JP2018131511A - Resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a resin composition having both excellent impact strength and tensile elongation at break while maintaining excellent characteristics of a polyarylene sulfide resin.SOLUTION: The resin composition is a polyarylene sulfide resin composition containing, based on (A) 100 pts.wt. of a polyarylene sulfide resin (component A), (B) 10-150 pts.wt. of wholly aromatic polyamide fibers (component B) and (C) 5-100 pts.wt. of a fluororesin (component C). The component A has a number average molecular weight (Mn) of 9,000 or less, and the degree of dispersion (Mw/Mn) represented by a weight average molecular weight (Mw) and the number average molecular weight (Mn) is 5.0 or less.SELECTED DRAWING: None

Description

  The present invention is a resin composition comprising a polyarylene sulfide resin having a specific number average molecular weight and a dispersity, a wholly aromatic polyamide fiber, and a fluororesin, while maintaining the excellent properties of the polyarylene sulfide resin, The present invention relates to a resin composition having both excellent impact strength and tensile elongation at break.

  Polyarylene sulfide resin is an engineering plastic that is excellent in chemical resistance, heat resistance, mechanical properties, and the like. For this reason, polyarylene sulfide resins are widely used as electrical and electronic parts, vehicle-related parts, aircraft parts, and residential equipment parts. In recent years, electronic devices such as digital cameras and tablets have been made thinner as products become smaller, and vehicle-related parts such as automobiles have become lighter due to energy savings. Electrification of self-propelled vehicles such as hybrid vehicles and electric vehicles for the purpose of fossil and fossil fuel reduction is progressing. In these related applications, resin conversion from conventional metals has been studied for the purpose of reducing the weight of products, and in particular, replacement of metals used for applications such as gears and bearings in resin conversion of these mechanical parts. The resin material to be used is required to have high sliding characteristics, impact strength, and ductility characteristics. However, although the polyarylene sulfide resin itself has sliding characteristics as compared with other resins, impact strength and tensile elongation at break are not sufficient for use in these applications.

  As means for solving this problem, Patent Documents 1 and 2 describe polyphenylene sulfide resin, fluororesin and aromatic polyamide fiber, or polyphenylene sulfide resin, conductive potassium titanate in order to improve sliding characteristics and mechanical characteristics. Various resin compositions composed of whiskers, polytetrafluoroethylene resin, metal oxides and aromatic polyamide fibers have been proposed, respectively, but with respect to impact strength and tensile elongation at break, although mentioning slidability and mechanical strength. Not listed. Patent Document 3 proposes a resin composition comprising a polyphenylene sulfide resin, a fluororesin, an aromatic polyester resin, and a para-aromatic polyamide fiber. There is no description regarding tensile elongation at break. Patent Document 4 proposes a resin composition composed of a polyarylene sulfide resin and an aramid fiber having high toughness, but does not describe the impact strength although it mentions tensile elongation at break. Patent Documents 5 to 10 propose polyarylene sulfide resins having excellent processability, low gas properties, hue, mechanical properties, and the production method thereof, but mention the average molecular weight, the degree of dispersion, and the polymerization method thereof. However, it does not describe the improvement in impact strength and tensile breaking elongation of a resin composition comprising a wholly aromatic polyamide fiber and a fluororesin.

Japanese Examined Patent Publication No. 4-65866 JP-A-11-217504 JP-A-8-85758 JP-A-10-310700 Special table 2013-528680 gazette Special table 2013-522385 gazette Special table 2013-522386 gazette Special table 2013-522387 Japanese Patent Laid-Open No. 2006-166342 Japanese Patent Laid-Open No. 2006-156025

  An object of the present invention is a resin composition comprising a polyarylene sulfide resin having a specific number average molecular weight and a dispersity, a wholly aromatic polyamide fiber, and a fluororesin, and retains the excellent characteristics of the polyarylene sulfide resin. On the other hand, it is to provide a resin composition having both excellent impact strength and tensile elongation at break.

  As a result of intensive studies, the present inventors have found that a polyarylene sulfide resin having a specific number average molecular weight and degree of dispersion, a resin composition comprising a wholly aromatic polyamide fiber and a fluororesin has excellent characteristics possessed by the polyarylene sulfide resin. The present inventors have found that excellent impact strength and tensile elongation at break can be expressed while maintaining the above.

Specifically, the above-mentioned problem is that (A) polyarylene sulfide resin (component A) 100 parts by weight, (B) wholly aromatic polyamide fiber (component B) 10 to 150 parts by weight and (C) fluororesin ( C component) a polyarylene sulfide resin composition containing 5 to 100 parts by weight, the number average molecular weight (Mn) of the A component is 9,000 or less, the weight average molecular weight (Mw) and the number average molecular weight (Mn) This is achieved by a resin composition having a dispersity (Mw / Mn) of 5.0 or less.
Details of the present invention will be described below.

