JP7092573B2 - Resin composition - Google Patents

Description

The present invention is a resin composition composed of a polyarylene sulfide resin having a specific number average molecular weight and dispersibility, a total aromatic polyamide fiber, a fluororesin and an epoxy resin, and retains the excellent properties of the polyarylene sulfide resin. However, the present invention relates to a resin composition having excellent impact strength, tensile breaking strength and tensile breaking elongation.

Polyarylene sulfide resin is an engineering plastic having excellent 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 housing equipment parts. In recent years, with the miniaturization of electronic devices such as digital cameras and tablets, the thickness of the housing of the product used has been reduced, and the weight of vehicle-related parts such as automobiles has been reduced due to energy saving. Self-propelled vehicles such as hybrid vehicles and electric vehicles are being electrified for the purpose of reducing fossil fuels and fossil fuels. In these related applications, resinification from conventional metals is being considered for the purpose of reducing the weight of products. Above all, in resinification of these mechanical parts, metal substitution used especially for applications such as gears and bearings. 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 properties as compared with other resins, its impact strength, tensile breaking strength and tensile breaking elongation are not sufficient for use in these applications.

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

Special Fair 4-655866 Bulletin Japanese Unexamined Patent Publication No. 11-217504 Japanese Unexamined Patent Publication No. 8-85758 Japanese Unexamined Patent Publication No. 10-310700 Special Table 2013-528680 Gazette Special Table 2013-522385 Gazette Special Table 2013-522386 Publication No. Special Table 2013-522387A Gazette Japanese Unexamined Patent Publication No. 2016-166342 Japanese Unexamined Patent Publication No. 2016-1506025

An object of the present invention is a resin composition composed of a polyarylene sulfide resin having a specific number average molecular weight and a degree of dispersion, a total aromatic polyamide fiber, a fluororesin and an epoxy resin, and excellent properties of the polyarylene sulfide resin. It is an object of the present invention to provide a resin composition having excellent impact strength, tensile breaking strength and tensile breaking elongation while maintaining the above.

As a result of diligent studies by the present inventor, the polyarylene sulfide resin has a resin composition consisting of a polyarylene sulfide resin having a specific number average molecular weight and a degree of dispersion, a total aromatic polyamide fiber, a fluororesin and an epoxy resin. We have found that it is possible to exhibit excellent impact strength, tensile breaking strength and tensile breaking elongation while maintaining excellent characteristics, and have reached the present invention.

Specifically, the above-mentioned problems are (A) 100 parts by weight of the polyarylene sulfide resin (component A), (B) 10 to 150 parts by weight of the total aromatic polyamide fiber (component B), and (C) a fluororesin (C). A polyarylene sulfide resin composition containing 5 to 100 parts by weight of C component and 0.1 to 30 parts by weight of (D) epoxy resin (D component), and the number average molecular weight (Mn) of component A is 9,000. It is achieved by the resin composition having the following, characterized in that the degree of dispersion (Mw / Mn) represented by the weight average molecular weight (Mw) and the number average molecular weight (Mn) is 5.0 or less.

Hereinafter, the details of the present invention will be described.

(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, as its constituent units, 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. , Phenylene sulfide unit containing substituent, phenylene sulfide unit containing branched structure, etc., among which 70 mol% or more, particularly 90 mol% or more of p-phenylene sulfide unit is contained. Preferred, more preferably poly (p-phenylene sulfide).

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, and more preferably 8,000 or less. The lower limit of the number average molecular weight is not particularly specified, 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 decrease. 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. 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, and more preferably 4.8 or less. .. If the dispersity is greater than 5.0, the impact strength and tensile elongation at break of the resin composition will decrease. The lower limit of the degree of dispersion (Mw / Mn) is not particularly specified, but is preferably 2.7 or more. If the degree of dispersion is less than 2.7, burrs may be 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). 1-Chloronaphthalene was used as a solvent, and the column temperature was 210 ° C.

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. When the total chlorine content exceeds 500 ppm, the amount of generated gas may increase and the weld strength may decrease.

