JP5625588B2 - Method for producing thermoplastic resin composition - Google Patents

Description

  The present invention, when producing a thermoplastic resin composition containing a compound having a reactive functional group by reactive processing, melt kneading with a notched mixing screw after melt-kneading while stretching and flowing, the screw length Even if the throughput is increased with a general-purpose large extruder with a short L / D ratio L / D, the resin degradation due to heat generation is suppressed, and characteristics that cannot be achieved with conventional manufacturing methods (heat resistance The present invention relates to a production method for obtaining a thermoplastic resin composition having a balance of property and impact resistance, impact absorbability and the like.

  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 alloys between thermoplastic resins and resins having reactive functional groups, impact resistance, heat resistance, large load and high speed impact are achieved by increasing the reaction rate using an extruder with L / D = 100. Although it is described that the absorbability can be obtained, an extruder with a long L / D has difficulty in equipment maintenance and long-time continuous operation, and a simpler production method has been demanded. Further, the L / D = 100 extruder has a problem that it is difficult to increase the size of the screw shaft due to the design of the screw shaft.

  Patent Document 3 proposes a production method using an extensional flow instead of a shearing flow generally used at the time of melt kneading. A new melt-kneading device using elongational flow has been described for the purpose of reducing screw wear, suppressing shear heat generation during melt-kneading, and improving filler dispersibility. There is no disclosure or suggestion about the application.

  Further, Patent Document 4 proposes a kneading method using a single thread reverse screw notch screw to suppress thermal deterioration of the resin. However, the length of the kneading zone with the notch screw is as short as 0.2D to 2.5D (D is the screw diameter), and disclosure of the effectiveness of the combined use of the extension flow and the notch screw for reactive processing is also suggested. Also not at all.

JP 2006-347151 A JP 2008-156604 A JP 2007-237679 A JP 2001-310369 A

  In the present invention, even when the throughput is increased by a general-purpose large extruder having a short screw length L to screw diameter D ratio L / D, resin deterioration due to heat generation is suppressed, and a balance between heat resistance and impact resistance is achieved. Another object of the present invention is to provide a production method for obtaining a thermoplastic resin composition excellent in impact absorbability and the like.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention cut a product after melt-kneading while stretching and flowing when producing a thermoplastic resin composition containing a compound having a reactive functional group by reactive processing. By melting and kneading with a notched mixing screw, even if the throughput is increased with a general-purpose large extruder with a short ratio L / D of screw length L to screw diameter D, resin deterioration due to heat generation is suppressed, and this The present inventors have found that it is possible to produce a thermoplastic resin composition having properties (such as a balance of heat resistance and impact resistance, shock absorption, etc.) that could not be achieved by the above production methods, and completed the present invention. .

That is, the present invention
1. When the thermoplastic resin composition of the following (I) or (II) is produced by an extruder, the thermoplastic resin composition is melt-kneaded with a notched mixing screw after being melt-kneaded while stretching and flowing. In the manufacturing method , the ratio of the total length of the melt-kneading zone (extension flow zone) while stretching and flowing with respect to the full length of the screw of the extruder is 5 to 40%, and the cutting with respect to the full length of the screw of the extruder A method for producing a thermoplastic resin composition, characterized in that the ratio of the total length of the zone (mixing zone) for melting and kneading with a notched mixing screw is 15 to 40%,
(I) Thermoplastic resin (A) and thermoplastic resin composition formed by blending resin (B) having a reactive functional group (II) Thermoplastic resin (A), heat different from thermoplastic resin (A) 1. A thermoplastic resin composition comprising a plastic resin (C) and a compound (D) having a reactive functional group . Process for producing a pre-Symbol extensible thermoplastic resin composition according to 1, inflow effects pressure drop across it, characterized in that a 10~1000kg / cm ² flow zone,
3 . 3. The thermoplastic resin composition according to 1 or 2 , wherein Lk / D = 2 to 10 is satisfied, where Lk is a length of one extension flow zone in the screw of the extruder and D is a screw diameter. Production method,
4 . The mixing zone is configured by connecting notch type mixing screws having a single thread and a screw pitch length of 0.1D to 0.5D and a notch number of 8 to 16 per pitch. A method for producing a thermoplastic resin composition according to any one of 1 to 3 ,
5 . The method for producing a thermoplastic resin composition according to any one of 1 to 4 , wherein Lm / D = 4 to 20 is satisfied, where Lx is a length of one mixing zone and D is a screw diameter,
6 . The method for producing a thermoplastic resin composition according to any one of 1 to 5 , wherein the mixing zone is provided at two or more locations,
7 . The thermoplastic resin composition according to any one of 1 to 6 , wherein 70% or more of the notched mixing screw constituting the mixing zone is a screw-turning direction opposite to a rotation direction of the screw shaft. Manufacturing method ,
8 . The extruder cylinder temperature of stretched flow zone Ck, when the extruder cylinder temperature in the mixing zone and Cm, according to any one of 1 to 7, wherein the melt-kneading while satisfying the Ck-Cm ≧ 40 A method for producing a thermoplastic resin composition of
9 . The extruder cylinder temperature of stretched flow zone Ck, when the extruder cylinder temperature in the mixing zone and Cm, according to any one of 1 to 8, wherein the melt-kneading while satisfying the Ck-Cm ≧ 60 A method for producing a thermoplastic resin composition of
10 . The production of the thermoplastic resin composition according to any one of 1 to 9 , wherein melt-kneading is performed using a twin screw extruder having a ratio L / D of a screw length L to a screw diameter D of less than 50. Method,
11 . The thermoplastic resin (A) is at least one selected from polyamide resin, polyester resin, polyphenylene sulfide resin, polyacetal resin, styrene resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, and polypropylene resin. The method for producing a thermoplastic resin composition according to any one of 1 to 10 ,
12 . The thermoplastic resin (C) is different from the thermoplastic resin (A), from polyamide resin, polyester resin, polyphenylene sulfide resin, polyacetal resin, styrene resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, and polypropylene resin. The method for producing a thermoplastic resin composition according to any one of 1 to 11 , which is at least one selected
13 . Resin having a reactive functional group (B) is from 1 to 12, wherein the at least one selected from polyphenylene oxide resins having rubber-like polymer having a reactive functional group, and a reactive functional group A method for producing the thermoplastic resin composition according to any one of the above,
14 . The reactive functional group of the resin (B) having a 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. A method for producing a thermoplastic resin composition according to any one of 1 to 13 ,
15 . The reactive functional group of the compound (D) having a 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 method for producing a thermoplastic resin composition according to any one of 1 to 12 ,
16 . The method for producing a thermoplastic resin composition according to any one of 1 to 15 , wherein the thermoplastic resin (A) is a polyamide resin,
17 . In the tensile test, the obtained thermoplastic resin composition has E (V1) and E (V2) when the tensile elastic modulus is V1 and V2, and when V1 <V2, E (V1)> E ( V2), The method for producing a thermoplastic resin composition according to any one of 1 to 16 ,
18 . In the tensile test, when the obtained thermoplastic resin composition has tensile elongation at break of ε (V1) and ε (V2) at tensile speeds V1 and V2, ε (V1) <ε when V1 <V2. (V2) A method for producing a thermoplastic resin composition according to any one of 1 to 17 ,
19 . A thermoplastic resin composition obtained by the production method according to any one of 1 to 18 ,
20 . A molded article comprising the thermoplastic resin composition according to 19 ,
21 . 20. The molded product according to 20 , wherein the molded product is at least one selected from a film, a sheet, and a fiber.
Is to provide.