(Component A: polyarylene sulfide resin)
As the polyarylene sulfide resin used as the component A of the present invention, any polyarylene sulfide resin may be used as long as it belongs to the category called polyarylene sulfide resin.
The polyarylene sulfide resin has, for example, p-phenylene sulfide unit, m-phenylene sulfide unit, o-phenylene sulfide unit, phenylene sulfide sulfone unit, phenylene sulfide ketone unit, phenylene sulfide ether unit, diphenylene sulfide unit as structural units. , A substituent-containing phenylene sulfide unit, a branched structure-containing phenylene sulfide unit, and the like. Among them, those containing a p-phenylene sulfide unit of 70 mol% or more, particularly 90 mol% or more. Furthermore, poly (p-phenylene sulfide) is more preferable.

  The number average molecular weight (Mn) of the polyarylene sulfide resin used as the component A of the present invention is 9,000 or less, preferably 8,500 or less, more preferably 8,000 or less. The lower limit of the number average molecular weight is not particularly defined, but is preferably 2,000 or more. When the number average molecular weight is higher than 9,000, the impact strength and tensile elongation at break of the resin composition are lowered. Further, if the number average molecular weight is 2,000 or less, there may be a problem in the productivity of the product by the resin composition. Further, the dispersity (Mw / Mn) represented by the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 5.0 or less, preferably 4.9 or less, more preferably 4.8 or less. . When the degree of dispersion is greater than 5.0, the impact strength and tensile breaking elongation of the resin composition are reduced. The lower limit of the degree of dispersion (Mw / Mn) is not particularly specified, but is preferably 2.7 or more. When the degree of dispersion is less than 2.7, burrs are often generated during molding. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values calculated in terms of polystyrene by gel permeation chromatography (GPC) (molecular weight measuring device: Pl gel 220). Note that 1-chloronaphthalene was used as the solvent, and the column temperature was 210 ° C.

  Further, the total chlorine content of the polyarylene sulfide resin used as the component A of the present invention is preferably 500 ppm or less, more preferably 450 ppm or less, still more preferably 300 ppm or less, and particularly preferably 50 ppm or less. If the total chlorine content exceeds 500 ppm, the amount of gas generated may increase and the weld strength may be reduced.

  The total sodium content of the polyarylene sulfide resin used as the component A of the present invention is preferably 39 ppm or less, more preferably 30 ppm or less, still more preferably 10 ppm or less, and particularly preferably 8 ppm or less. If it exceeds 39 ppm, not only the weld strength is reduced due to an increase in the generated gas, but also the heat and moisture resistance is reduced due to an increase in the water absorption of the resin due to the coordinate bond between sodium metal and water molecules in a high temperature and high humidity environment. There is a case.

  The method for producing the polyarylene sulfide resin is not particularly limited, and the polymerization is carried out by a known method, but as a particularly suitable polymerization method, there are US Pat. Nos. 4,746,758 and 4,786. No. 713, Special Table 2013-522385, Japanese Patent Application Laid-Open No. 2012-233210, Japanese Patent No. 5167276, and the like. These production methods are methods in which a diiodoaryl compound and solid sulfur are polymerized by direct heating without a polar solvent.

  The production method includes an iodination step and a polymerization step. In the iodination step, an aryl compound is reacted with iodo to obtain a diiodoaryl compound. In the subsequent polymerization step, a polyarylene sulfide resin is produced by polymerizing the diiodoaryl compound with solid sulfur using a polymerization terminator. Iodine is generated in a gaseous state in this step, and this is recovered and used again in the iodination step. Essentially iodine is a catalyst.

A typical solid sulfur used in the production method includes a cyclooctasulfur form (S ₈ ) in which ₈ atoms are linked at room temperature. However, the sulfur compound used in the polymerization reaction is not limited, and any form can be used as long as it is solid or liquid at room temperature.

  Representative diiodoaryl compounds used in the production method include at least one selected from the group consisting of diiodobenzene, diiodonaphthalene, diiodobiphenyl, diiodobisphenol and diiodobenzophenone, and alkyl A derivative of an iodoaryl compound in which a group or a sulfone group is bonded or oxygen or nitrogen is introduced is also used. Iodoaryl compounds are classified into different isomers depending on the bonding position of the iodo atom, and preferred examples of these isomers are p-diiodobenzene, 2,6-diiodonaphthalene, and p, p′-diiodo. A compound in which iodine is symmetrically located at both ends of an aryl compound molecule, such as biphenyl. The content of the iodoaryl compound is preferably 500 to 10,000 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined taking into account the formation of disulfide bonds.