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. When it exceeds 39 ppm, not only the weld strength is lowered due to the increase in generated gas, but also the moisture absorption resistance is lowered by the increase in the water absorption amount of the resin due to the coordination bond between the sodium metal and the water molecule in a high temperature and high humidity environment. In some cases.

The method for producing the polyarylene sulfide resin is not particularly limited, and polymerization is carried out by a known method, but particularly suitable polymerization methods are US Registered Patents No. 4,746,758 and 4,786. , 713, Japanese Patent Application Laid-Open No. 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 directly heated and polymerized without a polar solvent.

The production method includes an iodide step and a polymerization step. In the iodination step, the aryl compound is reacted with iodine to obtain a diiodoaryl compound. In the subsequent polymerization step, a polyarylene sulfide resin is produced by polymerizing a diiodoaryl compound with solid sulfur using a polymerization inhibitor. Iodine is generated in the form of a gas in this step, and it is recovered and used again in the iodide step. Iodine is essentially a catalyst.

As a typical solid sulfur used in the above-mentioned production method, a cycloocta-sulfur form ( _S8 ) in which eight atoms are linked at room temperature can be mentioned. 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 examples of the diiodoaryl compound used in the above-mentioned production method include at least one selected from the group consisting of diiodobenzene, diiodonaphthalene, diiodobiphenyl, diiodobisphenol and diiodobenzophenone, and alkyl. Derivatives of iodoaryl compounds to which groups or sulfon groups are bonded or oxygen or nitrogen is introduced are also used. Iodoaryl compounds are classified into different isomers depending on the bond position of their iodine atom, and preferred examples of these isomers are p-diiodobenzene, 2,6-diiodonaphthalene, and p, p'-diiodine. Iodine is a compound such as biphenyl that is symmetrically located at both ends of the molecule of the aryl compound. The content of the iodine aryl 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 in consideration of the formation of disulfide bonds.

Typical polymerization terminators used in the above-mentioned production method include monoiodoaryl compounds, benzothiazoles, benzothiazolesulfenamides, thiurams, dithiocarbamates, aromatic sulfide compounds and the like. Preferred examples of the monoiodoaryl compound include at least one selected from the group consisting of iodobiphenyl, iodophenol, iodoaniline, and iodobenzophenone. Preferred examples of the benzothiazoles include at least one selected from the group consisting of 2-mercaptobenzothiazole and 2,2'-dithiobisbenzothiazole. Preferred examples of the benzothiazole sulfenamides are N-cyclohexylbenzothiazole2-sulfenamide, N, N-dicyclohexyl-2-benzothiazolesulfenamide, 2-morpholinothiobenzothiazole, benzothiazolesulfenamide. , Dibenzothiazole disulfide, N-dicyclohexylbenzothiazole 2-sulfenamide, at least one selected from the group. Preferred examples of thiurams include at least one selected from the group consisting of tetramethylthiuram monosulfide and tetramethylthiuram disulfide. Preferred examples of the dithiocarbamates include at least one selected from the group consisting of zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate. Preferred 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. Further, in any of the polymerization inhibitors, 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, a nitro group and the like, preferred examples thereof include a carboxyl group and an amino group, and further preferred examples thereof include a carboxyl group and an amino group. Examples include a carboxyl group and an amino group showing a peak of 1600 to 1800 cm ^-1 or 3300 to 3500 cm ^-1 on the FT-IR spectrum. The content of the polymerization inhibitor is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

A polymerization reaction catalyst may be used in the above-mentioned production method, and a nitrobenzene-based catalyst can be mentioned as a typical polymerization reaction catalyst. Preferred examples of nitrobenzene-based catalysts are 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, iodonitrobenzene, and 2,6-diiodo-4-. At least one selected from the group consisting of nitroamines may be mentioned. 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 in consideration of 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 having excellent cost performance can be obtained.

Further, the polyphenylene sulfide resin of the present invention may contain a polyphenylene sulfide resin obtained by another polymerization method.

