Polyarylene sulfide resin composition and molded article made therefrom

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]

[0001] The present invention relates to a resin composition and a molded article made therefrom that possess excellent impact strength, tensile strength, tensile elongation, and dynamic friction coefficient while retaining the excellent properties of polyarylene sulfide resin. [Background technology]

[0002] Polyarylene sulfide resin is an engineering plastic with excellent chemical resistance, heat resistance, and mechanical properties. For this reason, polyarylene sulfide resin is widely used in electrical and electronic components, 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 casings of the products used are becoming thinner. In vehicle-related parts such as automobiles, electrification of self-propelled vehicles, including hybrid and electric vehicles, is progressing with the aim of reducing vehicle weight and fossil fuel consumption in line with energy conservation. In these related applications, the replacement of conventional metals with resins is being considered in order to reduce the weight of products, and in particular, resin materials that replace metals used in applications such as gears and bearings require impact strength, ductility, and sliding properties such as low wear and low coefficient of friction. However, although polyarylene sulfide resin itself has sliding properties compared to other resins, its impact strength, tensile breaking strength, and tensile breaking elongation are not sufficient for use in these applications. Furthermore, in recent years, there has been a demand for components that can achieve a long lifespan even under harsh environments such as high temperatures and heavy loads, requiring more advanced sliding properties than before.

[0003] As a means to solve this problem, Patent Documents 1 and 2 disclose resin compositions consisting of polyphenylene sulfide resin, fluororesin and aromatic polyamide fibers, and resin compositions consisting of polyphenylene sulfide resin, conductive potassium titanate whiskers, polytetrafluoroethylene resin, metal oxide and aromatic polyamide fibers, respectively, for the purpose of improving sliding properties and mechanical properties. However, while sliding properties and mechanical strength are mentioned, impact strength and tensile elongation at break are not described. Patent Document 3 discloses a resin composition consisting of polyphenylene sulfide resin, fluororesin, aromatic polyester resin and para-aromatic polyamide fibers. While heat resistance and sliding properties are mentioned, impact strength, tensile strength at break and tensile elongation at break are not described. Patent Document 4 discloses a resin composition consisting of highly tough polyarylene sulfide resin and aramid fibers. While tensile strength at break and tensile elongation at break are mentioned, impact strength and sliding properties are not described. Patent Document 5 proposes a resin composition comprising a polyarylene sulfide resin having a specific number-average molecular weight and degree of dispersion, all aromatic polyamide fibers, and a fluororesin. While it mentions impact strength, tensile breaking strength, and tensile breaking elongation, it does not describe the coefficient of dynamic friction. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Special Publication No. 4-65866 [Patent Document 2] Japanese Patent Application Publication No. 11-217504 [Patent Document 3] Japanese Patent Application Publication No. 8-85758 [Patent Document 4] Japanese Patent Application Publication No. 10-310700 [Patent Document 5] Japanese Patent Publication No. 2020-002208 [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide a resin composition and a molded article made therefrom that possess excellent impact strength, tensile strength, tensile elongation at break, and dynamic friction coefficient, while retaining the excellent properties of polyarylene sulfide resin. [Means for solving the problem]

[0006] As a result of diligent research, the inventors discovered that a resin composition comprising polyarylene sulfide resin, fully aromatic polyamide fibers, polyolefin resin having a specific melt flow rate (MFR) value, olefin copolymer, and epoxy resin possesses excellent impact strength, tensile breaking strength, tensile breaking elongation, and dynamic friction coefficient while retaining the excellent properties of polyarylene sulfide resin, leading to the present invention.

[0007] In other words, the present invention is as follows: 1. A polyarylene sulfide resin composition characterized by containing, per 100 parts by weight of (A) polyarylene sulfide resin (component A), 10 to 150 parts by weight of (B) fully aromatic polyamide fibers (component B), 3 to 50 parts by weight of (C) non-polar group polyolefin resin (component C) having a melt flow rate (MFR) of 20 g / 10 min or less measured under conditions of 190°C and a 10 kg load, 0.1 to 20 parts by weight of (D) olefin copolymer (component D) having at least one functional group selected from the group consisting of epoxy groups and acid anhydride groups, and 0.1 to 20 parts by weight of epoxy resin (component E). 2. The resin composition according to item 1 above, characterized in that component A is a polyarylene sulfide resin comprising 10 to 100% by weight of a polyarylene sulfide resin (component A-1) having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group at the (A-1) terminus, and 0 to 90% by weight of a polyarylene sulfide resin (component A-2) not containing the aforementioned functional group at the (A-2) terminus. 3. The resin composition according to item 1 or 2 above, characterized in that component C is polyethylene resin. 4. The resin composition according to any one of items 1 to 3 above, characterized in that component D is an α-olefin copolymer having an epoxy group. 5. A resin composition according to any one of items 1 to 4 above, characterized in that component E is an epoxy resin having an epoxy equivalent of 100 to 10,000 g / eq. 6. A molded article made from any of the resin compositions described in items 1 to 5 above.

[0008] The details of the present invention will be described below. (Component A: Polyarylene sulfide resin) Any polyarylene sulfide resin belonging to the category of polyarylene sulfide resins may be used as component A of the present invention.

