JP2003342483A - Electroconductive elastomer - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electroconductive elastomer having a low specific gravity, a high conductivity and moldability because there is conventionally known a blend of surfactants and a large amount of electroconductive substance as for an elastomer where an electrical conductivity is imparted, however, there are problems of bleedout to the surface of molded article, increase in the specific gravity of molded article and the like, respectively. <P>SOLUTION: The conductive elastomer comprises a block polymer (A) having a structure wherein polyolefin blocks (a) and hydrophilic polymer blocks (b) having a volume specific resistance of 1×10<SP>5</SP>to 1×10<SP>11</SP>are alternately bonded to each other, and an electroconductive substance (B). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a conductive elastomer. More specifically, it relates to a conductive elastomer having excellent moldability.

[0002]

2. Description of the Related Art Conventionally, olefin elastomers, vinyl chloride elastomers, styrene elastomers, urethane elastomers, polyester elastomers, polyamide elastomers, fluorine elastomers, syndiotactic-1,2-PB elastomers, chlorinated products. As a method for imparting conductivity to an elastomer such as an ethylene copolymer crosslinked alloy, a chlorinated polyethylene and an ester / halogen-based polymer alloy, a method of blending an electrolyte salt or a surfactant with a polyether ester amide (for example, Patent Document 1). A method of blending a conductive substance such as carbon or metal fiber or powder with polyetheresteramide (see, for example, Patent Document 2) and the like are known.

[0003]

[Patent Document 1] JP-A-7-10989

[Patent Document 2] JP-A-7-216224

[0004]

However, in the above, the compounded electrolyte salt or surfactant bleeds out on the surface of the molded article with the passage of time, and the appearance is impaired.
There is a problem that the conductivity is highly dependent on humidity. Further, in the above, since it is necessary to mix a relatively large amount of the conductive substance, there is a problem that the specific gravity becomes large and the molded product becomes heavy, and the low fluidity causes extremely poor handling during molding. That is, the present invention aims to provide a conductive elastomer having excellent conductivity and moldability.

[Means for Solving the Problems]

As a result of earnest studies to achieve the above object, the inventors of the present invention have found that a conductive elastomer having a low specific gravity and excellent moldability can be obtained by containing a specific block polymer and a conductive substance. And has reached the present invention. That is, the present invention provides a block polymer (A having a structure in which a block of a polyolefin (a) and a block of a hydrophilic polymer (b) having a volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ are repeatedly and alternately bonded. And a conductive substance (B), a conductive elastomer; a molded article obtained by molding the conductive elastomer;
And a molded article obtained by applying coating or printing to the molded body.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION As the block polymer (A) in the present invention, the block polymer described in WO00 / 47652 can be used. Since the polyolefin (a) constituting the component (A), the hydrophilic polymer (b), specific examples of the bonding structure thereof and the production method, the preferable range, and the like are described in the above specification, the following (A) is simple. Described in. In the present invention, the block polymer (A) having a structure in which the block of the polyolefin (a) and the block of the hydrophilic polymer (b) are alternately and repeatedly bonded is composed of the block (a) and the block (b). , An ester bond, an amide bond, an ether bond, a urethane bond, and an imide bond.

Examples of (a) include a polyolefin (a1) having a carbonyl group-containing group (preferably a carboxyl group, the same applies hereinafter) at both ends of the polymer, and a polyolefin (a2) having a hydroxyl group at both ends of the polymer. ,
A polyolefin (a3) having amino groups at both ends of the polymer can be used. Furthermore, a polyolefin (a having a carbonyl group-containing group at one end of the polymer)
4), a polyolefin (a5) having a hydroxyl group at one end of the polymer and a polyolefin (a6) having an amino group at one end of the polymer can be used. Of these, the polyolefins (a1) and (a4) having a group containing a carbonyl group are preferable because they are easily modified.

As (a1), a polyolefin whose both ends can be modified is a main component (content of 50% or more, preferably 7%).
(5% or more) that has a carbonyl group-containing group introduced at both ends of the polyolefin (a0) is used.
In the above and below,% used for notation of content means% by weight. As (a2), those having hydroxyl groups introduced at both ends of (a0) are used. As (a3), (a3)
A product obtained by introducing an amino group into both terminals of 0) is used.

(A0) is a polyolefin obtained by (co) polymerization (meaning polymerization or copolymerization; the same applies hereinafter) of one or a mixture of two or more olefins having 2 to 30 carbon atoms [polymerization method]. ] And a low molecular weight polyolefin obtained by thermal degradation of a high molecular weight polyolefin (a polyolefin obtained by polymerizing an olefin having 2 to 30 carbon atoms) [thermal degradation method] can be used.

As the olefin having 2 to 30 carbon atoms,
Ethylene, propylene, carbon number 4-30 (preferably 4)
.About.12, more preferably 4 to 10) .alpha.-olefin, and a C4 to C30 (preferably 4 to 18, more preferably 4 to 8) diene and the like. α-
Examples of the olefin include 1-butene, 4-methyl-1-pentene, 1-pentene, 1-octene, 1-decene and 1-dodecene, and the diene includes butadiene, isoprene, cyclopentadiene and 1,1.
1-dodecadiene and the like. Of these, preferred are those having 2 to 12 carbon atoms (such as ethylene, propylene, α-olefin having 4 to 12 carbon atoms, butadiene and / or isoprene), and more preferred are those having 2 to 12 carbon atoms.
10 (such as ethylene, propylene, α-olefins having 4 to 10 carbon atoms and / or butadiene), particularly preferably ethylene, propylene and / or butadiene.

The low molecular weight polyolefin obtained by the thermal degradation method can be easily obtained, for example, by the method described in JP-A-3-62804. The polyolefin obtained by the polymerization method can be produced by a known method, for example, easily obtained by a method of (co) polymerizing the above olefin in the presence of a radical catalyst, a metal oxide catalyst, a Ziegler catalyst and a Ziegler-Natta catalyst. be able to. As the radical catalyst, known ones, for example, di-t-butyl peroxide, t-butyl benzoate, decanol peroxide, lauryl peroxide, peroxy-di-carbonate ester, azo compound, etc., and a γ-alumina carrier are oxidized. Examples thereof include those to which molybdenum is attached. As a metal oxide catalyst,
Examples include silica-alumina carriers to which chromium oxide is attached. Ziegler catalysts and Ziegler - The Natta catalysts include _{(C 2 H 5) 3 Al} -TiCl 4 or the like. Ease of introducing a carbonyl group that is a modifying group,
Also, from the viewpoint of easy availability, a low molecular weight polyolefin obtained by the thermal degradation method is preferable.

The number average molecular weight (hereinafter referred to as Mn) of the gel permeation chromatography (GPC) of (a0).
And abbreviated. ) Is preferably 800 to 20,000, more preferably 1.00 from the viewpoint of the resin physical properties of the elastomer.
0 to 10,000, particularly preferably 1,200 to 6,0
00. The amount of double bonds in (a0) is preferably 1 to 40, more preferably 2 to 30, and most preferably 4 to 20 per 1,000 carbon atoms from the viewpoint of the conductivity of the elastomer. . The average number of double bonds per molecule is preferably 1.1 to 5 from the viewpoint of repeat structure forming properties and the resin physical properties of the elastomer.
The number is more preferably 1.3 to 3, particularly preferably 1.5 to 2.5, and most preferably 1.8 to 2.2. In the thermal degradation method, Mn is 800 to 6,000.
, The average number of terminal double bonds per molecule is 1.5
˜2 low molecular weight polyolefins are easily obtained [see, for example, Katsuhide Murata, Tadahiko Makino, Journal of the Chemical Society of Japan, p. 192 (1975)].

The measurement conditions of Mn are as follows (hereinafter, Mn is measured under the same conditions). Apparatus: High temperature gel permeation chromatography Solvent: Orthodichlorobenzene Reference substance: Polystyrene Sample concentration: 3 mg / ml Column stationary phase: PLgel MIXED-B Column temperature: 135 ° C

As (a4), a polyolefin whose one end can be modified is a main component (content is 50% or more, preferably 7%).
(5% or more) is used in which a group containing a carbonyl group is introduced at one end of the polyolefin (a00). As (a5), the one obtained by introducing a hydroxyl group into one end of (a00) is used. As (a6), (a0
A product obtained by introducing an amino group into one end of 0) is used.

(A00) can be obtained in the same manner as (a0), and the Mn of (a00) is preferably 2,000 to 50,000, more preferably 2,500 to 30 from the viewpoint of the resin physical properties of the elastomer. 1,000, particularly preferably 3,000 to 20,000. (A00) is preferably 0.3 to 20, more preferably 0.5 to 15, and particularly preferably 0.7 to 1,000 carbon atoms per 1,000.
It has 10 double bonds. In terms of ease of modification, a low molecular weight polyolefin (especially Mn is 2,
000-20,000 polyethylene and polypropylene) are preferred. Although (a0) and (a00) are usually obtained as a mixture thereof, these mixtures may be used as they are or after being purified and separated before use.

