewpoint of improving reactivity when melt-kneading with the twin-screw extruder. Such a supercritical fluid is a fluid that exceeds the limit point (critical point) at which gas and liquid can coexist, and has both gas properties (diffusibility) and liquid properties (solubility). is there. Such supercritical fluids include supercritical carbon dioxide, supercritical nitrogen, supercritical water, etc., preferably supercritical carbon dioxide and supercritical nitrogen can be used, most preferably supercritical carbon dioxide can be used. .

  The molding method of the thermoplastic resin composition of the present invention can be any method, and the molding shape can be any shape. Examples of the molding method include extrusion molding, injection molding, hollow molding, calendar molding, compression molding, vacuum molding, foam molding, and the like. Pellet, plate, fiber, strand, film or sheet, pipe Shape, hollow shape, box shape and the like.

  The molded article of the present invention thus obtained is excellent in heat resistance and impact absorption, but particularly in the case of thin molded articles, elongated molded articles, fibers and films, the unique viscoelastic properties are remarkably exhibited. It has a special effect.

  In general, when a molded article, a fiber, or a film made of a thermoplastic resin is evaluated for tensile properties by changing the tensile speed, the higher the tensile speed, the higher the tensile elastic modulus and the lower the tensile elongation. In contrast, molded articles, fibers and films molded from the thermoplastic resin composition of the present invention exhibit unique viscoelastic properties that the tensile modulus decreases as the tensile speed increases, and the tensile elongation is further reduced. It can be seen that it exhibits the exact opposite characteristic of increasing. In addition, since it is remarkably excellent in shock absorption for large loads and high-speed impacts, it is useful as a molded article, fiber, or film that requires unique shock absorption characteristics. In particular, such unique non-viscoelastic properties and impact absorption properties are recognized particularly in thin molded products, elongated molded products, drawn fibers and drawn films, and are particularly useful.

  When producing fibers from the thermoplastic resin composition of the present invention, known spinning / drawing techniques can be used. Examples of the drawing / spinning technology include, for example, a method in which a melt-spun yarn or a strand discharged from an extruder is temporarily wound and then drawn, or a melt-spun yarn or a strand discharged from an extruder is temporarily wound. For example, a continuous stretching method is used.

  When manufacturing a film from the thermoplastic resin composition of this invention, a well-known film forming technique can be used. For example, a method of extruding a flat film by placing a T die in an extruder, a method of obtaining a stretched film by further stretching this film in a uniaxial or biaxial direction, and a cylindrical film by arranging a circular die in an extruder A method such as an inflation method is used to inflate.

  Moreover, when manufacturing the thermoplastic resin composition of this invention with a twin-screw extruder, you may make it implement said yarn-making process or film forming process directly from the twin-screw extruder.

  Furthermore, a molded article made of the thermoplastic resin composition of the present invention has a feature that the peak value of loss tangent (tan δ) becomes large, and exhibits excellent characteristics in vibration energy absorption performance. For this reason, it is particularly useful for applications that require sound absorption, heat absorption, vibration control, seismic isolation, and the like.

  Applications of the molded product of the thermoplastic resin composition of the present invention include connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickups, oscillators Various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computers Besides being suitable for electronic component applications such as parts, generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, breakers, knife switches, Other pole rod, electrical parts cabinet Electrical equipment parts such as audio / video equipment parts such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs (registered trademark) / compact discs, DVDs, etc. , Lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home appliances, office electrical product parts; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning equipment Machine-related parts represented by tools, motor parts, lighters, typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, etc., precision machine-related parts; Alternator terminals, alternator connectors, IC regulators, light deer Potentiometer Various valves such as base and exhaust gas valve, fuel-related / cooling system / brake system / wiper system / exhaust system / intake system pipe / hose / tube, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor Main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, battery peripheral parts, thermostat base for air conditioner, Heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, dus Tributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, coil for fuel related electromagnetic valve, wire harness connector, SMJ connector, PCB connector, door grommet connector, fuse connector, etc. Connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, torque control lever, safety belt component, register blade, washer lever , Window regulator handle, knob of window regulator handle, passing light levelー, Sun visor bracket, instrument panel, airbag peripheral parts, door pad, pillar, console box, various motor housings, roof rail, fender, garnish, bumper, door panel, roof panel, hood panel, trunk lid, door mirror stay, spoiler, It is suitably used for shock absorbing members for automobile / vehicle related parts such as hood louvers, wheel covers, wheel caps, grill apron cover frames, lamp bezels, door handles, door moldings, rear finishers and wipers.

