JP2007277363A - Electroconductive aromatic amide block copolymer resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electroconductive aromatic amide block copolymer resin composition excellent in electroconductivity, ambient temperature stability, heat resistance, low-temperature resistance, and flexibility. <P>SOLUTION: The electroconductive aromatic amide block copolymer resin composition comprises an aromatic amide block copolymer comprising aromatic amide units each represented by formula (1) and at least one type of units selected from the group consisting of a polyester, an aliphatic poly(oxyalkylene), a polycarbonate, a polyolefin, a polyorganosiloxane, a polydiene, and copolymers thereof and carbon nanotubes. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel conductive aromatic amide block copolymer resin composition excellent in conductivity, environmental temperature stability, heat resistance and flexibility.

  In recent years, problems such as destruction of a semiconductor due to charged static electricity or malfunction of an electronic device have occurred, and techniques for preventing charging of charges and techniques for removing static charges safely have become important. On the other hand, in a copying machine, a printer, and the like, a technique for printing using a charged charge is used, and it is an important technique to charge the charge stably. That is, it is important to control the charge to be charged, and therefore it is required to control the conductivity of thermoplastic elastomers that are generally insulating.

  In general, in order to impart conductivity, for example, filling with a conductive filler such as carbon black; addition of an antistatic agent such as cationic, anionic or nonionic is generally performed. However, in conventional thermoplastic elastomers such as polyester elastomers and polyurethane elastomers, it is difficult to uniformly disperse conductive fillers such as carbon black, and there is also a charge charged due to non-uniform dispersion. There are problems such as non-uniformity. In addition, the antistatic agent is uniformly dispersed so that a uniform charged state can be obtained, but the surface electrical resistance value is deteriorated when the humidity is high, the antistatic property is remarkably lowered after a long period of time, and performance by washing with water, etc. Have problems such as lowering. In order to solve these problems, a composition comprising bis (trifluoromethanesulfonyl) imide lithium and / or tris (trifluoromethanesulfonyl) methide lithium as a component in a thermoplastic elastomer such as a polyester elastomer or a polyurethane elastomer has been proposed (for example, , See Patent Documents 1 to 4.) However, even in these methods, it is difficult to realize excellent electrical stability against environmental changes such as temperature and humidity.

  Based on this background, carbon nanotubes are attracting attention as conductive materials that are less susceptible to environmental influences. It is known that when carbon nanotubes are added to thermoplastic resins, thermosetting resins, elastomers, rubbers, and the like, thermal conductivity, electrical conductivity, mechanical properties, and the like are improved. However, carbon nanotubes, like conductive carbon black, do not dissolve in organic solvents and have high cohesive strength. Therefore, they are extremely difficult to disperse in resin compared to carbon black, etc. There was a problem that had to be lengthened. For example, a technique related to a conductive material containing carbon nanotubes is disclosed (see, for example, Patent Document 5). In the production thereof, first, carbon nanotubes and a thermoplastic resin are kneaded to form a master batch, and then again. A method of re-kneading with a large amount of thermoplastic resin is described. However, in order to uniformly disperse the carbon nanotubes in the resin, it is an economically disadvantageous method of kneading in two stages. In addition, in this method, in order to obtain a resin having a good surface electric resistance value, 1 to 2% by weight of carbon nanotubes are required. Further, melt kneading with a resin has a problem that the aspect ratio is lowered due to the breakage of the carbon nanotubes, and the conductivity is lowered.

Furthermore, in one such example, a method for producing a molded body having an anisotropic surface electrical resistance value obtained by kneading carbon nanotubes into a thermoplastic resin, a thermosetting resin, rubber, an elastomer or the like is described (for example, , See Patent Document 6). In this technique, for example, a method is disclosed in which carbon nanotubes are dispersed in unsaturated polyester and then cured, but untreated carbon nanotubes are highly aggregated, and these aggregates are converted into independent carbon nanotubes by stirring or the like. It is difficult to disperse. Moreover, the surface electrical resistance value of the obtained molded body is as high as 10 ³ (Ω) order when the added amount of carbon nanotubes is 1% by weight, and a reduction in the surface electrical resistance value is required.

  As a means for improving dispersibility, a method of chemically modifying carbon nanotubes with albumin protein and glucosamine has been reported. For example, it describes about albumin protein modification (for example, refer nonpatent literature 1) and glucosamine modification (for example, refer nonpatent literature 2). However, in these techniques, although proteins or the like are covalently bonded to the carbon nanotubes, they are not in the category of carbon nanotubes that are not high molecular weight polymers but are simply chemically modified as a whole. In addition, in blends that do not involve chemical bonding, contamination by additives in the resin may become a problem in precision parts applications such as electronic equipment applications, as in carbon bun racks.

JP 2002-146178 A JP 2003-277622 A JP 2004-43614 A JP 2003-73554 A JP 2003-100147 A JP 2002-273741 A Nano Letters, Vol. 4, 311, 2002 J. et al. Phys. Chem. B, 105, 2525, 2001

  However, carbon nanotubes are inferior in compatibility with the resin, and a composition having the characteristics of carbon nanotubes has not been realized. Accordingly, an object of the present invention is to provide a composition in which carbon nanotubes having excellent physical properties are highly dispersed.

  In order to solve the above problems, the present inventors have attempted to disperse carbon nanotubes in various elastomers. As a result, the specific aromatic amide block copolymer of the present invention highly specifically disperses carbon nanotubes. As a result, the present inventors have found that the resulting resin composition is excellent in environmental temperature stability, heat resistance, cold resistance and flexibility in addition to conductivity.

  That is, the present invention is from the group consisting of an aromatic amide unit represented by the following general formula (1) and a polyester, aliphatic poly (oxyalkylene), polycarbonate, polyolefin, polyorganosiloxane, polydiene or a copolymer thereof. The present invention relates to an aromatic amide block copolymer composed of one or more selected units and a conductive aromatic amide block copolymer resin composition composed of carbon nanotubes.