Typical polymerization terminators used in the production method include monoiodoaryl compounds, benzothiazoles, benzothiazole sulfenamides, thiurams, dithiocarbamates, aromatic sulfide compounds and the like. Preferable examples of monoiodoaryl compounds include at least one selected from the group consisting of iodobiphenyl, iodophenol, iodoaniline, and iodobenzophenone. Preferable examples of the benzothiazoles include at least one selected from the group consisting of 2-mercaptobenzothiazole and 2,2′-dithiobisbenzothiazole. Preferred examples of benzothiazole sulfenamides include N-cyclohexylbenzothiazole 2-sulfenamide, N, N-dicyclohexyl-2-benzothiazole sulfenamide, 2-morpholinothiobenzothiazole, benzothiazole sulfenamide , Dibenzothiazole disulfide, and at least one selected from the group consisting of N-dicyclohexylbenzothiazole 2-sulfenamide. Preferable examples of thiurams include at least one selected from the group consisting of tetramethylthiuram monosulfide and tetramethylthiuram disulfide. Preferable examples of the dithiocarbamates include at least one selected from the group consisting of zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate. Preferable examples of the aromatic sulfide compound include at least one selected from the group consisting of diphenyl sulfide, diphenyl disulfide, diphenyl ether, biphenyl, and benzophenone. In any polymerization terminator, one or more functional groups may be substituted on the conjugated aromatic ring skeleton. Examples of the functional group include a hydroxy group, a carboxyl group, a mercapto group, an amino group, a cyano group, a sulfo group, and a nitro group. Preferred examples include a carboxyl group and an amino group, and more preferred examples. in the FT-IR spectrum, a carboxyl group showing the peak of 1600～1800Cm ^-1 or 3300～3500Cm ^-1, and amino groups. The content of the polymerization terminator is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined taking into account the formation of disulfide bonds.

  In the production method, a polymerization reaction catalyst may be used. As a typical polymerization reaction catalyst, a nitrobenzene-based catalyst can be used. Preferred examples of the nitrobenzene catalyst include 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, iodonitrobenzene, and 2,6-diiodo-4- There may be mentioned at least one selected from the group consisting of nitroamines. The content of the polymerization reaction catalyst is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined taking into account the formation of disulfide bonds.

By using this polymerization method, it is not necessary to substantially reduce the chlorine content and the sodium content, and a polyphenylene sulfide resin excellent in cost performance can be obtained.
The polyphenylene sulfide resin of the present invention may contain a polyphenylene sulfide resin obtained by other polymerization method.

(B component: wholly aromatic polyamide fiber)
As the wholly aromatic polyamide fiber used as the component B of the present invention, any fiber may be used as long as it belongs to the category called aramid fiber. Examples of the aramid fibers include meta-aramid fibers and para-aramid fibers, and among them, para-aramid fibers are preferable.

  The wholly aromatic polyamide constituting the fiber of the present invention is substantially obtained from one or more aromatic diamines and one or more aromatic dicarboxylic acid halides. However, for example, a condensing agent represented by a triphenyl phosphite and pyridine system may be added to one or more aromatic diamines and one or more aromatic dicarboxylic acids. The wholly aromatic polyamide may be para type or meta type, but para type is more preferable. Preferred aromatic diamines include p-phenylenediamine, benzidine, 4,4 "-diamino-p-terphenyl, 2,7-diaminofluorene, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1, 4-bis- (4-aminophenoxy) benzene, 4,4′-bis- (4-aminophenoxy) biphenyl, 9,10-bis- (4-aminophenyl) anthracene, etc. Aromatic dicarboxylic acid halides. Are particularly preferably acid chlorides, such as terephthalic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4′-diphenyldicarboxylic acid chloride, and one or more lower alkyl groups, lower alkoxy groups, halogeno groups on the aromatic ring thereof. And those containing non-reactive functional groups such as nitro groups Further, when an aromatic dicarboxylic acid is used, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-diphenyldicarboxylic acid, and one or more lower alkyl groups and lower alkoxy groups in the aromatic ring And those containing non-reactive functional groups such as halogeno groups, nitro groups, etc. Further, the structure of the wholly aromatic polyamide preferred in the present invention has a main skeleton represented by the following formula.

（但し、Ａｒ_１、Ａｒ_２は下記一般式［Ｉ］〜［ＩＶ］からなる群より選ばれる少なくとも１種類の芳香族残基を示す。なおＡｒ_１、Ａｒ_２は互いに同一であっても異なるものであってもよい。また、これらの芳香族残基は、その水素原子の一部がハロゲン原子または低級アルキル基で置換されていてもよい。）

(However, Ar ₁ and Ar ₂ represent at least one aromatic residue selected from the group consisting of the following general formulas [I] to [IV]. Ar ₁ and Ar ₂ may be the same or different. In addition, in these aromatic residues, a part of the hydrogen atoms may be substituted with a halogen atom or a lower alkyl group.)