  The thermoplastic resin composition of the present invention is also suitable for film and sheet applications. Films and sheets for packaging, films and sheets for automobile parts, films and sheets for industrial use, films and sheets for agriculture and civil engineering, films for medical use and It is suitably used for impact absorbing members such as sheets, films and sheets for electrical and electronic equipment members, films for household goods, and sheets.

  The thermoplastic resin composition of the present invention is also suitable as a fiber, and may be any of a long fiber, a short fiber, a monofilament, a crimped yarn, and the like, and a uniform, a working wear, sportswear, a T-shirt, etc. For general clothing, nets, ropes, spunbonds, polishing brushes, industrial brushes, filters, papermaking nets, etc., for blankets, futon bedding, curtains and other bedding / interior products, toothbrushes It is suitably used for shock absorbing members for household goods such as body brushes, eyeglass frames, umbrellas, covers, shopping bags and furoshiki.

  The thermoplastic resin composition of the present invention is suitably used for impact absorbing members such as automobile interior and exterior parts and automobile outer plates.

  The thermoplastic resin composition of the present invention is also suitable as a building material, such as civil engineering building walls, roofs, ceiling material related parts, window material related parts, heat insulating material related parts, flooring related parts, seismic isolation / damping. It is suitably used for impact absorbing members such as member-related parts and lifeline-related parts.

  The thermoplastic resin composition of the present invention is also suitable as sports equipment, golf-related equipment such as golf clubs, shafts, grips, and golf balls, sports racquet-related equipment such as tennis rackets, badminton rackets and their guts, and American football. Such as masks for baseball and softball, helmets, breast pads, elbow pads, knee pads, sports body protection products, sportswear and other wear-related products, sports shoe bottoms and other shoe-related products, fishing rods, fishing lines, etc. It is suitably used for shock absorbing members such as fishing equipment-related products, summer sports-related products such as surfing, winter sports-related products such as ski and snowboard, and other indoor and outdoor sports-related products.

  Hereinafter, the effects of the present invention will be described more specifically with reference to examples. In addition, this invention is not limited to the following Example.

The thermoplastic resin (A) used in this example and the comparative example is as follows.
(A-1): Nylon 6 resin having a melting point of 225 ° C., a relative viscosity of 2.75 at 98 g / ml in 98% sulfuric acid, and a moisture content of 500 ppm.
(A-2): Nylon 6 resin having a melting point of 225 ° C., a relative viscosity of 2.75 at 98 g / ml in 98% sulfuric acid, and a water content of 7000 ppm.
(A-3): Nylon 66 resin having a melting point of 265 ° C., a relative viscosity of 2.75 at 98 g / ml in 98% sulfuric acid, and a moisture content of 500 ppm.
(A-4): Nylon 610 resin having a melting point of 225 ° C., a relative viscosity of 2.70 at 98 g / ml in 98% sulfuric acid, and a moisture content of 500 ppm.
(A-5): Nylon 11 resin having a melting point of 190 ° C., a relative viscosity of 2.55 at 0.01 g / ml in 98% sulfuric acid, and a moisture content of 500 ppm.
(A-6): Polybutylene terephthalate resin having a melting point of 225 ° C., an intrinsic viscosity of 0.70 measured with a 0.5% solution in o-chlorophenol, a carboxyl end group amount of 35 eq / t, and a moisture content of 100 ppm.

