JP2009041008A - Thermoplastic resin composition and molded article thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition which contains no bleeding-out component, the mechanical properties of which are not deteriorated but which has improved fluidity and to provide molded articles made from the thermoplastic resin composition. <P>SOLUTION: The thermoplastic resin composition is composed of 90-99.9 wt.% thermoplastic resin (a) and 0.1-10 wt.% fluidity improving agent (b) and further contains a resin additive (c) of 0.01-5 parts weight on the basis of 100 parts weight resin composition. Such a phase structure is observed by an electron microscope that the fluidity improving agent (b) particles of 0.5-200 nm particle size are dispersed in a phase of the thermoplastic resin (a). The interfacial tension between the thermoplastic resin (a) and the fluidity improving agent (b) is ≥0.4 mN/m. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a thermoplastic resin composition and a molded article comprising the same, and more particularly to a thermoplastic resin composition having a significantly improved fluidity and a molded article comprising the same without causing bleed-out or deterioration of mechanical properties. is there.

  Thermoplastic resins, especially engineering plastics having excellent mechanical properties and thermal properties, are used in various applications by taking advantage of their excellent properties. Polyamide resin, which is a kind of engineering plastic, has a good balance between mechanical properties and toughness. Therefore, it is used for various electrical and electronic parts, mechanical parts and automobile parts mainly for injection molding. Polybutylene terephthalate (hereinafter referred to as PBT) Is widely used as a material for industrial molded products such as connectors, relays, switches and the like of automobiles and electrical / electronic devices, taking advantage of moldability, heat resistance, mechanical properties and chemical resistance.

However, in recent years, improvement in fluidity has been demanded as a material to be used in order to cope with the reduction in thickness of molded products accompanying the modularization and weight reduction of large automobile parts. On the other hand, it is known that the fluidity is improved by mixing a liquid crystalline resin with a thermoplastic resin, and various studies have been made so far. Patent Documents 1 to 5 describe resin compositions using hyperbranched polymers, which have a certain degree of fluidity improvement effect. In order to respond, further development of good fluidization methods is required.
International Publication No. 2005/75563 (Claims) International Publication No. 2005/75565 (Claims) International Publication No. 2006/42705 (Claims) European Patent No. 142360 (claim) JP 2007-146123 A (Claims)

  An object of the present invention is to provide a thermoplastic resin composition having improved fluidity and no molded product comprising the same without causing bleed-out or deterioration of mechanical properties.

  The present invention employs the following means as a result of intensive studies to solve the above problems.

That is, the present invention is as follows.
1. With respect to 100 parts by weight of the resin composition comprising 90 to 99.9% by weight of the thermoplastic resin (a) and 0.1 to 10% by weight of the fluidity improver (b), the resin additive (c) 0.01 to A phase structure comprising a resin composition containing 5 parts by weight and having a fluidity improver (b) observed by an electron microscope dispersed in a thermoplastic resin (a) with a dispersed particle size of 0.5 to 200 nm. A thermoplastic resin composition characterized by being formed and having an interfacial tension between the thermoplastic resin (a) and the fluidity improver (b) of 0.4 mN / m or more.
2. 2. The thermoplastic resin composition according to 1, wherein the fluidity improver (b) is at least one selected from a branched polymer and a cyclic compound.
3. The thermoplastic resin (a) is at least one selected from polyamide resins, polyester resins, polyphenylene sulfide resins, polycarbonate resins, polyphenylene ether resins, and polyolefin resins. Thermoplastic resin composition.
4). 4. The thermoplastic resin composition according to 3, wherein the thermoplastic resin (a) is at least one selected from a polyamide resin, a polyester resin, and a polyphenylene sulfide resin.
5. The thermoplastic resin composition according to any one of 1 to 4, wherein the resin additive (c) is at least one selected from a hindered phenol compound and a phosphorus compound.
6.1 A molded article obtained by melt-molding the thermoplastic resin composition according to any one of 1 to 5.
7. The molded article according to claim 6, wherein the melt molding is any one selected from injection molding, injection compression molding, and compression molding.

According to the present invention, it is possible to provide a thermoplastic resin composition excellent in fluidity and highly balanced in mechanical properties and impact resistance without problems such as bleeding out of a good fluidizing component. The thermoplastic resin composition of the present invention is a molded article or sheet having excellent surface appearance (color tone) and mechanical properties by a molding method such as normal injection molding, injection compression molding, compression molding, extrusion molding, press molding, or the like. It can be processed into pipes, films, fibers and the like.

  The thermoplastic resin (a) used in the present invention may be any resin that can be melt-molded. For example, polyamide resin, polyester resin, polyacetal resin, polycarbonate resin, polyphenylene ether resin, polyphenylene ether resin may be used as another resin. Modified polyphenylene ether resin, polyarylate resin, polysulfone resin, polyphenylene sulfide resin, polyethersulfone resin, polyketone resin, polyetherketone resin, polyetheretherketone resin, polyimide resin, polyamideimide modified by blending or graft polymerization with Resin, polyetherimide resin, thermoplastic polyurethane resin, high density polyethylene resin, low density polyethylene resin, linear low density polyethylene resin, polypropylene resin, polymethyl Pentene resin, cyclic olefin resin, poly 1-butene resin, poly 1-pentene resin, polymethylpentene resin, ethylene / α-olefin copolymer, (ethylene and / or propylene) and (unsaturated carboxylic acid and / or A copolymer of (unsaturated carboxylic acid ester), (ethylene and / or propylene) and (unsaturated carboxylic acid and / or copolymer of unsaturated carboxylic acid ester) at least part of the carboxyl group is metallized Polyolefin obtained, block copolymer of conjugated diene and vinyl aromatic hydrocarbon, hydride of block copolymer of conjugated diene and vinyl aromatic hydrocarbon, polyvinyl chloride resin, polystyrene resin, polyacrylate resin, poly Acrylic resin such as methacrylic ester resin, acrylonitrile Acrylonitrile-based copolymer, acrylonitrile-butanediene-styrene (ABS) resin, acrylonitrile-styrene (AS) resin, cellulose resin such as cellulose acetate, vinyl chloride / ethylene copolymer, vinyl chloride / vinyl acetate Examples thereof include a copolymer, an ethylene / vinyl acetate copolymer, and a saponified ethylene / vinyl acetate copolymer, which may be used alone or in combination of two or more as a polymer alloy. It can also be modified with at least one compound selected from unsaturated carboxylic acids, acid anhydrides or derivatives thereof, among which polyamide resins, polyester resins, polyphenylenes are preferred in terms of heat resistance, moldability and mechanical properties. Sulfide resin, polycarbonate resin, polyphenylene ether Le resins, polyolefin resins are preferred, particularly preferably a polyamide resin, a polyester resin, polyphenylene sulfide resin.

  In the present invention, preferred polyamide resins are polyamides mainly composed of amino acids, lactams or diamines and dicarboxylic acids. Representative examples of the main constituents 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, pentamethylenediamine , Hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, Metaxylylenediamine, paraxylylenediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, Bis (4-aminosi Chlohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, aliphatic, alicyclic, aromatic Diamines, and adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid Examples include aliphatic, alicyclic, and aromatic dicarboxylic acids such as acids, 2,6-naphthalenedicarboxylic acid, hexahydroterephthalic acid, and hexahydroisophthalic acid. In the present invention, nylon derived from these raw materials Homopolymers or copolymers, each alone or in the form of a mixture It can be used.

  In the present invention, a particularly useful polyamide resin is a polyamide resin having a melting point of 150 ° C. or more and excellent in heat resistance and strength. Specific examples include polycaproamide (nylon 6), polyhexamethylene adipamide. (Nylon 66), polypentamethylene adipamide (nylon 56), polyhexamethylene sebamide (nylon 610), polyhexamethylene dodecane (nylon 612), polyundecanamide (nylon 11), polydodecanamide (nylon) 12), polycaproamide / polyhexamethylene adipamide copolymer (nylon 6/66), polycaproamide / polyhexamethylene terephthalamide copolymer (nylon 6 / 6T), polyhexamethylene adipamide / polyhexamethylene terephthalamide Copolymer (Nai 66 / 6T), polyhexamethylene adipamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6I), polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 6T / 6I), polyhexamethylene terephthalamide / Polydodecanamide copolymer (nylon 6T / 12), polyhexamethylene adipamide / polyhexamethylene terephthalamide / polyhexamethylene isophthalamide copolymer (nylon 66 / 6T / 6I), polyxylylene adipamide (nylon XD6) Polyhexamethylene terephthalamide / poly-2-methylpentamethylene terephthalamide copolymer (nylon 6T / M5T), polynonamethylene terephthalamide (nylon 9T) and Mixtures of al and the like.

  Among these, preferable polyamide resins include nylon 6, nylon 66, nylon 12, nylon 610, nylon 6/66 copolymer, nylon 6T / 66 copolymer, nylon 6T / 6I copolymer, nylon 6T / 12, nylon 6T / 6 copolymer, and the like. The copolymer which has the hexamethyl terephthalamide unit of this can be mentioned, Especially preferably, nylon 6 can be mentioned. Furthermore, it is also practically preferable to use these polyamide resins as a mixture depending on necessary properties such as impact resistance and molding processability.

  The degree of polymerization of these polyamide resins is not particularly limited, but the relative viscosity measured at 25 ° C. in a 98% concentrated sulfuric acid solution having a sample concentration of 0.01 g / ml is in the range of 1.5 to 7.0. Particularly preferred is a polyamide resin in the range of 2.0 to 6.0.

  Moreover, a copper compound is preferably used in the polyamide resin of the present invention in order to improve long-term heat resistance. Specific examples of copper compounds include cuprous chloride, cupric chloride, cuprous bromide, cupric bromide, cuprous iodide, cupric iodide, cupric sulfate, nitric acid. Cupric, copper phosphate, cuprous acetate, cupric acetate, cupric salicylate, cupric stearate, cupric benzoate and inorganic copper halides and xylylenediamine, 2-mercaptobenzimidazole And complex compounds such as benzimidazole. Of these, monovalent copper compounds, particularly monovalent copper halide compounds are preferred, and cuprous acetate, cuprous iodide, and the like can be exemplified as particularly suitable copper compounds. The addition amount of the copper compound is usually preferably 0.01 to 2 parts by weight and more preferably 0.015 to 1 part by weight with respect to 100 parts by weight of the polyamide resin. If the amount added is too large, liberation of metallic copper occurs during melt molding, and the value of the product is reduced by coloring. In the present invention, an alkali halide can be added in combination with a copper compound. Examples of the alkali halide compound include lithium chloride, lithium bromide, lithium iodide, potassium chloride, potassium bromide, potassium iodide, sodium bromide and sodium iodide. Sodium chloride is particularly preferred.

  The polyester resin preferable in the present invention is a polymer having an ester bond in the main chain and not exhibiting melt liquid crystallinity, and (i) a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof ( (B) A polymer or copolymer having at least one selected from hydroxycarboxylic acid or an ester-forming derivative thereof and (c) lactone as a main structural unit.

  Examples of the dicarboxylic acid or ester-forming derivative thereof include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, Aromatic dicarboxylic acids such as 4,4'-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, oxalic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malon Examples thereof include aliphatic dicarboxylic acids such as acid, glutaric acid and dimer acid, alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid, and ester-forming derivatives thereof.

  Examples of the diol or ester-forming derivatives thereof include aliphatic glycols having 2 to 20 carbon atoms, that is, ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1, Aroma such as 6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol or the like, or a long chain glycol having a molecular weight of 200 to 100,000, that is, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc. Group dioxy compounds, namely 4,4′-dihydroxybiphenyl, hydroquinone, t-butylhydroquinone, bisphenol A, bisphenol S, bisphenol F and these And ester forming derivatives thereof.

