JP2004002898A - Electroconductive master pellet and its composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin composition with excellent electroconductivity, and a balance between fluidity and impact resistance, and a process for its manufacture. <P>SOLUTION: The electroconductive resin composition is prepared using a twin-screw extruder equipped with one feed opening at an upper stream side and at least one feed opening at a down stream side, supplying a polyamide from the feed opening at the upper stream side and supplying a carbon filler for electroconduction from the feed opening at the down stream side to melt and mix them to give polyamide master pellets, and supplying polyphenylene ether, a compatibilized and a cushioning improving material to melt and mix them, followed by supplying the polyamide and the polyamide master pellets to the feed opening at the down stream and further melt and kneading them. <P>COPYRIGHT: (C)2004,JPO

Description

(4) The present invention relates to a resin composition having an excellent balance between conductivity, fluidity and impact resistance, and a method for producing the same. The composition of the present invention can be applied to a wide range of fields such as electric / electronic parts, OA parts, automobile parts, and mechanical parts, and can be suitably used especially for automobile exterior parts which can be electrostatically coated.

Polyphenylene ether-based resins are used in a wide range because of their excellent mechanical properties, electrical properties and heat resistance, and because of their excellent dimensional stability. For this reason, Patent Document 1 proposes a technique of blending a polyamide resin. Since then, various improvements have been made, and the material is now used for a wide variety of applications.
With the recent rise in environmental consciousness, studies are being made to use resin as a material for vehicle outer panels in order to improve fuel efficiency of vehicles.
Particularly in Europe, there is a growing need for a material that can be electrostatically coated on the same coating line as a steel plate, and a material having conductivity is required.
Thus, the need for conductive materials having impact resistance, such as automobile parts that require electrostatic coating and IC tray materials, has been greatly increased.
In order to impart conductivity to a polymer alloy of polyphenylene ether and polyamide, for example, Patent Document 2 discloses a technique relating to a mixture of polyphenylene ether, polyamide, and carbon black.
However, according to the technique disclosed in Patent Document 2, impact resistance and fluidity are significantly deteriorated.
As described above, at present, it is impossible to obtain a material having an excellent balance between conductivity, fluidity and impact resistance by the conventional technology.
JP-B-45-997 JP-A-2-201811

The present invention is to solve the above-mentioned problems that cannot be solved by the conventional technology. That is, an object of the present invention is to provide a resin composition having improved conductivity, fluidity and impact resistance, and a method for producing the same.

The present inventor has repeatedly studied to solve the above problem, and surprisingly, supplied polyamide from the upstream supply port, supplied the conductive carbon-based filler from the downstream supply port, and melt-kneaded. The present inventors have found that a conductive resin composition produced using a polyamide master pellet characterized by the fact that the present invention provides a resin composition having an excellent balance between conductivity, fluidity and impact resistance.
That is, the present invention uses a twin-screw extruder provided with one supply port on the upstream side and at least one supply port on the downstream side, supplies polyamide from the upstream supply port, and supplies the conductive carbon-based filler from the downstream supply port. And melt kneading the polyamide master pellets.
Further, the present invention uses a twin-screw extruder having one supply port on the upstream side and at least one supply port on the downstream side, and supplies polyphenylene ether and a compatibilizer from the upstream supply port, and after melt-kneading, The present invention also relates to a conductive resin composition characterized in that polyamide and the polyamide master pellet are supplied from a downstream supply port and further melt-kneaded.
Furthermore, the present invention relates to a method for producing the above-mentioned master pellet and the conductive resin composition.

樹脂 The resin composition of the present invention is a resin composition having an excellent balance between conductivity, fluidity and impact resistance.

Hereinafter, the present invention will be described in detail.
As the kind of polyamide that can be used in the present invention, any polyamide having an amide bond {—NH—C (＝ O) —} in the polymer main chain can be used.
In general, polyamide is obtained by ring-opening polymerization of lactams, polycondensation of diamine and dicarboxylic acid, polycondensation of aminocarboxylic acid, and the like, but is not limited thereto.
The diamines are roughly classified into aliphatic, alicyclic, and aromatic diamines. Specific examples thereof include tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, tridecamethylene diamine, and 2,2. , 4-trimethylhexamethylenediamine, 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, 1,3-bisaminomethylcyclohexane, 1,4-bisaminomethylcyclohexane, m-phenylenediamine, p -Phenylenediamine, m-xylylenediamine, p-xylylenediamine.

The dicarboxylic acids are roughly classified into aliphatic, alicyclic, and aromatic dicarboxylic acids. Specific examples thereof include adipic acid, suberic acid, azelaic acid, sebacic acid, dodecandioic acid, and 1,1,3-tridecane. Examples thereof include diacid, 1,3-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, and dimer acid.
Specific examples of lactams include ε-caprolactam, enantholactam, ω-laurolactam and the like.
Examples of the aminocarboxylic acid include ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, and 13-aminotricarboxylic acid. Decanoic acid and the like.
In the present invention, any of these lactams, diamines, dicarboxylic acids, and aminocarboxylic acids may be used alone or in the form of a mixture of two or more copolymerized polyamides.
Also, those obtained by polymerizing these lactams, diamines, dicarboxylic acids, and aminocarboxylic acids to a low molecular weight oligomer stage in a polymerization reactor and increasing the molecular weight by an extruder or the like can be suitably used.

In particular, polyamides useful in the present invention include polyamide 6, polyamide 6,6, polyamide 4,6, polyamide 11, polyamide 12, polyamide 6,10, polyamide 6,12, and polyamide 6 / 6,6. Polyamide 6 / 6,12, polyamide MXD, 6 (MXD: m-xylylenediamine), polyamide 6 / MXD, 6, polyamide 6,6 / MXD, 6, polyamide 6, T, polyamide 6, I, polyamide 6 / 6, T, polyamide 6/6, I, polyamide 6,6 / 6, T, polyamide 6,6 / 6, I, polyamide 6/6, T / 6, I, polyamide 6,6 / 6, T / 6 , I, polyamide 6/12/6, T, polyamide 6, 6/12/6, T, polyamide 6/12/6, I, polyamide 6, 6/12/6, I and the like. Polyamides obtained by copolymerizing the number of the polyamide in the extruder or the like may be used.
These may of course be used in combination of two or more.
The preferred number average molecular weight of the polyamide used in the present invention is from 5,000 to 100,000, more preferably from 10,000 to 30,000.

The polyamide in the present invention may be a mixture of a plurality of polyamides having different molecular weights. For example, a mixture of a low molecular weight polyamide having a number average molecular weight of 10,000 or less and a high molecular weight polyamide having a number average molecular weight of 10,000 or less, and a mixture of a low molecular weight polyamide having a number average molecular weight of 10,000 or less and a general polyamide having a number of about 15,000. Examples include mixtures, but are not limited thereto.
Also, different kinds of polyamides having different molecular weights may be mixed.
The end groups of the polyamide participate in the reaction with the polyphenylene ether. Polyamide generally has an amino group and a carboxyl group as a terminal group. Generally, in a polyamide / polyphenylene ether-based alloy, when the carboxyl group concentration exceeds the amino group concentration, the impact resistance is reduced and the fluidity is reduced. When the amino group concentration exceeds the carboxyl group concentration, the impact resistance is improved and the fluidity is reduced.
These preferred ratios are 9/1 to 1/9, more preferably 8/2 to 1/9, and still more preferably 6/4 to 1/9, in terms of amino group / carboxyl group ratio.