Similarly, the resin (B) having a reactive functional group is as follows.
(B-1): Glycidyl methacrylate-modified polyethylene copolymer having a moisture content of 200 ppm (hereinafter abbreviated as GMA-modified PE copolymer) “Bond First BF-7L” (manufactured by Sumitomo Chemical Co., Ltd.)
(B-2): Maleic anhydride-modified ethylene-1-butene copolymer “Tuffmer MH7020” having a moisture content of 200 ppm (manufactured by Mitsui Chemicals, Inc.)
(B-3): Ethylene-methacrylic acid-zinc methacrylate copolymer “High Milan 1706” having a moisture content of 200 ppm (Mitsui / DuPont Polychemical Co., Ltd.)
Similarly, resins other than (A) and (B) are as follows.
(C-1): Unmodified polyethylene copolymer having a moisture content of 200 ppm (hereinafter abbreviated as unmodified PE copolymer) “LOTRYL29MA03” (manufactured by Arkema)
(D-1): Thermoplastic polyurethane “Elastolan NY97A” (manufactured by BASF)
(1) Moisture content measurement of raw material It measured according to ISO15512 using Mitsubishi Chemical Corporation CA-100 Moisturemeter. A specific measurement method is described below. About 10 g of a sample is weighed into a clear conical stoppered Erlenmeyer flask, and 20 ml of methanol is added with a dispenser. Attach a reflux condenser with a silica gel tube to the flask and boil at 150 ° C. for 3 hours. Then, it is left to cool at room temperature for 45 minutes, and 0.5 ml of the methanol extract is collected with a syringe, and injected into a digital trace moisture measuring device (CA-100 Moisture meter manufactured by Mitsubishi Chemical Corporation), and the display is read ( a). The same experiment is performed with methanol alone as a reference, the display is read (b), and the moisture content is calculated by the following equation.
Moisture content (ppm) = (a−b) ÷ (W × V1 / V2) × 10 ⁶
a: Water content in 0.5 ml of extracted methanol (g)
b: Moisture content in 0.5 ml of reference extracted methanol (g)
W: Sample weight (about 10 g)
V1: Amount of syringe collected (0.5 ml)
V2: Amount of methanol used for extraction (20 ml)
(2) Injection molding of test piece Using an injection molding machine (NP7-1F) manufactured by Nissei Plastic Industry Co., Ltd., a molding temperature of 260 ° C. (in Example 8, Comparative Example 8, 280 ° C., Example 10, Comparative Example 7, Comparison) JIS-5A dumbbell test piece (75 mm length × 12 mm end width) under the conditions of 220 ° C. in Example 10), mold temperature 80 ° C. (20 ° C. in Comparative Example 7), lower limit of injection pressure + 5 kgf / cm ² . 5 mm × thickness 2 mm) and JIS-1 strip type test pieces (length 80 mm × width 10 mm × thickness 4 mm).

(3) Morphological observation with a three-dimensional electron microscope After cutting a JIS-5A dumbbell-shaped test piece obtained by injection molding into 1 to 2 mm square and dyeing with ruthenium tetroxide, an ultrathin section with a thickness of 80 nm is obtained. It cut out at the temperature (liquid nitrogen temperature) of -196 degreeC with the ultramicrotome made from Leica. A few drops of gold particles having a diameter of about 10 nm dispersed in ethanol were dropped on the surface of the ultrathin slice to uniformly disperse the gold particles on the sample surface. Thereafter, it is subjected to a three-dimensional electron microscope JEM-2200FS (manufactured by JEOL), an observation magnification of 50000 times, an acceleration partial pressure of 200 kV, and a step angle of 1 ° in a range of −60 ° to + 60 ° inclination angle. The sample was tilted and transmission images were taken to obtain 121 inclined transmission images. Three-dimensional data was reconstructed from these inclined transmission images to obtain a three-dimensional transmission image. By rotating the three-dimensional transmission image, it was confirmed whether or not the three-dimensional connection structure Cs including the continuous phase component in the dispersed phase was formed. Further, from the transmission image at an inclination angle of 0 °, the ratio of the area of the connected structure Cs in the cross section of the dispersed phase Dp having an average particle diameter of 1000 nm or less was calculated using the image analysis software “Scion Image” manufactured by Scion Corporation. .

(4) Evaluation of tensile elastic modulus and tensile elongation at break by tensile test JIS-5A dumbbell-type test piece obtained by injection molding was subjected to Autograph AG100kNG (manufactured by Shimadzu Corporation), and the distance between chucks was set to 50 mm, and 100 mm. / Min, 500 mm / min, and 1000 mm / min were subjected to a tensile test, and the tensile elastic modulus and tensile elongation at break at each speed were evaluated. Note that the tensile elongation at break was the elongation at break based on a distance between chucks of 50 mm.

(5) Evaluation of impact strength The JIS-1 strip type test piece obtained by injection molding is subjected to a Charpy impact tester 611 manufactured by Toyo Seiki Co., Ltd., and a Charpy impact test is performed at 23 ° C. and 50% RH in accordance with ISO179. did.

(6) Evaluation of deflection temperature under load The JIS-1 strip type test piece obtained by injection molding was subjected to HDT tester S3-MH manufactured by Toyo Seiki Co., Ltd., and conditioned for 48 hours under conditions of 23 ° C. and 50% RH. With respect to the sample, the deflection temperature under load (load 0.45 MPa) was measured in accordance with ISO75-1,2.