  Polymers or copolymers containing dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as structural units include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyhexylene terephthalate. , Polyethylene isophthalate, polypropylene isophthalate, polybutylene isophthalate, polycyclohexanedimethylene isophthalate, polyhexylene isophthalate, polyethylene naphthalate, polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / Terephthalate, polybutylene isophthalate / terephthalate, poly Tylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate, polybutylene terephthalate / decane dicarboxylate, polyethylene terephthalate / cyclohexanedimethylene terephthalate, polyethylene terephthalate / 5-sodium sulfoisophthalate, polypropylene terephthalate / 5-sodium sulfo Isophthalate, polybutylene terephthalate / 5-sodium sulfoisophthalate, polyethylene terephthalate / polyethylene glycol, polypropylene terephthalate / polyethylene glycol, polybutylene terephthalate / polyethylene glycol, polyethylene terephthalate / polytetramethylene glycol, polypropylene Terephthalate / polytetramethylene glycol, polybutylene terephthalate / polytetramethylene glycol, polyethylene terephthalate / isophthalate / polytetramethylene glycol, polypropylene terephthalate / isophthalate / polytetramethylene glycol, polybutylene terephthalate / isophthalate / polytetramethylene glycol , Polyethylene terephthalate / succinate, polypropylene terephthalate / succinate, polybutylene terephthalate / succinate, polyethylene terephthalate / adipate, polypropylene terephthalate / adipate, polybutylene terephthalate / adipate, polyethylene terephthalate / sebacate, polypropylene terephthalate / sebacate, poly Fragrances such as butylene terephthalate / sebacate, polyethylene terephthalate / isophthalate / adipate, polypropylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / succinate, polybutylene terephthalate / isophthalate / adipate, polybutylene terephthalate / isophthalate / sebacate Group polyester resin, polyethylene oxalate, polypropylene oxalate, polybutylene oxalate, polyethylene succinate, polypropylene succinate, polybutylene succinate, polyethylene adipate, polypropylene adipate, polybutylene adipate, polyneopentyl glycol adipate, polyethylene sebacate, Polypropylene Sebakei , Polybutylene sebacate, polyethylene succinate / adipate, polypropylene succinate / adipate, aliphatic polyester resins such as polybutylene succinate / adipate and the like.

  Examples of the hydroxycarboxylic acid include glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, hydroxybenzoic acid, p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, and these Examples of the polymer or copolymer having these as a structural unit include polyglycolic acid, polylactic acid, polyglycolic acid / lactic acid, polyhydroxybutyric acid / β-hydroxybutyric acid / β-hydroxyyoshide. Aliphatic polyester resins such as herbic acid can be mentioned.

  Examples of the lactone include caprolactone, valerolactone, propiolactone, undecalactone, and 1,5-oxepan-2-one. Examples of the polymer or copolymer having these as structural units include polycaprolactone. , Polyvalerolactone, polypropiolactone, polycaprolactone / valerolactone, and the like.

  Among these, a polymer or copolymer having a main structural unit of dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative is preferable, and aromatic dicarboxylic acid or its ester-forming derivative and aliphatic diol. Alternatively, a polymer or copolymer having an ester-forming derivative as a main structural unit is more preferable, and an aliphatic diol selected from terephthalic acid or an ester-forming derivative thereof and ethylene glycol, propylene glycol, or butanediol or an ester-forming property thereof. A polymer or copolymer having a derivative as a main structural unit is more preferable, among which polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate. Aromatic polyester resins such as polypropylene naphthalate, polybutylene naphthalate, polyethylene isophthalate / terephthalate, polypropylene isophthalate / terephthalate, polybutylene isophthalate / terephthalate, polyethylene terephthalate / naphthalate, polypropylene terephthalate / naphthalate, polybutylene terephthalate / naphthalate Are particularly preferred, and polybutylene terephthalate is most preferred.

In the present invention, the ratio of terephthalic acid or its ester-forming derivative to the total dicarboxylic acid in the polymer or copolymer having the dicarboxylic acid or its ester-forming derivative and diol or its ester-forming derivative as the main structural unit is It is preferably 30 mol% or more, and more preferably 40 mol% or more.
In the present invention, it is preferable to use two or more kinds of polyester resins in terms of hydrolysis resistance.

  The amount of carboxyl end groups of the polyester resin used in the present invention is not particularly limited, but is preferably 50 eq / t or less, more preferably 30 eq / t or less in terms of hydrolysis resistance and heat resistance. It is more preferably 20 eq / t or less, and particularly preferably 10 eq / t or less. The lower limit is 0 eq / t. In the present invention, the amount of carboxyl end groups of the polyester resin is a value measured by dissolving in an o-cresol / chloroform solvent and titrating with ethanolic potassium hydroxide.

  The amount of vinyl end groups of the polyester resin used in the present invention is not particularly limited, but is preferably 15 eq / t or less, more preferably 10 eq / t or less, and more preferably 5 eq / t or less in terms of color tone. More preferably. The lower limit is 0 eq / t. In the present invention, the amount of vinyl end groups of the polyester resin is a value measured by 1H-NMR using a deuterated hexafluoroisopropanol solvent.

  The amount of hydroxyl terminal groups of the polyester resin used in the present invention is not particularly limited, but is preferably 50 eq / t or more, more preferably 80 eq / t or more, and 100 eq / t or more in terms of moldability. More preferably, it is 120 eq / t or more. The upper limit is not particularly limited, but is 180 eq / t. In the present invention, the polyester resin has a value measured by 1H-NMR using a deuterated hexafluoroisopropanol solvent.

The viscosity of the polyester resin used in the present invention is not particularly limited, but the intrinsic viscosity when the o-chlorophenol solution is measured at 25 ° C. is preferably in the range of 0.36 to 1.60 dl / g. A range of 50 to 1.25 dl / g is more preferable.
The molecular weight of the polyester resin used in the present invention is preferably in the range of 50,000 to 500,000 in weight average molecular weight (Mw), more preferably in the range of 100,000 to 300,000 in terms of heat resistance. More preferably, it is in the range of 10,000 to 250,000.

  The production method of the polyester resin used in the present invention is not particularly limited and can be produced by a known polycondensation method or ring-opening polymerization method, and may be either batch polymerization or continuous polymerization. Either a transesterification reaction or a reaction by direct polymerization can be applied, but continuous polymerization can be performed in that the amount of carboxyl end groups can be reduced and the effect of improving fluidity and hydrolysis resistance is increased. Direct polymerization is preferred from the viewpoint of cost.

  When the polyester resin used in the present invention is a polymer or copolymer obtained by a condensation reaction mainly comprising a dicarboxylic acid or an ester-forming derivative thereof and a diol or an ester-forming derivative thereof, a dicarboxylic acid Alternatively, an ester-forming derivative thereof and a diol or an ester-forming derivative thereof can be produced by an esterification reaction or an ester exchange reaction and then a polycondensation reaction. In order to effectively advance the esterification reaction or transesterification reaction and the polycondensation reaction, it is preferable to add a polymerization reaction catalyst during these reactions. Specific examples of the polymerization reaction catalyst include methyl ester of titanic acid, Organic titanium such as tetra-n-propyl ester, tetra-n-butyl ester, tetraisopropyl ester, tetraisobutyl ester, tetra-tert-butyl ester, cyclohexyl ester, phenyl ester, benzyl ester, tolyl ester, or mixed esters thereof Compound, dibutyltin oxide, methylphenyltin oxide, tetraethyltin, hexaethylditin oxide, cyclohexahexylditin oxide, didodecyltin oxide, triethyltin hydroxide, Riphenyltin hydroxide, triisobutyltin acetate, dibutyltin diacetate, diphenyltin dilaurate, monobutyltin trichloride, dibutyltin dichloride, tributyltin chloride, dibutyltin sulfide and butylhydroxytin oxide, methylstannic acid, ethylstannic acid, butylstannon Examples include tin compounds such as alkylstannic acids such as acids, zirconia compounds such as zirconium tetra-n-butoxide, antimony compounds such as antimony trioxide and antimony acetate, and among these, organic titanium compounds and tin compounds include Further, titanic acid tetra-n-propyl ester, tetra-n-butyl ester and tetraisopropyl ester are preferred. Properly, tetra -n- butyl ester of titanic acid is especially preferred. These polymerization reaction catalysts may be used alone or in combination of two or more. The addition amount of the polymerization reaction catalyst is preferably in the range of 0.005 to 0.5 parts by weight, and 0.01 to 0.2 parts by weight with respect to 100 parts by weight of the polyester resin in terms of mechanical properties, moldability and color tone. A range of parts is more preferred.

  As the polyphenylene sulfide resin preferably used in the present invention, a polymer having a repeating unit represented by the following structural formula can be used.

  From the viewpoint of heat resistance, a polymer containing 70 mol% or more, more preferably 90 mol% or more of the repeating unit represented by the structural formula is preferable. In addition, in the polyphenylene sulfide resin, about less than 30 mol% of the repeating units may be composed of repeating units having any of the following structures. Of these, a p-phenylene sulfide / m-phenylene sulfide copolymer (m-phenylene sulfide unit of 20% or less) can be preferably used because it has both moldability and barrier properties.

  Such a polyphenylene sulfide resin can be produced in high yield by recovering and post-treating a polyphenylene sulfide resin obtained by reacting a polyhalogen aromatic compound and a sulfiding agent in a polar organic solvent. Specifically, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or a relatively molecular weight described in JP-B-52-12240 and JP-A-61-7332 is disclosed. It can also be produced by a method for obtaining a large polymer. Crosslinking / high molecular weight of the polyphenylene sulfide resin obtained as described above by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or under reduced pressure, washing with organic solvent, hot water, acid aqueous solution, etc., acid anhydride It can also be used after various treatments such as activation with functional group-containing compounds such as products, amines, isocyanates, functional group-containing disulfide compounds.

  Specific methods for crosslinking / high molecular weight polyphenylene sulfide resin by heating include an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. Thus, a method of heating at a predetermined temperature in a heating container until a desired melt viscosity is obtained can be exemplified. The heat treatment temperature is usually 170 to 280 ° C, preferably 200 to 270 ° C. The heat treatment time is usually selected from 0.5 to 100 hours, preferably from 2 to 50 hours. By controlling both of these, the target viscosity level can be obtained. The heat treatment apparatus may be a normal hot air drier, or a heating apparatus with a rotary type or a stirring blade, but for efficient and more uniform processing, a heating type with a rotary type or a stirring blade is used. It is preferable to use an apparatus.

  As a specific method for heat-treating the polyphenylene sulfide resin under an inert gas atmosphere such as nitrogen or under reduced pressure, a heat treatment temperature of 150 to 280 ° C., preferably 200, under an inert gas atmosphere such as nitrogen or under reduced pressure. A method of heat treatment at ˜270 ° C. and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours can be exemplified. The heat treatment apparatus may be a normal hot air drier, or a heating apparatus with a rotary type or a stirring blade, but for efficient and more uniform processing, a heating type with a rotary type or a stirring blade is used. More preferably, an apparatus is used.

  The polyphenylene sulfide resin used in the present invention is preferably a polyphenylene sulfide resin that has been subjected to a washing treatment. Specific examples of the cleaning treatment include acid aqueous solution washing treatment, hot water washing treatment, and organic solvent washing treatment. These treatments may be used in combination of two or more methods.

