Polyarylene sulfide resin composition

Abstract

To provide a resin composition which is excellent in low burr-forming property while maintaining high thermal stability.SOLUTION: A polyarylene sulfide resin composition contains, with respect to 100 pts.wt. of the total of (A) a polyarylene sulfide resin (component A) and (B) a polycarbonate resin (component B), 0.1-30 pts.wt. of (C) a hydrotalcite compound and 10-300 pts.wt. of (D) a glass fiber (component D), wherein the component (C) is a hydrotalcite compound represented by the following general formula (1),and a ratio (molar ratio) (M2+ / M3+) of M2+ and M3+ in the formula (1) is less than 2.5. Formula (1): [M2+1-xM3+x(OH)2]x+[An-x / n mH2O]x-. In the formula, M2+ is a divalent metal ion, M3+ is a trivalent metal ion, An- is an n-valent anion, and x, m and n are numbers satisfying 0<x≤0.33, 0≤m≤5 and 0<n≤4.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a resin composition comprising a polyarylene sulfide resin, a polycarbonate resin, a hydrotalcite compound and glass fibers, which resin composition has excellent low burr properties while maintaining high thermal stability. [Background technology]

[0002] Polyarylene sulfide resin is an engineering plastic that is excellent in chemical resistance, heat resistance, mechanical properties, etc. For this reason, polyarylene sulfide resin is widely used as a metal substitute material in applications such as electrical and electronics, vehicles, aircraft, and housing facilities, taking advantage of its excellent properties. In particular, polyarylene sulfide resin is a material with high fluidity, so it is widely used in small parts and thin-walled molded products. However, polyarylene sulfide resin has a problem that burrs are generated during molding due to its fluidity. If burrs are generated on molded products, it leads to poor contact in electrical and electronic parts and increased costs due to the burr removal process. As a means to solve this problem, Patent Document 1 discloses a resin composition containing a polycarbonate resin for a polyarylene sulfide resin. However, the resin composition described in Patent Document 1 does not sufficiently suppress burrs, and no mention is made of thermal stability. Patent Document 2 proposes a resin composition containing a hydrotalcite compound for a polyarylene sulfide resin, but does not mention low burrs. Patent Documents 3 and 4 propose polyarylene sulfide resins in which the crystallization temperature is increased by using a crystal nucleating agent, but the effect is not sufficient. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2020-132832 A [Patent Document 2] JP 2012-122009 A [Patent Document 3] JP 2003-96300 A [Patent Document 4] JP 2016-147967 A Summary of the Invention [Problem to be solved by the invention]

[0004] An object of the present invention is to provide a resin composition that maintains high thermal stability and has excellent low flash properties. [Means for solving the problem]

[0005] As a result of extensive research, the inventors discovered that a resin composition comprising a polyarylene sulfide resin, a polycarbonate resin, a hydrotalcite-type compound and glass fibers is a resin composition that maintains high thermal stability while exhibiting excellent low-burr properties, and thus arrived at the present invention.

[0006] Specifically, the above-mentioned problem is solved by a resin composition containing 0.1 to 30 parts by weight of (C) a hydrotalcite-type compound (component C) and 10 to 300 parts by weight of (D) glass fiber (component D) relative to a total of 100 parts by weight of (A) a polyarylene sulfide resin (component A) and (B) a polycarbonate resin (component B), wherein the component C is a hydrotalcite-type compound represented by the following general formula (1), and M 2+ and M. 3+ Ratio (molar ratio) (M 2+ / M 3+ The above-mentioned object is achieved by the polyarylene sulfide resin composition, characterized in that the molecular weight ratio (Mw) is less than 2.5. [M 2+ 1-x M 3+ x (OH)2] x+ [A n- x / n mH2O] x- (1) (In the formula, M 2+ is a divalent metal ion, M 3+ is a trivalent metal ion, A n-represents an n-valent anion. x, m, and n are numbers satisfying 0 < x ≤ 0.33, 0 ≤ m ≤ 5, and 0 < n ≤ 4. )

[0007] Hereinafter, the details of the present invention will be described.

[0008] (Component A: Polyarylene sulfide resin) As the polyarylene sulfide resin used as Component A of the present invention, any resin belonging to the category called polyarylene sulfide resin may be used.

