JP5901893B2 - Conductive agent and conductive resin composition - Google Patents

Description

  The present invention relates to a conductive agent and a conductive resin composition. More specifically, a carbon nanotube-containing conductive agent that imparts excellent conductivity to the molded product without impairing the excellent mechanical properties and good appearance of the thermoplastic resin molded product, and the conductive agent and the thermoplastic resin. It is related with the conductive resin composition formed.

  Conventionally, as a method of imparting conductivity to a highly insulating thermoplastic resin, (1) a method of kneading a low molecular weight surfactant or a polymer type antistatic agent, and (2) a metal filler or conductive carbon black The method of kneading is known. However, a molded product obtained by molding the resin composition obtained by the method (1) is excellent in mechanical properties and appearance, but generally has a problem of low conductivity. In addition, although the molded product by the method (2) is excellent in conductivity, a large amount of addition of a metal filler or the like is required, so that the moldability deteriorates due to the decrease in fluidity of the resin composition, and the impact resistance There was a problem that decreased. Therefore, as a method for solving these problems, (3) a method of kneading carbon nanotubes into a thermoplastic resin (for example, see Patent Document 1) has been proposed.

JP 2003-306607 A JP 2006-143532 A JP 2008-31461 A

  However, Patent Document 1 discloses a technique for easily dispersing carbon nanotubes in a resin by plasma treatment, and Patent Document 2 discloses a technique for dispersing carbon nanotubes in a resin by using a special crusher. In addition, the resin composition obtained has poor flowability and has a large problem in moldability. Patent Document 3 proposes an antistatic agent comprising a mixture of a carbon nanotube and a dispersant having a conjugated double bond and a hydrophilic group-containing polymer. However, this method cannot be obtained by kneading the antistatic agent into a resin. Although the resin composition obtained has excellent moldability and mechanical properties, there is a problem that satisfactory conductivity cannot be imparted.

  An object of the present invention is to provide a conductive agent that gives sufficient conductivity to the molded product without impairing the excellent moldability of the thermoplastic resin, the excellent mechanical properties of the resulting molded product, the good appearance, and the like. An object of the present invention is to provide a conductive resin composition containing an agent and a thermoplastic resin.

  As a result of intensive studies to solve the above problems, the present inventor has reached the present invention. That is, the present invention provides a carbon nanotube (A) having a reactive functional group (a), and a block polymer (B) composed of a hydrophobic polymer (b1) block and a hydrophilic polymer (b2) block. It is the electrically conductive agent (X) formed.

The conductive resin composition containing the conductive agent of the present invention has the following effects.
(1) Excellent formability.
(2) The molded product obtained has a high degree of electrical conductivity that has not been obtained before, and is excellent in appearance and mechanical properties.

[Conducting agent (X)]
The conductive agent (X) of the present invention comprises a carbon nanotube (A) having a reactive functional group (a), and a block polymer comprising a block of a hydrophobic polymer (b1) and a block of a hydrophilic polymer (b2) (B) is contained.

[Carbon nanotube (A)]
The carbon nanotube constituting the carbon nanotube (A) in the present invention has a structure in which a graphite layer composed of carbon atoms is a single-layer or multilayer coaxial tube. (A) includes a single-layer structure (single-walled carbon nanotube, hereinafter abbreviated as SWNT), a double-layer structure (double-walled carbon nanotube, hereinafter abbreviated as DWNT), and a multilayer structure (multi-walled carbon nanotube, hereinafter In the present invention, these can be used alone or in combination.
The diameter of the carbon nanotube is about 0.4 to 5 nm in the case of SWNT, about 10 to 50 nm in the case of DWNT or MWNT, and in some cases it is known that the diameter exceeds 100 nm. From the viewpoint, it is preferably 0.4 to 200 nm, and more preferably 1 to 100 nm. Regarding the numerical ranges herein and below, among the viewpoints shown before and after “and”, the viewpoint shown above prescribes the lower limit of the numerical range, and the viewpoint shown below prescribes the upper limit of the numerical range. It means to be there.
In addition, the aspect ratio (length / diameter ratio) of the carbon nanotube is preferably 5 to 1,000, more preferably 10 to 1,000 from the same viewpoint.
Carbon nanotubes can be produced by known methods such as arc discharge method, laser ablation method, chemical vapor deposition method, thermal decomposition method, method using plasma discharge, etc. It may be obtained by a method.

(A) in the present invention is a carbon nanotube having a reactive functional group (a). Examples of (a) include alkenyl groups [carbon number (hereinafter abbreviated as C) 2 to 30], organic acid groups (carboxyl groups, carboxylic anhydride groups, etc.), hydroxyl groups, amino groups, epoxy groups, and the like.
As a modification method for introducing (a) into a carbon nanotube, for example, the Diels-Alder reaction [J. Am. Chem. Soc, 114, 7301 (1992), etc.], hydroxylation reaction [described in J. Chem. Soc., Chem. Commun., 1791 (1992), etc.], epoxidation reaction [Science, 252, 548 (1991). , J. Am. Chem. Soc, 114, 1103 (1992), etc.] or addition reaction of amine [described in Angew. Chem. Int. Ed. Engl., 30, 1309 (1991), etc.].
Of the above (a), a carboxyl group and a hydroxyl group are preferable from the viewpoint of dispersibility of (A) in the block polymer (B) described later and ease of production, and a carboxyl group is more preferable. .
In the present invention, the carbon nanotube (A) having a reactive functional group (a)
It may be called a functional group-modified carbon nanotube (for example, carboxyl group-modified carbon nanotube).

  In the present invention, the amount of the reactive functional group (a) in (A) can be analyzed by an acid value, a hydroxyl value, etc. by ordinary acid-alkali titration, and (a) is a hydrophobic polymer (b1) described later. From the viewpoint of the dispersibility and conductivity of (A) in (B) by reacting with hydrophilic polymer (b2) and / or block polymer (B), the acid value of (A) is preferably 0.1-100 (a unit is mgKOH / g. Below, only a numerical value is described), More preferably, it is 1-50. From the same viewpoint, the hydroxyl value of (A) is preferably 0.1 to 100, more preferably 1 to 50.

[Hydrophobic polymer (b1)]
The hydrophobic polymer (b1) in the present invention includes at least one hydrophobic polymer selected from the group consisting of polyolefin (b11), polyamide (b12), polyamideimide (b13) and polyester (b14). Here, the hydrophobic polymer means a polymer having a volume resistivity value exceeding 1 × 10 ¹¹ Ω · cm.

As the polyolefin (b11), a polyolefin (b111) having carbonyl groups (preferably carboxyl groups, the same shall apply hereinafter) at both ends of the polymer, a polyolefin (112) having hydroxyl groups at both ends of the polymer, and an amino group as a polymer The polyolefin (b113) having both ends thereof and the polyolefin (b114) having isocyanate groups at both ends of the polymer can be used.
Further, a polyolefin having a carbonyl group at one end of the polymer (b115), a polyolefin having a hydroxyl group at one end of the polymer (b116), a polyolefin having an amino group at one end of the polymer (b117), and an isocyanate group having a fragment of the polymer Polyolefin (b118) having a terminal can be used.
Among these, polyolefins (b111) and (b115) having a carbonyl group are preferable because of easy modification.

(B111) is a carbonyl group at both ends of the polyolefin (b110) having as a main component (preferably a content of 50% or more, more preferably 75% or more, particularly preferably 80 to 100%) of a polyolefin that can be modified at both ends. A group into which a group is introduced is used.
As (b112), those in which hydroxyl groups are introduced at both ends of (b110) are used.
As (b113), those in which amino groups are introduced at both ends of (b110) are used.
As (b114), those obtained by introducing isocyanate groups at both ends of (b110) are used.

As (b115), one end of a polyolefin (b1100) having a main component (preferably a content of 50% or more, more preferably 75% or more, particularly preferably 80 to 100%) of a polyolefin that can be modified at one end is bonded to a carbonyl at one end. A group into which a group is introduced is used.
As (b116), one obtained by introducing a hydroxyl group at one end of (b1100) is used.
As (b117), an amino group introduced at one end of (b1100) is used.
As (b118), one obtained by introducing an isocyanate group at one end of (b1100) is used.

(B110) means (co) polymerization (polymerization or copolymerization) of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. )) And degraded polyolefin {high molecular weight polyolefin [preferably number average molecular weight [hereinafter abbreviated as Mn]. The measurement is based on a gel permeation chromatography (GPC) method described later. 50,000-150,000] mechanically, thermally or chemically degraded} (degradation method).
From the viewpoint of easy modification and availability of introduction of a carbonyl group, a hydroxyl group, an amino group or an isocyanate group, a degraded polyolefin, particularly a thermally degraded polyolefin is preferred.

Examples of the thermally degraded polyolefin include those that have been thermally degraded by heating high molecular weight polyolefin in an inert gas (such as nitrogen) (usually at 300 to 450 ° C. for 0.5 to 10 hours). 3-62804).
Examples of the high molecular weight polyolefin used in the thermal degradation method include (co) polymers of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. Can be used. As the C2-30 olefin, the same as those used for the production of the polyolefin (polymerization method) described later can be used, and among these, ethylene, propylene, C4-12 α-olefin and two or more of these are preferable. More preferred are ethylene, propylene, C4-10 α-olefins and mixtures of two or more thereof, particularly preferred are ethylene, propylene, and mixtures of two or more thereof.