  The following method can be illustrated as a specific method when the polyphenylene sulfide resin is washed with an organic solvent. That is, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing polyphenylene sulfide resin. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, and dimethylacetamide, dimethyl Sulfoxide such as sulfoxide, dimethylsulfone, sulfone solvent, ketone solvent such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvent such as dimethyl ether, dipropyl ether, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, Halogenated solvents such as dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol , Propylene glycol, phenol, cresol, alcohols such as polyethylene glycol, phenolic solvents, benzene, toluene, and aromatic hydrocarbon solvents such as xylene. Among these organic solvents, use of N-methylpyrrolidone, acetone, dimethylformamide, chloroform or the like is preferable. These organic solvents are used alone or in combination of two or more. As a method of washing with an organic solvent, there is a method of immersing a polyphenylene sulfide resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning polyphenylene sulfide resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. The polyphenylene sulfide resin that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent.

  The following method can be illustrated as a specific method when the polyphenylene sulfide resin is washed with hot water. That is, it is preferable that the water used is distilled water or deionized water in order to develop a preferable chemical modification effect of the polyphenylene sulfide resin by hot water washing. The operation of the hot water treatment is usually performed by charging a predetermined amount of polyphenylene sulfide resin into a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of the polyphenylene sulfide resin and water is preferably as much as possible, but usually a bath ratio of 200 g or less of polyphenylene sulfide resin is selected per liter of water.

  Further, when washing with hot water, it is preferable to use an aqueous solution containing a Group II metal element of the periodic table. The aqueous solution containing a Group II metal element of the periodic table is obtained by adding a water-soluble salt containing a Group II metal element of the periodic table to the water. The concentration of the water-soluble salt having a Group II metal element in the periodic table with respect to water is preferably in the range of about 0.001 to 5% by weight.

Examples of preferable metal elements among Group II metal elements of the periodic table used herein include Ca, Mg, Ba and Zn. Other anions include acetate ions, halide ions, hydroxide ions, and the like. Examples include carbonate ions. More specific and preferred compounds include Ca acetate, Mg acetate, Zn acetate, CaCl ₂ , CaBr ₂ , ZnCl ₂ , CaCO ₃ , Ca (OH) ₂ and CaO, and particularly preferably Ca acetate. is there.

  The temperature of the aqueous solution containing a Group II metal element in the periodic table is preferably 130 ° C. or higher, more preferably 150 ° C. or higher. Although there is no restriction | limiting in particular about the upper limit of washing | cleaning temperature, When using a normal autoclave, about 250 degreeC is a limit.

  The bath ratio of the aqueous solution containing the Group II metal element in the periodic table is preferably selected in the range of 2 to 100, more preferably 4 to 50, and 5 to 15 with respect to the dry polymer 1 by weight. More preferably, it is in the range.

  The following method can be illustrated as a specific method when the polyphenylene sulfide resin is washed with an acid aqueous solution. That is, there is a method of immersing a polyphenylene sulfide resin in an acid or an acid aqueous solution, and stirring or heating can be performed as necessary. The acid used is not particularly limited as long as it does not have the action of decomposing polyphenylene sulfide resin, and is saturated with aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo-substituted fatty acids such as chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated monocarboxylic acid such as aromatic saturated carboxylic acid, acrylic acid, crotonic acid, aromatic carboxylic acid such as benzoic acid, salicylic acid, dicarboxylic acid such as oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid, Examples include inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid. Of these, acetic acid and hydrochloric acid are more preferably used. The polyphenylene sulfide resin that has been subjected to acid treatment is preferably washed several times with water or warm water in order to remove the remaining acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that the effect of the preferred chemical modification of the polyphenylene sulfide resin by acid treatment is not impaired.

  The amount of ash content of the polyphenylene sulfide resin used in the present invention is preferably a relatively large range of 0.1 to 2% by weight from the viewpoint of imparting characteristics such as fluidity during processing and molding cycle, and is preferably 0.2 to 1% by weight. % Is more preferable, and a range of 0.3 to 0.8% by weight is more preferable.

Here, the amount of ash refers to the amount of inorganic components in the polyphenylene sulfide resin determined by the following method.
(1) Weigh 5-6 g of polyphenylene sulfide resin in a platinum dish fired and cooled at 583 ° C.
(2) A polyphenylene sulfide resin is pre-fired at 450 to 500 ° C. together with a platinum dish.
(3) A polyphenylene sulfide sample pre-fired with a platinum dish is placed in a muffle furnace set at 583 ° C. and fired for about 6 hours until it completely incinerates.
(4) Weigh after cooling in a desiccator.
(5) Calculate the ash content by the formula: ash content (% by weight) = (weight of ash content (g) / sample weight (g)) × 100.

The melt viscosity of the polyphenylene sulfide resin used in the present invention is in the range of ¹ to 2000 Pa · s (300 ° C., shear rate 1000 sec ⁻¹ ) from the viewpoint of imparting characteristics such as improved chemical resistance and fluidity during processing. Is preferably selected, more preferably in the range of 1 to 200 Pa · s, and still more preferably in the range of 1 to 50 Pa · s. Here, the melt viscosity is a value measured by a Koka flow tester using a nozzle having a nozzle diameter of 0.5 mmφ and a nozzle length of 10 mm under conditions of a shear rate of 1000 sec ⁻¹ .

  Chloroform extraction amount (calculated from the residual amount at the time of Soxhlet extraction for 5 hours) as an index of the amount of organic low polymerization component (oligomer) of polyphenylene sulfide resin used in the present invention is chemical resistance. From the point of imparting characteristics such as improvement of the fluidity and fluidity during processing, a relatively large range of 1 to 5% by weight is preferable, a range of 1.5 to 4% by weight is more preferable, and a range of 2 to 4% by weight More preferably it is.

  The fluidity improver (b) used in the present invention has a function of greatly reducing the melt viscosity of the thermoplastic resin by being blended with the thermoplastic resin (a). Specific examples include branched polymers, liquid crystal polymers, cyclic compounds, low molecular weight linear polyesters, low molecular weight linear polycarbonates, aromatic low molecular compounds, acrylic compounds, etc., preferably branched polymers, It is a cyclic compound. A branched polymer is a polymer having a small entanglement between molecules due to its three-dimensional branch structure and a small self-aggregation force. This is preferable for controlling the dispersed particle diameter and interfacial tension, which are requirements of the present invention. In addition, since the cyclic compound does not have a terminal structure as compared with a normal linear compound or linear polymer, the entanglement between molecules is small, and it is preferably used for controlling the dispersed particle size and interfacial tension which are the requirements of the present invention. It is done. Among these, a more preferable fluidity improver is a branched polymer, and a branched polymer having liquid crystallinity is particularly preferable. These fluidity improvers may be used in combination of two or more.

  In the present invention, the branched polymer refers to a polymer having a branched structure, and specifically refers to a polymer having a multi-branched structure. As the branched structure, a plurality of linear segments are radially formed from the central core. A star polymer having a branched chain, a graft polymer having a structure in which a polymer that has a number of branch points in a main linear polymer chain and from which a branched polymer is introduced, has a three-dimensionally branched structure, and is repeated Examples include hyperbranched polymers having a branched structure in the unit, and dendrimers with a precisely controlled molecular weight distribution and degree of branching, and star polymers and hyperbranched polymers are preferred because they are easy to produce industrially. In view of this, a hyperbranched polymer is more preferable.

  In the present invention, the branched polymer is not particularly limited as long as it is a polymer having a branched structure, but in terms of fluidity, polyamide, polyester, polyesteramide, polycarbonate, polyester polycarbonate, polyether, polystyrene, polyphenylene, polyimide, It is preferable to include any one selected from polyphenylene sulfide and polyurethane, and polyester and polycarbonate are more preferable in terms of heat resistance, mechanical properties, hydrolysis resistance, and recyclability, and polyester is particularly preferable.

  In the present invention, the method for producing the branched polymer is not particularly limited. In the case of a star polymer, after synthesizing a linear segment that becomes a branched chain, an arm-first method of grafting to the core and a multifunctional initiator as a component that becomes the core, and then a branched chain Any of the co-first methods for synthesizing a linear segment may be used. In the case of a dendrimer, either the Divergent method in which a stepwise reaction is repeated from the core to increase branching, or the Convergent method in which the outer shell components are repeatedly stepped and finally bonded to the core may be used. In the case of a hyperbranched polymer, a method of self-polycondensation using a compound having a total of 3 or more of two types of substituents in one molecule, a sequential reaction using a bifunctional compound and a trifunctional compound May be any one of a method of conducting polycondensation, a method of chain-reacting self-polycondensation using a vinyl monomer having an initiator site, and a method of chain-reacting ring-opening polymerization using a cyclic monomer. Preferred are a method of sequential self-polycondensation using a compound having a total of 3 or more of two kinds of substituents in the molecule and a method of successive reactive polycondensation using a bifunctional compound and a compound having a functionality of three or more. .

  In the present invention, when the branched polymer is a hyperbranched polymer, the raw material monomer is not particularly limited as long as the above production method can be carried out. As a specific example, compounds used in a method in which a compound having a total of 3 or more of two kinds of substituents in a molecule is used for sequential self-polycondensation include diphenolic acid, 5- (2-hydroxyethoxy) isophthalate. Acid, 5-acetoxyisophthalic acid, 5-phenoxyisophthalic acid, 3,5-dihydroxybenzoic acid, 3,5-acetoxybenzoic acid, 3,5-bis (2-hydroxyethoxy) benzoic acid, 3,5-bis ( 2-hydroxyethoxy) benzoic acid methyl, 3,5-bis (trimethylsiloxy) benzoic acid chloride, 4,4- (4′-hydroxyphenyl) pentanoic acid, methyl 4,4- (4′-hydroxyphenyl) pentanoate 3,5-dibromophenol, 5- (bromomethyl) -1,3-dihydroxybenzene, 3,5-diaminobenzoic acid, 3, -Bis (4-aminophenoxy) benzoic acid, 5-aminoisophthalic acid, phenol-3,5-diglycidyl ether, (3,5-dibromophenyl) boronic acid, 6-bromo-1- (4-hydroxy-4) '-Biphenylyl) -2- (4-hydroxyphenyl) hexane, 13-bromo-1- (4-hydroxyphenyl) -2- (4-hydroxy-4' '-p-terphenylyl) tridecane, 13- Bromo-1- (4-hydroxyphenyl) -2- [4- (6-hydroxy-2-naphthalenylyl) phenyl] tridecane and the like, and in terms of fluidity, recyclability, mechanical properties and hydrolysis resistance, 5- (2-hydroxyethoxy) isophthalic acid, 5-acetoxyisophthalic acid, 3,5-diacetoxybenzoic acid, 3,5-bis (2-hydride) Xyloxy) benzoic acid, methyl 3,5-bis (2-hydroxyethoxy) benzoate, 3,5-bis (trimethylsiloxy) benzoic acid chloride, 4,4- (4′-hydroxyphenyl) pentanoic acid, 3,5 -Bis (4-aminophenoxy) benzoic acid, 13-bromo-1- (4-hydroxyphenyl) -2- (4-hydroxy-4 ''-p-terphenylyl) tridecane is preferred.