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

The total aromatic polyamide constituting the fiber of the present invention is obtained by substantially one or more aromatic diamines and one or more aromatic dicarboxylic acid halides. However, a condensing agent typified by a system of triphenylphosphine and pyridine can be added to one or more aromatic diamines and one or more aromatic dicarboxylic acids. The total aromatic polyamide may be para-type or meta-type, but para-type is more preferable. Preferred aromatic diamines include p-phenylenediamine, benzene, 4,4 "-diamino-p-terphenyl, 2,7-diaminofluorene, 3,4-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 1, Examples thereof include 4-bis- (4-aminophenoxy) benzene, 4,4'-bis- (4-aminophenoxy) biphenyl, 9,10-bis- (4-aminophenyl) anthracene, and the like. Aromatic dicarboxylic acid halide. As, acid chloride is particularly preferable, and terephthalic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4'-diphenyldicarboxylic acid chloride, and one or more lower alkyl groups, lower alkoxy groups, and halogenos in the aromatic ring thereof. Examples thereof include those containing a non-reactive functional group such as a group and a nitro group. Further, when an aromatic dicarboxylic acid is used, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid and the like can be mentioned. Examples thereof include acids and those containing a non-reactive functional group such as one or more lower alkyl groups, lower alkoxy groups, halogeno groups, nitro groups, etc. in the aromatic ring thereof. Further, all aromatic polyamides preferred in the present invention. The main skeleton of the structure is expressed 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 indicate at least one kind of aromatic residue selected from the group consisting of the following general formulas [I] to [IV]. Note that Ar ₁ and Ar ₂ are different even if they are the same as each other. These aromatic residues may be partially substituted with a halogen atom or a lower alkyl group.)

Above all, when the total of Ar ₁ and Ar ₂ is 100 mol%, the total of the general formula [I] and the general formula [II], the total of the general formula [I] and the general formula [III], It is preferable that the total of the general formula [I] and the general formula [IV], or the general formula [I] 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. 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 [II] or the general formula [II] is used. [III] is 1 to 20 mol%.

The aromatic polyamide dope used as the undiluted solution for spinning may be solution-polymerized or a separately obtained total aromatic polyamide dissolved in a solvent, but a solution polymerization reaction is preferable. Further, a small amount of an inorganic salt may be added as a dissolution aid in order to improve the solubility. Examples of such an inorganic salt include lithium chloride and calcium chloride.

A generally known aprotonic organic polar solvent is used as the polymerization solvent or the redissolving solvent. For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N, N-dimethylformamide, N. , N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N, N-butylamide, N, N-dimethylisobutylamide, N-methylcaprolactam, N, N-dimethylmethoxyacetamide, N- Acetylpyrrolidine, N-acetylpiperidin, N-methylpiperidone-2, N, N'-dimethylethyleneurea, N, N'-dimethylpropyleneurea, N, N, N', N'-tetramethylmalonamide, N-acetyl There are pyrrolidone, N, N, N', N'-tetramethylurea, dimethylsulfoxide and the like, and examples of the redissolving solvent include strong acids such as concentrated sulfuric acid and methanesulfonic acid.

The degree of polymerization of the total aromatic polyamide is not particularly limited, but it is preferable that the degree of polymerization is high if it is soluble in a solvent. When the total aromatic polyamide is solution-polymerized, the ratio of the acid component to the diamine component is substantially the same molar reaction, but either component can be excessively used to control the degree of polymerization. Further, a monofunctional acid component and an amine component may be used as the terminal blocker.

When molding the total aromatic polyamide into a fibrous form, a method of wet-molding the total aromatic polyamide dope is usually used, and a method of directly discharging the dope into the coagulation bath or a method of providing an air gap is provided in the coagulation bath. There is a method of discharging inside. A poor solvent for the total aromatic polyamide is used in the coagulation bath, but usually a good solvent is added to solidify the total aromatic polyamide fibers so that the solvent for the total aromatic polyamide dope rapidly escapes and the total aromatic polyamide fibers are not defective. Adjust the speed. Generally, it is preferable to use water as a poor solvent and a solvent doped with an all-aromatic polyamide as a good solvent. The ratio of good solvent / poor solvent depends on the solubility and coagulation property of the total aromatic polyamide, but is preferably 15/85 to 40/60.