Examples of the C2-30 olefin used for the production of the polyolefin (polymerization method) include ethylene, propylene, C4-30 (preferably 4-12, more preferably 4-10) α-olefin and C4-30. A diene of (preferably 4-18, more preferably 4-8) is used.
Examples of the α-olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene.
Examples of the diene include butadiene, isoprene, cyclopentadiene, 1,11-dodecadiene, and the like.
Of these, ethylene, propylene, C4-12 α-olefin, butadiene and isoprene are preferred, ethylene, propylene, C4-10 α-olefin and butadiene are more preferred, and ethylene, propylene and butadiene are particularly preferred. is there.

Mn of the polyolefin (b110) mainly composed of a polyolefin which can be modified at both ends is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000. is there. When Mn is within this range, the conductivity is further improved.
The amount of double bonds in (b110) is preferably 1 to 40, more preferably 2 to 30, and particularly preferably 4 to 20 per 1,000 carbon atoms. When the amount of the double bond is within this range, the conductivity is further improved.
The average number of double bonds per molecule is preferably 1.1 to 5.0, more preferably 1.3 to 3.0, particularly preferably 1.5 to 2.5, most preferably 1.8 to 2.2. When the average number of double bonds is within this range, it becomes easier to take a repeating structure, and the conductivity is further improved.
With low molecular weight polyolefins by thermal degradation, low molecular weight polyolefins with an average terminal double bond amount of 1.5 to 2 per molecule can be easily obtained with Mn in the range of 800 to 6,000 [Katsuhide Murata Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].

(B1100) can be obtained in the same manner as (b110), and Mn of (b1100) is usually 2,000 to 50,000, preferably 2,500 to 30,000, more preferably 3,000 to 3,000. 20,000.
(B1100) has 0.3 to 20, preferably 0.5 to 15, more preferably 0.7 to 10 double bonds per 1,000 carbon atoms. From the viewpoint of easy modification, low molecular weight polyolefins (particularly polyethylene and / or polypropylene having Mn of 2,000 to 20,000) by thermal degradation are preferred.
In the low molecular weight polyolefin by the thermal degradation method, those having an average terminal double bond amount of 1 to 1.5 per molecule are obtained with Mn in the range of 5,000 to 30,000.

  (B110) and (b1100) are usually obtained as a mixture thereof, but these mixtures may be used as they are, or may be used after purification and separation. From the viewpoint of production cost and the like, it is preferably used as a mixture.

The measurement conditions for Mn are as follows. In the present invention, Mn is measured under the same conditions.
Equipment: High-temperature GPC [Model name “Alliance GPCV2000”, Waters
Manufactured by]
Column: PLgel 10 μL MIXED-B [manufactured by Polymer Laboratories, Inc.]
PLgel 10 μL Guard [manufactured by Polymer Laboratories, Inc.,
Guard column]
Solvent: Orthodichlorobenzene Reference substance: Polystyrene sample concentration: 3 mg / ml
Column temperature: 135 ° C

  Hereinafter, (b111) to (b114) having a carbonyl group, a hydroxyl group, an amino group or an isocyanate group at both ends of the polyolefin (b110) will be described. However, these groups are present at one end of the polyolefin (b1100) (b115). ˜ (b118) can be obtained in the same manner as (b111) ˜ (b114) by replacing (b110) with (b1100).

  As the polyolefin (b111) having carbonyl groups at both ends of the polymer, the end of (b110) is α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, its C1-4 alkyl) This means an ester or an anhydride thereof. The same shall apply hereinafter.) Polyolefin (b111-1) having a structure modified with (b111-1) and polyolefin having a structure obtained by secondary modification of (b111-1) with a lactam or an aminocarboxylic acid (b111- 2), a polyolefin (b111-3) having a structure obtained by modifying (b110) by oxidation or hydroformylation, and a polyolefin (b111-4) having a structure obtained by secondary modification of (b111-3) with a lactam or aminocarboxylic acid ) And a mixture of two or more of these.

(B111-1) can be obtained by modifying (b110) with an α, β-unsaturated carboxylic acid (anhydride).
As α, β-unsaturated carboxylic acid (anhydride) used for modification, monocarboxylic acid, dicarboxylic acid, alkyl (C1-4) ester thereof and anhydride thereof can be used, for example, (meth) acrylic acid (Means acrylic acid or methacrylic acid; the same shall apply hereinafter), methyl (meth) acrylate, butyl (meth) acrylate, maleic acid (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride) , Diethyl itaconate and citraconic acid (anhydride).
Among these, preferred are dicarboxylic acids, their alkyl esters and their anhydrides, more preferred are maleic acid (anhydride) and fumaric acid, and particularly preferred is maleic acid (anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used for the modification is preferably 0.5 to 40%, more preferably 1 to 30%, particularly preferably 2 based on the weight of the polyolefin (b110). ~ 20%. When the amount of α, β-unsaturated carboxylic acid (anhydride) is within this range, it becomes easier to take a repeating structure, and the conductivity is further improved.
The modification with α, β-unsaturated carboxylic acid (anhydride) can be carried out by various methods. For example, the terminal double bond of (b110) can be modified by either solution method or melt method. , Β-unsaturated carboxylic acid (anhydride) can be thermally added (ene reaction). The temperature at which (b110) is reacted with the α, β-unsaturated carboxylic acid (anhydride) is usually 170 to 230 ° C.

(B111-2) can be obtained by secondarily modifying (b111-1) with a lactam or an aminocarboxylic acid.
As the lactam used for the secondary modification, a C6-12 (preferably 6-8, more preferably 6) lactam or the like can be used, and examples thereof include caprolactam, enantolactam, laurolactam, and undecanolactam.
As the aminocarboxylic acid, C2-12 (preferably 4-12, more preferably 6-12) aminocarboxylic acid and the like can be used. For example, amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.) ), Ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Of these, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and caprolactam, laurolactam, ω-aminocaprylic acid, 11-amino are more preferred. Undecanoic acid and 12-aminododecanoic acid, particularly preferably caprolactam and 12-aminododecanoic acid.
The amount of lactam or aminocarboxylic acid used for secondary modification is preferably 0.1 to 50, more preferably 0.3 to 20 per carboxyl group of α, β unsaturated carboxylic acid (anhydride). The number is particularly preferably 0.5 to 10, most preferably 1 to 2. When this amount is within this range, it becomes easier to take a repeating structure, and the conductivity is further improved.

(B111-3) can be obtained by introducing (b110) a carbonyl group by oxidation with oxygen and / or ozone or hydroformylation with an oxo method.
The introduction of the carbonyl group by the oxidation method can be performed by a known method, for example, the method described in US Pat. No. 3,692,877. Introduction of a carbonyl group by hydroformylation can be carried out by a known method, for example, see Macromolecules, Vol. 31, 5, 943 page.
(B111-4) can be obtained by secondarily modifying (b111-3) with a lactam or an aminocarboxylic acid.
The lactam and aminocarboxylic acid and preferred ranges thereof are the same as those which can be used in the production of (b111-2). The amount of lactam and aminocarboxylic acid used is the same.

Mn of (b111) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b2) described later. 500 to 10,000.
The acid value of (b111) is preferably 4 to 280 (unit is mg KOH / g. In the following, only numerical values are described), more preferably 4 to 100, from the viewpoint of reactivity with (b2). Especially preferably, it is 5-50.

As the polyolefin (b112) having a hydroxyl group at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying the polyolefin (b111) having the carbonyl group at both ends of the polymer with hydroxylamine and a mixture of two or more of these are used. it can.
Hydroxylamines that can be used for modification include C2-10 hydroxylamines such as 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-aminobutanol, 5-aminopentanol, 6-amino. Examples include hexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol.
Of these, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-aminohexanol are more preferable, 2-aminoethanol and 4-aminobutanol are particularly preferable. Is 2-aminoethanol.

The amount of hydroxylamine used for modification is preferably from 0.1 to 2, more preferably from 0.3 to 1.5, in particular, per residue of α, β-unsaturated carboxylic acid (anhydride). The number is preferably 0.5 to 1.2, and most preferably 1. When the amount of hydroxylamine is within this range, it becomes easier to take a repeating structure, and the conductivity is further improved.
Mn of (b112) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b2) described later. 500 to 10,000.
The hydroxyl value of (b112) is preferably 4 to 280 (mg KOH / g. In the following, only numerical values are described), more preferably 4 to 100, particularly from the viewpoint of reactivity with (b2). Preferably it is 5-50.

The polyolefin (b113) having amino groups at both ends of the polymer includes a polyolefin having an amino group obtained by modifying the polyolefin (b111) having the carbonyl group at both ends of the polymer with a diamine (Q1), and two or more kinds thereof. Mixtures can be used.
As diamine (Q1) used for this modification | denaturation, C2-12 diamine etc. can be used, For example, ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, etc. are mentioned.
Among these, ethylenediamine, hexamethylenediamine, heptamethylenediamine and octamethylenediamine are preferable, ethylenediamine and hexamethylenediamine are more preferable, and ethylenediamine is particularly preferable.