The concentration of the terminal amino group is preferably at least 10 meq / kg. It is more preferably at least 30 meq / kg.
A method for adjusting the terminal groups of these polyamides may be a known method as will be apparent to those skilled in the art. For example, addition of a diamine or a dicarboxylic acid or addition of a monocarboxylic acid at the time of polymerization of a polyamide may be mentioned.
Of course, the polyamide in the present invention may be a mixture of a plurality of polyamides having different terminal group concentrations.
Further, known additives which may be added to the polyamide may be added in an amount of less than 10 parts by weight based on 100 parts by weight of the polyamide.
The polyphenylene ether that can be used in the present invention is a homopolymer and / or a copolymer composed of structural units represented by the following formulas.

〔Ｒ₁ 〜Ｒ₄ は、それぞれ独立して、水素、ハロゲン、第一級もしくは第二級の低級アルキル、フェニル、ハロアルキル、アミノアルキル、炭化水素オキシ、又はハロ炭化水素オキシ（但し、少なくとも２個の炭素原子がハロゲン原子と酸素原子を隔てている）を表す。〕

[R _{1 to} R ₄ are each independently hydrogen, halogen, primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl, hydrocarbonoxy, or halohydrocarbonoxy (however, at least two A carbon atom separates a halogen atom and an oxygen atom). ]

Specific examples of the polyphenylene ether of the present invention include, for example, poly (2,6-dimethyl-1,4-phenylene ether), poly (2-methyl-6-ethyl-1,4-phenylene ether), (2-methyl-6-phenyl-1,4-phenylene ether), poly (2,6-dichloro-1,4-phenylene ether) and the like. Further, 2,6-dimethylphenol and other phenols ( For example, a polyphenylene ether copolymer such as a copolymer with 2,3,6-trimethylphenol or 2-methyl-6-butylphenol) may also be used. Among them, poly (2,6-dimethyl-1,4-phenylene ether) and a copolymer of 2,6-dimethylphenol and 2,3,6-trimethylphenol are preferable, and poly (2,6-dimethyl-1) is more preferable. , 4-phenylene ether) are preferred.
The method for producing the polyphenylene ether used in the present invention is not particularly limited as long as it can be obtained by a known method.For example, as described in U.S. Pat. The complex can be easily produced by oxidative polymerization of 2,6-dimethylphenol using the complex as a catalyst. In addition, U.S. Pat. Nos. 3,306,875, 3,257,357 and 3,257,358, It can be easily produced by the methods described in JP-B-52-17880, JP-A-50-51197, and JP-A-63-152628.

The reduced viscosity (0.5 g / dl, chloroform solution, measured at 30 ° C.) of the polyphenylene ether that can be used in the present invention is preferably in the range of 0.15 to 0.70 dl / g, more preferably 0 to 0.70 dl / g. The range is from 0.20 to 0.60 dl / g, more preferably from 0.40 to 0.55 dl / g.
These can be used without any problem even if two or more kinds of polyphenylene ethers having different reduced viscosities are blended. For example, a mixture of a polyphenylene ether having a reduced viscosity of 0.45 dl / g or less and a polyphenylene ether having a reduced viscosity of 0.50 dl / g or more, a low molecular weight polyphenylene ether having a reduced viscosity of 0.40 dl / g or less, and a reduced viscosity of 0.50 dl / g or more But of course, the invention is not limited thereto.
In the polyphenylene ether used in the present invention, the organic solvent derived from the polymerization solvent may remain in an amount of less than 5% by weight based on 100 parts by weight of the polyphenylene ether. It is difficult to completely remove the organic solvent resulting from the polymerization solvent in the drying step after the polymerization, and usually the organic solvent remains in the range of several hundred ppm to several%. Examples of the organic solvent caused by the polymerization solvent include at least one of toluene, xylene isomers, ethylbenzene, C1-5 alcohols, chloroform, dichloromethane, chlorobenzene, and dichlorobenzene.

Further, the polyphenylene ether that can be used in the present invention may contain a modified polyphenylene ether.
The modified polyphenylene ether as used herein means at least one carbon-carbon double bond or triple bond in the molecular structure and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group. Or a polyphenylene ether modified with at least one modifying compound having a glycidyl group.
The method for producing the modified polyphenylene ether includes: (1) a modified compound without melting the polyphenylene ether at a temperature in the range of 100 ° C. or more and less than the glass transition temperature of the polyphenylene ether in the presence or absence of a radical initiator; (2) a method of melt-kneading and reacting with a modified compound at a temperature in the range of the glass transition temperature of polyphenylene ether to 360 ° C. or less in the presence or absence of a radical initiator, and (3) a radical initiator. A method in which a polyphenylene ether and a modified compound are reacted in a solution at a temperature lower than the glass transition temperature of the polyphenylene ether in the presence or absence of the polyphenylene ether, and any of these methods may be used. Method 2) is preferred.

Next, at least one modified compound having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in the molecular structure. Is specifically described.
Examples of the modified compound having a carbon-carbon double bond, a carboxylic acid group, and an acid anhydride group in the molecule include maleic acid, fumaric acid, chloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, and these. Acid anhydrides and the like. Particularly, fumaric acid, maleic acid and maleic anhydride are preferable, and fumaric acid and maleic anhydride are particularly preferable.
Further, those in which one or two of the carboxyl groups of these unsaturated dicarboxylic acids are converted into esters, and those in which the ester is decomposed at the processing temperature to change into carboxyl groups can be used.
Examples of the modified compound having a carbon-carbon double bond and a glycidyl group in a molecule include allyl glycidyl ether, glycidyl acrylate, glycidyl methacrylate, and epoxidized natural fats and oils.
Of these, glycidyl acrylate and glycidyl methacrylate are particularly preferred.

Examples of the modified compound having a carbon-carbon double bond and a hydroxyl group in the molecule at the same time include the general formula C _n H _2n-3 OH such as allyl alcohol, 4-penten-1-ol and 1,4-pentadien-3-ol. (n is a positive integer) of unsaturated alcohols of the general formula _{C n H 2n-5 OH,} ( n is a positive integer) C _n H _2n-7 OH include unsaturated alcohols such as.
The above-mentioned modifying compounds may be used alone or in combination of two or more.
The amount of the modified compound to be added when producing the modified polyphenylene ether is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, per 100 parts by weight of the polyphenylene ether.
The preferred amount of the radical initiator when producing the polyphenylene ether modified with the radical initiator is 0.001 to 1 part by weight based on 100 parts by weight of the polyphenylene ether.

Further, the addition rate of the modified compound in the modified polyphenylene ether is preferably 0.01 to 5% by weight. More preferably, it is 0.1 to 3% by weight.
In the modified polyphenylene ether, an unreacted modified compound and / or a polymer of the modified compound may remain. The amount of the unreacted modified compound and / or the polymer of the modified compound remaining in the modified polyphenylene ether is preferably less than 1% by weight, particularly preferably less than 0.5% by weight.
In order to reduce the amount of the modified compound and / or the polymer of the modified compound remaining in the modified polyphenylene ether, when producing the modified polyphenylene ether, an amide bond and / or A compound having an amino group may be added.

