JP2012177015A - Polyarylene sulfide resin composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene sulfide resin composition showing high permittivity and a low dielectric loss tangent, and having superior molding property and improved impact resistance.SOLUTION: The polyarylene sulfide resin composition is prepared by compounding, in 100 parts by weight of (A) a polyarylene sulfide resin having a carboxyl terminal group, 10 to 400 pts.wt. of (B) an alkaline earth metal salt of titanic acid having a dielectric constant of 50 or more and a dielectric loss tangent of 0.05 or less at a frequency of 1 MHz, and 0.5 to 20 parts by weight of (C) an olefin copolymer essentially comprising α-olefin and a glycidyl ester of an α,β-unsaturated acid, in which the content of the glydicyl ester of α,β-unsaturated acid in the olefin copolymer is 4 to 8 wt.%. The content of a copolymer component derived from the (C) glycidyl ester in the polyarylene sulfide resin composition is 0.2 to 0.5 mol%; and the ratio of the content (mmol/kg) of the copolymer component derived from the (C) glycidyl ester to the amount of the carboxyl terminal group (mmol/kg) of (A) is from 0.4 to 1.0.

Description

  The present invention relates to a polyarylene sulfide resin composition that exhibits a high dielectric constant and a low dielectric loss tangent, has excellent moldability, and has improved impact resistance.

  Polyarylene sulfide (hereinafter sometimes abbreviated as PAS) resin, represented by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) resin, has high heat resistance, mechanical properties, chemical resistance, dimensional stability, flame resistance Therefore, it is widely used for electrical and electronic equipment parts materials. On the other hand, in recent years, remarkable technological developments have been made in the field of information communication, such as mobile phones, wireless LANs, or ITS technologies such as GPS, VICS, and ETC. There is a strong need for high-performance, high-frequency electronic components, and materials constituting these electronic components are required to have appropriate dielectric properties according to their designs.

  Thermoplastic resins such as PAS resin are widely used for injection molding applications, and due to their easy moldability, it is easy to create parts with relatively complex shapes. Metals, thermosetting resins, ceramics, and the like that have been used as an advantage have a superior design freedom that has been limited. Moreover, it can be said that it is more advantageous than conventional technical materials in terms of environment such as recyclability.

  From such a background, various high dielectric constant resin compositions having PAS resin as a matrix have been proposed (Patent Documents 1 to 4). According to these methods, although a PAS resin composition having a high relative dielectric constant can be obtained, the resin composition described in Patent Document 1 has a relatively high dielectric loss tangent, and the resins described in Patent Documents 2 to 4 The composition has a high melt viscosity and is not necessarily suitable for injection molding applications. In addition, these resin compositions have a weak point in impact resistance because a large amount of an inorganic filler having a high dielectric constant is added. When applied to communication devices typified by mobile phones, there is a high demand for impact resistance that can withstand a drop impact, and there is a need for improvement.

Japanese Patent No. 2814288 Japanese Patent No. 2873541 JP-A-2005-93096 Japanese Patent Laid-Open No. 2005-94068

  The object of the present invention is to provide a PAS resin composition that solves the above-mentioned problems of the prior art, exhibits a high dielectric constant and a low dielectric loss tangent, has excellent moldability, and has improved impact resistance.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained impact resistance by blending a specific amount of a specific olefin copolymer into a high dielectric constant resin composition using a PAS resin as a matrix. It was found that can be improved.

That is, the present invention
(A) For 100 parts by weight of polyarylene sulfide resin having a carboxyl end group,
(B) 10 to 400 parts by weight of an alkaline earth metal titanate having a relative dielectric constant at 1 MHz of 50 or more and a dielectric loss tangent of 0.05 or less, and
(C) an olefin copolymer mainly composed of α-olefin and α, β-unsaturated glycidyl ester, and containing glycidyl ester of α, β-unsaturated acid in the olefin copolymer A polyarylene sulfide resin composition comprising 0.5 to 20 parts by weight of an olefin copolymer having an amount of 4 to 8% by weight, which is derived from (C) glycidyl ester in the polyarylene sulfide resin composition The content of the copolymerization component is 0.2 to 0.5 mol%, and the content of the copolymerization component (mmol / kg) derived from the glycidyl ester of (C) with respect to the carboxyl end group content (mmol / kg) of (A) A polyarylene sulfide resin composition having a ratio of 0.4 to 1.0.