[0009] Examples of the polyarylene sulfide resin include those composed of, as its structural units, 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 them, those containing 70 mol% or more, particularly 90 mol% or more of p-phenylene sulfide units are preferred, and further, poly(p-phenylene sulfide) is more preferred.

[0010] The total chlorine content of the polyarylene sulfide resin used as Component A of the present invention is preferably 500 ppm or less, more preferably 450 ppm or less, still more preferably 300 ppm or less, and particularly preferably 50 ppm or less. When the total chlorine content exceeds 500 ppm, the amount of generated gas may increase, the mold deposit may increase, and the peelability may deteriorate.

[0011] The total sodium content of the polyarylene sulfide resin used as the A component of the present invention is preferably 39 ppm or less, more preferably 30 ppm or less, even more preferably 10 ppm or less, and particularly preferably 8 ppm or less. If it exceeds 39 ppm, not only the physical properties are reduced due to the promotion of decomposition of the resin, but also the moisture and heat resistance may be reduced due to the increase in the water absorption of the resin caused by the coordinate bond between sodium metal and water molecules under high temperature and high humidity conditions. The total sodium content was measured by ICP atomic emission spectrometry (ICP-AES method).

[0012] The polyarylene sulfide resin used as component A of the present invention preferably has a polydispersity (Mw / Mn) expressed by the weight average molecular weight (Mw) and the number average molecular weight (Mn) of 2.7 or more, more preferably 2.8 or more, and even more preferably 2.9 or more. If the polydispersity is less than 2.7, there may be a large amount of burrs generated during molding. The upper limit of the polydispersity (Mw / Mn) is not particularly specified, but it is preferably 10 or less. Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​calculated in terms of polystyrene by gel permeation chromatography (GPC). 1-chloronaphthalene was used as the solvent, and the column temperature was set to 210°C.

[0013] The method for producing the polyarylene sulfide resin is not particularly limited, and polymerization can be performed by a known method, but particularly suitable polymerization methods include those described in U.S. Patent Nos. 4,746,758 and 4,786,713, JP-A-2013-522385, JP-A-2012-233210, and JP-A-5167276, etc. These production methods involve directly heating a diiodoaryl compound and solid sulfur without a polar solvent to polymerize them.

[0014] The 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 terminator to obtain a polyarylene sulfide resin. Iodine is generated in gas form during this process, which is then recovered and reused in the iodine process. Iodine is essentially a catalyst.

[0015] A representative example of solid sulfur used in the above-mentioned preparation method is cyclooctasulfur (S8) in which eight atoms are linked at room temperature. However, the sulfur compound used in the polymerization reaction is not limited, and any form that is solid or liquid at room temperature can be used.

[0016] Representative diiodoaryl compounds used in the above-mentioned production method include at least one selected from the group consisting of diiodobenzene, diiodonaphthalene, diiodobiphenyl, diiodobisphenol, and diiodobenzophenone. Also, derivatives of iodoaryl compounds to which an alkyl group or a sulfone group is bonded, or to which oxygen or nitrogen is introduced, are used. Iodoaryl compounds are classified into different isomers depending on the bonding position of the iodine atom, and preferred examples of these isomers are compounds in which iodine is symmetrically located at both ends of the molecule of the aryl compound, 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 based on 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

[0017] Representative examples of polymerization terminators used in the above-mentioned production 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 of the thiurams is at least one selected from the group consisting of tetramethylthiuram monosulfide and tetramethylthiuram disulfide. A preferred example of the dithiocarbamates is at least one selected from the group consisting of zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate. A preferred example of the aromatic sulfide compound is at least one selected from the group consisting of diphenyl sulfide, diphenyl disulfide, diphenyl ether, biphenyl, and benzophenone. In any of the polymerization terminators, 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, and a nitro group, and preferred examples include a carboxy group and an amino group, and more preferred examples include a functional group having a peak at 1600 to 1800 cm in the FT-IR spectrum. -1 The content of the polymerization terminator is preferably 1 to 30 parts by weight based on 100 parts by weight of the solid sulfur. This amount is determined taking into consideration the formation of disulfide bonds.