The compound having an amide bond here is a compound having an amide bond {-NH-C (= O)-} structure in a molecular structure, and a compound having an amino group is a compound having an {-NH ₂ } structure at a terminal. Is a compound having Specific examples of these compounds include aliphatic amines such as octylamine, nonylamine, tetramethylenediamine, hexamethylenediamine, aniline, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, and p-xylylenediamine. And the like, but not limited thereto, aromatic amines such as amides, reaction products of the above amines with carboxylic acids and dicarboxylic acids, lactams such as ε-caprolactam, and polyamide resins.
The preferable addition amount of the compound having an amide bond or an amino group is 0.001 to 5 parts by weight based on 100 parts by weight of the polyphenylene ether. Preferably it is 0.01 to 1 part by weight, more preferably 0.01 to 0.1 part by weight.

In the present invention, the styrene-based thermoplastic resin may be blended in an amount of less than 5 parts by weight based on 100 parts by weight of the total of polyamide and polyphenylene ether.
The styrene-based thermoplastic resin referred to in the present invention includes polystyrene (including syndiotactic polystyrene), high impact polystyrene (HIPS), styrene-acrylonitrile copolymer (AS resin), and styrene-rubber polymer-acrylonitrile copolymer. Coalescence (ABS resin) and the like.
Further, known additives which may be added to the polyphenylene ether may be added in an amount of less than 10 parts by weight based on 100 parts by weight of the polyphenylene ether.
Impact modifiers that can be used in the present invention are natural and synthetic polymeric substances that are elastic at room temperature (23 ° C.).

Specific examples thereof include natural rubber, conjugated diene compound polymer, aromatic vinyl compound-conjugated diene compound copolymer, hydrogenated aromatic vinyl compound-conjugated diene compound copolymer, polyolefin, polyester elastomer, and polyurethane. Elastomers, polyamide elastomers, and acrylate-based core-shell copolymers.
Among these, aromatic vinyl compound-conjugated diene compound copolymer, hydrogenated aromatic vinyl compound-conjugated diene compound copolymer, and polyolefin are preferable, and aromatic vinyl compound-conjugated diene compound block copolymer, One or more selected from a hydrogenated aromatic vinyl compound-conjugated diene compound block copolymer and an ethylene-α-olefin copolymer are most preferred.
The aromatic vinyl compound-conjugated diene compound block copolymer referred to herein is composed of a polymer block segment (A) mainly composed of an aromatic vinyl compound and a polymer block segment (B) mainly composed of a conjugated diene compound. Block copolymers in which each block is at least one member selected from the group consisting of AB type, ABA type and ABAB type, more preferably ABA type, ABAB Type.

The weight ratio of the aromatic vinyl compound to the conjugated diene compound in the block copolymer is desirably 10/90 to 90/10. More preferably, it is 15/85 to 80/20. More preferably, it is 15/85 to 65/35, and most preferably, it is 20/80 to 45/55.
Further, two or more of these compounds having different weight ratios of the aromatic vinyl compound and the conjugated diene compound may be blended.
Specific examples of the aromatic vinyl compound include styrene, α-methylstyrene, vinyltoluene, and the like. One or more compounds selected from these are used, and styrene is particularly preferred.
Specific examples of the conjugated diene compound include butadiene, isoprene, piperylene, 1,3-pentadiene and the like, and one or more compounds selected from these are used. Among them, butadiene, isoprene and a combination thereof are preferable. .
The microstructure of the conjugated diene compound block portion of the block copolymer is preferably such that the 1,2-vinyl content or the total amount of the 1,2-vinyl content and the 3,4-vinyl content is from 5 to 80%, more preferably from 10 to 50%. %, Most preferably 15 to 40%.

In addition, the hydrogenated product of the aromatic vinyl compound and the conjugated diene compound block copolymer is obtained by subjecting the above-described aromatic vinyl compound and the conjugated diene compound block copolymer to a hydrogenation treatment, thereby mainly forming the diene compound. In which the number of aliphatic double bonds in the polymer block segment is controlled in the range of more than 0 to 100%. The hydrogenation rate of the hydrogenated product of the block copolymer is preferably 50% or more, more preferably 80% or more, and most preferably 98% or more.
In addition, the molecular weight of the block copolymer of the aromatic vinyl compound and the conjugated diene compound and the hydrogenated product thereof in the present invention is measured with a GPC apparatus [SYSTEM21] manufactured by Showa Denko using chloroform as a solvent at 40 ° C. using a polystyrene standard. The number average molecular weight (Mn) is preferably 10,000 to 500,000, and most preferably 40,000 to 250,000.
These aromatic vinyl compound-conjugated diene compound block copolymers have different bonding types, different molecular weights, different aromatic vinyl compound types, different conjugated diene compound types, 1,2-vinyl content. Alternatively, two or more of those having different 1,2-vinyl contents and 3,4-vinyl contents, different aromatic vinyl compound component contents, different hydrogenation rates, and the like may be used.

The ethylene-α-olefin copolymer that can be used in the present invention is a copolymer of ethylene and one or more α-olefins having 3 to 20 carbon atoms. It is more preferably a copolymer with one or more α-olefins having 3 to 16 carbon atoms, and most preferably a copolymer with one or more α-olefins having 3 to 12 carbon atoms.
Examples of the α-olefin that can be copolymerized with the ethylene unit include propylene, butene-1, pentene-1, 4-methylpentene-1, hexene-1, heptene-1, octene-1, nonene-1, decene-1, undecene and the like. -1, dodecene-1, tridecene-1, tetradecene-1, pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1, or eicosene-1, isobutylene.
The preferred ethylene unit content of the ethylene-α-olefin copolymer in the present invention is 30 to 95% by weight based on the total amount of the ethylene-α-olefin copolymer.

Further, the ethylene-α-olefin copolymer in the present invention is more preferably an ethylene-α-olefin copolymer produced using a single-site catalyst. Ethylene-α-olefin copolymers produced using single-site catalysts are commercially available and known. For example, Japanese Patent Publication No. Hei 4-12283, Japanese Patent Application Laid-Open No. Sho 60-35006, Japanese Patent Application Laid-Open No. Sho 60-35007, Japanese Patent Application Laid-Open No. Sho 60-35008, Japanese Patent Application Laid-Open No. Hei 5-155930, Japanese Patent Laid-Open No. Hei 3-1630088 And U.S. Pat. No. 5,272,236.
The single-site catalyst is a catalyst having uniform active site properties such as a metallocene catalyst containing 1 to 3 molecules of cyclopentadienyl or substituted cyclopentadienyl and a catalyst controlled by geometric control. The α-olefin copolymer can be polymerized by a gas phase method or a solution method described in the above publication. A preferred polymerization method is a solution method.