  According to the present invention, it is possible to provide a PAS resin composition that exhibits a high dielectric constant and a low dielectric loss tangent, is excellent in moldability, and has improved impact resistance, and the PAS resin composition of the present invention comprises a microwave. It is suitably used for high-performance high-frequency electronic components that can be applied in the high-frequency region of millimeter waves.

  Hereinafter, the present invention will be described in detail. The PAS resin as the component (A) used in the present invention is mainly composed of — (Ar—S) — (wherein Ar is an arylene group) as a repeating unit. Examples of the arylene group include p-phenylene group, m-phenylene group, o-phenylene group, substituted phenylene group, p, p′-diphenylene sulfone group, p, p′-biphenylene group, and p, p′-di. A phenylene ether group, p, p′-diphenylenecarbonyl group, naphthalene group, and the like can be used. In this case, among the arylene sulfide groups composed of the above-mentioned arylene groups, in addition to a polymer using the same repeating unit, that is, a homopolymer, a copolymer containing different repeating units from the viewpoint of processability of the composition May be preferred.

  As the homopolymer, those having a p-phenylene sulfide group as a repeating unit and using a p-phenylene group as an arylene group are particularly preferably used. As the copolymer, among the arylene sulfide groups comprising the above-mentioned arylene groups, two or more different combinations can be used, and among them, a combination containing a p-phenylene sulfide group and an m-phenylene sulfide group is particularly preferably used. It is done. Among these, those containing 70 mol% or more, preferably 80 mol% or more of p-phenylene sulfide groups are suitable from the viewpoint of physical properties such as heat resistance, fluidity (moldability) and mechanical properties.

  Further, among these PAS resins, a high molecular weight polymer having a substantially linear structure obtained by condensation polymerization from a monomer mainly composed of a bifunctional halogen aromatic compound can be particularly preferably used. In addition to the PAS resin having a structure, a polymer in which a branched structure or a crosslinked structure is partially formed by using a small amount of a monomer such as a polyhaloaromatic compound having three or more halogen substituents when polycondensation is performed. A polymer having a linear structure polymer having a relatively low molecular weight that is heated at a high temperature in the presence of oxygen or an oxidant to increase the melt viscosity by oxidative crosslinking or thermal crosslinking, thereby improving the moldability, or these A mixture of these can also be used.

The component (A) PAS resin is mainly composed of the above-mentioned linear PAS resin (viscosity at 310 ° C. and shear rate of 1200 sec ⁻¹ of 10 to 300 Pa · s), and a part thereof (1 to 30% by weight, preferably May be a mixed system with a branched or cross-linked PAS resin having a relatively high viscosity (300 to 3000 Pa · s, preferably 500 to 2000 Pa · s). The PAS resin used in the present invention can be produced by a conventionally known polymerization method. Usually, in order to remove by-product impurities and the like, after polymerization, the PAS resin is washed several times with water or acetone, and then washed with acetic acid, ammonium chloride or the like. As a result, the PAS resin terminal contains a predetermined amount of carboxyl terminal groups.

  As will be described later, in the present invention, the carboxyl end group amount of the PAS resin needs to be adjusted to a specific range with respect to the content of the copolymer component derived from the glycidyl ester of α, β-unsaturated acid. In this invention, the value obtained by the method described in the Example is employ | adopted for the amount of carboxyl terminal groups.

  Next, the alkaline earth titanate metal salt as component (B) used in the present invention has a relative dielectric constant of 50 or more and a dielectric loss tangent of 0.05 or less at 1 MHz. By using a high dielectric constant metal titanate having a relative dielectric constant of 50 or more at 1 MHz, a molded article having a high dielectric constant can be efficiently obtained. When the relative permittivity is less than 50, the permittivity does not increase so much and the practicality is lacking. In addition, the dielectric loss tangent at 1 MHz needs to be 0.05 or less, and when it is larger than 0.05, the dielectric loss becomes large, leading to performance deterioration as an electronic component.

  Examples of such an alkaline earth metal titanate having a relative dielectric constant at 1 MHz of 50 or more and a dielectric loss tangent of 0.05 or less include calcium titanate and barium titanate.