(7) Production of cylindrical molded product A cylindrical molded product having an outermost diameter of 50 mm, a thickness of 2 mm, and a height of 150 mm was produced in the following manner. First, the thermoplastic resin composition vacuum-dried at 80 ° C. for 12 hours or more is put into a single screw extruder (manufactured by Rikua) having a screw diameter of 35 mm and L / D ₀ = 25, an extrusion temperature of 260 ° C., a screw rotation speed of 12 rpm, A round bar having a diameter of 50 mm was produced by extrusion molding under the condition of a take-up speed of 0.4 m / h. Next, the round bar was cut into a length of 150 mm, and finally a lathe was used to cut out the thermoplastic resin composition therein to a thickness of 2 mm. Here, the outermost diameter is 1 in FIG. 1, the thickness is 2 in FIG. 1, and the height is 3 in FIG.

(8) Evaluation of maximum load and presence / absence of fracture by free load impact test with high load and high speed The test was carried out as follows using a falling weight tester manufactured by GSE, owned by Japan Automobile Research Institute. Free standing from a height of 0.5m so that the weight (weight) with a mass of 193kg is in contact with the circle of the cylindrical molded product in parallel with the cylindrical molded product circle on the horizontal base. It was dropped and tested. The speed immediately before contacting the cylindrical molded product is 11.3 km / h. In the test, a laser displacement meter (Special Order LBP300 manufactured by Keyence Corporation), a load meter (CLP-30BS manufactured by Tokyo Sokki Co., Ltd.), a dynamic strain meter (DPM-13A manufactured by Kyowa Denki Co., Ltd.), a data recorder (SIR1000W manufactured by Sony Corporation), a low-pass filter ( NF P-84) and A / D conversion data recording device (Kyowa Denki Co., Ltd. M03-6358) are used to analyze the relationship between the load applied to the weight and displacement, and to determine the maximum point load applied to the weight. It was. Moreover, the molded article after the completion of the test was observed, and the presence or absence of a crack of 5 cm or more was examined visually.

Examples 1 and 2
Nylon 6 resin (A-1) having a moisture content of 500 ppm was used as the thermoplastic resin (A), and GMA-modified PE copolymer (B-1) was used as the resin (B) having a reactive functional group. While mixing with the composition shown and performing nitrogen flow, the screw diameter is 37 mm and the screw is a twin screw L / D ₀ = 100, in the same direction rotating fully meshed twin screw extruder (manufactured by Toshiba Machine Co., Ltd.) , TEM-37BS-26 / 2V), melt temperature kneading with a cylinder temperature of 260 ° C., screw rotation number and extrusion amount shown in Table 1, and a strand-like molten resin from the discharge port (L / D = 100) Was discharged. At that time, the coloring agent was added together with the raw materials, and the time during which the coloring of the extrudate was maximized was measured as the residence time. The residence time is shown in Table 1. Further, as the screw configuration: A, seven kneading zones starting from the positions of L / D ₀ = 22, 28, 43, 55, 69, 77, 93 are provided, and the length Lk / D _{0 of} each kneading zone is provided. Were, in order, Lk / D ₀ = 1.8, 1.8, 2.3, 2.3, 2.3, 2.3, 3.0. Further, a reverse screw zone is provided on the downstream side of each kneading zone, and the length Lr / D ₀ of each reverse screw zone is Lr / D ₀ = 0.4, 0.4, 0.8, ₀ . It was set to 8, 0.4, 0.8, and 0.4. Moreover, when the ratio (%) of the total length of the kneading zone to the total length of the screw is calculated by (total length of the kneading zone) / (total length of the screw) × 100, the ratio of the total length of the kneading zone is 16%. Resin pressure gauges installed in multiple full flight zones from the maximum resin pressure Pkmax (MPa) in the kneading zone among the resin pressures indicated by the resin pressure gauges installed in multiple kneading zones Table 1 shows values obtained by subtracting the minimum resin pressure Pfmin (MPa) of the full flight zone among the resin pressures indicated by. Table 1 shows the highest resin temperature as the highest resin temperature measured by resin thermometers installed evenly at a plurality of locations in the extruder. A vent vacuum zone was provided at a position of L / D ₀ = 96, and volatile components were removed at a gauge pressure of −0.1 MPa. The discharged strand-shaped molten resin was cooled by passing through a cooling bath, and cut while being taken out by a pelletizer, thereby obtaining a pellet-shaped sample of the thermoplastic resin composition. The sample was vacuum-dried at 80 ° C. for 12 hours or more, and then subjected to the above-described injection molding and extrusion molding, and various evaluations were performed. Table 1 shows the kneading conditions and various evaluation results.

