JP2012072221A - Thermoplastic resin composition and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition that exhibits unique viscoelastic characteristics in which the faster the deformation speed becomes, the larger the tensile fracture elongation becomes even when left in melt retention for a long time.SOLUTION: The thermoplastic resin composition is obtained by blending a thermoplastic resin (A), a rubbery polymer (B) having a functional group reactive to a functional group of the thermoplastic resin (A), and a compound (C) which blocks the functional group of the thermoplastic resin (A), and has the following characteristics (I) and (II): (I) assuming the tensile fracture elongations are ε(V1) and ε(V2) when tension rates are V1 and V2 respectively in a tensile test, ε(V1)<ε(V2) when V1<V2; (II) the ratio of the melt flow rate (MFR) when left in melt retention at a temperature of the melting point of the thermoplastic resin (A)+35°C for 30 minutes to that for 3 minutes is MFR (30 minutes)/MFR (3 minutes)≥0.7.

Description

  The present invention relates to a thermoplastic resin composition excellent in impact absorption and melt residence stability. More specifically, the present invention relates to a thermoplastic resin composition that can exhibit a unique viscoelastic property that tensile elongation at break increases as the deformation speed increases even when melted and retained for a long time.

  The reactive processing method is a method in which a processing machine that melts and kneads a polymer is used in a reaction field. Among them, so-called “reactive extrusion processing”, particularly using an extruder, has high industrial added value, and its use is very active worldwide.

  When reactive processing is performed in an extruder, the extruder is required to control temperature, ensure reaction time (residence time), uniformly disperse the catalyst, removability of by-products, etc. Ensuring the reaction time (residence time) is one of the extremely important factors in controlling the reaction in the extruder.

  In Patent Documents 1 and 2, as one method for securing the reaction time (residence time) in the extruder, a method using an extruder having a long ratio L / D between the screw length L and the screw diameter D is attempted. And a method of reactive processing in an extruder having an L / D of 50 or more is disclosed. In the production of an alloy of a thermoplastic polymer and a rubbery polymer having a functional group that reacts with a functional group of the thermoplastic resin, the tensile rate V1, V2 is increased by increasing the reaction rate using an extruder with L / D = 100. When the tensile elongation at break ε (V1) and ε (V2) is V1 <V2, a thermoplastic resin composition having a specific viscoelastic behavior is obtained, where ε (V1) <ε (V2). However, an extruder with a long L / D has difficulty in equipment maintenance and long-time continuous operation, and a simpler manufacturing method has been demanded. The L / D = 100 extruder also has a problem that it is difficult to increase the size of the screw shaft due to the design of the screw shaft.

  On the other hand, in Patent Document 3, a general-purpose extruder of L / D = 45 is obtained by melt-kneading a thermoplastic polymer and a rubbery polymer having a functional group that reacts with a functional group of the thermoplastic resin while stretching and flowing. Is used, when the tensile breaking elongations ε (V1) and ε (V2) at the tensile speeds V1 and V2 are V1 <V2, the specific viscosity is ε (V1) <ε (V2). It is disclosed that a thermoplastic resin composition having an elastic behavior can be obtained. However, in the melt molding of the composition, when the melt residence time becomes long in sheet extrusion molding or large part molding, the thermoplastic polymer and the rubbery polymer having a functional group that reacts with the functional group of the thermoplastic resin are used. Residual functional groups were excessively reacted, the melt viscosity (melt flow rate) was changed, and the tensile properties tended not to be exhibited.

  Patent Document 4 discloses a resin composition comprising a semi-aromatic polyamide / polyphenylene ether / compatibilizer and having a small viscosity change at the time of melt molding. Semi-aromatic polyamides with end-capping agents sealed with amino end groups are used, but if a polyamide with less amino end groups is used, the melt retention stability will be good, but the usual kneading method However, the reaction with the polyphenylene ether and the compatibilizing agent is difficult to proceed, and the impact resistance tends to decrease.

JP 2006-89701 A JP 2008-156604 A JP 2010-195853 A JP 2007-154107 A

  It is an object of the present invention to provide a thermoplastic resin composition that can exhibit a unique viscoelastic property that tensile elongation at break increases as the deformation speed increases even when melted and retained for a long time.

  As a result of intensive studies to solve the above problems, the present inventors have determined that the thermoplastic resin (A), the rubbery polymer (B) having a functional group that reacts with the functional group of the thermoplastic resin (A), and the heat Compound (C) for blocking the functional group of the plastic resin (A) is melt-kneaded while stretching and flowing while applying a large kneading energy, and the functional group of the thermoplastic resin (A) and the thermoplastic resin (A) After melting and kneading the rubbery polymer (B) having a functional group that reacts with the compound while stretching and flowing, the compound (C) that blocks the functional group of the thermoplastic resin (A) is added and melted, thereby The present inventors have found that the problems can be solved and have completed the present invention.

That is, the present invention is as follows.
1. A thermoplastic resin (A), a rubbery polymer (B) having a functional group that reacts with a functional group of the thermoplastic resin (A), and a compound (C) that blocks the functional group of the thermoplastic resin (A) A thermoplastic resin composition having the following characteristics (I) and (II):
(I) 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.
(II) Melting point of MFR (30 minutes) / MFR (3 minutes) ≧ 0.7 when melting and staying at the temperature of melting point of thermoplastic resin (A) + 35 ° C. for 3 minutes and 30 minutes. .
2. 2. The thermoplastic resin according to 1, wherein the thermoplastic resin (A) is at least one selected from polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, and polypropylene resin. Resin composition.
3. The rubbery polymer (B) having a functional group that reacts with the functional group of the thermoplastic resin (A) 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. 3. The thermoplastic resin composition according to 1 or 2, wherein the thermoplastic resin composition is a rubbery polymer having various functional groups.
4). The rubbery polymer (B) having a functional group that reacts with the functional group of the thermoplastic resin (A) is a rubbery polymer having a functional group that reacts with the terminal amino group of the polyamide resin. 4. The thermoplastic resin composition according to any one of 3.
5. The thermoplastic resin composition according to any one of 1 to 4, wherein the compound (C) that blocks the functional group of the thermoplastic resin (A) is an acid anhydride.
6). Rubber polymer (B) having a functional group that reacts with a functional group of thermoplastic resin (A), 5 to 95 parts by weight of thermoplastic resin (A), with the total of (A) and (B) being 100 parts by weight The thermoplastic resin composition according to any one of 1 to 5, comprising 5 to 95 parts by weight of 0.01 to 50 parts by weight of the compound (C) that blocks the functional group of the thermoplastic resin (A).
7). A thermoplastic resin (A), a rubbery polymer (B) having a functional group that reacts with a functional group of the thermoplastic resin (A), and a compound (C) that blocks the functional group of the thermoplastic resin (A), 7. The method for producing a thermoplastic resin composition according to any one of 1 to 6, wherein melt kneading is performed while stretching and flowing.
8). The thermoplastic resin (A), the rubbery polymer (B) having a functional group that reacts with the functional group of the thermoplastic resin (A), and the compound (C) that blocks the functional group of the thermoplastic resin (A), 7. The method for producing a thermoplastic resin composition according to any one of 1 to 6, wherein kneading energy is applied at 0.35 kWh / kg or more and melt kneading while stretching and flowing.
9. After the thermoplastic resin (A) and the rubbery polymer (B) having a functional group that reacts with the functional group of the thermoplastic resin (A) are melt-kneaded while stretching and flowing, the functional group of the thermoplastic resin (A) is changed. The method for producing a thermoplastic resin composition according to any one of 1 to 6, wherein the compound (C) to be sequestered is added and melted.

