JP2023063213A - Polyarylene sulfide resin composition and molded article made of the same - Google Patents

Abstract

To provide a resin composition which has excellent impact strength, tensile breaking strength, tensile breaking elongation and dynamic friction coefficient while holding excellent characteristics that a polyarylene sulfide resin has.SOLUTION: A polyarylene sulfide resin composition contains, with respect to 100 pts.wt. of (A) a polyarylene sulfide resin (component A), 10-150 pts.wt. of (B) a wholly aromatic polyamide fiber (component B), 3-50 pts.wt. of (C) a polyolefin resin (component C) which has a melt flow rate (MFR) measured under conditions of 190°C and a 10 kg load of 20 g/10 min or less and has no polar group, 0.1-20 pts.wt. of (D) an olefinic copolymer (component D) having at least one functional group selected from the group consisting of an epoxy group and an acid anhydride group, and 0.1-20 pts.wt. of (E) an epoxy resin (component E).SELECTED DRAWING: None

Description

TECHNICAL FIELD The present invention relates to a resin composition having excellent impact strength, tensile strength at break, tensile elongation at break and dynamic friction coefficient while maintaining the excellent properties of polyarylene sulfide resin, and a molded article made therefrom.

Polyarylene sulfide resins are engineering plastics that are excellent in chemical resistance, heat resistance, mechanical properties, and the like. Therefore, 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 digital cameras, tablets, and other electronic devices, the housings used in these products are becoming thinner. The electrification of self-propelled vehicles, including hybrid vehicles and electric vehicles, is progressing for the purpose of reducing emissions and fossil fuel consumption. In these related applications, the use of resin instead of conventional metals is being studied in order to reduce the weight of products. The resin material used for this purpose is required to have impact strength, ductility, and sliding properties such as low wear and a low coefficient of friction. However, although polyarylene sulfide resins themselves have sliding properties compared to other resins, they are not sufficient in impact strength, tensile strength at break and tensile elongation at break for use in these applications. In addition, in recent years, there has been a demand for members that can achieve a long life even in harsh environments such as high temperatures and high loads, requiring higher sliding properties than ever before.

As means for solving this problem, Patent Documents 1 and 2 disclose a resin composition comprising polyphenylene sulfide resin, fluororesin and aromatic polyamide fiber, polyphenylene sulfide, for the purpose of improving sliding properties and mechanical properties. A resin composition comprising a resin, a conductive potassium titanate whisker, a polytetrafluoroethylene resin, a metal oxide and an aromatic polyamide fiber is disclosed, respectively. No mention is made of strength and tensile elongation at break. Patent Document 3 discloses a resin composition comprising a polyphenylene sulfide resin, a fluororesin, an aromatic polyester resin, and a para-aromatic polyamide fiber. No mention is made of tensile strength at break and tensile elongation at break. Patent Document 4 discloses a resin composition composed of a polyarylene sulfide resin and aramid fibers having high tenacity. Although it mentions tensile strength at break and tensile elongation at break, it describes impact strength and slidability. not Patent Document 5 proposes a resin composition comprising a polyarylene sulfide resin having a specific number-average molecular weight and degree of dispersion, a wholly aromatic polyamide fiber, and a fluororesin. Although it mentions elongation, it does not mention a dynamic friction coefficient.

Japanese Patent Publication No. 4-65866 JP-A-11-217504 JP-A-8-85758 JP-A-10-310700 Japanese Patent Application Laid-Open No. 2020-002208

An object of the present invention is to provide a resin composition having excellent impact strength, tensile strength at break, tensile elongation at break and coefficient of dynamic friction while maintaining the excellent properties of polyarylene sulfide resin, and a molded product made of the same. be.

As a result of extensive studies, the inventors of the present invention have found a resin composition comprising a polyarylene sulfide resin, a wholly aromatic polyamide fiber, a polyolefin resin having a specific melt flow rate (MFR) value, an olefin copolymer and an epoxy resin. , while maintaining the excellent properties possessed by polyarylene sulfide resins, they also have excellent impact strength, tensile strength at break, tensile elongation at break and dynamic friction coefficient, leading to the present invention.

That is, the present invention is as follows.
1. (A) Polyarylene sulfide resin (component A) 100 parts by weight, (B) wholly aromatic polyamide fiber (component B) 10 to 150 parts by weight, (C) 190 ° C., melt measured under 10 kg load 3 to 50 parts by weight of a polyolefin resin (component C) having no polar group and having a flow rate (MFR) of 20 g/10 min or less; A polyarylene sulfide resin composition characterized by containing 0.1 to 20 parts by weight of an olefin copolymer having a functional group (component D) and 0.1 to 20 parts by weight of (E) an epoxy resin (component E). thing.
2. Component A comprises (A-1) a polyarylene sulfide resin (Component A-1) having at least one functional group selected from the group consisting of a hydroxy group, an amino group and a carboxy group at the end (Component A-1) 10 to 100% by weight and ( A-2) The resin composition according to item 1 above, which is a polyarylene sulfide resin containing 0 to 90% by weight of a polyarylene sulfide resin (component A-2) that does not contain the functional group at its end.
3. 3. The resin composition according to item 1 or 2, wherein the C component is a polyethylene resin.
4. 4. The resin composition as described in any one of 1 to 3 above, wherein component D is an α-olefin copolymer having an epoxy group.
5. 5. The resin composition as described in any one of 1 to 4 above, wherein the E component is an epoxy resin having an epoxy equivalent of 100 to 10,000 g/eq.
6. A molded article made of the resin composition according to any one of 1 to 5 above.