Example 3
The screw diameter is 37 mm, the screw is installed in a twin screw twin screw extruder (Toshiba Machine Co., Ltd., TEM-37BS-26 / 2V) with two screws L / D ₀ = 100. Except that the thermoplastic resin composition was discharged from the sampling valve of L / D ₀ = 72, the vent vacuum zone was set at L / D ₀ = 68, and the volatile component was removed at a gauge pressure of −0.1 MPa. Was melt-kneaded in the same manner as in Example 1 to obtain a thermoplastic resin composition. Table 1 shows the kneading conditions and various evaluation results. When the ratio (%) of the total length of the kneading zone to the total length of the screw is calculated by (total length of kneading zone) / (total length of screw) × 100, the ratio of the total length of the kneading zone is 15%.

Example 4
Except that the gauge pressure in the vent vacuum zone was −0.05 MPa, melt kneading was performed in the same manner as in Example 1 to obtain a thermoplastic resin composition. Table 1 shows the kneading conditions and various evaluation results.

Example 5
Except for using a nylon 6 resin (A-2) having a water content of 7000 ppm as the thermoplastic resin (A), melt-kneading was carried out in the same manner as in Example 1 to obtain a thermoplastic resin composition. Table 1 shows the kneading conditions and various evaluation results.

Example 6
A thermoplastic resin composition was obtained by performing melt-kneading in the same manner as in Example 1 except that the temperature was set to 330 ° C. and melt-kneading. Table 1 shows the kneading conditions and various evaluation results.

Example 7
A thermoplastic resin was melt kneaded in the same manner as in Example 1 except that the maleic anhydride-modified ethylene-1-butene copolymer (B-2) was used as the resin (B) having a reactive functional group. A composition was obtained. Table 1 shows the kneading conditions and various evaluation results.

Comparative Examples 1 and 2
Screw configuration: As B, 7 kneading zones starting from positions of L / D ₀ = 22, 28, 43, 55, 69, 77, 93 are provided, and the length Lk / D ₀ of each kneading zone is In order, Lk / D ₀ = 1.8, 1.8, 2.3, 2.3, 2.3, 2.3, 3.0, and no reverse screw zone was provided. Further, melt kneading was carried out in the same manner as in Examples 1 and 2 except that the gauge pressure in the vent vacuum zone was set to -0.05 MPa to obtain a thermoplastic resin composition. Table 1 shows the kneading conditions and various evaluation results.

Comparative Example 3
A thermoplastic resin composition was obtained by performing melt-kneading in the same manner as in Example 3 except that the screw configuration was B and the gauge pressure in the vent vacuum zone was -0.05 MPa. Table 1 shows the kneading conditions and various evaluation results.

Comparative Example 4
The screw configuration is B, the screw diameter is 37 mm, and the screw is a double screw L / D ₀ = 100 in the same direction rotating fully meshing twin screw extruder (Toshiba Machine Co., Ltd., TEM-37BS-26 / 2 V), the thermoplastic resin composition is discharged from a sampling valve of L / D ₀ = 40, and a vent vacuum zone is provided at a position at L / D ₀ = 36, and a volatile component at a gauge pressure of −0.05 MPa. The thermoplastic resin composition was obtained by carrying out melt-kneading in the same manner as in Comparative Example 1 except that the material was removed and discharged at an extrusion rate of 20 kg / h. Table 1 shows the kneading conditions and various evaluation results. When the ratio (%) of the total length of the kneading zone to the total length of the screw is calculated by (total length of kneading zone) / (total length of screw) × 100, the ratio of the total length of the kneading zone is It was 9%.

Comparative Example 5
Except for using the unmodified PE copolymer (C-1) instead of the resin (B) having a reactive functional group, melt kneading was carried out in the same manner as in Example 4 to obtain a thermoplastic resin composition. It was. Table 1 shows the kneading conditions and various evaluation results.

Comparative Example 6
Melt-kneading was carried out in the same manner as in Comparative Example 4 except that an ethylene-methacrylic acid-zinc methacrylate copolymer (B-3) was used as the resin (B) having a reactive functional group and the composition was changed. It carried out and obtained the thermoplastic resin composition. Table 1 shows the kneading conditions and various evaluation results.

Comparative Example 7
Table 1 shows various evaluation results of thermoplastic polyurethane (D-1), which is a typical shock absorbing material.

  From Examples 1 to 7, the thermoplastic resin composition of the present invention has sufficient heat resistance at room temperature, and the maximum point load given to the object even in the large load and high speed free drop impact test described above. Is less than 20 kilonewtons, and the molded product itself does not generate cracks of 5 cm or more, so there is no major breakage and it is excellent for use as an impact absorbing member. In the present invention, it is important to melt knead by controlling the resin pressure, vent vacuum pressure, moisture content, and resin temperature during melt kneading, and as a result, a three-dimensional connection including a continuous phase component in the dispersed phase. The structure Cs is formed, and the area ratio of the connection structure Cs in the cross section of the dispersed phase Dp having an average particle diameter of 1000 nm or less is increased. Also in a tensile test using a test piece, as the tensile speed is increased, the tensile elastic modulus is remarkably lowered and the tensile elongation at break is also greatly increased.

