KR101939186B1 - A method of suppressing a decrease in bending fracture deformation of the resin composition and the resin composition - Google Patents

Abstract

[PROBLEMS] To provide a resin composition having a black color tone and suppressed performance deterioration such as bending rupture strain characteristics.
(A) a polyarylene sulfide sulfide resin, and (B) a filler (B) in an amount of 65 to 300 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A) And (C) carbon black having an arithmetic mean particle diameter of 10 to 15 nm or more in an amount of 0.2 parts by mass or more based on the mass part.

Description

A method of suppressing a decrease in bending fracture deformation of the resin composition and the resin composition

The present invention relates to a resin composition comprising a polyarylene sulfide resin, a filler and carbon black, and a method for suppressing a decrease in flexural fracture deformation of a polyarylene sulfide resin composition.

The polyarylene sulfide resin (hereinafter sometimes referred to as "PAS") resin represented by polyphenylene sulfide (hereinafter also referred to as "PPS") resin has high heat resistance, mechanical properties, chemical resistance, Stability, and flame retardancy. For this reason, PAS resin is widely used in parts for electric / electronic devices, automobile parts, chemical equipment parts, and the like, and is used particularly in applications where the use temperature is high.

The PAS resin has high heat resistance, mechanical properties, chemical resistance, dimensional stability and flame retardancy, but is insufficient in toughness and weak. Therefore, in general, PAS resin is often used as a composite material (resin composition) in which a filler such as glass fiber is added, and it can be considered that mechanical strength such as toughness is improved by adding a filler.

Further, it is known that carbon black is added to a resin composition containing a PAS resin for the purpose of coloring (see, for example, Patent Documents 1 to 6).

Japanese Unexamined Patent Application Publication No. 2014-214203 Japanese Laid-Open Patent Application No. 2011-32319 Japanese Patent Application Laid-Open No. 2015-101627 Japanese Unexamined Patent Application Publication No. 2015-101628 Japanese Unexamined Patent Application Publication No. 2015-101632 Japanese Unexamined Patent Application Publication No. 2000-230120

In the case of forming a molded article by injection molding, although not limited to PAS resin, if a welded portion (a groove occurring in a merged portion of a flowing resin) occurs in a molded product, the mechanical strength of the portion becomes different from that of a non- And it is known that cracks are likely to occur.

Particularly, the welded part has a durability in the case of alternately exposed to a high temperature and a low temperature, that is, a so-called heat shock resistance (low temperature impact resistance). In addition, in the insert molding in which the metal is inserted into the resin, depending on the shape, when the resin flows as if avoiding the metal to be inserted in the mold, there is often a merged portion between the resins, and the welded portion is likely to be generated.

For this reason, there is a demand for a material having a property of not being easily cracked (excellent heat shock resistance) even under an environment of temperature change.

On the other hand, it has been newly found that when carbon black is added to a PAS resin-containing composition containing a filler at a high concentration, performance such as flexural rupture strain characteristics, which may be considered to be an index of heat shock resistance, is lowered.

Therefore, the embodiment of the present invention is a resin composition comprising a PAS resin, a filler having a high concentration of 65 to 300 parts by mass based on 100 parts by mass of the PAS resin, and carbon black, and has a black color tone, , And to provide a method for suppressing a decrease in flexural fracture deformation of a resin composition.

An embodiment of the present invention relates to the following resin composition.

(1) A resin composition comprising (A) a polyarylene sulfide resin,

(B) a filler in an amount of 65 to 300 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A)

(C) carbon black having an arithmetic average particle size of 10 to 15 nm, at least 0.2 part by mass based on 100 parts by mass of the (A) polyarylene sulfide resin.

Resin composition.

(2) The resin composition according to (1), wherein the polyarylene sulfide resin (A) comprises a polyphenylene sulfide resin.

(3) The resin composition according to (1) or (2), wherein the (C) carbon black has an arithmetic mean particle diameter of 13 to 15 nm.

(4) The resin composition according to any one of (1) to (3), wherein the content of the carbon black (C) is 0.2 to 6 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin (A).

(5) The resin composition according to any one of (1) to (4), wherein the (B) filler comprises (B-1) glass fibers.

(6) The resin composition according to (5), wherein the content of the glass fiber (B-1) is 50 mass% or more with respect to the total amount of the filler (B).

(7) The resin composition according to any one of (1) to (6), wherein the volatile content of the carbon black (C) is 7 mass% or less.

(8) The resin composition according to any one of (1) to (7), further comprising (D) an elastomer (D) in an amount of 3 to 35 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A).