（１）
（ここで、Ｒ^１およびＲ^２は、それぞれ独立して炭素数１〜２０の二価のオキシアルキレン基、アルキレンカルバモイル基、またはアリーレンカルバモイル基を示す。）
以下に本発明を詳細に説明する。

(1)
(Here, R ¹ and R ² each independently represent a divalent oxyalkylene group having 1 to 20 carbon atoms, an alkylenecarbamoyl group, or an arylenecarbamoyl group.)
The present invention is described in detail below.

  The conductive aromatic amide block copolymer resin composition of the present invention comprises an aromatic amide unit represented by the general formula (1), polyester, aliphatic poly (oxyalkylene), polycarbonate, polyolefin, polyorganosiloxane, A resin composition comprising an aromatic amide block copolymer comprising one or more units selected from the group consisting of polydienes or copolymers thereof and carbon nanotubes.

Here, R ¹ and R ² in the aromatic amide unit represented by the general formula (1) constituting the aromatic amide block copolymer used in the conductive aromatic amide block copolymer resin composition of the present invention are: Are each independently a divalent oxyalkylene group having 1 to 20 carbon atoms, an alkylenecarbamoyl group, or an arylenecarbamoyl group, and R ¹ and R ² may be the same or different, and may be linear or branched. It may be a shape.

  Examples of the oxyalkylene group include unsubstituted oxyalkylene groups such as oxyethylene group, oxytrimethylene group, oxytetramethylene group, oxypentamethylene group and oxyhexamethylene group, or alkyl substitution such as methyl group and ethyl group. Group or one or more aryl substituents such as phenyl group bonded thereto. Furthermore, two or more of the above unsubstituted oxyalkylene group units and alkyl or aryl-substituted oxyalkylene group units may be bonded together, and one or more of these may be used. Of these, an oxyethylene group and an oxypropylene group are preferable. In addition, it is preferable that oxygen in these oxyalkylene groups is directly bonded to the benzene ring in the general formula (1).

  Examples of the alkylenecarbamoyl group include a methylenecarbamoyl group, an ethylenecarbamoyl group, a trimethylenecarbamoyl group, a tetramethylenecarbamoyl group, a pentamethylenecarbamoyl group, a 2,2-dimethyltrimethylenecarbamoyl group, a neopentylcarbamoyl group, and a hexamethylenecarbamoyl group. , 3-methylpentamethylenecarbamoyl group, 2-methylheptamethylenecarbamoyl group, heptamethylenecarbamoyl group, octamethylenecarbamoyl group, nonamethylenecarbamoyl group, decamethylenecarbamoyl group, 1,4-cyclohexylenecarbamoyl group, etc. One or more of these can be used. Of these, an ethylenecarbamoyl group is preferable.

  Examples of the arylenecarbamoyl group include 2-benzylcarbamoyl group, 3-benzylcarbamoyl group, 4-benzylcarbamoyl group, 1,2-phenylenecarbamoyl group, 1,3-phenylenecarbamoyl group, 1,4-phenylenecarbamoyl group and the like. One or more of these may be used.

  Polyester, aliphatic poly (oxyalkylene), polycarbonate, polyolefin, polyorganosiloxane, polydiene or a copolymer thereof constituting the aromatic amide block copolymer used in the conductive aromatic amide block copolymer resin composition of the present invention. The one or more units selected from the group consisting of polymers are not particularly limited as long as they are known.

  The polyester can be obtained, for example, by condensation polymerization of a dicarboxylic acid or dicarboxylic acid anhydride and a short chain polyol. Examples of the dicarboxylic acid or dicarboxylic acid anhydride include succinic acid, glutaric acid, adipic acid, azelaic acid, sebacic acid, dodecanoic acid, phthalic acid, isophthalic acid, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, maleic anhydride, Examples thereof include fumaric acid and itaconic acid, and one or more of these are used. On the other hand, examples of the short-chain polyol include aliphatic, alicyclic, aromatic, substituted aliphatic or heterocyclic dihydroxy compounds; trihydroxy compounds; tetrahydroxy compounds, and the like. For example, 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, butenediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, 1,10- Decamethylenediol, 2,5-dimethyl-2,5-hexanediol, neopentyl glycol, diethylene glycol, 1,4-cyclohexanedimethanol, 2-methyl-1,8-octanediol, 1,9-nonanediol, bis (Β-hydroxyethoxy) benzene, p-xylenediol, dihydroxyethyl ester La hydro phthalate, trimethylolpropane, glycerin, 2-methylpropane-1,2,3-triol, 1,2,6-hexane triol and the like, one or more of these can be used.

  Other methods for obtaining the polyester include, for example, β-propiolactone, pivalolactone, δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone, methyl-ε-caprolactone, dimethyl-ε-caprolactone, trimethyl- It is also possible to use a method in which one or more lactone compounds such as ε-caprolactone are reacted with a hydroxy compound.

  Examples of the aliphatic poly (oxyalkylene) include poly (oxyethylene), poly (oxypropylene), poly (oxytetramethylene), poly (oxyhexamethylene), a copolymer of ethylene oxide and propylene oxide, and ethylene oxide and tetrahydrofuran. And an ethylene oxide addition polymer of poly (propylene oxide), and one or more of these are used.

  Examples of the polycarbonate include those obtained by a transesterification method of one or more of hydroxy compounds and a carbonate compound such as diallyl carbonate, dialkyl carbonate, and ethylene carbonate. As specific polycarbonates, Examples thereof include poly (1,6-hexamethylene carbonate) and poly (2,2′-bis (4-hydroxyhexyl) propylene carbonate). Moreover, as another method of obtaining a polycarbonate, it can also obtain by what is called a phosgene method.

  Examples of the polydiene include polybutadiene and polyisoprene.

  Examples of the polyolefin include polyolefins obtained by hydrogenating polydiene; homopolymers of olefins such as ethylene, propylene, and isobutylene; random copolymers; alternating copolymers; block copolymers.

  Examples of the polyorganosiloxane include poly (dimethylsiloxane), poly (diphenylsiloxane), poly (methylphenylsiloxane) and the like.