The fiber length of the total 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 it is less than 0.1 mm, the reinforcing effect may not be sufficient and the improvement of impact resistance may be insufficient, and if it exceeds 6 mm, it becomes difficult to handle during manufacturing, the fluidity of the composition is poor, and the moldability is poor. It may be defective.

Further, the totally aromatic polyamide fiber exerts an effect regardless of the presence or absence of focusing, but the focused fiber is preferable because it is easy to handle. Examples of the binder for focusing include polyester, polyurethane, and a polyether sulfone 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 kinds.

The content of the B component is 10 to 150 parts by weight, preferably 15 to 120 parts by weight, and more preferably 20 to 100 parts by weight with respect to 100 parts by weight of the A component. If the content of component B is less than 10 parts by weight, the impact strength, tensile breaking strength and tensile breaking elongation are not sufficiently improved, and if it exceeds 150 parts by weight, strand breakage and surging occur during kneading extrusion, resulting in productivity or workability. The problem arises that

(C component: fluororesin)
The fluororesin used as the C component of the present invention is a polymer having a carbon chain in the main chain and a bond of a fluorine atom 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, and tetrafluoroethylene-fluoroalkyl vinyl ether-. Examples thereof include fluoroolefin copolymers and ethylene-trichlorofluoroethylene copolymers. Of these, polytetrafluoroethylene is preferable, and either calcined or uncalcined polytetrafluoroethylene can be used. However, since polytetrafluoroethylene is easily reaggregated, a calcining treatment is performed to prevent reaggregation. In the form of powder, which has been subjected to the above, is preferable, and in particular, polytetrafluoroethylene which has been calcined at a calcining treatment temperature of 360 ° C. or higher is preferable. The melting point of polytetrafluoroethylene is preferably 320 to 335 ° C, more preferably 325 to 330 ° C, as measured by the DSC method in order to prevent reaggregation. The particle size of polytetrafluoroethylene is preferably 0.1 to 100 μm on average, more preferably 1 μm to 20 μm, by a method of measuring a dispersion dispersed in perchlorethylene by a light transmission method. The average particle size referred to here is a weight average particle size measured by a laser diffraction / scattering method (MICOTRAC method). Further, this polytetrafluoroethylene preferably has a number average molecular weight of 100,000 or more, and more preferably 200,000 or more.

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

The content of the C component is 5 to 100 parts by weight, preferably 5 to 80 parts by weight, and more preferably 5 to 35 parts by weight with respect to 100 parts by weight of the A component. If the content is less than 5 parts by weight, sufficient impact strength and tensile elongation at break cannot be obtained, and if it exceeds 100 parts by weight, strand breakage and surging occur during kneading.

(D component: epoxy resin)
The resin composition of the present invention contains an epoxy resin as a D component. The epoxy resin used as the D component may be any compound having an epoxy group in the molecular structure, and is preferably an epoxy resin having two or more epoxy groups in one molecule. When an epoxy resin having two or more epoxy groups in one molecule is used, the tensile breaking strength can be further improved by the cross-linking reaction of the epoxy resin. Specific examples thereof include bisphenol type epoxy, novolak type epoxy, cyclic aliphatic type epoxy, glycidyl ester type epoxy, glycidylamine type epoxy, trisphenolmethane type epoxy, dicyclopentadiene type epoxy, biphenyl type epoxy and the like. The D component can be used alone or in combination of two or more kinds of compounds. Examples of such epoxy resins are jER154, jER1001, jER1010, jER1256, YX4000 from Mitsubishi Chemical Corporation, EHPE3150 from Daicel Corporation, NC-3000, NC-7000, and XD-1000 from Nippon Kayaku Corporation. , EPPN-501H, which is commercially available and easily available.