As the polyolefin (a1) having carbonyl groups at both ends of the polymer, (a0) has both ends of α, β-unsaturated carboxylic acid (anhydride) (α, β-unsaturated carboxylic acid, its carbon A polyolefin (a1-1) or (a) having a structure modified with an alkyl ester of formulas 1 to 4 and / or its anhydride.
Polyolefin (a1-2) having a structure in which 1-1) is secondarily modified with lactam or aminocarboxylic acid, (a
0) is a polyolefin (a1-3) having a structure obtained by oxidation or hydroformylation modification, a polyolefin (a1-4) having a structure in which (a1-3) is secondarily modified with a lactam or an aminocarboxylic acid, and two or more thereof. And the like.

(A1-1) has α and α at both ends of (a0).
It is obtained by modifying with β-unsaturated carboxylic acid (anhydride). As the α, β-unsaturated carboxylic acid (anhydride), a carboxylic acid having 3 to 12 carbon atoms, for example, monocarboxylic acid [(meth) acrylic acid or the like], dicarboxylic acid (maleic acid, fumaric acid, itaconic acid, citracone) Acid, etc.), these alkyl (C1-4) esters [methyl (meth) acrylate, butyl (meth) acrylate, diethyl itaconate, etc.] and their anhydrides. Of these, from the viewpoint of reactivity with (a0), dicarboxylic acids, their alkyl esters and their anhydrides, more preferably maleic acid (anhydride) and fumaric acid, and particularly preferably maleic acid. (Anhydrous).

The amount of the α, β-unsaturated carboxylic acid (anhydride) used is preferably 0.5 to 40 from the viewpoint of the repeating structure forming property and the resin physical properties of the elastomer, based on the weight of the polyolefin (a0). %, More preferably 1 to 30% by weight, particularly preferably 2 to 20% by weight. The modification of the polyolefin (a0) with α, β-unsaturated carboxylic acid (anhydride) is known in the art, for example, (a
It can be carried out by thermally adding (ene reaction) α, β-unsaturated carboxylic acid (anhydride) to the terminal double bond of 0) by either a solution method or a melting method. As the solution method, α, β-unsaturated carboxylic acid (anhydride) is added to (a0) in the presence of a hydrocarbon solvent such as xylene or toluene, and the mixture is added in an inert gas atmosphere such as nitrogen 170.
Examples include a method of reacting at ˜230 ° C. Examples of the melting method include a method in which (a0) is heated and melted, then α, β-unsaturated carboxylic acid (anhydride) is added, and the mixture is reacted at 170 to 230 ° C. in an atmosphere of an inert gas such as nitrogen. Among these methods, the solution method is preferable from the viewpoint of reaction uniformity.

(A1-2) is obtained by secondarily modifying (a1-1) with a lactam or an aminocarboxylic acid. Examples of lactams include lactams having 6 to 12 carbon atoms (preferably 6 to 8 and more preferably 6), such as caprolactam, enantolactam, undecanolactam and laurolactam. As the aminocarboxylic acid, an aminocarboxylic acid having 2 to 12 carbon atoms (preferably 4 to 12, more preferably 6 to 12), 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, 1
1-aminoundecanoic acid and 12-aminododecanoic acid are mentioned. Of these, glycine, leucine, and more preferably caprolactam, laurolactam, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12 are preferred from the viewpoint of reactivity of secondary modification.
-Aminododecanoic acid, particularly preferred are caprolactam and 12-aminododecanoic acid. The amount of lactam or aminocarboxylic acid used is preferably 0.1 to 20 lactam or aminocarboxylic acid per residue obtained by removing a carboxyl group from an α, β-unsaturated carboxylic acid from the viewpoint of the resin physical properties of the elastomer. The number is more preferably 0.3 to 15, and most preferably 0.5 to 10.

The modification of (a1-1) with a lactam or an aminocarboxylic acid is known in the art, for example, (a1-
After 1) is heated and melted, lactam or aminocarboxylic acid is added, and 170 to 23 in an atmosphere of an inert gas such as nitrogen.
Examples include a method of reacting at 0 ° C.

In (a1-3), (a0) is replaced with oxygen and / or
Alternatively, it can be obtained by oxidation with ozone or hydroformylation by the oxo method to introduce a carbonyl group. The carbonyl group can be introduced by oxidation 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, Macromo
lecules, Vol. It can be carried out by the method described on pages 31, 5943.

(A1-4) is obtained by secondarily modifying (a1-3) with a lactam or an aminocarboxylic acid. Examples of lactams and aminocarboxylic acids include (a
The examples are described in 1-2), and the amount used and the modification method are also the same.

The Mn of the polyolefin (a1) having carbonyl groups at both ends of the polymer is preferably 800 to 25,000, more preferably 800 to 25,000 from the viewpoint of heat resistance and reactivity with the hydrophilic polymer (b) described later. 1,00
0 to 20,000, particularly preferably 2,500 to 10,
It is 000. The acid value of (a1) is preferably 4 to 280 (mgKOH /
g, only numerical values will be described below. ), More preferably 4 to 100, particularly preferably 5 to 50.

As the polyolefin (a2) having hydroxyl groups at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying (a1) with hydroxylamine and a mixture of two or more thereof can be used. Examples of the hydroxylamine include hydroxylamine having 2 to 12 carbon atoms, for example, 2-aminoethanol, 3-aminopropanol, 1-amino-2-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol, 3 -Aminomethyl-3,5,5-trimethylcyclohexanol and the like. Of these, 5-aminopentanol, 6-aminohexanol, and more preferably 2-aminoethanol or 4-aminobutanol, and particularly preferably 2-amino, from the viewpoint of easiness of modification. It is ethanol.
The hydroxyl value of (a2) is the hydrophilic polymer (b) described later.
From the viewpoint of reactivity with, preferably 4-280 (mgK
OH / g, only numerical values will be described below. ), More preferably 4 to 100, particularly preferably 5 to 50.

The modification of (a1) with hydroxylamine is carried out by a known method, for example, after heating (a1) by heating,
A method of adding hydroxylamine and reacting at 170 to 230 ° C. in an atmosphere of an inert gas such as nitrogen can be mentioned.

As the polyolefin (a3) having amino groups at both ends of the polymer, a polyolefin having an amino group obtained by modifying (a1) with a diamine, and these 2
Mixtures of more than one can be used. As the diamine, a diamine having 2 to 20 carbon atoms, for example, an aliphatic diamine (ethylenediamine, trimethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine, etc.), alicyclic diamine (dicyclohexylmethanediamine, Isophorone diamine), aromatic (aliphatic) diamine (phenylenediamine, tolylenediamine, diethyltolylenediamine, xylylenediamine, diphenylmethanediamine, diphenyletherdiamine, etc.) and the like. Of these, aliphatic diamines are preferable, ethylenediamine, trimethylenediamine, hexamethylenediamine, and heptamethylenediamine are more preferable, and ethylenediamine is particularly preferable, from the viewpoint of easy modification. The amine value of (a3) is preferably 4 to 280 from the viewpoint of reactivity with the hydrophilic polymer (b) described later.
(MgKOH / g, only numerical values will be described below), more preferably 4 to 100, particularly preferably 5 to 50.

The modification of (a1) with a diamine can be carried out by a known method, for example, by heating and melting (a1), adding diamine and reacting it at 170 to 230 ° C. in an atmosphere of an inert gas such as nitrogen.

The polyolefin (a4) having a group containing a carbonyl group at one end of the polymer is (a0
0) the terminal of which is modified with an α, β-unsaturated carboxylic acid (anhydride) (the above), a polyolefin (a4-1),
A polyolefin (a4-2) obtained by secondary modification of (a4-1) with a lactam or an aminocarboxylic acid (as described above),
Polyolefin (a4-3) having a structure in which (a00) is oxidized or hydroformylated by oxygen and / or ozone, and (a4-3) is secondarily modified with a lactam or an aminocarboxylic acid (as described above) (a4). -4) and mixtures of two or more thereof can be used. The denaturing method is the same as the above-mentioned (a1). (A
The acid value of 4) is preferably 1 to 70, particularly preferably 2 from the viewpoint of reactivity with the hydrophilic polymer (b) described later.
~ 50.

As (a5), a polyolefin having hydroxyl groups obtained by modifying (a4) with hydroxylamine (described above) and a mixture of two or more thereof can be used. The modification method is the same as the above-mentioned (a2). The hydroxyl value of (a5) is preferably 1 to 70, particularly preferably 2 to 50 from the viewpoint of reactivity with the hydrophilic polymer (b) described later. As (a6), (a6)
Amino group-containing polyolefins obtained by modifying 4) with diamines (described above) and mixtures of two or more thereof can be used. The modification method is the same as the above-mentioned (a3). The amine value of (a6) is preferably 1 to 70, particularly preferably 2 to 50 from the viewpoint of reactivity with the hydrophilic polymer (b) described later.