  On the other hand, in the conventional thermoplastic resin compositions shown in Comparative Examples 1 to 3, since the melt-kneading conditions are not highly controlled, a three-dimensional connection structure Cs including a continuous phase component is formed in the dispersed phase. Although the ratio of the area of the connection structure Cs in the cross section of the dispersed phase Dp having an average particle diameter of 1000 nm or less is small and the impact strength as a test piece is high, Has a high maximum point load applied to the object, and the molded product itself generates a crack of 5 cm or more. Also in a tensile test using a test piece, the tensile elastic modulus decreases and the tensile elongation at break increases as the tensile speed is increased, but the degree is not large.

  Further, even in the conventional thermoplastic resin compositions shown in Comparative Examples 4 to 6, since the melt-kneading conditions are not highly controlled, the three-dimensional connection structure Cs containing the continuous phase component in the dispersed phase is not formed. In the large load, high speed free drop impact test described above, the maximum point load applied to the object is higher, and the molded product itself generates a crack of 5 cm or more. In a tensile test using a test piece, as the tensile speed is increased, the tensile elastic modulus increases and the tensile elongation at break also decreases.

  In thermoplastic polyurethane, which is a representative shock absorbing material shown in Comparative Example 7, the maximum point load applied to the object in the large load and high speed free drop impact test is as low as less than 20 kilonewtons, and molding is performed. Although the product itself does not crack more than 5 cm, it can be seen that the range of use is likely to be limited because the deflection temperature under load is as low as less than 20 ° C.

Example 8
A melt kneading was carried out in the same manner as in Example 1 except that a nylon 66 resin (A-3) having a moisture content of 500 ppm was used as the thermoplastic resin (A) and the cylinder temperature was set at 280 ° C. A thermoplastic resin composition was obtained. Table 2 shows the kneading conditions and various evaluation results.

Example 9
Except for using a nylon 610 resin (A-4) having a moisture content of 500 ppm as the thermoplastic resin (A), melt-kneading was carried out in the same manner as in Example 1 to obtain a thermoplastic resin composition. Table 2 shows the kneading conditions and various evaluation results.

Example 10
A melt kneading was carried out in the same manner as in Example 1 except that a nylon 11 resin (A-5) having a moisture content of 500 ppm was used as the thermoplastic resin (A) and the cylinder temperature was set at 220 ° C. A thermoplastic resin composition was obtained. Table 2 shows the kneading conditions and various evaluation results.

Example 11
A thermoplastic resin composition was obtained by carrying out melt-kneading in the same manner as in Example 1 except that the polybutylene terephthalate resin (A-6) having a moisture content of 100 ppm was used as the thermoplastic resin (A). Table 2 shows the kneading conditions and various evaluation results.

Comparative Example 8
A melt kneading was carried out in the same manner as in Comparative Example 1 except that a nylon 66 resin (A-3) having a moisture content of 500 ppm was used as the thermoplastic resin (A) and the cylinder temperature was set to 280 ° C. A thermoplastic resin composition was obtained. Table 2 shows the kneading conditions and various evaluation results.

Comparative Example 9
A thermoplastic resin composition was obtained by melt-kneading in the same manner as in Comparative Example 1 except that a nylon 610 resin (A-4) having a moisture content of 500 ppm was used as the thermoplastic resin (A). Table 2 shows the kneading conditions and various evaluation results.

Comparative Example 10
A melt kneading was carried out in the same manner as in Comparative Example 1 except that a nylon 11 resin (A-5) having a moisture content of 500 ppm was used as the thermoplastic resin (A) and the cylinder temperature was set to 220 ° C. A thermoplastic resin composition was obtained. Table 2 shows the kneading conditions and various evaluation results.

Comparative Example 11
A thermoplastic resin composition was obtained by carrying out melt kneading in the same manner as in Comparative Example 1 except that a polybutylene terephthalate resin (A-6) having a moisture content of 100 ppm was used as the thermoplastic resin (A). Table 2 shows the kneading conditions and various evaluation results.