Another embodiment of the present invention relates to the following method.

(9) A resin composition comprising (A) a polyarylene sulfide resin, (B) a filler (B) in an amount of 65 to 300 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A) , Wherein carbon black having an arithmetic average particle size of 10 to 15 nm as the carbon black (C) is used in an amount of not less than 0.2 part by mass based on 100 parts by mass of the polyarylene sulfide resin (A), the bending fracture strain / RTI >

(10) The method according to (9), wherein the polyarylene sulfide resin (A) comprises a polyphenylene sulfide resin.

(11) The method according to (9) or (10), wherein the (C) carbon black has an arithmetic average particle diameter of 13 to 15 nm.

(12) The method according to any one of (9) to (11), wherein the content of the carbon black (C) is 0.2 to 6 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin (A).

(13) The method according to any one of (9) to (12), wherein the filler (B) comprises (B-1) glass fibers.

(14) The method according to (13), wherein the content of the glass fiber (B-1) is 50 mass% or more with respect to the total amount of the filler (B).

(15) The method according to any one of (9) to (14), wherein the volatile content of the carbon black (C) is 7 mass% or less.

(16) The method according to any one of (9) to (15), wherein the resin composition further comprises 3 to 35 parts by mass of (D) an elastomer based on 100 parts by mass of the polyarylene sulfide resin (A).

According to the embodiment of the present invention, by selecting a specific carbon black in a resin composition comprising a PAS resin, a high concentration of 65 to 300 parts by mass based on 100 parts by mass of the PAS resin, and a carbon black, Performance deterioration such as characteristics can be suppressed while a black color tone can be given.

Further, according to another embodiment of the present invention, it is possible to suppress the lowering of the bending fracture deformation of the resin composition.

Hereinafter, the embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments, but can be appropriately modified within the scope of the object of the present invention.

In the present specification, when referring to the amount of each component in the composition, a plurality of substances corresponding to each component in the composition means the total amount of a plurality of substances present in the composition unless otherwise specified.

≪ Resin composition &

The resin composition of the embodiment of the present invention comprises (A) a polyarylene sulfide resin, (B) a filler (B) in an amount of 65 to 300 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A) And (C) carbon black having an arithmetic average particle size of 10 to 15 nm in an amount of 0.2 parts by mass or more based on 100 parts by mass of the arylene sulfide resin.

By using the resin composition, a molded article having a black color tone can be obtained while suppressing deterioration of properties such as bending fracture strain (F?).

The molded article obtained by using the above resin composition can be used for electrical and electronic parts, automobile parts, chemical equipment parts, water use peripheral parts, and the like. Particularly, Parts and the like. Further, the resin composition can be preferably used for insert molding.

≪ (A) Polyarylene sulfide resin >

The polyarylene sulfide resin used in the present invention contains a repeating unit - (Ar-S) - ("Ar" represents an arylene group) as a main component. In the present invention, a generally known PAS resin having a molecular structure can be used.

Examples of the arylene group include, but are not limited to, p-phenylene, m-phenylene, o-phenylene, substituted phenylene, p, p'- , p, p'-diphenylene ether group, p, p'-diphenylenecarbonyl group, naphthalene group and the like.

The PAS resin may be a homopolymer composed of only one type of repeating unit, or may be a copolymer including a plurality of types of repeating units.

As the homopolymer, it is preferable to use, for example, a repeating unit of a p-phenylene sulfide group as an arylene group. A homopolymer having a repeating unit of p-phenylene sulfide has high heat resistance and exhibits high strength, high rigidity and high dimensional stability in a wide temperature range.

As the copolymer, a combination of two or more arylene sulfide groups having different arylene groups among the above-mentioned arylene sulfide groups containing an arylene group can be used. Among these, a combination comprising a p-phenylene sulfide group and an m-phenylene sulfide group is preferable in view of physical properties such as heat resistance, moldability and mechanical properties. Further, a polymer containing a p-phenylene sulfide group in an amount of 70 mol% or more is more preferable, and a polymer containing 80 mol% or more is more preferable. The PAS resin having a phenylene sulfide group is a PPS resin.

The PAS resin can be produced by conventionally known polymerization methods. The PAS resin produced by a general polymerization method is usually washed several times with water or acetone to remove by-product impurities and then washed with acetic acid, ammonium chloride, or the like. As a result, the terminal of the PAS resin contains a carboxyl terminal group in a predetermined amount.