Although (a1) and (a4) are usually obtained as a mixture of these, these mixtures may be used as they are, or may be purified and separated before use. From the viewpoint of production cost and the like, it is preferable to use it as a mixture. Further, (a2) and (a5) and (a3) and (a6) may be purified and separated in the same manner before use.
From the viewpoint of production cost and the like, it is preferable to use it as a mixture. From the viewpoint of heat resistance and reactivity with a hydrophilic polymer (b) described later, Mn of (a1), (a2) and (a3) is preferably 800 to 25,000, more preferably 1,000 to 20. 1,000, particularly preferably 2,
500 to 10,000, and Mn of (a4), (a5) and (a6) is preferably 800 to 50,000,
It is more preferably 1,000 to 30,000, and particularly preferably 2,000 to 20,000.

As the hydrophilic polymer (b), polyether (b1) and polyether-containing hydrophilic polymer (b
2), cationic polymers (b3) and anionic polymers (b4) can be used. As (b1), polyether diol (b1-1), polyether diamine (b1-2) and modified products thereof (b1-3) can be used.

As the polyether diol (b1-1), a diol (b01) or a dihydric phenol (b0) is used.
2) having a structure obtained by addition reaction of alkylene oxide (hereinafter, abbreviated as AO) (having 2 to 12 carbon atoms) to, for example, a general formula: H (OA ¹ ) _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 (b01) or (b02),
A ¹ has 2 to 1 carbon atoms which may include a halogen atom.
2 (preferably 2-8, more preferably 2-4) alkylene groups; m and m ′ are 1-300, preferably 2
To 250, particularly preferably 10 to 100, and m and m ′ may be the same or different. Also,
The m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and when they are composed of two or more oxyalkylene groups, the bonding form is block or random. Alternatively, any combination thereof may be used.

The diol (b01) has 2 to 2 carbon atoms.
12 (preferably 2 to 10, more preferably 2 to 8)
Dihydric alcohols (aliphatic, cycloaliphatic and araliphatic 2
(Hydric alcohols) and tertiary amino group-containing diols having 3 to 36 carbon atoms. Examples of the aliphatic dihydric alcohol include ethylene glycol, propylene glycol,
1,4-butanediol, 1,6-hexanediol,
Examples include neopentyl glycol and 1,12-dodecane diol. Examples of the alicyclic dihydric alcohol include 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-cyclooctanediol and 1,3-cyclopentanediol. Examples of the araliphatic dihydric alcohol include xylylenediol, 1-phenyl-1,2-ethanediol, 1,4-bis (hydroxyethyl) benzene and the like.

As the tertiary amino group-containing diol, an aliphatic or alicyclic primary monoamine (having 1 to 12 carbon atoms, preferably 2 to 10 carbon atoms, more preferably 2 to 8 carbon atoms) bishydroxyalkyl (carbon having an alkyl group) Number 1 to 12, preferably 2 to 10, and more preferably 2 to 8) compound and bishydroxyalkyl (alkyl group having 1 to 12 carbon atoms) of aromatic (aliphatic) primary monoamine (carbon number 6 to 12). Etc. The bishydroxyalkylated product of monoamine can be prepared by a known method, for example, monoamine and carbon number 2
4 to AO [ethylene oxide (hereinafter abbreviated as EO) propylene oxide (hereinafter abbreviated as PO), butylene oxide, etc.] or a monoamine and 2 to 2 carbon atoms.
It can be easily obtained by reacting with 12 hydroxyalkyl halides (2-bromoethyl alcohol, 3-chloropropyl alcohol, etc.).

As the aliphatic primary monoamine, methylamine, ethylamine, 1- and 2-propylamine,
n- and i-amylamine, hexylamine, 1,3
-Dimethylbutylamine, 3,3-dimethylbutylamine, 2- and 3-aminoheptane, heptylamine,
Examples include nonylamine, decylamine, undecylamine and dodecylamine. Examples of the alicyclic primary monoamine include cyclopropylamine, cyclopentylamine, cyclohexylamine and the like. Examples of aromatic (aliphatic) primary monoamines include aniline and benzylamine.

The dihydric phenol (b02) has 6 to 24 carbon atoms (preferably 8 to 18 carbon atoms, more preferably 1 carbon atom).
0-15), for example, monocyclic divalent phenol (hydroquinone, catechol, resorcin, urushiol, etc.), polycyclic divalent phenol (dihydroxybiphenyl, etc.), bisphenol (bisphenol A, bisphenol F,
Bisphenol S, 4,4′-dihydroxydiphenyl-2,2-butane) and condensed polycyclic divalent phenols (dihydroxynaphthalene, binaphthol, etc.) and the like.

Among (b01) and (b02), the dihydric alcohol and dihydric phenol are preferable from the viewpoint of the conductivity of the elastomer, and the aliphatic 2 is more preferable.
Polyhydric alcohols and bisphenols, particularly preferred are ethylene glycol and bisphenol A.

The AO to be added to the diol (b01) or the dihydric phenol (b02) has a carbon number of 2 to
4 AO (EO, PO, 1,2-, 1,4-, 2,3-
And 1,3-butylene oxide and a mixture of two or more kinds thereof, but if necessary, other AO
And substituted AO may be used in combination. Other AO and substituted AO include epoxidized α-olefins having 5 to 12 carbon atoms, styrene oxide and epihalohydrin (epichlorohydrin and epibromohydrin, etc.).
Etc. The amount of each of the other AO and the substituted AO used is preferably 30% by weight or less, more preferably 0 or 25% by weight or less, particularly preferably 0 or 20% by weight, from the viewpoint of conductivity, based on the weight of all AO. % Or less.

When two or more kinds of AO are used in combination, the binding form may be random and / or block.
Of the AO, EO alone is preferable from the viewpoint of conductivity,
And EO and a combination of AO other than EO (block and / or random addition), more preferred is EO alone and combined use of EO and PO, and particularly preferred is EO alone. From the viewpoint of the volume resistivity of the hydrophilic polymer (b), the number of moles of AO added is preferably 1 to 300 moles, more preferably 2 to 250 moles, and particularly preferably 2 to 250 moles per one hydroxyl group of (b01) or (b02). Preferably 10 to 1
It is 00 mol.

The addition reaction of AO is carried out by a known method, for example, an alkali catalyst (potassium hydroxide, sodium hydroxide, etc.).
In the presence of 100-200 ° C., pressure 0-0.5 MPaG
It can be performed under the conditions of. The content of oxyalkylene units in the polyether diol (b1-1) is (b
From the viewpoint of the volume resistivity value of the hydrophilic polymer (b) based on the weight of 1-1), preferably 5 to 99.8% by weight, more preferably 8 to 99.6% by weight, and particularly preferably 10 to 10. It is 98% by weight. The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100% by weight, more preferably 10 to 100% from the viewpoint of the volume resistivity value of (b) based on the weight of the polyoxyalkylene chain. % By weight, particularly preferably 50 to 1
It is 00% by weight, most preferably 60 to 100% by weight.

The polyether diamine (b1-2) has a structure in which the hydroxyl group of the polyether diol (b1-1) is modified to an amino group (primary or secondary amino group), for example, general formula: RNH- A ² − (OA ¹ ) _m O−E ¹ −
_{^{O (A 1 O) m '}} -A 2 -NHR or RNH-R'COO-
_{^{A 2 - (OA 1) m}} O-E 1 -O (A 1 O) m '-A 2 -OCOR'
-NHR. The symbols E ¹ , A ¹ , m and m ′ in the formula are the same as above, and A ² has 2 to 12 carbon atoms (preferably 2) which may contain a halogen atom.
~ 8, and more preferably 2 to 4), and A ¹ and A ² may be the same or different. R represents H or an alkyl group having 1 to 4 carbon atoms (preferably 1 or 2), and R ′ represents an alkylene group having 2 to 12 carbon atoms. (B
1-2) can be easily obtained by converting the hydroxyl groups at both ends of (b1-1) into amino groups by a known method. As a method for converting a hydroxyl group into an amino group, a known method, for example, a method in which a terminal cyanoalkyl group obtained by cyanoalkylating the hydroxyl group in (b1-1) is reduced to an amino group [for example, (b1-1 ) With acrylonitrile and hydrogenating the resulting cyanoethylated compound], a method of reacting (b1-1) with an aminocarboxylic acid or a lactam, and (b1-1) with an amine halide under alkaline conditions. The method of reacting with is mentioned.

As the modified product (b1-3), for example,
Examples thereof 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 (b1-1) or (b1-2). The modified aminocarboxylic acid is (b1
It can be obtained by reacting -1) or (b1-2) with an aminocarboxylic acid (as described above) or a lactam (as described above).

