KR101875266B1 - Electroconductive polyamide/polyphenylene ether resin composition and molded product for vehicle using the same - Google Patents
Electroconductive polyamide/polyphenylene ether resin composition and molded product for vehicle using the same Download PDFInfo
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- KR101875266B1 KR101875266B1 KR1020160018068A KR20160018068A KR101875266B1 KR 101875266 B1 KR101875266 B1 KR 101875266B1 KR 1020160018068 A KR1020160018068 A KR 1020160018068A KR 20160018068 A KR20160018068 A KR 20160018068A KR 101875266 B1 KR101875266 B1 KR 101875266B1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L71/00—Compositions of polyethers obtained by reactions forming an ether link in the main chain; Compositions of derivatives of such polymers
- C08L71/08—Polyethers derived from hydroxy compounds or from their metallic derivatives
- C08L71/10—Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
- C08L71/12—Polyphenylene oxides
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
- D01F9/12—Carbon filaments; Apparatus specially adapted for the manufacture thereof
Abstract
The conductive polyamide / polyphenylene ether resin composition of the present invention is a polyphenylene ether; Polyamide; Olefinic polymers; Impact modifiers; Compatibilizers; Wherein the polyphenylene ether and the impact modifier form domains, and the polyamide, the olefin-based polymer, and the carbon fibrils form a matrix, the domains having a diameter of from 0.1 to < RTI ID = A surface resistance of a 100 mm x 100 mm x 0.5 mm size specimen including 90 vol% or more of a particle type domain having a size of 2.0 m and measured at 23 deg. C and a relative humidity of 50% is 10 8 ? /? Or less . The conductive polyamide / polyphenylene ether resin composition and the molded article for automobile manufactured therefrom are excellent in mechanical strength, heat resistance, impact resistance and conductivity.
Description
The present invention relates to a conductive polyamide / polyphenylene ether resin composition and an automotive molded article produced therefrom. More specifically, the present invention relates to a polyamide / polyphenylene ether resin composition having excellent mechanical strength, heat resistance, impact resistance and conductivity, and a molded article for an automobile manufactured therefrom.
Plastic materials are widely used in fields requiring various functions and performances such as lightweight, freedom of design, molding processability, and industrial materials such as household goods, automobile, electric, electronic and industrial fields.
Of these, polyphenylene ether has excellent electrical and mechanical properties, has a high heat distortion temperature, can be used in a wide range of engineering plastic materials, and is used as a useful industrial material in the form of a blend with high-impact polystyrene and the like. In recent years, polyamide / polyphenylene ether, a polypropylene / polyphenylene ether such as polypropylene / polyphenylene ether which is added with a compatibilizing agent as a third component, and the like have been produced by using a reaction extrusion technique in which an emulsion blend is commercialized by a chemical method alloy.
Particularly, the polyamide / polyphenylene ether can exhibit a balance of physical properties such as heat resistance, impact resistance and chemical resistance, and can be used as an outer part of a vehicle such as a wheel cap, a junction box, under the hood.
In recent years, there has been a demand for a plastic external component material capable of performing electrostatic painting at the same time as other metallic material parts. Conductive polyamide / polyphenylene ether developed by General Electric Company can be electrostatically coated at the same time as other metal parts and can be used for automobile fender parts, and a separate coating process is not required Thereby reducing the production cost.
In order to impart conductivity to polyamide / polyphenylene ether, a method of adding a conductive filler such as carbon fiber or carbon black has been proposed. However, when carbon fiber is used, there is a fear that moldability and the like are lowered. It is necessary to add a large amount of carbon black in order to achieve conductivity required for electrostatic painting, so that there is a possibility that the impact resistance and the moldability are lowered.
(Carbon fibrils) or conductive carbon black of nano unit size can be used in order to solve problems of reduction in impact resistance and moldability of conductive polyamide / polyphenylene ether. In this case, polyamide / poly The compatibility of the phenylene ether may be lowered.
In order to solve the problem of lowering the compatibility and to produce polyamide / polyphenylene ether of excellent physical properties, the compatibilizing reaction occurring between the polyphenylene ether and the polyamide and the compatibilizer at the time of extrusion processing proceeds smoothly . Conventionally, a method of compatibilizing polyamide and polyphenylene ether and then adding conductive carbon black has been used in order to facilitate the commercialization reaction.
However, this method requires the addition of polyamide / polyphenylene ether, compatibilizer and other additives in a specific order of addition, using a special extrusion processing facility with a plurality of side feeders. This is uneconomical due to a large amount of facility investment, and there is a problem that the productivity is lowered due to the restriction of the order of inputting the raw materials.
Accordingly, in order to solve the above problems, the present invention provides a conductive polyamide / polyphenylene ether which maintains excellent properties originally possessed by polyamide / polyphenylene ether and can be applied to on-line electrostatic painting, Were investigated.
The background art of the present invention is disclosed in European Patent EP 0685527 B1, Japanese Patent JP 2756545 B2 and the like.
It is an object of the present invention to provide a conductive polyamide / polyphenylene ether resin composition which is excellent in mechanical strength, heat resistance, impact resistance and conductivity and applicable to electrostatic painting, and a molded article for an automobile manufactured therefrom.
Another object of the present invention is to provide a conductive polyamide / polyphenylene ether resin composition and a molded article for an automobile manufactured from the conductive polyamide / polyphenylene ether resin composition, which are excellent in productivity and economy, by using a conductive master batch.
The above and other objects of the present invention can be achieved by the present invention described below.