The weight average molecular weight (Mw) of the PAS resin used in the present invention is not particularly limited, but is preferably 15,000 or more and 40,000 or less, and more preferably 20,000 or more and 38,000 or less. Within this range, the resin composition has a better balance of mechanical properties and fluidity. The weight average molecular weight (Mw) was measured by a high temperature gel permeation chromatographic method (measuring apparatus; Senshu Science " SSC-7000 ", UV detector (detection wavelength: 360 nm)) to calculate the weight average molecular weight in terms of standard polystyrene Value.

<(B) Filler>

The resin composition in the embodiment of the present invention contains a filler in an amount of 65 to 300 parts by mass based on 100 parts by mass of the polyarylene sulfide resin.

The filler may be either inorganic or organic filler, or a combination thereof. Further, it may be any shape such as a fibrous shape, a divided shape, and a plate shape, and these can be selected according to the purpose.

As the fibrous filler, inorganic fillers such as glass fibers, carbon fibers, silica fibers, silica-alumina fibers, zirconia fibers, boron nitride fibers, boron fibers, potassium titanate fibers, and fibrous materials such as stainless steel, aluminum, titanium, Fibrous materials. High melting point organic fiber materials such as polyamide, fluororesin, and acrylic resin can also be used.

Examples of the granular filler include silicates such as silica, quartz powder, glass beads, glass powder, calcium silicate, aluminum silicate, kaolin, talc, clay, diatomaceous earth and wollastonite, metal oxides such as iron oxide, titanium oxide and zinc oxide, A carbonate of a metal such as magnesium carbonate, a sulfate of a metal such as calcium sulfate and barium sulfate, and other silicon carbide, silicon nitride, boron nitride, and various metal powders.

Examples of the plate filler include mica and glass flakes.

The fillers may be used singly or in combination of two or more.

As the filler, glass fiber, calcium carbonate, or a combination thereof is preferably used. In particular, the filler preferably comprises glass fibers.

The fiber diameter of the glass fiber is not particularly limited, but may be, for example, 9 mu m or more and 13 mu m or less. Here, the fiber diameter of the glass fiber refers to the long diameter of the fiber cross section of the glass fiber.

The cross-sectional shape of the glass fiber may be, for example, a round shape, an oval shape or the like. There is no particular limitation on the kind of the glass fiber, and for example, A glass, C glass, E glass and the like can be used. Among them, E glass (non-alkali glass) is preferably used. Further, the glass fiber may or may not have been subjected to the surface treatment. Examples of the surface treatment for the glass fiber include a treatment with a coating or focusing agent such as an epoxy type, an acrylic type or a urethane type, and a treatment with a silane coupling agent such as an aminosilane or an epoxy silane.

The glass fiber is preferably used as a shatter strand (shot glass fiber) obtained by cutting a plurality of such fibers into a predetermined length. The cut length of the glass fiberglass is not particularly limited and may be, for example, about 1 to 10 mm.

The calcium carbonate is not particularly limited. The average particle diameter may be, for example, 10 μm or more and 50 μm or less.

The calcium carbonate is not particularly limited, and for example, heavy calcium carbonate, precipitated calcium carbonate (light calcium carbonate, colloidal calcium carbonate) and the like can be used. It is also possible to use calcium carbonate (surface-treated calcium carbonate) whose surface is treated with a fatty acid, a fatty acid ester, a resin acid, a higher alcohol-added isocyanate compound or the like.

In the resin composition of the embodiment of the present invention, the amount of the filler is preferably 65 to 300 parts by mass, more preferably 65 to 200 parts by mass, and still more preferably 65 to 200 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin. 68 to 160 parts by mass.

The amount of the glass fiber is not particularly limited, but is preferably 50% by mass or more based on the total amount of the filler from the viewpoint of physical properties such as mechanical properties.

<(C) Carbon Black>

The resin composition of the embodiment of the present invention contains carbon black having an arithmetic mean particle diameter of 10 to 15 nm or more, in an amount of 0.2 parts by mass or more based on 100 parts by mass of the polyarylene sulfide resin.

Examples of the carbon black include furnace black, thermal black, channel black, and Ketjen black. Examples of the carbon black include gas black, oil black, and acetylene black. These carbon blacks may be used alone, or a plurality of carbon blacks may be used in combination.

The arithmetic mean particle diameter of the carbon black is preferably 10 to 15 nm. The arithmetic average particle diameter of the carbon black is an arithmetic mean diameter obtained by observing 1000 carbon black particles with an electron microscope.