The isocyanate-modified product can be obtained by reacting (b1-1) or (b1-2) with an organic diisocyanate or by reacting (b1-2) with phosgene.

As the organic diisocyanate, an aromatic diisocyanate having 6 to 20 carbon atoms (excluding carbons in the NCO group, the same applies hereinafter), such as 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / Or 2,6-tolylene diisocyanate (TD
I), 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI) 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-
Diisocyanatobiphenyl, 3,3′-dimethyl-4,
4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate; aliphatic diisocyanates having 2 to 18 carbon atoms, such as ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4 -Trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate; alicyclic diisocyanates having 4 to 15 carbon atoms ,
For example, isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate, cyclohexylene diisocyanate, methylcyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate, 2,5 -And / or 2,6-norbornane diisocyanate; and mixtures of two or more thereof can be used. Of these, preferred are TDI, MDI,
And particularly preferred is HDI.

The epoxy modified product is (b1-1) or (b
1-2) and diepoxide [epoxy equivalent 85-600
Epoxy compounds such as diglycidyl ethers (bisphenol A diglycidyl ether, bisphenol F diglycidyl ether and ethylene glycol diglycidyl ether), diglycidyl esters (bisphenol A 2 mol and linole dimer acid diglycidyl ester, etc.) Alicyclic diepoxide (7-oxabicycloheptane-3-carboxylic acid, 7-oxabicyclohept-3-ylmethyl ester, vinyl-cyclohexene dioxide and 2- (3 ′, 4′-epoxycyclohexyl) -5 , 1 ″ -spiro-3 ″, 4 ″ -epoxycyclohexane-1,3-dioxane etc.)] or by reacting (b1-1) with epihalohydrin (having 3 to 12 carbon atoms, such as epichlorohydrin). Get by Door can be.

From the viewpoint of heat resistance and reactivity with (a), Mn (b1) is preferably 150 to 20,000.
0, more preferably 300 to 20,000, particularly preferably 1,000 to 15,000, most preferably 1,
It is 200 to 8,000.

As (b2), a polyether ester amide (b2) having a segment of polyether diol (b1-1) as a polyether segment forming component is used.
-1), a polyether amide imide (b2-2) having a segment of (b1-1) as well as (b1-
1) Polyether ester having a segment (b2)
-3), the polyether amide (b2-4) which also has the segment of (b1-2) and the polyether urethane (b2-5) which also has the segment of (b1-1) or (b1-2) can be used. . The content of the polyether (b1) segment in (b2) is preferably 30 to 80% by weight, more preferably 40 to 7 from the viewpoint of moldability.
It is 0% by weight.

Examples of (b2-1) include, for example, JP-A-6-
The polyether ester amides described in JP-A-287547 and JP-B-4-5691 can be mentioned.

Examples of (Q1) include (1) lactam ring-opening polymer, (2) polycondensation product of aminocarboxylic acid, and (3)
Examples thereof include polycondensates of dicarboxylic acids and diamines. Among the amide-forming monomers that form these polyamides, the lactam in (1) has 6 to 12 carbon atoms.
Of the above, such as caprolactam, enantolactam, undecanolactam, laurolactam. The aminocarboxylic acid in (2) has 6 to 12 carbon atoms, for example, ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid. , 12-aminododecanoic acid. Examples of the dicarboxylic acid in (3) include an aliphatic dicarboxylic acid, an aromatic (aliphatic) dicarboxylic acid, an alicyclic dicarboxylic acid, an amide-forming derivative thereof [an acid anhydride, a lower one (having 1 to 1 carbon atoms).
4) Alkyl ester] and mixtures of two or more thereof.

The aliphatic dicarboxylic acid has 4 to 4 carbon atoms.
20, for example, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid, and itaconic acid. The aromatic (aliphatic) dicarboxylic acid has 8 to 20 carbon atoms, for example, ortho-, iso- and terephthalic acid, naphthalene-2,6- and -2,7.
-Alkali metal (sodium, potassium, etc.) salts of dicarboxylic acid, diphenyl-4,4'-dicarboxylic acid, diphenoxyethanedicarboxylic acid and 3-sulfoisophthalic acid. The alicyclic dicarboxylic acid has 5 to 14 carbon atoms, for example, cyclopropanedicarboxylic acid,
1,4-cyclohexane dicarboxylic acid, cyclohexene dicarboxylic acid, and dicyclohexyl-4,4-dicarboxylic acid can be mentioned. Among the amide-forming derivatives, acid anhydrides include anhydrides of the above dicarboxylic acids, such as maleic anhydride, itaconic anhydride, and phthalic anhydride, and lower (C1-4) alkyl esters include the above dicarboxylic acids. Lower alkyl esters of, for example, dimethyl adipate, ortho-, iso- and dimethyl terephthalate.

The diamine has 2 to 20 carbon atoms.
Aliphatic diamine (ethylenediamine, propylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, decamethylenediamine,
1,12-dodecanediamine, etc.), alicyclic diamine having 6 to 15 carbon atoms (1,4-cyclohexanediamine, isophoronediamine, 4,4′-diaminodicyclohexylmethane, 4,4′-diaminobicyclohexyl, etc.), Aroaliphatic diamine having 8 to 15 carbon atoms (such as xylylenediamine), aromatic diamine having 6 to 15 carbon atoms [p-phenylenediamine, 2,4- and / or 2,6-tolylenediamine, 2,2 -Bis (4,4'-
Diaminophenyl) propane, etc.] and the like.

Two or more of the above amide-forming monomers may be used in combination. Among these, caprolactam, 12-aminododecanoic acid and adipic acid / hexamethylenediamine are preferable from the viewpoint of conductivity, and caprolactam is particularly preferable.

The polyamide (Q1) uses one or more dicarboxylic acids having 4 to 20 carbon atoms as a molecular weight modifier,
It can be obtained by ring-opening polymerization or polycondensation of the amide-forming monomer in the presence thereof by a conventional method. Examples of the dicarboxylic acid having 4 to 20 carbon atoms include the above (3)
Among these, aliphatic dicarboxylic acids, aromatic dicarboxylic acids, and 3-sulfoisophthalic acid alkali metal salts are preferable from the viewpoint of conductivity, and more preferable are adipic acid, sebacic acid, and terephthalic acid. , Isophthalic acid and sodium 3-sulfoisophthalate.

The amount of the above-mentioned molecular weight modifier used is preferably 2 to 75% by weight from the viewpoint of the conductivity of the elastomer, based on the total weight of the amide-forming monomer and the molecular weight modifier.
More preferably, it is 4 to 60% by weight.

From the viewpoint of the reactivity with (b1-1) and the heat resistance of (b2-1) obtained, Mn of (Q1) is preferably 200 to 5,000, more preferably 500 to 3,0.
00. The Mn of (b1-1) is preferably 300 to 5,000, more preferably 50 from the viewpoint of conductivity.
It is 0 to 4,000.

The ratio of (b1-1) based on the total weight of (Q1) and (b1-1) is preferably 30 to 80% by weight, more preferably 40 to 70% by weight, from the viewpoint of the conductivity of the elastomer. Is.

Polyether ester amide (b2-1)
Examples of the production method of include the following production methods and
It is not particularly limited. Production method: An amide-forming monomer is reacted with a dicarboxylic acid (molecular weight modifier) to form (Q1), which is then added to (b
1-1), and the polymerization reaction is carried out at a high temperature (160 to 270 ° C.) under reduced pressure (0.03 to 3 kPa). Production method: An amide-forming monomer, a dicarboxylic acid (molecular weight adjusting agent) and (b1-1) are simultaneously charged into a reaction tank,
High temperature (160-270) in the presence or absence of water.
The intermediate (Q1) is produced by pressure (0.1 to 1 MPa) reaction at 0 ° C.), and then under reduced pressure (0.03).
~ 3 kPa) to carry out a polymerization reaction with (b1-1). Of the above production methods, the production method is preferable from the viewpoint of reaction control.

In the above polymerization reaction, a commonly used known esterification catalyst is used. Examples of the catalyst include antimony catalysts (such as antimony trioxide), tin catalysts (such as monobutyltin oxide), titanium catalysts (such as tetrabutyl titanate), zirconium catalysts (such as tetrabutyl zirconate), metal acetate catalysts (zinc acetate, Zirconyl acetate etc.) and the like. The amount of the catalyst used is usually 0.1 to 5% by weight based on the total weight of (Q1) and (b1-1), and preferably 0.2 to 3% by weight from the viewpoint of reactivity and resin physical properties. .

The polyether amide (b2-4) is composed of polyamide (Q1) and polyether diamine (b1-2). (B2-4) is (Q1) and (b1-
It is obtained by reacting with 2). The reaction conditions and the like are the same as in (b2-1). (B in 4-2)
The ratio of 1-2) is preferably 30 to 30 from the viewpoint of moldability.
It is 80% by weight, more preferably 40 to 70% by weight.