The epoxy equivalent of the D component is preferably 100 to 10,000 g / eq, more preferably 125 to 9,500 g / eq, and even more preferably 150 to 9,000 g / eq. If the epoxy equivalent is less than 100 g / eq, thickening during kneading and extrusion is likely to occur, and if it exceeds 10,000 g / eq, sufficient tensile breaking strength may not be obtained. The epoxy equivalent of the D component is measured according to JIS K 7236.

The content of the D component is 0.1 to 30 parts by weight, preferably 1 to 28 parts by weight, and more preferably 2 to 25 parts by weight with respect to 100 parts by weight of the A component. If the content is less than 0.1 parts by weight, sufficient tensile breaking strength cannot be obtained, and if it exceeds 30 parts by weight, the viscosity increases due to the heat during kneading extrusion, and it becomes difficult to pull the strands.

(Other ingredients)
The resin composition in the present invention may 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), methylmethacrylate / butadiene-styrene copolymer (MBS resin) and silicone-acrylic composite rubber graft copolymer. Examples thereof include graft copolymer resins, and 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.

The resin composition in the present invention may contain other thermoplastic resins as long as the effects of the present invention are not impaired. Examples of other thermoplastic resins include general-purpose plastics typified by polyethylene resin, polypropylene resin, polyalkyl methacrylate resin, polyphenylene ether resin, polyacetal resin, aromatic polyester resin, liquid crystal polyester resin, and cyclic polyolefin resin. Engineering plastics typified by polyarylate resins (acrystalline polyarylate, liquid crystal polyarylate), etc., so-called super engineering plastics such as polyether ether ketone, polyetherimide, polysulfone, polyether sulfone, etc. Can be mentioned.

In the resin composition of the present invention, antioxidants, heat-stabilizing agents (hindered phenol-based, hydroquinone-based, phosphite-based and their substitutes, etc.) and weather resistant agents (resorcinol) are contained as long as the effects of the present invention are not impaired. System, salicylate system, benzotriazole system, benzophenone system, hindered amine system, etc.), mold release agent and lubricant (montanoic acid and its metal salt, its ester, its half ester, stearyl alcohol, stearamide, various bisamides, bisurea and polyethylene wax. Etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (niglosin, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizing agents (octyl oxybenzoate, N-butylbenzene sulfone, etc.) Antistatic agents (alkylsulfate-type anionic antistatic agents, quaternary ammonium salt-type cationic antistatic agents, non-ionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine-based amphoteric antistatic agents) Agents, etc.), flame retardants (eg, hydroxides such as red phosphorus, phosphate ester, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, etc. A brominated epoxy resin or a combination of these bromine-based flame retardants and antimony trioxide, etc.) and other polymers can be added.

The resin composition in the present invention may contain a filler other than the total aromatic polyamide fiber as long as the effect of the present invention is not impaired. The material is not particularly limited, but a filler such as fibrous, plate-like, powder-like, or 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, stone wool fiber, metal fiber, warastenite, seri. Silicates such as site, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, swellable layered silicates such as montmorillonite, synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide. Metal compounds such as calcium carbonate, magnesium carbonate, carbonates such as dolomite, sulfates such as calcium sulfate, barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and non-fibers such as silica. Examples thereof include the state fillers, which may be hollow, and further, two or more kinds of these fillers can be used in combination.

In addition, these fillers are pretreated with organic onium ions for coupling agents such as isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds, and swellable layered silicates. It is preferable to use it in the sense of obtaining better mechanical strength.

The resin composition of the present invention may contain a conductive filler as a filler in order to impart further conductivity. The material is not particularly limited, but the conductive filler is not particularly limited as long as it is a conductive filler usually used for making a resin conductive, and specific examples thereof include the carbon fibers and metals described above. Examples include powder, metal flakes, metal ribbons, metal fibers, metal oxides, carbon fibers coated with a conductive substance, inorganic fillers, carbon powder, graphite, carbon flakes, scaly carbon and the like.