  From Examples 8 to 11, even when the thermoplastic resin (A) is changed, by controlling the resin pressure during melt kneading, the vent vacuum pressure, the amount of water, and the resin temperature to melt knead, A three-dimensional connection structure Cs containing a continuous phase component is formed, and the proportion of the area of the connection structure Cs in the cross section of the dispersed phase Dp having an average particle diameter of 1000 nm or less can be increased. It has sufficient heat resistance, and even in the above-described large load and high speed free drop impact test, the maximum point load applied to the object is as low as less than 20 kilonewtons, and the molded product itself does not crack more than 5 cm. A thermoplastic resin composition excellent in use for impact absorbing members can be obtained.

  On the other hand, in the conventional thermoplastic resin compositions shown in Comparative Examples 8 to 11, since the melt-kneading conditions are not highly controlled, a three-dimensional connection structure Cs including a continuous phase component is formed in the dispersed phase. Although the ratio of the area of the connection structure Cs in the cross section of the dispersed phase Dp having an average particle diameter of 1000 nm or less is small and the impact strength as a test piece is high, Has a high maximum point load applied to the object, and the molded product itself generates a crack of 5 cm or more.

These results, in the thermoplastic resin composition comprising a resin (B) having a thermoplastic resin (A) and the reactive functional group, at a screw length L and the ratio L / D ₀ of the screw diameter D ₀ is 50 or more Using a certain twin screw extruder, the resin pressure, vent vacuum pressure, moisture content, and resin temperature are controlled and melt-kneaded, so that the structure in the dispersed phase can be highly controlled and sufficient heat resistance at room temperature. Even when subjected to a large load and a high speed impact, the thermoplastic resin composition excellent for shock absorbing members that has a low maximum load applied to the object and does not cause large breakage can be obtained. I understand that I can do it.

It is a figure which shows the shape of the cylindrical molded product used for a heavy load and a high-speed free drop impact test. It is a figure which shows the mode of the free load impact test of the heavy load and high speed of Example 1 of this invention. It is a figure which shows the mode of the heavy load and high-speed free drop impact test of the comparative example 6 of this invention. It is a figure which shows the three-dimensional transmission image (50000 times, 250 nm x 250 nm x 75 nm) in the inclination angle of 0 degree of Example 1 of this invention. The schematic diagram (whole figure) of the three-dimensional transmission image in the inclination angle of 0 degree of this invention. The schematic diagram (dispersion phase enlarged view) of the three-dimensional transmission image in the inclination angle of 0 degree of this invention.

Claims (26)