Examples of the polyether amide imide (b2-2) include the polyether amide imides described in JP-B-7-119342 and JP-A-06-172609. (B2-2) is at least 1
It is composed of a polyamideimide (Q2) having one imide ring and a polyether diol (b1-1). (Q
As 2), a polymer composed of a lactam and a trivalent or tetravalent aromatic polycarboxylic acid (including an acid anhydride, the same applies hereinafter) capable of reacting with an amino group to form at least one imide ring. A polymer composed of an aminocarboxylic acid and the aromatic polycarboxylic acid; a polymer composed of an amide of a diamine and a dicarboxylic acid and the aromatic polycarboxylic acid; and a mixture thereof. The same lactam, aminocarboxylic acid, diamine and dicarboxylic acid as described above can be used. (B2
The content of (b1-1) in -2) is preferably from 30 to 80% by weight, more preferably from 40 to 70% by weight, from the viewpoint of imparting chargeability to the elastomer and moldability of the resin composition.
Is. Among (b2-2), from the viewpoint of heat resistance, caprolactam, a trivalent or tetravalent aromatic polycarboxylic acid capable of reacting with an amino group to form at least one imide ring, and (b1-1) ), (B
It is a polyether amide imide having a content of 1-1) of 30 to 80% by weight.

Among the above-mentioned aromatic polycarboxylic acids, the trivalent aromatic polycarboxylic acid has 9 to 18 carbon atoms, for example, 1,2,4-trimellitic acid, 1,2,5- and 2,6. , 7-Naphthalenetricarboxylic acid, 3,3 ′, 4
-Diphenyltricarboxylic acid, benzophenone-3,
3 ', 4-tricarboxylic acid, diphenyl sulfone-3,
3 ', 4-tricarboxylic acid, diphenyl ether-3,
3 ', 4-tricarboxylic acid and their acid anhydrides;
The tetravalent aromatic polycarboxylic acid has 10 to 2 carbon atoms.
0, for example pyromellitic acid, diphenyl-2,2 ',
3,3′-tetracarboxylic acid, benzophenone-2,
2 ', 3,3'-tetracarboxylic acid, diphenyl sulfone-2,2', 3,3'-tetracarboxylic acid, diphenyl ether-2,2 ', 3,3'-tetracarboxylic acid,
And these acid anhydrides.

[0062]

The equivalent ratio in the reaction of the aromatic polycarboxylic acid and (b1-1) is usually 0.9 / 1 to 1.1 / 1,
From the viewpoint of resin properties, it is preferably 0.95 / 1 to 1.05
/ 1 mol.

The content of the polyamide-imide (Q2) constituting (b2-2) is preferably 20 to 70% by weight, more preferably 30 to 60% by weight from the viewpoint of imparting resin physical properties to the elastomer. In addition, polyamide imide (Q
The Mn of 2) is preferably 500 to 3,000, more preferably 800 to 2,000 from the viewpoint of the resin physical properties of the elastomer (b2-2).

The method for producing (b2-2) includes the following methods depending on the cases of the polyamideimide (Q2) and the above, but is not particularly limited. That is, lactam, aromatic polycarboxylic acid and (b1-1) are combined with aromatic polycarboxylic acid (b
The equivalent ratio of 1-1) is usually 0.9 to 1.1 (preferably 0.95 to 1.05) with respect to the total weight of lactam, aromatic polycarboxylic acid and (b1-1). From the viewpoint of the conductivity of the elastomer, (b1-1) is mixed in an amount of 30 to 80% by weight, preferably 40 to 70% by weight, and the water content of the resulting polymer is 0.1 to 1%.
It is a method in which polycondensation is usually carried out at 150 to 300 ° C., preferably 180 to 280 ° C. while maintaining the weight ratio. During the polycondensation, the reaction temperature can be raised stepwise. At this time, a part of the lactam remains unreacted, but it is desirable to remove it from the reaction mixture by distilling it off under reduced pressure from the viewpoint of the resin physical properties of the molded article described later. The reaction mixture after removing the unreacted lactam is polymerized under reduced pressure (0.03 to 3 kPa), if necessary, usually at 200 to 300 ° C (preferably 230 to 280 ° C) to obtain a polymer having a higher molecular weight. Can be united. Also, (Q2)
Is a polyether amide imide composed of an aminocarboxylic acid and the aromatic polycarboxylic acid, and (Q2) is a polyether amide imide composed of an amide of a diamine and a dicarboxylic acid, and the aromatic polycarboxylic acid. Can be manufactured in.

Examples of the polyether ester (b2-3) include the polyether ester described in JP-B-58-19696. (B2-3) is composed of polyester (Q3) and (b1-1).
As (Q3), a polyester of a dicarboxylic acid (previously described) and a diol (b01); a lactone having 6 to 12 carbon atoms or a polyester of oxycarboxylic acid having 6 to 12 carbon atoms; and a mixture thereof can be used. (B
Examples of the production method of 2-3) include the following production methods and, but are not particularly limited thereto. Manufacturing method:
The dicarboxylic acids exemplified as the constituents of (b1-1) and (b2-1) or their ester-forming derivatives [lower (C1-4) alkyl esters, acid anhydrides, etc.] are heated at high temperature (160-270 ° C.). ), Under reduced pressure (0.03-
A method of carrying out a polymerization reaction at 3 kPa). Manufacturing method: (b1-
A method of performing transesterification of 1) with polyethylene terephthalate, polybutylene terephthalate, etc. at high temperature (160 to 270 ° C.) under reduced pressure (0.03 to 3 kPa). Of the above production methods, the production method is preferable from the viewpoint of reaction control.

The content of (b1-1) in (b2-3) is
From the viewpoints of imparting chargeability to the elastomer and moldability of the resin composition, it is preferably 30 to 80% by weight, more preferably 40 to 70% by weight, and the melting point of (b2-3) [measurement is by a differential scanning calorimetry ( Hereinafter, according to the DSC method) is preferably 100 ° C. or higher, more preferably 120 to 210 ° C. from the viewpoint of heat resistance.

The polyether urethane (b2-5) is the same as the organic polyisocyanate (b1-1) or (b1).
-2) and optionally a chain extender [the dihydric alcohol and diamine (the above-mentioned ones in the above (b01)] and the like], for example, JP-B-47-35300.
JP-A-62-236854, JP-B-3-2965
Examples thereof include those described in Japanese Patent No. 65. (B2-5)
Is an organic polyisocyanate, and (b1-1) or (b
It can be obtained by reacting one or more selected from 1-2), and optionally a chain extender. The isocyanate group / hydroxyl group or amino group equivalent ratio in the reaction is 1/1 to 20/1, preferably 1 / 1.2 to 1
It is 0/1, and more preferably 1 / 1.5 to 5/1.

As the organic polyisocyanate, the above-mentioned ones can be used, and TDI, MDI and HDI are preferable from the viewpoint of the resin physical properties of the elastomer, and HDI is particularly preferable.

Polyether urethane is produced by a one-step method (one-shot method) and a multi-step method [wherein an isocyanate group-terminated prepolymer is previously formed and reacted with (b1-1) or (b1-2) to form a polyurethane. Prepolymer method or semi-prepolymer method].

As the cationic polymer (b3), a cationic polymer having 2 to 80, preferably 3 to 60, cationic groups (c2) separated by a nonionic molecular chain (c1) in the molecule. Can be used. (C1) is a divalent hydrocarbon group; at least one selected from ether bond, thioether bond, carbonyl bond, ester bond, imino bond, amide bond, imide bond, urethane bond, urea bond, carbonate bond and siloxy bond. And at least one divalent organic group selected from the group consisting of a divalent organic group having two kinds of bonds; and a divalent organic group having a heterocyclic structure containing a nitrogen atom or an oxygen atom.

The divalent hydrocarbon group has 1 to 1 carbon atoms.
8 (preferably 2 to 8) linear or branched aliphatic hydrocarbon group (alkylene group and alkenylene group, etc.), carbon number 6
To 20 aromatic hydrocarbon groups and C4 to C15 alicyclic hydrocarbon groups and the like. Ether bond, thioether bond, carbonyl bond, ester bond, imino bond,
Amide bond, imide bond, urethane bond, urea bond,
Examples of the divalent organic group having a carbonate bond or a siloxy bond include a (poly) oxyalkylene group, for example, a residue obtained by removing the hydroxyl group of the polyether diol (b1-1) and a residue obtained by removing the hydroxyl group of the monoether diol. A residue obtained by removing an SH group of a polythioether corresponding to the above (where an oxygen atom is replaced by a sulfur atom); a residue obtained by removing a hydroxyl group, an amino group or a carboxyl group from polyester and / or polyamide; a polyurethane and / Or a residue obtained by removing a hydroxyl group, an amino group or an isocyanate group from polyurea; polycarbonate [the above-mentioned diol (b01)
Derived from phosgene] and a residue obtained by removing a hydroxyl group; a residue of polyorganosiloxane and the like.