  Examples of the bifunctional compound used in the method of sequential polycondensation using a bifunctional compound and a trifunctional or higher compound include terephthalic acid, isophthalic acid, phthalic acid, 2,6-naphthalenedicarboxylic acid, Aromatic dicarboxylic acids such as 5-naphthalenedicarboxylic acid, bis (p-carboxyphenyl) methane, anthracene dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 5-tetrabutylphosphonium isophthalic acid, 5-sodium sulfoisophthalic acid, Acids, succinic acid, adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, malonic acid, glutaric acid, dimer acid and other aliphatic dicarboxylic acids, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, etc. Alicyclic dicarboxylic acids and their esters Dicarboxylic acid components such as synthetic derivatives, hydroxycarboxylic acid components such as p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, glycolic acid, lactic acid, hydroxypropionic acid, hydroxybutyric acid, hydroxyvaleric acid, hydroxycaproic acid, Ethylene glycol, propylene glycol, 1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, decamethylene glycol, cyclohexanedimethanol, cyclohexanediol, dimer diol, etc., or a molecular weight of 200 to 200 100,000 long-chain glycols, ie, polyethylene glycol, poly-1,3-propylene glycol, polytetramethylene glycol, etc., 4,4′-dihydroxybiphenyl, hydroquinone, t Diol components such as butyl hydroquinone, bisphenol A, bisphenol S, bisphenol F and their ester-forming derivatives, ethylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, p Examples include diamine components such as -phenylenediamine and p-xylylenediamine, and trifunctional or higher functional compounds include glycerol, trimethylolpropane, tricarballylic acid, diaminopropanol, diaminopropionic acid, trimesic acid, trimellitic acid, 4-hydroxy-1,2-benzenedicarboxylic acid, phloroglucinol, α-resorcinic acid, β-resorcinic acid, γ-resorcinic acid, tricarboxynaphthalene, dihydroxy Naphthoic acid, aminophthalic acid, 5-aminoisophthalic acid, aminoterephthalic acid, diaminobenzoic acid, tris (4-aminophenyl) amine, 1,3,5-tris (4-aminophenoxy) benzene, melamine, cyanuric acid, erythritol , Pentaerythritol, threitol, xylitol, glucitol, mannitol, 1,2,3,4-butanetetracarboxylic acid, 1,2,4,5-cyclohexanetetraol, 1,2,3,4,5-cyclohexanepentaneol 1,2,3,4,5,6-cyclohexanehexane, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2,3,4,5-cyclohexanepentacarboxylic acid, 1,2,3 , 4,5,6-cyclohexanehexacarboxylic acid, citric acid, tartaric acid, 1,2, , 5-benzenetetraol, 1,2,3,4-benzenetetraol, 1,2,3,5-benzenetetraol, 1,2,3,4,5-benzenepentaneol -L, 1,2,3,4,5,6-benzenehexaneol, 2,2 ', 3,3'-tetrahydroxybiphenyl, 2,2', 4,4'-tetrahydroxybiphenyl, 3 , 3 ′, 4,4′-tetrahydroxybiphenyl, 3,3 ′, 5,5′-tetrahydroxybiphenyl, 2,3,6,7-naphthalenetetraol, 1,4,5,8-naphthalenetetraol , Pyromellitic acid, merophanic acid, planitic acid, meritic acid, 2,2 ′, 3,3′-biphenyltetracarboxylic acid, 2,2 ′, 4,4′-biphenyltetracarboxylic acid, 3,3 ′, 4 , 4'-biphenyltetracarboxylic acid 3,3 ′, 5,5′-biphenyltetracarboxylic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7- Naphthalenetetraol, 1,4,5,8-naphthalenetetraol, 1,2,4,5,6,8-naphthalenehexaol, 1,2,4,5,6,8-naphthalenehexacarboxylic acid, gallic An acid etc. are mentioned. In this case, the content of the trifunctional or higher functional compound is preferably in the range of 10 to 50 mol%, more preferably 15 to 40 mol% with respect to the entire branched polymer. When a branched polymer containing a trifunctional or higher compound in the above range is used, a thermoplastic resin composition having good dispersibility is obtained, which is preferable.

  The branched polymer is preferably a polymer containing an aromatic ring from the viewpoint of heat resistance, and is preferably a branched polymer having liquid crystallinity from the viewpoint of fluidity. Here, to show liquid crystallinity means to show a liquid crystal state in a certain temperature range when the temperature is raised from room temperature. The liquid crystal state is a state showing optical anisotropy under shear.

  Particularly preferred branched polymers are p-hydroxybenzoic acid, 6-hydroxy-2-naphthoic acid, 4,4′-dihydroxybiphenyl, hydroquinone, ethylene glycol, terephthalic acid, isophthalic acid, trimesic acid, α-resorcylic acid, phlorog. Examples thereof include branched polymers containing lucinol, 1,2,4,5-benzenetetraol, pyromellitic acid, merophanic acid, planitic acid, and gallic acid.

  The terminal group of the branched polymer is not particularly limited, but it is considered that the terminal group structure that can suppress the exchange reaction with the thermoplastic resin is effective, and as a specific method for achieving it, Includes a method of adding a monofunctional compound during production of the branched polymer, a method of end-blocking the terminal group of the branched polymer with a reactive compound, and the like. Examples of the monofunctional compound used in the method of adding the monofunctional compound include monocarboxylic acid, alcohol, monoamine, and the like. From the viewpoint of fluidity, monocarboxylic acid is preferable. Specific examples include benzoic acid, Examples thereof include methyl benzoic acid, tert-butyl benzoic acid, naphthoic acid, and stearic acid. The reactive compound used in the method of end-blocking the terminal group of the branched polymer with a reactive compound is at least one selected from glycidyl compounds, acid anhydrides, carbodiimide compounds, oxazoline compounds, and orthoesters. And the like. In addition, the reactive compound may be 1 type and may use 2 or more types together.

  The molecular weight of the branched polymer used in the present invention is not particularly limited, but in terms of fluidity, the number average molecular weight (Mn) is preferably in the range of 300 to 30,000, more preferably in the range of 400 to 10,000. Preferably, it is in the range of 500 to 5000, the weight average molecular weight (Mw) is preferably in the range of 500 to 150,000, more preferably in the range of 600 to 50000, and in the range of 800 to 30000. It is particularly preferred. Although it does not specifically limit about molecular weight distribution (Mw / Mn), It is preferable that it is the range of 1-5, and the range of 1-4 is more preferable at the point of fluidity | liquidity.

  In the present invention, Mn, Mw and Mw / Mn of the branched polymer are expressed as absolute molecular weights by GPC-LS (gel permeation chromatography-light scattering) method using a solvent in which the branched polymer is soluble as an eluent. It is a measured value.

  The glass transition temperature (Tg) of the branched polymer used in the present invention is not particularly limited, but is preferably in the range of −60 to 200 ° C. and in the range of 0 to 150 ° C. in terms of fluidity. More preferably, it is more preferable that it is the range of 50-120 degreeC. In the present invention, Tg can be determined from measurement by a differential scanning calorimeter (DSC).

  The melting point (Tm) of the branched polymer used in the present invention is not particularly limited, but is preferably 150 ° C. or higher, particularly preferably 200 ° C. or higher in terms of heat resistance. In the present invention, Tm can be determined from measurement by a differential scanning calorimeter (DSC).

The cyclic compound used in the present invention is a compound in which the ends of the linear polymer are bonded to each other to form a cyclic structure. Examples of the cyclic compound include cyclic polyamide, cyclic polyester, and cyclic polyphenylene sulfide. From the viewpoint of heat resistance, the cyclic compound is cyclic. Polyphenylene sulfide is preferred.
The cyclic polyphenylene sulfide used in the present invention is a mixture of cyclic polyphenylene sulfide compounds represented by the following general formula (1) and represented by an integer of m = 4 to 20.

(M is an integer from 4 to 20)

  The repeating unit m in the above formula is an integer of 4 to 20, preferably 4 to 15, and more preferably 4 to 12.

  In addition, cyclic polyphenylene sulfide alone having a single m has a difference in easiness of crystallization, but is obtained as a crystal, and therefore tends to have a high melting point. On the other hand, in the case of a mixture having a different m, the melting temperature is specifically lowered and the melt processing temperature can be reduced as compared with the cyclic polyphenylene sulfide alone, and the cyclic polyphenylene sulfide mixture (mixture of m = 4 to 20) ) In a thermoplastic resin is preferable because it has a particularly excellent fluidity improving effect during melt processing, which is the object of the present invention.

  The ratio of each different m in the cyclic polyphenylene sulfide mixture is not particularly limited, but in order to achieve the effect of the present invention, the cyclic polyphenylene sulfide mixture has the highest melting point and is easily crystallized. The content of polyphenylene sulfide alone is preferably less than 50% by weight, more preferably 30% by weight, particularly preferably less than 10% by weight (m = 6 cyclic polyphenylene sulfide (weight) / (cyclic polyphenylene sulfide mixture ( (Weight) × 100) Here, the content of the cyclic polyphenylene sulfide alone of m = 6 in the cyclic polyphenylene sulfide mixture was determined by dividing the cyclic polyphenylene sulfide mixture into components by high performance liquid chromatography equipped with a UV detector. Has polyphenylene sulfide structure The ratio of the peak area attributed to the cyclic polyphenylene sulfide alone of m = 6 to the total peak area attributed to the compound having a polyphenylene sulfide structure is at least the phenylene sulfide structure. A compound having, for example, a cyclic polyphenylene sulfide compound or a linear polyphenylene sulfide and having a structure other than phenylene sulfide in a part thereof (for example, as a terminal structure) also belongs to the compound having a polyphenylene sulfide structure. In addition, the qualitative characteristics of each peak divided into components by this high performance liquid chromatography can be obtained by separating each peak by preparative liquid chromatography and performing an absorption spectrum or mass analysis in infrared spectroscopic analysis.

  Such a cyclic polyphenylene sulfide mixture is obtained by obtaining a polyphenylene sulfide mixture containing a polyphenylene sulfide and a cyclic polyphenylene sulfide mixture by a known method for producing polyphenylene sulfide, and then extracting the cyclic polyphenylene sulfide mixture from the polyphenylene sulfide mixture. be able to.

  The fluidity improver (b) used in the present invention is dispersed in the thermoplastic resin (a) with a dispersed particle diameter of 0.5 to 200 nm. The dispersed particle size referred to here is an average dispersed particle size obtained by observing an arbitrary molded product obtained by molding the thermoplastic resin composition of the present invention with a transmission electron microscope (magnification: 10,000 times). . For example, an ASTM No. 1 dumbbell piece is molded at an arbitrary molding temperature selected from a melting point of a thermoplastic resin forming a continuous phase + 20 ° C. or a glass transition temperature + 100 ° C., and a thin piece having a thickness of 80 nm is formed from the center of the dumbbell piece. For 100 dispersed particles randomly selected when observed with a transmission electron microscope (magnification: 10,000 times), first measure the maximum and minimum diameters to obtain the average value, Thereafter, the average value of the 100 dispersed particles can be obtained by number averaging. A more preferable range of the dispersed particle diameter is 1 to 150 nm, and particularly preferably 1 to 100 nm. When the dispersed particle size of the dispersed phase exceeds 200 nm, the mechanical properties are significantly lowered along with the improvement of fluidity. When the dispersed particle size of the dispersed phase is smaller than 0.5 nm, it is not possible to obtain a thermoplastic resin composition with improved fluidity, which is an object of the present invention.

  In the thermoplastic resin composition of the present invention, the thermoplastic resin (a) and the flowability improver (b) are composed of 90 to 99.9% by weight of the thermoplastic resin (a) and the flowability improver (b) 0. 1 to 10% by weight, preferably 92.5 to 99.7% by weight of thermoplastic resin (a), 0.3 to 7.5% by weight of fluidity improver (b), more preferably thermoplastic resin ( a) 95 to 99.5% by weight, fluidity improver (b) 0.5 to 5% by weight. When the fluidity improver (b) is more than 20% by weight, problems such as deterioration of mechanical properties and bleed out occur, and when it is less than 0.1% by weight, it is difficult to improve fluidity.

  Moreover, the interfacial tension between the fluidity improver (b) and the thermoplastic resin (a) used in the present invention is 0.4 mN / m or more. The interfacial tension is measured here by measuring the thickness of the interface between the fluidity improver (b) and the thermoplastic resin (a) and then Polymer Engineering and Science, vol. 27, No. 5, 335-343 (1987). ) Can be calculated using the equation (1) described in (1).