The details of the present invention will be described below.
(A component: polyarylene sulfide resin)
As the polyarylene sulfide resin used as component A in the present invention, any resin may be used as long as it belongs to the category called polyarylene sulfide resin.

Examples of polyarylene sulfide resins include p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, and diphenylene sulfide units. , substituent-containing phenylene sulfide units, branched structure-containing phenylene sulfide units, etc. Among them, those containing 70 mol% or more, particularly 90 mol% or more of p-phenylene sulfide units are preferable. Furthermore, poly(p-phenylene sulfide) is more preferred.

The terminal functional group of the polyarylene sulfide resin is not particularly limited, but polyarylene sulfide resin having at least one functional group selected from the group consisting of hydroxyl group, amino group and carboxy group at the terminal (component A-1) 10- A polyarylene sulfide resin comprising 100% by weight and 0 to 90% by weight of a polyarylene sulfide resin having no functional group at its end (component A-2) is preferred.

The method for producing the polyarylene sulfide resin is not particularly limited, and it is polymerized by a known method. , 713, JP-A-2013-522385, JP-A-2012-233210, and the production methods described in Japanese Patent No. 5167276. These production methods are methods in which a diiodoaryl compound and solid sulfur are directly heated and polymerized without a polar solvent.

The manufacturing method includes an iodination step and a polymerization step. In the iodination step, an aryl compound is reacted with iodine to give a diiodoaryl compound. In the subsequent polymerization step, the diiodoaryl compound is polymerized with solid sulfur using a polymerization terminator to prepare a polyarylene sulfide resin. Iodine is generated in gaseous form in this process, and this is recovered and used again in the iodination process. Iodine is essentially a catalyst.

A representative solid sulfur used in the method of preparation includes the cyclooctasulphur form (S ₈ ) with 8 atoms linked at room temperature. However, the sulfur compound used in the polymerization reaction is not limited and may be used in any form as long as it is solid or liquid at room temperature.

Typical 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 Derivatives of iodoaryl compounds to which a group or sulfone group is attached, or to which oxygen or nitrogen is introduced are also used. Iodoaryl compounds are classified into different isomers depending on the bonding position of the iodine atom, and preferred examples of these isomers are p-diiodobenzene, 2,6-diiodonaphthalene, and p,p'-diiodine. It is a compound in which iodine is symmetrically positioned at both ends of an aryl compound, 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 in consideration of the formation of disulfide bonds.

Typical polymerization terminator used in the production method include monoiodoaryl compounds, benzothiazoles, benzothiazolesulfenamides, thiurams, dithiocarbamates, aromatic sulfide compounds and the like. Preferred examples of monoiodoaryl compounds include at least one selected from the group consisting of iodobiphenyl, iodophenol, iodoaniline, and iodobenzophenone. Preferred examples of benzothiazoles include at least one selected from the group consisting of 2-mercaptobenzothiazole and 2,2'-dithiobisbenzothiazole. Preferred examples of benzothiazolesulfenamides include N-cyclohexylbenzothiazole 2-sulfenamide, N,N-dicyclohexyl-2-benzothiazolesulfenamide, 2-morpholinothiobenzothiazole, and benzothiazolesulfenamide. , dibenzothiazole disulfide, and N-dicyclohexylbenzothiazole 2-sulfenamide. Preferred examples of thiurams include at least one selected from the group consisting of tetramethylthiuram monosulfide and tetramethylthiuram disulfide. Preferred examples of dithiocarbamates include at least one selected from the group consisting of zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate. Preferred examples of aromatic sulfide compounds 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 carboxy group, a mercapto group, an amino group, a cyano group, a sulfo group, a nitro group, etc. Preferred examples include a hydroxy group, an amino group and a carboxy group. Preferred examples include hydroxy, amino and carboxy groups showing peaks at 3200-3600 cm ^-1 , 1600-1800 cm ^-1 and 3300-3500 cm ^-1 on the FT-IR spectrum. 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 in consideration of the formation of disulfide bonds.

A polymerization reaction catalyst may be used in the production method, and a typical polymerization reaction catalyst is a nitrobenzene-based catalyst. Preferred examples of nitrobenzene-based catalysts include 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, iodonitrobenzene, 2,6-diiodo-4- At least one selected from the group consisting of nitroamines can 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 possible to obtain a polyphenylene sulfide resin excellent in cost performance without substantially reducing the chlorine content and sodium content.
The polyphenylene sulfide resin of the present invention may also contain polyphenylene sulfide resins obtained by other polymerization methods.