  From the present invention, it is possible to provide a thermoplastic resin composition capable of expressing a unique viscoelastic property that tensile elongation at break increases as the deformation rate increases even when melted for a long time. It can be preferably used for a long sheet extrusion molded product or a large molded part.

It is explanatory drawing of a notch type mixing screw.

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

  The thermoplastic resin composition of the present invention comprises a thermoplastic resin (A), a rubbery polymer (B) having a functional group that reacts with a functional group of the thermoplastic resin (A), and a functionality of the thermoplastic resin (A). It is a thermoplastic resin composition formed by blending the compound (C) for blocking the 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 Preferable examples include at least one resin selected from resins, polypropylene resins, styrene resins such as polystyrene resins and ABS resins, and polyalkylene oxide resins.

  Among the thermoplastic resins shown above, polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, and polypropylene resin are preferred, and polyamide resin, polyester resin, and polyphenylene are particularly preferable. Sulfide resins and polyphenylene oxide resins are preferred because of the high reactivity of the end groups, and most preferably used are polyamide resins.

  The polyamide resin used in the present invention is a resin composed of a polymer having an amide bond, and is mainly composed of amino acids, lactams or diamines and dicarboxylic acids. 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, nonamethylenediamine, decamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5 -Methyl nonamethylenediamine, metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5 , 5-trime Such as til cyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, etc. 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-methyl Aliphatic, alicyclic, and aromatic dicarboxylic acids such as isophthalic acid, 5-sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid, and the like. Polyamide homopolymer derived from these raw materials It can be used in the form of each alone or as a mixture of copolymers.

  In the present invention, a particularly useful polyamide resin is a polyamide resin having a crystal melting temperature of 150 ° C. or more and excellent in heat resistance and strength. Specific examples thereof include polycaproamide (polyamide 6), polyhexamethylene azide. Pamide (polyamide 66), polypentamethylene adipamide (polyamide 56), polytetramethylene adipamide (polyamide 46), polyhexamethylene sebacamide (polyamide 610), polypentamethylene sebacamide (polyamide 510) Polytetramethylene sebamide (polyamide 410), polyhexamethylene dodecane (polyamide 612), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polycaproamide / polyhexamethylene adipamide copolymer ( Polyamide 6 / 6), polycaproamide / polyhexamethylene terephthalamide copolymer (polyamide 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide copolymer (polyamide 66 / 6T), polyhexamethylene adipamide / polyhexamethylene Isophthalamide copolymer (polyamide 66 / 6I), polyhexamethylene adipamide / polyhexamethylene isophthalamide / polycaproamide copolymer (polyamide 66 / 6I / 6), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (polyamide) 6T / 6I), polyhexamethylene terephthalamide / polydecanamide copolymer (polyamide 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalate Amide / polyhexamethylene isophthalamide copolymer (polyamide 66 / 6T / 6I), polyxylylene adipamide (polyamide XD6), polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (polyamide 6T / M5T) , Polyhexamethylene terephthalamide / polypentamethylene terephthalamide copolymer (polyamide 6T / 5T), polypentamethylene terephthalamide / polypentamethylene adipamide copolymer (5T / 56), polynonamethylene terephthalamide (polyamide 9T), poly Examples include decamethylene terephthalamide (polyamide 10T) and mixtures or copolymers thereof.

  Particularly preferred are polyamide 6, polyamide 66, polyamide 56, polyamide 610, polyamide 510, polyamide 410, polyamide 612, polyamide 11, polyamide 12, polyamide 6/66, polyamide 66 / 6T, polyamide 6T / 6I, polyamide 66. Examples include / 6I / 6, polyamide 6T / 5T, 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, polyamide 66 / 6T are most preferred.

The terminal group concentration of these polyamide resins is not particularly limited, but those having a terminal amino group concentration of 3 × 10 ⁻⁵ mol / g or more have a functional group that reacts with the functional group of the thermoplastic resin (A). It is preferable in terms of reactivity with the rubber polymer (B). The terminal amino group concentration here can be measured by dissolving a sample in an 85% phenol-ethanol solution, using thymol blue as an indicator, and titrating with an aqueous hydrochloric acid solution.

  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 impact absorption characteristic of the thermoplastic resin composition of the present invention. When the relative viscosity is more than 7.0, the melt viscosity of the thermoplastic resin composition is difficult. Increases significantly, making it difficult to mold the molded body, which is not preferable.

  The polyester resin used in the present invention 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 copolymer obtained by a condensation reaction containing as a main component, 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 and most preferred is polybutylene terephthalate (polybutylene terephthalate resin).

  The polybutylene terephthalate resin has an intrinsic viscosity measured at 25 ° C. in a 0.5% o-chlorophenol solution in the range of 0.35 to 2.00, more preferably in the range of 0.50 to 1.50. Are suitable. 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.

  Furthermore, the polybutylene terephthalate resin has a COOH end group amount determined by potentiometric titration of an m-cresol solution with an alkaline solution in the range of 1 to 50 eq / t (end group amount per ton of polymer). It is preferable in terms of reactivity with the rubbery polymer (B) having a functional group that reacts with the functional group of the plastic resin (A).

  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-diphenyl-1,4-phenylene oxide), poly (2-methyl-6-phenyl-1,4-phenylene oxide), poly (2,6-dichloro-1,4-phenylene oxide), etc. 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 at 30 ° C. in a 0.5 g / dl chloroform solution 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 polyphenylene oxide resin obtained as described above is further subjected to various treatments such as modification or activation with functional group-containing compounds such as acid anhydride groups, epoxy groups, and isocyanate groups. It is of course possible to use it.

  The polypropylene resin used in the present invention is one in which a functional group is introduced into the terminal or main chain. Examples of the functional group include at least one selected from amino groups, carboxyl groups, carboxyl metal salts, hydroxyl groups, epoxy groups, acid anhydride groups, isocyanate groups, mercapto groups, oxazoline groups, sulfonic acid groups, and the like.

  When the acid anhydride group is introduced into the polypropylene resin, the method can be usually performed by a known technique, and there is no particular limitation, but a method of grafting the acid anhydride onto the polypropylene resin can be used. For example, it is obtained by dry blending 0.1 to 10 parts by weight of maleic anhydride and 0.01 to 1 part by weight of a radical generator with respect to 100 parts by weight of polypropylene resin, and melt-kneading at a cylinder temperature of 200 to 230 ° C. Can do.