なかでも、前記Ａｒ_１、Ａｒ_２の合計を１００モル％としたときに、一般式［Ｉ］と一般式［ＩＩ］との合計、一般式［Ｉ］と一般式［ＩＩＩ］との合計、一般式［Ｉ］と一般式［ＩＶ］との合計、または一般式［Ｉ］が８０モル％以上であることが好ましい。より好ましくは一般式［Ｉ］と一般式［ＩＩ］との合計、または一般式［Ｉ］と一般式［ＩＩＩ］との合計が８０モル％以上である。さらに好ましくは一般式［Ｉ］と一般式［ＩＩ］との合計、または一般式［Ｉ］と一般式［ＩＩＩ］との合計が８０モル％以上であり、且つ一般式［ＩＩ］または一般式［ＩＩＩ］が１〜２０モル％のものである。

Among them, when the total of Ar ₁ and Ar ₂ is 100 mol%, the total of general formula [I] and general formula [II], the total of general formula [I] and general formula [III], The total of the general formula [I] and the general formula [IV] or the general formula [I] is preferably 80 mol% or more. More preferably, the total of the general formula [I] and the general formula [II] or the total of the general formula [I] and the general formula [III] is 80 mol% or more. More preferably, the total of the general formula [I] and the general formula [II], or the total of the general formula [I] and the general formula [III] is 80 mol% or more, and the general formula [II] or the general formula [III] is from 1 to 20 mol%.

  The aromatic polyamide dope used as the spinning dope may be solution-polymerized or may be obtained by dissolving a separately obtained wholly aromatic polyamide in a solvent, but is preferably subjected to a solution polymerization reaction. Further, a small amount of an inorganic salt may be added as a solubilizer in order to improve solubility. Examples of such inorganic salts include lithium chloride and calcium chloride.

  As a polymerization solvent or a redissolving solvent, generally known aprotic organic polar solvents are used. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylformamide, N , N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N, N-butyramide, N, N-dimethylisobutyramide, N-methylcaprolactam, N, N-dimethylmethoxyacetamide, N- Acetylpyrrolidine, N-acetylpiperidine, N-methylpiperidone-2, N, N′-dimethylethyleneurea, N, N′-dimethylpropyleneurea, N, N, N ′, N′-tetramethylmalonamide, N-acetyl Pyrrolidone, N, N, N ′, N′-tetramethylurea, dimethyl sulfoxide, etc. Ri, as a further re-dissolving solvent include strong acid such as concentrated sulfuric acid or methanesulfonic acid.

  The degree of polymerization of the wholly aromatic polyamide is not particularly limited, but it is preferable that the degree of polymerization is large if it dissolves in a solvent. When solution polymerization of a wholly aromatic polyamide is carried out, the ratio of the acid component to the diamine component is made to react in substantially equimolar amounts, but either component can be used in excess to control the degree of polymerization. Moreover, you may use a monofunctional acid component and an amine component as a terminal blocker.

  In the case of forming a wholly aromatic polyamide into a fiber, a method of wet molding a wholly aromatic polyamide dope is usually used. A method of directly discharging the dope into a coagulation bath or an air gap is provided to provide a coagulation bath. There is a method of discharging inside. A poor solvent for wholly aromatic polyamide is used for the coagulation bath. Usually, a good solvent is added to coagulate so that the solvent for the wholly aromatic polyamide dope quickly escapes and no defect occurs in the wholly aromatic polyamide fiber. Adjust the speed. In general, it is preferable to use water as a poor solvent and a solvent of wholly aromatic polyamide dope as a good solvent. The ratio of good solvent / poor solvent is preferably 15/85 to 40/60, although it depends on the solubility and coagulability of the wholly aromatic polyamide.

  The fiber length of the wholly aromatic polyamide fiber is preferably 0.1 mm or more and 6 mm or less, and more preferably 0.5 mm or more and 3 mm or less. If the thickness is less than 0.1 mm, the reinforcing effect may not be sufficient, and the impact resistance may not be sufficiently improved. If the thickness exceeds 6 mm, handling during production becomes difficult and the fluidity of the composition is inferior, and the moldability is low. It may become defective.

  Such wholly aromatic polyamide fibers exhibit an effect regardless of the presence or absence of bundling, but those that are bundled are preferred because they are easy to handle. Examples of the binder for bundling include polyester, polyurethane, and polyethersulfone resin, and among them, aromatic polyester is preferable. In the present invention, such heat-resistant organic fibers can be used alone or as a mixture of two or more.