  Among these, since the conductive aromatic amide block copolymer resin composition excellent in heat resistance is obtained, the aromatic amide block copolymer is an aromatic amide unit represented by the general formula (1) and a polyester. It is preferable to consist of an aromatic amide unit represented by the general formula (1) and poly (ε-caprolactone).

  The aromatic amide block copolymer used in the conductive aromatic amide block copolymer resin composition of the present invention comprises an aromatic amide unit represented by the general formula (1), polyester, aliphatic poly (oxyalkylene), One or more units selected from the group consisting of polycarbonate, polyolefin, polyorganosiloxane, polydiene, and copolymers thereof may be directly bonded or may contain other compound residues. Examples of other compound residues include bifunctional halide compounds, difunctional isocyanate compounds, difunctional carbonate compounds, bifunctional ester compounds, bifunctional acyllactam compounds, bifunctional epoxy compounds, and bifunctional tetra compounds. The compound residue derived from a carboxylic anhydride etc. is mentioned, These 1 type (s) or 2 or more types may be contained.

  Examples of the compound residue derived from a bifunctional halide compound include oxalic acid dichloride, malonic acid dichloride, succinic acid dichloride, glutaric acid dichloride, adipic acid dichloride, pimelic acid dichloride, suberic acid dichloride, azelaic acid dichloride, and sebacic acid. Compound residues derived from bifunctional acid chlorides such as dichloride, dodecanoic acid dichloride, terephthalic acid dichloride, isophthalic acid dichloride, phthalic acid dichloride; oxalic acid dibromide, malonic acid dibromide, succinic acid dibromide, glutaric acid dichloride Bromide, adipic acid dibromide, pimelic acid dibromide, suberic acid dibromide, azelaic acid dibromide, sebacic acid dibromide, dodecanoic acid dibromide, terephthalate Examples include compound residues derived from difunctional acid bromides such as dibromide, isophthalic acid dibromide, and phthalic acid dibromide. Among them, they are highly reactive and efficiently conductive aromatic amide block copolymer resins. A compound residue derived from adipic acid dichloride is preferred because an aromatic amide block copolymer used in the composition is obtained.

  Examples of the compound residue derived from the bifunctional isocyanate compound include diphenylmethane-4,4′-diisocyanate, toluene diisocyanate, phenylene diisocyanate, xylene diisocyanate, xylylene diisocyanate, tetramethylxylene diisocyanate, hexamethylene diisocyanate, isophorone diisocyanate, Examples include compound residues derived from naphthalene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, dimer acid diisocyanate, dicyclohexylmethane diisocyanate, methylcyclohexane diisocyanate, norbornene diisocyanate, etc. These may be used alone or in combination of two or more It may be use. Among them, since the aromatic amide block copolymer used in the conductive aromatic amide block copolymer resin composition is excellent in reactivity and efficiently, diphenylmethane-4,4′-diisocyanate, toluene diisocyanate, hexamethylene A compound residue derived from diisocyanate, dicyclohexylmethane diisocyanate, isophorone diisocyanate or the like is preferred, and a compound residue derived from hexamethylene diisocyanate is particularly preferred.

  As the compound residue derived from a bifunctional carbonate compound, for example, a compound residue derived from dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diphenyl carbonate, etc., among them excellent in reactivity, A compound residue derived from dimethyl carbonate, diphenyl carbonate or the like is preferable because an aromatic amide block copolymer used for the conductive aromatic amide block copolymer resin composition can be obtained efficiently.

  Examples of the compound residue derived from the bifunctional ester compound include diphenyl terephthalate, diphenyl isophthalate, diphenyl phthalate, diphenyl 2,6-naphthalenedicarboxylate, diphenyl 2,7-naphthalenedicarboxylate, 4,4- Diphenyl biphenyl dicarboxylate, dimethyl terephthalate, dimethyl isophthalate, dimethyl phthalate, dimethyl 2,6-naphthalenedicarboxylate, dimethyl 2,7-naphthalenedicarboxylate, dimethyl 4,4-biphenyldicarboxylate, diethyl terephthalate, isophthalic acid Compound residues derived from diethyl, diethyl phthalate, diethyl 2,6-naphthalenedicarboxylate, diethyl 2,7-naphthalenedicarboxylate, diethyl 4,4-biphenyldicarboxylate, etc. Since the aromatic amide block copolymer used in the conductive aromatic amide block copolymer resin composition is excellent in flexibility, it can be obtained from diphenyl terephthalate, dimethyl terephthalate, diphenyl isophthalate, dimethyl isophthalate, etc. Derived compound residues are preferred.

  Examples of the compound residue derived from a bifunctional acyllactam compound include terephthaloyl bis (ε-caprolactam), isophthaloyl bis (ε-caprolactam), adipyl bis (ε-caprolactam), succinyl bis (ε-caprolactam). ) And the like, and among them, the aromatic amide block copolymer used in the conductive aromatic amide block copolymer resin composition is obtained with excellent reactivity and efficiency. Compound residues derived from phthaloyl bis (ε-caprolactam) are preferred.

  Examples of the compound residue derived from a bifunctional epoxy compound include a compound residue derived from an aromatic dicarboxylic acid diglycidyl ester such as terephthalic acid diglycidyl ester, isophthalic acid diglycidyl ester, and phthalic acid diglycidyl ester; Compound residue derived from aromatic diglycidyl ether such as p-phenylene diglycidyl ether; Compound residue derived from aliphatic dicarboxylic acid diglycidyl ester such as diethylene glycol diglycidyl ester; Aliphatic such as diethylene glycol diglycidyl ether Examples thereof include a compound residue derived from dicarboxylic acid diglycidyl ether.

  Examples of the compound residue derived from a bifunctional aromatic tetracarboxylic anhydride include pyromellitic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 3,3 ′, Examples thereof include compound residues derived from 4,4′-benzophenone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, and the like.