  From the present invention, even if the throughput is increased with a general-purpose large extruder with a short ratio L / D of screw length L and screw diameter D, resin deterioration due to heat generation is suppressed, and a balance between heat resistance and impact resistance is achieved. It is possible to provide a production method for obtaining a thermoplastic resin composition excellent in impact absorption and the like.

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 is
(I) a thermoplastic resin composition obtained by blending a thermoplastic resin (A) and a resin (B) having a reactive functional group, or (II) a thermoplastic resin (A) or a thermoplastic resin (A) It is a thermoplastic resin composition comprising a different thermoplastic resin (C) and a compound (D) 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, polyacetal resin, polyphenylene oxide resin, Polycarbonate resin, polylactic acid 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 resin selected from resins, polypropylene resins, styrene resins such as polystyrene resins and ABS resins, rubbery polymers, polyalkylene oxide resins, and the like. .

    Of the thermoplastic resins shown above, polyamide resins, polyester resins, polyphenylene sulfide resins, polyphenylene oxide resins, polycarbonate resins, polylactic acid resins, polypropylene resins, and styrene resins are preferred. Polyester resins, polyphenylene 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, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylene Diamine, metaxylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane ,Screw Aliphatic and fats such as (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine Cyclic and 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 -Aliphatic, alicyclic and aromatic dicarboxylic acids such as sodium sulfoisophthalic acid, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like. In the present invention, from these raw materials Each derived polyamide homopolymer or copolymer alone Others can be used in the form of mixtures.

  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) and A mixture or copolymer thereof may be used.

  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 are resins (B) having reactive functional groups, or reactive functional groups. It is preferable in terms of reactivity with the compound (D). 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 develop the impact resistance and impact absorption characteristics of the thermoplastic resin composition of the present invention, and when the relative viscosity is more than 7.0, the thermoplastic resin composition This is not preferable because the melt viscosity of the product is remarkably increased and it becomes difficult to form a molded article.

  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). From the viewpoint of reactivity with the resin (B) having a reactive functional group or the compound (D) having a reactive functional group.

  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 resin (B) having a reactive functional group of the present invention is a resin having a reactive functional group in a molecular chain.

  The resin serving as the base of the resin (B) having a reactive functional group of the present invention is not particularly limited. For example, polyamide resin, polyester resin, polyphenylene sulfide resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, polysulfone resin , Polyacetal resin, Polytetrafluoroethylene resin, Polyetherimide resin, Polyamideimide resin, Polyimide resin, Polyethersulfone resin, Polyetherketone resin, Polythioetherketone resin, Polyetheretherketone resin, Polyethylene resin, Polypropylene resin, Polystyrene Used as at least one kind of resin different from the above-mentioned thermoplastic resin (A) selected from styrene resins such as resin and ABS resin, rubbery polymer, polyalkylene oxide resin, etc. Rukoto can. Among these, polyethylene resins, polypropylene resins, styrene resins, and rubbery polymers are preferable from the viewpoint of easy introduction of reactive functional groups, and rubber polymers are more preferable from the viewpoint of imparting impact resistance and shock absorption.

  Such a rubbery polymer generally contains a polymer having a glass transition temperature lower than room temperature, and some of the molecules are bound to each other by covalent bonds, ionic bonds, van der Waals forces, entanglement, etc. It refers to a polymer. 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 polyphenylene oxide resin used as a base of the resin (B) having a reactive functional group of the present invention has a reduced viscosity measured at 30 ° C. in a 0.5 g / dl chloroform solution of 0.15 to 0. Those in the range of .70 are preferred. 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.

  Unlike the thermoplastic resin (A), the thermoplastic resin (C) of 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 , Polyacetal resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, polysulfone resin, polytetrafluoroethylene resin, polyetherimide resin, polyamideimide resin, polyimide resin, polyethersulfone resin, polyetherketone resin, polythioetherketone resin Different from the thermoplastic resin (A) selected from polyether ether ketone resin, polyethylene resin, polypropylene resin, styrene resin such as polystyrene resin and ABS resin, rubber polymer, polyalkylene oxide resin, etc. , It can be used as at least one or more resins.

  The compound (D) having a reactive functional group of the present invention is a compound having a reactive functional group in a molecular chain. Such a compound may be a low molecular weight body or a high molecular weight body.

  The reactive functional group present in the resin (B) having a reactive functional group or the compound (D) having a reactive functional group according to the present invention refers to the thermoplastic resin (A) or the thermoplastic resin (C). There is no particular limitation as long as it reacts with the existing functional group, for example, amino group, carboxyl group, carboxyl metal salt, hydroxyl group, epoxy group, acid anhydride group, isocyanate group, mercapto group, oxazoline group, sulfonic acid There may be mentioned at least one selected from 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.