[0009] Examples of polyarylene sulfide resins include those whose constituent units consist of, for example, p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, diphenylene sulfide units, substituent-containing phenylene sulfide units, branched structure-containing phenylene sulfide units, etc. Among these, those containing 70 mol% or more, particularly 90 mol% or more, of p-phenylene sulfide units are preferred, and poly(p-phenylene sulfide) is even more preferred.

[0010] The terminal functional groups of the polyarylene sulfide resin are not particularly limited, but a polyarylene sulfide resin consisting of 10 to 100% by weight of a polyarylene sulfide resin (component A-1) having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group at its terminal, and 0 to 90% by weight of a polyarylene sulfide resin (component A-2) not having the aforementioned functional group at its terminal is preferred.

[0011] The method for producing polyarylene sulfide resin is not particularly limited and can be polymerized by known methods, but particularly preferred polymerization methods include those described in U.S. Patent Nos. 4,746,758, 4,786,713, JP 2013-522385, JP 2012-233210, and JP 5167276. These methods involve polymerizing a diiodoaryl compound and solid sulfur by direct heating without a polar solvent.

[0012] The above manufacturing method includes an iodization step and a polymerization step. In the iodization step, an aryl compound is reacted with iodine to obtain a diiodoaryl compound. In the subsequent polymerization step, the diiodoaryl compound is polymerized with solid sulfur using a polymerization inhibitor to produce a polyarylene sulfide resin. Iodine is generated in gaseous form in this step, which is recovered and reused in the iodization step. The iodine is substantially a catalyst.

[0013] A typical example of solid sulfur used in the aforementioned manufacturing method is cycloocta-sulfur (S8), in which eight atoms are linked together at room temperature. However, the sulfur compound used in the polymerization reaction is not limited to this form; any form that is solid or liquid at room temperature can be used.

[0014] Typical diiodoaryl compounds used in the above-mentioned manufacturing method include at least one selected from the group consisting of diiodobenzene, diiodonaphthalene, diiodobiphenyl, diiodobisphenol, and diiodobenzophenone. Derivatives of iodoaryl compounds that have alkyl or sulfone groups attached, or into which oxygen or nitrogen has been introduced, are also used. Iodoaryl compounds are classified into different isomers depending on the bond position of the iodine atom. Preferred examples of these isomers are compounds in which iodine is symmetrically located at both ends of the aryl compound molecule, such as p-diiodobenzene, 2,6-diiodonaphthalene, and p,p'-diiodobiphenyl. The content of the iodoaryl compound is preferably 500 to 10,000 parts by weight per 100 parts by weight of solid sulfur. This amount is determined considering the formation of disulfide bonds.

[0015] Typical polymerization inhibitors used in the above-mentioned manufacturing method include monoiodoaryl compounds, benzothiazoles, benzothiazole sulfenamides, thiurams, dithiocarbamates, and aromatic sulfide compounds. 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 benzothiazole sulfenamides include at least one selected from the group consisting of N-cyclohexylbenzothiazole 2-sulfenamide, N,N-dicyclohexyl-2-benzothiazole sulfenamide, 2-morpholinothiobenzothiazole, benzothiazole sulfenamide, dibenzothiazole disulfide, and N-dicyclohexylbenzothiazole 2-sulfenamide. A preferred example among thiurams is at least one selected from the group consisting of tetramethylthiuram monosulfide and tetramethylthiuram disulfide. A preferred example among dithiocarbamates is at least one selected from the group consisting of zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate. A preferred example among aromatic sulfide compounds is at least one selected from the group consisting of diphenyl sulfide, diphenyl disulfide, diphenyl ether, biphenyl, and benzophenone. In addition, one or more functional groups may be substituted on the conjugated aromatic ring skeleton of any of the polymerization inhibitors. Examples of the functional groups include hydroxyl groups, carboxyl groups, mercapto groups, amino groups, cyano groups, sulfo groups, and nitro groups, with preferred examples being hydroxyl groups, amino groups, and carboxyl groups, and even more preferred examples being those with an FT-IR spectrum of 3200-3600 cm⁻¹. -1 , 1600~1800cm -1 and 3300~3500cm -1Examples include a hydroxy group, an amino group, and a carboxy group that indicate peaks. 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.

[0016] In the above production method, a polymerization reaction catalyst may be used. Representative polymerization reaction catalysts include nitrobenzene-based catalysts. Preferred examples of nitrobenzene-based catalysts include at least one selected from the group consisting of 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, iodonitrobenzene, and 2,6-diiodo-4-nitroamine. 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.

[0017] By using this polymerization method, it is not necessary to substantially reduce the chlorine content and sodium content, and a polyphenylene sulfide resin with excellent cost performance can be obtained. Moreover, the polyphenylene sulfide resin of the present invention may contain polyphenylene sulfide resins obtained by other polymerization methods.

[0018] (Component B: wholly aromatic polyamide fiber) As the wholly aromatic polyamide fiber used as Component B of the present invention, any fiber belonging to the category called wholly aromatic aramid fiber may be used. By using a wholly aromatic polyamide fiber, it is possible to achieve both ensuring the mechanical strength and toughness required for a sliding member and exhibiting excellent low wear properties. Examples of wholly aromatic aramid fibers include meta-aramid fibers and para-aramid fibers, among which para-aramid fibers are preferred.