  Further, the content of the aromatic amide unit in the aromatic amide block copolymer used in the conductive aromatic amide block copolymer resin composition of the present invention is not particularly limited, and the conductivity, environmental temperature stability, flexibility From the viewpoint of obtaining a conductive aromatic amide block copolymer resin composition excellent in heat resistance and cold resistance, the content of the aromatic amide unit is preferably in the range of 5 to 95% by weight, particularly 5 It is preferably in the range of ˜50% by weight, more preferably 15 to 45% by weight.

  The aromatic amide block copolymer used in the conductive aromatic amide block copolymer resin composition of the present invention is a number average in terms of standard polystyrene measured by gel permeation chromatography (hereinafter referred to as GPC). The molecular weight is preferably 10,000 to 1,000,000, particularly preferably 30,000 to 500,000. The aromatic amide block copolymer preferably has a hardness of a type A durometer hardness (JIS K6253: 1997) of 50 to 99, particularly preferably 65 to 98.

  The method for producing the aromatic amide block copolymer used in the conductive aromatic amide block copolymer resin composition of the present invention includes an aromatic amide unit represented by the general formula (1), polyester, aliphatic poly ( Oxyalkylene), polycarbonate, polyolefin, polyorganosiloxane, polydiene or any method as long as it is possible to produce an aromatic amide block copolymer comprising one or more units selected from the group consisting of these copolymers For example, a monomer containing an aromatic amide unit represented by the general formula (1) and having a carboxylic acid group or a hydroxyl group at both ends, a polyester containing a hydroxyl group or a carboxylic acid group at both ends, and an aliphatic polymer (Oxyalkylene), polycarbonate, polyolefin, polyorganosiloxane A method of directly reacting a compound containing one or more units selected from the group consisting of styrene, polydiene, and copolymers thereof; containing an aromatic amide unit represented by the general formula (1) and having hydroxyl groups at both ends The monomer is reacted with one or more units selected from the group consisting of a polyester containing hydroxyl groups at both ends, aliphatic poly (oxyalkylene), polycarbonate, polyolefin, polyorganosiloxane, polydiene or a copolymer thereof. On the other hand, from bifunctional halide compounds, bifunctional isocyanate compounds, bifunctional carbonate compounds, bifunctional ester compounds, bifunctional acyllactam compounds, bifunctional epoxy compounds, bifunctional tetracarboxylic acid anhydrides, etc. A method of reacting in the presence of one or more chain extender units selected from the group consisting of After reacting a monomer having an aromatic amide unit represented by the general formula (1) and having hydroxyl groups at both ends with a cyclic ester compound such as ε-caprolactone to obtain a prepolymer, one or more chain extenders described above are used. Examples thereof include a method of adding and reacting. Examples of the polymerization method at that time include a solution polymerization method, a melt polymerization method, an interfacial polymerization method, a solid phase polymerization method, and the like. Among them, since an aromatic amide block copolymer having an increased molecular weight can be easily obtained, it is preferable to perform melt condensation after performing a solution polymerization method.

  The carbon nanotubes (CNT) used in the conductive aromatic amide block copolymer resin composition of the present invention are not particularly limited in kind and production method. For example, a single-walled carbon nanotube (SWCNT) having a diameter of 1 to 5 nanometers, a multi-walled carbon nanotube (MWCNT) having an inner diameter of 1 to 20 nanometers, and an outer diameter of 2 to 40 nanometers is used. Further, it is possible to use a carbon nanotube defined by the chiral index notation (n, m). For example, an armchair type carbon nanotube defined by the chiral index (n, n), a chiral index (n, m) 0) and zigzag carbon nanotubes defined by chiral index (n, m) (n ≠ m) and the like, and these are not intended to limit the present invention. Any carbon nanotube can be used without any problem. Moreover, as a shape of a carbon nanotube, a cylindrical shape and a spiral shape can be used. In addition, fullerene-encapsulated CNTs called peapods can be used, and in this case, both SWCNT and MWCNT types can be used.

  Carbon nanotubes constituting the conductive aromatic amide block copolymer resin composition of the present invention can be produced by various production methods, such as arc discharge method, laser vapor deposition method, thermal decomposition. The carbon nanotube manufactured by methods, such as a method and a plasma discharge method, can be used. Moreover, as the carbon nanotube, a carbon nanotube containing impurities such as amorphous carbon, fullerenes, and metals can be used. Since fullerenes and the like are soluble in an organic solvent, they can be extracted by dissolving in an organic solvent such as toluene or benzene. In addition, carbon nanotubes containing inorganic and organic substances can also be used.

  In the present invention, the carbon nanotubes have a high aspect ratio and can be used alone. Further, the carbon nanotubes are dispersed by ultrasonic waves, chemically or mechanically pulverized, and the concentration of terminal reactive groups is determined. Improved ones can also be used.

  The conductive aromatic amide block copolymer resin composition of the present invention is a resin composition capable of highly dispersing carbon nanotubes specifically by using a specific aromatic amide block copolymer.

  The conductive aromatic amide block copolymer resin composition of the present invention is obtained by mixing an aromatic amide block copolymer and CNT, and the amount of CNTs in that case is not particularly limited, and preferably conductive. It is 0.001-20 weight part of CNT with respect to 100 weight part of aromatic amide block copolymers used for an aromatic amide block copolymer resin composition, Especially preferably, it is 0.01-10 weight part, More preferably, it is 0. .1 to 5 parts by weight.

  When the aromatic amide block copolymer and CNT are mixed, they may be mixed at one time, or may be mixed in two or more stages in order to achieve a good dispersion state. . Examples of the mixing method at that time include solution mixing, melt mixing, and the like, and among them, solution mixing in which CNTs are difficult to cut is preferably used. Moreover, when mixing, it is preferable to stir at low speed in order to add CNT to the solution of an aromatic amide block copolymer and to suppress CNT breakage as much as possible.

  Any solvent can be used as the solvent for the solution mixing as long as the aromatic amide block copolymer is dissolved. Examples thereof include amide solvents such as N-methylpyrrolidone and dimethylacetamide, and cyclic ethers such as tetrahydrofuran (THF). Etc. are exemplified.