When the arithmetic average particle size of the carbon black is 10 nm or more, the black color tone is excellent, and when it is 15 nm or less, the performance deterioration such as the bending rupture strain characteristic is excellent. The arithmetic average particle diameter of carbon black is more preferably from 13 to 15 nm from the viewpoint of balancing effect of suppressing performance deterioration such as black color tone and bending rupture deformation characteristics.

The carbon black is preferably contained in an amount of 0.2 part by mass or more, more preferably 0.2 part by mass to 6 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin in the resin composition.

When the amount of carbon black is 0.2 parts by mass or more based on 100 parts by mass of the polyarylene sulfide resin, the resulting composition is excellent in black color tone. When the carbon black is 6 parts by mass or less based on 100 parts by mass of the polyarylene sulfide resin, mechanical properties such as bending rupture strain characteristics are excellent. The content of the carbon black is preferably 0.2 to 4 parts by mass, more preferably 0.3 to 2.5 parts by mass, more preferably 0.3 to 2.5 parts by mass, based on 100 parts by mass of the polyarylene sulfide resin, from the viewpoint of balance of performances such as black color tone and bending- Particularly preferably 0.3 to 2.0 parts by mass.

The nitrogen adsorption specific surface area (NSA) of carbon black is not particularly limited, but is preferably 160 to 600 m ² / g. The nitrogen adsorption specific surface area of carbon black is the specific surface area determined by the S-BET equation from the nitrogen adsorption amount in JIS K 6217. Generally, the smaller the particle diameter, the larger the specific surface area.

DBP (dibutyl phthalate) absorption amount of carbon black is not particularly limited, but the 45 ~ 200cm ² / 100g is preferred. The amount of DBP absorption of carbon black is an amount of DBP (dibutyl phthalate) absorbed by 100 g of carbon black and measured according to the method described in JIS K6221. Generally, the more the structure is developed, the greater the DBP absorption.

The volatile content of the carbon black is not particularly limited, but is preferably 7% or less. Volatile matter of carbon black is the amount of volatilization (weight ratio of volatile matter to original weight) when carbon black is heated at 950 ° C for 7 minutes. In general, the more surface functional groups, the more volatile components are produced.

<(D) Elastomer>

The resin composition of the embodiment of the present invention preferably contains an elastomer in order to further improve toughness and resistance to heat shock.

As the elastomer, for example, an epoxy group-containing olefin-based copolymer can be mentioned. The elastomers may be used singly or in combination of two or more.

As the epoxy group-containing olefin-based copolymer, an olefin-based copolymer containing a constituent unit derived from an -olefin and a constituent unit derived from a glycidyl ester of an?,? - unsaturated acid is preferable.

In addition, from the standpoint of easily obtaining a polyarylene sulfide resin composition excellent in moldability, mechanical properties, and adhesion with the insert member, the epoxy group-containing olefin-based copolymer is preferably a copolymer comprising a constituent unit derived from an- - In addition to the constituent unit derived from the glycidyl ester of the unsaturated acid, it is also preferable to include a constituent unit derived from a (meth) acrylic acid ester. Hereinafter, the (meth) acrylic acid ester is also referred to as (meth) acrylate. For example, glycidyl (meth) acrylate is also referred to as glycidyl (meth) acrylate. In the present specification, "(meth) acrylic acid" means both of acrylic acid and methacrylic acid, and "(meth) acrylate" means both of acrylate and methacrylate.

The? -olefin is not particularly limited and includes, for example, ethylene, propylene and butylene, with ethylene being particularly preferred. The? -olefin may be used singly or in combination of two or more. Since the epoxy group-containing olefin-based copolymer contains a constituent unit derived from an -olefin, flexibility is easily imparted to the molded article formed using the polyarylene sulfide resin composition. When the molded article has flexibility, it is easy to increase the bonding strength between the insert member, particularly, the metal insert member and the resin member, when manufacturing the insert molded article.

The glycidyl ester of an alpha, beta -unsaturated acid is not particularly limited and includes, for example, glycidyl acrylate ester, glycidyl methacrylate ester, glycidyl ethacrylate ester, and the like. Methacrylic acid glycidyl esters are preferable. The glycidyl esters of?,? - unsaturated acids may be used singly or in combination of two or more. When the epoxy group-containing olefin-based copolymer contains glycidyl ester of?,? - unsaturated acid, it is easy to increase the bonding strength between the insert member and the resin member when the insert molded article is produced.