The amount of diamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, and still more preferably, per residue of α, β unsaturated carboxylic acid (anhydride). 0.5 to 1.2, particularly preferably 1. When the amount of diamine is within this range, it becomes easier to take a repeating structure, and the conductivity is further improved.
In actual production, in order to prevent polyamide (imide) formation, 2 to 1,000, more preferably 5 to 800, per residue of α, β unsaturated carboxylic acid (anhydride) are used. Particularly preferably, 10 to 500 diamines are used, and it is preferable to remove unreacted excess diamine under reduced pressure (usually 120 ° C. to 230 ° C.).

Mn of (b113) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b2) described later. 500 to 10,000.
In addition, the amine value of (b113) is preferably 4 to 280 (unit is mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (b2), more preferably 4 to 100, Especially preferably, it is 5-50.

  The polyolefin (b114) having an isocyanate group at both ends includes a polyolefin having an isocyanate group obtained by modifying (b112) with poly (2-3 or more) isocyanate (hereinafter abbreviated as PI) and a mixture of two or more of these. Can be used. As PI, C (excluding C in the NCO group, the same shall apply hereinafter) 6 to 20 aromatic PI, C2 to 18 aliphatic PI, C4 to 15 alicyclic PI, and C8 to 15 araliphatic PI , Modified products of these PIs, and mixtures of two or more thereof.

  Specific examples of the aromatic PI include 1,3- and / or 1,4-phenylene diisocyanate (diisocyanate is hereinafter abbreviated as DI), 2,4- and / or 2,6-tolylene DI (TDI), crude TDI, 2,4′- and / or 4,4′-diphenylmethane DI (MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene DI and the like can be mentioned.

  Specific examples of the aliphatic PI include ethylene DI, tetramethylene DI, hexamethylene DI (HDI), dodecamethylene DI, 2,2,4-trimethylhexamethylene DI, lysine DI, 2,6-diisocyanatomethyl carbonate. Examples include proate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate.

  Specific examples of the alicyclic PI include isophorone DI (IPDI), dicyclohexylmethane-4,4′-DI (hydrogenated MDI), cyclohexylene DI, methylcyclohexylene DI (hydrogenated TDI), bis (2- And isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5- and / or 2,6-norbornane DI.

  Specific examples of the araliphatic PI include m- and / or p-xylylene DI (XDI), α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI), and the like.

Examples of the modified PI include urethane-modified, urea-modified, carbodiimide-modified, uretdione-modified, and the like.
Of these, TDI, MDI and HDI are preferred, and HDI is more preferred.

The reaction between (b112) and PI can be carried out in the same manner as a normal urethanization reaction.
The equivalent ratio (NCO / OH ratio) between PI and (b112) in forming the isocyanate-modified polyolefin is usually 1.8 / 1 to 3/1, preferably 2/1.
In order to accelerate the reaction, a catalyst usually used for polyurethane may be used if necessary. Examples of such catalysts include metal catalysts such as tin catalysts [dibutyltin dilaurate, stannous octoate, etc.], lead catalysts [lead 2-ethylhexanoate, lead octenoate, etc.], other metal catalysts [metal naphthenates] (Cobalt naphthenate, etc.), phenylmercuric propionate, etc.]; amine catalysts such as triethylenediamine, diazabicycloalkenes [1,8-diazabicyclo [5,4,0] undecene-7 [DBU (San Apro Corporation) Manufactured, registered trademark)], etc.], dialkylaminoalkylamine [dimethylaminoethylamine, dimethylaminooctylamine, etc.], heterocyclic aminoalkylamine [2- (1-aziridinyl) ethylamine, 4- (1-piperidinyl) -2 -Hexylamine etc.] carbonates and organic acid salts (eg formate), N-methyl Beauty - ethylmorpholine, triethylamine, diethyl - and dimethylethanolamine; and use of two or more types of system thereof.
The amount of these catalysts used is usually 3% or less, preferably 0.001 to 2%, based on the total weight of PI and (b112).

  Mn of (b114) is preferably 800 to 25,000, more preferably 1,000 to 20,000, and particularly preferably 2, from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b2) described later. 500 to 10,000.

Among the hydrophobic polymers (b1), examples of the polyamide (b12) include those obtained by ring-opening polymerization or polycondensation of amide-forming monomers.
Amide-forming monomers include lactam (b121), aminocarboxylic acid (b122), and diamine (b123) / dicarboxylic acid (b124).
The lactam (b121) includes C6-12, such as caprolactam, enantolactam, laurolactam, and undecanolactam.
Examples of the ring-opening polymer (b121) include nylon 4, -5, -6, -8, and -12.

As aminocarboxylic acid (b122), C6-12, for example, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, 12 -Aminododecanoic acid and mixtures thereof.
Examples of the self-polycondensate of (b122) include nylon 7 by polycondensation of ω-aminoenanthic acid, nylon 11 by polycondensation of ω-aminoundecanoic acid, and nylon 12 by polycondensation of 12-aminododecanoic acid. .

Diamine (b123) includes C2-40, such as aliphatic, alicyclic and aromatic (aliphatic) diamines, and mixtures thereof.
Aliphatic diamines include C2-40, such as ethylene diamine, propylene diamine, hexamethylene diamine, decamethylene diamine, 1,12-dodecane diamine, 1,18-octadecane diamine and 1,20-eicosane diamine.
Alicyclic diamines include C5-40, such as 1,3- and 1,4-cyclohexanediamine, isophorone diamine, 4,4'-diaminocyclohexylmethane and 2,2-bis (4-aminocyclohexyl) propane. It is done.
Examples of araliphatic diamines include C7-20, such as (para or meta) xylylenediamine, bis (aminoethyl) benzene, bis (aminopropyl) benzene and bis (aminobutyl) benzene.
Aromatic diamines include C6-40, such as p-phenylenediamine, 2,4- and 2,6-toluylenediamine and 2,2-bis (4,4'-diaminophenyl) propane.

  Examples of the dicarboxylic acid (b124) include C2-40 dicarboxylic acids such as aliphatic dicarboxylic acids, aromatic ring-containing dicarboxylic acids, alicyclic dicarboxylic acids, derivatives of these dicarboxylic acids [for example, acid anhydrides, lower (C1-4 ) Alkyl esters and dicarboxylates [alkali metal (eg, lithium, sodium and potassium) salts]] and mixtures of two or more thereof.

Examples of the aliphatic dicarboxylic acid include C2 to 40 (preferably 4 to 20, more preferably 6 to 12 from the viewpoint of conductivity), such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, and sebacin. Examples include acids, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid and itaconic acid.
Examples of the aromatic ring-containing dicarboxylic acid include C8-40 (preferably 8 to 16, more preferably 8-14 from the viewpoint of conductivity), such as ortho-, iso- and terephthalic acid, 2,6- and -2,7. -Naphthalenedicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid, tolylene dicarboxylic acid, xylylene dicarboxylic acid and alkali metal 5-sulfoisophthalic acid (same as above) salts.
Examples of the alicyclic dicarboxylic acid include C5-40 (preferably 6-18, more preferably 8-14 from the viewpoint of conductivity), such as cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, dicyclohexyl. -4,4'-dicarboxylic acid and camphoric acid. Of these, aliphatic dicarboxylic acids and aromatic ring-containing dicarboxylic acids are preferable from the viewpoint of conductivity, and adipic acid, sebacic acid, terephthalic acid, isophthalic acid, and sodium 3-sulfoisophthalate are more preferable.
Among the dicarboxylic acid derivatives, examples of the acid anhydride include anhydrides of the above dicarboxylic acids, such as maleic anhydride, itaconic anhydride and phthalic anhydride; examples of lower (C1-4) alkyl esters include lower alkyl esters of the above dicarboxylic acids, such as Mention is made of dimethyl adipate and ortho-, iso- and dimethyl terephthalate.

Polycondensates of diamines and dicarboxylic acids include nylon 66, -610, -69 or -612, respectively, and tetramethylene by polycondensation of hexamethylenediamine and adipic acid, sebacic acid, azelaic acid or dodecanedioic acid. Mention may be made of nylon 46 or MXD6 by polycondensation of diamine or metaxylylenediamine and adipic acid.
Examples of the copolymer nylon include nylon 6/66 (adipic acid / hexamethylenediamine nylon salt and caprolactam copolymer) and nylon 6/12 (12-aminododecanoic acid and caprolactam copolymer). .

  Among the amide-forming monomers, caprolactam, 12-aminododecanoic acid, adipic acid / metaxylylenediamine and adipic acid / hexamethylenediamine are more preferable, and caprolactam is more preferable from the viewpoint of conductivity.

The production method of the polyamide (b12) is one or more of the dicarboxylic acid (b124) (C2-40, preferably 4-20) or the diamine (b123) (C2-40, preferably 4-20). May be used as a molecular weight modifier, and in the presence thereof, the amide-forming monomer may be subjected to ring-opening polymerization or polycondensation.
Examples of the C2-40 diamine include those exemplified as the above (b123). Of these, aliphatic diamines are preferable from the viewpoint of reactivity with other amide-forming monomers, and hexamethylenediamine is more preferable. And decamethylenediamine.
Examples of the C2-40 dicarboxylic acid include those exemplified as the above (b124). Among these, aliphatic dicarboxylic acids and aromatic ring-containing dicarboxylic acids are preferable from the viewpoint of reactivity with other amide-forming monomers. Acids, more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate.