  The blending amount of the (B) alkaline earth metal titanate is 10 to 400 parts by weight with respect to 100 parts by weight of the PAS resin. When the blending amount is less than 10 parts by weight, the effect of improving the dielectric constant is small, and when it exceeds 400 parts by weight, the workability deteriorates.

  Further, the alkaline earth titanate metal salt used in the present invention preferably has a metal ion content of less than 500 ppm, particularly less than 100 ppm, in the alkaline earth titanate metal salt extracted with hot water. More preferably. Such an alkaline earth titanate metal salt is obtained by combining an alkaline earth titanate metal salt synthesized by a conventionally known method such as a flux method with an inorganic acid such as hot water or hydrochloric acid, sulfuric acid, nitric acid and phosphoric acid. It can obtain by processing with. If the amount of metal ions extracted with hot water is less than 500 ppm, the increase in melt viscosity of the resin composition is small and the moldability is unlikely to deteriorate.

  Next, the (C) olefin copolymer used in the present invention is an olefin copolymer mainly composed of an α-olefin and a glycidyl ester of an α, β-unsaturated acid.

  In the olefin-based copolymer (C) used in the present invention, the PAS can be used even if the content of the copolymer component derived from the glycidyl ester of α, β-unsaturated acid contained in the copolymer is too much or too little. This is accompanied by a decrease in productivity or dielectric properties of the resin composition. By selecting an olefin copolymer within a specific range, the impact resistance of the high dielectric constant PAS resin composition can be improved without impairing productivity and dielectric properties. From this point, it is necessary that the content of the glycidyl ester of α, β-unsaturated acid in the olefin copolymer is 4 to 8% by weight.

  Further, the blending amount of the (C) olefin copolymer is 0.5 to 20 parts by weight, preferably 2 to 11 parts by weight with respect to 100 parts by weight of the (A) PAS resin.

  (C) The α-olefin, which is one component constituting the olefin copolymer, includes ethylene, propylene, butylene, etc., and ethylene is preferred. Two or more of these α-olefins can be used. Moreover, the glycidyl ester of α, β-unsaturated acid which is the other component constituting the olefin copolymer is represented by the general formula (1)

(However, R ₁ represents hydrogen or a lower alkyl group.)
And glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, and the like, with glycidyl methacrylate being preferred.

  An olefin copolymer comprising an α-olefin (for example, ethylene) and a glycidyl ester of an α, β-unsaturated acid can be obtained by copolymerization by a well-known radical polymerization reaction. The (C) olefin copolymer is preferably copolymerized using 1 to 40 parts by weight of a glycidyl ester of an α, β-unsaturated acid with respect to 100 parts by weight of the α-olefin.

  Furthermore, the (C) olefin copolymer has one or more of a polymer or copolymer composed of a repeating unit represented by the following general formula (2) for improving impact resistance and heat resistance. A graft copolymer that is chemically bonded in a branched or crosslinked structure is preferred.

(However, R is hydrogen or a lower alkyl group, X is -COOCH ₃ , -COOC ₂ H ₅ , -COOC ₄ H ₉ , -COOCH ₂ CH (C ₂ H ₅ ) C ₄ H ₉ , -C ₆ H ₅ , One or more groups selected from —CN are shown.)
The polymer or copolymer segment to be graft copolymerized as a branched or cross-linked chain may be one or two selected from acrylic acid, methacrylic acid, methyl acrylate, methyl methacrylate, butyl acrylate, butyl methacrylate, acrylonitrile and styrene. Examples include polymers or copolymers composed of more than one species. Preferred are a methacrylic acid polymer, a copolymer of acrylonitrile and styrene, a copolymer of methyl methacrylate and butyl acrylate, and the like, particularly preferably a copolymer of methyl methacrylate and butyl acrylate. These polymers or copolymers are usually prepared by well-known radical polymerization.

  In addition, the branching or crosslinking reaction of these polymers or copolymers can be easily prepared by radical reaction. For example, by generating free radicals in these polymers or copolymers with peroxides or the like, and melting and kneading an olefin copolymer of α-olefin and a glycidyl ester of α, β-unsaturated acid, Graft copolymers can be prepared.

  The polymer or copolymer that becomes a branched or crosslinked chain branches or crosslinks 10 to 100 parts by weight with respect to 100 parts by weight of an olefin copolymer of glycidyl ester of α-olefin and α, β-unsaturated acid. Is preferred.