(Meth) acrylic acid ester is not particularly limited, and examples thereof include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, n-hexyl acrylate, Acrylic acid esters; N-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, n-amyl methacrylate, methacrylic acid- methacrylic acid esters such as n-octyl. Of these, methyl acrylate is particularly preferable. The (meth) acrylic acid esters may be used singly or in combination of two or more kinds. When the epoxy group-containing olefin-based copolymer contains a constituent unit derived from a (meth) acrylate ester, it is easy to increase the bonding strength between the insert member and the resin member when the insert molded article is produced.

an epoxy group-containing olefin-based copolymer containing a constituent unit derived from an -olefin and a constituent unit derived from a glycidyl ester of an?,? - unsaturated acid, and an epoxy group further containing a constituent unit derived from a (meth) Containing olefin-based copolymer can be produced by copolymerization by a known method.

For example, the copolymer can be obtained by carrying out copolymerization by a commonly known radical polymerization reaction. The kind of the copolymer is not particularly limited and may be, for example, a random copolymer or a block copolymer. Examples of the olefin-based copolymer include polyolefins such as polymethyl methacrylate, ethyl polymethacrylate, methyl polyacrylate, ethyl polyacrylate, butyl polyacrylate, 2-ethylhexyl polyacrylate, polystyrene, polyacrylonitrile, An acrylonitrile-styrene copolymer, a butyl acrylate-styrene copolymer, or the like, may be an olefin-based graft copolymer which is chemically bonded in a branched or crosslinked structure.

The epoxy group-containing olefin-based copolymer containing a constituent unit derived from an -olefin and a constituent unit derived from a glycidyl ester of an?,? - unsaturated acid may contain a constituent unit derived from another copolymerizable constituent have.

More specifically, examples of the epoxy group-containing olefin-based copolymer include glycidyl methacrylate-modified ethylenic copolymer and glycidyl ether-modified ethylene copolymer. Of these, glycidyl methacrylate Acrylate-modified ethylenic copolymer is preferable.

Examples of the glycidyl methacrylate-modified ethylenic copolymer include glycidyl methacrylate graft-modified ethylene polymer, ethylene-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate-methyl acrylate copolymer . Of these, an ethylene-glycidyl methacrylate copolymer and an ethylene-glycidyl methacrylate-methyl acrylate copolymer are preferable in that a particularly excellent metal-resin composite molded article can be obtained, and ethylene-glycidyl methacrylate Acrylate-methyl acrylate copolymer is particularly preferable. Specific examples of the ethylene-glycidyl methacrylate copolymer and the ethylene-glycidyl methacrylate-methyl acrylate copolymer include "Bondfast (registered trademark)" (manufactured by Sumitomo Chemical Co., Ltd.) .

Examples of glycidyl ether-modified ethylene copolymers include glycidyl ether graft-modified ethylene copolymers and glycidyl ether-ethylene copolymers.

From the viewpoint of improving the toughness, the resin composition of the embodiment of the present invention preferably contains an elastomer in an amount of 3 to 35 parts by mass, more preferably 7 to 25 parts by mass, per 100 parts by mass of the polyarylene sulfide resin Do.

<Other ingredients>

The resin composition of the embodiment of the present invention may contain other resins within the range not hindering the effect of the present invention. In order to impart desired properties to the molded product, additives such as a nucleating agent, a pigment other than carbon black (for example, an inorganic fired pigment), an antioxidant, a stabilizer, a plasticizer, a lubricant, a releasing agent, Can be added. Such a resin composition imparted with desired characteristics is also included in the PAS resin composition used in the present invention.

&Lt; Preparation of Resin Composition >

The resin composition of the embodiment of the present invention can be prepared by a conventionally known method. Concretely, for example, there is a method of preparing pellets by mixing and kneading the respective components described above and kneading them with an extruder, preparing pellets having different compositions at one time, mixing the pellets in a predetermined amount, Any method such as a method of obtaining a molded article having a desired composition after molding, a method of directly introducing one or more of the components into a molding machine, and the like can be used suitably.

&Lt; Method for suppressing lowering of bending fracture strain of resin composition &

(A) a polyarylene sulfide resin; (B) from 65 to 300 parts by mass of (B) based on 100 parts by mass of the polyarylene sulfide resin (A) (C) a carbon black having an arithmetic mean particle diameter of 10 to 15 nm as the carbon black (C), and a carbon black having an arithmetic average particle diameter of 10 to 15 nm, with respect to 100 parts by mass of the polyarylene sulfide resin (A) Is used in an amount of not less than 0.2 part by mass, thereby suppressing the lowering of the bending fracture strain (%) of the resin composition.