  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 resin serving as the base of (B), the method can be performed by a generally known technique and is not particularly limited. For example, an unsaturated carboxylic acid-based monomer having a carboxyl group For example, a method of copolymerizing the body with a monomer that is a raw material of the resin serving as a base of (B) can be used. Specific examples of the unsaturated carboxylic acid include (meth) acrylic acid. Examples of the resin (B) having a reactive functional group include ethylene-unsaturated carboxylic acid copolymers such as ethylene-acrylic acid and ethylene-methacrylic 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 resin (B) having a reactive functional group 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. Etc. 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.

  When introducing a carboxyl group and an acid anhydride group into the polyphenylene oxide resin, it can be carried out by a generally known technique. Typically, 100 parts by weight of polyphenylene oxide resin, 0.1 to 10 parts by weight of α, β-unsaturated dicarboxylic acid and derivatives thereof such as citric acid, fumaric acid, maleic acid and maleic anhydride, 0.01% of radical generator A method of dry blending ˜1 part by weight and melt-kneading at a cylinder temperature of 300 to 320 ° C. can be used.

  In the resin (B) having a reactive functional group and the compound (D) having a reactive functional group, the number of functional groups per molecular chain is not particularly limited, but usually 1 to 10 is preferable, such as crosslinking. In order to reduce the side reaction, 1 to 5 is 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 the resin (B) which has a reactive functional group in this invention, (weight of (A)) / (weight of (B)) is 5 / The range of 95 to 95/5 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.

  Although there is no restriction | limiting in particular about the compounding ratio with the thermoplastic resin (A) and thermoplastic resin (C) in this invention, (weight of (A)) / (weight of (C)) is 5 / 95-95 / The range of 5 is preferred, the range of 10/90 to 90/10 is more preferred, and the range of 15/85 to 85/15 is most preferred.

  The addition amount of the compound (D) having a reactive functional group with respect to 100 parts by weight of the sum of the weights of the thermoplastic resin (A) and the thermoplastic resin (C) in the present invention is not particularly limited, but is preferably 0.1 -50 parts by weight, more preferably 0.2-40 parts by weight, still more preferably 0.3-30 parts by weight.

  When producing the thermoplastic resin composition of the present invention, it is necessary to melt and knead it with a notched mixing screw after using an extruder to melt and knead it while stretching and flowing.

  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, it is necessary to melt and knead with a notch mixing screw after melt kneading while stretching and flowing. 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 Thermoplastic resin composition that suppresses resin degradation due to heat generation and has excellent balance of heat resistance and impact resistance, shock absorption, etc., even when the throughput is increased with a general purpose large extruder with a short D ratio L / D Things can be obtained.

  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 small, and 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, impact resistance, and heat resistance during high-speed tension are reduced.

  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.

  Further, 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, a resin that generates heat A thermoplastic resin composition that suppresses deterioration and has heat resistance, impact resistance, impact absorption, and the like can be obtained.

  In the present invention, the ratio of the total length of the zone (extension flow zone) for melting and kneading while stretching and flowing with respect to the total length of the screw of the extruder is 5 to 40%, and the notch mold with respect to 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 the mixing screw is preferably 15 to 40% from the viewpoint of improving the cooling efficiency of the molten resin by filling the resin, improving the kneadability, and improving the reactivity. More preferably, 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. If the residence time is less than 6 seconds, the reaction time in the extruder is short, the reaction is not sufficiently promoted, and the properties of the thermoplastic resin composition (balance of heat resistance, impact resistance, etc.) are improved, It is difficult to realize an improvement in impact absorbency that makes a distinctive viscoelastic property remarkably manifest. 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.

  The thermoplastic resin composition produced according to the present invention has a significant non-viscoelastic property that it becomes more flexible as it is deformed at high speed, and the maximum load applied to the object even when subjected to a large load or a high-speed impact. Can absorb large energy without causing destruction.

  In the tensile test, the thermoplastic resin composition produced according to the present invention has an elastic modulus of E (V1) and E (V2) at a tensile velocity of V1 and V2, and when V1 <V2, E (V1 )> E (V2). 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.

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

  In the thermoplastic resin composition manufactured by this invention, you may add other components other than said (A)-(D) as needed in the range which does not impair the characteristic.

  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)-(D) 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)-(D) 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 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) and (B ), Or a method of simultaneously adding (A), (C), and (D), a method of adding by a method such as side feed during melt kneading, or adding to a melt-kneaded thermoplastic resin composition And a method of first adding to one resin and melt-kneading and then blending the remaining resin.

  The molding method of the thermoplastic resin composition produced according to 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 impact resistance, heat resistance, and shock absorption, but has a special effect particularly in the case of thin molded articles, elongated molded articles, fibers and films. Is.

  In the case of producing fibers from the thermoplastic resin composition produced according to 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 manufactured by 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.

  The molded product of the thermoplastic resin composition produced according to the present invention is used for connectors, coils, sensors, LED lamps, sockets, resistors, relay cases, small switches, coil bobbins, capacitors, variable capacitor cases, optical pickups. , Oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, power module, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna In addition to being suitable for electrical / electronic parts applications such as computer-related parts, generators, motors, transformers, current transformers, voltage regulators, rectifiers, inverters, relays, power contacts, switches, breakers Machine, knife switch, other pole lock , Electrical equipment parts such as electrical parts cabinets, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs (registered trademark) / compact discs, DVDs, etc. Video equipment parts, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, homes represented by electronic equipment cases such as personal computers, office electrical product parts; office computer related parts, telephone equipment related parts, facsimile related Machine-related parts represented by parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, precision machine-related parts; Alternator terminals , Alternator connector, IC legi , Various valves such as exhaust gas valves, fuel related, cooling system, brake system, wiper system, exhaust system, intake system, various pipes, hoses, tubes, air intake nozzle snorkel, intake manifold, Fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant 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, tar Bimbein, wiper 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 Connectors, 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, wind leg Rotator 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 It is suitably used for automobile / vehicle-related parts such as lids, door mirror stays, spoilers, hood louvers, wheel covers, wheel caps, grill apron cover frames, lamp bezels, door handles, door moldings, rear finishers, wipers and the like.

  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 produced according to the present invention is also suitable as a fiber, and may be any of long fibers, short fibers, monofilaments, crimped yarns, etc. For clothing such as T-shirts, nets, ropes, spunbonds, abrasive brushes, industrial brushes, filters, papermaking nets, etc., general materials / industrial materials / industrial materials, blankets, duvets, curtains, etc. , Toothbrushes, body brushes, eyeglass frames, umbrellas, covers, shopping bags, furnishings, and other household goods.