  The solid content concentration of the aromatic amide block copolymer in the melt mixing is preferably 0.1 to 50% by weight, particularly preferably 10 to 30% by weight.

  For melt mixing, for example, a machine such as a Banbury mixer (manufactured by Farrell), a pressure kneader (manufactured by Moriyama Seisakusho), an internal mixer (manufactured by Kurimoto Iron Works), an intensive mixer (manufactured by Nippon Roll Manufacturing Co., Ltd.), etc. A kneading and molding machine used for processing plastics or rubber, such as a pressure kneader; an extrusion molding machine such as a roll molding machine, a single screw extruder, or a twin screw extruder; can be used. The temperature at the time of melt mixing is preferably 120 to 350 ° C, particularly preferably 150 to 300 ° C.

Since the conductive aromatic amide block copolymer resin composition of the present invention has excellent conductivity, the surface electrical resistance value is preferably 0.1 to 10 ⁶ Ω, particularly 0.1 to It is preferably 6 × 10 ² Ω, more preferably 0.1 to 0.9Ω.

  Moreover, since it becomes the conductive aromatic amide block copolymer resin composition excellent in heat resistance, it is preferable that the softening point of this resin composition is 150-300 degreeC, and it is especially 180-270 degreeC. Is preferred.

  The conductive aromatic amide block copolymer resin composition of the present invention can be molded into various molded products. Examples of the molded products include injection molded products, extruded molded products, blow molded products, foamed products, and heated products. Examples include molded bodies, vacuum molded bodies, compression molded bodies, inflation molded bodies, cable coverings, sheets / films, hollow molded bodies, rolls, threads, etc. Among them, cable coverings, sheets / films, hollows are preferred. A molded body, a roll, a thread and the like can be mentioned.

  As a more specific molded body, for example, insulated wires, electronic device wiring wires, automotive wires, device wires, flexible wires, tape wires, power cords, indoor wires insulated wires, power wires, control wires, Cables for communication wires, instrument wires, signal wires, mobile wires, ship wires, vehicle wires, aircraft wires, heating wires, fire and heat resistant wires for fire fighting, nuclear power plant wires, etc .; magnetic Tapes, tapes such as ferromagnetic thin film tapes; photographic films, packaging films, films for electronic components, electrical insulation films, films for laminating metal plates, films for glass displays, prism lens sheets for liquid crystal display members, Base films for touch panels, backlights, etc .; polarizing plates, optical lenses, covers for various instruments, window glass for automobiles, trains, etc. Anti-reflection film used for LCD; base film for display explosion-proof film; optical sheet for liquid crystal display substrate, organic EL display element substrate, color filter substrate, touch panel substrate, solar cell substrate; optical lens, screen, etc. Lens sheets used for medical treatments: Base materials for medical aid tapes such as emergency bond creation, surgical tapes, rehabilitation tapes, etc .; base materials for tapes for treatment of diseases such as anti-inflammatory, analgesic and blood circulation; surgical gloves; Article fixing tape substrate; antistatic sheet, roofing sheet, etc .; semiconductive film, antistatic film, pharmaceutical film, etc .; pneumatic tube, hydraulic tube, heat shrinkable tube, etc .; empty Pressure hose, hydraulic hose, heat shrink hose, oxygen hose, steam hose, oil supply / absorption hose, gas Hoses, braided hoses, cloth-wrapped hoses, high-pressure hoses, suction hoses, duct hoses, spray hoses, hose for water supply / drainage, pressure-resistant reinforcement hoses, antistatic hoses, etc .; rack & pinion boots, constant velocity joint boots, steering Boots such as boots, dust boots, suspension boots; air ducts; industrial rolls such as printing rolls, paper rolls, spinning rolls, iron rolls, dyed fiber rolls; rolls for office equipment; charging rolls, transfer Rolls for OA equipment such as rolls, paper feed rolls, fixing rolls, transport rolls; rolls for various equipment such as rolls for automation equipment; rolls for agricultural machinery such as rice hullers, swimwear, ski wear, cycling wear, leotards, lingerie , Foundation, clothing such as underwear; pantyhose Miscellaneous goods such as kings, socks, supporters, hats, gloves, power nets, bandages, etc .; tapes for fixing sanitary goods such as paper diapers and napkins; guts for tennis rackets; grounds for car seats; metal-coated threads for robot arms; non-woven fabrics; Color filters, optical filters such as light selective absorption filters; sports clothing applications; conveyor belts such as conveyor belts, resin conveyor belts, steeply inclined conveyors, cylindrical conveyor belts; power transmission belts such as V-belts and toothed belts Anti-vibration rubber for automobiles, railways, industrial machinery, and civil engineering; lining of various materials such as fenders and metals; decorative panels; packing for mobile phones, electrical appliances, remote controls, etc .; sealing Motion seals such as wood, waterproofing materials, oil seals, mechanical seals, molded packings, gland packings, etc. Seals for fixing O-rings, gaskets, etc .; gaskets for syringes; masks; sack; gloves; condoms; water pillows; nipples for baby bottles; cap containers; rainwares • diaphragms • rubber dams; Containers; Golf balls, soccer balls, etc .; Sports floors; Fence cushioning rubber; Chains; Paving blocks; Automobile boots; Weather strips; Architectural gaskets; Laminated glass; Water stop plate; Stretchable joint; Yarn rubber; Rubber strap; Hand rail; Grommet; Insulator; Stopper; Wiper blade; Joint; Damping rubber; Tennis racket, ski paw Grip portion and the like; sealant; electrical components; electronic components; tire; precision equipment, vibration-absorbing material of precision processing machinery; sports equipment; can be used on the seat, and the like; a grocery.

  The present invention can provide a novel conductive aromatic amide block copolymer resin composition excellent in conductivity, heat resistance and flexibility.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these Examples. The reagents used were commercially available unless otherwise noted.

  The equipment and methods used for evaluation and analysis are shown below.