(B component: wholly aromatic polyamide fiber)
As the wholly 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 wholly aromatic aramid fiber. By using a wholly aromatic polyamide fiber, it is possible to ensure both the mechanical strength and toughness required for the sliding member, and to exhibit excellent low abrasion resistance. Examples of wholly aromatic aramid fibers include meta-aramid fibers and para-aramid fibers, among which para-aramid fibers are preferred.

The wholly aromatic polyamide constituting the fiber of the present invention is substantially obtained by combining one or more aromatic diamines and one or more aromatic dicarboxylic acid halides. However, to one or more aromatic diamines and one or more aromatic dicarboxylic acids, it is also possible to add a condensing agent represented by, for example, the system of triphenylphosphite and pyridine. 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 As, acid chlorides are particularly preferred, and terephthalic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4'-diphenyldicarboxylic acid chloride, and one or more lower alkyl groups, lower alkoxy groups, halogeno group, nitro group, etc. When using an aromatic dicarboxylic acid, terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid. acids, and those containing non-reactive functional groups such as one or more lower alkyl groups, lower alkoxy groups, halogeno groups, nitro groups, etc. in the aromatic ring thereof. The structure is such that the main skeleton is represented by the following formula (1).

—NH—Ar ₁ —NH—CO—Ar ₂ —CO— (1)
(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]. Note that Ar ₁ and Ar ₂ are the same or different In addition, some of the hydrogen atoms in these aromatic residues may be substituted with halogen atoms or lower alkyl groups.)

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

The aromatic polyamide dope, which is the spinning stock solution, may be obtained by solution polymerization or by dissolving a separately obtained wholly aromatic polyamide in a solvent, but it is preferably obtained by solution polymerization reaction. In order to improve solubility, a small amount of inorganic salt may be added as a dissolution aid. Examples of such inorganic salts include lithium chloride and calcium chloride.

As a polymerization solvent or re-dissolving solvent, generally known aprotic organic polar solvents are used. , 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, dimethylsulfoxide, etc., and the re-dissolving solvent includes strong acids such as concentrated sulfuric acid and methanesulfonic acid.

Although the degree of polymerization of the wholly aromatic polyamide is not particularly limited, a higher degree of polymerization is preferable as long as it is soluble in a solvent. When the wholly aromatic polyamide is solution polymerized, the acid component and the diamine component are reacted at a substantially equimolar ratio, but either component can be used in excess for controlling the degree of polymerization. Moreover, you may use a monofunctional acid component and an amine component as a terminal blocking agent.

When a wholly aromatic polyamide is molded into a fibrous form, a method of wet molding a wholly aromatic polyamide dope is usually used. There is a way to eject inside. A poor solvent for the wholly aromatic polyamide is used in the coagulation bath, but in order to prevent the solvent from the wholly aromatic polyamide dope from escaping rapidly and causing defects in the wholly aromatic polyamide fiber, a good solvent is usually added to coagulate. Adjust speed. Generally, it is preferable to use water as the poor solvent and a solvent for the wholly aromatic polyamide dope as the good solvent. The good solvent/poor solvent ratio is preferably 15/85 to 40/60, depending on the solubility and coagulability of the wholly aromatic polyamide.

The fiber length of such a wholly aromatic polyamide fiber is preferably 0.1 mm or more and 6 mm or less, more preferably 0.5 mm or more and 4 mm or less. If it is less than 0.1 mm, the reinforcing effect may not be sufficient, and the improvement in impact resistance may be insufficient. It may become defective.

Such a wholly aromatic polyamide fiber exerts its effect regardless of whether it is bundled or not, but bundled fibers are preferable because they are easy to handle. Binders for bundling include polyester resins, polyurethane resins, polyethersulfone resins, etc. Among them, aromatic polyester resins are preferred. In the present invention, such heat-resistant organic fibers can be used singly or as a mixture of two or more.

The form of the wholly aromatic polyamide fiber is not particularly limited, and any form can be used, but it is preferable that the fiber is twisted from the viewpoint of handleability during production of the resin composition. By using a fiber bundle with a large twist number, the supply of the wholly aromatic polyamide fiber to the extruder may be stabilized. The twist number of the wholly aromatic polyamide fiber is preferably 10 to 500 twists/m, more preferably 50 to 450 twists/m, and still more preferably 100 to 400 twists/m.

The content of component B is 10 to 150 parts by weight, preferably 12 to 100 parts by weight, more preferably 13 to 60 parts by weight, still more preferably 14 to 40 parts by weight, per 100 parts by weight of component A. If the content of component B is less than 10 parts by weight, impact strength, tensile strength at break and tensile elongation at break will not be sufficiently improved, and if it exceeds 150 parts by weight, strand breakage and surging will occur during kneading extrusion, resulting in productivity or workability. is reduced.