One aspect of the present invention relates to a conductive polyamide / polyphenylene ether resin composition. The conductive polyamide / polyphenylene ether resin composition includes polyphenylene ether; Polyamide; Olefinic polymers; Impact modifiers; Compatibilizers; Wherein the polyphenylene ether and the impact modifier form domains, and the polyamide, the olefin-based polymer, and the carbon fibrils form a matrix, the domains having a diameter of from 0.1 to < RTI ID = A surface resistance of a 100 mm x 100 mm x 0.5 mm size specimen including 90 vol% or more of a particle type domain having a size of 2.0 m and measured at 23 deg. C and a relative humidity of 50% is 10 8 ? /? Or less .
In an embodiment, the conductive polyamide / polyphenylene ether resin composition comprises 100 parts by weight of a base resin containing 10 to 65% by weight of the polyphenylene ether and 35 to 90% by weight of the polyamide, 15 to 15 parts by weight of the impact modifier, 1 to 15 parts by weight of the impact modifier, 0.2 to 10 parts by weight of the compatibilizer and 0.1 to 5 parts by weight of the carbon fibril.
In an embodiment, the polyphenylene ether is selected from the group consisting of poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6- Ether), poly (2-methyl-6-propyl-1, 4-phenylene) ether (2,6-dimethyl-1,4-phenylene) ether, poly (2, 6-dimethyl- Copolymers of poly (2,3,6-trimethyl-1,4-phenylene) ether and poly (2,6-dimethyl-1,4-phenylene) 6-triethyl-1, 4-phenylene) ether.
In an embodiment, the polyamide is selected from the group consisting of polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66, polyamide 6/612, polyamide Polyamide 6 / 6T, polyamide 6 / 6I, polyamide 66 / 6T, polyamide 66 / 6I, polyamide 6 / 6D, polyamide 6 / MXD6, polyamide 6 / MXD6, polyamide 66 / MXD6, polyamide 6T, 6T / 6I, polyamide 66 / 6T / 6I, polyamide 9T, polyamide 9I, polyamide 6 / 9T, polyamide 6 / 9I, polyamide 66 / 9T, polyamide 6/12 / 9T, polyamide 66 / 12 / 9T, polyamide 6/12 / 9I and polyamide 66/12 / 6I.
In an embodiment, the olefin-based polymer is at least one selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene -? - olefin copolymer,?,? -Unsaturated dicarboxylic acid, Modified low-density polyethylene, modified linear low-density polyethylene, modified polypropylene, and modified ethylene-? -Olefin copolymer modified with at least one compound selected from the group consisting of a modified high-density polyethylene and a modified low-density polyethylene.
In an embodiment, the impact modifier is a hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising an aromatic vinyl compound and a conjugated diene compound, a block copolymer comprising an aromatic vinyl compound and a conjugated diene compound, , a modified block copolymer modified with a compound selected from the group consisting of? -unsaturated dicarboxylic acid and?,? -unsaturated dicarboxylic acid derivatives, and a modified block copolymer obtained by modifying the hydrogenated block copolymer with?,? -unsaturated dicarboxylic acid and?,? -Unsaturated dicarboxylic acid derivatives and modified hydrogenated block copolymers modified with a compound selected from the group of unsaturated dicarboxylic acid derivatives.
In an embodiment, the compatibilizer comprises at least one of maleic acid, maleic anhydride, maleic acid hydrazide, dichloromaleic anhydride, unsaturated dicarboxylic acid, fumaric acid, citric acid, citric acid anhydride, malic acid and agaric acid can do.
In an embodiment, the carbon fibrils may have a pH of from 4 to 8.
In an embodiment, the carbon fibrils may include 0.1 to 5% by weight of an aromatic compound having a molecular weight of 120 to 1,000 g / mol.
In an embodiment, the conductive polyamide / polyphenylene ether resin composition may further comprise a part or all of the polyamide and a part or all of the carbon fibril and a part or all of the olefinic polymer and the impact modifier, Kneading to form a conductive master batch, adding the remaining components not contained in the conductive master batch, and melt-kneading.
Another aspect of the present invention relates to an automotive molded article produced from the conductive polyamide / polyphenylene ether resin composition.
The present invention relates to a conductive polyamide / polyphenylene ether resin composition having excellent mechanical strength, heat resistance, impact resistance and conductivity and being applicable to electrostatic painting and having excellent productivity and economy using a conductive master batch at the time of manufacture, And has the effect of providing the manufactured molded article for automobiles.
Hereinafter, the present invention will be described in detail.
The conductive polyamide / polyphenylene ether resin composition according to the present invention comprises (A) a base resin (A) comprising polyphenylene ether and (A-2) polyamide, (B) an olefinic polymer, A morphology composed of a matrix and a domain may be formed as a commercial blend containing a polymer (A), an impact modifier, (D) a compatibilizer, and (E) carbon fibrils.
Here, the matrix refers to a continuous image surrounding a dispersed phase, and the domain refers to a non-continuous phase as opposed to a matrix. The matrix and the domain are also referred to as a continuous phase and a dispersed phase, respectively. In this specification, the matrix and the continuous phase, the domain and the dispersed phase can be used in combination.
Also, in this specification, a compatibilized blend refers to a composition that is physically or chemically compatible with a compatibilizer. Compatibility refers to the degree of commercialization. High compatibility means commercialization, and low compatibility means commercialization is difficult.
(A) Base resin
The base resin according to one embodiment of the present invention may include a polyphenylene ether (A-1) and a polyamide (A-2). In the conductive polyamide / polyphenylene ether resin composition, the polyphenylene ether may form a domain, and the polyamide may form a matrix.