[0018] Furthermore, as the polyarylene sulfide resin used as component A of the present invention, in order to obtain higher compatibility, a polyarylene sulfide resin having a reactive functional group at the end, such as a carboxy group or a carboxy group derivative group, a thiol group, a sulfone group, a hydroxy group, an amino group, an epoxy group, a mercapto group, a cyano group, or a nitro group, can also be used. By using the polyarylene sulfide resin having the reactive functional group at the end, it is possible to obtain a high degree of compatibility with other polymer materials. In some cases, it is possible to obtain a resin composition that exhibits excellent compatibility with fibers, carbon fibers, etc., has excellent releasability, and has higher mechanical strength. A more preferred example of the polyarylene sulfide resin having a reactive functional group at its end is a polyarylene sulfide resin having at least one end group structure selected from a carboxy group and an amino group. The polyarylene sulfide resin having at least one end group structure selected from a carboxy group and an amino group is a polyarylene sulfide resin having a carboxy group-derived peak at about 1600 to 1800 cm in the FT-IR spectrum of FT-IR spectroscopy. -1 Or, amino group-derived 3300-3500 cm -1 and 1400-1600 cm -1 When the height intensity of the aromatic ring stretching peak appearing at about 1600 to 1800 cm is taken as 100%, -1 Or about 3300~3500cm -1 The relative height intensity of the peak is 0.001 to 10%.

[0019] A particularly preferred example of the polyarylene sulfide resin having at least one type of end group structure selected from the carboxy group and the amino group is a polyarylene sulfide resin having a carboxy group end group structure, which is represented by a structural unit represented by the following general formula (2). -(SAr)n-COOH (2) (In the formula, Ar is an arylene group, and n is the number of repeating units.)

[0020] Here, the arylene group can be a p-phenylene group, an m-phenylene group, an o-phenylene group, a substituted phenylene group, etc. Specifically, the substituted phenylene group is a phenylene group optionally substituted with one or more of F, Cl, Br, C1-C3 alkyl, trifluoromethyl, C1-C3 alkoxy, trifluoromethoxy, trifluoromethylthio, dimethylamino, cyano, (C1-C3 alkyl)SO2-, (C1-C3 alkyl)NHSO2-, (C1-C3 alkyl)2NSO2-, and NH2SO2-.

[0021] The method of introducing the reactive functional group into the polyarylene sulfide resin is not particularly limited, and the polymerization is carried out by a known method, but a method of using a polymerization terminator having one or more groups on a conjugated aromatic ring skeleton can be mentioned. Examples of the conjugated aromatic ring skeleton used in the polymerization terminator include diphenyl disulfide, monoiodobenzene, thiophenol, 2,2'-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazolyl sulfenamide, 2-(morpholinothio)benzothiazole, and N,N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide.

[0022] A suitable polymerization method for producing a polyarylene sulfide resin having a terminal group structure of a carboxy group includes a step of polymerizing a diiodo aromatic compound and a reactant containing sulfur element, and a production method in which a compound having a carboxy group is added while the polymerization reaction step is proceeding to substitute the terminal group of the polyarylene sulfide main chain with a carboxy group. A representative example of the compound having a carboxy group is at least one selected from the group consisting of 2-iodobenzoic acid, 3-iodobenzoic acid, 4-iodobenzoic acid, and 2,2'-dithiobenzoic acid. The compound having a carboxy group can be added in an amount of about 0.0001 to 5 parts by weight based on 100 parts by weight of the diiodo aromatic compound.

[0023] In the above-mentioned production method, a polymerization catalyst may be used, and a representative example of the polymerization catalyst is a nitrobenzene-based catalyst. A preferred example of the nitrobenzene-based catalyst is 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 catalyst is preferably 0.01 to 20 parts by weight based on 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

[0024] A typical example of the reaction conditions for this production method is to proceed for 1 to 30 hours while increasing the temperature and decreasing the pressure from initial reaction conditions of 180 to 250°C temperature and 50 to 450 Torr (6.7 to 60 kPa) to final reaction conditions of 270 to 350°C temperature and 0.001 to 20 Torr (0.00013 to 2.7 kPa). Preferably, the initial reaction conditions are a temperature of 180°C or higher and a pressure of 450 Torr (60 kPa) or lower, taking into account the reaction rate, and the final reaction conditions are a temperature of 350°C or lower and a pressure of 20 Torr (2.7 kPa) or lower, taking into account the thermal decomposition of the polymer.