  The rubbery polymer (B) having a functional group that reacts with the functional group of the thermoplastic resin (A) of the present invention generally contains a polymer having a glass transition temperature lower than room temperature. , Refers to polymers in which a part of the molecules are constrained to each other by covalent bonds, ionic bonds, van der Waals forces, entanglement, and the like. For example, polybutadiene, polyisoprene, random copolymer and block copolymer of styrene-butadiene, hydrogenated product of the block copolymer, acrylonitrile-butadiene copolymer, diene rubber such as butadiene-isoprene copolymer, ethylene -Random copolymer and block copolymer of propylene, Random copolymer and block copolymer of ethylene-butene, Copolymer of ethylene and α-olefin, Ethylene-acrylic acid ester, Ethylene-methacrylic acid ester, etc. Ethylene-unsaturated carboxylic acid ester copolymers, acrylic acid ester-butadiene copolymers, acrylic elastic polymers such as butyl acrylate-butadiene copolymer, and ethylene-vinyl acetate and other ethylene-fatty acid copolymers. Polymer, Eth Ethylene-propylene non-conjugated diene terpolymers such as ethylene-propylene-ethylidene norbornene copolymer, ethylene-propylene-hexadiene copolymer, butylene-isoprene copolymer, chlorinated polyethylene, polyamide elastomer, polyester elastomer, etc. Preferred examples include thermoplastic elastomers. Among these, when a polyamide resin is used as the thermoplastic resin (A), an ethylene-unsaturated carboxylic acid ester copolymer is preferably used from the viewpoint of compatibility.

  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.

  The functional group present in the rubbery polymer (B) of the present invention is not particularly limited as long as it reacts with the functional group of the thermoplastic resin (A), and examples thereof include amino groups, carboxyl groups, and carboxyl groups. Examples thereof include at least one selected from metal salts, hydroxyl groups, epoxy groups, acid anhydride groups, isocyanate groups, mercapto groups, oxazoline groups, sulfonic acid groups, and the like. Of these, amino groups, carboxyl groups, carboxyl metal salts, epoxy groups, acid anhydride groups, and oxazoline groups are preferably used because of their high reactivity and low side reactions such as decomposition and crosslinking.

  In particular, when a polyamide resin is used for the thermoplastic resin (A), the rubbery polymer (B) is preferably a rubbery polymer having a functional group that reacts with the terminal amino group of the polyamide resin.

  Examples of the acid anhydride in the acid anhydride group include maleic anhydride, itaconic anhydride, endic anhydride, citraconic anhydride, 1-butene-3,4-dicarboxylic anhydride, and the like. Two or more of these may be used simultaneously. Of these, maleic anhydride and itaconic anhydride are preferably used.

  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, the acid anhydride group and the raw material for the rubbery polymer can be used. A method of copolymerizing with a monomer, a method of grafting an acid anhydride onto a rubber polymer, and the like can be used.

  In addition, when an epoxy group is introduced into a rubbery polymer, the method can be carried out by a generally known technique and is not particularly limited. For example, a vinyl monomer having an epoxy group is added to a rubbery polymer. A method of copolymerizing with a monomer that is a raw material of the coalescence, a method of polymerizing a rubbery polymer using a polymerization initiator or a chain transfer agent having the functional group, a method of grafting an epoxy compound onto a rubbery polymer, etc. Can be used.

  Examples of the vinyl monomer having an epoxy group include glycidyl ester compounds of α, β-unsaturated acids such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and glycidyl itaconate.

  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.

  When the carboxyl 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, an unsaturated carboxylic acid monomer having a carboxyl group is added to the rubbery polymer. A method of copolymerizing with a monomer that is a raw material of the polymer can be used. Specific examples of the unsaturated carboxylic acid include (meth) acrylic acid.

A carboxyl metal salt in which a part of the carboxyl group is a metal salt is also effective as a reactive functional group, and examples thereof include (meth) acrylic acid metal salts. Although the metal of a metal salt is not specifically limited, Preferably, alkali metals, such as sodium, alkaline-earth metals, such as magnesium, zinc etc. are mentioned. Examples of the rubber polymer include ethylene-unsaturated carboxylic acid-unsaturated carboxylic acid metal salt copolymers such as ethylene-acrylic acid-acrylic acid metal salt and ethylene-methacrylic acid-methacrylic acid metal salt. The weight ratio of the unsaturated carboxylic acid component and the unsaturated carboxylic acid metal salt component in the copolymer is not particularly limited, but is preferably 95/5 to 5/95, more preferably 90/10 to 10/90. is there.
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.

  In the rubbery polymer (B) having a functional group that reacts with the functional group of the thermoplastic resin (A), the number of functional groups per molecular chain is not particularly limited, but usually 1 to 10 is preferable. In order to reduce side reactions such as crosslinking, 1 to 5 are preferable. 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 rubber-like polymer (B) in this invention, (weight of (A) / weight of (B))) is 5 / 95-95. The range of / 5 is preferable, the range of 10/90 to 90/10 is more preferable, and the range of 15/85 to 85/15 is most preferable. In order to develop the viscoelastic characteristics of the thermoplastic resin composition of the present invention, ((weight of (A)) / (weight of (B))) is preferably in the range of 50/50 to 95/5, and 60/40. The range of ˜90 / 10 is more preferable, and the range of 65/35 to 85/15 is most preferable.

  The compound (C) for blocking the functional group of the thermoplastic resin (A) used in the present invention blocks the functional group of the thermoplastic resin (A), and the thermoplastic resin (A) and the rubber polymer (B ) Is a compound that suppresses excessive reaction during melt residence. Such a compound may be a low molecular weight substance or a high molecular weight substance.

  In particular, when a polyamide resin is used for the thermoplastic resin (A), an acid anhydride capable of blocking the amino terminal of the polyamide resin with high probability is preferably used for the compound (C). Specific examples of acid anhydrides include benzoic anhydride, isobutyric anhydride, itaconic anhydride, octanoic anhydride, glutaric anhydride, succinic anhydride, acetic anhydride, dimethylmaleic anhydride, decanoic anhydride, and trimellitic anhydride. Examples include acid, 1,8-naphthalic anhydride, phthalic anhydride, maleic anhydride, and derivatives thereof. Of these, phthalic anhydride and succinic anhydride are preferably used, and phthalic anhydride is particularly preferably used.

  The amount of the compound (C) added relative to 100 parts by weight of the sum of the weights of the thermoplastic resin (A) and the rubbery polymer (B) is not particularly limited, but is preferably 0.01 to 50 parts by weight, more preferably 0.05 to 30 parts by weight.

  In the thermoplastic resin composition of the present invention, in the tensile test, assuming that the tensile elongation at break is ε (V1) and ε (V2) at the tensile speeds V1 and V2, when V1 <V2, ε (V1) < It is necessary to be ε (V2). The tensile elongation at break indicates the elongation at the moment of fracture. The relational expression is as follows. In a JIS-5A dumbbell-shaped test piece (length 75 mm × end width 12.5 mm × center width 4 mm × thickness 2 mm) adjusted by melting and staying in an injection molding machine for 3 minutes, a tensile speed of 10 mm / It is preferable for all V1 and V2 in the range of min to 500 mm / min, and for all V1 and V2 in the range of 1 mm / min to 1000 mm / min.