(A-1) Polyphenylene ether
The polyphenylene ether according to one embodiment of the present invention may be a polyphenylene ether polymer, a mixture of a polyphenylene ether polymer and a vinyl aromatic polymer, a modified polyphenylene ether polymer in which a reactive monomer is reacted with a polyphenylene ether polymer, . ≪ / RTI >
In an embodiment, the polyphenylene ether polymer includes poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6- (2-methyl-6-propyl-1, 4-phenylene) ether, ) Ether, poly (2-ethyl-6-propyl-1,4-phenylene) ether, poly (2,6- Copolymers of poly (2, 6-dimethyl-1,4-phenylene) ether and poly (2,3,6-trimethyl- 3,6-triethyl-1,4-phenylene) ether, and combinations thereof, but are not limited thereto. For example, poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6- 4-phenylene) ether and the like can be used. Specifically, poly (2,6-dimethyl-1,4-phenylene) ether can be used.
In an embodiment, the vinyl aromatic polymer may be a polymer obtained by polymerizing a vinyl aromatic monomer including styrene, p-methylstyrene,? -Methylstyrene, 4-n-propylstyrene, or a combination thereof. Do not. For example, a vinyl aromatic polymer obtained by polymerizing a vinyl aromatic monomer containing at least one of styrene and -methylstyrene can be used.
In an embodiment, the reactive monomer is a compound containing an unsaturated carboxylic acid or its anhydride group or the like, or the unsaturated carboxylic acid or its anhydride group reacted with the unsaturated carboxylic acid or its anhydride group. The reactive monomer may be a polyphenylene ether polymer according to one embodiment of the present invention Whereby a modified polyphenylene ether polymer can be formed. Examples of the reactive monomer include, but are not limited to, citric acid, citric anhydride, maleic anhydride, maleic acid, itaconic anhydride, fumaric acid, (meth) acrylic acid, (meth) acrylic acid ester, and combinations thereof.
In the specific examples, the modified polyphenylene ether polymer reacted with the reactive monomer is not particularly limited, but it is prepared by grafting reaction in a melt-kneaded state using a phosphite-based heat stabilizer in consideration of a relatively high working temperature effective.
In an embodiment, the polyphenylene ether may have an intrinsic viscosity of 0.2 to 0.8 dl / g, for example 0.3 to 0.6 dl / g, as measured in chloroform solvent at 25 ° C. Within the above range, the conductive polyamide / polyphenylene ether resin composition may have excellent heat resistance, mechanical strength, processability, and the like.
In an embodiment, the polyphenylene ether may be contained in an amount of 10 to 65 wt%, for example 20 to 60 wt%, of 100 wt% of the base resin. Within the above range, the conductive polyamide / polyphenylene ether resin composition may have excellent mechanical strength, heat resistance, flexibility, chemical resistance, processability, and the like.
(A-2) Polyamide
The polyamide according to one embodiment of the present invention may be a polymer that is polymerized with an amino acid, a lactam, a diamine, and a dicarboxylic acid as a main monomer component. For example, the polyamide may include a polyamide homopolymer or copolymer derived from the main monomer component, either individually or in the form of a mixture.
In an embodiment, examples of the main monomer component include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and paraaminomethylbenzoic acid;慣 -caprolactam, ω-laurolactam; Tetramethylenediamine, hexamethylenediamine, 2-methylpentamethylenediamine, nonamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methyl (Aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3 , 5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2- Propyl) piperazine, aminoethylpiperazine, and other aliphatic, alicyclic, aromatic diamines; 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, 2, 3-dodecanedioic acid, 2-ethylhexylphthalic acid, Naphthalene dicarboxylic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like, and the like can be given as examples of the dicarboxylic acid.
In an embodiment, the polyamide includes polyamide 6, polyamide 66, polyamide 46, polyamide 11, polyamide 12, polyamide 610, polyamide 612, polyamide 6/66, polyamide 6/612, poly Amide MXD6, polyamide 6 / MXD6, polyamide 66 / MXD6, polyamide 6T, polyamide 6I, polyamide 6 / 6T, polyamide 6 / 6I, polyamide 66 / 6T, polyamide 66 / / 6T / 6I, polyamide 66 / 6T / 6I, polyamide 9T, polyamide 9I, polyamide 6 / 9T, polyamide 6 / 9I, polyamide 66 / 9T, polyamide 6/12 / 9T, polyamide 66 / 12 / 9T, polyamide 6/12 / 9I, polyamide 66/12 / 6I, combinations thereof and the like.
In an embodiment, the polyamide may have a melting point of from 220 to 360 ° C, for example from 230 to 320 ° C, specifically from 240 to 300 ° C, and may be prepared by adding 1% by weight of polyamide to m- The relative viscosity may be at least 2 dl / g, for example between 2 and 4 dl / g. Within the above range, the conductive polyamide / polyphenylene ether resin composition may have excellent heat resistance, mechanical strength, compatibility and the like.
In an embodiment, the polyamide may comprise 35 to 90 wt%, for example 40 to 80 wt%, of 100 wt% of the base resin. In the specific examples, the polyphenylene ether may have excellent mechanical strength, heat resistance, compatibility and the like of the conductive polyamide / polyphenylene ether resin composition within the above range.
(B) an olefin-based polymer
The olefin polymer according to one embodiment of the present invention is a copolymer of (co) polymer obtained by polymerization with an olefin monomer, a copolymer of an olefin monomer and an acrylic monomer, a copolymer of the (co) polymer with an?,? - unsaturated dicarboxylic acid, , a? -unsaturated dicarboxylic acid derivative, a modified olefin-based polymer modified with a compound containing at least one reactive group, and combinations thereof.
In an embodiment, the olefinic monomer may be an alkylene having 1 to 19 carbon atoms, but is not limited thereto. For example, ethylene, propylene, isopropylene, butylene, isobutylene or octene may be used, and these may be used alone or in combination.
In an embodiment, (meth) acrylic acid alkyl ester or (meth) acrylic acid may be used as the acrylic monomer. The alkyl (meth) acrylate includes alkyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl And the like. For example, methyl (meth) acrylate and the like can be used.