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

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

  The thermoplastic resin composition produced according to the present invention is also suitable as a building material, such as a civil engineering building wall, roof, ceiling material-related component, window material-related component, heat insulating material-related component, flooring-related component, seismic isolation. -It is also suitable for vibration damping member related parts and lifeline related parts.

  The thermoplastic resin composition produced according to the present invention is also suitable for sports equipment, golf-related equipment such as golf clubs, shafts, grips, and golf balls, and sports racquet-related equipment such as tennis rackets, badminton rackets, and guts thereof. , American football, baseball, softball masks, helmets, chest 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, It is also suitably used for fishing gear related items such as fishing lines, summer sports related items such as surfing, winter sports related items such as skis and snowboards, and other indoor and outdoor sports related items.

  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 225 ° C., relative viscosity 2.35 at 98 g / ml in 98% sulfuric acid, amino end group amount 4.4 × 10 ⁻⁵ mol / g, carboxyl end group amount 7.3 × 10 ⁻⁵ mol / g of polyamide 6 resin.
(A-3): 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-4): Melting point 225 ° C., relative viscosity 2.70 at 98 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-5): Polyamide 11 resin having a melting point of 190 ° C. and a relative viscosity of 2.55 at 0.01 g / ml in 98% sulfuric acid.
(A-6): Polyamide 12 resin having a melting point of 180 ° C., a relative viscosity of 2.55 at 0.01 g / ml in 98% sulfuric acid.
(A-7): 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.
(A-8): 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, and a carboxyl end group amount of 35 eq / ton.
(A-9): Polyethylene terephthalate resin having a melting point of 265 ° C., an intrinsic viscosity of 0.85 measured with a 0.5% solution in o-chlorophenol, and a carboxyl end group amount of 26 eq / ton.
(A-10): Melting point 170 ° C., weight average molecular weight 210,000 (gel permeation chromatography method, 1,1,1,3,3,3-hexafluoro-2-propanol eluent, converted to PMMA), D-form Poly L lactic acid resin with a content of 1.2%.
(A-11): Polyphenylene oxide resin “Iupiace PX-100F” (Mitsubishi Engineering Plastics).
(A-12): Polyphenylene sulfide resin having a melting point of 280 ° C., MFR = 500 g / 30 minutes (315.5 ° C., 5 kg load), and carboxyl end group amount of 50 eq / ton.
(A-13): Melting point 160 ° C., MFR = 0.5 g / 10 min (230 ° C., 2.16 kg load), density 0.910 g / cm ³ of polypropylene resin 100 parts by weight, maleic anhydride 1 part by weight and radical A polypropylene resin obtained by dry blending 0.1 part by weight of a generator (Perhexa 25B: NOF Corporation) and melt-kneading at a cylinder temperature of 230 ° C.
(A-14): Melting point 225 ° C., relative viscosity 2.30 at 98 g in sulfuric acid at 0.01 g / ml, amino end group amount 9.1 × 10 ⁻⁵ mol / g, carboxyl end group amount 5.1 × 10 ⁻⁵ mol / g of polyamide 6 resin.
(A-15): Melting point 225 ° C., relative viscosity 2.65 at 98 g / ml in 98% sulfuric acid, amino end group amount 11.4 × 10 ⁻⁵ mol / g, carboxyl end group amount 2.3 × 10 ⁻⁵ mol / g polyamide 66 resin.

Similarly, the resin (B) having a reactive functional group is as follows.
(B-1): Glycidyl methacrylate-modified polyethylene copolymer “Bond First BF-7L” (manufactured by Sumitomo Chemical Co., Ltd.).
(B-2): Glycidyl methacrylate-modified polyethylene copolymer “Bond First BF-7M” (manufactured by Sumitomo Chemical Co., Ltd.).
(B-3): Maleic anhydride-modified ethylene-1-butene copolymer “Tuffmer MH7020” (manufactured by Mitsui Chemicals).
(B-4): Glycidyl methacrylate-modified polyethylene copolymer-g-PMMA resin “Modiper A4200” (manufactured by NOF Corporation).
(B-5): Ethylene-methacrylic acid-zinc methacrylate copolymer “Himiran 1706” (Mitsui / DuPont Polychemical Co., Ltd.).
(B-6): 100 parts by weight of polyphenylene oxide resin “Iupiace PX-100F” (Mitsubishi Engineering Plastics), 1.2 parts by weight of maleic anhydride, radical generator (Perhexine 25B: NOF Corporation) A modified polyphenylene oxide resin obtained by dry blending 1 part by weight and melt-kneading at a cylinder temperature of 320 ° C.

Similarly, the thermoplastic resin (C) is as follows.
(C-1): Polyphenylene oxide resin “Iupiace PX-100F” (manufactured by Mitsubishi Engineering Plastics).

Similarly, the compound (D) having a reactive functional group is as follows.
(D-1): Styrene-maleic anhydride copolymer “Dairaku 332” (manufactured by Nova Chemical Co.).

Similarly, components other than (A), (B), (C) and (D) are as follows.
(E-1): Unmodified polyethylene copolymer (hereinafter abbreviated as unmodified PE copolymer) “LOTRYL29MA03” (manufactured by Arkema).
(E-2): Styrene-butadiene-styrene copolymer hydrogenated product “Clayton G1651” (manufactured by Kraton Polymer Japan).
(F-1): Thermal stabilizer “IR1098” (manufactured by Ciba Specialty Chemicals).
(F-2): Thermal stabilizer “IR1010” (manufactured by Ciba Specialty Chemicals).
(F-3): Thermal stabilizer “PEP36” (manufactured by ADEKA).
(F-4): Thermal stabilizer “AO80” (manufactured by ADEKA).