The molecular weight of the ethylene-α-olefin copolymer in the present invention is determined by the number average molecular weight (Mn) measured with a Waters 150c-GPC apparatus using 1,2,4-trichlorobenzene as a solvent at 140 ° C. and a polystyrene standard. Is preferably 10,000 or more, more preferably 10,000 to 100,000. More preferably, it is 20,000 to 60,000.
Further, the molecular weight distribution (weight average molecular weight / number average molecular weight: Mw / Mn) of the ethylene-α-olefin copolymer in the present invention determined by the above-described GPC is preferably 3 or less, more preferably 1.8. -2.7 is more preferable.
Further, the impact improving material that can be used in the present invention may be an impact improving material in which all or a part thereof is modified.
The modified impact modifier referred to herein has at least one carbon-carbon double bond or triple bond in the molecular structure, and has at least one carboxylic acid group, acid anhydride group, amino group, Refers to an impact modifier modified with at least one modifying compound having a hydroxyl group or a glycidyl group.

The method for producing the modified impact modifier is as follows: (1) In the presence or absence of a radical initiator, melt-knead with the modifying compound at a temperature in the range of the softening point temperature of the impact modifier to 250 ° C. or less to cause a reaction. A method, (2) a method in which an impact modifier and a modifying compound are reacted in a solution at a temperature equal to or lower than the softening point of the impact modifier in the presence or absence of a radical initiator, and (3) in the presence of a radical initiator. A method in which the impact modifier is reacted with the modifying compound at a temperature equal to or lower than the softening point of the impact modifier in the absence of the impact modifier without melting, and any of these methods may be used. More preferably, among (1), the method performed in the presence of a radical initiator is most preferable.
At least one having at least one carbon-carbon double bond or triple bond in the molecular structure and having at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group. The kind of the modifying compound is the same as the modifying compound described for the modified polyphenylene ether.

Further, in the impact improving material of the present invention, an oil containing paraffin as a main component may be used in advance.
In this case, the preferred amount of oil containing paraffin as a main component is 70 parts by weight or less based on 100 parts by weight of the impact modifier.
The oil containing paraffin as a main component here is an aromatic ring-containing compound, a naphthene ring-containing compound, and a mixture of hydrocarbon compounds having a weight average molecular weight in the range of 500 to 10,000 in which the three of the paraffin compounds are combined. And the content of the paraffinic compound is 50% by weight or more.
More preferably, the paraffinic compound is 50 to 90% by weight, the naphthene ring-containing compound is 10 to 40% by weight, and the aromatic ring-containing compound is 5% by weight or less.
These oils containing paraffin as a main component are commercially available, and include, for example, PW380 manufactured by Idemitsu Kosan Co., Ltd.
As a method for mixing the above oil with the aromatic impact modifier, a method of adding a desired amount of paraffin-based oil to the pellet-like or powder-like impact modifier so as to be uniform and leaving it to stand, a method of mixing the desired amount from the middle of the extruder, And melt kneading by adding paraffin-based oil of the formula (1), but not limited thereto.

Next, the conductive filler used in the present invention will be described. The conductive filler referred to in the present invention includes all fillers added for imparting conductive performance to a resin, and includes granular, flake-like and fibrous fillers.
As specific examples, conductive carbon black, nanotube carbon, carbon fiber, graphite and the like can be preferably used, and among these, conductive carbon black is most preferable.
The conductive carbon black referred to in the present invention is a carbon black having a DBP absorption of 250 ml / 100 g or more, more preferably a DBP oil absorption of 300 ml / 100 g or more, and still more preferably 350 ml / 100 g or more.
The DBP oil absorption here is a value measured by a method specified in ASTM D2414.
Further, the conductive carbon black of the present invention preferably has a BET surface area of 200 m ² / g or more, more preferably 400 m ² / g or more.

Commercially available conductive carbon blacks include Ketjen Black EC-600JD [DBP absorption = 495 ml / 100 g, BET surface area = 1270 m ² / g] and Ketjen Black EC [DBP] manufactured by Ketjen Black International. Absorption amount = 360 ml / 100 g, BET surface area = 800 m ² / g].
The nanotube carbon that can be used in the present invention is a hollow carbon-based fiber having a fiber diameter of 1 μm or less, and includes a coil-shaped form in which a helix makes a round at a pitch of 1 μm or less.
The carbon fibers usable in the present invention include polyacrylonitrile (PAN) or fibers obtained by firing and carbonizing fibers made from pitch or the like at 1000 ° C. to 3500 ° C. in an inert atmosphere. Are all included. A preferred fiber diameter is 3 to 30 μm, more preferably 5 to 20 μm.
The graphite that can be used in the present invention includes not only those obtained by heating anthracite, pitch and the like at a high temperature in an arc furnace, but also graphite that is naturally produced. The preferred weight average particle diameter is 0.1 to 50 μm, more preferably 1 to 30 μm.
These conductive carbon-based fillers may of course use known various coupling agents and / or sizing agents to improve the adhesion to the resin and the handleability.

In the present invention, the amount of the conductive carbon filler is 0 to 100 parts by weight of a mixture mainly composed of 40 to 90 parts by weight of a polyamide, 5 to 50 parts by weight of a polyphenylene ether, and 5 to 30 parts by weight of an impact modifier. It is preferred that the content be in the range of 0.5 to 5 parts by weight.
In the present invention, a compatibilizer may be used during the production of the composition.
The main purpose of using the compatibilizer is to improve the physical properties of the polyamide-polyphenylene ether mixture. The compatibilizer that can be used in the present invention refers to a polyfunctional compound that interacts with polyphenylene ether, polyamide, or both. This interaction may be chemical (eg, grafting) or physical (eg, a change in the surface properties of the dispersed phase). In any case, the resulting polyamide-polyphenylene ether mixture shows improved compatibility.
Examples of various compatibilizers that can be used in the practice of the present invention include, as described below, liquid diene polymers, functional group-containing polymers, epoxy compounds, oxidized polyolefin waxes, quinones, organosilane compounds, and , Polyfunctional compounds.

Liquid diene polymers suitable for use in the present invention include homopolymers of conjugated dienes, as well as conjugated dienes and other conjugated dienes, vinyl monomers (eg, styrene and α-methylstyrene), olefins (eg, ethylene, propylene, Copolymers with at least one monomer selected from the group consisting of butene-1, isobutylene, hexene-1, octene-1 and dodecene-1), and mixtures thereof, having a number average molecular weight of 150 to It is 10,000, preferably 150 to 5,000. These homopolymers and copolymers can be prepared, for example, by the methods described in U.S. Pat. Nos. 4,054,612, 3,876,721 and 3,428,699. Among these polymers, in particular, polybutadiene, polyisoprene, poly (1,3-pentadiene), poly (butadiene-isoprene), poly (styrene-butadiene), polychloroprene, poly (butadiene-α-methylstyrene), Poly (butadiene-styrene-isoprene), poly (butylene-butadiene), and the like.

The functional group-containing polymer suitable for use in the present invention includes at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group in the molecular structure. And a vinyl compound containing at least one functional group having a hydroxyl group or a glycidyl group and a copolymer of an aromatic vinyl compound. Contains at least one functional group having at least one carbon-carbon double bond or triple bond and at least one carboxylic acid group, acid anhydride group, amino group, hydroxyl group, or glycidyl group in the molecular structure The vinyl compound thus obtained is the same as that which can be used as a modified compound of polyphenylene ether, and one or more selected from these can be used. Among these, maleic anhydride, glycidyl acrylate, and glycidyl methacrylate are preferred. Examples of the aromatic vinyl compound include styrene, α-methylstyrene, and vinyltoluene. One or more compounds selected from these are used, and styrene is particularly preferred. Among these functional group-containing polymers, the most preferred is a styrene-maleic anhydride copolymer.