(Component C: polyolefin resin having no polar group)
The present invention contains a polyolefin resin having no polar group as the C component. A polyolefin resin is a synthetic resin obtained by polymerizing or copolymerizing an olefinic monomer having a radically polymerizable double bond. The olefinic monomer is not particularly limited, and examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, α- Examples include olefins and conjugated dienes such as butadiene and isoprene. The olefinic monomers may be used alone or in combination of two or more. The polyolefin resin is not particularly limited, and examples thereof include homopolymers of ethylene, copolymers of ethylene and α-olefins other than ethylene, homopolymers of propylene, and copolymers of propylene and α-olefins other than propylene. ethylene homopolymers, copolymers of ethylene and α-olefins other than ethylene are preferred. Ethylene homopolymers are more preferred. Furthermore, polyethylene obtained by polymerizing ultra-high molecular weight ethylene and high or low molecular weight polyethylene by a multistage polymerization method is particularly preferable. Polyolefin resins may be used alone or in combination of two or more.

The polyolefin resin used as the C component in the present invention is a polyolefin resin having a melt flow rate (MFR) of 20 g/10 min or less measured under conditions of 190° C. and 10 kg load. The MFR is preferably 17 g/10 min or less, more preferably 15 g/10 min or less. If the MFR exceeds 20 g/10 min, the tensile strength at break will decrease. Although the lower limit of the MFR is not particularly limited, it is preferably 0.5 g/10 min or more. The above MFR was measured by a method based on JIS K7210.

The content of component C is 3 to 50 parts by weight, preferably 5 to 30 parts by weight, more preferably 7 to 20 parts by weight, per 100 parts by weight of component A. If the content is less than 3 parts by weight, the dynamic friction coefficient increases and the impact strength and tensile elongation at break decrease. If it exceeds 50 parts by weight, the tensile strength at break decreases.

(Component D: Olefin-based copolymer)
The olefinic copolymer used as component D in the present invention is an olefinic copolymer containing at least one functional group selected from the group consisting of epoxy groups and acid anhydride groups. In addition, a carboxylic anhydride group, a sulfonic anhydride group, etc. are mentioned as an acid anhydride group. The copolymer is preferably an α-olefin copolymer containing an epoxy group, more preferably a copolymer of an α-olefin and a glycidyl ester of an α,β-unsaturated carboxylic acid. Examples of the α-olefin include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, etc. Among them, ethylene is preferably used. Two or more of these α-olefins can also be used. Examples of glycidyl esters of α,β-unsaturated carboxylic acids include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. In addition, these copolymers further include α,β-unsaturated carboxylic acids such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, and butyl methacrylate, and their alkyl esters, acrylonitrile, and styrene. etc. may be copolymerized.

The content of component D is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 7 parts by weight, per 100 parts by weight of component A. If the content is less than 0.1 parts by weight, sufficient tensile breaking strength and impact strength cannot be obtained, and if it exceeds 20 parts by weight, there is a problem that strand breakage, surging, etc. occur during kneading extrusion, resulting in a decrease in productivity or processability. occur.

(E component: epoxy resin)
The epoxy resin used as component E may be any compound having an epoxy group in its molecular structure, 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, it may be possible to further improve the tensile strength at break due to the crosslinking reaction of the epoxy resin. Specific examples include bisphenol-type epoxy, novolac-type epoxy, cycloaliphatic-type epoxy, glycidyl ester-type epoxy, glycidylamine-type epoxy, trisphenolmethane-type epoxy, dicyclopentadiene-type epoxy, and biphenyl-type epoxy. Component E can be used alone or in combination of two or more compounds. Examples of such epoxy resins include jER154, jER1001, jER1010, jER1256, and YX4000 from Mitsubishi Chemical Corporation, EHPE3150 from Daicel Co., Ltd., and NC-3000, NC-7000, and XD-1000 from Nippon Kayaku Co., Ltd. , EPPN-502H, and EOCN-104S, and are readily available.

The epoxy equivalent of component E is preferably 100 to 10,000 g/eq, more preferably 125 to 9,500 g/eq, even more preferably 150 to 9,000 g/eq. If the epoxy equivalent is less than 100 g/eq, thickening tends to occur during kneading and extrusion, and if it exceeds 10,000 g/eq, sufficient tensile strength at break may not be obtained. In addition, the epoxy equivalent of E component is measured according to JISK7236.

The content of component E is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 7 parts by weight, per 100 parts by weight of component A. If the content is less than 0.1 parts by weight, sufficient tensile strength at break and impact strength cannot be obtained, and if it exceeds 20 parts by weight, the viscosity increases due to heat during kneading and extrusion, making it difficult to draw strands.

(other ingredients)
The resin composition of the present invention may contain an elastomer component within a range that does not impair the effects of the present invention. Suitable elastomer components include acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), and core-shell such as silicone-acrylic composite rubber graft copolymer. Examples thereof include graft copolymer resins, thermoplastic elastomers such as silicone thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers, and polyurethane thermoplastic elastomers.