(1-1) Injection molding of test piece Using an injection molding machine (NP7-1F) manufactured by Nissei Plastic Industrial Co., Ltd., a molding temperature of 260 ° C. (Examples 17 and 24 and Comparative Examples 8 and 15, 280 ° C., Example 19) 20 and Comparative Examples 10 and 11, 220 ° C., Example 21 and Comparative Example 12 are 310 ° C., Examples 25 and 28 and Comparative Examples 16 and 19 are 200 ° C., Examples 26 and 27 and Comparative Examples 17 and 18 are 300 ° C., Examples 39 to 54 and Comparative Examples 28 to 35 are 290 ° C.), Mold temperature is 80 ° C. (Examples 24 and 27 and Comparative Examples 15 and 18 are 130 ° C.), Injection pressure lower limit pressure + 5 kgf / cm ² JIS-5A dumbbell-type test pieces (length 75 mm × end width 12.5 mm × thickness 2 mm) and JIS-1 strip test pieces (length 80 mm × width 10 mm × thickness 4 mm) were prepared depending on conditions. .

(1-2) Evaluation of tensile elastic modulus and tensile elongation at break by tensile test JIS-5A dumbbell-shaped 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. , 100 mm / min, 500 mm / min, and 1000 mm / min, tensile tests were performed, and the tensile 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.

(1-3) Evaluation of impact strength The JIS-1 strip test piece obtained by injection molding was subjected to a Charpy impact tester 611 manufactured by Toyo Seiki Co., Ltd., and a Charpy impact test at 50% RH was carried out according to ISO179. . The measurement was performed at 23 ° C, -20 ° C, and -30 ° C.

(1-4) Evaluation of deflection temperature under load The JIS-1 strip test piece obtained by injection molding was subjected to HDT tester S3-MH manufactured by Toyo Seiki Co., Ltd., and adjusted for 48 hours under conditions of 23 ° C. and 50% RH. With respect to the wet sample, the deflection temperature under load (loads 0.45 MPa, 1.80 MPa) was measured in accordance with ISO75-1,2.

Examples 1 to 10, 17 to 30, 33 to 36, 39 to 48, Comparative Example 7
While mixing with the composition shown in Tables 1, 2, 3, 4, 5, 8, 9, 10 and performing nitrogen flow, the screw diameter is 65 mm and the screw is L / D of two screws of two threads. The cylinder temperature and screw rotation shown in Tables 1, 2, 3, 4, 5, 8, 9, and 10 using 45 co-rotating fully meshed twin screw extruder (manufactured by Nippon Steel Works, TEX-65αII) Melt kneading was performed at a number and extrusion amount, and a strand of molten resin was discharged from the discharge port (L / D = 45). At that time, the coloring agent was added together with the raw materials, and the time when the coloring to the extrudate was maximized was measured as the residence time. The residence time is shown in Tables 1, 2, 3, 4, 5, 8, 9, and 10. It was. Also, the screw configuration is A, and the twist angle in which the helical angle θ, which is the angle between the top of the kneading disk and the top of the kneading disk, is 20 ° in the half rotation direction of the screw from the position of L / D = 13. The kneading disks were connected at Lk / D = 5.0 minutes to form a zone (extension flow zone) in which the kneading disk melted and kneaded while stretching. 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%. In addition, 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 . Furthermore, from a position of L / D = 23 and 31, a notch type mixing screw having a single thread screw and a screw pitch of 0.25D and a number of notches of 12 per pitch is connected to Lm / D = 5.0 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 22%. Further, in the notch type 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 80%. The vent vacuum zone was provided at a position of L / D = 38, and volatile components were removed at a gauge pressure of −0.1 MPa. The molten resin discharged from the 4 mmφ × 23 hole through the die head was measured for the resin temperature with a thermometer, and the presence or absence of the gelled product was visually confirmed. Thereafter, the discharged resin was drawn in a strand shape, passed through a cooling bath, cooled, and cut while being taken out by a pelletizer, thereby obtaining a pellet-like sample of the thermoplastic resin composition. The sample was vacuum-dried at 80 ° C. for 12 hours or more, and then the above-described injection molding was carried out for various evaluations. Tables 1, 2, 3, 4, 5, 8, 9, and 10 show the kneading conditions and various evaluation results.

Examples 11-15, 31, 32, 37, 38, 49-54
While mixing with the composition shown in Tables 2, 8, 9, and 10 and performing nitrogen flow, the screw diameter is 65 mm and the screw is a double screw L / D = 31.5 in the same direction of rotation. Using a meshing type twin screw extruder (manufactured by Nippon Steel Works, TEX-65αII), melt kneading was performed at the cylinder temperatures, screw rotation speeds, and extrusion amounts shown in Tables 2, 8, 9, and 10, and the discharge port (L /D=31.5), strand-like molten resin was discharged. At that time, the coloring agent was added together with the raw materials, and the time during which the coloration on the extrudate was maximized was measured as the residence time. The residence times are shown in Tables 2, 8, 9, and 10. In addition, the screw configuration is B, and the twist angle in which the helical angle θ, which is the angle between the top of the kneading disk and the top of the kneading disk, is 20 ° in the half rotation direction of the screw from the position of L / D = 10. The kneading disks were connected at Lk / D = 4.0 minutes to form a zone (extension flow zone) in which the kneading disks melt and knead while being extended and flowed. 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 13%. 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 = 16 and 21, 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 25%. 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 = 27, and volatile components were removed at a gauge pressure of −0.1 MPa. The molten resin discharged from the 4 mmφ × 23 hole through the die head was measured for the resin temperature with a thermometer, and the presence or absence of the gelled product was visually confirmed. Thereafter, the discharged resin was drawn in a strand shape, passed through a cooling bath, cooled, and cut while being taken out by a pelletizer, thereby obtaining a pellet-like sample of the thermoplastic resin composition. The sample was vacuum-dried at 80 ° C. for 12 hours or more, and then the above-described injection molding was carried out for various evaluations. Tables 2, 8, 9, and 10 show the kneading conditions and various evaluation results.