[0019] The all-aromatic polyamide constituting the fibers of the present invention is obtained substantially from one or more aromatic diamines and one or more aromatic dicarboxylic acid halides. However, a condensing agent, such as a system of triphenyl phosphite and pyridine, may also be added to one or more aromatic diamines and one or more aromatic dicarboxylic acids. The all-aromatic polyamide may be para-type or meta-type, but the para-type is more preferred. 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, and 9,10-bis-(4-aminophenyl)anthracene. As aromatic dicarboxylic acid halides, acid chlorides are particularly preferred, including terephthalic acid chloride, 2,6-naphthalenedicarboxylic acid chloride, 4,4'-diphenyldicarboxylic acid chloride, and those containing one or more non-reactive functional groups such as lower alkyl groups, lower alkoxy groups, halogeno groups, or nitro groups on their aromatic rings. Furthermore, when aromatic dicarboxylic acids are used, examples include terephthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-diphenyldicarboxylic acid, and those containing one or more non-reactive functional groups such as lower alkyl groups, lower alkoxy groups, halogeno groups, or nitro groups on their aromatic rings. Furthermore, the structure of the all-aromatic polyamide preferred in the present invention is one in which the main skeleton is represented by the following formula (1).

[0020] -NH-Ar1-NH-CO-Ar2-CO- (1) (However, Ar1 and Ar2 represent at least one aromatic residue selected from the group consisting of the following general formulas [I] to [IV]. Ar1 and Ar2 may be the same or different. Furthermore, some of the hydrogen atoms in these aromatic residues may be substituted with halogen atoms or lower alkyl groups.)

[0021] [ka]

[0022] In particular, when the total of Ar1 and Ar2 is 100 mol%, it is preferable that the sum of general formula [I] and general formula [II], the sum of general formula [I] and general formula [III], the sum of general formula [I] and general formula [IV], or general formula [I] is 80 mol% or more. More preferably, the sum of general formula [I] and general formula [II], or the sum of general formula [I] and general formula [III] is 80 mol% or more. Even more preferably, the sum of general formula [I] and general formula [II], or the sum 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%.

[0023] The aromatic polyamide dope used as the spinning solution may be obtained by solution polymerization or by dissolving a separately obtained total aromatic polyamide in a solvent, but solution polymerization is preferred. In addition, a small amount of inorganic salt may be added as a solubilizer to improve solubility. Examples of such inorganic salts include lithium chloride and calcium chloride.

[0024] Generally, known aprotic organic polar solvents are used as polymerization solvents or redissolution solvents. Examples include 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-acetylpiperidine, N-methylpiperidone-2, N,N'-dimethylethyleneurea, N,N'-dimethylpropyleneurea, N,N,N',N'-tetramethylmalonamide, N-acetylpyrrolidone, N,N,N',N'-tetramethylurea, and dimethyl sulfoxide. Furthermore, strong acids such as concentrated sulfuric acid and methanesulfonic acid can be used as redissolution solvents.

[0025] There are no particular restrictions on the degree of polymerization of the fully aromatic polyamide, but a higher degree of polymerization is preferable if it is soluble in the solvent. When fully aromatic polyamide is polymerized in solution, the ratio of the acid component to the diamine component is substantially equimolar, but either component can be used in excess to control the degree of polymerization. Monofunctional acid and amine components may also be used as end-capping agents.

[0026] When forming fully aromatic polyamides into fibers, a wet molding method of the fully aromatic polyamide dope is usually used. This can be done by directly extruding the dope into the solidification bath or by extruding it into the solidification bath through an air gap. A poor solvent for the fully aromatic polyamide is used in the solidification bath, but a good solvent is usually added to adjust the solidification rate so that the solvent of the fully aromatic polyamide dope does not rapidly escape and cause defects in the fully aromatic polyamide fibers. Generally, it is preferable to use water as the poor solvent and the solvent of the fully aromatic polyamide dope as the good solvent. The ratio of good solvent to poor solvent depends on the solubility and solidification properties of the fully aromatic polyamide, but 15 / 85 to 40 / 60 is preferred.

[0027] The fiber length of such fully aromatic polyamide fibers is preferably 0.1 mm to 6 mm, and more preferably 0.5 mm to 4 mm. If the fiber length is less than 0.1 mm, the reinforcing effect may not be sufficient, and the improvement in impact resistance may be insufficient. If the fiber length exceeds 6 mm, handling during manufacturing becomes difficult, and the fluidity of the composition may be poor, resulting in poor moldability.

[0028] Furthermore, while such fully aromatic polyamide fibers are effective whether or not they are bundled, bundled ones are preferable because they are easier to handle. Examples of binders for bundling include polyester resins, polyurethane resins, and polyethersulfone resins, among which aromatic polyester resins are preferred. In the present invention, such heat-resistant organic fibers can be used alone or as a mixture of two or more types.

[0029] Furthermore, the form of the all-aromatic polyamide fibers is not particularly limited, and any form can be used, however, from the viewpoint of handling during the production of the resin composition, it is preferable that they are twisted. Using fiber bundles with a large number of twists may stabilize the supply of all-aromatic polyamide fibers to the extruder. The preferred number of twists for the all-aromatic polyamide fibers is 10 to 500 twists / m, more preferably 50 to 450 twists / m, and even more preferably 100 to 400 twists / m.