Other thermoplastic resins may be contained in the resin composition of the present invention as long as the effects of the present invention are not impaired. Other thermoplastic resins include, for example, general-purpose plastics represented by polyalkyl methacrylate resins, polyphenylene ether resins, polyacetal resins, aromatic polyester resins, liquid crystalline polyester resins, cyclic polyolefin resins, polyarylate resins (amorphous and so-called super engineering plastics such as polyetheretherketone, polyetherimide, polysulfone, and polyethersulfone.

Antioxidants, heat stabilizers (hindered phenols, hydroquinones, phosphites and substituted products thereof, etc.), weathering agents (resorcinol , salicylates, benzotriazoles, benzophenones, hindered amines, etc.), release agents and lubricants (montanic acid and its metal salts, its esters, its half esters, stearyl alcohol, stearamide, various bisamides, bisurea and polyethylene waxes etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfone amide, etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents agent, etc.), flame retardants (e.g., red phosphorus, phosphates, melamine cyanurate, magnesium hydroxide, hydroxides such as aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resins or combinations of these brominated flame retardants with antimony trioxide), other polymers can be added.

The resin composition of the present invention may contain a filler other than the wholly aromatic polyamide fiber within a range that does not impair the effects of the present invention. Although the material is not particularly limited, fillers such as fibrous, plate-like, powdery and granular fillers can be used. Specifically, for example, fibrous fillers such as carbon fiber, glass fiber, potash titanate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, metal fiber, wollastonite, ceri Site, kaolin, mica, clay, bentonite, asbestos, talc, silicates such as alumina silicate, swelling layered silicates such as montmorillonite and synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide Carbonates such as calcium carbonate, magnesium carbonate, dolomite, sulfates such as calcium sulfate, barium sulfate, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate and non-fibers such as silica These fillers may be hollow, and two or more of these fillers may be used in combination.

These fillers are pretreated with coupling agents such as isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds, and organic onium ions in the case of swelling layered silicates. Its use is preferable in terms 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 that is usually used for making resin conductive, and specific examples thereof include the carbon fiber and metal Powder, metal flakes, metal ribbons, metal fibers, metal oxides, carbon fibers coated with a conductive substance, inorganic fillers, carbon powder, graphite, carbon flakes, scale-like carbon, and the like. Specific examples of metal powders, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. Specific examples of metal species of metal fibers include iron, copper, stainless steel, aluminum, and brass. Such metal powders, metal flakes, metal ribbons, and metal fibers may be surface-treated with a titanate-based, aluminum-based, or silane-based surface treatment agent. Specific examples of metal oxides include SnO ₂ (antimony-doped), In ₂ O ₃ (antimony-doped), and ZnO (aluminum-doped). It may be surface-treated with a treating agent. Specific examples of conductive substances in inorganic fillers coated with conductive substances include aluminum, nickel, silver, carbon, SnO ₂ (antimony-doped), and In ₂ O ₃ (antimony-doped). 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, titanate whiskers, silicon carbide whiskers, and the like. can be exemplified. Examples of coating methods include a vacuum deposition method, a sputtering method, an electroless plating method, and a baking method. Moreover, 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, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disk black, etc. according to its raw material and manufacturing method. The raw material and manufacturing method of the carbon powder that can be used in the present invention are not particularly limited, 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 at the same time or in any order using a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading rolls, and extruder. Melt-kneading by a twin-screw extruder is preferable, and if necessary, it is preferable to feed optional components into other melt-mixed components from a second feed port using a side feeder or the like. The resin extruded as described above is either directly cut and pelletized, or is pelletized by forming strands and then cutting the strands with a pelletizer. It is preferable to clean the atmosphere around the extruder when it is necessary to reduce the influence of external dust during pelletization. The shape of the obtained pellets can take general shapes such as cylinders, prisms, and spheres, but cylinders are more preferable. The diameter of such a cylinder is preferably 1-5 mm, more preferably 1.5-4 mm, still more preferably 2-3.5 mm. On the other hand, the length of the cylinder is preferably 1-30 mm, more preferably 2-5 mm, and even more preferably 2.5-4 mm.

(About molded products)
A molded article using the resin composition of the present invention can be obtained by molding the pellets produced as described above. It is preferably 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, heat insulation metal Mold molding, rapid heating and cooling mold molding, two-color molding, multi-color molding, sandwich molding, ultra-high speed injection molding and the like can be mentioned. For molding, either cold runner method or hot runner method can be selected. Extrusion molding can also provide various shaped extruded products, sheets, films, and the like. Inflation method, calendering method, casting method and the like can be used for forming sheets and films. Furthermore, it can be molded as a heat-shrinkable tube by subjecting it to a specific stretching operation. The resin composition of the present invention can also be molded by rotational molding, blow molding, or the like.