  The amount of the molecular weight modifier used is based on the total weight of the amide-forming monomer and the molecular weight modifier, and the lower limit is from the viewpoint of the conductivity of the molded article described later, and the upper limit is preferably from the viewpoint of the heat resistance of the molded article. It is 2 to 80%, more preferably 4 to 75%.

  Mn of the polyamide (b12) is preferably 200 to 5,000, more preferably 500 to 4,000 from the viewpoints of moldability and production of a conductive agent.

  Among the hydrophobic polymers (b1), the polyamide-imide (b13) includes the amide-forming monomer and a trivalent or tetravalent aromatic polymer that can form at least one imide ring with the amide-forming monomer. Carboxylic acid or its anhydride [hereinafter abbreviated as aromatic polycarboxylic acid (anhydride). (Hereinafter sometimes referred to as an amidoimide-forming monomer), and mixtures thereof. The diamine (b123) and the dicarboxylic acid (b124) can also be used as a molecular weight modifier during polymerization.

  Examples of the aromatic polycarboxylic acid (anhydride) include monocyclic (C9-12) and polycyclic (C13-20) carboxylic acids such as trivalent [monocyclic (trimellitic acid, etc.), polycyclic (1,2 , 5- and 2,6,7-naphthalenetricarboxylic acid, 3,3 ′, 4-biphenyltricarboxylic acid, benzophenone-3,3 ′, 4-tricarboxylic acid, diphenylsulfone-3,3 ′, 4-tricarboxylic acid, Diphenyl ether-3,3 ′, 4-tricarboxylic acid and the like, and their anhydrides] carboxylic acid; and tetravalent [monocyclic (pyromellitic acid etc.), polycyclic (biphenyl-2,2 ′, 3,3 ′] -Tetracarboxylic acid, benzophenone-2,2 ', 3,3'-tetracarboxylic acid, diphenylsulfone-2,2', 3,3'-tetracarboxylic acid, diphenylether-2,2 ', 3,3 - tetracarboxylic acid, etc.), and these anhydrides], and carboxylic acids.

As a method for producing the polyamideimide (b13), as in the case of the polyamide (b12), one or more of the dicarboxylic acid (C2-40) or the diamine (C2-40) is used as a molecular weight modifier, Examples thereof include a method of ring-opening polymerization or polycondensation of the amidoimide-forming monomer in the presence thereof. Preferred among the dicarboxylic acid and diamine are the same as in the case of (b12).
The amount of the molecular weight modifier used is based on the total weight of the amide imide-forming monomer and the molecular weight modifier, and the lower limit is from the viewpoint of the conductivity of the molded article described later, and the upper limit is preferably from the viewpoint of the heat resistance of the molded article. It is 2 to 80%, more preferably 4 to 75%.

  Mn of (b13) is preferably 200 to 5,000, more preferably 500 to 4,000 from the viewpoints of moldability and production of a conductive agent.

Among the hydrophobic polymers (b1), examples of the polyester (b14) include those obtained by subjecting an ester-forming monomer to ring-opening polymerization, polycondensation or transesterification by a conventional method.
Examples of the ester-forming monomer include lactones, hydroxycarboxylic acids, combinations of the diol (b0) and the dicarboxylic acid (b124), and mixtures thereof.

  Examples of the lactone include C4-20, such as γ-butyrolactone, γ-valerolactone, ε-caprolactone, γ-pimerolactone, γ-caprolactone, γ-decanolactone, enanthlactone, laurolactone, undecanolactone, and eicosanolactone. Is mentioned.

  Examples of the hydroxycarboxylic acid include C2-20, such as hydroxyacetic acid, lactic acid, ω-hydroxycaproic acid, ω-hydroxyenanthic acid, ω-hydroxycaprylic acid, ω-hydroxypergonic acid, ω-hydroxycapric acid, 11- Examples include hydroxyundecanoic acid, 12-hydroxydodecanoic acid and 20-hydroxyeicosanoic acid, tropic acid, and benzylic acid.

  As a method for producing the polyester (b14), one or more of the diol (b0) or the dicarboxylic acid (b124) is used as a molecular weight modifier, and the ester-forming monomer is used in the presence of the conventional method. Can be used for ring-opening polymerization, polycondensation or transesterification.

  Mn of (b14) is preferably 200 to 5,000, more preferably 500 to 4,000 from the viewpoints of moldability and production of a conductive agent.

[Hydrophilic polymer (b2)]
Examples of the hydrophilic polymer (b2) in the present invention include at least one selected from the group consisting of a polyether (b21), a cationic polymer (b22), and an anionic polymer (b23). Here, the hydrophilic polymer in the present invention means a polymer having a volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm.

Examples of the polyether (b21) include polyether diol (b211), polyether diamine (b212), and modified products thereof (b213).
Examples of the cationic polymer (b22) include cationic polymers having 2 to 80, preferably 3 to 60, cationic groups (c2) separated in the nonionic molecular chain (c1) in the molecule. .
As the anionic polymer (b23), the dicarboxylic acid (e1) having a sulfo group and the diol (b0) or the polyether (b21) are essential structural units, and 2 to 80, preferably 3 to An anionic polymer having 60 sulfo groups may be mentioned.

The polyether (b21) will be described.
Of (b21), the polyether diol (b211) has a structure obtained by addition reaction of alkylene oxide (hereinafter abbreviated as AO) to the diol (b0). The general formula: H- (OA ¹ ) those represented by ^{_{m -O-E 1 -O- (A}} 1 O) m '-H and the like.
In the formula, E ¹ is a residue obtained by removing a hydroxyl group from the diol (b0), A ¹ is an alkylene group having 2 to 4 carbon atoms (hereinafter abbreviated as C), and m and m ′ are per hydroxyl group of the diol (b0). Represents the AO addition number. m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form in the case where they are composed of two or more oxyalkylene groups is a block or Either random or a combination thereof may be used. m and m ′ are generally integers of 1 to 300, preferably 2 to 250, and more preferably 10 to 100. M and m ′ may be the same or different.

Examples of the diol (b0) include dihydric alcohols (for example, C2-12 aliphatic, alicyclic and aromatic ring-containing dihydric alcohols), C6-18 dihydric phenols, and tertiary amino group-containing diols.
Examples of the aliphatic dihydric alcohol include alkylene glycol [ethylene glycol, propylene glycol (hereinafter abbreviated as EG and PG, respectively)], 1,4-butanediol, 1,6-hexanediol, neopentyl glycol (hereinafter 1 each). , 4-BD, 1,6-HD, abbreviated as NPG), 1,12-dodecanediol;
Examples of the alicyclic dihydric alcohol include cyclohexanedimethanol;
Examples of the aromatic ring-containing dihydric alcohol include xylylene diol.
Examples of the divalent phenol include monocyclic divalent phenols (hydroquinone, catechol, resorcin, urushiol, etc.), bisphenols (bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane, Dihydroxybiphenyl and the like) and condensed polycyclic dihydric phenols (dihydroxynaphthalene, binaphthol and the like).

Examples of the tertiary amino group-containing diol include C1-12 aliphatic or alicyclic primary monoamines (methylamine, ethylamine, 1- and 2-propylamine, hexylamine, decylamine, dodecylamine, cyclopropylamine, And bishydroxyalkylated products of C6-12 aromatic ring-containing primary monoamines (aniline, benzylamine, etc.).
Of these, aliphatic dihydric alcohol and bisphenol are preferred from the viewpoint of conductivity, and EG and bisphenol A are more preferred.

The polyether diol (b211) can be produced by adding AO to the diol (b0).
AO includes C2-4 AO [ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- and 1,3-butylene oxide (hereinafter abbreviated as EO, PO, BO, respectively), and Two or more of these combined systems are used, and if necessary, other AO or substituted AO (hereinafter collectively referred to as AO) such as C5-12 α-olefin, styrene oxide, epihalohydrin (epichlorohydrin). Etc.) can be used together in a small proportion (for example, 30% or less based on the weight of the total AO).
When two or more kinds of AO are used in combination, the coupling form may be random and / or block. Preferred as AO is EO alone or a combination of EO and another AO (random and / or block addition). The added number of AO is an integer of usually 1 to 300, preferably 2 to 250, more preferably 10 to 100 per hydroxyl group of the diol (b0).

AO can be added by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst. The content of C2-4 oxyalkylene units in (b211) is usually 5 to 99.8%, preferably 8 to 99.6%, more preferably 10 to 98%.
The content of oxyethylene units in the polyoxyalkylene chain is usually 5 to 100%, preferably 10 to 100%, more preferably 50 to 100%, and particularly preferably 60 to 100%.