[0030] The content of component B is 10 to 150 parts by weight per 100 parts by weight of component A, preferably 12 to 100 parts by weight, more preferably 13 to 60 parts by weight, and even more preferably 14 to 40 parts by weight. If the content of component B is less than 10 parts by weight, the impact strength, tensile breaking strength, and tensile breaking elongation do not improve sufficiently, and if it exceeds 150 parts by weight, problems such as strand breakage and surging occur during kneading and extrusion, resulting in a decrease in productivity or processability.

[0031] (Component C: Polyolefin resin without polar groups) The present invention contains a polyolefin resin that does not have polar groups as component C. The polyolefin resin is a synthetic resin obtained by polymerizing or copolymerizing olefin monomers having radically polymerizable double bonds. The olefin monomer is not particularly limited and includes, for example, α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, and 4-methyl-1-pentene, and conjugated dienes such as butadiene and isoprene. The olefin monomer may be used alone or in combination of two or more. The polyolefin resin is not particularly limited and includes, for example, a homopolymer of ethylene, a copolymer of ethylene and an α-olefin other than ethylene, a homopolymer of propylene, a copolymer of propylene and an α-olefin other than propylene, a homopolymer of butene, and a homopolymer or copolymer of conjugated dienes such as butadiene and isoprene. A homopolymer of ethylene and a copolymer of ethylene and an α-olefin other than ethylene are preferred, and a homopolymer of ethylene is more preferred. Furthermore, it is particularly preferable that the polyethylene is obtained by polymerizing ultra-high molecular weight ethylene with high molecular weight or low molecular weight polyethylene using a multi-stage polymerization method. The polyolefin resin may be used alone or in combination of two or more types.

[0032] The polyolefin resin used as component C in this 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 a 10 kg load. The MFR is preferably 17 g / 10 min or less, and more preferably 15 g / 10 min or less. If the MFR exceeds 20 g / 10 min, a decrease in tensile breaking strength occurs. While there is no particular lower limit to the MFR, it is preferably 0.5 g / 10 min or more. The above MFR was measured according to the method compliant with JIS K 7210.

[0033] The content of component C is 3 to 50 parts by weight, preferably 5 to 30 parts by weight, and 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 coefficient of dynamic friction increases, and the impact strength and tensile elongation at fracture decrease. If it exceeds 50 parts by weight, the tensile strength at fracture decreases.

[0034] (Component D: Olefin copolymer) The olefin copolymer used as component D of the present invention is an olefin copolymer containing at least one functional group selected from the group consisting of epoxy groups and acid anhydride groups. Examples of acid anhydride groups include carboxylic acid anhydride groups and sulfonic acid anhydride groups. As the copolymer, an α-olefin copolymer containing an epoxy group is preferred, and a copolymer of an α-olefin and a glycidyl ester of an α,β-unsaturated carboxylic acid is more preferred. Examples of α-olefins include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, and 1-octene, with ethylene being particularly preferred. 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 ethanolate. Furthermore, these copolymers may be further copolymerized with α,β-unsaturated carboxylic acids and their alkyl esters, such as acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, and butyl methacrylate, as well as acrylonitrile, styrene, and the like.

[0035] The content of component D is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, and 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, problems such as strand breakage and surging occur during kneading and extrusion, resulting in a decrease in productivity or processability.

[0036] (Component E: epoxy resin) The epoxy resin used as component E can be any compound having epoxy groups in its molecular structure, but it is preferable to use an epoxy resin having two or more epoxy groups per molecule. When an epoxy resin having two or more epoxy groups per molecule is used, the tensile breaking strength may be further improved due to the crosslinking reaction of the epoxy resin. Specific examples include bisphenol-type epoxy, novolac-type epoxy, cyclic aliphatic-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 Corporation, and NC-3000, NC-7000, XD-1000, EPPN-502H, and EOCN-104S from Nippon Kayaku Co., Ltd., all of which are commercially available and readily available.

[0037] The epoxy equivalent of component E 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 is likely to occur during kneading and extrusion, and if it exceeds 10,000 g / eq, sufficient tensile breaking strength may not be obtained. The epoxy equivalent of component E is measured in accordance with JIS K 7236.

[0038] The content of component E is 0.1 to 20 parts by weight, preferably 1 to 10 parts by weight, and 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, it will thicken due to the heat generated during kneading and extrusion, making it difficult to draw the strand.

[0039] (Other ingredients) The resin composition in the present invention may contain elastomer components to the extent that it does not impair the effects of the present invention. Suitable elastomer components include core-shell graft copolymer resins such as acrylonitrile-butadiene-styrene copolymer (ABS resin), methyl methacrylate-butadiene-styrene copolymer (MBS resin), and silicone-acrylic composite rubber graft copolymer, or thermoplastic elastomers such as silicone-based thermoplastic elastomers, polyamide-based thermoplastic elastomers, polyester-based thermoplastic elastomers, and polyurethane-based thermoplastic elastomers.