  Furthermore, the thermoplastic resin composition of the present invention has a MFR (30 minutes) / MFR ratio of melt flow rate (MFR) when melted and retained for 3 minutes and 30 minutes at the melting point of the thermoplastic resin (A) + 35 ° C. (3 minutes) ≧ 0.7. It is more preferable that MFR (30 minutes) / MFR (3 minutes) ≧ 0.8, as this ratio is closer to 1, since the melt retention stability is better. When the condition of MFR (30 minutes) / MFR (3 minutes) ≧ 0.7 is satisfied, even when a JIS-5A dumbbell type test piece prepared by melting and staying in an injection molding machine for 30 minutes is satisfied when V1 <V2. There is a tendency that (V1) <ε (V2).

  In the thermoplastic resin composition of the present invention, the thermoplastic resin (A) forms a continuous phase, the rubbery polymer (B) forms a dispersed phase, and the dispersed phase (B) is in a morphology observed with an electron microscope. It is preferable that fine particles of 1 to 100 nm made of the compound produced by the reaction of (A) and (B) are contained, and the area occupied by the fine particles in the dispersed phase (B) is 20% or more. Here, a well-known technique can be applied for morphological observation, and the center part in the cross-section direction of a JIS-5A dumbbell-shaped test piece which has been melted and retained for 3 minutes and injection-molded is cut into 1 to 2 mm square, and reactive functionalities with ruthenium tetroxide. After dyeing the group-containing resin (A2), an ultrathin section of 0.1 μm or less (about 80 nm) is cut with an ultramicrotome at −196 ° C., magnified 35,000 times, and observed with a transmission electron microscope A method is mentioned. For the obtained image, the basic structure and the presence or absence of fine particles of 1 to 100 nm in the dispersed phase (A2) were confirmed, and the area occupied by the fine particles in the dispersed phase was determined by using the image analysis software “Scion Image” manufactured by Scion Corporation. Use and calculate.

  The thermoplastic resin composition of the present invention comprises a thermoplastic resin (A), a rubbery polymer (B) having a functional group that reacts with a functional group of the thermoplastic resin (A), and a functionality of the thermoplastic resin (A). The compound (C) for blocking the group is preferably produced by melt kneading while stretching and flowing in an extruder.

  Furthermore, the thermoplastic resin composition of the present invention is more preferably produced by applying kneading energy of 0.35 kWh / kg or more to (A), (B), and (C) and melt-kneading while stretching and flowing. The kneading energy here refers to the work of the extruder per discharge amount (kW / (kg / h)). When (A), (B) and (C) are produced by batch kneading, the functional group blocking reaction of (A) by (C) also proceeds in concert with the progress of the reactions of (A) and (B). Therefore, when the kneading energy is low, the reaction of (A) and (B) becomes insufficient, and the unique tensile properties that are the characteristics of the present invention tend to be difficult to develop, but the screw rotation speed of the extruder is increased. By applying a high kneading energy, it is possible to increase the number of collisions of (A) and (B) to advance the reaction, and a thermoplastic resin composition having unique tensile properties excellent in melt residence stability. You will be able to get

In addition, the thermoplastic resin composition of the present invention melts a thermoplastic polymer (A) and a rubbery polymer (B) having a functional group that reacts with a functional group of the thermoplastic resin (A) while stretching and flowing with an extruder. It is also preferable to manufacture by kneading and then adding and melting the compound (C) that blocks the functional group of the thermoplastic resin (A). Specific examples include the following methods (1) to (3). The term “molding” as used herein refers to an arbitrary method such as generally known injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, and spinning. In this method, since the reaction of (A) and (B) is allowed to proceed and (C) is added, it becomes possible to block the residual functional group of (A) with a high probability, and more stable melt retention. It becomes possible to obtain a thermoplastic resin composition having excellent tensile properties.
(1) (A) and (B) are introduced from the root of the extruder and melt kneaded while stretching and flowing, and (C) is introduced from the side feed or the extruder tip (2) (A) and (B) (C) is dry-blended with the pellets obtained by melt-kneading while stretching and flowing with an extruder and melt-combined during molding (3) (A) and (B) are melt-kneaded while stretching and flowing with an extruder The pellets obtained in this manner and the master pellets containing (C) at a high concentration obtained by melting and kneading (A) and (C) with an extruder are dry blended and melt-combined at the time of molding.

  Here, the extension flow is a flow method in which molten resin is stretched in two flows flowing in opposite directions. On the other hand, generally used shear flow is a flow method in which molten resin undergoes deformation in two flows having different velocities in the same direction. The extension flow has a higher dispersion efficiency than the shear flow generally used during melt-kneading, so the reaction can proceed efficiently, especially in the case of alloying with reaction such as reactive processing. It becomes.

In the present invention, the inflow effect pressure drop before and after the zone of melt-kneading while stretching and flowing (extension flow zone) is preferably 10 to 1000 kg / cm ² . The inflow effect pressure drop before and after the extension flow zone can be obtained by subtracting the pressure difference (ΔP ₀ ) in the extension flow zone from the pressure difference (ΔP) before the extension flow zone. When the inflow effect pressure drop before and after the extension flow zone is less than 10 kg / cm ^2, it is preferable because the rate of extension flow formation in the extension flow zone is low and the pressure distribution becomes non-uniform. Absent. Further, when the inflow effect pressure drop before and after the extension flow zone is larger than 1000 kg / cm ² , the back pressure in the extruder becomes too large, and it is not preferable because stable production becomes difficult. The inflow effect pressure drop across the stretched flow zone is preferably in the range of 30~600kg / cm ^2, more preferably in the range of 50~600kg / cm ^2, more being most preferred range of 100 to 500 kg / cm ² .

In the present invention, when the length of one extension flow zone in the screw of the extruder is Lk and the screw diameter is D, Lk / D = 2 to 10 from the viewpoint of kneadability and reactivity. preferable. More preferably, it is 2.5-9, More preferably, it is 3-8.
In the present invention, as a specific method for forming the extension flow zone, a kneading disk is used, and the helical angle θ, which is the angle between the top of the kneading disk at the front end of the disk and the top of the rear surface, is set. A twist kneading disc that is in the range of 0 ° <θ <90 ° in the half-rotation direction of the screw, or a flight screw, and the flight part of the flight screw is directed from the screw front side to the rear end side. Preferred examples include a resin passage having a reduced cross-sectional area and a resin passage in which the cross-sectional area through which the molten resin passes in the extruder is temporarily reduced.

  In the present invention, a method of melt kneading with a notch mixing screw after melt kneading while stretching and flowing with an extruder can also be preferably used. Here, the notch indicates a shape obtained by cutting a mountain portion of a screw flight as indicated by 1 in FIG.

  The notch type mixing screw can increase the resin filling rate, and the molten resin passing through the mixing zone to which the notch type mixing screw is connected is easily affected by the extruder cylinder temperature. Therefore, even the molten resin that generates heat by promoting the reaction in the extension flow zone in the first half of the extruder is efficiently cooled in the mixing zone, and the resin temperature can be lowered. In addition, since the reaction is accelerated in the first half of the extension flow zone, the melt viscosity of the resin when passing through the mixing zone is high, and shearing due to the notch of the notch mixing screw works effectively to accelerate the reaction. Will come to be. That is, the method of melt kneading with a notched mixing screw after melt kneading while stretching and flowing can improve kneadability and reactivity while suppressing the resin temperature rise, and the screw length L and screw diameter Even when the throughput is increased by a general-purpose large extruder having a short D ratio L / D, it is possible to obtain a thermoplastic resin composition that suppresses resin degradation due to heat generation and is excellent in impact absorption and the like.