  Here, the interfacial thickness is the thickness of the region where both components coexist at the boundary between the fluidity improver (b) and the thermoplastic resin (a), and is a value measured using an atomic force microscope. Using an atomic force microscope, measure a region of 250 nm square on one side in phase mode, measure the thickness of the largest interfacial thickness of randomly selected dispersed particles as shown in FIG. The measurement can be performed at 10 places and the number average can be calculated.

  The interfacial tension can also be measured using the improved embedded fiber shrinkage method described in Nihon Reoroji Gakkaishi, 27, 109-115 (1999). In the improved embedded fiber shrinkage method, the fluidity improver (b) processed into a fibrous piece is present in the thermoplastic resin (a), and the melting point of the thermoplastic resin (a) and the fluidity improver (b) Heated to a temperature selected from the higher melting point to the melting point + 50 ° C. or the glass transition temperature to the glass transition temperature + 150 ° C., and the flow-like fluidity improver (b) gradually passes through the ellipsoidal sphere. It is a method of measuring the time until the change to, and the rate of change, and calculating from the relationship.

  The interfacial tension is an index indicating the interaction between the fluidity improver (b) and the thermoplastic resin (a), and when the interfacial tension is less than 0.4 mN / m, the fluidity improver (b) and the thermoplasticity. This shows that the interaction of the resin (a) is large, and the effect of improving the fluidity becomes small. The interfacial tension is preferably 0.6 mN / m or more, particularly preferably 0.8 mN / m or more. The upper limit of the interfacial tension is not particularly limited, but is preferably 20 mN / m or less from the viewpoint of molding processability and mechanical properties.

  In the thermoplastic resin composition of the present invention, when the thermoplastic resin (a) is added to the fluidity improver (b), a reaction between them occurs, or the decomposition reaction of the fluidity improver is suppressed. The resin additive (c) is used. By adding the resin additive (c), the dispersed particle diameter and the interfacial tension can be appropriately controlled. Examples of the resin additive (c) used in the present invention include phosphorus compounds, hindered phenol compounds, thioether compounds, vitamin compounds, triazole compounds, polyamine compounds, and hydrazine derivative compounds. These may be used in combination. Of these, phosphorus compounds and hindered phenol compounds are preferred.

  Specific examples of the hindered phenol compound include n-octadecyl-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) -propionate, n-octadecyl-3- (3′-methyl). -5'-t-butyl-4'-hydroxyphenyl) -propionate, n-tetradecyl-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) -propionate, 1,6-hexane Diol-bis- [3- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate], 1,4-butanediol-bis- [3- (3,5-di-t-butyl- 4-hydroxyphenyl) -propionate], 2,2′-methylenebis- (4-methyl-t-butylphenol), triethylene glycol-bis- [3- (3-t-butyl) 5-methyl-4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, 3,9-bis [2- {3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy} -1,1-dimethylethyl] 2,4,8,10-tetraoxaspiro (5,5) undecane, N, N′-bis-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionylhexamethylenediamine, N, N′-tetramethylene-bis-3- (3′-methyl-5) '-T-butyl-4'-hydroxyphenol) propionyldiamine, N, N'-bis- [3- (3,5-di-t-butyl-4-hydroxyphenol) propionyl] Dorazine, N-salicyloyl-N′-salicylidenehydrazine, 3- (N-salicyloyl) amino-1,2,4-triazole, N, N′-bis [2- {3- (3,5-di- t-butyl-4-hydroxyphenyl) propionyloxy} ethyl] oxyamide, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylene Bis- (3,5-di-t-butyl-4-hydroxy-hydrocinnamide) and the like. Preferably, triethylene glycol-bis- [3- (3-t-butyl-5-methyl- 4-hydroxyphenyl) -propionate], tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate Acid] methane, 1,6-hexanediol-bis- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) -propionate], pentaerythrityl-tetrakis [3- (3,5- Di-t-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis- (3,5-di-t-butyl-4-hydroxy-hydrocinnamide). Specific product names of hindered phenol compounds include “Adeka Stub” AO-20, AO-30, AO-40, AO-50, AO-60, AO-70, AO-80, manufactured by Asahi Denka Kogyo Co., Ltd. AO-330, “Irganox” 245, 259, 565, 1010, 1035, 1076, 1098, 1222, 1330, 1425, 1520, 3114, 5057 manufactured by Ciba Specialty Chemicals, “Sumilyzer” BHT-R manufactured by Sumitomo Chemical Co., Ltd. Examples thereof include MDP-S, BBM-S, WX-R, NW, BP-76, BP-101, GA-80, GM, GS, “Cyanox” CY-1790 manufactured by Cyanamid.

  Specific examples of the thioether compound include dilauryl thiodipropionate, ditridecyl thiodipropionate, dimyristyl thiodipropionate, distearyl thiodipropionate, pentaerythritol tetrakis (3-lauryl thiopropionate) Pentaerythritol-tetrakis (3-dodecylthiopropionate), pentaerythritol-tetrakis (3-octadecylthiopropionate), pentaerythritol-tetrakis (3-myristylthiopropionate), pentaerythritol-tetrakis (3- Stearylthiopropionate). Specific product names of thioether compounds include “Adeka Stub” A0-23, AO-412S, AO-503A from Asahi Denka Kogyo Co., Ltd., “Irganox” PS802 from Ciba Specialty Chemicals, and “Sumilyzer” from Sumitomo Chemical Co., Ltd. Examples include TPL-R, TPM, TPS, TP-D, Yoshitomi's DSTP, DLTP, DLTOIB, DMTP, Cypro Kasei's “Sinox” 412S, and Cyamide's “Sianox” 1212.

Specific examples of the vitamin compound include d-α-tocopherol acetate, d-α-tocopherol succinate, d-α-tocopherol, d-β-tocopherol, d-γ-tocopherol, d-δ-tocopherol, d- Natural products such as α-tocotrienol, d-β-tocofetrienol, d-γ-tocofetrienol, d-δ-tocofetrienol, dl-α-tocopherol, dl-α-tocopherol acetate, succinic acid Synthetic products such as dl-α-tocopherol calcium and dl-α-tocopherol nicotinate can be mentioned. Specific product names of vitamin compounds include “Tocopherol” from Eisai and “Irganox” E201 from Ciba Specialty Chemicals.
Specific examples of the triazole compound include benzotriazole, 3- (N-salicyloyl) amino-1,2,4-triazole, and the like.

  Specific examples of the polyvalent amine compound include 3,9-bis [2- (3,5-diamino-2,4,6-triazaphenyl) ethyl] -2,4,8,10-tetraoxaspiro. [5.5] Undecane, ethylenediamine-tetraacetic acid, alkali metal salt (Li, Na, K) salt of ethylenediamine-tetraacetic acid, N, N'-disalicylidene-ethylenediamine, N, N'-disalicylidene-1 , 2-propylenediamine, N, N ″ -disalicylidene-N′-methyl-dipropylenetriamine, 3-salicyloylamino-1,2,4-triazole and the like.

  Specific examples of the hydrazine derivative-based compound include decamethylene dicarboxyl acid-bis (N′-salicyloyl hydrazide), bis (2-phenoxypropionyl hydrazide) isophthalate, N-formyl-N′-salicyloyl hydrazine. 2,2-oxamide bis- [ethyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], oxalyl-bis-benzylidene-hydrazide, nickel-bis (1-phenyl-3- Methyl-4-decanoyl-5-pyrazolate), 2-ethoxy-2′-ethyloxanilide, 5-t-butyl-2-ethoxy-2′-ethyloxanilide, N, N-diethyl-N ′, N'-diphenyloxamide, N, N'-diethyl-N, N'-diphenyloxamide, oxalic acid De-bis (benzylidenehydrazide), thiodipropionic acid-bis (benzylidenehydrazide), bis (salicyloylhydrazine), N-salicylidene-N′-salicyloylhydrazone, N, N′-bis [3- ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, N, N′-bis [2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] Ethyl] oxamide and the like.

  Examples of phosphorus compounds include phosphite compounds and phosphate compounds. Specific examples of such phosphite compounds include tetrakis [2-t-butyl-4-thio (2′-methyl-4′-hydroxy-5′-t-butylphenyl) -5-methylphenyl] -1, 6-hexamethylene-bis (N-hydroxyethyl-N-methylsemicarbazide) -diphosphite, tetrakis [2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-5'-tert-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid-di-hydroxyethylcarbonylhydrazide-diphosphite, tetrakis [2-tert-butyl-4-thio (2'-methyl-4'-hydroxy-) 5'-t-butylphenyl) -5-methylphenyl] -1,10-decamethylene-di-carboxylic acid di-sali Roylhydrazide-diphosphite, tetrakis [2-tert-butyl-4-thio (2′-methyl-4′-hydroxy-5′-tert-butylphenyl) -5-methylphenyl] -di (hydroxyethylcarbonyl) hydrazide— Diphosphite, tetrakis [2-t-butyl-4-thio (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -5-methylphenyl] -N, N'-bis (hydroxyethyl) oxamide -Diphosphite and the like are mentioned, and those in which at least one PO bond is bonded to an aromatic group are more preferable. Specific examples include tris (2,4-di-t-butylphenyl) phosphite, Tetrakis (2,4-di-t-butylphenyl) 4,4′-biphenylene phosphonite, bis (2,4-di-t-butylphenyl) Pentaerythritol-di-phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) Octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, 1,1,3-tris (2-methyl-4-ditridecyl phosphite— 5-t-butyl-phenyl) butane, tris (mixed mono and di-nonylphenyl) phosphite, tris (nonylphenyl) phosphite, 4,4'-isopropylidenebis (phenyl-dialkyl phosphite) and the like Tris (2,4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di) t-butylphenyl) octyl phosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, tetrakis (2,4-di-t-butylphenyl) -4, 4′-biphenylenephosphonite and the like can be preferably used. Specific product names of the phosphite compounds include “ADK STAB” PEP-4C, PEP-8, PEP-11C, PEP-24G, PEP-36, HP-10, 2112, 260, 522A manufactured by Asahi Denka Kogyo Co., Ltd. 329A, 1178, 1500, C, 135A, 3010, TPP, “Irgaphos” 168 from Ciba Specialty Chemicals, “Smilizer” P-16 from Sumitomo Chemical, “Sand Stub” from Clariant P-EPQ, GE “Weston” 618, 619G, 624 and the like.

  Specific examples of the phosphate compound include monostearyl acid phosphate, distearyl acid phosphate, methyl acid phosphate, isopropyl acid phosphate, butyl acid phosphate, octyl acid phosphate, isodecyl acid phosphate, etc., among which monostearyl acid phosphate Distearyl acid phosphate is preferred. Specific product names of phosphate compounds include “Irganox” MD1024 from Ciba Specialty Chemicals, “Inhibitor” OABH from Eastman Kodak, “Adekastab” CDA-1, CDA-6 from Asahi Denka Kogyo, AX-71, Mitsui Toatsu Fine's "Quunox", Uniroyal's "Nauguard" XL-1.

  Content of the resin additive (c) in this invention is 0.01-5 weight part with respect to 100 weight part of resin compositions which consist of a thermoplastic resin (a) and a fluidity improver (b). Preferably it is 0.05-4 weight part, More preferably, it is 0.1-3 weight part.