[0040] The resin composition in the present invention may contain other thermoplastic resins, to the extent that it does not impair the effects of the present invention. Examples of other thermoplastic resins include general-purpose plastics such as polyalkyl methacrylate resins, engineering plastics such as polyphenylene ether resins, polyacetal resins, aromatic polyester resins, liquid crystalline polyester resins, cyclic polyolefin resins, polyarylate resins (amorphous polyarylate, liquid crystalline polyarylate), and so-called super engineering plastics such as polyetheretherketone, polyetherimide, polysulfone, and polyethersulfone.

[0041] The resin composition of the present invention may contain, to the extent that it does not impair the effects of the present invention, antioxidants and heat stabilizers (hindered phenols, hydroquinones, phosphates and their derivatives, etc.), weathering agents (resorcinols, salicylates, benzotriazoles, benzophenones, hindered amines, etc.), mold release agents and lubricants (montanic acid and its metal salts, its esters, its half-esters, stearyl alcohol, stearamides, various bisamides, bisurea and polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, etc.), nucleating agents (talc, silica, kaolin, clay, etc.), and plasticizers (p-O). Other polymers can be added, such as octyl xybenzoate, N-butylbenzenesulfonamide, antistatic agents (alkyl sulfate anionic antistatic agents, quaternary ammonium salt cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine-based amphoteric antistatic agents, etc.), flame retardants (e.g., red phosphorus, phosphate esters, melamine cyanurate, hydroxides such as magnesium hydroxide and aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin, or combinations of these brominated flame retardants with antimony trioxide, etc.).

[0042] The resin composition in the present invention may contain fillers other than fully aromatic polyamide fibers, as long as the effects of the present invention are not impaired. The material is not particularly limited, but fillers in the form of fibers, plates, powders, granules, etc., can be used. Specifically, examples include fibrous fillers such as carbon fiber, glass fiber, potassium titanate whiskers, zinc oxide whiskers, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, and metal fiber; silicates such as warlastenite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, and alumina silicate; swellable layered silicates such as montmorillonite and synthetic mica; metal compounds such as alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, and iron oxide; carbonates such as calcium carbonate, magnesium carbonate, and dolomite; sulfates such as calcium sulfate and barium sulfate; glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate, and silica. These may be hollow, and it is also possible to use two or more of these fillers in combination.

[0043] Furthermore, pre-treating these fillers with coupling agents such as isocyanate compounds, organosilane compounds, organotitanate compounds, organoborane compounds, and epoxy compounds, as well as with organic onium ions in the case of swellable layered silicates, is preferable in terms of obtaining superior mechanical strength.

[0044] The resin composition of the present invention may contain a conductive filler as a filler to impart further conductivity. The material is not particularly limited, but as a conductive filler, there is no particular restriction as long as it is a conductive filler that is normally used to make resins conductive. Specific examples include the carbon fibers, metal powders, metal flakes, metal ribbons, metal fibers, metal oxides, carbon fibers coated with conductive materials, inorganic fillers, carbon powder, graphite, carbon flakes, and flaky carbon mentioned above. Specific examples of metal species for 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 for 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 surface treatment agents such as titanate-based, aluminum-based, or silane-based agents. Specific examples of metal oxides include SnO2 (antimond-doped), In2O3 (antimond-doped), and ZnO (aluminum-doped), which may be surface-treated with surface treatment agents such as titanate-based, aluminum-based, or silane-based coupling agents. Specific examples of conductive materials in inorganic fillers coated with conductive materials include aluminum, nickel, silver, carbon, SnO2 (antimond-doped), and In2O3 (antimond-doped). Examples of 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-based whiskers, titanate-based whiskers, and silicon carbide whiskers. Coating methods include vacuum deposition, sputtering, electroless plating, and baking. These may also be surface-treated with surface treatment agents such as titanate-based, aluminum-based, or silane-based coupling agents.

[0045] Carbon powders are classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, and disc black based on their raw materials and manufacturing methods. The carbon powders that can be used in this invention are not particularly limited in terms of raw materials and manufacturing methods, but acetylene black and furnace black are particularly preferred.

[0046] (Manufacturing of resin compositions) The resin composition of the present invention can be manufactured by mixing the above components simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauter mixer, Banbury mixer, kneading roll, or extruder. Preferably, melt kneading is performed using a twin-screw extruder, and if necessary, any component is supplied to the other molten components from a second supply port using a side feeder or the like. The resin extruded as described above is either directly cut to form pellets, or strands are formed and then cut with a pelletizer to form pellets. If it is necessary to reduce the influence of external dust during pelletization, it is preferable to clean the atmosphere around the extruder. The resulting pellets can take general shapes such as cylinders, prismatics, and spheres, but are more preferably cylindrical. The diameter of such cylinders is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.5 mm. On the other hand, the length of the cylinders is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 4 mm.