The content of the polyarylene sulfide resin (A), the filler (B), the carbon black (C), and other components that can be contained in the resin composition are the same as those in the above resin composition, And the preferable range thereof are the same as those in the above-mentioned resin composition.

The bending fracture strain F? Is a characteristic that can be considered to be an index of heat shock resistance. In the method of the present embodiment, "suppressing the lowering of the bending fracture deformation of the resin composition" means that when the bending fracture deformation of the resin composition is denoted by A and the bending fracture deformation of the resin composition not containing carbon black is denoted by B, (F? Ratio) ((A / B)? 100) with respect to B is 96.0% or more as shown by the following formula.

(A / B) Х100 (%) ≥96.0%

It is more preferable that the ratio of A to B (F? Ratio) is 97.0% or more.

The bending fracture deformation was measured by preparing a test piece (width 10 mm, thickness 4 mmt) conforming to ISO 316 at a cylinder temperature of 320 캜 and a mold temperature of 150 캜 by injection molding using the resin composition, Value.

[ Example ]

Hereinafter, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples.

[Examples 1 to 9, Comparative Examples 1 to 5 and Reference Examples 1 to 4]

«Materials»

[(A) PAS resin]

PAS resin: PPS resin (weight average molecular weight: Mw: 20,000), Kureza Co., Ltd. "Portron KPS"

(Synthesis method of PAS resin)

A method of synthesizing the above-mentioned PAS resin will be described below. First, 5700 g of NMP (N-methyl-2-pyrrolidone) was added to a 20 L autoclave, air in the autoclave was replaced with nitrogen gas, stirring was carried out at a stirrer rotation speed of 250 rpm over about 1 hour, Lt; 0 &gt; C. After the 100 ℃ reached, the concentration NaOH aqueous solution of 74.7% by weight 1170g, sulfur raw solution 1990g (NaSH = 21.8 mol and Na ₂ includes S = 0.50 mole), and was added to NMP 1000g, slowly 200 ℃ over about 2 hours , And 945 g of water, 1590 g of NMP and 0.31 mol of hydrogen sulfide were discharged out of the system.

Next, after the dewatering process described above, the mixture was cooled to 170 DEG C, 2324 g of p-DCB (p-dichlorobenzene) 3524 g, NMP 2800 g, water 133 g and NaOH concentration of 97 wt% were added, . Then, the mixture was heated to 180 deg. C over 30 minutes while stirring at 250 rpm, and further heated from 180 deg. C to 220 deg. C over 60 minutes. The reaction was carried out at this temperature for 60 minutes, then the temperature was raised to 230 ° C over 30 minutes, and the reaction was carried out at 230 ° C for 90 minutes to carry out shear polymerization (preliminary polymerization).

Next, after completion of the shear polymerization, the number of revolutions of the stirrer was immediately increased to 400 rpm and 340 g of water was press-fitted. After the water was press-fitted, the temperature was raised to 260 ° C over 1 hour, and the reaction was carried out at this temperature for 5 hours to perform the post polymerization (post polymerization). After completion of the rear end polymerization, the reaction mixture was cooled to a temperature near room temperature, and the contents were sieved by using a 100 mesh screen, followed by washing with acetone three times, washing with water three times, washing with 0.3% Thereafter, water washing was carried out four times to obtain washed particulate polymer. The granular polymer was dried at 105 DEG C for 13 hours. This operation was repeated five times to obtain a required amount of polymer (PPS resin).

(Measurement of weight average molecular weight of PAS resin)

The weight average molecular weight of the PAS resin was measured. Concretely, 1-chloronaphthalene was used as a solvent, and the solution was heated and dissolved in an oil bath at 230 占 폚 for 10 minutes, and purified by high-temperature filtration if necessary to prepare a 0.05 mass% concentration solution. A weight average molecular weight was calculated in terms of standard polystyrene in accordance with a high temperature gel permeation chromatographic method (measuring apparatus; Senshu Science &quot; SSC-7000 &quot;, UV detector (detection wavelength: 360 nm)). As a result of the calculation, as described above, the weight average molecular weight of the PAS resin was Mw: 20,000.