[0025] However, the polymerization reaction conditions depend on the structural design and production rate of the reactor, and are known to those skilled in the art, so they are not particularly limited. The reaction conditions can be appropriately set by those skilled in the art in consideration of the process conditions.

[0026] By using this polymerization method, it is not necessary to substantially reduce the sodium content, and a polyphenylene sulfide resin having excellent cost performance can be obtained.

[0027] (B component: polycarbonate resin) The polycarbonate resin used in the present invention is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of reaction methods include interfacial polymerization, melt transesterification, solid-phase transesterification of carbonate prepolymers, and ring-opening polymerization of cyclic carbonate compounds, but the melt transesterification method is preferred. The polycarbonate resin may also be a branched polycarbonate resin obtained by polymerizing trifunctional phenols, or may be a copolymerized polycarbonate obtained by copolymerizing an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a divalent aliphatic or alicyclic alcohol.

[0028] The viscosity average molecular weight (M) of the polycarbonate resin is preferably 1.3×10 4 ~4.0×10 4 , more preferably 1.5×10 4 ~3.8×10 4 The viscosity average molecular weight (M) of aromatic polycarbonate resin is calculated by the specific viscosity (η sp ) into the following formula. Details of such polycarbonate resins are described in JP-A-2002-129003. η sp / c=[η]+0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η]=1.23×10 -4 M 0.83 c=0.7

[0029] The polycarbonate resin used in the present invention may be any of various polycarbonate resins having high heat resistance or low water absorption rate polymerized using other dihydric phenols other than the commonly used bisphenol A polycarbonate. Specific examples of various polycarbonate resins having high heat resistance or low water absorption rate polymerized using other dihydric phenols include the following.

[0030] (1) A copolymer polycarbonate in which, based on 100 mol % of dihydric phenol components constituting the polycarbonate, 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter abbreviated as "BPM") components account for 20 to 80 mol % (more preferably 40 to 75 mol %, and even more preferably 45 to 65 mol %) and 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter abbreviated as "BCF") components account for 20 to 80 mol % (more preferably 25 to 60 mol %, and even more preferably 35 to 55 mol %). (2) Of the dihydric phenol components constituting the polycarbonate, 100 mol % is bisphenol A copolymer polycarbonate having a group A component of 10 to 95 mol % (more preferably 50 to 90 mol %, and even more preferably 60 to 85 mol %) and a BCF component of 5 to 90 mol % (more preferably 10 to 50 mol %, and even more preferably 15 to 40 mol %). (3) A copolymer polycarbonate in which, relative to 100 mol % of the dihydric phenol components constituting the polycarbonate, the BPM component accounts for 20 to 80 mol % (more preferably 40 to 75 mol %, and even more preferably 45 to 65 mol %) and the 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane component accounts for 20 to 80 mol % (more preferably 25 to 60 mol %, and even more preferably 35 to 55 mol %).

[0031] These special polycarbonates may be used alone or in a suitable mixture of two or more. They may also be used in a mixture with the commonly used bisphenol A polycarbonate. The manufacturing method and properties of these special polycarbonates are described in detail in, for example, JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. Furthermore, polycarbonate-polyorganosiloxane copolymers in which polyorganosiloxane units are copolymerized may also be used.

[0032] Polycarbonate resin can be produced not only from virgin raw materials, but also from polycarbonate resin recycled from used products, such as containers such as water bottles, optical disks, and automobile headlamps.

[0033] The ratio (weight ratio) of component A to component B (component A / component B) is preferably 99 / 1 to 50 / 50, more preferably 90 / 10 to 60 / 40, and even more preferably 85 / 15 to 65 / 35. If the weight ratio is 99 / 1 or more, the characteristics of the polycarbonate resin may not be expressed and the generation of burrs may not be suppressed, while if it is less than 50 / 50, the decomposition of the polycarbonate resin may be significant, the thermal stability may decrease, and the low burr property may be inferior.