The polyether diamine (b212) has the general formula: H ₂ N—A ² — (OA ¹ ) _m —O—E ¹ —O
— (A ¹ O) _{m ′} —A ² —NH ₂ (wherein symbols E ¹ , A ¹ , m and m ′ are the same as described above, and A ² is a C2-4 alkylene group. A ¹ And A ² may be the same or different.
(B212) can be obtained by changing the hydroxyl group of (b211) to an amino group by a known method. For example, the terminal obtained by cyanoalkylating the hydroxyl group of (b111) is reduced to an amino group. Can be used.
For example, it can be produced by reacting (b211) with acrylonitrile and hydrogenating the resulting cyanoethylated product.

Examples of the modified product (b213) include the aminocarboxylic acid modified product (terminal amino group), the isocyanate modified product (terminal isocyanate group) and the epoxy modified product (terminal epoxy group) of (b211) or (b212). It is done.
The modified aminocarboxylic acid can be obtained by reacting (b211) or (b212) with aminocarboxylic acid or lactam.
The isocyanate-modified product can be obtained by reacting (b211) or (b212) with a polyisocyanate as described below or reacting (b212) with phosgene.
The epoxy modified product is obtained by reacting (b211) or (b212) with diepoxide (epoxy resin such as diglycidyl ether, diglycidyl ester, alicyclic diepoxide: epoxy equivalent 85 to 600), or (b211) and epihalohydrin. It can be obtained by reacting with (e.g. epichlorohydrin).

  The Mn of the polyether (b2) is usually from 150 to 20,000, and preferably from 300 to 18,000, more preferably from 500 to 185, from the viewpoint of heat resistance and reactivity with the hydrophobic polymer (b2). 15,000, particularly preferably 1,200 to 8,000.

Next, the cationic polymer (b22) will be described. (B22) is a hydrophilic polymer having 2 to 80, preferably 3 to 60, cationic groups (c2) separated in the molecule by a nonionic molecular chain (c1).
Examples of the cationic group (c2) include a quaternary ammonium base or a phosphonium base. Examples of the counter anion of (c2) include a super strong acid anion and other anions.
The super strong acid anion includes an anion of a super strong acid (tetrafluoroboric acid, hexafluorophosphoric acid, etc.) derived from a combination of a protonic acid (d1) and a Lewis acid (d2), a super strong acid anion such as trifluoromethanesulfonic acid, etc. Examples include strong acid anions.
Examples of other anions include halogen ions (F ⁻ , Cl ⁻ , Br ⁻ , I ⁻ etc.), OH ⁻ , PO ₄ ⁻ , CH ₃ OSO ₄ ⁻ , C ₂ H ₅ OSO ₄ ⁻ , ClO ₄ ^{− and the} like. Can be mentioned.
Specific examples of the protonic acid (d1) that induces a super strong acid include hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, and the like.
Specific examples of the Lewis acid (d2) include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, and tantalum pentafluoride.

Nonionic molecular chain (c1) includes divalent organic group (divalent hydrocarbon group; ether bond, thioether bond, carbonyl bond, ester bond, imino bond, amide bond, imide bond, urethane bond, urea bond. A divalent carbon containing at least one heteroatom selected from the group consisting of a hydrocarbon group having a carbonate bond and / or a siloxy bond, and a hydrocarbon group having a heterocyclic structure containing a nitrogen atom or an oxygen atom Hydrogen group); and a combination of two or more of these.
Among these (c1), a divalent hydrocarbon group containing a divalent hydrocarbon group and a hetero atom having an ether bond is preferable.

  Mn of the cationic polymer (b22) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly from the viewpoint of antistatic properties and reactivity with the hydrophobic polymer (b2). Preferably, it is 1,200 to 8,000.

  Specific examples of the cationic polymer (b22) include cationic polymers described in JP-A No. 2001-278985.

Next, the polymer (b23) having an anionic group will be described.
(B23) comprises dicarboxylic acid (e1) having a sulfo group and diol (b0) or polyether (b21) as essential structural units, and 2 to 80, preferably 3 to 60 sulfo groups in the molecule. An anionic polymer having a group.
As the dicarboxylic acid (e1), an aromatic dicarboxylic acid having a sulfo group, an aliphatic dicarboxylic acid having a sulfo group, and those in which only these sulfo groups are converted into salts can be used.

Examples of the aromatic dicarboxylic acid having a sulfo group include 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid and ester-forming derivatives thereof [lower Alkyl (C1-4) ester (methyl ester, ethyl ester, etc.), acid anhydride, etc.].
Examples of the aliphatic dicarboxylic acid having a sulfo group include sulfosuccinic acid and ester-forming derivatives thereof [lower alkyl (C1-4) ester (methyl ester, ethyl ester, etc.), acid anhydride, etc.].
Examples of the salts formed by only these sulfo groups include salts of alkali metals (lithium, sodium, potassium, etc.), salts of alkaline earth metals (magnesium, calcium, etc.), ammonium salts, hydroxyalkyl (C2-4). ) Amine salts, such as mono-, di- and tri-amines having organic groups (organic amine salts such as mono-, di- and tri-ethylamine, mono-, di- and tri-ethanolamine, diethylethanolamine), these Examples include quaternary ammonium salts of amines and combinations of two or more of these.
Among these, preferred are aromatic dicarboxylic acids having a sulfo group, more preferred are 5-sulfoisophthalic acid salts, and particularly preferred are 5-sulfoisophthalic acid sodium salt and 5-sulfoisophthalic acid potassium salt.

Among (b0) and (b21) constituting (b23), C2-10 alkanediol, EG, polyethylene glycol (hereinafter abbreviated as PEG) (degree of polymerization 2-20), bisphenol (bisphenol A, etc.) EO adduct (number of added moles 2 to 60) and a mixture of two or more thereof.
As a manufacturing method of (b23), the normal polyester manufacturing method can be applied as it is. The polyesterification reaction is usually performed in a temperature range of 150 to 240 ° C. under reduced pressure, and the reaction time is 0.5 to 20 hours. Moreover, in this esterification reaction, you may use the catalyst used for normal esterification reaction as needed.
Examples of esterification catalysts include antimony catalysts (such as antimony trioxide), tin catalysts (such as monobutyltin oxide and dibutyltin oxide), titanium catalysts (such as tetrabutyl titanate), zirconium catalysts (such as tetrabutylzirconate), and metal acetate. Examples thereof include salt catalysts (such as zinc acetate).

  Mn of (b23) is preferably 500 to 20,000, more preferably 1,000 to 15,000, particularly preferably 1, from the viewpoint of conductivity and reactivity with the hydrophobic polymer (b1). 200-8,000.

[Block polymer (B)]
The block polymer (B) of the present invention is composed of the hydrophobic polymer (b1) block and the hydrophilic polymer (b2) block. Further, from the viewpoint of conductivity, it is preferable that the block (b1) and the block (b2) are at least selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond, a urethane bond and a urea bond. It has a structure bonded through one type of bond.
The proportion of the block (b2) based on the weight of the (B) is preferably 20 to 80%, more preferably 30 to 70% from the viewpoint of conductivity and mechanical properties.

The structure (B1) and the block (b2) combined with the block (b1) are composed of (b1)-(b2) type, (b1)-(b2)-(b1) type, (b2 )-(B1)-(b2) type and [(b1)-(b2)] n type (n represents the average number of repetitions).
The structure of the block polymer (B) is preferably a [(b1)-(b2)] n type structure in which (b1) and (b2) are repeatedly and alternately bonded from the viewpoint of conductivity.
[(B1)-(b2)] The average number n of repeating units of the n-type structure is preferably 2 to 50, more preferably 2.3 to 30, particularly preferably from the viewpoint of conductivity and mechanical properties of the molded product. Is 2.7-20, most preferably 3-10. n can be determined by Mn and 1H-NMR analysis of the block polymer (B).

  The Mn of the block polymer (B) is preferably 2,000 to 100,000, more preferably 5,000 to 60,000, particularly preferably 10,000 to 40,000 from the viewpoint of melt viscosity.

Of the bonds between the blocks (b1) and (b2), the ester bond, amide bond and imide bond are, for example, polyether (b21) [(b211) or (b212)] and the hydrophobic polymer (b1) [ (B111) or (b115) etc.], and the ether bond is, for example, the above-mentioned epoxy modified product obtained by reacting an epihalohydrin with a polyether diol (b211), and a polyolefin having hydroxyl groups at both ends of the polymer (b112 ).
The urethane bond is formed by reaction of, for example, polyether diol (b211) and polyolefin (b114) having isocyanate groups at both ends, and the urea bond is formed by, for example, polyetherdiamine (b212) and isocyanate groups at both ends. It is formed by reaction with polyolefin (b114).

(B) includes the following (B1), (B2) and a mixture of two or more thereof.
(B1): The polyolefin (b11) block and the polyether (b21) block are at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond, a urethane bond, and a urea bond. Block polymer (B2) having a structure bonded via a block: Polyamide ester amide block polymer (B3) composed of a block of polyamide (b12) and a block of polyether (b21): Block of polyamideimide (b13) And a polyetheramide block polymer (B4) composed of a block of polyether (b21): a polyether ester block polymer composed of a block of polyester (b14) and a block of polyether (b21) , Conductivity view From the viewpoint, (B1) and (B2) are preferable.

[Conducting agent (X)]
The conductive agent (X) of the present invention contains the carbon nanotube (A) and the block polymer (B). The content of (A) based on the total weight of (A) and (B) is preferably 0.1 to 5%, more preferably 0.5 to 5% from the viewpoints of conductivity and dispersibility.