In an embodiment, the olefin-based polymer includes a reactive group capable of reacting with the polyamide, which is effective in improving the compatibility of the polyphenylene ether and the polyamide, and accordingly, the modification with the compound containing the reactive group An olefin-based polymer or the like may be preferably used. The above-mentioned modified olefin-based polymer is obtained by reacting a compound containing a reactive group such as an?,? -Unsaturated dicarboxylic acid,?,? -Unsaturated dicarboxylic acid derivative or the like in the main chain composed of an olefinic monomer or a copolymer of an olefinic monomer and an acrylic monomer May have a grafted structure. For example, maleic anhydride groups and epoxy groups are effective as the reactive groups. Specifically, examples of the modified olefin-based polymer include a maleic anhydride-modified ethylene-? -Olefin copolymer in which a maleic anhydride group is grafted, a maleic anhydride-modified low-density polyethylene, and the like.
In an embodiment, the olefinic polymer is at least one selected from the group consisting of high density polyethylene, low density polyethylene, linear low density polyethylene, polypropylene, ethylene -? - olefin copolymer and?,? - unsaturated dicarboxylic acid,?, Modified low-density polyethylene, modified linear low-density polyethylene, modified polypropylene, modified ethylene -? - olefin copolymer, combinations thereof, and the like, which are modified with at least one compound selected from the group consisting of dicarboxylic acid derivatives.
In an embodiment, the olefin-based polymer may be included in an amount of 1 to 15 parts by weight, for example, 2.5 to 10 parts by weight, based on 100 parts by weight of the base resin. In the above range, carbon fibrils in the conductive polyamide / polyphenylene ether resin composition can be easily transferred from the domain to the matrix, and the conductivity of the conductive polyamide / polyphenylene ether resin composition can be excellent.
(C) Impact modifier
The impact modifier according to one embodiment of the present invention can improve the impact resistance and the like of the conductive polyamide / polyphenylene ether resin composition, and can be a styrene elastomer or the like.
In an embodiment, the styrene-based elastomer is a block copolymer comprising an aromatic vinyl compound and a conjugated diene compound; A hydrogenated block copolymer obtained by hydrogenating a block copolymer comprising an aromatic vinyl compound and a conjugated diene compound; Modified block copolymer obtained by modifying said block copolymer with a compound selected from the group consisting of?,? -Unsaturated dicarboxylic acid and?,? - unsaturated dicarboxylic acid derivatives, and a modified block copolymer obtained by modifying said hydrogenated block copolymer with?,? A modified hydrogenated block copolymer modified with a compound selected from the group consisting of a carboxylic acid and an?,? - unsaturated dicarboxylic acid derivative, a combination thereof, and the like.
In an embodiment, the aromatic vinyl compound may be styrene, p-methylstyrene,? -Methylstyrene, bromostyrene, chlorostyrene, combinations thereof, and the like. For example, styrene,? -Methylstyrene, a combination of these, and the like can be used.
In an embodiment, the styrenic elastomer is derived from an aromatic vinyl compound, the form of which comprises a diblock (AB block), a triblock (ABA block), a tetrablock (ABAB block) and a pentablock Linear structure as well as a linear structure containing a total of six or more A and B blocks.
In an embodiment, preferred examples of the styrene elastomer include styrene-ethylene-butylene-styrene copolymer, styrene-butadiene-styrene copolymer, styrene-ethylene-propylene-styrene copolymer, styrene- Styrene-ethylene-butadiene-styrene copolymer, and the like, and modified styrene derivatives obtained by modifying the above materials with a compound selected from the group of?,? -Unsaturated dicarboxylic acids and?,? - unsaturated dicarboxylic acid derivatives Butadiene-styrene copolymers, modified styrene-ethylene-propylene-styrene copolymers, modified styrene-isoprene-styrene copolymers, modified styrene-ethylene copolymers, modified styrene-ethylene copolymers, -Butadiene-styrene copolymer, and the like. These may be used alone or in combination of two or more.
In an embodiment, the impact modifier may be included in an amount of 1 to 15 parts by weight, for example, 2.5 to 10 parts by weight, based on 100 parts by weight of the base resin. The impact resistance and the like of the conductive polyamide / polyphenylene ether resin composition in the above range can be excellent.
(D) a compatibilizer
A compatibilizer according to one embodiment of the present invention may be a compound containing two types of functional groups, a compound which is reacted to be modified with a compound containing two types of functional groups, and the like. One of the functional groups may be a carbon-carbon double bond or a carbon-carbon triple bond, and the other may be selected from a functional group of a carboxyl group, an acid anhydride, an epoxy group, an imide group, an amide group, an ester group, .
In embodiments, the compatibilizer may be selected from the group consisting of maleic acid, maleic anhydride, maleic hydrazide, dichloromaleic anhydride, unsaturated dicarboxylic acid, fumaric acid, citric acid, citric acid anhydride, malic acid, Agaric acid, combinations thereof and the like can be used.
In an embodiment, the compatibilizer or the denaturant of the compatibilizer may react with polyphenylene ether and polyamide to produce a polyphenylene ether and a polyamide block copolymer. The block copolymer is distributed on the interface between two components (polyamide and polyphenylene ether) in the polyamide / polyphenylene ether resin composition to stabilize the morphology of the resin composition. Particularly, when the polyphenylene ether forms a morphology in which the polyphenylene ether is a domain (dispersed phase) and the polyamide is a matrix (continuous phase) in a polyamide / polyphenylene ether resin composition, the particle diameter of the domain is about 1 m It seems that the block copolymer plays an important role in the control (Polymer Engineering and Science, 1990, vol. 30, No. 17, pp. 1056-1062).