Epoxy compounds suitable for use in the present invention include (1) epoxy resins formed by condensing polyhydric phenols (eg, bisphenol A, tetrabromobisphenol A, resorcinol, and hydroquinone) with epichlorohydrin; 2) an epoxy resin formed by condensing epichlorohydrin with a polyhydric alcohol (for example, ethylene glycol, propylene glycol, butylene glycol, polyethylene glycol, polypropylene glycol, pentaerythritol, and trimethylolethane); Glycidyl etherification products of alcohols and monohydric phenols such as phenyl glycidyl ether, butyl glycidyl ether and cresyl glycidyl ether; Glycidyl derivatives of goods, there is for example diglycidyl derivatives of aniline, and (5) higher olefin or epoxidation products and epoxidized products of the liquid diene polymer of cycloalkene, or natural unsaturated oils (e.g. soybean).

Oxidized polyolefin waxes suitable for use in the present invention are known, and their description and their preparation are described in U.S. Pat. Nos. 3,822,227 and 3,756,999 and German Offenlegungsschrifts 3047915 and 2201862. Generally, they are produced by the oxidation or suspension oxidation of polyolefins.
Characteristics of quinone compounds suitable for use in the present invention have at least one six-membered carbon ring in the molecule of the unsubstituted derivative and at least two carbonyl groups in the ring structure (these are Both may be in the same ring or, if there is more than one ring, in different rings, provided that these are 1,2 configurations of monocyclic quinones or 1,4 Occupies a position corresponding to the configuration) and has at least two carbon-carbon double bonds in the ring structure (this carbon-carbon double bond and the carbon-oxygen double bond of carbonyl are not present in the ring structure). The carbon-carbon double bond and the carbon-oxygen double bond of the carbonyl are conjugated to each other). When two or more rings are present in the unsubstituted quinone, these rings may be fused, unfused, or both. Non-fused rings may be linked together by a direct carbon-carbon double bond or a hydrocarbon group having conjugated unsaturation such as = CC =.

Also, substituted quinones fall within the scope of the present invention. If substitution is desired, the degree of substitution can be from 1 to the maximum number of replaceable hydrogen atoms. Examples of various substituents that may be present on the unsubstituted quinone structure include hydrocarbon groups such as halogens such as chlorine, bromine and fluorine, for example, branched or unbranched saturated or unsaturated alkyl groups, aryl groups, Alkylaryl and cycloalkyl groups, and their halogenated derivatives, and similar hydrocarbon groups having a heteroatom, especially oxygen, sulfur or phosphorus, which are bonded via a heteroatom, for example, by an oxygen bond. To the quinone ring).
Examples of various quinones include 1,2-benzoquinone, 1,4-benzoquinone, 2,6-diphenylquinone, tetramethyldiquinone, 2,2'-diphenoquinone, 4,4'-diphenoquinone, and 1,2-benzoquinone. Examples include naphthoquinone, 1,4-naphthoquinone, 2,6-naphthoquinone, chloranil, 2-chloro-1,4-benzoquinone, and 2,6-dimethylbenzoquinone.

The organosilane compounds suitable for use in the compatibilizer of the present invention are characterized by (a) at least one silicon atom bonded to carbon through an oxygen bond, and (b) carbon-carbon It has at least one functional group selected from the group consisting of a double bond or a carbon-carbon triple bond and / or an amine group and a mercapto group (however, these functional groups are not directly bonded to a silicon atom) That is.
In such compounds, the CO-Si component is usually present as an alkoxyl or acetoxy group directly bonded to a silicon atom, and these alkoxyl and acetoxy groups generally have less than 15 carbon atoms and are heteroatoms ( For example, oxygen) may be contained. Furthermore, more than one silicon atom may be present in the compound, and when such multiple silicon atoms are present, they may be oxygen-bonded (eg, siloxane), silicon-bonded or difunctional organic groups. (For example, a methylene group or a phenylene group).
Examples of suitable organosilane compounds include γ-aminopropyltriethoxysilane, 2- (3-cyclohexanyl) ethyltrimethoxysilane, 1,3-divinyltetraethoxysilane, vinyltris- (2-methoxyethoxy) silane , 5-bicycloheptenyltriethoxysilane and γ-mercaptopropyltrimethoxysilane.

Next, there are three types of polyfunctional compounds suitable as compatibilizers of the present invention. The first type of polyfunctional compound comprises, in the molecule, (a) a carbon-carbon double bond or a carbon-carbon triple bond, and (b) at least one carboxylic acid group, acid anhydride group, acid halogen. It has a compound group, an anhydride group, an acid halide anhydride group, an acid amide group, an acid ester group, an imide group, an amino group or a hydroxy group. Examples of such polyfunctional compounds include maleic acid, maleic anhydride, fumaric acid, citraconic acid, itaconic acid, maleimide, maleic hydrazide, diamine and maleic anhydride, maleic acid, fumaric acid and the like. Reaction products obtained from acids, dichloromaleic anhydride, maleic amide, unsaturated dicarboxylic acids (for example, acrylic acid, butenoic acid, methacrylic acid, t-ethylacrylic acid, pentenoic acid, decenoic acid, undecenoic acid, dodecenoic acid) , Linoleic acid, etc.), esters of the above unsaturated carboxylic acids, acid amides or anhydrides, unsaturated alcohols (e.g., alkyl alcohol, crotyl alcohol, methyl vinyl carbinol, 4-pentene-1-ol, 1, 4-hexadien-3-ol, 3-butene-1,4-diol 2,5-dimethyl-3-hexene-2,5-diol and formula _{C n H 2n-5 OH,} C n H 2n-7 OH, and C _n H _2n-9 OH (where, n is a positive up to 30 alcohols) integer) of, or more unsaturated alcohol -OH groups (one or more) to be replaced with an NH ₂ group unsaturated amines resulting, well, there is a functionalized diene polymers and copolymers. Of these, preferred compatibilizers for the compositions of the present invention are maleic anhydride and fumaric acid. This type of compatibilizer can be pre-reacted with the polyphenylene ether of the composition.

A second group of polyfunctional compatibilizer compounds suitable for use in the present invention include (a) groups of formula (OR) wherein R is hydrogen or an alkyl, aryl, acyl, Or (b) carboxylic acid, acid halide, acid anhydride, anhydride, acid halide anhydride, acid ester, acid amide, imide, amino and salts thereof. And at least two groups which may be the same or different. Typical examples of this group of compatibilizers are aliphatic polycarboxylic acids, acid esters and acid amides of the formula
_{(R I O) m R (} COOR II) n (CONR III R IV) s

Wherein, R is 2-20 carbon atoms, preferably a saturated aliphatic hydrocarbon straight or branched chain with 2-10, 1-10 is R _I hydrogen or carbon atoms, preferably 1 Selected from the group consisting of -6, most preferably 1-4 alkyl, aryl, acyl or carbonyldioxy groups, wherein R _II is each independently hydrogen or 1-20 carbon atoms, Preferably selected from the group consisting of 1 to 10 alkyl or aryl groups, each of R _III and R _IV independently is hydrogen or 1 to 10, preferably 1 to 6, most preferably Selected from the group consisting essentially of 1 to 4 alkyl or aryl groups, m is equal to 1, (n + s) is greater than or equal to 2, preferably equal to 2 or 3, and n and s are each Is 0 or more. (OR _I ) is α or β to the carbonyl group, and at least two carbonyl groups are separated by 2 to 6 carbon atoms. Obviously, R _I , R _II , R _III and R _IV cannot be aryl if these substituents have less than 6 carbon atoms.