  The conductive agent (X) reacts with the reactive functional group (a) of (A) and the hydrophobic polymer (b1), hydrophilic polymer (b2) and / or block polymer (B). Those that are bound, those that are not bound (A), those that are not bound (B), and the like are included.

The following (1) to (3) may be mentioned as a method for producing the conductive agent (X).
(1) Method of melt-mixing (A) and (B) (2) (A) and hydrophobic polymer (b1) are mixed in advance, then (b2) is added, and (b1) and (b2) To obtain (B) in the presence of (A) (3) (A) and the hydrophilic polymer (b2) are mixed in advance, then (b1) is added, and (b2) and (b1 ) Is reacted to obtain (B) in the presence of (A) Of these, (3) is preferred from the viewpoint of the dispersibility of (A) in (B).
Further, when mixing (A) and (b2) of (3) above, a dispersion of (A) is obtained using a disperser in an aqueous medium containing (b2) or (b2). The method is further preferred from the same viewpoint. As the aqueous medium, water or alcohol (C1-4, for example, methanol, isopropanol) can be used, and as the disperser, for example, an ultrasonic disperser can be used.

[Conductive resin composition]
The conductive resin composition of the present invention contains a conductive agent (X) and a thermoplastic resin (D). The content of (X) based on the total weight of (X) and (D) is preferably 1 to 20%, more preferably 3 to 15% from the viewpoints of conductivity and mechanical properties.

  As the thermoplastic resin (D), polyphenylene ether (PPE) resin (D1); vinyl resin [polyolefin resin (D2) [for example, polypropylene (PP), polyethylene (PE), ethylene-vinyl acetate copolymer resin (EVA), Ethylene-ethyl acrylate copolymer resin], poly (meth) acrylic resin (D3) [for example, polymethyl methacrylate], polystyrene resin (D4) [vinyl group-containing aromatic hydrocarbon alone or vinyl group-containing aromatic hydrocarbon, Copolymers having at least one selected from the group consisting of (meth) acrylic acid esters, (meth) acrylonitrile and butadiene as structural units, such as polystyrene, high impact polystyrene (HIPS), styrene / acrylonitrile copolymers ( AN resin), acrylonitrile / butadi / Styrene copolymer (ABS resin), methyl methacrylate / butadiene / styrene copolymer (MBS resin), styrene / methyl methacrylate copolymer (MS resin)], etc.]; polyester resin (D5) [for example, polyethylene Terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate]; polyamide resin (D6) [eg nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6 / 66, nylon 6/12]; polycarbonate resin (D7) [for example, polycarbonate (PC), polycarbonate (PC) / ABS alloy resin]; polyacetal resin (D8), and two or more of these Compounds, and the like.

  Among these, (D1), (D2), (D3), (D4) are preferable from the viewpoint of the mechanical properties of the molded product described later and the dispersibility of the conductive agent (X) of the present invention in (D). And (D7), more preferably (D2), (D4) and (D7).

The conductive resin composition of the present invention may further contain a conductivity improver (C) as necessary within a range not inhibiting the effects of the present invention.
(C) includes alkali metal or alkaline earth metal salt (C1), quaternary ammonium salt (C2), surfactant (C3), ionic liquid (C4), compatibilizer (C5) and the like. included. These may be used alone or in combination of two or more.

  Examples of the alkali metal or alkaline earth metal salt (C1) include organic acids (monolithic C1-7) of metals [alkali metals (lithium, sodium, potassium, etc.) or alkaline earth metals (magnesium, calcium, etc.)]. And salts of di-carboxylic acids such as formic acid, acetic acid, propionic acid, oxalic acid, succinic acid; C1-7 sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid; thiocyanic acid, and inorganic acids [halogens] Salt of hydrofluoric acid (hydrochloric acid, hydrobromic acid, etc.), perchloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.].

  As the quaternary ammonium salt (C2), organic acids such as amidinium (1-ethyl-3-methylimidazolium, etc.), guanidinium (2-dimethylamino-1,3,4-trimethylimidazolinium, etc.) ( And salts of inorganic acids (above).

  Surfactant (C3) includes nonionic, anionic, cationic and amphoteric surfactants and mixtures thereof.

  The ionic liquid (C4) is a compound other than the above (C1) to (C3), has a melting point of room temperature or lower, and at least one of the constituent cations or anions is an organic ion and has an initial conductivity of 1 to 1. A room temperature molten salt of 200 ms / cm (preferably 10 to 200 ms / cm), for example, a room temperature molten salt described in WO95 / 15572.

  Examples of the compatibilizer (C5) include a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group, and a polyoxyalkylene group: A polymer described in JP-A-3-258850, a modified vinyl polymer having a sulfonic acid group described in JP-A-6-345927, a block weight having a polyolefin portion and an aromatic vinyl polymer portion. Examples include coalescence.

The total content of the conductivity improver (C) is usually 5% or less, based on the weight of the thermoplastic resin (D), from the viewpoint of providing a resin molded product having a good appearance without being deposited on the conductivity and the resin surface. Preferably it is 0.001 to 3%, More preferably, it is 0.01 to 2.5%.
From the same viewpoint, the content based on the weight of the thermoplastic resin (D) of each component of (C1) to (C5) is preferably 0.001 to 3%, more preferably 0.01 to 2.5%. It is.

  As a method for adding (C) to the conductive resin composition of the present invention, it is preferable that the conductive resin composition is dispersed in advance in the conductive agent (X) in order not to impair the appearance of the molded product described later. The method of containing (C) during the production of () is more preferred. There is no particular limitation on the timing of containing (C) during the production of (B), and any of before, during and after polymerization is preferable, but it is preferable to contain it in the raw material before polymerization.

The conductive resin composition of the present invention can be obtained by melt-mixing the conductive agent (X), the thermoplastic resin (D), and, if necessary, (C). As a method of melt mixing, generally, a method in which pellets or powdery components are mixed with an appropriate mixer such as a Henschel mixer, and then melt mixed with an extruder to be pelletized can be applied.
The order of addition of each component during melt mixing is not particularly limited. For example, after (1) melting the conductive agent (X), (D) and, if necessary, melt mixing (C) together (2) After melting (X), a part of (D) is melted and mixed in advance, and a high concentration (preferably 40 to 80% by weight, more preferably 50 to 70% by weight) of (X) A method of preparing a product (masterbatch resin composition) and then melt-mixing the remaining (D) and (C) as necessary.

[Conductive resin molded product]
The conductive resin molded article of the present invention is obtained by molding the conductive resin composition. Examples of the molding method include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method, etc.) and the like. Molding can be performed by any method that incorporates means such as layer molding, multilayer molding, and foam molding.

The molded article of the present invention has excellent mechanical properties and electrical conductivity, as well as good paintability and printability, and a molded article can be obtained by coating and / or printing the molded article.
Examples of the method for coating the molded product include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, immersion coating, roller coating, and brush coating.
Examples of the paint include paints generally used for plastic coating such as polyester melamine resin paint, epoxy melamine resin paint, acrylic melamine resin paint, and acrylic urethane resin paint.
The coating film thickness (dry film thickness) can be appropriately selected according to the purpose, but is usually 10 to 50 μm.

In addition, as a method of printing after coating the molded product or the molded product, any printing method generally used for plastic printing can be used. For example, gravure printing, flexographic printing , Screen printing, pad printing, dry offset printing, offset printing, and the like.
As the printing ink, those usually used for printing plastics, for example, gravure ink, flexographic ink, screen ink, pad ink, dry offset ink and offset ink can be used.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the part in an Example represents a weight part and% represents weight%.

Production Example 1 [Carboxyl group-modified carbon nanotube (A-1)]
A glass reaction vessel is charged with 10 parts of single-walled carbon nanotubes [trade name “S-SWNT”, manufactured by NTP (Shenten Nanotech Port Co.), diameter 10 nm, aspect ratio 500], and 50 parts of tetrahydrofuran, and subjected to ultrasonic waves. Ultrasonic waves (output: 100 W, frequency: 42 kHz, the same applies hereinafter) were applied for 10 minutes using a disperser. Next, 2 parts of 4,4-azobis (4-cyanovaleric acid) was charged with stirring at 40 ° C. in a nitrogen atmosphere, and then reacted at 140 ° C. for 5 hours. After completion of the reaction, the reaction mixture was cooled to room temperature (20 to 30 ° C.), and a black solid was filtered from the reaction solution. An operation of adding 50 parts of tetrahydrofuran to the black solid and washing it was performed twice, followed by drying under reduced pressure to obtain carboxyl group-modified carbon nanotubes (A-1). The acid value of (A-1) was 22. Thereafter, water was added to (A-1), followed by irradiation with ultrasonic waves for 10 minutes to obtain a 10% aqueous dispersion of (A-1).

Production Example 2 [Hydroxyl group-modified carbon nanotube (A-2)]
In Production Example 1, instead of 2 parts of 4,4-azobis (4-cyanovaleric acid), 2 parts of 2,2-azobis [2- (hydroxymethyl) propionitrile] were used and Production Example 1 Similarly, a hydroxyl group-modified carbon nanotube (A-2) was obtained. The hydroxyl value of (A-2) was 15. Thereafter, water was added to (A-2), followed by irradiation with ultrasonic waves for 10 minutes to obtain a 10% aqueous dispersion of (A-2).