  In the thermoplastic resin composition of the present invention, a filler can be further blended in order to impart mechanical strength and other characteristics. Although a filler is not specifically limited, Any fillers, such as fibrous form, plate shape, powder form, and a granular form, can be used. Fillers include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber , Fibrous fillers such as metal fibers, or silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, silicon oxide, magnesium oxide, alumina, Metal compounds such as zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, Hydroxides such as calcium oxide, calcium hydroxide, magnesium hydroxide, aluminum hydroxide, glass flakes, glass powder, carbon black and silica, non-fibrous fillers such as graphite, and montmorillonite, beidellite, nontronite, saponite , Smectite clay minerals such as hectorite and soconite, and various clay minerals such as vermiculite, halloysite, kanemite, kenyanite, zirconium phosphate, titanium phosphate, Li type fluorine teniolite, Na type fluorine teniolite, Na type tetrasilicon fluorine mica, Li type Layered silicates typified by swelling mica such as tetrasilicon fluorine mica are used. The layered silicate may be a layered silicate in which exchangeable cations existing between layers are exchanged with organic onium ions, and examples of the organic onium ions include ammonium ions, phosphonium ions, and sulfonium ions. Of these, ammonium ions and phosphonium ions are preferred, and ammonium ions are particularly preferred. As the ammonium ion, any of primary ammonium, secondary ammonium, tertiary ammonium, and quaternary ammonium may be used. Primary ammonium ions include decyl ammonium, dodecyl ammonium, octadecyl ammonium, oleyl ammonium, benzyl ammonium and the like. Secondary ammonium ions include methyl dodecyl ammonium and methyl octadecyl ammonium. Examples of tertiary ammonium ions include dimethyl dodecyl ammonium and dimethyl octadecyl ammonium. Quaternary ammonium ions include benzyltrialkylammonium ions such as benzyltrimethylammonium, benzyltriethylammonium, benzyltributylammonium, benzyldimethyldodecylammonium, benzyldimethyloctadecylammonium, trioctylmethylammonium, trimethyloctylammonium, trimethyldodecylammonium, trimethyloctadecyl. Examples thereof include alkyltrimethylammonium ions such as ammonium, dimethyldialkylammonium ions such as dimethyldioctylammonium, dimethyldidodecylammonium, and dimethyldioctadecylammonium. Besides these, it is derived from aniline, p-phenylenediamine, α-naphthylamine, p-aminodimethylaniline, benzidine, pyridine, piperidine, 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. And ammonium ions. Among these ammonium ions, trioctylmethylammonium, trimethyloctadecylammonium, benzyldimethyloctadecylammonium, ammonium ions derived from 12-aminododecanoic acid, and the like are preferable. Layered silicates in which exchangeable cations present between layers are exchanged with organic onium ions can be produced by reacting layered silicates having exchangeable cations between layers and organic onium ions by a known method. it can. Specifically, a method by an ion exchange reaction in a polar solvent such as water, methanol, ethanol, or a method by directly reacting a layered silicate with a liquid or melted ammonium salt may be used. Among these fillers, preferred are glass fibers, talc, wollastonite, layered silicates such as montmorillonite and synthetic mica, and particularly preferred are glass fibers. Moreover, said filler can also be used in combination of 2 or more types. The surface of the filler used in the present invention can be used by treating the surface with a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agents. . The type of glass fiber used in the present invention is not particularly limited as long as it is generally used for reinforcing a resin, and can be selected from, for example, a long fiber type or a short fiber type chopped strand, a milled fiber, or the like. Further, weakly alkaline glass fibers are excellent in terms of mechanical strength and can be preferably used. The glass fiber is preferably treated with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, an epoxy-based, urethane-based, acrylic-based coating or sizing agent, and an epoxy-based resin is particularly preferable. Further, it is preferably treated with a silane-based or titanate-based coupling agent or other surface treatment agent, and an epoxysilane or aminosilane-based coupling agent is particularly preferable. The blending amount of the filler is usually 5 to 400 parts by weight, preferably 20 to 300 parts by weight with respect to 100 parts by weight of the thermoplastic resin composition.

  The thermoplastic resin composition of the present invention further includes an ultraviolet absorber (for example, resorcinol, salicylate), a coloring preventing agent such as phosphite and hypophosphite, a lubricant and a release agent (stearic acid, montanic acid and Its metal salts, its esters, its half esters, stearyl alcohol, stearamide and polyethylene wax, etc., colorants including dyes and pigments, carbon black, crystal nucleating agents, plasticizers, flame retardants (bromine based) Normal additives such as flame retardants, phosphorus flame retardants, red phosphorus, silicone flame retardants), flame retardant aids, and antistatic agents, and polymers other than thermoplastic resins are blended to achieve predetermined characteristics. Further, it can be given.

  The method for producing the thermoplastic resin composition of the present invention is preferably by melt kneading, and a known method can be used for melt kneading. For example, using a Banbury mixer, a rubber roll machine, a kneader, a single screw or a twin screw extruder, etc., it can be melt kneaded at a temperature higher than the melting temperature of the thermoplastic resin to obtain a resin composition. Among these, a twin screw extruder is preferable. As the kneading method, 1) a method of kneading a thermoplastic resin, a fluidity improver, and a resin additive at once; 2) a resin composition (master pellet) containing the thermoplastic resin in a high concentration of the fluidity improver and the resin additive ), And then adding the resin composition and the thermoplastic resin so as to obtain a prescribed concentration and melt kneading (master pellet method), etc., and any kneading method can be used. It doesn't matter.

  The resin composition of the present invention can be molded by any known method such as injection molding, injection compression molding, compression molding, extrusion molding, blow molding, press molding, spinning, etc., and processed into various molded products for use. can do. As molded products, it can be used as injection molded products, extrusion molded products, blow molded products, films, sheets, fibers, etc., as films, as various films such as unstretched, uniaxially stretched, biaxially stretched, as fibers, It can be used as various fibers such as undrawn yarn, drawn yarn, and super-drawn yarn. In particular, in the present invention, taking advantage of the excellent fluidity, it can be processed into large injection molded products such as automobile parts and injection molded products having a thin portion having a thickness of 0.01 to 1.0 mm.

  In the present invention, the above-mentioned various molded products can be used for various applications such as automobile parts, electrical / electronic parts, building members, various containers, daily necessities, household goods and sanitary goods. Specific applications include air flow meters, air pumps, thermostat housings, engine mounts, ignition hobbins, ignition cases, clutch bobbins, sensor housings, idle speed control valves, vacuum switching valves, ECU housings, vacuum pump cases, inhibitor switches, rotations Sensor, Accelerometer, Distributor cap, Coil base, ABS actuator case, Radiator tank top and bottom, Cooling fan, Fan shroud, Engine cover, Cylinder head cover, Oil cap, Oil pan, Oil filter, Fuel cap, Fuel strainer , Distributor cap, vapor canister Automotive underhood parts such as uzing, air cleaner housing, timing belt cover, brake booster parts, various cases, various tubes, various tanks, various hoses, various clips, various valves, various pipes, torque control lever, safety belt parts, Car interior parts such as register blade, washer lever, window regulator handle, window regulator handle knob, passing light lever, sun visor bracket, various motor housings, roof rail, fender, garnish, bumper, door mirror stay, spoiler, food louver, Wheel covers, wheel caps, grill apron cover frames, lamp reflectors, lamp bezels, door handles, etc. Car exterior parts, wire harness connectors, SMJ connectors, PCB connectors, door grommet connectors, various automotive connectors, relay cases, coil bobbins, optical pickup chassis, motor cases, laptop computer housings and internal parts, CRT display housings and internal parts, Printer housings and internal parts, mobile terminal housings and internal parts such as mobile phones, mobile PCs, handheld mobiles, recording medium (CD, DVD, PD, FDD, etc.) drive housings and internal parts, copier housings and internal parts And electrical / electronic parts such as facsimile housings and internal parts, parabolic antennas, and the like. Furthermore, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, video camera parts, video equipment parts such as projectors, laser discs (registered trademark), compact discs (CD), CD-ROMs , CD-R, CD-RW, DVD-ROM, DVD-R, DVD-RW, DVD-RAM, Blu-ray disc and other optical recording media substrates, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts , Etc., home and office electrical appliance parts. Also, housings and internal parts of electronic musical instruments, home game machines, portable game machines, various gears, various cases, sensors, LEP lamps, connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, Optical pickups, oscillators, various terminal boards, transformers, plugs, printed wiring boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, power modules, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders , Electrical and electronic parts such as transformer members, coil bobbins, sash doors, blind curtain parts, piping joints, curtain liners, blind parts, gas meter parts, water meter parts, water heater parts, roof panels, Hot walls, adjusters, plastic bundles, ceiling fishing gear, staircases, doors, floors and other building materials, fishing lines, fishing nets, seaweed aquaculture nets, fishing bait bags and other marine products, vegetation nets, vegetation mats, weedproof bags, protection Grass net, curing sheet, slope protection sheet, fly ash holding sheet, drain sheet, water retention sheet, sludge / sludge dehydration bag, concrete formwork and other civil engineering related parts, gears, screws, springs, bearings, levers, key stems, cams , Ratchet, roller, water supply parts, toy parts, cable ties, clips, fans, tegus, pipes, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches and other mechanical parts, multi-films, tunnel films, prevention Bird sheet, Non-woven fabric for vegetation protection, Pot for seedling, Vegetation pile, Seed string tape, Germination sheet, House lining sheet, Agricultural fastener, Slow-release fertilizer, Agricultural materials such as root sheets, garden nets, insect nets, infant tree nets, print laminates, fertilizer bags, sample bags, sandbags, beast damage nets, inducement strings, windproof nets, paper diapers, sanitary wrapping materials, cotton swabs, towels , Hygiene items such as toilet seat wipes, medical non-woven fabric (stitching reinforcement, anti-adhesion membrane, prosthetic repair material), wound dressing, wound tape bandage, sticker base fabric, surgical suture, fracture reinforcement, medical Medical supplies such as film, calendar, stationery, clothing, food packaging film, tray, blister, knife, fork, spoon, tube, plastic can, pouch, container, tank, basket, etc. Fill containers, microwave cooking containers, cosmetic containers, wraps, foam buffers, paper laminates, shampoo bottles, beverage bottles, cups, candy packaging, Containers such as shrink labels, lid materials, envelopes with windows, fruit baskets, hand cut tape, easy peel packaging, egg packs, HDD packaging, compost bags, recording media packaging, shopping bags, wrapping films for electrical and electronic parts, etc. Packaging, natural fiber composites, polo shirts, T-shirts, innerwear, uniforms, sweaters, socks, ties, and other clothing, curtains, chairs, carpets, tablecloths, futons, wallpaper, furoshiki and other interior goods, carrier tape, Print lamination, heat sensitive stencil printing film, release film, porous film, container bag, credit card, cash card, ID card, IC card, paper, leather, non-woven fabric hot melt binder, magnetic material, zinc sulfide, electrode Powder binders for materials, optical elements, Electric embossed tape, IC tray, golf tee, garbage bag, plastic bag, various nets, toothbrush, stationery, draining net, body towel, hand towel, tea pack, drainage filter, clear file, coating agent, adhesive, bag Useful as chair, table, cooler box, kumade, hose reel, planter, hose nozzle, dining table, desk surface, furniture panel, kitchen cabinet, pen cap, gas lighter, etc., automotive interior parts, automotive exterior parts It is particularly useful as a connector for automobiles.

  Hereinafter, although an example explains the present invention still in detail, the gist of the present invention is not limited only to the following example.

Reference example 1
In a reaction vessel equipped with a stirring blade and a distillation tube, 48.0 g (0.35 mol) of p-hydroxybenzoic acid, 30.9 g (0.17 mol) of 4,4′-dihydroxybiphenyl, 5.41 g of terephthalic acid ( 0.033 mol), 10.4 g (0.054 mol) of PET having an intrinsic viscosity of about 0.6 dl / g, 42.0 g (0.20 mol) of trimesic acid, and 76.3 g of acetic anhydride (total of phenolic hydroxyl groups) 1.1 equivalents), and the mixture was reacted at 145 ° C. for 1.5 hours with stirring in a nitrogen gas atmosphere, and then heated to 250 ° C. to conduct a deacetic acid condensation reaction. After the reactor internal temperature reached 250 ° C., 14.7 g (0.12 mol) of benzoic acid was added and the temperature was raised to 280 ° C. When 100% of the theoretical distillation amount of acetic acid was distilled, heating and stirring were stopped, and the contents were discharged into cold water to obtain a fluidity improver (B-1).