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

Specific examples of the metal oxide include SnO ₂ (antimony doping), In ₂ O ₃ (antimony doping), ZnO (aluminum doping), and the like, and these are surfaces of titanate-based, aluminum-based, silane-based coupling agents, and the like. The surface may be treated with a treatment agent.

Specific examples of the conductive substance in the inorganic filler coated with the conductive substance include aluminum, nickel, silver, carbon, SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope) and the like. The inorganic fillers to be coated include mica, glass beads, glass fibers, potassium titanate whiskers, barium sulfate, zinc oxide, titanium oxide, aluminum borate whiskers, zinc oxide whiskers, titanium acid whiskers, silicon carbide whiskers, etc. Can be exemplified. Examples of the coating method include a vacuum vapor deposition method, a sputtering method, an electroless plating method, and a baking method. Further, these may be surface-treated with a surface treatment agent such as a titanate-based, aluminum-based, or silane-based coupling agent.

Carbon powder is classified into acetylene black, gas black, oil black, naphthalin black, thermal black, furnace black, lamp black, channel black, roll black, disc black, etc. according to its raw material and manufacturing 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.

(Manufacturing 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, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, or an extruder. It is preferable to melt-knead by a twin-screw extruder, and if necessary, it is preferable to supply an arbitrary component to other melt-mixed components from a second supply port using a side feeder or the like.

The resin extruded as described above is either directly cut and pelletized, or the strands are cut and pelletized with a pelletizer after forming the strands. When it is necessary to reduce the influence of external dust and the like during pelletization, it is preferable to clean the atmosphere around the extruder. The shape of the obtained pellet can take a general shape such as a cylinder, a prism, and a sphere, but is more preferably a cylinder. The diameter of the cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, 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, 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, still more preferably 50 ppm or less. When the total chlorine content exceeds 500 ppm, the amount of generated gas may increase and the weld strength may decrease.

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. When it exceeds 39 ppm, not only the weld strength is lowered due to the increase in generated gas, but also the moisture absorption resistance is lowered by the increase in the water absorption amount of the resin due to the coordination bond between the sodium metal and the water molecule in a high temperature and high humidity environment. In some cases.

(About molded products)
A molded product using the resin composition of the present invention can be obtained by molding 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 insulating metal. Examples thereof include mold molding, rapid heating / cooling mold molding, two-color molding, multicolor molding, sandwich molding, and ultra-high-speed injection molding. In addition, either a cold runner method or a hot runner method can be selected for molding. Further, in extrusion molding, various deformed extruded products, sheets, films and the like can be obtained. Inflation method, calendar method, casting method, etc. can also be used for forming sheets and films. Further, it can be molded as a heat-shrinkable tube by applying a specific stretching operation. Further, the resin composition of the present invention can be made into a molded product by rotary molding, blow molding or the like.

Since the resin composition of the present invention is a resin composition having excellent impact strength, tensile breaking strength and tensile breaking elongation while retaining the excellent properties of the polyarylene sulfide resin, it is a personal computer (notebook, ultra). Books), tablets, housings for mobile phones, displays, OA devices, mobile phones, mobile information terminals, facsimiles, compact disks, portable MDs, portable radio cassettes, PDA (portable information terminals such as electronic notebooks), video cameras, digital Electric and electronic equipment housings such as still cameras, optical equipment, audio equipment, air conditioners, lighting equipment, entertainment equipment, toy equipment, and other home appliances, and internal parts such as trays and chassis, and building materials such as cases, mechanical parts, and panels. Applications, motor parts, alternator terminals, alternator connectors, IC regulators, potential meter bases for light diers, suspension parts, various valves such as exhaust gas valves, fuel-related, exhaust system or intake system various pipes, air intake nozzle snorkel, intake manifold, Various arms, various frames, various hinges, various bearings, fuel pumps, gasoline tanks, CNG tanks, engine cooling water joints, carburetor main body, carburetor spacers, exhaust gas sensors, cooling water sensors, oil temperature sensors, brake pad wear sensors, Throttle position sensor, crank shaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distribution Butter, starter switch, starter relay, wire harness for transmission, window washer nozzle, air conditioner panel switch board, coil for fuel-related electromagnetic valve, 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 Filters, igniter cases, undercovers, scuff plates, pillar trims, propeller shafts, wheels, fenders, facers, bumpers, bumper beams, bonnets, aero parts, platforms, cowl louvers, roofs, instrument panels, spoilers and various modules. Automotive, two-wheeled vehicle related parts, parts and outer panels and landing gear pods, winglets, spoilers, edges, rudder, elevators, failing, ribs and other aircraft related parts, parts and outer panels, windmill blades, hybrid vehicles and electric vehicles. It is widely useful in electronic equipment housings such as inverter housings for automobiles, and because it is particularly excellent in impact strength and tensile elongation at break, bearings and gears for automobiles, industrial machinery and leisure tools, packing, guide rail related parts, automobile engines It is useful for peripheral wiring covers (corrugated tubes), etc., and its industrial effect is exceptional.