Production Example 3 [Carboxyl group-modified carbon nanotube (A-3)]
Manufacture except that multi-walled carbon nanotube [trade name “MWNT-AP”, manufactured by Sun Nanotech Co., Ltd., diameter 1 nm, aspect ratio 500] was used instead of 10 parts of single-walled carbon nanotube in Manufacturing Example 1. In the same manner as in Example 1, a carboxyl group-modified carbon nanotube (A-3) was obtained. The acid value of (A-3) was 26. Thereafter, water was added to (A-3), followed by irradiation with ultrasonic waves for 10 minutes to obtain a 10% aqueous dispersion of (A-3).

Production Example 4 [Production of acid-modified polyolefin (b1-1)]
Low molecular weight ethylene / propylene random copolymer obtained by thermal degradation method (ethylene content 2%, Mn 3,500, density 0.89 g / cm 3, double bond amount per 1,000 C) on stainless steel autoclave 1 unit, average number of double bonds per molecule 1.8, content of polyolefin that can be modified at both ends 90%) 95 parts, maleic anhydride 10 parts, xylene 30 parts, nitrogen gas atmosphere (sealed) Then, it was melted at 200 ° C. and reacted at 200 ° C. for 20 hours. Then, excess maleic anhydride and xylene were distilled off under reduced pressure at 200 ° C. for 3 hours to obtain an acid-modified polyolefin (b1-1). The acid value of (b1-1) was 27.2, Mn was 3,700, and the volume resistivity value was 9 × 10 ¹⁵ Ω · cm.

Production Example 5 [Production of secondary modified polyolefin (b1-2)]
A stainless steel autoclave is charged with 88 parts of acid-modified polyolefin (b1-1) and 12 parts of 12-aminododecanoic acid, melted at 200 ° C. in a nitrogen gas atmosphere (sealed), 200 ° C., 3 hours, 1.3 kPa or less. Was subjected to reaction under reduced pressure to obtain a secondary modified polyolefin (b1-2). The acid value of (b1-2) was 24.0, Mn was 4,200, and the volume resistivity value was 3 × 10 ¹⁵ Ω · cm.

Production Example 6 [Production of Modified Polyolefin (b1-3) Having Hydroxyl Groups at Both Ends of Polymer]
A stainless steel autoclave was charged with 95 parts of acid-modified polyolefin (b1-1) and 5 parts of ethanolamine, melted at 180 ° C. in a nitrogen gas atmosphere (sealed), and reacted at 180 ° C. for 2 hours. Thereafter, excess ethanolamine was distilled off under reduced pressure at 180 ° C. for 2 hours to obtain a modified polyolefin (b1-3) having hydroxyl groups at both ends of the polymer. The hydroxyl value of (b1-3) was 26.0, the amine value was 0.01, Mn was 3,900, and the volume resistivity value was 8 × 10 ¹⁵ Ω · cm.

Production Example 7 [Production of Modified Polyolefin (b1-4) Having Amino Groups at Both Ends of Polymer]
In a stainless steel autoclave, 95 parts of acid-modified polyolefin (b1-1) and 40 parts of bis (2-aminoethyl) ether were charged and melted at 200 ° C. with stirring in a nitrogen gas atmosphere (sealed). The reaction was performed for 2 hours. Thereafter, excess bis (2-aminoethyl) ether was distilled off under reduced pressure at 200 ° C. for 2 hours to obtain a modified polyolefin (b1-4) having amino groups at both ends. The amine value of (b1-4) was 25.5, Mn was 4,000, and the volume resistivity value was 5 × 10 ¹⁵ Ω · cm.

Production Example 8 [Production of polyamide (b1-5) having carboxyl groups at both ends]
In a stainless steel autoclave, 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, an antioxidant [trade name “Irganox 1010”, manufactured by Ciba Specialty Chemicals Co., Ltd., tetrakis [methylene-3- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate] methane, and so on. ] 0.3 parts and 6 parts of water were charged, the inside of the autoclave was purged with nitrogen, and then heated and stirred at 220 ° C. under pressure (0.3 to 0.4 MPa, the same applies hereinafter) for 4 hours. A polyamide (b1-5) having a group was obtained. Mn of (b1-5) was 1,000, the acid value was 112, and the volume resistivity value was 7 × 10 ¹⁴ Ω · cm.

Production Example 9 [Production of Cationic Polymer (b2-4)]
A glass autoclave was charged with 41 parts of N-methyldiethanolamine, 49 parts of adipic acid and 0.3 part of zirconyl acetate. After purging with nitrogen, the temperature was raised to 220 ° C. over 2 hours and reduced to 0.13 kPa over 1 hour. The polyesterification reaction was performed. After completion of the reaction, the mixture was cooled to 50 ° C. and 100 parts of methanol was added and dissolved. While stirring, the temperature of the solution was maintained at 120 ° C., 31 parts of dimethyl carbonate was gradually added dropwise over 3 hours, and the mixture was aged at the same temperature for 6 hours. After cooling to room temperature, 110 parts of dioctyl phosphoric acid was added and stirred at room temperature for 1 hour. Subsequently, methanol was distilled off under reduced pressure to obtain a cationic polymer (b2-4) having an average of 12 quaternary ammonium groups in one molecule. The hydroxyl value of (b2-4) was 16.5, the acid value was 0.5, Mn was 6,800, and the volume resistivity value was 1 × 10 ⁵ Ω · cm.

Production Example 10 [Production of anionic polymer (b2-5)]
A stainless steel autoclave is charged with 67 parts of PEG of Mn300, 49 parts of sodium salt of 5-sulfoisophthalic acid dimethyl ester and 0.2 part of dibutyltin oxide, heated to 190 ° C. under a reduced pressure of 0.67 kPa, and methanol produced by the reaction. An anionic polymer (b2-5) having an average of 5 sodium sulfonate bases in one molecule was obtained by carrying out a transesterification reaction for 6 hours while distilling off. The hydroxyl value of (b2-5) was 29.6, the acid value was 0.4, Mn was 3,500, and the volume resistivity value was 2 × 10 ⁶ Ω · cm.

Example 1 [Production of Conductive Agent (X-1)]
A stainless steel autoclave was charged with 10 parts of a 10% aqueous dispersion of (A-1) and 39.1 parts of PEG 3000 (Mn 3,000) (b2-1) and stirred and homogenized at 80 ° C. Next, 59.9 parts of secondary modified polyolefin (b1-2), 0.3 part of antioxidant and 0.5 part of zirconyl acetate were charged and polymerized for 4 hours at 230 ° C. under a reduced pressure of 0.13 kPa or less. Obtained a polymer. The polymer was taken out in the form of a strand on the belt and pelletized to obtain a conductive agent (X-1) containing (A-1) in the block polymer structure.

Example 2 [Production of Conductive Agent (X-2)]
In Example 1, instead of (b2-1) 39.1 parts and (b1-2) 59.9 parts, modified polyolefin (b1-3) having 41 parts of (b2-1) and hydroxyl groups at both ends of the polymer A conductive agent (X-2) containing (A-1) in the block polymer structure was obtained in the same manner as in Example 1 except that 58 parts and 6 parts of dodecanedioic acid were used.

Example 3 [Production of Conductive Agent (X-3)]
In Example 1, instead of 39.1 parts of (b2-1) and 59.9 parts of secondary modified polyolefin (b1-2), 40.5 parts of (b2-1) have amino groups at both ends of the polymer. Conductive agent (X-3) containing (A-1) in the block polymer structure in the same manner as in Example 1 except that 58.6 parts of modified polyolefin (b1-4) and 6 parts of dodecanedioic acid were used. )

Example 4 [Production of Conductive Agent (X-4)]
In Example 1, instead of 39.1 parts of (b2-1) and 59.9 parts of secondary modified polyolefin (b1-2), an EO adduct of bisphenol A (Mn2,000) (b2-2) 66. Conductive agent containing (A-1) in the block polymer structure in the same manner as in Example 1 except that 1 part and 32.9 parts of polyamide (b1-5) having carboxyl groups at both ends were used. X-4) was obtained.

Example 5 [Production of Conductive Agent (X-5)]
In Example 1, instead of 10 parts of a 10% aqueous dispersion of (A-1), 39.1 parts of (b2-1), 59.9 parts of secondary modified polyolefin (b1-2), (A-2 ) 10% aqueous dispersion, (b2-1) 38.5 parts, (b1-2) 60.5 parts were used in the same manner as in Example 1 except that (A -2) containing the conductive agent (X-5) was obtained.

Example 6 [Production of Conductive Agent (X-6)]
A stainless steel autoclave was charged with 10 parts of a 10% aqueous dispersion of (A-2) and 40.3 parts of (b2-1), homogenized at 80 ° C., dehydrated under reduced pressure, and water content of 0.1% or less. did. Next, 6.7 parts of MDI was charged and reacted at 90 ° C. to obtain a mixture of terminal isocyanate group-modified PEG (b2-3) and isocyanate group modification (A-2). Thereafter, 51.3 parts of modified polyolefin (b1-3) having hydroxyl groups at both ends of the polymer, 0.3 part of an antioxidant and 0.5 part of zirconyl acetate were added, and the mixture was heated under reduced pressure at 230 ° C. and 0.13 kPa or less. A viscous polymer was obtained by time polymerization. The polymer was taken out in a strand form on a belt and pelletized to obtain a conductive agent (X-6) containing (A-2) in the block polymer structure.