  As such an olefin copolymer having a glycidyl ester content of α, β-unsaturated acid of 4 to 8% by weight, a commercially available one can be used, for example, Bond First manufactured by Sumitomo Chemical Co., Ltd. 2C and the like.

  Further, the content of the copolymer component derived from the (C) glycidyl ester in the PAS resin composition is 0.2 to 0.5 mol%, and the glycidyl of (C) with respect to the carboxyl end group amount (mmol / kg) of (A) The content ratio (mmol / kg) of the copolymer component derived from the ester (content of copolymer component derived from the glycidyl ester / carboxyl end group content) needs to be 0.4 to 1.0.

  In the present invention, when the glycidyl ester in the elastomer (olefin copolymer) reacts with the carboxyl group end group of the PAS resin, the interaction between the PAS resin and the olefin copolymer increases, and the impact characteristics are improved. Guessed.

  Here, if the content of the copolymer component derived from the glycidyl ester is too large, the glycidyl groups of the olefin copolymer react with each other. As a result, the viscosity of the resin increases, and the fluidity of the resin composition This is undesirable because it causes a filling failure (short shot), a mold release failure and the like, resulting in poor molding stability or difficulty in molding a thin molded product.

  In addition, if the content of the copolymer component derived from the glycidyl ester is too small, the reaction between the PAS resin and the olefin copolymer does not occur, so that the effect of improving impact characteristics cannot be sufficiently obtained.

  For this reason, as described above, the ratio (glycidyl ester content / carboxyl group amount) between the content of the copolymer component derived from the glycidyl ester and the carboxyl group terminal amount of the PAS resin is adjusted to a specific range (0.4 to 1.0). There is a need to.

  In the present invention, as the component (D), one or more compounds selected from alkali metal hydroxides or alkaline earth metal hydroxides are further blended to obtain a high dielectric constant and a low dielectric loss tangent. In addition, a PAS resin composition having further improved metal corrosivity while maintaining excellent moldability can be obtained. Examples of the metal of such a compound include sodium, lithium, potassium, calcium, strontium, barium and magnesium, preferably calcium.

  (D) The compounding amount of one or more compounds selected from alkali metal hydroxides or alkaline earth metal hydroxides is 0.01 to 15 parts by weight with respect to 100 parts by weight of the PAS resin. If the blending amount is less than 0.01 parts by weight, the effect of improving metal corrosion is small, and if it is more than 15 parts by weight, the melt viscosity of the resin composition increases and the moldability deteriorates.

  The resin composition of the present invention can be blended with an inorganic filler to improve performance such as mechanical strength, heat resistance, dimensional stability (deformation resistance, warpage) and electrical properties. Correspondingly, fibrous, granular and plate-like fillers are used.

  Examples of fibrous fillers include glass fiber, asbestos fiber, carbon fiber, silica fiber, silica / alumina fiber, zirconia fiber, boron nitride fiber, boron fiber, potassium titanate fiber, stainless steel, aluminum, titanium, copper, brass, etc. Examples thereof include inorganic fibrous materials such as metal fibrous materials. Particularly typical fibrous fillers are glass fibers or carbon fibers. High melting point organic fiber materials such as polyamide, fluororesin and acrylic resin can also be used. On the other hand, as particulate filler, carbon black, silica, quartz powder, glass beads, glass powder, calcium oxalate, aluminum oxalate, kaolin, talc, clay, diatomaceous earth, wollastonite such as wollastonite, oxidation Metal oxides such as iron, titanium oxide, zinc oxide and alumina, metal carbonates such as calcium carbonate and magnesium carbonate, metal sulfates such as calcium sulfate and barium sulfate, other silicon carbide, silicon nitride, boron nitride, Various metal powders are mentioned. Examples of the plate-like filler include mica, glass flakes, and various metal foils. These inorganic fillers can be used alone or in combination of two or more.

  In using these fillers, it is desirable to use a sizing agent or a surface treatment agent if necessary. Examples of this are functional compounds such as epoxy compounds, isocyanate compounds, silane compounds, and titanate compounds. These compounds may be used after being subjected to surface treatment or convergence treatment in advance, or may be added at the same time as material preparation.

  The amount of the inorganic filler used is not particularly limited, but is generally 10 to 300 parts by weight per 100 parts by weight of the component (A) PAS resin. If it is too small, the mechanical strength is slightly inferior. If it is too large, the molding operation becomes difficult, and there is also a problem in mechanical strength.