Example 16
While mixing with the composition shown in Table 2 and carrying out nitrogen flow, the screw diameter is 90 mm, the screw is a twin screw, L / D = 31.5, the same direction rotation fully meshed twin screw extruder (Manufactured by Nippon Steel Works Co., Ltd., TEX-90), melt kneading is performed at the cylinder temperature, screw rotation speed, and extrusion amount shown in Table 2, and melted in a strand form from the discharge port (L / D = 31.5) Resin was discharged. At that time, the coloring agent was added together with the raw materials, and the time during which the coloration on the extrudate was maximized was measured as the residence time. The residence time is shown in Table 2. In addition, the screw configuration is B, and the twist angle in which the helical angle θ, which is the angle between the top of the kneading disk and the top of the kneading disk, is 20 ° in the half rotation direction of the screw from the position of L / D = 10. The kneading disks were connected at Lk / D = 4.0 minutes to form a zone (extension flow zone) in which the kneading disks melt and knead while being extended and flowed. 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 13%. 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 = 16 and 21, 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 25%. 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 = 27, and volatile components were removed at a gauge pressure of −0.1 MPa. The molten resin discharged from the 4 mmφ × 23 hole through the die head was measured for the resin temperature with a thermometer, and the presence or absence of the gelled product was visually confirmed. Thereafter, the discharged resin was drawn in a strand shape, passed through a cooling bath, cooled, and cut while being taken out by a pelletizer, thereby obtaining a pellet-like sample of the thermoplastic resin composition. The sample was vacuum-dried at 80 ° C. for 12 hours or more, and then the above-described injection molding was carried out for various evaluations. Table 2 shows the kneading conditions and various evaluation results.

Comparative Examples 1, 2, 20, 24, 28-30
While mixing with the composition shown in Tables 3, 8, 9, and 11 and performing nitrogen flow, the screw diameter is 65 mm, and the screw is a double thread L / D = 45 in the same direction rotation complete meshing type Using a twin-screw extruder (manufactured by Nippon Steel Works, TEX-65αII), melt kneading was performed at the cylinder temperatures, screw revolutions, and extrusion amounts shown in Tables 3, 8, 9, and 11, and the discharge port (L / D = 45) Strand-like molten resin was discharged. At that time, the coloring agent was added together with the raw materials, and the time during which the coloration on the extrudate was maximized was measured as the residence time. The residence times are shown in Tables 3, 8, 9, and 11. Also, the screw configuration was C, and general kneading disks were connected at L / D = 13, 23, and 31 for Lk / D = 5.0 minutes to form a kneading zone. Further, a reverse screw zone with L / D = 0.5 was provided downstream of the 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 33%. The vent vacuum zone was provided at a position of L / D = 38, and volatile components were removed at a gauge pressure of −0.1 MPa. The molten resin discharged from the 4 mmφ × 23 hole through the die head was measured for the resin temperature with a thermometer, and the presence or absence of the gelled product was visually confirmed. Thereafter, the discharged resin was drawn in a strand shape, passed through a cooling bath, cooled, and cut while being taken out by a pelletizer, thereby obtaining a pellet-like sample of the thermoplastic resin composition. The sample was vacuum-dried at 80 ° C. for 12 hours or more, and then the above-described injection molding was carried out for various evaluations. Tables 3, 8, 9, and 11 show the kneading conditions and various evaluation results.

Comparative Examples 3, 4, 21, 25
While mixing with the composition shown in Tables 3, 8, and 9 and performing nitrogen flow, the screw diameter is 65 mm, the screw is a twin screw, L / D = 45, the same direction rotation complete meshing type biaxial Using an extruder (manufactured by Nippon Steel Works, TEX-65αII), melt kneading was performed at the cylinder temperature, screw rotation speed, and extrusion amount shown in Tables 3, 8, and 9, and from the discharge port (L / D = 45). Strand-shaped molten resin was discharged. At that time, the coloring agent was added together with the raw materials, and the time when the coloring to the extrudate was maximized was measured as the residence time. The residence times are shown in Tables 3, 8 and 9. In addition, the screw configuration is D, and a general kneading disk is connected for Lk / D = 5.0 minutes from a position of L / D = 13 to form a kneading zone. Further, a reverse screw zone with L / D = 0.5 was provided downstream of the 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 11%. Furthermore, at the position of L / D = 25, a notch-type mixing screw with a single thread and a screw pitch of 0.25D and a number of notches of 13 per pitch is connected to the mixing zone by Lm / D = 2.0 minutes. 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 4%. Further, in the notch type mixing screw constituting the mixing zone, the ratio (%) of the screw that is in the screw rotation direction opposite to the rotation direction of the screw shaft was 100%. The vent vacuum zone was provided at a position of L / D = 38, and volatile components were removed at a gauge pressure of −0.1 MPa. The molten resin discharged from the 4 mmφ × 23 hole through the die head was measured for the resin temperature with a thermometer, and the presence or absence of the gelled product was visually confirmed. Thereafter, the discharged resin was drawn in a strand shape, passed through a cooling bath, cooled, and cut while being taken out by a pelletizer, thereby obtaining a pellet-like sample of the thermoplastic resin composition. The sample was vacuum-dried at 80 ° C. for 12 hours or more, and then the above-described injection molding was carried out for various evaluations. Tables 3, 8, and 9 show the kneading conditions and various evaluation results.

Comparative Examples 5, 6, 8-19, 22, 23, 26, 27, 31-35
While mixing with the composition shown in Tables 3, 6, 7, 8, 9, and 11, and performing nitrogen flow, the screw diameter is 65 mm, the screw is the same direction of L / D = 45 of the two screws of the double thread Using a rotary fully meshed twin screw extruder (manufactured by Nippon Steel Works, TEX-65αII), melt kneading was performed at the cylinder temperatures, screw rotation speeds, and extrusion amounts shown in Tables 3, 6, 7, 8, 9, and 11. The strand-shaped molten resin was discharged from the discharge port (L / D = 45). 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 times are shown in Tables 3, 6, 7, 8, 9, and 11. The screw configuration was E, and a general kneading disk was connected for Lk / D = 5.0 minutes from the position of L / D = 13 to form a kneading zone. Further, a reverse screw zone with L / D = 0.5 was provided downstream of the 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 11%. Furthermore, at the positions of L / D = 23, 28, 33, a notch type mixing screw having a single thread screw with a screw pitch of 0.25D and a number of notches of 13 per pitch, respectively, is Lm / D = 2.0 minutes. They were connected to form three mixing zones. 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 13%. Further, in the notch type mixing screw constituting the mixing zone, the ratio (%) of the screw that is in the screw rotation direction opposite to the rotation direction of the screw shaft was 100%. The vent vacuum zone was provided at a position of L / D = 38, and volatile components were removed at a gauge pressure of −0.1 MPa. The molten resin discharged from the 4 mmφ × 23 hole through the die head was measured for the resin temperature with a thermometer, and the presence or absence of the gelled product was visually confirmed. Thereafter, the discharged resin was drawn in a strand shape, passed through a cooling bath, cooled, and cut while being taken out by a pelletizer, thereby obtaining a pellet-like sample of the thermoplastic resin composition. The sample was vacuum-dried at 80 ° C. for 12 hours or more, and then the above-described injection molding was carried out for various evaluations. Tables 3, 6, 7, 8, 9, and 11 show the kneading conditions and various evaluation results.