  Content of B component is 10-150 weight part with respect to 100 weight part of A component, Preferably it is 15-120 weight part, More preferably, it is 20-100 weight part. If the content of component B is less than 10 parts by weight, impact strength and tensile breakage will not be sufficiently improved. If it exceeds 150 parts by weight, strand breakage or surging will occur during kneading extrusion, resulting in reduced productivity or workability. Problems arise.

(C component: fluororesin)
The fluororesin used as the component C of the present invention is a polymer having a carbon chain in the main chain and a fluorine atom bond in the side chain, or a copolymer having such a polymer. Specific examples include polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-fluoroalkyl vinyl ether- Examples include fluoroolefin copolymers and ethylene-trichlorofluoroethylene copolymers. Among them, polytetrafluoroethylene is preferable, and both baked and unfired polytetrafluoroethylene can be used. However, since polytetrafluoroethylene is easily re-agglomerated, a baking treatment is performed to make it difficult to re-agglomerate. Etc. are preferable, and polytetrafluoroethylene baked at a baking temperature of 360 ° C. or higher is particularly preferable. The melting point of polytetrafluoroethylene is preferably 320 to 335 ° C., more preferably 325 to 330 ° C., as measured by DSC method to make re-aggregation difficult. The particle diameter of polytetrafluoroethylene is preferably 0.1 to 100 μm on average, more preferably 1 to 20 μm, by measuring the dispersion dispersed in perchlorethylene by a light transmission method. Here, the average particle diameter is a weight average particle diameter measured using a laser diffraction / scattering method (MICOTRAC method). The polytetrafluoroethylene has a number average molecular weight of preferably 100,000 or more, more preferably 200,000 or more.

  Examples of such polytetrafluoroethylene include KTL-620 and KTL-450A from Kitamura Co., Ltd., Lubron L-5 and L-2 from Daikin Industries, Ltd., and Asahi Ishii-Iefluoropolymers ( It is commercially available as L150J, L169J, L170J, and L172J from Mitsui and DuPont Fluorochemical Co., Ltd. as Teflon (registered trademark) TLP-10F-1.

  Content of C component is 5-100 weight part with respect to 100 weight part of A component, Preferably it is 5-80 weight part, More preferably, it is 5-35 weight part. When the content is less than 5 parts by weight, sufficient impact strength and tensile elongation at break cannot be obtained. When the content exceeds 100 parts by weight, strand breakage or surging occurs during kneading.

(Other ingredients)
The resin composition in the present invention can contain an elastomer component as long as the effects of the present invention are not impaired. Suitable elastomer components include core-shells such as acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), and silicone-acrylic composite rubber-based graft copolymer. Examples of the graft copolymer resin include thermoplastic elastomers such as silicone-based thermoplastic elastomers, olefin-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers.

  In the resin composition in this invention, another thermoplastic resin can be included in the range which does not impair the effect of this invention. Other thermoplastic resins include, for example, general-purpose plastics represented by polyethylene resin, polypropylene resin, polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, aromatic polyester resin, liquid crystalline polyester resin, cyclic polyolefin resin, So-called super engineering plastics such as engineering plastics represented by polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate), polyether ether ketone, polyether imide, polysulfone, polyether sulfone, etc. Can be mentioned.

  In the resin composition of the present invention, an antioxidant, a heat stabilizer (hindered phenol-based, hydroquinone-based, phosphite-based and substituted products thereof), weathering agent (resorcinol, etc.) within a range not impairing the effects of the present invention. , Salicylates, benzotriazoles, benzophenones, hindered amines, etc., release agents and lubricants (montanic acid and its metal salts, its esters, their half esters, stearyl alcohol, stearamide, various bisamides, bisureas and polyethylene waxes) Etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (eg, nigrosine), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfone) Amides), antistatic agents (alkyl) Sulfate type anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), flame retardant (for example, Red phosphorus, phosphate, melamine cyanurate, magnesium hydroxide, aluminum hydroxide and other hydroxides, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resins or their bromines Combinations of flame retardant and antimony trioxide, etc.) and other polymers can be added.

  The resin composition in the present invention can contain fillers other than wholly aromatic polyamide fibers within a range not impairing the effects of the present invention. The material is not particularly limited, and fillers such as fibrous, plate-like, powdery, and granular can be used. Specifically, for example, fibrous fillers such as carbon fiber, glass fiber, potassium titanate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, wollastonite, selenium Sites, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, swellable layered silicates such as montmorillonite, synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide Non-fibers such as metal compounds such as carbonates, 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, calcium phosphate and silica Like fillers, these are May be empty, it is also possible to further combination of these fillers 2 or more.