In an embodiment, the compatibilizer may be included in an amount of 0.2 to 10 parts by weight, for example, 0.3 to 9 parts by weight, based on 100 parts by weight of the base resin. Within this range, the conductive polyamide / polyphenylene ether resin composition may have excellent compatibility and impact resistance.
(E) Carbon fibrils
The carbon fibril according to one embodiment of the present invention is a carbon material in the form of a fiber having a carbon element content of 90 wt% or more. For example, as the carbon fibrils, carbon nanotubes and the like can be used. Since the carbon nanotubes have a large aspect ratio and specific surface area and are excellent in mechanical characteristics, electrical characteristics, and thermal characteristics, they are effective materials for engineering plastic materials. The carbon nanotubes can be classified into a single wall, a double wall, and a multi-wall carbon nanotube according to the number of walls. Zigzag, armchair, chiral, Structure, but it can be variously used without being limited to kinds and structures. Specifically, a multi-walled carbon nanotube or the like can be used.
In an embodiment, the carbon nanotubes may have a diameter of 0.5 to 100 nm, for example 1 to 10 nm, and the length may be 0.01 to 100 탆, for example 0.5 to 10 탆. In the above range, the conductive polyamide / polyphenylene ether resin composition may have excellent conductivity and processability.
The aspect ratio (L / D) of the carbon nanotubes is preferably 100 to 1,000 in terms of improving the conductivity of the polyamide / polyphenylene ether resin composition.
In the specific example, when the conductive polyamide / polyphenylene ether resin composition is prepared, the carbon fibrils may be dispersed in both the domains and the matrix, and the content of the carbon fibrils dispersed in the matrix may be dispersed in the domains May be higher than the content of the carbon fibrils. Thereafter, in the melt-kneading process of the composition components, the carbon fibrils migrate from the domains to the matrix due to the olefinic polymers, and preferably the carbon fibrils present in the domains migrate to the matrix containing the polyamides Can bring about the best effect in improving the conductivity of the conductive polyamide / polyphenylene ether resin composition. If the content of the carbon fibrils dispersed in the domains is larger than the content of the carbon fibrils dispersed in the matrix, the conductivity may be significantly lowered.
In an embodiment, the carbon fibrils may have a pH of from 4 to 8, for example from 4.5 to 7.5. Since common carbon fibrils have a pH value of 9 and because of their high pH, they react with a compatibilizing agent such as maleic anhydride or citric acid anhydride to form a reactant. Therefore, the function of the compatibilizing agent is impaired and the polyphenylene ether and the polyamide It may hinder commercialization. By adjusting the pH of the carbon fibril to the above range, the present invention solves the problem that the compatibility between the polyamide and the polyphenylene ether due to the carbon fibril is poor, and the conductivity can be remarkably improved. The carbon fibrils having a pH of 4 to 8 can be obtained by neutralization or acidification treatment.
In an embodiment, the carbon fibrils may include 0.1 to 5% by weight of an aromatic compound having a molecular weight of 120 to 1,000 g / mol in 100% by weight of carbon fibrils. The aromatic compound may be a by-product produced during the production of carbon fibrils and may improve the conductivity of the resin composition. The content of the aromatic compound can be controlled by controlling post-treatment conditions of the carbon fibril. For example, the content of the aromatic compound can be controlled by adjusting the heat treatment temperature and time of the carbon fibril. Specifically, the aromatic compound may be contained in an amount of 0.1 to 5% by weight based on 100% by weight of the carbon fibrils by heat-treating the carbon fibrils at a temperature of 950 to 1,050 ° C and controlling the heat treatment time. The conductivity of the conductive polyamide / polyphenylene ether resin composition containing the carbon fibrils may be further excellent in the aromatic compound content range.
In an embodiment, the carbon fibrils can be prepared by contacting a carbon-containing gas with a metal catalyst in a reactor under reaction conditions comprising a specific temperature. The temperature range may be 400 to 850 캜, for example 600 to 750 캜. Specifically, it is preferable that the carbon fibrils are continuously produced by adding metal catalyst fine particles to a reactor having a reaction temperature within the above range, and continuously bringing the catalyst into contact with a carbon-containing gas.
In an embodiment, the carbonization-containing gas includes aliphatic hydrocarbons such as ethylene, propylene, propane, and methane; carbon monoxide; Aromatic hydrocarbons such as benzene, naphthalene and toluene; Oxidized hydrocarbons; Etc. may be used.
In an embodiment, the catalyst may be prepared using a non-aqueous solvent and may be selected from iron and Group V elements such as vanadium, Group VI elements such as molybdenum, tungsten, and chromium, Group VII elements such as manganese, Element (cerium and the like). The non-aqueous catalyst has the advantage of good regenerative power and careful pH control and no thermal history of the catalyst. Preferably, a catalyst in the form of fine metal particles adhered to a support such as alumina can be used.
When carbon fibrils are prepared in the same manner as described above, aromatic compounds are produced together as a by-product. Such an aromatic compound is not added separately as one component of the polyamide / polyphenylene ether resin composition but is a substance incidentally generated in the course of producing carbon fibrils. The content of the aromatic compound can be determined by extracting an aromatic compound from carbon fibrils using an organic solvent.
In an embodiment, the carbon fibrils may be included in an amount of 0.1 to 5 parts by weight, for example, 0.5 to 3 parts by weight, based on 100 parts by weight of the base resin. In the above range, the conductive polyamide / polyphenylene ether resin composition may have excellent conductivity and compatibility.
The conductive polyamide / polyphenylene ether resin composition according to one embodiment of the present invention further includes an additive including a flame retardant, a lubricant, a plasticizer, a heat stabilizer, an antioxidant, a light stabilizer, a colorant, an inorganic filler, can do.