-Measurement of number average molecular weight of aromatic amide block copolymer used in conductive aromatic amide block copolymer resin composition-
Conditions of column temperature of 40 ° C. and flow rate of 0.4 ml / min using a GPC apparatus (trade name HLC-8020, manufactured by Tosoh Corporation) equipped with a column (trade name: TSK-GEL GMHHR-H, manufactured by Tosoh Corporation) Below, it measured using 20 mmol / L lithium chloride-N-methyl-2-pyrrolidone solution for an eluent, and computed it in standard polystyrene conversion.

-Measurement of aromatic amide unit content of aromatic amide block copolymer used in conductive aromatic amide block copolymer resin composition-
Using a nuclear magnetic resonance measuring apparatus (manufactured by JEOL Ltd., trade name JNM-GSX270 type), ¹ H-NMR was measured in deuterated dimethyl sulfoxide at room temperature, and the peak of the methylene group of the aromatic group and the lactone unit was measured. Calculated from the intensity ratio.

-Measurement of melting point of aromatic amide block copolymer used in conductive aromatic amide block copolymer resin composition-
A differential scanning calorimeter (manufactured by Seiko Denshi Kogyo Co., Ltd., trade name DSC200) was used, and the temperature was measured at a temperature rising rate of 10 ° C./min and in the range of −100 to 300 ° C.

~ Type A durometer hardness of aromatic amide block copolymer used in conductive aromatic amide block copolymer resin composition ~
Type A durometer hardness (JIS K6253: 1997) was measured using a 2 mm thick sheet obtained by compression molding of an aromatic amide block copolymer.

~ Measurement of surface electrical resistance ~
For the conductive aromatic amide block copolymer resin compositions obtained in Examples and Comparative Examples, the surface electrical resistance value R (Ω) was determined from the following relational expression by the parallel terminal electrode method according to the JIS K6701 method.

R = dρv / wt = V / I
ρv is a volume resistivity (Ω · m) and is defined by ρv = V × w × t / (I × d). Here, V is the potential difference (V) after 1 minute of energization, w is the width (m) of the test piece, t is the thickness (m) of the test piece, I is the current (A) after 1 minute of energization, and d is This represents the distance (m) between the potential difference electrodes.

Synthesis Example 1 (Synthesis of dihydroxy aromatic amide compound)
In a 10 L four-necked flask equipped with a nitrogen inlet tube, a thermometer, and a stirring blade, 763 g (7.0 mol) of p-aminophenol and N-methyl-2-pyrrolidone (hereinafter referred to as NMP) are added under a nitrogen atmosphere. ) 2.1 L and 1.4 L of toluene were added and the temperature was raised to 50 ° C. to obtain a uniform solution. Separately, 710 g (3.5 mol) of terephthalic acid dichloride, 0.3 L of NMP and 1.4 L of toluene were added to a 3 L dropping funnel equipped with a nitrogen introduction tube to obtain a uniform solution. This solution was dropped into the previous solution over 30 minutes while maintaining 80 ° C., and further reacted at 80 ° C. for 2 hours.

  After cooling to room temperature, the solid content was collected by suction filtration and washed twice with 7 L of methanol to obtain N, N′-bis (4-hydroxyphenyl) -1,4-benzenedicarboxamide.

  Subsequently, 1045 g (3 of N, N′-bis (4-hydroxyphenyl) -1,4-benzenedicarboxamide was added to a 10 L four-necked flask equipped with a nitrogen introduction tube, a thermometer and a stirring blade under a nitrogen atmosphere. 0.0 mol), 555 g (6.3 mol) of ethylene carbonate, 0.95 g (9.0 mmol) of sodium carbonate as a catalyst, and 6.0 L of NMP were added and reacted at 180 ° C. for 3 hours. After cooling to room temperature, the solid content was collected by suction filtration, washed by stirring twice with NMP5L and then with 7.5L of methanol, and N, N′-bis (4- (2-hydroxyethoxy) phenyl) -1,4- 1110 g (yield 85%) of benzenedicarboxamide was obtained. Its structural formula is shown below. This compound is referred to as (a).

合成例２（ジヒドロキシ芳香族アミド化合物の合成）
窒素導入管、温度計および攪拌翼を備えた１０Ｌの４つ口フラスコに、窒素雰囲気下で４−アミノ−Ｎ−（２−ヒドロキシエチル）ベンズアミド１６００ｇ（８．９モル）、ＮＭＰ４．０Ｌを加え均一溶液を得た。別途に、窒素導入管を備えた３Ｌ滴下ロートに、イソフタル酸ジクロライド９０１ｇ（４．４モル）、ＮＭＰ２．０Ｌを加えて均一溶液とした。この溶液を先の溶液中に１時間かけて滴下し、さらに５０℃で２時間反応させた。室温まで冷却後、得られたスラリーをアセトン２５Ｌに投入し、吸引ろ過により白色固体を回収した。得られた固体をＮＭＰより再結晶し、Ｎ，Ｎ’−ビス（４−（２−ヒドロキシエチルカルバモイル）フェニル）−１，３−ベンゼンジカルボキサミド１８７３ｇ（収率８６％）を得た。その構造式を下記に示す。この化合物を（ｂ）と記す。

Synthesis Example 2 (Synthesis of dihydroxy aromatic amide compound)
To a 10 L four-necked flask equipped with a nitrogen introduction tube, a thermometer and a stirring blade, 1600 g (8.9 mol) of 4-amino-N- (2-hydroxyethyl) benzamide and 4.0 L of NMP were added under a nitrogen atmosphere. A homogeneous solution was obtained. Separately, 901 g (4.4 mol) of isophthalic acid dichloride and 2.0 L of NMP were added to a 3 L dropping funnel equipped with a nitrogen introduction tube to obtain a uniform solution. This solution was dropped into the previous solution over 1 hour, and further reacted at 50 ° C. for 2 hours. After cooling to room temperature, the obtained slurry was put into 25 L of acetone, and a white solid was recovered by suction filtration. The obtained solid was recrystallized from NMP to obtain 1873 g (yield 86%) of N, N′-bis (4- (2-hydroxyethylcarbamoyl) phenyl) -1,3-benzenedicarboxamide. Its structural formula is shown below. This compound is referred to as (b).