  In addition, these fillers are pretreated with an organic onium ion in the case of coupling agents such as isocyanate compounds, organosilane compounds, organic titanate compounds, organoborane compounds, and epoxy compounds, and swellable layered silicates. The use is preferable in terms of obtaining a higher mechanical strength.

  In order to impart further conductivity to the resin composition of the present invention, a conductive filler can be contained as a filler. The material is not particularly limited, but the conductive filler is not particularly limited as long as it is a conductive filler that is usually used for conducting a resin. Specific examples thereof include the carbon fiber and metal described above. Examples thereof include powder, metal flake, metal ribbon, metal fiber, metal oxide, carbon fiber coated with a conductive substance, inorganic filler, carbon powder, graphite, carbon flake, and scaly carbon.

  Specific examples of metal species of metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. Specific examples of the metal species of the metal fiber include iron, copper, stainless steel, aluminum, and brass. Such metal powders, metal flakes, metal ribbons, and metal fibers may be surface-treated with a surface treatment agent such as titanate, aluminum, or silane.

Specific examples of the metal oxide include SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope), ZnO (aluminum dope), etc., and these include the surface of titanate, aluminum, and silane coupling agents. Surface treatment may be performed with a treating agent.

Specific examples of the conductive material in the inorganic filler coated with the conductive material include aluminum, nickel, silver, carbon, SnO ₂ (antimony doped), and In ₂ O ₃ (antimony doped). Examples of the inorganic filler to be coated include mica, glass beads, glass fiber, potassium titanate whisker, barium sulfate, zinc oxide, titanium oxide, aluminum borate whisker, zinc oxide whisker, titanic acid whisker, silicon carbide whisker, and the like. Can be illustrated. Examples of the coating method include vacuum deposition, sputtering, electroless plating, and baking. These may be subjected to a surface treatment with a surface treatment agent such as a titanate, aluminum or silane coupling agent.

  Carbon powders are classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black, etc., depending on the raw materials and production method. The carbon powder that can be used in the present invention is not particularly limited in its raw material and production method, but acetylene black and furnace black are particularly preferably used.

(Manufacture of resin composition)
The resin composition of the present invention can be produced by mixing the above components simultaneously or in any order with a mixer such as a tumbler, V-type blender, nauter mixer, Banbury mixer, kneading roll, or extruder. Preferably, melt kneading with a twin-screw extruder is preferred, and if necessary, it is preferable to supply an optional component into the other melt-mixed component from the second supply port using a side feeder or the like.

  The resin extruded as described above is directly cut into pellets, or after forming strands, the strands are cut with a pelletizer to be pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. Although the shape of the obtained pellet can take general shapes, such as a cylinder, a prism, and a spherical shape, it is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and still more preferably 2 to 3.5 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and still more preferably 2.5 to 4 mm.

  The total chlorine content of the resin composition of the present invention is preferably 500 ppm or less, more preferably 300 ppm or less, and still more preferably 50 ppm or less. If the total chlorine content exceeds 500 ppm, the amount of gas generated may increase and the weld strength may be reduced.

  The total sodium content of the resin composition of the present invention is preferably 39 ppm or less, more preferably 30 ppm or less, still more preferably 10 ppm or less, and most preferably 8 ppm or less. If it exceeds 39 ppm, not only the weld strength is reduced due to an increase in the generated gas, but also the heat and moisture resistance is reduced due to an increase in the water absorption of the resin due to the coordinate bond between sodium metal and water molecules in a high temperature and high humidity environment. There is a case.

(About molded products)
A molded product using the resin composition of the present invention can be obtained by molding the pellets produced as described above. Preferably, it is obtained by injection molding or extrusion molding. In injection molding, not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, and heat insulation gold Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultrahigh-speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding. In extrusion molding, various shaped extrusion molded products, sheets, films and the like are obtained. For forming sheets and films, an inflation method, a calendar method, a casting method, or the like can be used. It is also possible to form a heat-shrinkable tube by applying a specific stretching operation. The resin composition of the present invention can also be formed into a molded product by rotational molding, blow molding or the like.