  As a result of the nuclear magnetic resonance spectrum analysis, this fluidity improver (B-1) was found to have a p-oxybenzoate unit of 2.0, 4, 4 in terms of the composition ratio of each component with respect to the structure derived from trimesic acid, which is a trifunctional compound. The '-dioxybiphenyl unit and the ethylene oxide unit were 0.5, the terephthalate unit was 0.5, and the content of the trifunctional compound was 25 mol%. Moreover, terminal structure was carboxylic acid and benzoic acid ester, and melting | fusing point Tm of the obtained dendritic polyester resin was 182 degreeC, and the number average molecular weight 2500 was. The melting point (Tm) is determined by differential calorimetry. After observing the endothermic peak temperature (Tm1) observed when the polymer is measured at room temperature to 20 ° C./minute, the temperature is maintained at Tm1 + 20 ° C. for 5 minutes. Then, after once cooling to room temperature under a temperature drop condition of 20 ° C./min, the endothermic peak temperature (Tm) observed when measured again under a temperature rise condition of 20 ° C./min was used. The molecular weight was measured by GPC-LS (gel permeation chromatography-light scattering) method using pentafluorophenol which is a solvent in which the present polymer is soluble, and the number average molecular weight was determined.

  The fluidity improver (B-1) exhibits liquid crystallinity and is sheared at 100 (1 / second) by a shear stress heating device (CSS-450), heated at a rate of 5.0 ° C./minute, and objective lens 60 times. The liquid crystal starting temperature measured as the temperature at which the entire field of view starts to flow was 163 ° C.

Reference example 2
A reaction vessel equipped with a stirring blade was charged with 100 g of the fluidity improver (B-1) obtained in Reference Example 1 and 35 g of 2-phenyl-2-oxazoline, and the mixture was stirred at 200 ° C. for 30 minutes in a nitrogen gas atmosphere. After the reaction, stirring was stopped, and the contents were discharged into cold water to obtain a fluidity improver (B-2). From the absorption spectrum in infrared spectroscopic analysis (apparatus; FTIR-8100A manufactured by Shimadzu Corp.), a peak decrease derived from the carboxylic acid terminal was confirmed. The obtained fluidity improver had a melting point Tm of 157 ° C. and a number average molecular weight of 2200, the polymer exhibited liquid crystallinity, and the liquid crystal starting temperature was 141 ° C.

Reference example 3
After charging 100 g of the fluidity improver (B-1) obtained in Reference Example 1 and 70 g of ethyl orthoacetate into a reaction vessel equipped with a stirring blade, the mixture was reacted at 200 ° C. for 30 minutes with stirring in a nitrogen gas atmosphere. Stirring was stopped, and the contents were discharged into cold water to obtain a fluidity improver (B-3). From the absorption spectrum in infrared spectroscopic analysis (apparatus; FTIR-8100A manufactured by Shimadzu Corp.), a peak decrease derived from the carboxylic acid terminal was confirmed. The obtained fluidity improver had a melting point Tm of 159 ° C. and a number average molecular weight of 1900, the polymer exhibited liquid crystallinity, and the liquid crystal starting temperature was 146 ° C.

Reference example 4
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 60.50 g (0.44 mol) of p-hydroxybenzoic acid, 30.49 g (0.162 mol) of 6-hydroxy-2-naphthoic acid, 4,4 After charging 18.62 g (0.10 mol) of '-dihydroxybiphenyl and 61.25 g of acetic anhydride (1.00 equivalent of total phenolic hydroxyl groups), the mixture was reacted at 145 ° C. for 2 hours with stirring in a nitrogen gas atmosphere. Then, 31.52 g (0.176 mol) of trimesic acid was added, the temperature was raised to 260 ° C., and the mixture was stirred for 3 hours. When 91% of the theoretical distillation amount of acetic acid was distilled, the heating and stirring were stopped, and the contents Was discharged into cold water to obtain a fluidity improver (B-4).

  This fluidity improver (B-4) was analyzed in the same manner as in Reference Example 1. As a result, the constituent ratio of each constituent component relative to the trifunctional compound-derived structure of trimesic acid was p-oxybenzoate units and 6-oxy-2. -The naphthoate unit was 3.42, the 4,4'-dioxybiphenyl unit was 0.58, and the content of the trifunctional compound was 20 mol%. The terminal structure was the ratio of carboxylic acid to hydroxyl group. The obtained fluidity improver had a melting point Tm of 168 ° C. and a number average molecular weight of 2100, the polymer exhibited liquid crystallinity, and the liquid crystal starting temperature was 145 ° C.

Reference Example 5
The reaction vessel was charged with 50 g of terephthalic acid and 37 g of ethylene glycol. After starting the reaction at 200 ° C. and 150 kPa, the temperature was gradually raised to 250 ° C. over 3 hours, and the internal pressure was returned to normal pressure to complete the reaction. 75 g of bishydroxyethyl terephthalate (BHET) was obtained. The reaction vessel equipped with a stirring blade and a cooler was purged with nitrogen, and then 50 g of BHET and 20 g of trimesic acid were added. After stirring for 15 minutes while stirring at 250 ° C. under a nitrogen stream, 0.1 g of dibutyltin oxide was added and polycondensed at 275 ° C. and 10 kPa for 1 hour. Then, it melt | dissolved in tetrahydrofuran 300mL, the deposit obtained by putting in 2 L of petroleum ether was dried at 90 degreeC using the hot air dryer, and the fluidity improver (B-5) was obtained. The number average molecular weight was 2800, the molecular weight distribution (Mw / Mn) was 2.8, and the Tg was 97 ° C. Molecular weight was analyzed using hexafluoroisopropanol as solvent.

Reference Example 6
After the reaction vessel equipped with a stirring blade and a cooler was purged with nitrogen, 50 g of 1,6-hexanediol-based polycarbonate diol (Mn600) and 20 g of trimesic acid were added. After maintaining for 15 minutes with stirring at 120 ° C. under a nitrogen stream, 0.1 g of dibutyltin oxide was added and polycondensed at 150 ° C. and 10 kPa for 3 hours. Then, it melt | dissolved in tetrahydrofuran 300mL, the deposit obtained by throwing into petroleum ether 2L was dried at 90 degreeC using the hot air dryer, and the fluidity improver (B-6) was obtained. The number average molecular weight was 6,500, the molecular weight distribution (Mw / Mn) was 2.3, and Tg was 45 ° C. Molecular weight was analyzed using hexafluoroisopropanol as solvent.

Reference Example 7
A reaction vessel equipped with a stirring blade was charged with 50 g of 3,5-bis (4-aminophenoxy) benzoic acid, purged with nitrogen, and then subjected to polycondensation at 240 ° C. and 67 Pa for 15 minutes. The product was dissolved in 300 mL of dimethylformamide, and the precipitate obtained by adding it to 2 L of petroleum ether was dried at 90 ° C. using a hot air dryer to obtain a fluidity improver (B-7). As a result of analyzing B-7, it was number average molecular weight 9000, molecular weight distribution (Mw / Mn) 1.7, and Tg 175 degreeC. Molecular weight was analyzed using hexafluoroisopropanol as solvent.

Reference Example 8
The reaction vessel equipped with a stirring blade and a condenser was purged with nitrogen, and then 5 parts of trimethylolpropane, 50 parts of 2,2′-bis (hydroxymethyl) heptanoic acid, 7 parts of stearic acid, and 0.2 of p-toluenesulfonic acid The mixture was reacted for 2 hours with stirring at 140 ° C. under a nitrogen stream, and further reacted at 140 ° C. and 67 Pa for 1 hour to obtain a fluidity improver (B-8). As a result of analyzing B-8, it was number average molecular weight 1900. Molecular weight was analyzed using hexafluoroisopropanol as solvent.

Reference Example 9
In a 1000 L autoclave with a stirrer, 42.7% sodium hydrosulfide 82.7 kg (700 mol), 96% sodium hydroxide 29.6 kg (710 mol), N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) In some cases, 114.4 kg (1156 mol) of sodium acetate, 17.2 kg (210 mol) of sodium acetate, and 100 kg of ion-exchanged water are gradually heated to about 240 ° C. over about 3 hours while flowing nitrogen at normal pressure. After distilling 143 kg of water and 2.8 kg of NMP through the rectification tower, the reaction vessel was cooled to 160 ° C. In addition, 0.02 mol of hydrogen sulfide per 1 mol of the sulfur component charged during this liquid removal operation was scattered out of the system. Next, 103 kg (703 mol) of p-dichlorobenzene and 90 kg (910 mol) of NMP were added, and the reaction vessel was sealed under nitrogen gas. While stirring at 240 rpm, the temperature was raised to 270 ° C. at a rate of 0.6 ° C./min and held at this temperature for 140 minutes. While 12.6 kg (700 mol) of water was injected over 15 minutes, it was cooled to 250 ° C. at a rate of 1.3 ° C./min. Thereafter, the mixture was cooled to 220 ° C. at a rate of 0.4 ° C./min, and then rapidly cooled to near room temperature to obtain slurry (I). This slurry (I) was diluted with 200 kg of NMP to obtain slurry (II). 100 kg of slurry (II) heated to 80 ° C. is filtered with a sieve (80 mesh, opening 0.175 mm) at a 25 kg / 1 batch scale, and granular PPS resin containing the slurry as a mesh-on component is used as a filtrate component. About 75 kg of slurry (III) was obtained. Of the obtained slurry (III), 75 kg was charged into a devolatilizer at 25 kg / batch, replaced with nitrogen, treated at 100 to 150 ° C. under reduced pressure for 1.5 hours, and then subjected to 150 times with a vacuum dryer. A solid was obtained by treatment at 1 ° C. for 1 hour. 100 kg of ion exchange water (1.2 times the amount of slurry (III)) was added to the solid, and the mixture was stirred again at 70 ° C. for 30 minutes to make a slurry again. This slurry was subjected to vacuum suction filtration with a filter having an opening of 10 to 16 μm. 100 kg of ion-exchanged water was added to the obtained white cake, and the mixture was stirred again at 70 ° C. for 30 minutes to form a slurry again. Similarly, after suction filtration, vacuum drying was performed at 70 ° C. for 5 hours to obtain 0.9 kg of a polyphenylene sulfide mixture. 500 g of the obtained polyphenylene sulfide mixture was collected, and 12 kg of chloroform was used as a solvent, and the polyphenylene sulfide mixture was contacted with the solvent by a Soxhlet extraction method at a bath temperature of about 80 ° C. for 3 hours to obtain an extract. The obtained extract was in the form of a slurry partially containing solid components at room temperature. Chloroform was distilled off from this extract slurry using an evaporator, and then treated with a vacuum dryer at 70 ° C. for 3 hours to obtain 210 g of a fluidity improver (B-9) (42% yield based on the polyphenylene sulfide mixture). Obtained. The obtained fluidity improver (B-9) was confirmed to be a compound having a phenylene sulfide skeleton from an absorption spectrum in infrared spectroscopic analysis (apparatus; FTIR-8100A manufactured by Shimadzu Corporation). In addition, mass spectrum analysis (device: Hitachi M-1200H) of components separated from high performance liquid chromatography (device; Shimadzu LC-10, column; C18, detector; photodiode array), MALDI-TOF -From the molecular weight information by MS and GPC, this fluidity improver (B-9) is a mixture mainly composed of cyclic polyphenylene sulfide having 4 to 12 repeating units, and the weight fraction of cyclic polyphenylene sulfide is about 87%. , 13% was found to be a linear polyphenylene sulfide oligomer and a mixture of cyclic polyphenylene sulfide having m = 13 or more (Mw = 2000).