Examples of suitable polycarboxylic acids include citric acid, malic acid, and agaric acid, including various commercial forms such as, for example, anhydrides and hydrated acids. Among these, citric acid and malic acid are one of the preferred compatibilizers.
Examples of acid esters useful in the present invention include, for example, acetyl citrate and monostearyl citrate and / or distearyl citrate.
Suitable acid amides useful in the present invention include, for example, N, N'-diethyl citrate, N-phenyl citrate, N-dodecyl enoate, N, N'-didodecyl enoate and N -There is dodecyl malic acid.
A third group of polyfunctional compatibilizer compounds suitable for use in the present invention are characterized by (a) acid halide groups, most preferably acid chloride groups, and (b) carboxyl groups in the molecule. It has both an acid group, a carboxylic acid anhydride group and an acid ester group or an acid amide group, preferably at least one of a carboxylic acid group and a carboxylic acid anhydride group. Examples of compatibilizers that fall into this group include trimellitic anhydride, chloride, chloroformylsuccinic anhydride, chloroformylsuccinic acid, chloroformylglutaric anhydride, chloroformylglutaric acid, and chloroacetylsuccinic anhydride. , Chloroacetylsuccinic acid, trimellitate chloride and chloroacetylglutaric acid.

Furthermore, it is possible to use the compatibilizer as a polyphenylene ether functionalized compound by pre-reacting the compatibilizer of this group with at least a portion of the polyphenylene ether.
The above compatibilizers are described in detail in U.S. Pat. Nos. 4,315,086 and 4,642,358, respectively. The above-mentioned compatibilizers may be used alone or in any combination thereof. In addition, they may be added directly during melt mixing, or may be pre-reacted with either or both polyphenylene ether or polyamide, or other resinous materials used in preparing the compositions of the present invention. You can leave it.
The preferred amount of these compatibilizers is 0.01 to 20 parts by weight, more preferably 0.1 to 10 parts by weight, based on 100 parts by weight of the mixture of polyamide and polyphenylene ether.
In the present invention, in addition to the above-described components, additional components may be added as needed as long as the effects of the present components are not impaired.

Examples of additional components are given below. That is, other thermoplastic resins such as polyester and polyolefin, inorganic fillers (such as talc, kaolin, zonotolite, wollastonite, titanium oxide, potassium titanate, carbon fiber, and glass fiber), and inorganic fillers and resins Known silane coupling agents, flame retardants (halogenated resins, silicone-based flame retardants, magnesium hydroxide, aluminum hydroxide, organic phosphate compounds, ammonium polyphosphate, red phosphorus, etc.) for increasing affinity, and dripping Fluoropolymers exhibiting protective effects, plasticizers (oil, low molecular weight polyolefin, polyethylene glycol, fatty acid esters, etc.), and flame retardant aids such as antimony trioxide, various peroxides, zinc oxide, zinc sulfide, antioxidants Agents, ultraviolet absorbers, light stabilizers and the like.
These components may be added in a range not exceeding 50 parts by weight in total with respect to 100 parts by weight of the total amount of polyphenylene ether, polyamide and impact modifier.

Specific processing machines for obtaining the composition of the present invention include, for example, a single-screw extruder, a twin-screw extruder, a roll, a kneader, a Brabender plastograph, a Banbury mixer and the like. A twin-screw extruder having an upstream feed port and one or more downstream feed ports is most preferable.
The melt-kneading temperature at this time is not particularly limited, but the temperature at which a suitable composition can be obtained is usually arbitrarily selected from 240 to 360 ° C.
The melt-kneading temperature at the time of producing the master batch is not particularly limited, but can be arbitrarily selected from the range of usually 150 to 300 ° C. for obtaining a suitable composition.
The composition of the present invention thus obtained can be formed into molded articles of various parts by various conventionally known methods, for example, injection molding, extrusion molding, and hollow molding.
The composition of the present invention is used, for example, for exterior parts of motorcycles such as cowls, interior parts of automobiles, fenders, door panels, front panels, rear panels, rocker panels, rear bumper panels, back door garnishes, emblem garnishes, and fuel injections. Entrance panels, over fenders, outer door handles, door mirror housings, bonnet air intakes, bumpers, bumper guards, roof rails, roof rail legs, pillar covers, wheel covers, various aero parts, etc. It can be suitably used for IC tray materials and the like, and especially suitable for automobile exterior parts requiring electrostatic coating.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.
(Raw materials used)
(1) Polyphenylene ether poly (2,6-dimethyl-1,4-phenylene ether)
(1-1) Reduced viscosity (0.5 g / dl chloroform solution, measured at 30 ° C.) = 0.52 dl / g (hereinafter abbreviated as PPE-H)
(1-2) Reduced viscosity = 0.42 dl / g (hereinafter abbreviated as PPE-L)
(2) Polyamide (2-1) Polyamide 6,6 resin (hereinafter abbreviated as PA66)
Number average molecular weight = 16,000
Terminal amino group concentration = 50 milliequivalents / kg
Terminal carboxyl group concentration = 80 milliequivalents / kg
As trace components, it contains 100 ppm of a copper-based heat stabilizer and 800 ppm of a slip agent (metal stearate). (2-2) Polyamide 6 resin (hereinafter abbreviated as PA6)
Sulfuric acid relative viscosity (1 g of polymer / 100 ml of 98% sulfuric acid, 25 ° C.) = 2.6
Terminal amino group concentration = 45 meq / kg,
Terminal carboxyl group concentration = 65 milliequivalents / kg
(2-3) Polyamide 6,6 resin (hereinafter abbreviated as PA66L)
Number average molecular weight = 9,100
Terminal amino group concentration = 55 meq / kg
Terminal carboxyl group concentration = 65 milliequivalents / kg
As trace components, it contains 100 ppm of a copper-based heat stabilizer and 800 ppm of a slip agent (metal stearate).