In an embodiment, the flame retardant is a combustible material which is a phosphate compound, a phosphite compound, a phosphonate compound, a polysiloxane, a phosphazene compound, a phosphinate, A compound, a melamine compound, a combination thereof, and the like, but the present invention is not limited thereto.
In an embodiment, the lubricant is a material that lubricates a metal surface in contact with the conductive polyamide / polyphenylene ether resin composition during processing, molding, or extrusion to aid flow or movement of the resin composition. .
In a specific example, the plasticizer may be a commonly used material that can increase the flexibility, workability, or extensibility of the conductive polyamide / polyphenylene ether resin composition.
In a specific example, the heat stabilizer may be a commonly used material that can inhibit thermal decomposition of the resin composition when the conductive polyamide / polyphenylene ether resin composition is kneaded or molded at a high temperature.
In the specific examples, the antioxidant is a substance that prevents the resin composition from being degraded to lose its inherent physical properties by inhibiting or blocking the chemical reaction between the conductive polyamide / polyphenylene ether resin composition and oxygen. Examples of the phenol type, phosphite Type, thioether-type, or amine-type antioxidant, but the present invention is not limited thereto.
In a specific example, the light stabilizer is a substance that inhibits or blocks the change of color or loss of mechanical properties of the conductive polyamide / polyphenylene ether resin composition from ultraviolet rays, for example, titanium oxide or the like can be used .
In an embodiment, the colorant may be a pigment or a dye.
In an embodiment, the additive may be included in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the base resin, but is not limited thereto. Within the above range, the intended properties can be improved without deteriorating physical properties such as mechanical properties and appearance characteristics of the conductive polyamide / polyphenylene ether resin composition.
As described above, the conductive polyamide / polyphenylene ether resin composition of the present invention may comprise a domain and a matrix, and the domain may include polyphenylene ether (A-1) and impact modifier (C) And the matrix may include a polyamide (A-2), an olefin-based polymer (B), and the carbon fibrils (E).
In an embodiment, the domain has a particle-shaped domain having a diameter in the range of 0.1 to 2.0 탆, for example 0.3 to 1.0 탆, of 90 vol% or more, for example 93 to 99 vol%, of 100 vol% 96 to 98% by volume. When the diameter of the domain of the particle type is more than 2.0 탆, the resin composition is formed in a state that the polyamide and the polyphenylene ether are not compatibly mixed. The mechanical strength of the conductive polyamide / polyphenylene ether resin composition, The impact resistance and conductivity may be deteriorated. When the thickness is less than 0.1 탆, the flowability and the like of the conductive polyamide / polyphenylene ether resin composition may be deteriorated and the appearance characteristics may be deteriorated in the production of the molded article.
In a specific example, the conductive polyamide / polyphenylene ether resin composition has a surface resistance of 10 8 Ω / □ or less, which is 100 mm × 100 mm × 0.5 mm, measured at 23 ° C. and 50% relative humidity, For example, 10 to 10 7 Ω / □, specifically, 10 2 to 10 5 Ω / □. The conductivity of the conductive polyamide / polyphenylene ether resin composition within the above range can be excellent.
The conductive polyamide / polyphenylene ether resin composition according to one embodiment of the present invention can be produced using a conductive master batch.
In an embodiment, the conductive polyamide / polyphenylene ether resin composition comprises a part or all of the polyamide (A-2) and a part or all of the carbon fibrils (E) and the olefinic polymer (B) (A-1), the polyamide (a), the polyamide (a-1), the polyamide (a-1), the polyamide -2), the remainder of the olefin polymer (B) and / or the impact modifier (C) and the compatibilizer (D)).
In the production of the conductive masterbatch, by adding the olefin-based polymer, the viscosity of the melt during melting and kneading is increased, and the degree of dispersion of the carbon fibrils is increased, so that the electrical characteristics can be improved. In addition, the conductive masterbatch surface may have a smooth, non-rigid, flexible shape, so that when the resulting masterbatch is extruded, the resulting strands are easily cut into pellets and thus productivity can be increased.
The molded article according to the present invention is characterized in that it is produced from the conductive polyamide / polyphenylene ether resin composition. For example, the conductive polyamide / polyphenylene ether resin composition in the form of pellets can be produced into various molded articles (products) by using molding methods such as injection molding, extrusion molding, vacuum molding, and casting molding. Such molding methods are well known to those of ordinary skill in the art to which the present invention pertains. Particularly, the conductive polyamide / polyphenylene ether resin composition is excellent in mechanical strength, heat resistance, impact resistance and conductivity, and can be used as automobile molded parts (parts) for automobile tailgate, automobile fuel door, automobile fender and door panel However, the scope of application is not limited thereto.
Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.
Example
The specifications of each component used in the following Production Examples, Examples and Comparative Examples are as follows.
(a) Basic resin
(a-1) Noryl PPO 646, a poly (2,6-dimethyl-1,4-phenylene) ether product of Sabic Innovative Plastics, was used.
(a-2) STABAMID 24 AE 1, a product of Polyamide 66 of Rhodia, was used.
(b) an olefin-based polymer
(b-1) maleic anhydride-modified ethylene-propylene copolymer was used.
(b-2) Maleic anhydride modified low density polyethylene was used.
(c) Impact reinforcement
Kraton G 1651, a product of Kraton polymers, a styrene-ethylene-butylene-styrene copolymer (SEBS), was used.
(d) a compatibilizer
Maleic anhydride from Sigma-Aldrich was used.
(e) Carbon fibrils
Nanocyl NC 7000, a carbon nanotube product of Nanocyl, was used.