[0034] (Component C: Hydrotalcite compound) The hydrotalcite compound used as Component C in the present invention is a compound represented by the following general formula (1). [M 2+ 1-x M 3+ x (OH)2] x+ [A n- x / n mH2O] x- (1) (In the formula, M 2+ is a divalent metal ion, M 3+ is a trivalent metal ion, A n- represents an anion having a valence of n. x, m, and n represent the numbers shown in the following formula. 0 <x≦0.33、0≦m≦5、0<n≦4)

[0035] M 2+ As for Mg 2+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ M 3+ As for Al 3+ , Fe 3+ , Cr 3+ , Co 3+ , In 3+A n- As for OH - , F - ,Cl - , Br - , NO3 - , CO3 2- , SO4 2- , Fe(CN)4 2- , CH3COO - , oxalate ion, salicylate ion, etc. 2+ and M. 3+ , A n- may each be composed of one type or two or more types.

[0036] In the present invention, the hydrotalcite compound is represented by M in the above general formula (1). 2+ and M. 3+ Ratio (molar ratio) (M 2+ / M 3+ ) is less than 2.5, preferably less than 2.3, and more preferably less than 2.1. If the molar ratio is 2.5 or more, the decomposition of the polycarbonate resin is promoted, low flash properties are not achieved, and physical properties are also deteriorated. The lower limit of the molar ratio is preferably 1.0 or more, more preferably 1.3 or more. Examples of such hydrotalcite compounds include DHT-4C from Kyowa Chemical Industry Co., Ltd. and STABIACE HT-9 from Sakai Chemical Industry Co., Ltd., and are easily available.

[0037] The content of component C is 0.1 to 30 parts by weight, preferably 0.5 to 20 parts by weight, and more preferably 1 to 10 parts by weight, relative to 100 parts by weight of the total of components A and B. If the content is less than 0.1 part by weight, a sufficient low-burr effect is not achieved, whereas if the content exceeds 30 parts by weight, a sufficient low-burr effect is not achieved and decomposition of the polycarbonate resin is promoted.

[0038] (D component: glass fiber) The glass fiber used in the present invention is not particularly limited to glass compositions such as A glass, C glass, E glass, etc., and may contain components such as TiO2, SO3, P2O5, etc., depending on the case. However, E glass (alkali-free glass) is more preferable when blended with a thermoplastic resin. Furthermore, it is possible to use two or more of these glass fibers in combination. Glass fibers are made by quenching molten glass while stretching it by various methods, and forming it into a predetermined fiber shape or milled shape. The quenching and stretching conditions in such cases are not particularly limited. In addition to a perfect circle, the cross-sectional shape may be an ellipse, a cocoon shape, a three-leaf shape, or other shapes other than a perfect circle. Furthermore, a mixture of a perfect circle glass fiber and a shape other than a perfect circle glass fiber may be used. Among these, a perfect circle glass fiber is more preferable. In addition, it is preferable to pretreat these glass fibers with coupling agents such as isocyanate compounds, organic silane compounds, organic titanate compounds, organic borane compounds, and epoxy compounds, or with organic onium ions in the case of swellable layered silicates, in order to obtain better mechanical strength. The glass fibers used in the present invention preferably have a diameter (D) of 6 to 13 μm, a cut length (L) of 30 μm to 9 mm, and an L / D ratio of 2.3 to 1500.

[0039] The content of component D is 10 to 300 parts by weight, preferably 20 to 250 parts by weight, and more preferably 30 to 200 parts by weight, per 100 parts by weight of the total of components A and B. If the content of component D is less than 10 parts by weight, low flash properties are not achieved, and if it exceeds 300 parts by weight, strand take-up by extrusion kneading is not possible.

[0040] (Other Ingredients) The resin composition of the present invention may contain a filler component other than component D, provided that the effect of the present invention is not impaired. Suitable filler components are not particularly limited, and may be fibrous, plate-like, powdery, granular, or other reinforcing materials. Specific examples include inorganic fibers such as wollastonite, carbon fiber, potassium titanate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, gypsum fiber, and metal fiber, and organic fibers such as fully aromatic polyamide fiber, with wollastonite, carbon fiber, and fully aromatic polyamide fiber being preferred. Other examples include silicates such as sericite, kaolin, mica, clay, bentonite, asbestos, talc, 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 magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, glass flakes, glass beads, ceramic beads, boron nitride, silicon carbide, calcium phosphate, and silica, and glass flakes, mica, talc, and glass beads are preferably used. These may be hollow, and two or more of these reinforcing materials may be used in combination.