合成例３（芳香族アミドブロック共重合体の合成）
窒素導入管を備えた１５Ｌのオートクレーブに、窒素雰囲気下で化合物（ａ）８９６ｇ（２．１モル）、ε−カプロラクトン２３４２ｇ（２０．５モル）、ＮＭＰ５３８０ｇを仕込み、１８０℃に昇温した後、テトラブチルチタネート１．４ｇ（４．１ミリモル）を加え、１８０℃で２時間開環重合を行った。引き続いて、テレフタロイルビス（ε−カプロラクタム）７３１ｇ（２．１モル）を添加し、１８０℃で５時間反応させた。その後、内温を２５０℃まで昇温しながら、ＮＭＰ及び副生成物のε−カプロラクタムを減圧下で２時間かけて留去し、更に２５０℃で１時間反応させた。続いて、系内を加圧にした後、オートクレーブ下部から溶融状態のポリマーをストランドとして抜き出し、カッティングして芳香族アミドブロック共重合体のペレット３１００ｇを得た。

Synthesis Example 3 (Synthesis of aromatic amide block copolymer)
In a 15 L autoclave equipped with a nitrogen introduction tube, 896 g (2.1 mol) of compound (a), 2342 g (20.5 mol) of ε-caprolactone and 5380 g of NMP were charged in a nitrogen atmosphere, and the temperature was raised to 180 ° C. Tetrabutyl titanate (1.4 g, 4.1 mmol) was added, and ring-opening polymerization was performed at 180 ° C. for 2 hours. Subsequently, 731 g (2.1 mol) of terephthaloyl bis (ε-caprolactam) was added and reacted at 180 ° C. for 5 hours. Thereafter, while raising the internal temperature to 250 ° C., NMP and ε-caprolactam as a by-product were distilled off under reduced pressure over 2 hours, and further reacted at 250 ° C. for 1 hour. Subsequently, after the inside of the system was pressurized, the molten polymer was extracted as a strand from the lower part of the autoclave and cut to obtain 3100 g of aromatic amide block copolymer pellets.

  The obtained aromatic amide block copolymer had a number average molecular weight of 78000, a melting point of 225 ° C., a type A durometer hardness of 95, and an aromatic amide unit content of 29% by weight.

Synthesis Example 4 (Synthesis of aromatic amide block copolymer)
A 15 L autoclave equipped with a nitrogen introduction tube was charged with 979 g (2.0 mol) of compound (b), 3991 g (35.0 mol) of ε-caprolactone and 3668 g of NMP under a nitrogen atmosphere, and heated to 180 ° C. 2.4 g (7.0 mmol) of tetrabutyl titanate was added, and ring-opening polymerization was performed at 180 ° C. for 8 hours. Subsequently, 711 g (2.0 mol) of terephthaloyl bis (ε-caprolactam) was added and reacted at 180 ° C. for 5 hours. Thereafter, while raising the internal temperature to 230 ° C., NMP and ε-caprolactam as a by-product were distilled off under reduced pressure over 2 hours, and further reacted at 230 ° C. for 1 hour. Subsequently, after pressurizing the system, the melted polymer was extracted as a strand from the lower part of the autoclave and cut to obtain 4700 g of aromatic amide block copolymer pellets.

  The obtained aromatic amide block copolymer had a number average molecular weight of 75,000, a melting point of 188 ° C., a type A durometer hardness of 80, and an aromatic amide unit content of 23% by weight.

Synthesis Example 5 (Synthesis of aromatic amide block copolymer)
In a 3 L four-necked flask equipped with a nitrogen inlet tube, a thermometer, and a stirring blade, 87.3 g (0.2 mol) of compound (a) and 456.6 g (4.0 mol) of ε-caprolactone were added under a nitrogen atmosphere. Then, 500 mL of NMP was charged and the temperature was raised to 180 ° C., 0.14 g (0.4 mmol) of tetrabutyl titanate was added, and ring-opening polymerization was performed at 180 ° C. for 1 hour. After cooling to room temperature, a solution of 32 g (0.4 mol) of pyridine and 36.6 g (0.2 mol) of adipic acid dichloride in 60 mL of NMP was added, and the mixture was further reacted at room temperature for 15 hours. NMP1L was added to the solution after completion of the reaction, diluted and dissolved, and poured into 15L of methanol. The obtained solid content was washed twice with 5 L of methanol and then dried under reduced pressure at 80 ° C. to obtain an aromatic amide block copolymer.

  The obtained aromatic amide block copolymer had a number average molecular weight of 96,000, a melting point of 160 ° C., a type A durometer hardness of 85, and an aromatic amide unit content of 28% by weight.

Example 1
To a solution obtained by dissolving 20 parts by weight of the aromatic amide block copolymer obtained in Synthesis Example 3 in 80 parts by weight of N-methylpyrrolidone, 0.1 part by weight of CNTs was added and stirred for a whole day and night. A dispersed conductive aromatic amide block copolymer resin composition solution was obtained. This solution was allowed to stand at room temperature for one day, and the presence or absence of CNT precipitation was observed. However, CNT was dispersed in the solution, no precipitate was observed, and the jet black solution was stable. This solution was cast on a polyethylene terephthalate (PET) film, dried under nitrogen, and then heated from 50 ° C. to 150 ° C. to obtain a flexible black film having a thickness of 50 μm. Subsequently, the surface electrical resistance value and softening point of the obtained film were measured. The measurement results are shown in Table 1.

Example 2
To a solution obtained by dissolving 20 parts by weight of the aromatic amide block copolymer obtained in Synthesis Example 3 in 80 parts by weight of N-methylpyrrolidone, 0.2 part by weight of CNT is added and stirred for a whole day and night, so that the CNT is uniformly in the solution. A dispersed conductive aromatic amide block copolymer resin composition solution was obtained. This solution was allowed to stand at room temperature for one day, and the presence or absence of CNT precipitation was observed. However, CNT was dispersed in the solution, no precipitate was observed, and the jet black solution was stable. This solution was cast on a PET film, dried under nitrogen, and then heated from 50 ° C. to 150 ° C. to obtain a flexible black film with a thickness of 48 μm. Subsequently, the surface electrical resistance value and softening point of the obtained film were measured. The measurement results are shown in Table 1.