  Moreover, the silane compound can be mix | blended with the resin composition of this invention in order to improve a burr | flash etc. in the range which does not impair the effect of this invention. The silane compound includes various types such as vinyl silane, methacryloxy silane, epoxy silane, amino silane, mercapto silane, etc., for example, vinyl trichloro silane, γ-methacryloxy propyl trimethoxy silane, γ-glycidoxy propyl trimethoxy silane. , Γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, and the like, but are not limited thereto.

  The resin composition of the present invention can be used in combination with a small amount of other thermoplastic resins in addition to the above components depending on the purpose. As the other thermoplastic resin, any thermoplastic resin that is stable at a high temperature may be used. For example, aromatic polyesters such as polyethylene terephthalate and polybutylene terephthalate and diol or oxycarboxylic acid, polyamide, polycarbonate, ABS, polyphenylene oxide, polyalkyl acrylate, polysulfone, polyethersulfone, polyetherimide , Polyether ketone, fluororesin, polyarylate and the like. These thermoplastic resins can be used in combination of two or more.

  Further, the resin composition of the present invention generally contains known substances generally added to thermoplastic resins, that is, stabilizers such as antioxidants, flame retardants, colorants such as dyes and pigments, lubricants, and crystallization accelerators. In addition, a crystal nucleating agent and the like can be appropriately added according to the required performance.

  The resin composition of the present invention can be prepared by facilities and methods generally used for preparing a synthetic resin composition. In general, necessary components can be mixed, melt-kneaded using a single-screw or twin-screw extruder, and extruded to form pellets for molding. It is also a preferred method to melt-extrude the resin component and add and mix an inorganic component such as glass fiber in the middle.

  The material pellets thus obtained can be molded using generally known thermoplastic resin molding methods such as injection molding, extrusion molding, vacuum molding, compression molding, etc., but injection molding is most preferred. .

Next, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited to these. The specific substances (A), (B), (C), and (D) used in Examples and Comparative Examples are as follows.
(A) Polyphenylene sulfide (PPS) resin (A-1): Kureha Fortron KPS (melting viscosity 30 Pa · s at 310 ° C, shear rate 1000 sec ^-1 )
After charging 5700 g of NMP (N-methyl-2-pyrrolidone) into a 20 L autoclave and replacing with nitrogen gas, the temperature was raised to 100 ° C. while stirring at 250 rpm for about 1 hour. After reaching 100 ° C., 1170 g of NaOH aqueous solution having a concentration of 74.7% by weight, 1990 g of sulfur source aqueous solution (including NaSH = 21.8 mol and Na 2 S = 0.50 mol), and NMP 1000 g were added, and over about 2 hours, The temperature was gradually raised to 200 ° C., and 945 g of water, 1590 g of NMP, and 0.31 mol of hydrogen sulfide were discharged out of the system.

  After the dehydration step, the temperature was lowered to 170 ° C., 3427 g of p-DCB (p-dichlorobenzene), 2800 g of NMP, 133 g of water, and 23 g of NaOH having a concentration of 97% by weight were added. . Subsequently, while stirring at a rotation speed of 250 rpm of the stirrer, the temperature was raised to 180 ° C. over 30 minutes, and further, the temperature was raised from 180 ° C. to 220 ° C. over 60 minutes. After reacting at that temperature for 60 minutes, the temperature was raised to 230 ° C. over 30 minutes, and the reaction was carried out at 230 ° C. for 90 minutes to perform pre-stage polymerization.

Immediately after the completion of the pre-polymerization, the rotation speed of the stirrer was increased to 400 rpm, and 340 g of water was injected. After water injection, the temperature was raised to 260 ° C. over 1 hour, and the reaction was carried out at that temperature for 5 hours to carry out post polymerization. After the post-polymerization is completed, the reaction mixture is cooled to near room temperature, and the contents are sieved with a 100-mesh screen, followed by washing with acetone three times, washing three times with water, and washing with 0.3% acetic acid. After that, washing with water was performed 4 times to obtain a washed granular polymer. The granulated polymer was dried at 105 ° C. for 13 hours. The granular polymer thus obtained had a melt viscosity of 30 Pa · s. This operation was repeated 5 times to obtain the required amount of polymer.
-(A-2): Kureha Fortron KPS (melting viscosity of 40 Pa · s at 310 ° C, shear rate of 1000 sec ^-1 )
In a 20 L autoclave, 5700 g of NMP was charged and replaced with nitrogen gas, and then the temperature was raised to 100 ° C. with stirring at 250 rpm for about 1 hour. After reaching 100 ° C., 1170 g of NaOH aqueous solution having a concentration of 74.7% by weight, 1990 g of sulfur source aqueous solution (including NaSH = 21.8 mol and Na 2 S = 0.50 mol), and NMP 1000 g were added, and over about 2 hours, The temperature was gradually raised to 200 ° C., and 945 g of water, 1590 g of NMP, and 0.31 mol of hydrogen sulfide were discharged out of the system.