(3) Impact modifier (3-1) Ethylene-octene copolymer (hereinafter abbreviated as EOR)
Octene content = 24% by weight
MFR = 30 g / 10 min (190 ° C., 2.16 kg load)
Melting point = 60 ° C (DSC method, heating rate 10 ° C / min)
(3-2) Modified maleic anhydride of ethylene-octene copolymer (hereinafter abbreviated as MEOR)
Octene content = 28% by weight
MFR = 0.8 g / 10 min (190 ° C., 2.16 kg load)
Melting point = 55 ° C (DSC method: heating rate 10 ° C / min)
Maleic anhydride addition rate = 1.0% by weight
(3-3) Type 3 high molecular weight hydrogenated styrene-butadiene copolymer (hereinafter abbreviated as HTR1)
Bonding type = 3 type (ABA type) block [A component is styrene block, B component is butadiene block]
Styrene content = 33% by weight
Total amount of vinyl content = 33% by weight
Number average molecular weight = 150,000

(3-4) Type 3 low molecular weight hydrogenated styrene-butadiene copolymer (hereinafter abbreviated as HTR2)
Bonding type = 3 type (ABA type) block [A component is styrene block, B component is butadiene block]
Styrene content = 29% by weight
Total amount of vinyl content = 32% by weight
Number average molecular weight = 51,000
(3-5) Type 4 low molecular weight hydrogenated styrene-butadiene copolymer (hereinafter abbreviated as HTR3)
Bonding type = 4 type (ABAB type) block [A component is styrene block, B component is butadiene block]
Styrene content = 29% by weight
Total amount of vinyl content = 32% by weight
Number average molecular weight = 51,000
(3-6) Oil-containing type 4 high molecular weight hydrogenated styrene-butadiene copolymer (hereinafter abbreviated as HTR4)
Bonding type = 4 type (ABAB type) block [A component is styrene block, B component is butadiene block] Styrene content = 35% by weight
Total amount of vinyl content = 36% by weight
Number average molecular weight = 120,000
Paraffin oil = PW-380 manufactured by Idemitsu Kosan Co., Ltd. Paraffin oil content = 50 parts by weight based on 100 parts by weight of hydrogenated styrene-butadiene copolymer.

(4) Conductive carbon-based filler (hereinafter abbreviated as KB)
Conductive carbon black [Product name: Ketjen Black EC-600JD]
DBP absorption = 495 ml / 100 g
BET surface area = 1,270 m ² / g
(5) Compatibilizer (abbreviated as MAH)
Maleic anhydride [manufactured by NOF CORPORATION]

[Production Example 1] Production of PA66-10% MB A twin-screw extruder [ZSK-25: manufactured by Werner & Friedler (Germany)] having one feed port on the upstream side and one feed port in the center of the extruder. The cylinder temperature was set to 280 ° C., and PA66 was supplied quantitatively from the upstream supply port (hereinafter abbreviated as Top-F) at a rate of 10 kg / h, and supplied to the central part of the extruder (hereinafter abbreviated as Side-F). ), KB was quantitatively supplied at an amount of 1.11 kg / h, melt-kneaded, and pelletized.
At this time, the screw rotation speed was 320 rotations / minute, and a vacuum vent was attached between Side-F and the die to remove volatile components, and vacuum suction was performed.
The obtained master pellet (KB content concentration: 10 wt%) is abbreviated as PA66-10% MB.
[Production Example 2] Production of PA66L-10% MB Except that PA66 was changed to PA66L, the same procedure as in Production Example 1 was carried out to obtain a master pellet.
The master pellet (KB concentration 10 wt%) obtained here is abbreviated as PA66L-10% MB.

[Production Example 3] Production of HTR2-10% MB The cylinder temperature of Production Example 1 was set to 220 ° C, PA66 was changed to HTR2, HTR2 was supplied from Top-F at a rate of 9 kg / h, and from Side-F. Except that KB was supplied at an amount of 1 kg / h, the same procedure was carried out as in Production Example 1 to obtain master pellets.
The obtained master pellet (KB content concentration: 10 wt%) is abbreviated as HTR2-10% MB.
[Production Example 4] Production of HTR3-10% MB A master pellet was obtained in the same manner as in Production Example 3 except that HTR2 in Production Example 3 was replaced with HTR3.
The obtained master pellet (KB content concentration: 10 wt%) is abbreviated as HTR3-10% MB.

[Production Example 5] Production of HTR4-10% MB A master pellet was obtained in the same manner as in Production Example 3 except that HTR2 in Production Example 3 was changed to HTR4.
The obtained master pellet (KB content: 10 wt%) is abbreviated as HTR4-10% MB.
[Production Example 6] Production of KI-MB PA66L was placed in a twin-screw extruder [PCM-30: manufactured by Ikegai Iron Works Co., Ltd.] having a cylinder temperature set at 280 ° C and having one supply port on the upstream side. 0.6 kg / h and powdery potassium iodide (hereinafter abbreviated as KI) were supplied from separate feeders at a rate of 0.4 kg / h, melt-kneaded, and pelletized.
The master pellet (KI content 4 wt%) obtained here is abbreviated as KI-MB.

[Production Example 7] Production of MPPE For 100 parts by weight of PPE, 2 parts by weight of MAH and 0.3 part by weight of a radical generator [Perhexa 25B: manufactured by NOF CORPORATION] were dry-blended, and the cylinder temperature was set to 320. The mixture was supplied to a twin-screw extruder [PCM-30: manufactured by Ikegai Iron Works Co., Ltd.] having a single supply port on the upstream side set at ℃, melt-kneaded, and pelletized.
Next, 1 g of the obtained pellet was taken, sandwiched between layers of a polytetrafluoroethylene sheet, an aluminum sheet, and an iron plate in this order from the inside, and using a press molding machine set at a temperature of 280 ° C. to obtain 100 kg / cm ^2.
To obtain a film.
The obtained film was subjected to infrared spectrometry using an FT / IR-420 type Fourier transform infrared spectrophotometer manufactured by JASCO Corporation.
In the measurement on the film, a peak derived from maleic acid added to polyphenylene ether was observed at 1790 cm -1.
Using a mixture of PPE and MAH, the addition rate of MAH calculated from a calibration curve formula prepared in advance was 0.54% by weight.
The obtained MAH-modified PPE is abbreviated as MPPE.

　ここで、ＶＲは体積固有抵抗（Ω・ｃｍ）、Ｒはテスターで測定した抵抗の加算平均値（Ω）、ｗは銀ペーストを塗布した部分の幅（ｃｍ）、ｔは銀ペーストを塗布した部分の高さ（ｃｍ）、ｌは銀ペースト塗布面間の距離（ｃｍ）である。 Next, each measurement method will be described in detail.
(Volume specific resistance -1)
A 3.2 mm thick tensile test piece is cut at both ends with a precision cut saw to obtain a strip test piece having a length of 50 mm and a cut surface having a uniform cross-sectional area (12.4 × 3.2 mm) at both ends. Was. A silver paste was applied to the cut surfaces at both ends of the test piece and dried sufficiently. Then, the resistance value between both ends was measured with a tester, and the volume resistivity was calculated using the equation (a).
This volume resistance value was expressed as volume specific resistance-1, and this value is shown in Table 1.

Here, VR is the volume specific resistance (Ω · cm), R is the average value of the resistance measured by a tester (Ω), w is the width (cm) of the portion to which the silver paste is applied, and t is the amount of the silver paste applied. The height of the portion (cm), l is the distance (cm) between the silver paste applied surfaces.

(Volume resistivity-2)
Apply a silver paste with an area of 30 mm x 2.5 mm to the center of opposing 50 mm x 2.5 mm surfaces of a flat molded piece with a length of 90 mm, a width of 50 mm, and a thickness of 2.5 mm, and dry sufficiently. After that, the resistance between both ends was measured with a tester. This was performed five times with different flat plates, the average value was obtained, and the volume resistivity was calculated using the equation (a). This volume resistance value was expressed as volume resistivity-2, and this value is shown in Table 1.
(Melt flow rate: MFR)
The test was performed at 280 ° C. under a load of 5 kg by a method based on ISO1133.
(Izod impact test)
According to ASTM D-256, a notch impact strength having a thickness of 3.2 mm was measured.