  In the present invention, a zone for mixing and kneading with a notch mixing screw (mixing zone) is a single screw with a screw pitch length of 0.1D to 0.5D, and a number of notches of 8 to 16 per pitch. It is preferable that a certain notch type mixing screw is connected in order to improve the cooling efficiency of the molten resin by filling the resin, the kneadability and the reactivity, and the screw pitch length is 0.1D to 0.00. It is more preferable that the notch-type mixing screw having 3D and 10-15 notches per pitch is connected. Here, the single thread indicates that the screw flight has one crest when the screw rotates 360 degrees. The length of the screw pitch indicates the screw length when the screw rotates 360 degrees as shown in 2 of FIG.

  In the present invention, when the length of one mixing zone in the screw of the extruder is Lm and the screw diameter is D, Lm / D = 4 to 20 is improved cooling efficiency of the molten resin by resin filling, kneading From the viewpoint of improving the reactivity and improving the reactivity. More preferably, it is 4.5-18, More preferably, it is 5-15.

  In the present invention, it is preferable to provide the mixing zone at two or more locations from the viewpoint of improving the cooling efficiency of the molten resin by filling the resin, improving the kneadability, and improving the reactivity.

  In the present invention, 70% or more of the notch type mixing screw constituting the mixing zone is in the direction of screw rotation in the direction opposite to the rotation direction of the screw shaft. It is preferable from a viewpoint of improvement and reactivity improvement, and it is more preferable that it is 75% or more.

  In the present invention, if the extruder cylinder set temperature in the extension flow zone is Ck, and the extruder cylinder set temperature in the mixing zone is Cm, melt kneading while satisfying Ck−Cm ≧ 40 is achieved. In addition to improving efficiency, kneadability and reactivity can be significantly improved, and it is preferable to melt-knead while satisfying Ck-Cm ≧ 60.

  In general, a chemical reaction tends to proceed at a higher reaction temperature. Conversely, when the resin temperature decreases, the reaction rate between the thermoplastic resin and the reactive functional group decreases. However, in the present invention, even if the resin temperature is lowered by lowering the cylinder setting temperature in the mixing zone, the reaction can be advanced, and the impact absorption, impact resistance, and heat resistance during high-speed tension can be further increased. This is because in the first half, a zone for melt-kneading while stretching and flowing is provided to promote the reaction between the thermoplastic resin and the reactive functional group, so the melt viscosity when passing through the mixing zone is high, and the resin temperature If the melt viscosity is further increased by lowering the viscosity, the shear due to the notch of the notch mixing screw will act more strongly, and the reaction will be promoted more than compensating for the decrease in the reaction rate due to the resin temperature decrease. It is done. This effect is manifested for the first time in a screw configuration in which a mixing zone comprising a notched mixing screw is provided after the extension flow zone.

  On the other hand, for example, when melt kneading with a general kneading disk that cannot form an extension flow in the first half, the reaction rate of the thermoplastic resin and the reactive functional group is low, so notched mixing after the kneading disk zone Even if a mixing zone composed of screws is provided, the melt viscosity when passing through the mixing zone is low. Therefore, the shear due to the notch of the notch mixing screw is also small, the reaction that just compensates for the decrease in the reaction rate due to the decrease in the resin temperature does not proceed, and the elongation at break during high-speed tension decreases.

  Examples of the extruder used in the present invention include, for example, a single-screw extruder, a twin-screw extruder, and a multi-screw extruder having three or more axes. Among them, a single-screw extruder and a twin-screw extruder are preferably used. In particular, a twin screw extruder is preferably used. Further, the screw of such a twin screw extruder is not particularly limited, and a fully meshed type, an incomplete meshed type, a non-meshed type screw, etc. can be used. It is a type. Further, the rotation direction of the screw may be either the same direction or a different direction, but from the viewpoint of kneading property and reactivity, the rotation direction is preferably the same direction. In the present invention, the most preferred screw is a co-rotating fully meshed type.

  The melt-kneading method of the present invention is preferably applied to melt-kneading using a general-purpose twin screw extruder having an L / D of less than 50, and even if the throughput is increased by a twin screw extruder having a large screw diameter D. Thus, it is possible to obtain a thermoplastic resin composition that suppresses resin deterioration due to heat generation and has impact absorbability and the like.

  In the melt-kneading method of the present invention, the ratio of the total length of the zone (extension flow zone) for melt-kneading while stretching and flowing to the total length of the screw of the extruder is 5 to 40%, and the total length of the screw of the extruder The ratio of the total length of the zone (mixing zone) for melting and kneading with a notched mixing screw is 15 to 40%, improving the cooling efficiency of the molten resin by filling the resin, improving the kneadability, and improving the reactivity In view of the above, it is more preferable that the ratio of the total length of the extension flow zone is 10 to 35%, and the ratio of the total length of the mixing zone is 20 to 35%.

  In the present invention, when melt kneading is performed using an extruder, the residence time of the thermoplastic resin composition in the extruder is preferably 6 to 1200 seconds. The residence time means that the thermoplastic resin composition is extruded from the discharge port of the extruder from the position of the screw base to which the raw material is supplied, and the colorant and the like are added together with the raw material. This is the time until the maximum degree of coloration of the extrudate by the colorant. When the residence time is less than 6 seconds, the reaction time in the extruder is short, the reaction is not sufficiently promoted, and the impact absorption that significantly enhances the properties of the thermoplastic resin composition and significantly manifests the unique tensile properties. It is difficult to improve the performance. When the residence time is longer than 1200 seconds, there is a possibility that the resin is thermally deteriorated due to the long residence time. The residence time in the present invention is preferably 18 to 900 seconds, more preferably 30 to 300 seconds.

  In the thermoplastic resin composition of the present invention, other components other than the above (A) to (C) may be added as necessary within the range not impairing the characteristics.

  For example, a filler may be added 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, It is preferable in terms of obtaining superior mechanical strength. In order to improve strength, dimensional stability, etc., when such a filler is used, its blending amount is not particularly limited, but is usually 0.1 to 400 parts by weight per 100 parts by weight of the thermoplastic resin composition. .

  Moreover, you may add thermoplastic resins other than said (A)-(C) as needed in the range which does not impair the characteristic. Examples of such thermoplastic resins include polyamide resins, polyester resins, polyphenylene sulfide resins, polyphenylene oxide resins, polycarbonate resins, polylactic acid resins, polyacetal resins, polysulfone resins, tetrafluoropolyethylene resins, polyetherimide resins, polyamideimides. Resin, polyimide resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, polyethylene resin, polypropylene resin, styrene resin such as polystyrene resin and ABS resin, polyalkylene oxide resin, etc. It is done. Two or more of these thermoplastic resins can be used in combination. When such thermoplastic resins are used, the blending amount is not particularly limited, but is preferably blended in an amount of 0.1 to 400 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.