  From Examples 1 to 16, when preparing a thermoplastic resin composition comprising a thermoplastic resin (A) and a resin (B) having a reactive functional group, a melt-kneaded mixture was melted and kneaded while stretching and flowing. By melting and kneading, even if the throughput is increased with a general-purpose large extruder with a short L / D, the elastic modulus decreases as the tensile speed increases while suppressing resin degradation (discharge resin temperature) due to heat generation. It can be seen that a thermoplastic resin composition having unique viscoelastic properties such as increased elongation at break, high impact properties, and high heat resistance can be obtained.

  Further, from the comparison between Example 2 and Examples 3 and 4, comparison between Example 12 and Example 14, and comparison between Example 13 and Example 15, the kneading is carried out with the cylinder setting temperature of the mixing zone being lowered, thereby generating heat. It is possible to improve the reaction rate of (A) and (B) while further suppressing resin deterioration (discharged resin temperature) due to, and decrease in elastic modulus and increase in elongation at break when the tensile speed is increased, impact resistance It can be seen that the property and heat resistance can be increased.

  On the other hand, in Comparative Examples 1 and 2, since melt kneading is performed with a screw configuration using a general kneading disk, if the throughput is increased with a large extruder, the resin deterioration due to heat generation becomes significant (the discharge resin temperature is reduced). In addition, it can be seen that the unique viscoelastic properties as in Examples do not appear, and the impact resistance and heat resistance are low.

  In Comparative Examples 3 to 6, melt kneading is performed with a screw configuration using a general kneading disk and a notched mixing screw, but there is no extension flow zone, and the ratio of the mixing zone to the total length is small. Because of the small size, if the throughput is increased with a large extruder, resin deterioration due to heat generation becomes significant (the discharge resin temperature becomes high), and the unique viscoelastic properties as in the examples do not appear. It can be seen that the impact resistance and heat resistance are also low. Further, from the comparison between Comparative Example 3 and Comparative Example 4 and the comparison between Comparative Example 5 and Comparative Example 6, in these screw configurations, when the cylinder set temperature in the mixing zone is lowered, the discharge resin temperature is lowered, but (A) and ( It can be seen that the reaction rate of B) decreases and the elongation at break, impact resistance, and heat resistance at the time of 1000 mm / min tension decrease.

  A notch-type mixing screw with a single-thread screw with a screw pitch length of 0.1D to 0.5D and a number of notches of 8 to 16 per pitch can increase the resin filling rate. Connecting the notch-type mixing screw to form a mixing zone of Lm / D = 4 to 20 and lowering the cylinder set temperature at that portion is effective for lowering the resin temperature because the molten resin can be cooled.

  Generally, when the resin temperature decreases, the reaction rate of (A) and (B) decreases. However, in the examples, even if the cylinder set temperature of the mixing zone is lowered and the resin temperature is lowered, the reaction can proceed in reverse, and the amount of decrease in elastic modulus and the amount of increase in breaking elongation when the tensile speed is increased. The impact resistance and heat resistance can be increased. This is because in the screw configurations A and B of the embodiment, a zone for melting and kneading while extending and flowing in the first half is provided to promote the reaction of (A) and (B), so that the melting when passing through the mixing zone When the resin temperature is lowered and the melt viscosity is further increased, the shear due to the notch of the notch mixing screw works effectively, and the reaction is more than compensated for the decrease in the reaction rate due to the resin temperature decrease. I think that it will be promoted. This effect is a feature of a screw configuration in which a mixing zone including a notch mixing screw is provided after the extension flow zone.

  On the other hand, in the screw configurations D and E of the comparative examples, since the first half is melt kneaded with a general kneading disk, the reaction rate of (A) and (B) is low, and the melt viscosity when passing through the mixing zone is low. . Therefore, the shear due to the notch of the notch mixing screw is 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, impact resistance, and heat resistance at 1000 mm / min are reduced. I think so.

  Since Comparative Example 7 is melt-kneaded using the unmodified PE copolymer (E) instead of the resin (B) having a reactive functional group, unique viscoelastic properties such as those in the examples are exhibited. No impact resistance and heat resistance are found.

  Even if various thermoplastic resins (A) are used from Examples 17 to 28, general-purpose large-scale extrusion with a short L / D is obtained by melt-kneading with a notch mixing screw after melt-kneading while stretching and flowing. Suppressing resin degradation (discharged resin temperature) due to heat generation even when the processing amount is increased by the machine, the elastic modulus decreases and the breaking elongation increases as the tensile speed increases, and the high impact It can be seen that a thermoplastic resin composition having good heat resistance and high heat resistance can be obtained.

  On the other hand, in Comparative Examples 8 to 19, melt kneading is performed with a screw configuration using a general kneading disk and a notched mixing screw, but there is no extension flow zone, and the ratio to the total length of the mixing zone is small. Due to the small size of the mixing zone, if the throughput is increased with a large extruder, the resin deterioration due to heat generation becomes significant (the temperature of the discharged resin increases), and the unique viscoelastic properties as in the examples are manifested. No impact resistance and heat resistance are found.

  From the comparison of Examples 29 to 32 and Comparative Examples 20 to 23, in the example in which melt kneading was performed while melt-kneading while stretching and flowing, and the melt-kneading was performed with a notch mixing screw, the throughput was reduced with a general-purpose large extruder having a short L / D. It can be seen that a thermoplastic resin composition having high impact properties and high heat resistance can be obtained while suppressing deterioration of the resin due to heat generation (discharged resin temperature) even if the amount is increased. In particular, in Examples 30 and 32 in which the cylinder setting temperature of the mixing zone was lowered and kneaded, it can be seen that a thermoplastic resin composition having higher impact and heat resistance could be obtained.