Example 3
1 part by weight of CNT was added to a solution in which 20 parts by weight of the aromatic amide block copolymer obtained in Synthesis Example 3 was dissolved in 80 parts by weight of N-methylpyrrolidone, and stirred for a whole day and night, so that the CNT was uniformly dispersed in the solution. A conductive aromatic amide block copolymer resin composition solution was obtained. This solution was allowed to stand at room temperature for one day, and the presence or absence of CNT precipitation was observed. However, CNT was dispersed in the solution, no precipitate was observed, and the jet black solution was stable. This solution was cast on a PET film, dried under nitrogen, and then heated from 50 ° C. to 150 ° C. to obtain a flexible black film with a thickness of 52 μm. Subsequently, the surface electrical resistance value and softening point of the obtained film were measured. The measurement results are shown in Table 1.

Example 4
2 parts by weight of CNT was added to a solution in which 20 parts by weight of the aromatic amide block copolymer obtained in Synthesis Example 3 was dissolved in 80 parts by weight of N-methylpyrrolidone and stirred for a whole day and night, so that the CNTs were uniformly dispersed in the solution. A conductive aromatic amide block copolymer resin composition solution was obtained. This solution was allowed to stand at room temperature for one day, and the presence or absence of CNT precipitation was observed. However, CNT was dispersed in the solution, no precipitate was observed, and the jet black solution was stable. This solution was cast on a PET film, dried under nitrogen, and then heated from 50 ° C. to 150 ° C. to obtain a flexible black film having a thickness of 51 μm. Subsequently, the surface electrical resistance value and softening point of the obtained film were measured. The measurement results are shown in Table 1.

Example 5
4 parts by weight of CNT was added to a solution in which 20 parts by weight of the aromatic amide block copolymer obtained in Synthesis Example 3 was dissolved in 80 parts by weight of N-methylpyrrolidone, and stirred for a whole day and night, so that CNT was uniformly dispersed in the solution. A conductive aromatic amide block copolymer resin composition solution was obtained. This solution was allowed to stand at room temperature for one day, and the presence or absence of CNT precipitation was observed. However, CNT was dispersed in the solution, no precipitate was observed, and the jet black solution was stable. This solution was cast on a PET film, dried under nitrogen, and then heated from 50 ° C. to 150 ° C. to obtain a flexible black film with a thickness of 49 μm. Subsequently, the surface electrical resistance value and softening point of the obtained film were measured. The measurement results are shown in Table 1.

Example 6-8
Example 1 except that the aromatic amide block copolymer obtained in Synthesis Example 3 was replaced with the aromatic amide block copolymer obtained in Synthesis Example 4 and the CNT content shown in Table 1 was used. In the same manner as above, a film of a conductive aromatic amide block copolymer resin composition was obtained. The surface electrical resistance value and softening point of the obtained film were measured. The measurement results are shown in Table 1.

Example 9-11
Example 1 except that the aromatic amide block copolymer obtained in Synthesis Example 3 was replaced with the aromatic amide block copolymer obtained in Synthesis Example 5 and the CNT content shown in Table 1 was used. In the same manner as above, a film of a conductive aromatic amide block copolymer resin composition was obtained. The surface electrical resistance value and softening point of the obtained film were measured. The measurement results are shown in Table 1.

Comparative Example 1
2 parts by weight of CNT was added to a solution in which 20 parts by weight of a polyester elastomer (Toyobo Co., Ltd .: Perprene P-70B) was dissolved in 80 parts by weight of methylene chloride, and stirred for 24 hours. When this solution was allowed to stand at room temperature for one day, the color of the solution became colorless and most of the CNTs precipitated, so that a composition in which CNTs were uniformly dispersed could not be obtained.

Comparative Example 2
2 parts by weight of CNT was added to a solution in which 20 parts by weight of a polyamide elastomer (Toray Industries, Inc .: Pebax 4033) was dissolved in 80 parts by weight of methylene chloride, and stirred overnight. When this solution was allowed to stand at room temperature for one day, the color of the solution became colorless and most of the CNTs precipitated, so that a composition in which CNTs were uniformly dispersed could not be obtained.

Comparative Example 3
A solution prepared by dissolving 20 parts by weight of the aromatic amide block copolymer obtained in Synthesis Example 3 in 80 parts by weight of N-methylpyrrolidone was cast on a polyethylene terephthalate (PET) film, dried under nitrogen, and then from 50 ° C. By heating to 150 ° C., a light yellow film having a flexible thickness of 51 μm was obtained. Subsequently, the surface electrical resistance value and softening point of the obtained film were measured. The measurement results are shown in Table 1.

Claims (4)

One or more kinds selected from the group consisting of an aromatic amide unit represented by the following general formula (1), polyester, aliphatic poly (oxyalkylene), polycarbonate, polyolefin, polyorganosiloxane, polydiene or a copolymer thereof. An aromatic amide block copolymer composed of units and a conductive aromatic amide block copolymer resin composition composed of carbon nanotubes.

(1)
(Here, R ¹ and R ² each independently represent a divalent oxyalkylene group having 1 to 20 carbon atoms, an alkylenecarbamoyl group, or an arylenecarbamoyl group.) The conductive aromatic amide block copolymer resin composition according to claim 1, wherein the aromatic amide block copolymer comprises an aromatic amide unit represented by the general formula (1) and a polyester. . The conductive aromatic amide according to claim 1 or 2, wherein the aromatic amide block copolymer comprises an aromatic amide unit represented by the general formula (1) and poly (ε-caprolactone). Block copolymer resin composition. The conductive aromatic amide block copolymer according to any one of claims 1 to 3, wherein 0.01 to 20 parts by weight of carbon nanotubes are blended with 100 parts by weight of the aromatic amide block copolymer. Polymer resin composition.