Production Examples 1 to 5: Preparation of Masterbatches
Each component described in the main supply of Table 1 below was dry-mixed according to the constituent components of the following Table 1 and quantitatively introduced continuously into a main feeding port of a twin-screw extruder TEX-40 (manufactured by JSW) The components described in the side feed of Table 1 below were continuously introduced into a side feeding port of a twin-screw extruder in a quantitative manner and melted and kneaded. Here, the content is 100% by weight based on 100% by weight of the sum of the polyamide (a-2), the olefinic polymer (b) or the impact modifier (c), and the content of the carbon fibril (e) . Further, the side feeder means an inlet located near the die of the extruder, and the screw rotation speed of the extruder was 400 rpm. Next, the molten strand discharged from the die of the extruder was cooled in a cooling water bath to obtain a solidified strand, and a pelletized master batch was obtained through a cutter. The conductive masterbatches of Preparation Examples 1 to 4 are the conductive masterbatches within the scope of the present invention, and the conductive masterbatches of Preparation Example 5 are the conductive masterbatches prepared by adding polyamide and carbonfibril. The surface roughness (Ra) and production amount of the strand were evaluated for the prepared master batch, and the results are shown in Table 1 below. The surface roughness of the strand was measured by the evaluation method specified in JIS B-0601 using a shape measuring laser microscope VK-X200 of Keyence. The production amount (production rate) means the highest production rate (speed) that can be stably produced in each production example.
From the results shown in Table 1, it can be seen that the conductive masterbatches of Production Examples 1 to 4 have a relatively smooth and uniform surface of the strand and a high production rate per unit time. Unlike the conductive masterbatch of Preparation Example 5, the extruded strand of the conductive masterbatches of Production Examples 1 to 4 contained an olefin-based polymer or an impact modifier, and thus had a hard and smooth surface. The strand of the conductive masterbatch was stably produced in the cooling water tank without fluctuating relatively easily, and was easy to cut and easy to obtain in the form of pellets because of easy cutting.
On the other hand, it can be seen that the extruded strand of the conductive master batch of Production Example 5 had a hard, rough surface, which was produced by relatively rocking in the water tank, resulting in breakage in the middle, stranding between the strands, It was difficult to cut smoothly into the state, and the production was remarkably decreased.
That is, rather than simply mixing the polyamide and the carbon fibril in the conductive master batch, the productivity of the conductive master batch itself is improved by forming the conductive master batch using the olefin polymer or the impact modifier, which can serve as the elastomer, as one component .
Example 1 to 4 and Comparative Example 1 to 3: Preparation of conductive polyamide / polyphenylene ether resin composition
The components described in the main feed of Table 2 below were dry mixed according to the constituents and contents in the following Table 2 and quantitatively continuously fed into the main feed section of a twin-screw extruder TEX-40 (manufactured by JSW) Was quantitatively continuously introduced into the side feed portion of the twin-screw extruder, followed by melt kneading. In the following Table 2, M / B 1 to M / B 5 mean the conductive master batches prepared in Preparation Examples 1 to 5, respectively, and the content of each component is in parts by weight. The screw rotation speed of the extruder was 400 rpm and the total production rate was 100 kg per hour. Then, a pelletized conductive polyamide / polyphenylene ether resin composition was produced through an extruder. The conductive polyamide / polyphenylene ether resin composition thus prepared had a bending modulus, a heat distortion temperature, a dart drop impact strength, a surface resistance, and a domain having a particle size of 0.1 to 2.0 탆 in particle size domain (dispersed phase) The volume% occupied by the whole domain was measured according to the following physical property measuring method, and the results are shown in Table 2 below.
How to measure property
(1) flexural modulus (unit: GPa)
Each pellet thus prepared was injection-molded into a specimen for bending modulus evaluation at a cylinder temperature of 280 DEG C and a mold temperature of 80 DEG C by using an injection molding machine of SELEX-TX150 (Woojin Cerex Co., Ltd.) , And flexural modulus.
(2) Heat deflection temperature (HDT, unit: ° C)
Each of the pellets thus prepared was injection-molded using a SELEX-TX150 (Woojin Cerex) injection molding machine at a cylinder temperature of 280 DEG C and a mold temperature of 80 DEG C as test specimens for evaluation of heat distortion temperature, The heat distortion temperature was measured under the condition of 0.45 MPa according to 2.
(3) Dart drop impact strength (unit: J)
Each of the pellets was injection-molded using a SELEX-TX150 (Woojin Cerex) injection molding machine under the conditions of a cylinder temperature of 280 占 폚 and a mold temperature of 80 占 폚 with a dart drop impact strength test piece of 100 mm 占 100 mm 占 3 mm (20 each). The injection molded specimens were conditioned for 6 hours at a temperature of 23 DEG C and a relative humidity of 50% and then subjected to a dart drop impact tester Fractovis Plus (CEAST) according to ASTM D3763, The total energy (J) of dart drop impact strength in a 50% environment was measured. Specifically, a head dart having a diameter of 12.7 mm adjusted to a weight of 1 to 10 kg according to the impact strength of each conductive polyamide / polyphenylene ether resin composition was dropped at a height of 1 m from each resin composition specimen, The fracture energy of each resin composition specimen was determined using a measuring device connected to a drop impact tester. The average value of the fracture energy obtained by measuring the measurement 20 times for each resin composition was defined as the dart drop impact strength of each resin composition.
(4) Surface resistance (unit: Ω / □)
Specimens for surface resistance measurements were prepared by thermal compression molding. 6 g of each pellet prepared from the conductive polyamide / polyphenylene ether resin composition of Examples 1 to 4 and Comparative Examples 1 to 3 was applied to a mold having a cavity of 100 mm x 100 mm x 0.5 mm And the mold was placed between a pair of metal plates and inserted into a thermal compression molding machine set at 300 ° C. A pressure of 50 kgf / cm < 2 > was applied to the mold and the metal plate for 3 minutes, then taken out of the thermocompression molding machine and inserted into a cold compression molding machine set at 25 deg. After applying a pressure of 50 kgf / cm 2 to the mold and the metal plate for 2 minutes, a specimen of 100 mm x 100 mm x 0.5 mm was taken out from the mold and the pair of metal plates Respectively. The compression molded specimens were conditioned for 6 hours at a temperature of 23 ° C and a relative humidity of 50%. Next, the surface resistivity of the specimen was measured using a Hiresta-UP MCP-HT450 resistance measurement system equipped with a probe MCP-HTP14 manufactured by Mitsubishi Chemical Analytech, under the conditions of a temperature of 23 DEG C and a relative humidity of 50% Respectively. During the measurement, a voltage of 250 V was maintained for 30 seconds.