  Since the resin composition of the present invention is a resin composition having both excellent impact strength and tensile elongation at break while maintaining the excellent properties of polyarylene sulfide resin, personal computers (notebooks, ultrabooks), tablets , Mobile phone housings, displays, OA equipment, mobile phones, personal digital assistants, facsimiles, compact discs, portable MDs, portable radio cassettes, PDAs (mobile information terminals such as electronic notebooks), video cameras, digital still cameras, optics Appliances such as equipment, audio, air conditioners, lighting equipment, entertainment goods, toy goods, and other household electrical appliances, and internal parts such as trays and chassis, and cases such as cases, mechanism parts, panels, and motor parts , Alternator terminal, alternator connector, C regulator, light meter potentiometer base, suspension parts, various valves such as exhaust gas valves, fuel-related, various exhaust system or intake system pipes, air intake nozzle snorkel, intake manifold, various arms, various frames, various hinges, various bearings , Fuel pump, gasoline tank, CNG tank, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow Meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, radiator motor Shush holder, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, fuel related electromagnetic valve coil, fuse connector, Battery tray, AT bracket, head lamp support, pedal housing, handle, door beam, protector, chassis, frame, armrest, horn terminal, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, noise shield, radiator support, Spare tire cover, seat shell, solenoid bobbin, engine oil filter, ignition device Installation cases, under covers, scuff plates, pillar trims, propeller shafts, wheels, fenders, fascias, bumpers, bumper beams, bonnets, aero parts, platforms, cowl louvers, roofs, instrument panels, spoilers and various modules, motorcycles, motorcycles Related parts, parts and skins and landing gear pods, winglets, spoilers, edges, ladders, elevators, failings, ribs and other aircraft parts, parts and skins, windmill blades, inverters for hybrid and electric vehicles It is useful in a wide range of housings for electronic devices such as housings, and is particularly excellent in impact strength and tensile elongation at break. Idoreru Related parts are useful in automobile engine around wiring cover (corrugated tube) and the like, the effect of industrial exert its is exceptional.

  The form of the present invention considered to be the best by the present inventor is a collection of the preferable ranges of the above requirements. For example, typical examples are described in the following examples. Of course, the present invention is not limited to these forms.

[Evaluation of resin composition]
(1) Impact strength A notch-free Charpy impact strength of a test piece (dimension: length 80 mm × width 10 mm × thickness 4 mm) was measured by a method according to ISO 179 in an atmosphere at a temperature of 23 ° C. and a relative humidity of 50% RH. The larger this value, the better the impact strength of the resin composition.
(2) Tensile breakage Tensile breakage strain was measured by a method based on ISO527. It means that the larger the numerical value, the better the tensile breakage of the resin composition.

[Examples 1-11, Comparative Examples 1-7]
A polyarylene sulfide resin, a wholly aromatic polyamide fiber, and a fluororesin were melt-kneaded with each blending amount shown in Table 1 using a vent type twin screw extruder to obtain pellets. The vent type twin screw extruder used was TEX-30XSST (completely meshed, rotating in the same direction) manufactured by Nippon Steel Works. The extrusion conditions were a discharge rate of 12 kg / h, a screw rotation speed of 150 rpm, a vent vacuum of 3 kPa, and an extrusion temperature of 320 ° C. from the first supply port to the die part. The polyarylene sulfide resin and the wholly aromatic polyamide fiber were supplied from the first supply port to the extruder. The first supply port here is the supply port farthest from the die. The obtained pellets were dried at 130 ° C. for 6 hours in a hot air circulating dryer, and then cylinder temperature 320 ° C., mold temperature 150 ° C. by injection molding machine (SG-150U, manufactured by Sumitomo Heavy Industries, Ltd.) A test piece for evaluation was molded. Each component of the symbol notation in Table 1 is as follows.

<A component>
PPS-1: Polyphenylene sulfide resin obtained by the following production method [Production method]
A reactant containing 400 g para-diiodobenzene, 34 g sulfur and 1.0 g 1,3-diiodo-4-nitrobenzene was melt mixed at 180 ° C. The mixed mixture was subjected to a polymerization reaction while raising the temperature from 180 ° C. to 340 ° C. and reducing the pressure from normal pressure to 10 torr. After 4 hours have passed since the start of polymerization, 0.5 g of sulfur was added, and after 5 hours of polymerization reaction, 0.5 g of sulfur was added, and then 1 hour of polymerization reaction was performed. I got a molecule. The produced polymer had a number average molecular weight (Mn) of 7,630 and a dispersity (Mw / Mn) of 4.7.
PPS-2: Example 1 except that 0.5 g of sulfur was added after 4 hours from the start of polymerization, and 0.5 g of sulfur was additionally added after 3 hours of polymerization reaction. Polymerization was carried out by the same method. The produced polymer had a number average molecular weight (Mn) of 5,160 and a dispersity (Mw / Mn) of 4.8.
PPS-3: Example 1 except that 0.5 g of sulfur was added after 4 hours from the start of polymerization, and 0.5 g of sulfur was additionally added after 6 hours of polymerization reaction. Polymerization was carried out by the same method. The produced polymer had a number average molecular weight (Mn) of 7,510 and a dispersity (Mw / Mn) of 3.0.
PPS-4: After 4 hours have passed since the start of polymerization, 0.5 g of sulfur was added, then 0.5 g of sulfur was added when the polymerization reaction was performed for 6 hours, and the polymerization reaction was further continued for 7 hours Polymerization was carried out in the same manner as in Example 1 except that 0.5 g of sulfur was additionally charged at the time of carrying out the process. The produced polymer had a number average molecular weight (Mn) of 10,700 and a dispersity (Mw / Mn) of 4.3.
PPS-5: After 4 hours have passed since the start of polymerization, 0.5 g of sulfur was added, then 0.5 g of sulfur was added when the polymerization reaction was performed for 6 hours, and the polymerization reaction was further continued for 7 hours Polymerization was carried out in the same manner as in Example 1 except that 1.0 g of sulfur was additionally charged at the time of carrying out. The produced polymer had a number average molecular weight (Mn) of 9,990 and a dispersity (Mw / Mn) of 5.4.
PPS-6: Implemented except that 0.5 g of sulfur was added after 4 hours from the start of polymerization, and 1.0 g of sulfur was changed to additional addition after 3 hours of polymerization reaction. Polymerization was carried out in the same manner as in Example 1. The produced polymer had a number average molecular weight (Mn) of 5,160 and a dispersity (Mw / Mn) of 5.3.