A thermoplastic resin composition comprising a thermoplastic resin (A) and a resin (B) having a reactive functional group, the deflection temperature under load at 0.45 MPa is 45 ° C. or more, the outermost diameter is 50 mm, and the thickness is 2 mm. In a cylindrical molded product having a height of 150 mm, when a weight body having a mass of 193 kg is freely dropped from a drop height of 0.5 m, the maximum point load applied to the weight body is less than 20 kilonewtons, and there is a crack of 5 cm or more. A thermoplastic resin composition for impact absorbing members that does not occur. In the morphology of the resin composition observed by a transmission electron beam tomography method, one of (A) or (B) forms a continuous phase, the other forms a dispersed phase, and the continuous phase component in the dispersed phase And a ratio of the area of the connection structure Cs in the cross section of the dispersion phase Dp having an average particle diameter of 1000 nm or less in the dispersed phase is 10% or more. The thermoplastic resin composition for an impact-absorbing member according to claim 1. In the tensile test, when the tensile elastic moduli at the tensile speeds V1 and V2 are E (V1) and E (V2), E (V1)> E (V2) when V1 <V2. The thermoplastic resin composition for impact absorbing members according to claim 1 or 2. In the tensile test, when the tensile breaking elongation at the tensile speeds V1 and V2 is ε (V1) and ε (V2), when V1 <V2, ε (V1) <ε (V2). The thermoplastic resin composition for impact absorbing members according to any one of claims 1 to 3. A twin screw extruder in which the ratio L / D _{0 of the} screw length L to the screw diameter D ₀ is 50 or more, the screw of the twin screw extruder has a plurality of full flight zones and kneading zones; When the maximum resin pressure of the resin pressure in the kneading zone in the screw is Pkmax (MPa), and the minimum resin pressure of the resin pressure in the full flight zone in the screw is Pfmin (MPa),
Pkmax ≧ Pfmin + 0.3
The thermoplastic resin composition for an impact-absorbing member according to any one of claims 1 to 4, wherein the thermoplastic resin composition is produced by melt-kneading under a condition that satisfies the conditions. It is characterized by being manufactured by melt-kneading under a condition that the residence time from the supply of the raw material to the extrusion to the extrusion is from 1 minute to 30 minutes and the extrusion amount is 0.01 kg / h or more per 1 rpm of the screw rotation. The thermoplastic resin composition for impact absorbing members according to any one of claims 1 to 5. The thermoplastic resin composition for an impact-absorbing member according to any one of claims 1 to 6, wherein the screw of the twin-screw extruder is a co-rotating fully meshed type. The thermoplastic resin composition for an impact-absorbing member according to any one of claims 1 to 7, wherein a total length of the kneading zone is 5 to 50% of the screw length. Each length Lk of the kneading zone satisfies Lk / D ₀ = 0.2-10, The thermoplastic resin composition for an impact absorbing member according to any one of claims 1 to 8. The thermoplastic resin composition for an impact-absorbing member according to any one of claims 1 to 9, wherein the thermoplastic resin composition is produced by melting and kneading while reducing the pressure to a pressure of -0.07 MPa or less in a vent vacuum zone. The thermoplastic resin composition for impact-absorbing members according to any one of claims 1 to 9, wherein the thermoplastic resin composition is produced by melt-kneading using a raw material having a moisture content of less than 5000 ppm. The thermoplastic resin composition for an impact-absorbing member according to any one of claims 1 to 9, wherein the thermoplastic resin composition is produced by melt-kneading while controlling the maximum resin temperature at 180 ° C to 330 ° C. The thermoplastic resin (A) is at least one selected from polyamide resin, polyester resin, polyphenylene sulfide resin, styrene resin, polyphenylene oxide resin, and polycarbonate resin. The thermoplastic resin composition for impact absorbing members described in 1. The thermoplastic resin composition for an impact-absorbing member according to any one of claims 1 to 13, wherein the resin serving as a base of the resin (B) having a reactive functional group is a rubber polymer. The reactive functional group of the resin (B) having the reactive functional group is at least one selected from an amino group, a carboxyl group, a carboxyl metal salt, an epoxy group, an acid anhydride group, and an oxazoline group. The thermoplastic resin composition for impact absorbing members according to any one of claims 1 to 14. A molded article comprising the thermoplastic resin composition for an impact absorbing member according to any one of claims 1 to 15. The molded article according to claim 16, wherein the molded article is at least one selected from a film, a sheet, and a fiber. The molded article according to claim 16 or 17, wherein the molded article is at least one selected from automotive parts, building materials, sports equipment, and electrical / electronic parts. A twin screw extruder in which the ratio L / D _{0 of the} screw length L to the screw diameter D ₀ is 50 or more, the screw of the twin screw extruder has a plurality of full flight zones and kneading zones; When the maximum resin pressure of the resin pressure in the kneading zone in the screw is Pkmax (MPa), and the minimum resin pressure of the resin pressure in the full flight zone in the screw is Pfmin (MPa),
Pkmax ≧ Pfmin + 0.3
The method for producing a thermoplastic resin composition for an impact-absorbing member according to any one of claims 1 to 15, wherein the melt-kneading is performed under a condition that satisfies the following conditions. 20. The melt kneading is carried out under the condition that the residence time from the supply of the raw material to the extrusion to the extrusion is from 1 minute to 30 minutes and the extrusion amount is 0.01 kg / h or more per 1 rpm of the screw rotation. The manufacturing method of the thermoplastic resin composition for impact-absorbing members of description. 21. The method for producing a thermoplastic resin composition for an impact-absorbing member according to claim 19, wherein the screw of the twin-screw extruder is a co-rotating fully meshing type. The method for producing a thermoplastic resin composition for an impact absorbing member according to any one of claims 19 to 21, wherein the total length of the kneading zone is 5 to 50% of the screw length. Respective lengths Lk of said kneading zones, the impact absorbing member for a thermoplastic resin composition according to any one of claims 19 to 22, characterized in that satisfy Lk / D 0 ₌ 0.2 to 10 Production method. 24. Manufacture of a thermoplastic resin composition for an impact absorbing member according to any one of claims 19 to 23, wherein the pressure is reduced to a gauge pressure of -0.07 MPa or less in a vent vacuum zone and melt kneaded. Method. 24. The method for producing a thermoplastic resin composition for an impact-absorbing member according to any one of claims 19 to 23, which is produced by melt-kneading using a raw material having a moisture content of less than 5000 ppm. The method for producing a thermoplastic resin composition for an impact-absorbing member according to any one of claims 19 to 23, wherein the thermoplastic resin composition is produced by melt-kneading while controlling the maximum resin temperature at 180 ° C to 330 ° C.

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