Of these (c1), from the viewpoint of the resin physical properties of the elastomer, a divalent hydrocarbon group and a divalent organic group having an ether bond are preferred, and an alkylene group having 2 to 8 carbon atoms is more preferred. (Hexamethylene group, etc.),
A phenylene group and a (poly) oxyalkylene group, particularly a (poly) oxyethylene group and a (poly) oxypropylene group. Mn of (c1) is usually 28 to 10,000.
It is 0, preferably 300 to 5,000.

Examples of the cationic group (c2) include groups having a quaternary ammonium salt or phosphonium salt. As the group having a quaternary ammonium salt, a divalent quaternary ammonium salt-containing heterocyclic group is preferable. Examples of the divalent quaternary ammonium salt group-containing heterocyclic group include a divalent tertiary amino group-containing heterocyclic group [for example, a divalent imidazole ring group (1,4-imidazolene group and 2-phenyl-1,4-phenyl group.
Imidazolene group, etc.), divalent piperidine ring group (2,3
-, 3,4- or 2,6-piperidylene group) and a divalent aromatic heterocyclic group (2,3-, 2,4-, 2,5-, 2,
6-, 3,4- or 3,5-pyridylene group, 2,5-pyrimidinylene group, 3,6-pyridazinylene group and 2,5
-Pyrazinylene group etc.)] is a group having a quaternized structure.

The counter anion of (c2) is Hamm
ett's acidity function (-H₀) Is 12 or more super acid (Pro
A combination of tonic acid and Lewis acid, etc.), and
And other anions. With anion of super strong acid
For example, BF_Four ^-, PF₆ ^-, SbF₆ ^-, AsF₆ ^-,
TLF₆ ^-, BF₃Cl^-, PF_FiveCl^-, SbF_FiveCl^-, A
sF_FiveCl^-, TLF_FiveCl^-, BF₃Br^-, PF_FiveBr^-,
SbF_FiveBr^-, AsF_FiveBr^-, TLF_FiveBr^-, BF
₃I^-, PF_FiveI^-, SbF_FiveI^- , AsF_FiveI^-And Tl
F_FiveI^-Is mentioned. As other anions, for example
If halogen ion (F^-, Cl^-, Br^-, I^-Etc.), OH
^-, PO_Four ^-, Alkylsulfate ion (CH₃OSO
₃ ^-, C₂H_FiveOSO₃ ^-, CF₃OSO₃ ^-Etc.), ClO_Four ^-etc
Is mentioned. Of these, the heat resistance of the elastomer
And SbF is preferable from the viewpoint of conductivity.₆ ^-, AsF₆ ^-,
TLF₆ ^-, And more preferably BF_Four ^-, PF₆ ^-so
is there.

From the viewpoint of reactivity with (a), the terminal structure of (b3) is preferably a group containing a carbonyl group, a hydroxyl group or an amino group. The Mn of (b3) is preferably from 500 to 500 from the viewpoint of conductivity and reactivity with (a).
20,000, more preferably 1,000 to 15,000
0, particularly preferably 1,200 to 8,000.

The anionic polymer (b4) includes a dicarboxylic acid having a sulfonyl group and a diol (b0).
1) or polyether (b1) as an essential constituent unit,
Further, an anionic polymer having 2 to 80, preferably 3 to 60, sulfonyl groups in the molecule can be used. As the dicarboxylic acid having a sulfonyl group, an aromatic dicarboxylic acid having a sulfonyl group, an aliphatic dicarboxylic acid having a sulfonyl group, and a salt of only these sulfonyl groups can be used.

The aromatic dicarboxylic acid having a sulfonyl group has 8 to 20 carbon atoms, for example, 5-sulfoisophthalic acid, 2-sulfoisophthalic acid, 4-sulfoisophthalic acid, 4-sulfo-2,6-naphthalenedicarboxylic acid. And ester-forming derivatives thereof [lower alkyl (C1 to C4) esters (methyl ester, ethyl ester, etc.), acid anhydrides, etc.]. Examples of the aliphatic dicarboxylic acid having a sulfonyl group include sulfosuccinic acid and its ester-forming derivative. Examples of salts formed by only these sulfonyl groups include alkali metal salts, alkaline earth metal salts, ammonium salts, amine salts such as mono-, di- or triamines having a hydroxyalkyl (C 2-4) group. , Quaternary ammonium salts of these amines, and combinations of two or more of these.
Among these, preferred are aromatic dicarboxylic acids having a sulfonyl group.

(B01) or (b) constituting (b4)
Preferred among 1) are alkane diols having 2 to 10 carbon atoms, ethylene glycol, polyethylene glycol (degree of polymerization 2 to 20), EO adducts of bisphenol (bisphenol A, etc.) (number of addition moles 2 to 60), and these. Is a mixture of two or more of Mn of (b4) is preferably 500 to 500 from the viewpoint of conductivity and reactivity with (a).
20,000, more preferably 1,000 to 15,000
0, particularly preferably 1,200 to 8,000.

(A) is a known method, for example, the polyether diol (b1-1) is added to the modified polyolefin (a1-1), and the polymerization (polycondensation) reaction is usually carried out at 200 to 250 ° C. under reduced pressure. It can be produced by a method of performing polymerization or a method of polymerizing using a uniaxial or biaxial extruder, usually at 160 to 250 ° C. and a residence time of 0.1 to 20 minutes. In the above polymerization reaction, known catalysts such as antimony catalyst (antimony trioxide etc.); tin catalyst (monobutyltin oxide etc.); titanium catalyst (tetrabutyl titanate etc.); zirconium catalyst (tetrabutyl zirconate etc.); organic acid Examples thereof include metal salt catalysts [zirconium organic acid salts (such as zirconyl acetate) and zinc acetate]; and mixtures of two or more of these. Of these, zirconium catalysts and zirconium organic acid salts are preferable, and zirconyl acetate is more preferable. The amount of the catalyst used is usually 0.00 based on the total weight of (a) and (b).
It is 1 to 5%, preferably 0.01 to 3%.

As a combination of (a) and (b),
(B1), (b) for (a1) and (a4)
2), (b3) and (b4); (a2) and (a
For (5), (b1-3), (b2), (b3) and (b4); for (a3) and (a6), (b1-
3), (b2), (b3) and (b4).

When (b2) is used, (b
After manufacturing 2), (a1), (a2), (a3),
(A4), (a5) and / or (a6) may be reacted, or (a1), (a2), (a3), (a4),
(B2) may be produced in the presence of (a5) and / or (a6).

The terminal of (A) is a carbonyl group derived from (a), an amino group, and / or an unmodified polyolefin terminal (a polyolefin terminal not modified at all, that is, an alkyl group or an alkenyl group), or (b) ) -Derived hydroxyl group, amino group, carbonyl group and /
Or is an isocyanate group. Of these, a carbonyl group, an amino group and a hydroxyl group are preferable as the terminal from the viewpoint of reactivity, and a carbonyl group and a hydroxyl group are more preferable.

The volume resistivity value of the hydrophilic polymer (b) (value measured by the method described below in an atmosphere of 23 ° C. and 50% RH) is 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm, It is preferably 1 × 10 ⁶ to 1 × 10 ⁹ Ω · cm. When the volume specific resistance value exceeds 1 × 10 ¹¹ Ω · cm, the electrical conductivity of the resin composition decreases, and when the volume specific resistance value is less than 1 × 10 ⁵ Ω · cm, the physical properties of the molded article using the conductive elastomer described later are poor. Become.

In the structure of the block polymer (A),
The average repeating number (Nn) of the repeating units of the block of (a) and the block of (b) is usually 2 to 50, preferably 2.3 to 30, more preferably 2.7 to 20, and particularly preferably. 3 to 10. When Nn is in this range,
It is preferable from the viewpoint of the resin physical properties of the elastomer. Nn is
From Mn and ¹ H-NMR analysis of (A), WO00 / 4
It can be determined by the method described in the 7652 specification.

From the viewpoint of conductivity, the Mn of the block polymer (A) is preferably 2,000 to 60,000, more preferably 5,000 to 40,000, and particularly preferably 8,000 to 30,000. is there. The amount of (b) constituting (A) is preferably 20 to 90%, more preferably 30 to 70%, from the viewpoint of conductivity, based on the total weight of (a) and (b).