The embodiment of the present invention, which the present inventor considers to be the best at present, is a collection of preferable ranges of the above-mentioned requirements. For example, a representative example thereof will be described in the following examples. Of course, the present invention is not limited to these forms.

[Evaluation of resin composition]
(1) Impact strength A test piece (dimensions: length 80 mm × width 10 mm × thickness 4 mm) was measured for notch-free Charpy impact strength in an atmosphere of a temperature of 23 ° C. and a relative humidity of 50% RH by a method compliant with ISO179. The larger this value is, the better the impact strength of the resin composition is.
(2) Tensile breaking strength The tensile breaking strength was measured by a method conforming to ISO527. The larger this value is, the better the tensile breaking strength of the resin composition is.
(3) Tensile breaking elongation The tensile breaking elongation was measured by a method conforming to ISO527. The larger this value is, the more excellent the tensile elongation at break of the resin composition is.

[Examples 1 to 17, Comparative Examples 1 to 9]
Polyarylene sulfide resin, total aromatic polyamide fiber, fluororesin and epoxy resin were melt-kneaded at each blending amount shown in Table 1 using a bent twin-screw extruder to obtain pellets. The vent type twin-screw extruder was manufactured by Japan Steel Works, Ltd .: TEX-30XSST (complete meshing, rotating in the same direction). The extrusion conditions were a discharge rate of 12 kg / h, a screw rotation speed of 150 rpm, a vacuum degree of vent of 3 kPa, and an extrusion temperature of 300 ° C. from the first supply port to the die portion. The polyarylene sulfide resin and the total aromatic polyamide fiber were supplied to the extruder from the first supply port. 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 circulation type dryer, and then used by an injection molding machine (SG-150U manufactured by Sumitomo Heavy Industries, Ltd.) to have a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. A test piece for evaluation was molded. Each component of the symbol notation in Table 1 is as follows.

<Component A>
PPS-1: Polyphenylene sulfide resin obtained by the following production method [Production method]
A reaction product containing 400 g of para-iodobenzene, 34 g of sulfur and 1.0 g of 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 polymerization was started, 0.5 g of sulfur was added, and then 0.5 g of sulfur was additionally added when the polymerization reaction was carried out for 5 hours, and then the polymerization reaction was carried out for 1 hour to obtain a high molecular weight. Obtained 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 4 hours after the start of the polymerization and 0.5 g of sulfur was additionally added when the polymerization reaction was carried out for 3 hours. Polymerization was carried out in the same manner as in the above. 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 4 hours after the start of polymerization and 0.5 g of sulfur was additionally added when the polymerization reaction was carried out for 6 hours. Polymerization was carried out in the same manner as in the above. 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 polymerization was started, 0.5 g of sulfur was added, and then 0.5 g of sulfur was additionally added when the polymerization reaction was carried out for 6 hours, and the polymerization reaction was further carried out for 7 hours. The polymerization was carried out by the same method as in Example 1 except that 0.5 g of sulfur was additionally added at the time of carrying out. 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 polymerization was started, 0.5 g of sulfur was added, and then 0.5 g of sulfur was additionally added when the polymerization reaction was carried out for 6 hours, and the polymerization reaction was further carried out for 7 hours. The polymerization was carried out by the same method as in Example 1 except that 1.0 g of sulfur was additionally added 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: Conducted except that 0.5 g of sulfur was added 4 hours after the start of polymerization and then 1.0 g of sulfur was added after the polymerization reaction was carried out for 3 hours. Polymerization was carried out by the same method 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: Total 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: Total 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: Total aromatic polyamide fiber (manufactured by Teijin Limited: para-aramid fiber T324 major axis 12 μm, cut length 3 mm, polyether sulfone-based focusing agent)