[(B) Filler]

(B-1) Glass fiber: "Strutland ECS03T-747H" (fiber diameter: 10.5 탆) manufactured by Nippon Denshikagaru Co.,

(B-2) Calcium carbonate: "Micron Calc MC-35W" manufactured by Asahi Komatsu, average particle diameter (50% d) 21 μm

[(C) carbon black]

(C-1) Wilbur Alice (Ltd.), "Raven 2500 Ultra", the arithmetic mean particle size: 13nm, specific surface area ^{(NSA): 270m 2 / g} , DBP absorption amount: 65cm ³ / 100g

(C-2) Wilbur Alice (Ltd.), "Raven 3500", the arithmetic mean particle size: 13nm, specific surface area (NSA): 375m ² / g, DBP absorption amount: 105cm ^3/100 g, volatile content: 5% by weight

(C-3) manufactured by Mitsubishi Chemical (Co., Ltd.), "# 2600", the arithmetic mean particle size: 13nm, specific surface area (NSA): 370m ² / g, DBP absorption amount: 77cm ^3/100 g, volatile content: 1.8% by weight

(C-4) manufactured by Mitsubishi Chemical (Co., Ltd.), "# 2300 B", the arithmetic mean particle size: 15nm, specific surface area (NSA): 320m ² / g, DBP absorption amount: 48cm ^3/100 g, volatile content: 2% by weight

(C-5) Wilbur Alice (Ltd.), "Raven 2350 Ultra", the arithmetic mean particle size: 15nm, specific surface area ^{(NSA): 195m 2 / g} , DBP absorption amount: 60cm ³ / 100g

(C-6) manufactured by Mitsubishi Chemical (Co., Ltd.), "# 980", the arithmetic mean particle size: 16nm, specific surface area (NSA): 260m ² / g, DBP absorption amount: 66cm ³ / 100g, volatile content: 1.5%

(C-7) manufactured by Mitsubishi Chemical (Co., Ltd.), "# 960B", the arithmetic mean particle size: 16nm, specific surface area (NSA): 260m ² / g, DBP absorption amount: 64cm ³ / 100g, volatile content: 1.5%

(C-8) manufactured by Mitsubishi Chemical (Co., Ltd.), "# 750B", the arithmetic mean particle size: 22nm, specific surface area (NSA): 124m ² / g, DBP absorption amount: 116cm ^3/100 g, volatile content: 1% by mass

(C-9), Wilbur-Alice (Ltd.), "Raven 5000 Ultra", the arithmetic mean particle diameter: 8nm, a specific surface area (NSA): 583m ² / g, DBP absorption amount: 95cm ^3/100 g, volatile content of 10.5% by mass

 The arithmetic mean particle diameter, specific surface area (NSA), DBP absorption amount, and volatile content of the carbon black are values measured by the method described in the carbon black term.

[(D) Elastomer]

Olefin-based copolymer: "Bond Fast (registered trademark) 7M" (glycidyl methacrylate (GMA) content: 6 mass%) manufactured by Sumitomo Chemical Co.,

[(E) Release agent]

Pentaerythritol stearic acid ester: "UNISTA (registered trademark) H476" manufactured by NIPPON KOGYO CO., LTD.

&Lt; Resin composition &

In each of the examples and comparative examples, each raw material component shown in Table 1 was driven and melted and kneaded in a twin-screw extruder having a cylinder temperature of 320 DEG C to pelletize. The glass fiber and calcium carbonate (all of the fillers) were introduced into an extruder using a side feeder and melted and kneaded. In Table 1, the blending amount of each component is the mass part.

The obtained resin composition was evaluated as follows. The results are shown in Table 2. Further, in Table 2, CB means carbon black.

«Evaluation»

(1) Bending fracture deformation

The pellets of the resin compositions of Examples and Comparative Examples were dried at 140 占 폚 for 3 hours and then subjected to injection molding at a cylinder temperature of 320 占 폚 and a mold temperature of 150 占 폚 to prepare test pieces (10 mm in width and 4 mm in thickness) conforming to ISO 316. Using this test piece, the bending fracture strain (F?) Was measured according to ISO178.

For each of the examples and comparative examples, pellets of a reference resin composition to which no carbon black had been added were prepared, and the bending fracture strain (F?) Was measured by the above-mentioned method. (%) ((A) / (B) Х100) of A with respect to B in the case where the bending fracture strain is A is obtained. Reference resin compositions to which no carbon black is added are shown in Tables 1 and 2 as reference examples. The following evaluation items are also shown in the same reference example.

(2) Tensile strength (TS) and tensile elongation (TE)

The pellets of the resin compositions of Examples and Comparative Examples were dried at 140 占 폚 for 3 hours and then molded into a dumbbell test piece having a thickness of 4 mm according to ISO3167 at a cylinder temperature of 320 占 폚 and a mold temperature of 150 占 폚 by injection molding. The tensile strength (MPa) and tensile elongation (%) were measured according to ISO 527-1,2 using the test specimens.