  Moreover, you may add rubbers other than said (A)-(C) as needed in the range which does not impair the characteristic. 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 is not particularly limited, but is usually 0.1 to 400 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.

  Moreover, you may add various additives other than said (A)-(C) as needed in the range which does not impair the characteristic. Such various additives are preferably crystal nucleating agents, anti-coloring agents, hindered phenols, hindered amines, hydroquinone-based, phosphite-based and substituted products thereof, copper halides, iodide compounds and the like, Stabilizers, resorcinol-based, salicylate-based, benzotriazole-based, benzophenone-based, hindered amine-based weathering agents, aliphatic alcohols, aliphatic amides, aliphatic bisamides, release agents such as ethylene bisstearylamide and higher fatty acid esters, p -Plasticizers such as octyl oxybenzoate and N-butylbenzenesulfonamide, lubricants, dyes such as nigrosine and aniline black, pigments such as cadmium sulfide, phthalocyanine and carbon black, alkyl sulfate type anionic antistatic agents Agent, Grade 4 ammo Um salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, hydroxide such as melamine cyanurate, magnesium hydroxide, aluminum hydroxide, Examples include flame retardants such as ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resins, or combinations of these brominated flame retardants and antimony trioxide, and foaming agents.

  As the antioxidant and the heat stabilizer, hindered phenol compounds and phosphorus compounds are preferably used. Specific examples of the hindered phenol compounds include triethylene glycol-bis [3-t-butyl- (5 -Methyl-4-hydroxyphenyl) propionate], N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ', 5'- Di-t-butyl-4′-hydroxyphenyl) propionate] methane, pentaerythrityltetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 1,3,5 -Tris (3,5-di-t-butyl-4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H -Trione, 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 4,4'-butylidenebis (3-methyl-6-t-butylphenol), n-octadecyl- 3- (3,5-di-tert-butyl-4-hydroxy-phenyl) propionate, 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy ) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di) -T-butyl-4-hydroxybenzyl) benzene and the like.

  Among them, ester type polymer hindered phenol type is preferable. Specifically, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, pentaerythrityl. Tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5- Methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane and the like are preferably used.

  Specific examples of such antioxidant and heat stabilizer phosphorus compounds include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2,4-dithio). -T-butylphenyl) pentaerythritol di-phosphite, bis (2,4-di-cumylphenyl) pentaerythritol di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis ( 2,4-di-t-butylphenyl) -4,4'-bisphenylene phosphite, di-stearyl pentaerythritol di-phosphite, triphenyl phosphite, 3,5-di-butyl-4-hydroxybenzyl Examples thereof include phosphonate diethyl ester.

  Two or more kinds of various additives can be used in combination. Although the compounding quantity does not have a restriction | limiting in particular, It is preferable that 0.01-20 weight part is mix | blended with respect to 100 weight part of thermoplastic resin compositions.

  These fillers, thermoplastic resins, rubbers, and various additives can be blended at any stage for producing the thermoplastic resin composition of the present invention. For example, (A) (B) The method of adding (C) at the same time, the method of adding by side feed or the like during melt kneading, the method of adding to the melt-kneaded thermoplastic resin composition, or first adding to one resin A method of blending the remaining resin after melt-kneading is mentioned.

  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, etc., and pellets, plates, films or sheets, pipes, hollows, boxes It can be formed into a shape such as a shape.

  The molded article of the present invention thus obtained is excellent in shock absorption and melt retention stability, but has particularly special effects in the case of thin molded articles, elongated molded articles, fibers and films. is there.

  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 implementing this invention with a twin-screw extruder, you may make it implement the said yarn making process or film forming process directly from the twin-screw extruder.

  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 In addition to being suitable for electrical and electronic parts applications such as parts, generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, circuit breakers, knives Switch, other pole, electrical parts key Electrical equipment parts such as vignettes, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs (registered trademark) / compact discs, audio / video equipment parts such as DVDs , Lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home appliances such as PCs, office electrical parts, office computer related parts, telephone related parts, facsimile related parts, copying Machine-related parts such as machine-related parts, cleaning jigs, motor parts, lighters, typewriters, etc .: Optical equipment such as microscopes, binoculars, cameras, watches, precision machine-related parts; Alternator terminals, alternator connectors , IC regulator, LA Potentiometer base for Todaya, various valves such as 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 Cooling water 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, water Iper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, wire harness connector, SMJ connector, PCB connector, door grommet connector, Various connectors such as fuse connectors, horn terminals, electrical component insulation plates, step motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, solenoid bobbins, engine oil filters, ignition device cases, torque control levers, safety belt parts , Register blade, washer lever, window regulator handle, window regulator handle Knob, passing light lever, 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 stays, spoilers, hood louvers, wheel covers, wheel caps, grill apron cover frames, lamp bezels, door handles, door moldings, rear finishers, wipers and other automobile / vehicle related parts.

  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 sheets, films and sheets for members of electric / electronic equipment, films and sheets for household goods.

  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 household goods such as body brushes, eyeglass frames, umbrellas, covers, shopping bags and furoshiki.

  The thermoplastic resin composition of the present invention is also suitably used for electronic equipment casings such as notebook personal computers, electric machines and electronic parts.

  The thermoplastic resin composition of the present invention is also suitably used for automobile interior / exterior parts, automobile outer plates and the like.

  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 also preferably used for member-related parts, lifeline-related parts and the like.

  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 also suitably used for fishing gear related products, summer sports related products such as surfing, winter sports related products such as skiing and snowboarding, 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): Melting point 225 ° C., relative viscosity 2.75 at 0.01 g / ml in 98% sulfuric acid, amino end group amount 5.8 × 10 ⁻⁵ mol / g, carboxyl end group amount 5.8 × 10 ⁻⁵ mol / g of polyamide 6 resin.
(A-2): Melting point 265 ° C., relative viscosity 3.60 at 98 g in sulfuric acid at 0.01 g / ml, amino end group amount 3.7 × 10 ⁻⁵ mol / g, carboxyl end group amount 5.5 × 10 ⁻⁵ mol / g polyamide 66 resin.
(A-3): Melting point 225 ° C., relative viscosity 2.70 at 0.01 g / ml in 98% sulfuric acid, amino end group amount 4.0 × 10 ⁻⁵ mol / g, carboxyl end group amount 6.4 × 10 ⁻⁵ mol / g of polyamide 610 resin.
(A-4): Polyamide 11 resin with a melting point of 190 ° C. and a relative viscosity of 2.55 at 0.01 g / ml in 98% sulfuric acid.
(A-5): Polyamide 12 resin having a relative viscosity of 2.55 at a melting point of 180 ° C. and 0.01 g / ml in 98% sulfuric acid.
(A-6): Polyamide 66 / 6T = 50/50 resin having a melting point of 295 ° C. and a relative viscosity of 2.70 at 98 g in sulfuric acid at 0.01 g / ml.