[0047] (Regarding molded products) Molded articles using the resin composition of the present invention can be obtained by molding pellets manufactured as described above. Preferably, they can be obtained by injection molding or extrusion molding. In injection molding, in addition to conventional molding methods, examples include 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-insulating mold molding, rapid heating and cooling mold molding, two-color molding, multi-color molding, sandwich molding, and ultra-high-speed injection molding. Molding can be selected from either the cold runner method or the hot runner method. In extrusion molding, various irregularly shaped extruded articles, sheets, films, etc., can be obtained. For molding sheets and films, the inflation method, calendering method, casting method, etc., can also be used. Furthermore, it is possible to mold them as heat-shrinkable tubes by applying a specific stretching operation. It is also possible to mold the resin composition of the present invention into molded articles by rotational molding, blow molding, etc. [Effects of the Invention]

[0048] The resin composition of the present invention retains the excellent properties of polyarylene sulfide resin while possessing excellent impact strength, tensile breaking strength, tensile breaking elongation, and dynamic friction coefficient. Therefore, it is suitable for use in electrical and electronic equipment such as personal computers (notebooks, ultrabooks), tablets, mobile phone housings, displays, office automation equipment, mobile phones, personal digital assistants, fax machines, compact discs, portable MDs, portable radio cassette players, PDAs (personal digital assistants such as electronic organizers), video cameras, digital still cameras, optical equipment, audio equipment, air conditioners, lighting equipment, entertainment goods, toys, and other home appliances. It is also suitable for use in internal components such as casings, trays, and chassis of electrical and electronic equipment, as well as mechanical components, panels, and other building materials. Applications include motor parts, alternator terminals, alternator connectors, IC regulators, light dew potentiometer bases, suspension parts, various valves such as exhaust gas valves, fuel-related components, exhaust or intake system pipes, air intake nozzle snorkels, intake manifolds, various arms, various frames, various hinges, various bearings, fuel pumps, gasoline tanks, CNG tanks, and more. Engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, brake pad wear sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, air conditioning thermostat base, heating hot air flow control valve, radiator motor brush holder, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, transmission wire harness, window washer nozzle, air conditioning panel switch circuit board, fuel-related solenoid valve coil, fuse connector, battery tray, AT bracket, headlamp support, pedal housing, steering wheel, 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,It is widely useful in automotive and motorcycle-related parts, components, and body panels such as engine oil filters, ignition system 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, as well as aircraft-related parts, components, and body panels such as landing gear pods, winglets, spoilers, edges, rudders, elevators, fillings, and ribs, wind turbine blades, and electronic equipment enclosures such as inverter housings for hybrid and electric vehicles. In particular, its excellent impact strength and tensile elongation make it useful in bearings and gears, packings, guide rail-related parts, and wiring covers (corrugated tubing) around automobile engines for automobiles, industrial machinery, and leisure equipment, and its industrial benefits are exceptional. [Modes for carrying out the invention]

[0049] The embodiment of the present invention that the inventors currently consider to be the best is a combination of the preferred ranges of the above requirements, and a representative example is described in the following examples. Of course, the present invention is not limited to these embodiments. [Examples]

[0050] [Evaluation of resin compositions] (1) Impact strength Test specimens prepared using the method described below (dimensions: length 80 mm x width 10 mm x thickness 4 mm) were measured for notched Charpy impact strength in accordance with ISO 179 under conditions of 23°C and 50% RH relative humidity. A higher value indicates superior impact strength of the resin composition.

[0051] (2) Tensile breaking strength The tensile breaking strength was measured using test specimens prepared according to the method described below, in accordance with ISO 527. A higher value indicates superior tensile breaking strength of the resin composition.

[0052] (3) Tensile elongation at fracture The tensile elongation at break was measured using test specimens prepared according to the method described below, in accordance with ISO 527. A higher value indicates better tensile elongation at break of the resin composition.

[0053] (4) Coefficient of kinetic friction In accordance with JIS K 7218 Method A, hollow cylindrical test specimens with an outer diameter of 25.6 mm, an inner diameter of 20 mm, and a height of 15 mm, prepared using the method described below, were slid against a similarly shaped test specimen made of steel (SUS304) using a friction and wear testing machine (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 coefficient of dynamic friction was measured every second in the sliding distance range of 300 to 3000 m, excluding initial wear, and the average value was calculated. The test was performed three times, and the average value was taken as the coefficient of dynamic friction of the composition. A smaller value indicates a better coefficient of dynamic friction of the resin composition.

[0054] [Examples 1-19, Comparative Examples 1-10] A polyphenylene sulfide resin, a wholly aromatic polyamide fiber, an olefin resin, an olefin copolymer, and an epoxy resin were melt-kneaded using a vented biaxial extruder at the respective compounding amounts described in Tables 1 and 2 to obtain pellets. The vented biaxial extruder used was TEX30α-38 (fully meshing, 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 vacuum degree of 3 kPa for the vent, and the extrusion temperature was set to 320 °C from the first feed port to the die part. The wholly aromatic polyamide fiber was supplied from the second feed port using the side feeder of the extruder, and the polyphenylene sulfide resin, olefin resin, olefin copolymer, and epoxy resin were supplied to the extruder from the first feed port. Here, the first feed port refers to the feed port farthest from the die, and the second feed port refers to the feed port located between the die and the first feed port of the extruder. After drying the obtained pellets at 130 °C for 5 hours using a hot air circulation dryer, test pieces for evaluating a tensile breaking strength test, a tensile breaking elongation test, an impact strength test, and a dynamic friction coefficient test were molded using an injection molding machine (EC130SXII-4Y manufactured by Toshiba Machine Co., Ltd.) at a cylinder temperature of 320 °C and a mold temperature of 140 °C.