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

<D component>
D-1: Naphthol novolac type epoxy (NC-7000L epoxy equivalent manufactured by Nippon Kayaku Co., Ltd. 223 to 238 g / eq)
D-2: Bisphenol A type epoxy (manufactured by Mitsubishi Chemical Corporation jER1256 epoxy equivalent 7,500-8,500 g / eq)
D-3: Phenol novolac type epoxy (NC-3000 epoxy equivalent manufactured by Nippon Kayaku Co., Ltd. 265 to 285 g / eq)
D-4: Trisphenol methane type epoxy (EPPN-501H epoxy equivalent manufactured by Nippon Kayaku Co., Ltd. 162-172 g / eq)
D-5: Dicyclopentadiene type epoxy (XD-1000 epoxy equivalent manufactured by Nippon Kayaku Co., Ltd. 245 to 260 g / eq)

Claims (13)

(A) Polyarylene sulfide resin (component A) 100 parts by weight, (B) total aromatic polyamide fiber (component B) 10 to 150 parts by weight, (C) fluororesin (component C) 5 to 100 parts by weight, and (D) 0.1 to 30 parts by weight of at least one epoxy resin (D component) selected from the group consisting of bisphenol type epoxy, novolak type epoxy, trisphenolmethane type epoxy, dicyclopentadiene type epoxy and biphenyl type epoxy . It is a polyarylene sulfide resin composition contained, and the number average molecular weight (Mn) of the component A is 9,000 or less, and the degree of dispersion (Mw /) represented by the weight average molecular weight (Mw) and the number average molecular weight (Mn). A resin composition having a Mn) of 5.0 or less. 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. The resin composition according to any one of claims 1 to 4, wherein the component B is a para-aramid fiber. Any of claims 1 to 5, wherein the component B is a total aromatic polyamide fiber focused with at least one sizing agent selected from the group consisting of polyester, polyurethane and a polyether sulfone resin. The resin composition according to. The resin composition according to claim 6, wherein the component B is a total aromatic polyamide fiber focused on an aromatic polyester. The resin composition according to any one of claims 1 to 7, wherein the component C is a polytetrafluoroethylene resin. The resin composition according to any one of claims 1 to 8, wherein the component D is an epoxy resin having two or more epoxy groups in one molecule. The resin composition according to any one of claims 1 to 9, wherein the epoxy equivalent of the D component is 100 to 10,000 g / eq. A molded product comprising the resin composition according to any one of claims 1 to 10. (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. 10 to 150 parts by weight of (B) total aromatic polyamide fiber (B component), 5 to 100 parts by weight of (C) fluororesin (C component), and (D) bisphenol type with respect to 100 parts by weight of sulfide resin (A component). Polyarylene sulfide containing 0.1 to 30 parts by weight of at least one epoxy resin (D component) selected from the group consisting of epoxy, novolak type epoxy, trisphenol methane type epoxy, dicyclopentadiene type epoxy and biphenyl type epoxy. A method for producing a resin composition. The component A is a polyarylene sulfide resin obtained by directly heating and polymerizing a diiodoaryl compound, solid sulfur, and a polymerization terminator and / or a polymerization reaction catalyst without using a polar solvent. The method for producing a resin composition according to claim 12.