[0041] In addition, it is preferable to pre-treat these reinforcing materials with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound or an epoxy compound, or with an organic onium ion in the case of a swellable layered silicate, in order to obtain better mechanical strength.

[0042] A conductive filler can be used as a reinforcing material to impart electrical conductivity to the resin composition of the present invention. The conductive filler is not particularly limited as long as it is a conductive filler that is usually used to make resins conductive, and specific examples thereof include metal powder, metal flakes, metal ribbons, metal fibers, metal oxides, inorganic fillers coated with conductive substances, carbon powder, graphite, carbon fibers, carbon flakes, and scaly carbon. Specific examples of the metal species of the metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. Specific examples of the metal species of the metal fibers include iron, copper, stainless steel, aluminum, and brass. Such metal powder, metal flakes, metal ribbons, and metal fibers may be surface-treated with a titanate-based, aluminum-based, silane-based, or other surface treatment agent.

[0043] Specific examples of metal oxides include SnO2 (antimony doped), In2O3 (antimony doped), ZnO (aluminum doped), etc., which may be surface-treated with a surface treatment agent such as a titanate-based, aluminum-based, or silane-based coupling agent.

[0044] Specific examples of the conductive material in the inorganic filler coated with a conductive material include aluminum, nickel, silver, carbon, SnO2 (antimony doped), and In2O3 (antimony doped). Examples of the inorganic filler to be coated include mica, glass beads, carbon fibers, potassium titanate whiskers, barium sulfate, zinc oxide, titanium oxide, aluminum borate whiskers, zinc oxide whiskers, titanic acid whiskers, and silicon carbide whiskers. Coating methods include vacuum deposition, sputtering, electroless plating, and baking. These may also be surface-treated with a surface treatment agent such as a titanate-based, aluminum-based, or silane-based coupling agent.

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

[0046] 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 core-shell graft copolymer resins such as acrylonitrile-butadiene-styrene copolymers (ABS resins), methyl methacrylate-butadiene-styrene copolymers (MBS resins), and silicone-acrylic composite rubber graft copolymers, or thermoplastic elastomers such as silicone thermoplastic elastomers, olefin thermoplastic elastomers, polyamide thermoplastic elastomers, polyester thermoplastic elastomers, and polyurethane thermoplastic elastomers.

[0047] The resin composition of the present invention may contain other thermoplastic resins within the range that does not impair the effects of the present invention. Examples of other thermoplastic resins include general-purpose plastics such as polyethylene resins, polypropylene resins, and polyalkyl methacrylate resins, engineering plastics such as polyphenylene ether resins, polyacetal resins, aromatic polyester resins, liquid crystal polyester resins, polyamide resins, cyclic polyolefin resins, and polyarylate resins (amorphous polyarylate, liquid crystal polyarylate), and so-called super engineering plastics such as polytetrafluoroethylene, polyether ether ketone, polyetherimide, polysulfone, and polyether sulfone.

[0048] The resin composition of the present invention may contain antioxidants and heat-resistant ammonium ions within the range not impairing the effects of the present invention. Fixing agents (hindered phenols, hydroquinones, phosphites, and their substituted derivatives, etc.), weathering agents (resorcinols, 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, bisureas, and polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, etc.), crystal nucleating agents (talc, silica, kaolin, clay, etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzene, etc.), Other examples of the antistatic agents that can be added include those used in the present invention, such as brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin, and combinations of these brominated flame retardants with antimony trioxide, and other polymers.

[0049] (Production of resin composition) The resin composition of the present invention can be produced by mixing the above-mentioned components simultaneously or in any order using a mixer such as a tumbler, a V-type blender, a Nauter mixer, a Banbury mixer, a kneading roll, an extruder, etc. Melt kneading using a twin-screw extruder is preferred, and if necessary, it is preferred to feed any component into the other melt-mixed components from a second feed port using a side feeder or the like.