[0055] Each component denoted by symbols in Tables 1 and 2 is as follows. <Component A> A-1: A polyphenylene sulfide resin having a carboxy group at the terminal obtained by the following production method [Production Method 1] In a 5L reactor equipped with a thermocouple capable of measuring the internal temperature of the reactor, nitrogen filling, and a vacuum line for applying vacuum, a reaction mixture containing 5130g of paradiiodobenzene (p-DIB), 450g of sulfur, and 4g of 1,3-diiodo-4-nitrobenzene as a reaction initiator was heated to 180°C to completely melt and mix. The polymerization reaction was then carried out starting with initial reaction conditions of 220°C and 350 Torr, gradually increasing the temperature and decreasing the pressure until the final reaction temperature reached 300°C and the pressure was below 1 Torr. When the polymerization reaction had progressed to 80% (the degree of polymerization progress was determined by measuring the relative ratio of the current viscosity to the target viscosity [(current viscosity / target viscosity) × 100 (%)]. The current viscosity was measured using a viscometer on a sample taken during polymerization), 25g of 2,2'-dithiobisbenzothiazole was added as a polymerization inhibitor, and the reaction was allowed to proceed for 1 hour. Next, when the polymerization reaction had progressed 90%, 51 g of 4-Iodobenzoic acid was added, and the reaction was allowed to proceed under a nitrogen atmosphere for 10 minutes. Then, a vacuum was gradually applied to below 0.5 Torr, and the reaction was allowed to proceed for 1 hour. The reaction was then terminated to synthesize a polyarylene sulfide resin having carboxyl groups at the ends of the main chain. The completed resin was produced in pellet form using a small strand cutter. The polyarylene sulfide resin was analyzed by FT-IR, and a spectral range of approximately 1600-1800 cm⁻¹ was observed. -1 The presence of a peak for the carboxyl group was confirmed. Furthermore, on the aforementioned FT-IR spectrum, approximately 1400-1600 cm⁻¹ was observed. -1 When the height intensity of the ring stretch peak that appears is taken as 100%, the aforementioned approximately 1600-1800 cm -1 The relative height intensity of the peak was approximately 3.4%. The weight-average molecular weight was 71.000. A-2: Polyphenylene sulfide resin having hydroxyl groups at the ends, obtained by the following manufacturing method.

[0056] [Manufacturing method 2] A thermocouple capable of measuring the internal temperature of the reactor, a 5L reactor with a vacuum line that can be filled with nitrogen and evacuated, was charged with 5130 g of para-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene mercaptobenzothiazole as a reaction initiator. The reactants were heated to 180 °C to completely melt and mix, and then starting from the initial reaction conditions of 220 °C and 350 Torr, the polymerization reaction was carried out while gradually increasing the temperature and decreasing the pressure in steps until the final reaction temperature was 300 °C and the pressure was 1 Torr or less. When the polymerization reaction had proceeded 80% (the progress of the polymerization reaction was determined by measuring the relative ratio of the current viscosity to the target viscosity [(current viscosity / target viscosity) × 100 (%)]. The current viscosity was measured with a viscometer by taking samples during the polymerization process.), 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 had proceeded 90%, 51 g of 4-Iodophenol was added, and after allowing the reaction to proceed for 10 minutes under a nitrogen atmosphere, the vacuum was gradually increased to 0.5 Torr or less and the reaction was allowed to proceed for 1 hour, and then the reaction was terminated to synthesize a polyarylene sulfide resin having a hydroxy group at the main chain end. The resin after the reaction was completed was manufactured in pellet form using a small strand cutter machine. The polyarylene sulfide resin was analyzed by FT-IR, and on the spectrum, the presence of a peak of the hydroxy group at about 3200 - 3600 cm -1 was confirmed. Also, on the FT-IR spectrum, when the height intensity of the Ring stretch peak appearing at about 1400 - 1600 cm -1 was taken as 100%, the relative height intensity of the peak at about 3200 - 3600 cm -1 was about 1.4%. Also, the weight average molecular weight was 71,400.

[0057] A-3: A polyphenylene sulfide resin having an amino group at the terminal obtained by the following production method [Production Method 3] In a 5L reactor equipped with a thermocouple capable of measuring the internal temperature of the reactor, nitrogen filling, and a vacuum line for applying vacuum, a reaction mixture containing 5130g of paradiiodobenzene (p-DIB), 450g of sulfur, and 4g of 1,3-diiodo-4-nitrobenzene mercaptobenzothiazole as a reaction initiator was heated to 180°C to completely melt and mix. The polymerization reaction was then carried out starting with initial reaction conditions of 220°C and 350 Torr, gradually increasing the temperature and decreasing the pressure until the final reaction temperature reached 300°C and the pressure was below 1 Torr. When the polymerization reaction had progressed to 80% (the degree of polymerization progress was determined by measuring the relative ratio of the current viscosity to the target viscosity [(current viscosity / target viscosity) × 100 (%)]. The current viscosity was measured using a viscometer on a sample taken during polymerization), 25g of 2,2'-dithiobisbenzothiazole was added as a polymerization inhibitor, and the reaction was allowed to proceed for 1 hour. Next, when the polymerization reaction had progressed 90%, 51 g of 4-Iodoaniline was added, and the reaction was allowed to proceed under a nitrogen atmosphere for 10 minutes. Then, a vacuum was gradually applied to below 0.5 Torr, and the reaction was allowed to proceed for 1 hour. The reaction was then terminated to synthesize a polyarylene sulfide resin having amino groups at the ends of the main chain. The completed resin was produced in pellet form using a small strand cutter. The polyarylene sulfide resin was analyzed by FT-IR, and a spectral range of approximately 3300-3500 cm⁻¹ was observed. -1 The presence of the amino group peak was confirmed. Furthermore, on the aforementioned FT-IR spectrum, approximately 1400-1600 cm⁻¹ was observed. -1 When the height intensity of the ring stretch peak that appears is taken as 100%, the aforementioned approximately 3300-3500 cm -1 The relative height intensity of the peak was approximately 1.4%. The weight-average molecular weight was 70,000.