Similarly, the rubbery polymer (B) having a functional group that reacts with the functional group of the thermoplastic resin (A) is as follows.
(B-1): Glycidyl methacrylate-modified polyethylene copolymer “Bond First BF-7L” (manufactured by Sumitomo Chemical Co., Ltd.).
(B-2): Maleic anhydride-modified ethylene-1-butene copolymer “Tuffmer MH7020” (manufactured by Mitsui Chemicals).

Similarly, the compound (C) that blocks the functional group of the thermoplastic resin (A) is as follows.
(C-1): Phthalic anhydride (Deer Class 1) (manufactured by Kanto Chemical Co., Inc.).
(C-2): Succinic anhydride (first grade) (manufactured by Kishida Chemical Co., Ltd.).

Similarly, components other than (A), (B) and (C) are as follows.
(D-1): Thermal stabilizer “IR1098” (manufactured by Ciba Specialty Chemicals).
(D-2): Thermal stabilizer “IR1010” (manufactured by Ciba Specialty Chemicals).

(1-1) Injection molding of test piece Using an injection molding machine (NP7-1F) manufactured by Nissei Plastic Industry Co., Ltd., cylinder temperature 260 ° C. (280 ° C. in Examples 7 and Comparative Example 6, Examples 9, 10 and comparison) JIS-5A dumbbell-shaped test piece (length: 75 mm × ^{2) under} the conditions of 220 ° C. in Examples 8 and 9, 315 ° C. in Example 11 and Comparative Example 10), mold temperature 80 ° C., lower limit of injection pressure + 5 kgf / cm ² End width 12.5 mm × center width 4 mm × thickness 2 mm) was produced. The injection molding was performed by melting and staying in the molding machine for 3 minutes and 30 minutes.

(1-2) Morphological observation The central part in the cross-sectional direction of a JIS-5A dumbbell-shaped test piece which was melt-stayed for 3 minutes and injection-molded was cut into a 1 to 2 mm square, and the rubber polymer (B) was dyed with ruthenium tetroxide. Thereafter, an ultrathin section of 0.1 μm or less (about 80 nm) was cut with an ultramicrotome at −196 ° C., magnified 35,000 times, and observed with a transmission electron microscope. For the obtained image, the basic structure and the presence or absence of fine particles of 1 to 100 nm in the dispersed phase (A2) were confirmed, and the area occupied by fine particles in the dispersed phase was determined by using the image analysis software “Scion Image” manufactured by Scion Corporation. Used and calculated.

(1-3) Evaluation of tensile elongation at break by tensile test JIS-5A dumbbell-shaped test piece melted and retained for 3 minutes and 30 minutes and subjected to injection molding is subjected to Autograph AG100kNG (manufactured by Shimadzu Corporation), and the distance between chucks is set. A tensile test was carried out at 50 mm, and at a speed of 100 mm / min, 500 mm / min, and 1000 mm / min, and the tensile breaking elongation at each speed was evaluated. Note that the tensile elongation at break was the elongation at break based on a distance between chucks of 50 mm.

(1-4) Evaluation of Melt Flow Rate (MFR) Using a Toyo Seiki melt indexer, melting point of (A) + 35 ° C. (Examples 1-6, 8, 12-14 and Comparative Examples 1-5, 7, 11, and 12, 260 ° C., Example 7 and Comparative Example 6 were 300 ° C., Example 9 and Comparative Example 8 were 225 ° C., Example 10 and Comparative Example 9 were 215 ° C., and Example 11 and Comparative Example 10 were The melt flow rate was measured at a load of 10 kg. The melt residence stability was evaluated by MFR (30 minutes) / MFR (3 minutes). As the samples to be used, in Examples 1 to 12 and Comparative Examples 1 to 12, pellets obtained by melt kneading were vacuum-dried. In Examples 13 and 14, an injection molded product obtained by melting and staying for 3 minutes was used. What was cut was used.

Reference example 1
(A-1) 93 parts by weight and (C-1) 7 parts by weight were dry blended, and while performing nitrogen flow, the screw diameter was 30 mm and the screw was L / D = 35 of two screws with two threads. Using a co-rotating fully meshed twin screw extruder (manufactured by Nippon Steel Works, TEX-30α), melt kneading is performed at a cylinder temperature of 230 ° C., a screw speed of 200 rpm, and an extrusion rate of 20 kg / h. / D = 35), strand-like molten resin was discharged. The screw configuration at that time is provided with three kneading zones starting from the positions of L / D = 7, 16, 25, and the length Lk / D of each kneading zone is Lk / D = 3.0 in order. 3.0 and 3.0. Furthermore, the reverse screw zone of L / D = 0.5 was provided in the downstream of each kneading zone. When the ratio (%) of the total length of the kneading zone to the total length of the screw was calculated by (total length of kneading zone) / (total length of screw) × 100, it was 26%. The vent is not decompressed by an open vent, and the molten resin discharged from the 4 mmφ × 2 hole through the die head is drawn in a strand shape, cooled by passing through a cooling bath, and cut while being taken out by a pelletizer. A sample of composition master pellets was obtained.

Examples 1-12, Comparative Examples 1-11
While mixing with the composition shown in Tables 1 to 4 and performing nitrogen flow, the screw diameter is 30 mm, the screw is a twin screw, L / D = 35, in the same direction rotating fully meshing type twin screw extruder (Manufactured by Nippon Steel Works Co., Ltd., TEX-30α), melt kneading at the cylinder temperature, screw rotation speed, and extrusion amount shown in Tables 1 to 4, and melted in strand form from the discharge port (L / D = 35) Resin was discharged. In this case, the screw configuration is A, and from the position of L / D = 13, the spiral angle θ, which is the angle between the apex on the tip side of the kneading disk and the apex on the rear side, is 20 ° in the half rotation direction of the screw. The twisted kneading discs were connected at Lk / D = 4.0 minutes to form a zone (extension flow zone) in which melt kneading is performed while stretching and flowing. Further, a reverse screw zone of L / D = 0.5 was provided downstream of the extension flow zone. When the ratio (%) of the total length of the extension flow zone to the total length of the screw was calculated by (total length of extension flow zone) ÷ (total length of screw) × 100, it was 11%. Further, by subtracting the pressure difference (ΔP ₀ ) in the extension flow zone from the pressure difference (ΔP) in front of the twist kneading disc, the inflow effect pressure drop before and after the extension flow zone was obtained. cm ² . Further, from a position of L / D = 19 and 24, a notch type mixing screw having a single screw and a screw pitch of 0.25D and a number of notches of 12 per pitch is connected to Lm / D = 4.0 minutes respectively. Thus, two mixing zones were formed. When the ratio (%) of the total length of the mixing zone to the total length of the screw was calculated by (total length of the mixing zone) / (total length of the screw) × 100, it was 23%. In the notch mixing screw constituting the mixing zone, the ratio (%) of the screw in the direction of screw rotation in the direction opposite to the rotation direction of the screw shaft was set to 75%. The vent vacuum zone was provided at a position of L / D = 30, and volatile components were removed at a gauge pressure of −0.1 MPa. The molten resin discharged from the 4 mmφ × 2 hole passing through the die head is drawn into a strand shape, cooled by passing through a cooling bath, and cut while being taken out by a pelletizer, thereby forming a pellet-shaped sample of the thermoplastic resin composition Got. The sample was vacuum-dried at 80 ° C. for 12 hours or longer and then subjected to the above-described injection molding, morphological observation, tensile test, and MFR evaluation. Tables 1 to 4 show the kneading conditions and various evaluation results.