[0050] The resin extruded as described above is directly cut and pelletized, or strands are formed and then the strands are cut by a pelletizer and pelletized. When it is necessary to reduce the influence of external dust during pelletization, it is preferable to purify the atmosphere around the extruder. The shape of the obtained pellets may be a general shape such as a cylinder, a prism, or a sphere, but is more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.5 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 4 mm.

[0051] (About molded products) Molded articles made of the resin composition of the present invention can be obtained by molding the pellets produced as described above. Preferably, they are obtained by injection molding or extrusion molding. Injection molding includes not only ordinary molding methods, but also injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including a method of injecting a 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 performed using either a cold runner method or a hot runner method. In addition, extrusion molding can produce various extrusion molded products, sheets, films, and the like. Sheets and films can also be molded using an inflation method, a calendar method, a casting method, and the like. Furthermore, it is possible to mold the resin composition of the present invention into a heat-shrinkable tube by applying a specific stretching operation. It is also possible to mold the resin composition of the present invention into a molded article by rotational molding, blow molding, and the like. Effect of the Invention

[0052] INDUSTRIAL APPLICABILITY The resin composition of the present invention is a resin composition which maintains high thermal stability and has excellent low flash properties, and is therefore useful for applications such as electric and electronic parts and vehicle parts, and the industrial effects thereof are exceptional. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0053] The present inventors currently consider the best embodiment of the present invention to be one that embodies the preferred ranges of the above-mentioned requirements, and representative examples thereof are described in the following examples, although the present invention is not limited to these embodiments. EXAMPLES

[0054] [Evaluation of resin composition] (1) Bali evaluation The evaluation of burrs was carried out by measuring the length of the burrs on the part of the test piece that contacted the gas vent conforming to the above ISO 527-1 and ISO 527-2. The thickness of the gas vent was 10 μm and the width was 5 mm.

[0055] (2) Viscosity average molecular weight of polycarbonate resin The resin composition obtained was extracted with methylene chloride, and the viscosity average molecular weight of the polycarbonate resin obtained was measured. The decrease rate of the viscosity average molecular weight relative to the viscosity average molecular weight of the polycarbonate resin of Comparative Example 1, which does not contain a hydrotalcite compound, was calculated by the following formula, and was evaluated as good (◯) when it was less than 5%, decreased (△) when it was 5-20%, and greatly decreased (×) when it was more than 20%. Viscosity average molecular weight reduction rate (%)=[(viscosity average molecular weight in each example and comparative example−viscosity average molecular weight in comparative example 1) / (viscosity average molecular weight in comparative example 1)]×100

[0056] [Examples 1 to 10, Comparative Examples 1 to 9] A polyphenylene sulfide resin, a polycarbonate resin, a hydrotalcite compound, and glass fiber were melt-kneaded using a vented twin-screw extruder at the respective compounding amounts shown in Table 1 to obtain pellets. The vented twin-screw 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 200 rpm, and a vent vacuum degree of 3 kPa, and the extrusion temperature was set to 320 °C from the first feed port to the die part. The glass fiber was supplied from the second feed port using the side feeder of the above extruder, and the polyphenylene sulfide resin, polycarbonate resin, and hydrotalcite compound 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.

[0057] Each component denoted by the symbol notation in Table 1 is as follows. <Component A> A-1: A polyphenylene sulfide resin having a phenyl 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, and a vacuum line capable of filling with nitrogen and applying a vacuum, reactants including 5130 g of paradiiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzenemercaptobenzothiazole as a reaction initiator were heated to 180°C to completely melt and mix, and then polymerization reaction was carried out while gradually increasing the temperature and decreasing the pressure 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. When the polymerization reaction had progressed 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) x 100 (%)]. The current viscosity was measured by taking a sample during polymerization and measuring it with a viscometer. ], 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. After that, the pressure was gradually reduced to 0.5 Torr or less until the target viscosity was reached, at which point the reaction was terminated to synthesize a polyarylene sulfide resin having a phenyl group at the end of the main chain. The resin after the reaction was produced in pellet form using a small strand cutter. The weight average molecular weight was 72,000.