Example 7 [Production of Conductive Agent (X-7)]
In Example 6, instead of (b2-1) 40.3 parts, MDI 6.7 parts, (b1-3) 51.3 parts, (b2-1) 33.3 parts, MDI 5.6 parts, Conductive agent (X) containing (A-2) in the block polymer structure in the same manner as in Example 6 except that 60.2 parts of modified polyolefin (b1-4) having amino groups at both ends of the polymer was used. -7) was obtained.

Example 8 [Production of Conductive Agent (X-8)]
In Example 1, instead of 10 parts of the 10% aqueous dispersion of (A-1), 10 parts of the 10% aqueous dispersion of (A-3) was used. A conductive agent (X-8) containing (A-3) in the polymer structure was obtained.

Example 9 [Production of Conductive Agent (X-9)]
In Example 1, instead of (b2-1) 39.1 parts and (b1-2) 59.9 parts, the cationic polymer (b2-4) 59.3 parts, (b1-2) 39.7 parts A conductive agent (X-9) containing (A-1) in the block polymer structure was obtained in the same manner as in Example 1 except that was used.

Example 10 [Production of Conductive Agent (X-10)]
In Example 1, instead of (b2-1) 39.1 parts and (b1-2) 59.9 parts, anionic polymer (b2-5) 44.8 parts, (b1-2) 54.2 parts A conductive agent (X-10) containing (A-1) in the block polymer structure was obtained in the same manner as in Example 1 except that was used.

Example 11 [Production of Conductive Agent (X-11)]
In Example 1, instead of 10 parts of 10% aqueous dispersion of (A-1) and 59.9 parts of (b1-2), 1 part of 10% aqueous dispersion of (A-1), (b1-2) ) A conductive agent (X-11) containing (A-1) in the block polymer structure was obtained in the same manner as in Example 1 except that 60.8 parts were used.

Example 12 [Production of Conductive Agent (X-12)]
In Example 1, instead of 10 parts of 10% aqueous dispersion of (A-1) and 59.9 parts of (b1-2), 50 parts of 10% aqueous dispersion of (A-1), (b1-2) ) A conductive agent (X-12) containing (A-1) in the block polymer structure was obtained in the same manner as in Example 1 except that 56.1 parts were used.

Comparative Example 1 [Production of Conductive Agent (Ratio X-1)]
In Example 1, except having not used (A-1), it carried out similarly to Example 1, and obtained the electrically conductive agent (ratio X-1) which consists of a block polymer.

Comparative Example 2 [Production of Conductive Agent (Ratio X-2)]
In Example 4, a conductive agent (ratio X-2) made of a block polymer was obtained in the same manner as in Example 4 except that (A-1) was not used.

Comparative Example 3 [Production of Conductive Agent (Ratio X-3)]
In Production Example 1, (A-1) dried under reduced pressure before adding water was directly used as a conductive agent (ratio X-3).

Examples 13 to 27, Comparative Examples 4 to 9
According to the formulation shown in Table 1, (X-1) to (X-12) or (Ratio X-1) to (Ratio X-3), the thermoplastic resin (D-1) or (D-2), and conductivity The property improver (C-1) was blended for 3 minutes with a Henschel mixer, then melt-kneaded in a twin-screw extruder with a vent at 220 ° C., 100 rpm, and a residence time of 5 minutes to obtain a resin composition (implemented) Examples 13 to 27 and Comparative Examples 4 to 9) were obtained.

The contents of the symbols in Table 1 are as follows.
C-1: Epoxidized polystyrene elastomer [trade name "Epofriend AT
501 ", manufactured by Daicel Chemical Industries, Ltd., a compatibilizer. ]
D-1: Polypropylene resin [Brand name "Sun Allomer PM771M", Sun Allomer Co., Ltd.]
D-2: ABS resin [trade name “Cebian-V320”, manufactured by Daicel Polymer Co., Ltd.]

<Performance test>
The resin composition obtained above was injected into an injection molding machine [model number “PS40E5ASE”, manufactured by Nissei Plastic Industry Co., Ltd. The same shall apply hereinafter, and test pieces were produced under conditions of a cylinder temperature of 220 ° C. and a mold temperature of 50 ° C., and the surface resistivity, impact strength, and moldability were evaluated. The results are shown in Table 1.

<Performance evaluation items>
(1) Surface specific resistance value Conforms to ASTM D257 (1984). Using a test piece (100 × 100 × 2 mm), measurement was performed in an atmosphere of 23 ° C. and humidity 50% RH with a super insulation meter [model number “DSM-8103”, manufactured by Toa Denpa Kogyo Co., Ltd.].

(2) Impact strength Conforms to ASTM D256 (with notch, 3.2 mm thickness) Method A.

(3) Formability (surface condition)
The surface condition of the molded product was compared with a molded product of a single thermoplastic resin and evaluated according to the following criteria.
(Evaluation criteria)
○ The surface of the molded product is the same as the molded product of a single thermoplastic resin and there is no unevenness.
× The surface of the molded product is uneven as compared with a molded product of a single thermoplastic resin.

  From Table 1, the resin composition of the present invention (Examples 13 to 27) has excellent moldability equivalent to that of the thermoplastic resin alone (Comparative Examples 8 and 9), and the obtained molded product is a thermoplastic resin. It can be seen that it has an impact strength (mechanical strength) equivalent to that of a simple substance, and its conductivity is far superior to that of comparative molded products (Comparative Examples 4-6, 8-9).

  Since the conductive resin composition of the present invention can impart excellent conductivity to the molded product without impairing the mechanical properties and good appearance of the thermoplastic resin molded product, various molding methods [injection molding, compression molding, Housing products [home appliances / OA equipment, game machines and office equipment] formed by calendar molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding and film molding (for example, casting method, tenter method and inflation method). Etc.], plastic container materials [tray used in clean rooms (IC trays, etc.), other containers, etc.], various cushioning materials, coating materials (wrapping film, protective film, etc.), flooring sheets, artificial grass, Can be widely used as a material for mats, tape base materials (for semiconductor manufacturing processes, etc.), and various molded products (automobile parts, etc.). It is useful.

Claims (7)

A carbon nanotube (A) having a reactive functional group (a) which is at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group, and at least selected from the group consisting of polyolefin, polyamide, polyamideimide and polyester 1 type and at least one selected from the group consisting of a block of a hydrophobic polymer (b1) having a volume resistivity exceeding 1 × 10 ¹¹ Ω · cm and a polyether, a cationic polymer and an anionic polymer A block polymer (B) composed of a block of a hydrophilic polymer (b2) having a volume resistivity of × 10 ⁵ to 1 × 10 ¹¹ Ω · cm, and the (B) is the following ( A conductive agent (X) which is at least one selected from the group consisting of B1) and (B2).
(B1): a structure in which a polyolefin block and a polyether block are bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond, a urethane bond and a urea bond. Block polymer (B2): Polyether amide block polymer composed of polyamide and polyether Conductive agent (X) according to claim 1 , polyphenylene ether resin (D1), polyolefin resin (D2), poly (meth) acrylic resin (D3), polystyrene resin (D4), polyester resin (D5), polyamide resin ( D6), a conductive resin composition comprising at least one thermoplastic resin (D) selected from the group consisting of polycarbonate resin (D7) and polyacetal resin (D8). The composition according to claim 2 , wherein the content of (X) based on the total weight of (X) and (D) is 1 to 20%. Further, an alkali metal or alkaline earth metal salts, quaternary ammonium salts, surfactants, claim formed by incorporating at least one conductivity enhancing agent selected from the group consisting of ionic liquid and compatibilizer The composition according to 2 or 3 . A molded product formed by molding the composition according to claim 2 . A molded article obtained by coating and / or printing the molded article according to claim 5 . Hydrophilic polymer (b2) or (b2) which is at least one selected from the group consisting of polyether, cationic polymer and anionic polymer and has a volume resistivity of 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm Step (I) for obtaining a dispersion of carbon nanotubes (A) having a reactive functional group (a) which is at least one functional group selected from the group consisting of a carboxyl group and a hydroxyl group in an aqueous medium containing And a hydrophobic polymer (b1) having a volume resistivity value of at least one selected from the group consisting of polyolefin, polyamide, polyamideimide and polyester and having a volume resistivity value exceeding 1 × 10 ¹¹ Ω · cm. In the presence of the carbon nanotube (A), a block composed of a block (b1) and a block (b2) Kkuporima and a step (II) to form (B), said (B) is the following (B1) and at least one kind of claim 1, wherein the conductive agent selected from the group consisting of (B2) (X) Manufacturing method.
(B1): a structure in which a polyolefin block and a polyether block are bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond, a urethane bond and a urea bond. Block polymer (B2): Polyether amide block polymer composed of polyamide and polyether