Reference Example 10
In a 500 mL reaction vessel equipped with a stirring blade and a distillation tube, 66.3 g (0.48 mol) of p-hydroxybenzoic acid, 8.38 g (0.045 mol) of 4,4′-dihydroxybiphenyl, and 7. 48 g (0.045 mol), 14.41 g (0.075 mol) of polyethylene terephthalate having an intrinsic viscosity of about 0.6 dl / g and 62.48 g of acetic anhydride (1.00 equivalent of total phenolic hydroxyl groups) The mixture was charged and reacted at 145 ° C. for 2 hours with stirring under a nitrogen gas atmosphere, then heated to 260 ° C. and stirred for 3 hours. When 91% of the theoretical distillation amount of acetic acid was distilled, heating and stirring were performed. The operation was stopped, and the contents were discharged into cold water to obtain a linear liquid crystal resin (E-1). The melting point of this liquid crystal resin (E-1) was 264 ° C., the liquid crystal starting temperature was 232 ° C., and the number average molecular weight was 2200.

(1) Dispersed particle diameter ASTM No. 1 dumbbell pieces were formed by injection molding (SG75H-MIV, manufactured by Sumitomo Heavy Industries, Ltd.), and a thin piece having a thickness of 80 nm was cut from the center, and observed with a transmission electron microscope. Select 100 randomly dispersed particles from the photograph of the injection-molded product observed at a magnification of 10,000 times, and use the image processing software “Scion Image” (manufactured by Scion Corporation) for the dispersed part. The diameter and the minimum diameter were measured to determine the average value, and then the 100 number average values were determined.

(2) Interfacial tension (interface thickness method)
An ASTM No. 1 dumbbell piece was molded by injection molding (SG75H-MIV, manufactured by Sumitomo Heavy Industries, Ltd.), and the center portion was cut with a diamond cutter to create a mirror surface. image) is measured in phase mode for a region of 250 nm square on one side, the thickness of the largest interfacial thickness of the randomly selected dispersed particles is measured from the cross-sectional profile, and the measurement is performed at 10 locations. The interface thickness was measured as a number average. The interfacial tension was calculated from the obtained interfacial thickness using equation (1).

(3) Fluidity Using SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd., set the cylinder temperature and mold temperature shown in the table, set the injection pressure to 30 MPa, 200 mm long x 10 mm wide x 1 mm thick rod flow test Using a piece, the rod flow length at a holding pressure of 0 was measured. The larger the flow length, the better the fluidity.

(4) Melt viscosity It is a value of a shear rate of 100 / s measured using a capillary having a capillary length (L) of 10 mm × capillary diameter (D) of 1 mm at a measurement temperature shown in the table by a capillograph (manufactured by Toyo Seiki). .

(5) Tensile strength, tensile elongation at break Tensile test was performed on ASTM No. 1 dumbbell test piece at a crosshead speed of 10 mm / min using a tester Tensilon UTA2.5T (made by Baldwin) according to ASTM D638.

(6) Impact resistance According to ASTM D256, the Izod impact strength of a molded product with a 3 mm thick notch at 23 ° C. was measured.

(7) Bleed-out resistance About the bleed-out resistance of the test piece shape | molded by SG75H-MIV made from Sumitomo Heavy Industries, Ltd., after heat-processing for 1 hour at 80 degreeC using a hot air dryer, it judged by touch and visual observation.
The surface appearance and bleed-out resistance were judged according to the following criteria.
A: The surface is smooth and glossy.
○: The surface is smooth but slightly sticky, and the gloss is slightly inferior.
X: The surface is sticky and has no gloss.

(Examples 1-18, Comparative Examples 1-11)
Each component shown below is dry blended in the proportions shown in Table 1, Table 2, and Table 3, and then supplied from the main feeder of the extruder, and is set at a cylinder setting temperature of 250 using a TEX30 type twin screw extruder manufactured by Nippon Steel Works. Melting and kneading were performed at a temperature of 200 ° C. and a screw rotation speed of 200 rpm, and the gut discharged from the die was immediately cooled in a water bath and pelletized by a strand cutter. Among the obtained pellets, Examples 1 to 7, 10, 11, 18 and Comparative Examples 1, 2, 7 to 9 were dried under reduced pressure at 80 ° C. for 12 hours. Examples 8, 9, 12, and Comparative Example 3 10 and 11 were hot-air dried at 80 ° C. for 12 hours, and Examples 13 to 17 and Comparative Examples 4 to 6 were pellets that were hot-air dried at 130 ° C. for 12 hours, and the cylinder temperatures and mold temperatures shown in the table were used. The test piece was prepared by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.). The results of evaluating the dispersed particle size, interfacial tension, fluidity, mechanical properties, and bleed-out resistance calculated by the interfacial thickness method for each sample are as shown in Table 1, Table 2, and Table 3. It is clear that the fluidity is improved in this example without deterioration in mechanical properties as compared with the fluidity improver and the thermoplastic resin to which no resin additive is added as shown in Comparative Examples 1-7. Further, in Comparative Example 8 in which the addition amount exceeding the upper limit of the addition amount of the fluidity improver of the present invention was added, although improvement in fluidity was observed, a slight decrease in physical properties and bleed out were observed. Comparative Examples 9 to 11 are systems to which a fluidity improver that does not satisfy the dispersed particle size and interfacial tension, which are requirements of the present invention, is added, but there are some cases where the effect of improving fluidity is small and problems such as bleeding out occur. It was. On the other hand, this example has excellent mechanical properties, fluidity, and bleed-out resistance in a balanced manner.

(Example 19, Comparative Example 12)
Each component shown below was dry blended in the proportions shown in Table 4 and then supplied from an extruder main feeder. Using a TEX30 twin screw extruder manufactured by Nippon Steel Works, the cylinder set temperature was 280 ° C. and the screw rotation speed was 200 rpm. The gut discharged from the die was immediately cooled in a water bath and pelletized with a strand cutter. The obtained pellets were dried under reduced pressure at 80 ° C. for 12 hours, and the test pieces were prepared by injection molding (SG75H-MIV manufactured by Sumitomo Heavy Industries, Ltd.) at the cylinder temperature and mold temperature shown in the table. Further, the interfacial tension of Example 19 was measured by using an improved embedded fiber shrinkage method. That is, using a capillograph (manufactured by Toyo Seiki Co., Ltd.), a capillary having a temperature of 230 ° C., a capillary length (L) of 10 mm × capillary diameter (D) of 0.5 mm, the fluidity improver was processed into a fibrous piece having a length of about 1 mm. A thermoplastic resin and a resin additive that were dry blended in the proportions shown in Table 4 were heated and melted at 280 ° C. for 5 minutes, and then a fluidity improver for the fibrous piece was placed on the melt and an optical microscope. Was used to observe the morphology over time. 19 minutes after passing through the ellipsoid, it changed to a sphere having a particle diameter of 400 μm. When the parameters (time and rate of change in shape) at that time were calculated by substituting them into the relational expressions described in Nihon Reoroji Gakkaishi, 27, 109-115 (1999), the interfacial tension was 0.4 mN / m. In addition, the results of evaluating the dispersed particle size, fluidity, mechanical properties, and bleed-out resistance of each sample are shown in Table 4. This example has excellent mechanical properties and fluidity in a balanced manner as compared with the comparative example.

The thermoplastic resin (a) used for the present Example and the comparative example is as follows.
A-1: Nylon 6 resin having a melting point of 225 ° C. and 98% sulfuric acid 1 g / dl and a relative viscosity of 2.80 (CM1010 manufactured by Toray Industries, Inc.)
A-2: Polybutylene terephthalate resin having a melting point of 225 ° C. and an intrinsic viscosity of 0.85 dl / g (1100S manufactured by Toray Industries, Inc.)
A-3: Polyethylene terephthalate resin having a melting point of 260 ° C. and an intrinsic viscosity of 1.20 dl / g (T-704, manufactured by Toray Industries, Inc.)
A-4: PPS resin (M2588 manufactured by Toray) having a melting point of 280 ° C. and MFR = 200 g / 10 minutes (315.5 ° C., 5 kg load).
A-5: Polycarbonate resin (Taflon A1900 manufactured by Idemitsu Petrochemical Co., Ltd.)
A-6: Nylon 66 resin with a melting point of 265 ° C. and 98% sulfuric acid 1 g / dl and a relative viscosity of 2.95 (CM3001N manufactured by Toray)
A-7: with respect to 100 parts by weight of a poly (2,6-dimethyl-1,4-phenylene) ether resin having a glass transition temperature of 220 ° C. and an intrinsic viscosity of 0.50 dL / g (30 ° C. in chloroform), Polyphenylene ether resin obtained by dry blending 1 part by weight of maleic anhydride and 0.1 part by weight of a radical generator (Perhexin 25B: manufactured by NOF Corporation) and melt-kneading at a cylinder temperature of 320 ° C.
A-8: Amorphous polyamide resin having a glass transition temperature of 160 ° C. (“Grillamide” TR55 manufactured by MMS)

Similarly, the fluidity improver (b) is as follows.
B-1: Reference Example 1
B-2: Reference example 2
B-3: Reference Example 3
B-4: Reference example 4
B-5: Reference Example 5
B-6: Reference Example 6
B-7: Reference Example 7
B-8: Reference Example 8
B-9: Reference Example 9.

Similarly, the resin additive (c) is as follows.
C-1: Hindered phenol compound (Irganox 1098 manufactured by Ciba Specialty Chemicals)
C-2: Hindered phenol compound (Irganox 1010 manufactured by Ciba Specialty Chemicals)
C-3: Phosphorus compound (Adeka Stub AX-71 manufactured by Asahi Denka Kogyo Co., Ltd.).

Similarly, chopped strand type glass fibers were used below.
D-1: Glass fiber (T-249 manufactured by Nippon Electric Glass)
D-2: Glass fiber (CS3J948 made by Nittobo)
D-3: Glass fiber (T-747 made by Nippon Electric Glass).

The following were used for the comparative examples.
E-1: Reference Example 10
E-2: Reference Example 11

It is a model figure which shows an example when the interface thickness of the fluid improvement agent disperse | distributed to the thermoplastic resin is measured using an atomic force microscope.

Claims (7)

With respect to 100 parts by weight of the resin composition comprising 90 to 99.9% by weight of the thermoplastic resin (a) and 0.1 to 10% by weight of the fluidity improver (b), the resin additive (c) 0.01 to A phase structure comprising a resin composition containing 5 parts by weight and having a fluidity improver (b) observed by an electron microscope dispersed in a thermoplastic resin (a) with a dispersed particle size of 0.5 to 200 nm. A thermoplastic resin composition characterized by being formed and having an interfacial tension between the thermoplastic resin (a) and the fluidity improver (b) of 0.4 mN / m or more. The thermoplastic resin composition according to claim 1, wherein the fluidity improver (b) is at least one selected from a branched polymer and a cyclic compound. The thermoplastic resin (a) is at least one selected from polyamide resins, polyester resins, polyphenylene sulfide resins, polycarbonate resins, polyphenylene ether resins, and polyolefin resins. The thermoplastic resin composition as described. The thermoplastic resin composition according to claim 3, wherein the thermoplastic resin (a) is at least one selected from a polyamide resin, a polyester resin, and a polyphenylene sulfide resin. The thermoplastic resin composition according to any one of claims 1 to 4, wherein the resin additive (c) is at least one selected from a hindered phenol compound and a phosphorus compound. A molded article obtained by melt-molding the thermoplastic resin composition according to any one of claims 1 to 5. The molded article according to claim 6, wherein the melt molding is any one selected from injection molding, injection compression molding, and compression molding.

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