Examples of the conductive substance (B) of the present invention include metals of Groups 6 to 14 of the periodic table of elements (for example, titanium, chromium,
Iron, copper, cobalt, nickel, palladium, zinc, tin,
Silver, gold, stainless steel, aluminum, etc.) and alloys thereof (copper-tin alloy, copper-zinc alloy, etc.), etc .; oxides (zinc oxide, titanium oxide, tin oxide, aluminum oxide, etc.), carbides ( Silicon carbide and titanium carbide, etc.),
Nitride (aluminum nitride, silicon nitride, titanium nitride, etc.) and salts [metal titanate salts (potassium titanate, sodium titanate, etc.), metal borate salts (magnesium borate, aluminum borate, etc.), metal silicate salts ( Calcium silicate, aluminum silicate, etc.), metal carbonate (calcium carbonate, etc.)]; carbon [carbon black (oil furnace black, channel black, lamp black, thermal black, acetylene black, etc.) and graphite (natural graphite, artificial graphite, etc.) ), Fullerene, carbon nanotube, etc.]; and combinations thereof.

Of these, metal, metal oxide, metal titanate, metal borate and carbon are preferred, metal oxide, metal titanate, metal borate and carbon are more preferred, and metal oxide is particularly preferred. They are zinc oxide, titanium oxide, potassium titanate, aluminum borate and carbon black, and carbon nanotubes.

Examples of the shape of (B) include fibrous shape (including whisker shape and tetrapot shape), needle shape, granular shape, flake shape and tube shape. The length of the fibrous conductive substance is preferably from 1 to 100 μm, more preferably from the viewpoint of moldability and conductivity of the conductive elastomer.
It is 5 to 70 μm, particularly preferably 2 to 50 μm. The thickness is preferably 0.01 to 10 μm, more preferably 0.02 to 5 μm, and particularly preferably 0.03 to 4 μm from the viewpoint of the moldability and conductivity of the conductive elastomer.
m.

The length of the major axis of the needle-shaped conductive material is from 1 to 100 from the viewpoint of moldability and conductivity of the conductive elastomer.
μm is preferable, 1.5 to 70 μm is more preferable, and 2 to 50 μm is particularly preferable. The ratio of the length of the major axis to the length of the minor axis (aspect ratio) is 10 to 1,000 from the viewpoint of the moldability and conductivity of the conductive elastomer.
Is more preferable, 50 to 800 is more preferable, and 100 to 500 is particularly preferable.

The primary (meaning non-aggregated) volume average particle diameter of the granular conductive material is preferably 0.01 to 5 from the viewpoint of moldability and conductivity of the conductive elastomer.
The thickness is 0 μm, more preferably 0.02 to 30 μm, and particularly preferably 0.03 to 10 μm.

The length of the major axis of the flaky conductive material is preferably 1 to 100 μm, more preferably 5 to 70 μm, from the viewpoint of moldability and conductivity of the conductive elastomer.
It is particularly preferably 10 to 50 μm. The aspect ratio is preferably 10 to 1,000, more preferably 5 from the viewpoint of the moldability and conductivity of the conductive elastomer.
0 to 800, particularly preferably 100 to 500.

The length of the tubular conductive material is preferably 1 to 100 μm, more preferably 1.5 to 70 μm, and particularly preferably 2 to 50 μm from the viewpoint of the moldability and conductivity of the conductive elastomer. The diameter is preferably 0.1 to 50 nm, more preferably 0.1 to 30 n, from the viewpoint of the moldability and conductivity of the conductive elastomer.
m, particularly preferably 0.1 to 20 nm.

From the viewpoint of conductivity, the combination of the composition and shape of the conductive material is preferably carbon fiber (PA
N-based carbon fibers and pitch-based carbon fibers), fullerenes and carbon flakes, and more preferably metal (aluminum, iron, copper, stainless steel, silver-plated copper and brass) fibers, metal oxide whiskers (zinc oxide whiskers, oxidation) Titanium whiskers, tin oxide whiskers, aluminum oxide whiskers, etc.), metal titanate salt whiskers (potassium titanate whiskers, sodium titanate whiskers, etc.),
Metal borate whiskers (magnesium borate whiskers and aluminum borate whiskers), carbon nanotubes and carbon black, particularly preferably zinc oxide whiskers, titanium oxide whiskers, potassium titanate whiskers, aluminum borate whiskers, carbon nanotubes and carbon. It is black.

[0095] The volume resistivity of the (B), the elastomer of the conductive's from the viewpoint 1 × 10 ^-6 ~1 × 10 ⁶
Ω · cm, more preferably 1 × 10 ⁻⁶ to 1 × 10 ⁵ Ω ·
cm, particularly preferably 1 × 10 ⁻⁶ to 1 × 10 ³ Ω · c
m, most preferably 1 × 10 ⁻⁶ to 1 × 10 ² Ω · cm.

The amount of (B) used is preferably 0.01 to 20%, more preferably 0.02 to 15%, particularly preferably 0.03, based on the total weight of (A) and (B).
-10%. If it is 0.01% or more, the conductivity is further improved, and if it is 20% or less, the moldability is further improved, and the specific gravity of the elastomer does not become too large.

The volume resistivity of the conductive elastomer of the present invention is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁸ Ω · cm,
It is more preferably 1 × 10 ⁻⁴ to 1 × 10 ⁶ Ω · cm, and particularly preferably 1 × 10 ⁰ to 1 × 10 ⁵ Ω · cm.

The conductive elastomer of the present invention may contain a thermoplastic resin (C), if necessary. Any thermoplastic resin may be used as (C) without particular limitation. For example, vinyl resin [polyolefin resin (C1), styrene resin (C2), acrylic resin (C)
3), diene (co) polymer (C4), etc.], amide resin (C5), ester resin (C6), acetal resin (C
7), a carbonate resin (C8), a thermoplastic urethane resin (C9), a mixture of two or more of these, and the like can be used. As the vinyl resin, a resin obtained by (co) polymerizing a vinyl monomer by an ordinary polymerization method (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.) can be used.

Examples of vinyl monomers include aliphatic hydrocarbon vinyl monomers, aromatic hydrocarbon vinyl monomers, acrylic monomers, other unsaturated mono- and dicarboxylic acid compounds, carboxylic acid esters of unsaturated alcohols,
Examples thereof include alkyl ethers of unsaturated alcohols, halogen-containing vinyl monomers, and combinations (random and / or block) of two or more of these.

As the aliphatic hydrocarbon vinyl monomer,
A vinyl monomer having 2 to 30 carbon atoms (preferably 2 to 220, more preferably 2 to 15) is used, and the olefin and diene (butadiene, isoprene, cyclopentadiene, 1,11-dodecadiene, etc.) are used. be able to.

As the aromatic hydrocarbon vinyl monomer,
Vinyl monomers having 8 to 30 carbon atoms (preferably 8 to 20, more preferably 10 to 16), for example, styrene, o
-, M- and p-alkylstyrenes (eg vinyltoluene, vinylethylbenzene), α-alkylstyrenes (eg α-methylstyrene, α-ethylstyrene) and halogenated styrenes (eg chlorostyrene, bromostyrene), etc. Is mentioned. Examples of the alkyl group in the above include alkyl groups having 1 to 10 carbon atoms (preferably 2 to 10, more preferably 4 to 8), such as methyl, ethyl, isobutyl, nonyl and decyl.

Examples of acrylic monomers include (meth) acrylic acid and its derivatives. Examples of the derivative of (meth) acrylic acid include alkyl (having 1 to 1 carbon atoms).
20, preferably 2 to 18, more preferably 4 to 14).
(Meth) acrylate {eg, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)
Acrylate, hexyl (meth) acrylate, undecyl (meth) acrylate, tetradecyl (meth) acrylate, etc.}, mono- or di-alkyl (having 1 to 1 carbon atoms
4) Aminoalkyl (C2-4) (meth) acrylate {for example, aminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, etc.}, (meth)
Examples thereof include acrylonitrile and (meth) acrylamide.

Other unsaturated mono- and di-carboxylic acid compounds have 4 to 30 carbon atoms (preferably 4 to 2 carbon atoms).
0, more preferably 6 to 15) unsaturated mono- and di-carboxylic acids (such as crotonic acid, maleic acid, fumaric acid and itaconic acid) and their derivatives [mono- and di-
Alkyl (C1-20) esters (methyl crotonic acid, dimethyl crotonic acid, diethyl malonate, diethyl malonate, diethyl itaconate, etc.), acid anhydrides (maleic anhydride, etc.) and imides (maleic acid imide, etc.), etc. ] Is mentioned. As the carboxylic acid ester of unsaturated alcohol, a carboxylic acid ester having 4 to 30 carbon atoms (preferably 4 to 20, more preferably 4 to 15), for example, carboxylic acid of vinyl alcohol and (meth) allyl alcohol (carbon number 2 to 4) esters (vinyl acetate, allyl acetate, etc.) can be mentioned.