The resin composition of the present invention is a resin composition having excellent impact strength, tensile strength at break, tensile elongation at break and dynamic friction coefficient while maintaining the excellent properties of polyarylene sulfide resin. books, ultrabooks), tablets, mobile phone housings, displays, OA equipment, mobile phones, personal digital assistants, facsimiles, compact discs, portable MDs, portable radio cassettes, PDAs (personal digital assistants such as electronic notebooks), videos Cameras, digital still cameras, optical equipment, audio equipment, air conditioners, lighting equipment, recreational goods, toys, and other electrical and electronic equipment housings and internal members such as trays and chassis, their cases, mechanical parts, and panels construction materials, motor parts, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light gear, suspension parts, various valves such as exhaust gas valves, fuel-related pipes, exhaust or intake system pipes, air intake nozzle snorkels, etc. Intake manifolds, various arms, various frames, various hinges, various bearings, fuel pumps, gasoline tanks, CNG tanks, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pads Wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake butt wear sensor, thermostat base for air conditioner, heating warm air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor Parts, distributors, starter switches, starter relays, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch boards, coils for fuel-related electromagnetic valves, fuse connectors, battery trays, AT brackets, headlamp supports, pedal housings, 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 cases, undercovers, 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 for automobiles , motorcycle-related parts, members and skins, aircraft-related parts such as landing gear pods, winglets, spoilers, edges, ladders, elevators, failings, ribs, members and skins, wind turbine blades, for hybrid and electric vehicles Inverter housings and other electronic device housings, etc., and especially excellent in impact strength and tensile elongation at break. It is useful for wiring covers (corrugated tubes) and the like, and its industrial effects are exceptional.

The best mode of the present invention, which the present inventors consider to be the best, summarizes the preferred ranges of the above requirements, and typical examples thereof 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 test piece (dimensions: length 80 mm x width 10 mm x thickness 4 mm) prepared by the following method was placed in an atmosphere of 23 ° C and relative humidity 50% RH. Strength was measured. The larger the numerical value, the better the impact strength of the resin composition.

(2) Tensile Breaking Strength Tensile breaking strength was measured by a method based on ISO527 using a test piece prepared by the following method. It means that the larger the numerical value, the better the tensile strength at break of the resin composition.

(3) Tensile elongation at break Using a test piece prepared by the following method, the tensile elongation at break was measured by a method based on ISO527. It means that the larger the numerical value, the better the tensile elongation at break of the resin composition.

(4) Coefficient of dynamic friction According to JIS K 7218 A method, a hollow cylindrical test piece with an outer diameter of 25.6 mm, an inner diameter of 20 mm, and a height of 15 mm was prepared by the following method. The pieces were slid using a friction wear tester (EFM-3-G, manufactured by Orientec Co., Ltd.) under the conditions of a surface pressure of 0.75 MPa, a sliding speed of 500 mm/s, and a sliding distance of 3000 m. The dynamic friction coefficient was measured every second over a sliding distance range of 300 to 3000 m, excluding initial wear, and the average value was calculated. The test was conducted three times, and the average value thereof was taken as the dynamic friction coefficient of the composition. It means that the smaller the numerical value, the better the dynamic friction coefficient of the resin composition.

[Examples 1 to 19, Comparative Examples 1 to 10]
A polyarylene sulfide resin, a wholly aromatic polyamide fiber, an olefin resin, an olefin copolymer, and an epoxy resin are melt-kneaded using a vented twin-screw extruder in the amounts shown in Tables 1 and 2 to form pellets. Obtained. The vented twin-screw extruder used was TEX30α-38 (completely meshed, co-rotating) manufactured by Japan Steel Works, Ltd. The extrusion conditions were a discharge rate of 20 kg/h, a screw rotation speed of 250 rpm, and a vent vacuum degree of 3 kPa. The wholly aromatic polyamide fiber is supplied from the second supply port using the side feeder of the extruder, and the polyarylene sulfide resin, olefin resin, olefin copolymer and epoxy resin are supplied from the first supply port to the extruder. supplied. The first feed port here is the feed port farthest from the die, and the second feed port is the feed port located between the die and the first feed port of the extruder. The obtained pellets were dried at 130°C for 5 hours in a hot air circulating dryer, and then tensile fractured at a cylinder temperature of 320°C and a mold temperature of 140°C using an injection molding machine (EC130SXII-4Y manufactured by Toshiba Machine Co., Ltd.). Test pieces for strength test, tensile elongation at break test, impact strength test and dynamic friction coefficient test evaluation were molded.