  After the dehydration step, the mixture was cooled to 170 ° C., and p-DCB 3427 g, NMP 2800 g, water 133 g, and 23 g NaOH at a concentration of 97% by weight were added. Subsequently, while stirring at a rotation speed of 250 rpm of the stirrer, the temperature was raised to 180 ° C. over 30 minutes, and further, the temperature was raised from 180 ° C. to 220 ° C. over 60 minutes. After reacting at that temperature for 60 minutes, the temperature was raised to 230 ° C. over 30 minutes, and the reaction was carried out at 230 ° C. for 90 minutes to perform pre-stage polymerization.

Immediately after the completion of the pre-polymerization, the rotation speed of the stirrer was increased to 400 rpm, and 340 g of water was injected. After water injection, the temperature was raised to 260 ° C. over 1 hour, and the reaction was carried out at that temperature for 5 hours to carry out post polymerization. After completion of the post-polymerization, the reaction mixture is cooled to around room temperature, and the contents are sieved with a 100-mesh screen, and then washed with acetone three times and with water five times. Obtained. The granulated polymer was dried at 105 ° C. for 13 hours. The granular polymer thus obtained had a melt viscosity of 40 Pa · s. This operation was repeated 5 times to obtain the required amount of polymer.
(B) Alkaline earth metal salt of calcium titanate / calcium titanate, fiber diameter 0.5 μm, fiber length 5 μm, relative permittivity 95 at 1 MHz, dielectric loss tangent 0.001, metal ion content of hot water extraction 80 ppm
Preparation method: Potassium titanate fibers were synthesized by a flux method, and then calcium carbonate was deposited using the titanate fibers subjected to dealkalization treatment as a raw material, followed by heat treatment to synthesize calcium titanate fibers. Thereafter, the mixture was poured into pure water at 90 ° C., stirred for 2 hours, and dried at 110 ° C. for 2 hours after the filter furnace.

  The amount of metal ions extracted from the obtained calcium titanate with hot water was determined by dispersing calcium titanate in pure water at 80 ° C. with a slurry concentration of 1% and stirring for 2 hours, and the amount of metal ions in the filtrate was atomically absorbed. The amount of metal ions contained in calcium titanate was determined by quantification by the method.

Filler dielectric constant: Using Toyo Seiki's Labo Plast Mill, blending and blending polyethylene with a filling rate, kneading the resulting sample, molding the test piece for dielectric property measurement, and using an impedance analyzer Obtained by measuring the relative dielectric constant (εr) and dielectric loss tangent (tan δ) at 1 MHz by the capacitance method (electrode contact method) using a dielectric test fixture (Agilent 16451B: conforming to ASTM D150) manufactured by Agilent Technologies. The data were plotted and graphed in relation to the filler filling rate, and the values at which the ratio of the filler was 100 vol% were taken as the relative dielectric constant (εr) and dielectric loss tangent (tan δ) of the filler, respectively.
(C) Olefin-based copolymer (C-1): Bond First 2C manufactured by Sumitomo Chemical Co., Ltd.
・ (C-2): Bond First 7L manufactured by Sumitomo Chemical Co., Ltd.
・ (C-3): Bond First E manufactured by Sumitomo Chemical Co., Ltd.
・ (C-4): “LOTADER AX8840” manufactured by ARKEMA
(D) Alkali metal hydroxide or alkaline earth metal hydroxide (D-1): Calcium hydroxide (D-2): Sodium hydroxide 30 wt% aqueous solution (however, the composition in Table 1) The amount is the value converted to sodium hydroxide.)