(3) Bending strength (FS) and flexural modulus (FM)

The pellets of the resin compositions of Examples and Comparative Examples were dried at 140 占 폚 for 3 hours, and then a test piece (10 mm in width and 4 mm in thickness) conforming to ISO 3167 was produced at a molding temperature of 320 占 폚 and a mold temperature of 150 占 폚 by injection molding. The bending strength (MPa) and flexural modulus (FM) of the specimen were measured according to ISO178.

(4) Charpy impact strength

The pellets of the resin compositions of the examples and comparative examples were dried at 140 占 폚 for 3 hours and then subjected to injection molding at a molding cylinder temperature of 320 占 폚 and a mold temperature of 150 占 폚 to prepare test pieces (10 mm in width and 4 mm in thickness) conforming to ISO3167. Using this test piece, the Charpy impact strength (notched) (kJ / m ² ) was measured in accordance with ISO 179/1 eA.

(5) Blackness (L value)

The L value of the dumbbell specimen produced in the same manner as in the tensile test was measured using Spectrophotometer SE6000 manufactured by Nippon Denshoku Industries Co., Ltd. The smaller the L value, the higher the degree of blackness and the better the black color tone.

It can be seen from Table 2 that in Examples 1 to 9, the flexural rupture strain ratio (Fγ ratio (%)) to the bending fracture deformation when the carbon black content is 0 is not less than 96%, and even when carbon black is added, Is suppressed from being lowered. It can also be seen that the tensile strength, the tensile elongation, the bending strength, the bending elastic modulus and the Charpy impact strength are substantially equal to each other as compared with the case where the carbon black content is zero. In addition, it can be seen that all the resin compositions of Examples 1 to 9 exhibit a good black color tone (blackness (L value)).

The disclosure of Japanese Patent Application No. 2015-179254 is incorporated herein by reference in its entirety.

All publications, patent applications, and technical specifications described in this specification are herein incorporated by reference to the same extent as if each individual document, patent application, and technical specification were specifically and individually indicated to be incorporated by reference.

Claims (16)

(A) a polyarylene sulfide resin, and
(B) a filler in an amount of 115 to 300 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A)
(C) carbon black having an arithmetic average particle size of 10 to 15 nm, more preferably 0.2 parts by mass or more based on 100 parts by mass of the polyarylene sulfide resin (A)
Wherein the filler (B) is composed of a combination of glass fiber and calcium carbonate,
Wherein the content of the glass fiber is not less than 69 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A)
Resin composition. The method according to claim 1,
Wherein the polyarylene sulfide resin (A) comprises a polyphenylene sulfide resin. The method according to claim 1,
Wherein the (C) carbon black has an arithmetic mean particle diameter of 13 to 15 nm. The method according to claim 1,
Wherein the content of the carbon black (C) is 0.2 to 6 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin (A). The method according to claim 1,
Wherein the glass fiber content is 50% by mass or more based on the total amount of the filler (B). The method according to claim 1,
And the volatile content of the carbon black (C) is 7 mass% or less. 7. The method according to any one of claims 1 to 6,
(D) an elastomer in an amount of 3 to 35 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A). (A) a polyarylene sulfide resin, (B) a filler (B) in an amount of 115 to 300 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A), and (C) carbon black,
Wherein the filler (B) is composed of a combination of glass fiber and calcium carbonate,
Wherein the content of the glass fiber is 69 parts by mass or more based on 100 parts by mass of the polyarylene sulfide resin (A)
By using carbon black having an arithmetic average particle size of 10 to 15 nm as the carbon black (C) in an amount of not less than 0.2 part by mass based on 100 parts by mass of the polyarylene sulfide resin (A), the lowering of the bending fracture deformation How to suppress. 9. The method of claim 8,
Wherein the polyarylene sulfide resin (A) comprises a polyphenylene sulfide resin. 9. The method of claim 8,
Wherein the (C) carbon black has an arithmetic mean particle diameter of 13 to 15 nm. 9. The method of claim 8,
Wherein the content of the carbon black (C) is 0.2 to 6 parts by mass relative to 100 parts by mass of the polyarylene sulfide resin (A). 12. The method of claim 11,
Wherein the content of the glass fiber is 50 mass% or more with respect to the total amount of the filler (B). 9. The method of claim 8,
And the volatile content of the carbon black (C) is 7 mass% or less. 14. The method according to any one of claims 8 to 13,
Wherein the resin composition further comprises (D) an elastomer in an amount of 3 to 35 parts by mass based on 100 parts by mass of the polyarylene sulfide resin (A). delete delete