Each component symbolized in Tables 1 and 2 is as follows.
<A component>
A-1: A polyphenylene sulfide resin having a terminal carboxyl group obtained by the following production method [manufacturing method 1]
5130 g of paradiiodobenzene (p-DIB), 450 g of sulfur, 1,3-diiodo- The reactants containing 4 g of 4-nitrobenzene were heated to 180° C. until completely melted and mixed, then stepped starting from initial reaction conditions of 220° C. and 350 Torr to a final reaction temperature of 300° C. and a pressure of 1 Torr or less. The polymerization reaction was allowed to proceed while the temperature was raised and the pressure was lowered. When the polymerization reaction has progressed 80% (the degree of progress of the polymerization reaction was determined by measuring the relative ratio of the current viscosity to the target viscosity [(current viscosity/target viscosity) x 100 (%)]. The viscosity was measured with a viscometer by collecting a sample during polymerization.), 25 g of 2,2'-dithiobisbenzothiazole was added as a polymerization terminator, and the reaction was allowed to proceed for 1 hour. Next, when the polymerization reaction has progressed 90%, 51 g of 4-Iodobenzoic acid is added, the reaction is allowed to proceed for 10 minutes under nitrogen atmosphere, and then the vacuum is gradually applied to 0.5 Torr or less to proceed the reaction for 1 hour. After the reaction was completed, a polyarylene sulfide resin having a carboxyl group at the main chain end was synthesized. The reaction-completed resin was produced in pellet form using a small strand cutter machine. The polyarylene sulfide resin was analyzed by FT-IR to confirm the presence of a carboxy group peak at about 1600 to 1800 cm ^-1 on the spectrum. Further, on the FT-IR spectrum, when the height intensity of the Ring stretch peak appearing at about 1400 to 1600 cm ^-1 is 100%, the relative height intensity of the peak at about 1600 to 1800 cm ^-1 is about 3. was 0.4%. Moreover, the weight average molecular weight was 71.000.
A-2: Polyphenylene sulfide resin having terminal hydroxy groups obtained by the following production method

[Manufacturing method 2]
5130 g of paradiiodobenzene (p-DIB), 450 g of sulfur, 1,3-diiodo- After the reactants containing 4 g of 4-nitrobenzenemercaptobenzothiazole were heated to 180° C. and completely melted and mixed, starting from initial reaction conditions of 220° C. and 350 Torr, the final reaction temperature was 300° C. and pressure was less than 1 Torr. The polymerization reaction was allowed to proceed while the temperature was raised and the pressure was lowered stepwise. When the polymerization reaction has progressed 80% (the degree of progress of the polymerization reaction was determined by measuring the relative ratio of the current viscosity to the target viscosity [(current viscosity/target viscosity) x 100 (%)]. The viscosity was measured with a viscometer by collecting a sample during polymerization.), 25 g of 2,2'-dithiobisbenzothiazole was added as a polymerization terminator, and the reaction was allowed to proceed for 1 hour. Next, when the polymerization reaction has progressed to 90%, 51 g of 4-Iodophenol is added, the reaction is allowed to proceed for 10 minutes under a nitrogen atmosphere, and then a vacuum is gradually applied to 0.5 Torr or less to allow the reaction to proceed for 1 hour. After the reaction was completed, a polyarylene sulfide resin having hydroxyl groups at the main chain ends was synthesized. The reaction-completed resin was produced in pellet form using a small strand cutter machine. The polyarylene sulfide resin was analyzed by FT-IR to confirm the presence of a hydroxyl group peak at about 3200 to 3600 cm ^-1 on the spectrum. Further, on the FT-IR spectrum, when the height intensity of the Ring stretch peak appearing at about 1400 to 1600 cm ^-1 is 100%, the relative height intensity of the peak at about 3200 to 3600 cm ^-1 is about 1 was 0.4%. Moreover, the weight average molecular weight was 71,400.

A-3: Polyphenylene sulfide resin having an amino group at the end obtained by the following production method [manufacturing method 3]
5130 g of paradiiodobenzene (p-DIB), 450 g of sulfur, 1,3-diiodo- After the reactants containing 4 g of 4-nitrobenzenemercaptobenzothiazole were heated to 180° C. and completely melted and mixed, starting from initial reaction conditions of 220° C. and 350 Torr, the final reaction temperature was 300° C. and pressure was less than 1 Torr. The polymerization reaction was allowed to proceed while the temperature was raised and the pressure was lowered stepwise. When the polymerization reaction has progressed 80% (the degree of progress of the polymerization reaction was determined by measuring the relative ratio of the current viscosity to the target viscosity [(current viscosity/target viscosity) x 100 (%)]. The viscosity was measured with a viscometer by collecting a sample during polymerization.), 25 g of 2,2'-dithiobisbenzothiazole was added as a polymerization terminator, and the reaction was allowed to proceed for 1 hour. Next, when the polymerization reaction has progressed 90%, 51 g of 4-Iodoaniline is added, the reaction is allowed to proceed for 10 minutes under nitrogen atmosphere, and then the reaction is allowed to proceed for 1 hour by gradually applying vacuum to 0.5 Torr or less. After the reaction was completed, a polyarylene sulfide resin having an amino group at the main chain end was synthesized. The reaction-completed resin was produced in pellet form using a small strand cutter machine. The polyarylene sulfide resin was analyzed by FT-IR to confirm the presence of an amino group peak at about 3300 to 3500 cm ^-1 on the spectrum. Further, on the FT-IR spectrum, when the height intensity of the Ring stretch peak appearing at about 1400 to 1600 cm ^-1 is 100%, the relative height intensity of the peak at about 3300 to 3500 cm ^-1 is about 1 was 0.4%. Moreover, the weight average molecular weight was 70,000.