Comparative Example 12
While mixing with the composition shown in Table 4 and performing nitrogen flow, the screw diameter is 30 mm, the screw is a twin screw, L / D = 35, in the same direction rotating fully meshed twin screw extruder (Japan) Tex-30α manufactured by Steelworks Co., Ltd. was used, and melt kneading was performed at the cylinder temperature, screw rotation speed, and extrusion amount shown in Table 4, and the strand-shaped molten resin was discharged from the discharge port (L / D = 35). . In this case, the screw configuration is B, and three kneading zones starting from the positions of L / D = 7, 16, 25 are provided, and the length Lk / D of each kneading zone is Lk / D = 3 in order. 0.0, 3.0, and 3.0. Furthermore, the reverse screw zone of L / D = 0.5 was provided in the downstream of each kneading zone. When the ratio (%) of the total length of the kneading zone to the total length of the screw was calculated by (total length of kneading zone) / (total length of screw) × 100, it was 26%. The vent vacuum zone was provided at a position of L / D = 30, and volatile components were removed at a gauge pressure of −0.1 MPa. The molten resin discharged from the 4 mmφ × 2 hole passing through the die head is drawn into a strand shape, cooled by passing through a cooling bath, and cut while being taken out by a pelletizer, thereby forming a pellet-shaped sample of the thermoplastic resin composition Got. The sample was vacuum-dried at 80 ° C. for 12 hours or longer and then subjected to the above-described injection molding, morphological observation, tensile test, and MFR evaluation. Table 4 shows the kneading conditions and various evaluation results.

From Examples 1 to 12, the thermoplastic resin (A), the rubbery polymer (B) having a functional group that reacts with the functional group of the thermoplastic resin (A), and the functional group of the thermoplastic resin (A) are blocked. Even if the compound (C) is melt-kneaded while stretching and flowing while applying a large kneading energy, the tensile breaking elongation increases as the tensile speed is increased, and even if it is melted and retained for 30 minutes, MFR It can be seen that a thermoplastic resin composition that retains the tensile properties can be obtained.
On the other hand, in Comparative Examples 1 to 10, (A) and (B) are melt-kneaded while stretching and flowing, but since (C) is not included, in a short time (3 minutes) of melt residence, the tensile speed is The characteristic that tensile elongation at break increases as the value increases is increased, but in the case of long-time (30 minutes) melt retention, the reaction of (A) and (B) proceeds excessively and the MFR decreases, and the tensile properties are increased. It can be seen that no longer appears.
In Comparative Example 11, the components (A), (B), and (C) are blended and melt-kneaded while stretching and flowing. However, because the kneading energy is small, the tensile elongation at break increases as the tensile speed is increased. It can be seen that the feature cannot be expressed.
Comparative Example 12 also contains the components (A), (B), and (C), but is melt kneaded with a screw configuration using a general kneading disk, so even if a large kneading energy is applied, the tensile strength is increased. It can be seen that the characteristic that the tensile elongation at break increases as the speed is increased cannot be expressed.

Examples 13 and 14
After dry blending each component described in Table 5, injection molding, morphological observation, and tensile test were performed. For MFR evaluation, an injection molded product obtained by melting and staying for 3 minutes was cut. Various evaluation results are shown in Table 5.

  The comparative example 1 obtained by melt-kneading (A) and (B) while stretching and flowing, the component (C) was dry blended in Example 13 and the comparative example 1 contained the component (C). In Example 14, which was injection blended by dry blending Reference Example 1 which is a master pellet, the MFR changes even when melted and retained for 30 minutes, while the tensile elongation at break increases as the tensile speed is increased. It turns out that the resin composition which is very small and can hold | maintain the said tensile characteristic notably can be obtained.

  In Examples 1 to 12, since (A), (B) and (C) are kneaded together, the reaction of (A) and (B) and the functional group blocking reaction of (A) by (C) proceed in concert. In Examples 13 and 14, the reaction between (A) and (B) is allowed to proceed, and then (C) is added, so that the remaining functional group (amino end group) of (A) is blocked with high probability. This makes it possible to obtain a thermoplastic resin composition having a unique tensile property that is more excellent in residence stability.

1: Notch 2: Screw pitch 3: Screw diameter D

Claims (9)

A thermoplastic resin (A), a rubbery polymer (B) having a functional group that reacts with a functional group of the thermoplastic resin (A), and a compound (C) that blocks the functional group of the thermoplastic resin (A) A thermoplastic resin composition having the following characteristics (I) and (II):
(I) 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.
(II) Melting point of MFR (30 minutes) / MFR (3 minutes) ≧ 0.7 when melting and staying at the temperature of melting point of thermoplastic resin (A) + 35 ° C. for 3 minutes and 30 minutes. . The thermoplastic resin (A) is at least one selected from polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, and polypropylene resin. Thermoplastic resin composition. The rubbery polymer (B) having a functional group that reacts with the functional group of the thermoplastic resin (A) 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 according to claim 1 or 2, wherein the thermoplastic resin composition is a rubbery polymer having various functional groups. The rubbery polymer (B) having a functional group that reacts with a functional group of the thermoplastic resin (A) is a rubbery polymer having a functional group that reacts with a terminal amino group of a polyamide resin. The thermoplastic resin composition in any one of 1-3. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the compound (C) that blocks the functional group of the thermoplastic resin (A) is an acid anhydride. Rubber polymer (B) having a functional group that reacts with a functional group of thermoplastic resin (A), 5 to 95 parts by weight of thermoplastic resin (A), with the total of (A) and (B) being 100 parts by weight The thermoplastic resin composition according to any one of claims 1 to 5, comprising 5 to 95 parts by weight of 0.01 to 50 parts by weight of the compound (C) for blocking the functional group of the thermoplastic resin (A). . A thermoplastic resin (A), a rubbery polymer (B) having a functional group that reacts with a functional group of the thermoplastic resin (A), and a compound (C) that blocks the functional group of the thermoplastic resin (A), The method for producing a thermoplastic resin composition according to any one of claims 1 to 6, wherein melt kneading is performed while stretching and flowing. The thermoplastic resin (A), the rubbery polymer (B) having a functional group that reacts with the functional group of the thermoplastic resin (A), and the compound (C) that blocks the functional group of the thermoplastic resin (A), The method for producing a thermoplastic resin composition according to any one of claims 1 to 6, wherein the kneading energy is applied at 0.35 kWh / kg or more and melt kneading while stretching and flowing. After the thermoplastic resin (A) and the rubbery polymer (B) having a functional group that reacts with the functional group of the thermoplastic resin (A) are melt-kneaded while stretching and flowing, the functional group of the thermoplastic resin (A) is changed. The method for producing a thermoplastic resin composition according to any one of claims 1 to 6, wherein the compound (C) to be sequestered is added and melted.

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