<B component>
B-1: wholly aromatic polyamide fiber (manufactured by Teijin Limited: para-aramid fiber T322EH major axis 12 μm, cut length 3 mm, polyester-based sizing agent)
B-2: Totally aromatic polyamide fiber (manufactured by Teijin Limited: Para-aramid fiber T322UR, major axis 12 μm, cut length 3 mm, urethane-based sizing agent)
B-3: Totally aromatic polyamide fiber (manufactured by Teijin Limited: Para-aramid fiber T324, major axis 12 μm, cut length 3 mm, polyethersulfone sizing agent)

<C component>
C-1: Polytetrafluoroethylene (manufactured by Kitamura KTL-620, baked type, melting point 328 ° C.)
C-2: Polytetrafluoroethylene (manufactured by Kitamura KTL-450A baked type melting point 328 ° C.)
C-3: Polytetrafluoroethylene (manufactured by Daikin Industries, Ltd. Lubron L-5 non-fired type, melting point 328 ° C.)

Claims (11)

  (A) 10 to 150 parts by weight of (B) wholly aromatic polyamide fiber (B component) and (C) 5 to 100 parts by weight of fluororesin (C component) with respect to 100 parts by weight of polyarylene sulfide resin (A component) The polyarylene sulfide resin composition to be contained, the number average molecular weight (Mn) of the component A is 9,000 or less, and the dispersity (Mw / Mw) expressed by the weight average molecular weight (Mw) and the number average molecular weight (Mn) Mn) is 5.0 or less, The resin composition characterized by the above-mentioned.   2. The resin composition according to claim 1, wherein the total chlorine content is 500 ppm or less, and the total sodium content is 39 ppm or less.   The resin composition according to claim 1 or 2, wherein the component A is a polyarylene sulfide resin having a total chlorine content of 500 ppm or less and a total sodium content of 39 ppm or less.   The resin composition according to any one of claims 1 to 3, wherein the component A is a polyarylene sulfide resin having a total chlorine content of 50 ppm or less and a total sodium content of 8 ppm or less.   B resin is a para-aramid fiber, The resin composition in any one of Claims 1-4 characterized by the above-mentioned.   The component B is a wholly aromatic polyamide fiber bundled with at least one sizing agent selected from the group consisting of polyester, polyurethane and polyethersulfone resin. The resin composition described in 1.   The resin composition according to claim 6, wherein the component B is a wholly aromatic polyamide fiber bundled with an aromatic polyester.   The resin composition according to claim 1, wherein the component C is a polytetrafluoroethylene resin.   A molded article comprising the resin composition according to claim 1.   (A) A polyarylene having a number average molecular weight (Mn) of 9,000 or less and a dispersity (Mw / Mn) represented by a weight average molecular weight (Mw) and a number average molecular weight (Mn) of 5.0 or less. Polyarylene sulfide containing (B) wholly aromatic polyamide fiber (component B) 10 to 150 parts by weight and (C) fluororesin (component C) 5 to 100 parts by weight with respect to 100 parts by weight of sulfide resin (component A) A method for producing a resin composition.   The component A is a polyarylene sulfide resin obtained by a method in which a diiodoaryl compound, solid sulfur, and a polymerization terminator and / or a polymerization reaction catalyst are polymerized by direct heating without using a polar solvent. The manufacturing method of the resin composition of Claim 10.