A-4: Polyphenylene sulfide resin having a phenyl group at the end obtained by the following production method [manufacturing method 4]
5130 g of paradiiodobenzene (p-DIB), 450 g of sulfur, 1,3-diiodo- After the reactants containing 4 g of 4-nitrobenzenemercaptobenzothiazole were heated to 180° C. and completely melted and mixed, starting from initial reaction conditions of 220° C. and 350 Torr, the final reaction temperature was 300° C. and pressure was less than 1 Torr. The polymerization reaction was allowed to proceed while the temperature was raised and the pressure was lowered stepwise. When the polymerization reaction has progressed 80% (the degree of progress of the polymerization reaction was determined by measuring the relative ratio of the current viscosity to the target viscosity [(current viscosity/target viscosity) x 100 (%)]. The viscosity was measured with a viscometer by taking a sample during polymerization.), 60 g of 2,2'-dithiobisbenzothiazole was added as a polymerization terminator, and the reaction was allowed to proceed for 10 minutes under a nitrogen atmosphere. , a vacuum was gradually applied to 0.5 Torr or less to reach the target viscosity, and then the reaction was terminated to synthesize a polyarylene sulfide resin having a phenyl group at the main chain end. The reaction-completed resin was produced in pellet form using a small strand cutter machine. The weight average molecular weight was 72,000.

A-5: Polyphenylene sulfide resin (manufactured by Solvay: Ryton QA281N (product name))
<B component>
B-1: Wholly aromatic polyamide fiber (manufactured by Teijin Limited: Technora T322EK (product name), para-aramid fiber, major diameter 12 μm, cut length 3 mm, polyester sizing agent, twist number 245 times / m)
B-2: Wholly aromatic polyamide fiber (manufactured by Teijin Limited: Conex ST2.2 (product name), meta-aramid fiber, major diameter 12 μm, cut length 3 mm)
B-3: Wholly aromatic polyamide fiber (manufactured by Teijin Limited: Twaron (registered trademark) 1488 (product name), para-aramid fiber, major diameter 12 μm, cut length 6 mm, polyester sizing agent)

<C component>
C-1: Ultra-high molecular weight polyethylene resin (manufactured by Mitsui Chemicals, Inc.: Lubmer 4000L (product name), MFR 5g/10min)
C-2: Ultra-high molecular weight polyethylene resin (manufactured by Mitsui Chemicals, Inc.: Lubmer 3000L (product name), MFR 15 g / 10 min)
C-3: Polyethylene resin (manufactured by Prime Polymer Co., Ltd.: Hi-Zex 2100J (product name), MFR 48 g / 10 min)
C-4: Polytetrafluoroethylene resin (manufactured by Kitamura Co., Ltd.: KT-600M (product name), baking type, melting point 328 ° C.)

<D component>
D-1: Ethylene glycidyl methacrylate copolymer [olefin copolymer having an epoxy group as a functional group] (manufactured by Sumitomo Chemical Co., Ltd.: Bond Fast BF-E (product name))
D-2: Copolymer of maleic anhydride and α-olefin [olefin copolymer having a carboxylic anhydride group as a functional group] (manufactured by Mitsubishi Chemical Corporation: Diacarna PA30M (product name))

<E component>
E-1: Trisphenolmethane type epoxy (manufactured by Nippon Kayaku Co., Ltd.: EPPN-501H (product name), epoxy equivalent 158 to 178 g / eq)
E-2: Cresol novolac type epoxy (manufactured by Nippon Kayaku Co., Ltd.: EOCN-104S (product name), epoxy equivalent 213 to 223 g / eq)
E-3: Bisphenol A type epoxy (manufactured by Mitsubishi Chemical Corporation: jER1256 (product name), epoxy equivalent 7,500 to 8,500 g/eq)

Claims (6)

(A) Polyarylene sulfide resin (component A) 100 parts by weight, (B) wholly aromatic polyamide fiber (component B) 10 to 150 parts by weight, (C) 190 ° C., melt measured under 10 kg load 3 to 50 parts by weight of a polyolefin resin (component C) having no polar group and having a flow rate (MFR) of 20 g/10 min or less; A polyarylene sulfide resin composition characterized by containing 0.1 to 20 parts by weight of an olefin copolymer having a functional group (component D) and 0.1 to 20 parts by weight of (E) an epoxy resin (component E). thing. Component A comprises (A-1) a polyarylene sulfide resin (Component A-1) having at least one functional group selected from the group consisting of a hydroxy group, an amino group and a carboxy group at the end (Component A-1) 10 to 100% by weight and ( A-2) The resin composition according to claim 1, which is a polyarylene sulfide resin containing 0 to 90% by weight of a polyarylene sulfide resin (component A-2) that does not contain the functional group at its end. 3. The resin composition according to claim 1, wherein the C component is a polyethylene resin. 3. The resin composition according to claim 1, wherein component D is an α-olefin copolymer having an epoxy group. 3. The resin composition according to claim 1, wherein the E component is an epoxy resin having an epoxy equivalent of 100 to 10,000 g/eq. A molded article made of the resin composition according to claim 1 or 2.