(Dart impact test)
The dirt impact test was performed using a graphic impact tester (manufactured by Toyo Seiki Seisaku-sho, Ltd.) using a flat molded piece having a length of 90 mm, a width of 50 mm, and a thickness of 2.5 mm.
The test method is such that a test piece is sandwiched in a sample holder having a diameter of 40 mm, and a spherical striker (weight 6.5 kg) having a tip diameter of 13 mm is freely dropped from a height of 100 cm above the test piece to break the test piece. At that time, the total energy required for destruction was measured and displayed as total absorbed energy.
This test was performed on ten samples, and the average of eight measured values excluding the maximum and minimum values of the ten data was taken as the total absorbed energy value of the sample.
In addition, the state of fracture of the test piece that was broken in this measurement was observed, and it was roughly classified into ductile fracture and brittle fracture, and the ductility rate was calculated from the ratio of the number of ductile fractured test pieces out of 10 test pieces. did.
Ductility [%] = Number of ductile fractures / 10 × 100

(Adhesion with coating film)
According to the method described in JP-A-60-65035, a thermosetting acrylic resin paint is diluted with a special thinner on a flat molded piece having a length of 90 mm, a width of 50 mm, and a thickness of 2.5 mm, and applied with a spray gun. After leaving at room temperature for 30 minutes, it was heated and cured at 150 ° C. for 30 minutes to obtain a coated product. Next, the coating film of this painted product was subjected to a 1 mm square grid test in accordance with JIS K5400-1979, and the number of grids that did not peel out of 100 meshes was determined.

[Examples 1-3] and [Comparative Examples 1-2]
The cylinder temperature of a twin-screw extruder [ZSK-40: manufactured by Werner & Friedler (Germany)] having one feed port on the upstream side and one feed port at the center of the extruder was measured from Top-F to Side-F. At 320 ° C., the temperature from Side-1 to the die was set at 280 ° C., and dry-blended from Top-F and Side-F at the ratios described in Examples 1 to 3 and Comparative Examples 1 to 2 in Table 1 were supplied. , Melt kneading and pelletizing.
At this time, the screw rotation speed was 300 rotations / minute, and a vacuum vent was attached at two places just before Side-F and between the Side-F and the die to remove volatile components, and vacuum suction was performed. Was.
Using an injection molding machine [IS-80EPN: manufactured by Toshiba Machine Co., Ltd. (Japan)], the obtained pellets were set at a cylinder temperature of 290 ° C. and a mold temperature of 80 ° C. to form molded pieces necessary for each measurement. It molded and measured each measurement item. The measurement results are also shown in Table 1.
[Examples 4 to 6]
All the procedures were performed in the same manner as in Example 1 except that the composition was changed to the ratio shown in Table 2. The results of the measurements performed are shown in the lower part of the composition of each example in Table 2.

[Examples 7 to 9]
All the procedures were performed in the same manner as in Example 1 except that the composition was changed to the ratio shown in Table 3. In Examples 7 to 9, in addition to the measurement items performed in Example 1, a volume resistivity-2 and a dart impact test were also performed.
The results of the measurements performed are also shown in the lower part of the composition of each example in Table 3.
Although there is a slight variation in the volume resistivity -1 as compared to the volume resistivity -2, there is no significant difference between the two. This is presumably because a gate in the form of a film is provided at one end of the plate-shaped molded piece, and the cut portion is cut, so that the resistance of the cut surface is substantially measured.
[Examples 10 and 11]
All the procedures were performed in the same manner as in Example 1 except that the composition was changed to the ratio shown in Table 4. In Examples 10 and 11, in addition to the measurement items performed in Example 1, a coating film adhesion test was also performed.
The results of the measurements performed are also shown in the lower part of the composition of each example in Table 4.

樹脂 The resin composition of the present invention is a resin composition having an excellent balance between conductivity, fluidity and impact resistance.

Claims (18)

Using a twin-screw extruder equipped with one supply port on the upstream side and at least one supply port on the downstream side, supply polyamide from the upstream supply port, supply conductive carbon-based filler from the downstream supply port, and melt-knead. A polyamide master pellet characterized by the fact that: Using a twin-screw extruder provided with one supply port on the upstream side and at least one supply port on the downstream side, polyphenylene ether and a compatibilizer are supplied from the upstream supply port, and after melt-kneading, the mixture is supplied from the downstream supply port. A conductive resin composition comprising a polyamide and the polyamide master pellet according to claim 1, which are further supplied and melt-kneaded. 3. The conductive resin composition according to claim 2, wherein an impact modifier is supplied from an upstream supply port in addition to the polyphenylene ether and the compatibilizer. The conductive resin composition according to claim 3, wherein the impact modifier is a hydrogenated product of a block copolymer of an aromatic vinyl compound and a conjugated diene compound. The conductive resin composition according to claim 2, wherein the content of the conductive carbon-based filler is 1.5 to 3.5% by weight. The polyamide master pellet according to claim 1, wherein the conductive carbon-based filler is carbon black having a DBP oil absorption of 350 ml / 100 g or more. The polyamide master pellet according to claim 1, wherein the polyamide is polyamide 66. The polyamide master pellet according to claim 1, wherein the polyamide used has an end group having an amino group concentration / carboxyl group concentration ratio of 6/4 to 1/9. The polyamide master pellet according to claim 1, wherein the content of the conductive carbon-based filler is 10% by weight. The polyamide master pellet according to claim 1, further comprising a step of vacuum suction after adding the conductive carbon-based filler. The polyamide master pellet according to claim 1, wherein the polyamide and the conductive carbon-based filler are quantitatively supplied to an extruder. Using a twin-screw extruder equipped with one supply port on the upstream side and at least one supply port on the downstream side, supply polyphenylene ether, a compatibilizer, and an impact modifier from the upstream supply port, and melt-knead them. The ethylene-α-olefin copolymer and / or the modified ethylene-α-olefin copolymer are supplied from the side supply port to the polyamide and the polyamide master pellet according to claim 1 and further melt-kneaded. The conductive resin composition characterized by the above. Using a twin-screw extruder equipped with one supply port on the upstream side and at least one supply port on the downstream side, supply polyamide from the upstream supply port, supply conductive carbon-based filler from the downstream supply port, and melt-knead. A method for producing polyamide master pellets. Using a twin-screw extruder equipped with one supply port on the upstream side and at least one supply port on the downstream side, supply polyphenylene ether, a compatibilizer, and an impact modifier from the upstream supply port, and melt-knead the mixture. A method for producing a conductive resin composition, comprising supplying polyamide and the polyamide master pellet according to claim 1 from a side supply port and further melt-kneading the polyamide and the polyamide master pellet. Using a twin-screw extruder equipped with one supply port on the upstream side and at least one supply port on the downstream side, supply polyphenylene ether, a compatibilizer, and an impact modifier from the upstream supply port, and melt-knead them. In addition to the polyamide and the polyamide master pellet according to claim 1, an ethylene-α-olefin copolymer and / or a modified ethylene-α-olefin copolymer are supplied from the side supply port and further melt-kneaded. A method for producing a conductive resin composition. A pellet comprising the resin composition according to claim 2. An automotive outer panel / exterior component formed from the resin composition according to claim 2. An automotive fender formed from the resin composition according to claim 2.