[0058] A-4: Polyphenylene sulfide resin having phenyl groups at the ends, obtained by the following manufacturing method. [Manufacturing method 4] A thermocouple capable of measuring the internal temperature of the reactor, a 5 L reactor with a vacuum line that can be filled with nitrogen and evacuated, was charged with 5130 g of para-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene mercaptobenzothiazole as a reaction initiator. The reactants were heated to 180 °C to be completely melted and mixed, and then starting from the initial reaction conditions of 220 °C and 350 Torr, the polymerization reaction was carried out while gradually increasing the temperature and decreasing the pressure step by step until the final reaction temperature reached 300 °C and the pressure reached 1 Torr or less. When the polymerization reaction proceeded to 80% (the progress of the polymerization reaction was determined by measuring the relative ratio of the current viscosity to the target viscosity [(current viscosity / target viscosity) × 100 (%)]. The current viscosity was measured with a viscometer by taking a sample during the polymerization process.), 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. Then, the vacuum was gradually increased to 0.5 Torr or less until the target viscosity was reached, and the reaction was terminated to synthesize a polyarylene sulfide resin having a phenyl group at the main chain end. The resin after the reaction was produced in pellet form using a small strand cutter machine. The weight average molecular weight was 72,000.

[0059] A-5: Polyphenylene sulfide resin (manufactured by Solvay: Ryton QA281N (product name)) <Component B> B-1: wholly aromatic polyamide fiber (manufactured by Teijin Limited: Technora T322EK (product name), para-aramid fiber, major axis 12 μm, cut length 3 mm, polyester-based sizing agent, twist number 245 turns / m) B-2: wholly aromatic polyamide fiber (manufactured by Teijin Limited: Conex ST2.2 (product name), meta-aramid fiber, major axis 12 μm, cut length 3 mm) B-3: wholly aromatic polyamide fiber (manufactured by Teijin Limited: Twaron® 1488 (product name), para-aramid fiber, major axis 12 μm, cut length 6 mm, polyester-based sizing agent)

[0060] <Component C> C-1: Ultra-high molecular weight polyethylene resin (manufactured by Mitsui Chemicals, Inc.: Lubmer 4000L (product name), MFR 5 g / 10 min) 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), fired type, melting point 328 °C)

[0061] <Component D> D-1: Ethylene glycidyl methacrylate copolymer [olefin copolymer having an epoxy group as a functional group] (manufactured by Sumitomo Chemical Co., Ltd.: Bondfast 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))

[0062] <Component E> E-1: Tris-phenol methane type epoxy (manufactured by Nippon Kayaku Co., Ltd.: EPPN-501H (product name), epoxy equivalent 158 - 178 g / eq) E-2: Cresol novolak type epoxy (manufactured by Nippon Kayaku Co., Ltd.: EOCN-104S (product name), epoxy equivalent 213 - 223 g / eq) E-3: Bisphenol A type epoxy (manufactured by Mitsubishi Chemical Corporation: jER1256 (product name), epoxy equivalent 7,500 - 8,500 g / eq)

[0063]

Table 1

[0064]

Table 2

Claims

1. A polyarylene sulfide resin composition characterized by containing (A) 100 parts by weight of polyarylene sulfide resin (component A), (B) 10 to 150 parts by weight of all aromatic polyamide fibers (component B), (C) 3 to 50 parts by weight of a non-polar group polyolefin resin (component C) having a melt flow rate (MFR) of 20 g / 10 min or less measured under conditions of 190°C and a 10 kg load, (D) 0.1 to 20 parts by weight of an olefin copolymer (component D) having at least one functional group selected from the group consisting of epoxy groups and acid anhydride groups, and (E) 0.1 to 20 parts by weight of an epoxy resin (component E) excluding an olefin copolymer having epoxy groups.

2. The resin composition according to claim 1, characterized in that component A is a polyarylene sulfide resin comprising 10 to 100% by weight of a polyarylene sulfide resin (component A-1) having at least one functional group selected from the group consisting of a hydroxyl group, an amino group, and a carboxyl group at the (A-1) terminus, and 0 to 90% by weight of a polyarylene sulfide resin (component A-2) not containing the aforementioned functional group at the (A-2) terminus.

3. The resin composition according to claim 1 or 2, characterized in that component C is polyethylene resin.

4. The resin composition according to claim 1 or 2, characterized in that component D is an α-olefin copolymer having an epoxy group.

5. The resin composition according to claim 1 or 2, characterized in that component E is an epoxy resin having an epoxy equivalent of 100 to 10,000 g / eq.

6. A molded article comprising the resin composition according to claim 1 or 2.

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