[0058] A-2: Polyphenylene sulfide resin having a carboxyl group at the end, obtained by the following manufacturing method: [Manufacturing method 2] A 5L reactor equipped with a thermocouple capable of measuring the internal temperature of the reactor and a vacuum line that can be filled with nitrogen and evacuated was charged with 5130 g of p-diiodobenzene (p-DIB), 450 g of sulfur, and 4 g of 1,3-diiodo-4-nitrobenzene 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 step by step until the final reaction temperature reached 300 °C and the pressure was reduced to 1 Torr or less. When the polymerization reaction had proceeded 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) × 100 (%)]. The current viscosity was measured with a viscometer by taking a sample 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-Iodobenzoic acid was added, and the reaction was allowed to proceed for 10 minutes under a nitrogen atmosphere. Then, the pressure was gradually reduced to 0.5 Torr or less, and the reaction was allowed to proceed for 1 hour before completion, synthesizing a polyarylene sulfide resin having a carboxyl group at the main chain end. The resin after the reaction was produced in pellet form using a small strand cutter machine. The polyarylene sulfide resin was analyzed by FT-IR, and the presence of a peak of the carboxyl group at about 1600 - 1800 cm -1 was confirmed on the spectrum. Also, when the height intensity of the Ring stretch peak appearing at about 1400 - 1600 cm -1 on the FT-IR spectrum was set to 100%, the relative height intensity of the peak at about 1600 - 1800 cm -1 was about 3.4%. The weight average molecular weight was 71,000. A-3: Polyphenylene sulfide resin (DIC-PPS MA-510 manufactured by DIC)

[0059] <Component B> B-1: Polycarbonate resin (L-1225WS manufactured by Teijin Limited, a polycarbonate resin with a viscosity average molecular weight of 20,900 produced by a conventional method from bisphenol A and phosgene)

[0060] <Component C> C-1: Hydrotalcite (DHT-4C manufactured by Kyowa Chemical Industry Co., Ltd., M 2+ / M 3+ (molar ratio): 2.08) C-2: Hydrotalcite (HT-9 manufactured by Sakai Chemical Industry Co., Ltd., M 2+ / M 3+ (molar ratio): 2.3) C-3: Hydrotalcite (DHT-6 manufactured by Kyowa Chemical Industry Co., Ltd., M 2+ / M 3+ (molar ratio): 3.0) C-4: Hydrotalcite (HT-6N manufactured by Kyowa Chemical Industry Co., Ltd., M 2+ / M 3+ (molar ratio): 3.0) C-5: Talc (Ultra5c manufactured by IMI FABI)

[0061] <Component D> D-1: Chopped glass fiber with circular cross-section (T-732H manufactured by Nippon Electric Glass Co., Ltd., diameter: 10.5 μm, cut length: 3 mm, epoxy-based sizing agent) D-2: Chopped glass fiber with circular cross-section (T-756H manufactured by Nippon Electric Glass Co., Ltd., diameter: 10.5 μm, cut length: 3 mm, urethane-based sizing agent)

[0062]

Table 1

Claims

1. A polyarylene sulfide resin composition containing 0.1 to 30 parts by weight of (C) a hydrotalcite-type compound (component C) and 10 to 300 parts by weight of (D) glass fiber (component D) relative to a total of 100 parts by weight of (A) a polyarylene sulfide resin (component A) and (B) a polycarbonate resin (component B), wherein component C is a hydrotalcite-type compound represented by the following general formula (1), and M ２＋ and M. ３＋ Ratio (molar ratio) to (M ２＋ / M ３＋ ) is less than 2.

5. [M ２＋ １－ｘ M ３＋ ｘ (OH) ２ ] ｘ＋ [A ｎ－ ｘ／ｎ ・mH ２ O] ｘ－ (1) (In the formula, M ２＋ is a divalent metal ion, M ３＋ is a trivalent metal ion, A ｎ－ represents an n-valent anion. x, m, and n are numbers that satisfy 0<x≦0.33, 0≦m≦5, and 0<n≦4.

2. 2. The polyarylene sulfide resin composition according to claim 1, wherein the weight ratio of component A to component B (component A / component B) is 99 / 1 to 50 / 50.

3. 3. The polyarylene sulfide resin composition according to claim 1, wherein the component A is a polyarylene sulfide resin containing a polyarylene sulfide resin having a reactive functional group.

4. 4. The polyarylene sulfide resin composition according to claim 1, wherein the component A is a polyarylene sulfide resin having a total sodium content of 39 ppm or less.

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