Examples 1-5, Comparative Examples 1-7
Ingredients (A), (B), (C) and, if necessary, (D) are mixed for 5 minutes with a Henschel mixer at the ratio shown in Table 1, and this is a twin screw extruder with a cylinder temperature of 320 ° C. And melt-kneaded at a resin temperature of 350 ° C. to produce pellets of the resin composition. Various evaluations were performed on the obtained pellets by the following methods. The results are shown in Table 1.

[Dielectric properties]
A test piece for dielectric property measurement was molded with an injection molding machine at a cylinder temperature of 320 ° C and a mold temperature of 150 ° C, and kept in an air-conditioned room at room temperature (23 ° C ± 2 ° C, 50% RH ± 5% RH) for 2 hours. After standing as above, the relative dielectric constant (εr) and dielectric loss tangent (tan δ) at 1 MHz are measured with a capacitance method (electrode contact method) using a dielectric test fixture (Agilent 16451B: ASTM D150 compliant) manufactured by Agilent Technologies using an impedance analyzer. ) Was measured.

[Melt viscosity]
Using a Toyo Seiki Capillograph, a 1 mmφ × 20 mmL / flat die was used as a capillary, and the melt viscosity at a barrel temperature of 310 ° C. and a shear rate of 1000 sec ⁻¹ was measured.

[Mechanical properties]
-Bending strength: A test piece (width: 10 mm, thickness 4 mm) according to ISO 3167 was molded and measured according to ISO 178.
-Charpy impact strength (no notch): A test piece according to ISO3167 (width: 10 mm, thickness 4 mm) was molded and measured according to ISO 179 / 1eU.
[Measurement of carboxyl end group amount] (The following method is an example)
(I) The peak height at the absorption peak 3065 cm ⁻¹ of the benzene ring of benzoic acid and the absorption peak 1704 cm ^{−1 of} the carboxyl group is measured by FT-IR measurement. They are 0.0117 and 0.143, respectively. Therefore, the relative intensity of the absorption peak of the carboxyl group with respect to the C—H bond of the benzene ring is 61.1.
(Ii) In order to remove the carboxyl group derived from impurities in the PPS resin, pellets obtained by once melt-kneading with a twin screw extruder having a cylinder temperature of 320 ° C. were used as samples. The obtained pellets were pressed FT-IR measurement of the peak height (absorption intensity) was 0.0071 at the position of 0.102,1704Cm ^-1 at the position of 3065cm ^-1.
(Iii) For the resin composition to be measured, in the same manner as described above, from the peak heights (3065 cm ⁻¹ and 1704 cm ⁻¹ ), the absorption peak of one carboxyl group for one C—H bond of the benzene ring The relative intensity was determined to be 0.28. From the relative intensity of the absorption peak of benzoic acid in which one carboxyl group is substituted on the benzene ring, it was determined that the carboxyl group was contained in an amount of 0.46 mol% with respect to the benzene ring.
(Iv) The amount of the repeating unit-(Ar-S)-(Ar is a benzene ring) contained in 1 kg of the PPS resin is 9.3 mol / kg, and the carboxyl group contained in 1 kg of the PPS resin is 42 mmol / kg. kg.

Claims (2)

(A) For 100 parts by weight of polyarylene sulfide resin having a carboxyl end group,
(B) 10 to 400 parts by weight of an alkaline earth metal titanate having a relative dielectric constant at 1 MHz of 50 or more and a dielectric loss tangent of 0.05 or less, and
(C) an olefin copolymer mainly composed of α-olefin and α, β-unsaturated glycidyl ester, and containing glycidyl ester of α, β-unsaturated acid in the olefin copolymer A polyarylene sulfide resin composition comprising 0.5 to 20 parts by weight of an olefin copolymer having an amount of 4 to 8% by weight, which is derived from (C) glycidyl ester in the polyarylene sulfide resin composition The content of the copolymerization component is 0.2 to 0.5 mol%, and the content of the copolymerization component (mmol / kg) derived from the glycidyl ester of (C) with respect to the carboxyl end group content (mmol / kg) of (A) A polyarylene sulfide resin composition having a ratio of 0.4 to 1.0.   Furthermore, 0.01 to 15 parts by weight of one or more compounds selected from alkali metal hydroxides or alkaline earth metal hydroxides as component (D) with respect to 100 parts by weight of component (A) The resin composition of Claim 1 formed by mix | blending.