  From comparison between Examples 33 to 38 and Comparative Examples 24 to 27, the thermoplastic resin (A), a thermoplastic resin (C) different from the thermoplastic resin (A), and a compound (D) having a reactive functional group are included. When producing thermoplastic resin compositions, even if the throughput is increased with a general-purpose large extruder with a short L / D by melting and kneading with a notch type mixing screw after melt-kneading while stretching and flowing, it generates heat. It can be seen that a thermoplastic resin composition having high impact resistance and high heat resistance can be obtained while suppressing resin deterioration (discharged resin temperature) due to. In particular, in Examples 34, 36 and 38 where the cylinder set temperature in the mixing zone was lowered, it was found that a thermoplastic resin composition having higher impact properties and higher heat resistance could be obtained.

  From the comparison between Examples 39 to 54 and Comparative Examples 28 to 35, it is also possible to reduce the throughput with a general-purpose large extruder having a short L / D by melt-kneading with a notch mixing screw after melt-kneading while stretching and flowing. It can be seen that a thermoplastic resin composition having high impact properties and high heat resistance can be obtained while suppressing resin deterioration (discharged resin temperature) due to heat generation even when the amount is increased. In particular, in Examples 44 to 48 and 52 to 54 in which the cylinder setting temperature of the mixing zone was lowered and kneaded, it can be seen that a thermoplastic resin composition having higher impact and heat resistance can be obtained.

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

Claims (21)

When the thermoplastic resin composition of the following (I) or (II) is produced by an extruder, the thermoplastic resin composition is melt-kneaded with a notched mixing screw after being melt-kneaded while stretching and flowing. In the manufacturing method , the ratio of the total length of the melt-kneading zone (extension flow zone) while stretching and flowing with respect to the full length of the screw of the extruder is 5 to 40%, and the cutting with respect to the full length of the screw of the extruder A method for producing a thermoplastic resin composition, characterized in that the ratio of the total length of the zone (mixing zone) for melting and kneading with a notched mixing screw is 15 to 40% .
(I) Thermoplastic resin (A) and thermoplastic resin composition formed by blending resin (B) having a reactive functional group (II) Thermoplastic resin (A), heat different from thermoplastic resin (A) A thermoplastic resin composition comprising a plastic resin (C) and a compound (D) having a reactive functional group. The inflow effect pressure drop before and after the extension flow zone is 10 to 1000 kg / cm. ² The method for producing a thermoplastic resin composition according to claim 1, wherein: The thermoplastic resin composition according to claim 1 or 2, wherein Lk / D = 2 to 10 is satisfied, where Lk is a length of one extension flow zone in the screw of the extruder and D is a screw diameter. Manufacturing method. The mixing zone is configured by connecting notch type mixing screws having a single thread and a screw pitch length of 0.1D to 0.5D and a notch number of 8 to 16 per pitch. The manufacturing method of the thermoplastic resin composition in any one of Claims 1-3 characterized by the above-mentioned. The length of one mixing zone is set to Lm, and the screw diameter is set to D, Lm / D = 4-20 is satisfy | filled, The thermoplastic resin composition in any one of Claims 1-4 characterized by the above-mentioned. Method. The said mixing zone is provided in two or more places, The manufacturing method of the thermoplastic resin composition in any one of Claims 1-5 characterized by the above-mentioned. The thermoplasticity according to any one of claims 1 to 6, wherein 70% or more of the notch-type mixing screw constituting the mixing zone is a screw-turning direction opposite to a rotation direction of the screw shaft. A method for producing a resin composition. 8. The melt kneading is performed while satisfying Ck−Cm ≧ 40, where Ck is an extruder cylinder set temperature in the extension flow zone and Cm is an extruder cylinder set temperature in the mixing zone. The manufacturing method of the thermoplastic resin composition as described in any one of. 9. The melt kneading is performed while satisfying Ck−Cm ≧ 60, where Ck is an extruder cylinder set temperature in the extension flow zone and Cm is an extruder cylinder set temperature in the mixing zone. The manufacturing method of the thermoplastic resin composition as described in any one of. The thermoplastic resin composition according to any one of claims 1 to 9, wherein the thermoplastic resin composition is melt kneaded using a twin screw extruder having a ratio L / D of a screw length L to a screw diameter D of less than 50. Manufacturing method. The thermoplastic resin (A) is at least one selected from polyamide resin, polyester resin, polyphenylene sulfide resin, polyacetal resin, styrene resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, and polypropylene resin. The manufacturing method of the thermoplastic resin composition in any one of Claims 1-10. The thermoplastic resin (C) is different from the thermoplastic resin (A), from polyamide resin, polyester resin, polyphenylene sulfide resin, polyacetal resin, styrene resin, polyphenylene oxide resin, polycarbonate resin, polylactic acid resin, and polypropylene resin. It is at least 1 sort (s) chosen, The manufacturing method of the thermoplastic resin composition in any one of Claims 1-11 characterized by the above-mentioned. The resin (B) having a reactive functional group is at least one selected from a rubbery polymer having a reactive functional group and a polyphenylene oxide resin having a reactive functional group. 12. A process for producing a thermoplastic resin composition according to any one of 12 above. The reactive functional group of the resin (B) having a 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 manufacturing method of the thermoplastic resin composition in any one of Claims 1-13. The reactive functional group of the compound (D) having a 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 manufacturing method of the thermoplastic resin composition in any one of Claims 1-12. The method for producing a thermoplastic resin composition according to any one of claims 1 to 15, wherein the thermoplastic resin (A) is a polyamide resin. In the tensile test, the obtained thermoplastic resin composition has E (V1) and E (V2) when the tensile elastic modulus is V1 and V2, and when V1 <V2, E (V1)> E ( It is V2), The manufacturing method of the thermoplastic resin composition in any one of Claims 1-16 characterized by the above-mentioned. In the tensile test, when the obtained thermoplastic resin composition has tensile elongation at break of ε (V1) and ε (V2) at tensile speeds V1 and V2, ε (V1) <ε when V1 <V2. It is (V2), The manufacturing method of the thermoplastic resin composition in any one of Claims 1-17 characterized by the above-mentioned. The thermoplastic resin composition obtained by the manufacturing method in any one of Claims 1-18. A molded article comprising the thermoplastic resin composition according to claim 19. The molded article according to claim 20, wherein the molded article is at least one selected from a film, a sheet, and a fiber.

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