(5) Volume average diameter (D v ) of the particle type domain and volume% (Vm% d = 0.1-2 탆 ) of the particle type domain having a diameter in the range of 0.1 to 2.0 탆
Ultra thin film specimens having a thickness of 1 占 퐉 were prepared using the conductive polyamide / polyphenylene ether resin compositions of Examples 1 to 4 and Comparative Examples 1 to 3, and then photographed at a transmission electron microscope (magnification: 4,000 times) The particle diameters of the domains were measured. The average of the major axis and minor axis of the particle type domain was assumed to be the diameter of the domain, and the diameter of at least 500 particle type domains was measured. Specifically, the volume average diameter of the domain particles of the particle type domain was calculated according to the following formula 1, and the volume percentage of the domain particles having a diameter in the range of 0.1 to 2.0 탆 in the domain particles was calculated by the following equation Respectively.
[Equation 1]
[Formula 2]
From the above results, it can be seen that the conductive polyamide / polyphenylene ether resin composition of the present invention (Examples 1 to 4) has excellent mechanical strength, heat resistance, impact resistance and conductivity.
On the other hand, in the case of Comparative Examples 1 and 2 using the conductive masterbatch (Preparation Example 5) prepared by adding only polyamide and carbon fibril in the production of the conductive polyamide / polyphenylene ether resin composition, It can be seen that it is inferior.
In addition, in Comparative Example 3 in which the conductive polyamide / polyphenylene ether resin composition was prepared without using the conductive master batch, all of the physical properties such as mechanical strength, heat resistance, impact resistance and conductivity were deteriorated.
The conductive polyamide / polyphenylene ether resin composition according to Comparative Examples 1 to 3 had a domain particle size significantly larger than that of the domain according to the examples, and the domain particles having a diameter in the range of 0.1 to 2.0 m in the domain particles were all Lt; RTI ID = 0.0 > 80% < / RTI >
That is, when a polyamide / polyphenylene ether resin composition is prepared using a conductive master batch prepared by adding an olefin-based polymer or an impact modifier, the particle size of the domain can be controlled to be small, It was found that a polyamide / polyphenylene ether resin composition could be realized.
It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (11)
1 to 15 parts by weight of an olefin-based polymer;
1 to 15 parts by weight of an impact modifier;
0.2 to 10 parts by weight of a compatibilizing agent; And
0.1 to 5 parts by weight of carbon fibrils, wherein the conductive polyamide /
The olefin-based polymer is a maleic anhydride-modified ethylene-propylene copolymer or a maleic anhydride-modified low-density polyethylene,
Wherein the polyphenylene ether and the impact modifier form domains, and the polyamide, the olefin-based polymer, and the carbon fibrils form a matrix,
Said domain comprising at least 90% by volume of a domain in particle form having a diameter of from 0.1 to 2.0 [mu] m,
The surface resistance of a 100 mm × 100 mm × 0.5 mm specimen measured at 23 ° C. and a relative humidity of 50% is 10 8 Ω / □ or less,
The conductive polyamide / polyphenylene ether resin composition may be prepared by melt-kneading at least a part or all of the polyamide and a part or all of the carbon fibrils, at least one or more of the olefinic polymer and the impact modifier, Wherein the conductive masterbatch is formed by forming the conductive masterbatch, adding the remaining components not contained in the conductive masterbatch, and melt-kneading the mixture.
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| EP16164150.1A EP3078712A1 (en) | 2015-04-10 | 2016-04-07 | Electrically conductive polyamide/polyphenylene ether resin composition and molded article for vehicle using the same |
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| KR102221621B1 (en) * | 2018-07-31 | 2021-02-26 | 롯데첨단소재(주) | Polymaide/polyphenylene ether resin composition and molded article using the same |
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| JP2002544308A (en) * | 1999-05-07 | 2002-12-24 | ゼネラル・エレクトリック・カンパニイ | Conductive composition whose volume resistivity is controlled by its composition |
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| JP2011162752A (en) * | 2010-02-15 | 2011-08-25 | Asahi Kasei Chemicals Corp | Electrically conductive masterbatch and manufacturing method therefor, and electrically conductive resin composition and molded product thereof obtained using the electrically conductive masterbatch |
| KR20130113118A (en) * | 2012-04-05 | 2013-10-15 | 한국화학연구원 | A composition of electrically conductive resin |
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| JP2002544308A (en) * | 1999-05-07 | 2002-12-24 | ゼネラル・エレクトリック・カンパニイ | Conductive composition whose volume resistivity is controlled by its composition |
| JP2009074043A (en) * | 2007-03-29 | 2009-04-09 | Asahi Kasei Chemicals Corp | Long fiber filler reinforced resin pellet |
| KR20110048376A (en) * | 2009-11-02 | 2011-05-11 | 제일모직주식회사 | Polyphenyleneether resin composition and molded product using the same |
| JP2011162752A (en) * | 2010-02-15 | 2011-08-25 | Asahi Kasei Chemicals Corp | Electrically conductive masterbatch and manufacturing method therefor, and electrically conductive resin composition and molded product thereof obtained using the electrically conductive masterbatch |
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