The alkyl ether of unsaturated alcohol is an alkyl ether having 3 to 20 carbon atoms (preferably 3 to 18 and more preferably 5 to 14), such as alkyl alcohol (carbon number of vinyl alcohol and (meth) allyl alcohol). 1-20) ether (vinyl methyl ether,
Vinyl ethyl ether, vinyl propion ether, vinyl butyl ether, vinyl-2-ethylhexyl ether, etc.) and the like. The halogen-containing vinyl monomer has 2 to 30 carbon atoms (preferably 2 to 20 and more preferably 2 to 10), and 1 to 20 halogen atoms.
(Preferably 1-10, more preferably 1-5) vinyl monomers such as vinyl chloride, allyl chloride, vinylidene chloride, chloroprene, 8-bromo-1-octene and 8-bromo-2,6-dimethyl-2. -Octene and the like.

(C1) includes the aliphatic hydrocarbon vinyl monomer (ethylene, propylene, α having 4 to 30 carbon atoms).
One or more (co) polymers of olefins) and one or more vinyl monomers copolymerizable with one or more aliphatic hydrocarbon vinyl monomers (aliphatic hydrocarbon vinyl monomers / copolymerizable vinyl monomers) The weight ratio of 51/49 ~
99/1, preferably 70/30 to 95/5, and more preferably 80/20 to 90/10). As the copolymerizable vinyl monomer, the vinyl monomer other than the aliphatic hydrocarbon vinyl monomer is used.

As the polyolefin resin (C1), for example, polypropylene, polyethylene, propylene / ethylene copolymer [random and / or block addition,
Copolymerization ratio (weight ratio) = 0.1 / 99.9 to 99.9 /
0.1], propylene and / or ethylene and other α
-Copolymer (random and / or block addition) with one or more olefins (having 4 to 12 carbon atoms) [propylene or ethylene / other α-olefin copolymerization ratio (weight ratio) = 99/1 to 5 / 95, ethylene / propylene / other α-olefin terpolymerization, copolymerization ratio (weight ratio)
= (1 to 99) / (1 to 99) / (1 to 80)], ethylene / vinyl acetate copolymer (EVA) [copolymerization ratio (weight ratio) = 95/5 to 60/40], ethylene / Ethyl acrylate copolymer (EEA) [copolymerization ratio (weight ratio) = 9
5/5 to 60/40]. Of these, polypropylene, polyethylene, propylene / ethylene copolymers, propylene and / or ethylene and a carbon number of 4 to 1 are preferable from the viewpoint of compatibility with the elastomer.
2. Copolymer with at least one α-olefin [Propylene or ethylene / other α-olefin copolymerization ratio (weight ratio) = 90/10 to 10/90, ethylene / propylene / α-olefin terpolymerization In case of, copolymerization ratio (weight ratio)
= (1 to 99) / (1 to 99) / (1 to 80), random and / or block addition].

The melt flow rate of (C1) (hereinafter, M
FR is abbreviated), preferably 0.5 to 150, more preferably 1 to 100, particularly preferably 2 to 80. M
FR is JIS K7210: 1999 B method (in the case of polypropylene resin; temperature 230 ° C, load 2.16 kg)
f, average mass of cut piece 5 g, polyethylene resin; temperature 190 ° C., load 2.16 kgf, other olefin resin; temperature 230 ° C., load 2.16 kgf
It can be measured according to the average mass of cut pieces 5 g).

Examples of the styrene resin (C2) include one or more (co) polymers of the above-mentioned aromatic hydrocarbon vinyl monomers and one or more vinyl monomers copolymerizable with one or more of these monomers (aromatics). Hydrocarbon vinyl monomer / copolymerizable vinyl monomer weight ratio is 51/49 to 99
/ 1, preferably 70/30 to 95/5, and more preferably 80/20 to 90/10). Examples of the copolymerizable vinyl monomer include the vinyl monomers and dienes other than the aromatic hydrocarbon vinyl monomers.

Examples of (C2) are selected from the group consisting of aromatic hydrocarbon vinyl polymers (polystyrene, polyvinyltoluene, etc.); aromatic hydrocarbon vinyl monomers and methyl (meth) acrylate, acrylonitrile and butadiene. Copolymer with one or more kinds of monomers [styrene / acrylonitrile copolymer (AS resin) [copolymerization ratio (weight ratio) = 70/30 to 80/20], styrene /
Methyl methacrylate copolymer (MS resin) [copolymerization ratio (weight ratio) = 60/40 to 90/10], styrene / butadiene copolymer [copolymerization ratio (weight ratio) = 60/40 to
95/5], acrylonitrile / butadiene / styrene copolymer (ABS resin) [copolymerization ratio (weight ratio) = (20
~ 30) / (5-40) / (40-70)], methyl methacrylate / butadiene / styrene copolymer (MBS resin) [copolymerization ratio (weight ratio) = (20-30) / (5-4)
0) / (40-70)] and the like]. Among these, styrene / butadiene copolymers are preferable, polystyrene, AS resin and ABS resin are more preferable, and polystyrene and ABS resin are particularly preferable, from the viewpoint of resin physical properties of the elastomer. (C2)
The MFR is preferably 0.5 to 150, more preferably 1 to 100, particularly preferably 2 to 80 from the viewpoint of the resin physical properties of the elastomer. MFR is JIS K72
10: Measured according to the 1999 B method.

Examples of (C3) include one or more (co) polymers [poly (meth) acrylic acid] of the acrylic monomers [alkyl (C1-20) (meth) acrylate, (meth) acrylonitrile, etc.]. Methyl, poly (meth) butyl acrylate, etc.] and a copolymer of one or more of these monomers with one or more of the above-mentioned vinyl monomers copolymerizable [acrylic monomer / vinyl monomer copolymerization ratio (weight ratio) is 51/49 to 99/1, preferably 70/30 to 95/5, and more preferably 80/20 to 90/10] from the viewpoint of resin physical properties. (C3)
As, for example, polymethyl methacrylate, polybutyl acrylate, polydimethylaminoethyl acrylate,
Examples thereof include polyacrylonitrile and polyacrylamide. Of these, polybutyl acrylate is preferable, and polymethyl methacrylate, polyacrylonitrile and polyacrylamide are more preferable, and polymethyl methacrylate and polyacrylamide are particularly preferable from the viewpoint of the resin physical properties of the elastomer. (C
The MFR of 3) is preferably 0.5 to 150, more preferably 1 to 100, particularly preferably 2 to 80. M
FR can be measured according to JIS K7210: 1999 B method.

The diene (co) polymer (C4) includes at least one (co) polymer of the above diene and at least one vinyl monomer copolymerizable with at least one of these monomers (diene monomer / diene monomer / The weight ratio of the copolymerizable vinyl monomer is 51/49 to 99/1, preferably 70/30 to
95/5, more preferably 80/20 to 90/10)
And copolymers thereof are included. Examples of the copolymerizable vinyl monomer include the vinyl monomers other than the aromatic hydrocarbon vinyl monomer. Examples of (C4) include polybutadiene, polyisoprene, polychloroprene, ethylene / propylene / butadiene copolymer [copolymerization ratio (weight) = (5 to 90) / (5 to 90 / (5 to 2
0)],] and an acrylonitrile / butadiene copolymer [copolymerization ratio (weight ratio) = 10/90 to 60/40]. Of these, acrylonitrile / butadiene copolymers are preferable, and polybutadiene and ethylene / propylene / butadiene copolymers are more preferable, and ethylene / propylene / butadiene copolymers are particularly preferable, from the viewpoint of the resin physical properties of the elastomer. is there. The Mooney viscosity of (C4) is preferably 1 to 200.
M, more preferably 5 to 150 M, particularly preferably 10
~ 100M. The Mooney viscosity is JIS K
6300: 1974, in principle, a temperature of 100
It is measured at 0 ° C, a large rotor (L type), a residual heat time of 1 minute, and a rotor operating time of 4 minutes, but when the viscosity exceeds 100 M, it is measured by a small rotor (S type).

As the amide resin (C5), for example, ε
-Nylon 6 by ring-opening polymerization of caprolactam, nylon 66 by condensation polymerization of hexamethylenediamine and adipic acid, nylon 610 by polycondensation of hexamethylenediamine and sebacic acid, nylon 11 by polycondensation of 11-aminoundecanoic acid, ω- Nylon 1 by ring-opening polymerization of laurolactam or polycondensation of 12-aminododecanoic acid
2, and copolymerized nylon containing two or more kinds of the components in the nylon. Of these, nylon 1 is preferable from the viewpoint of the resin physical properties of the elastomer.
2, and more preferably nylon 6 and nylon 6
6, nylon 6 is particularly preferred. M of (C5)
FR is preferably 0.5 to 150, more preferably 1
-100, particularly preferably 2-80. MFR is
It is measured according to JIS K7210: 1999 B method. The intrinsic viscosity of (C5) is not particularly limited, but is preferably 0.1 to 4, more preferably 0.2 to 3.5, and particularly preferably 0.3 to 3.0. Above and below, the intrinsic viscosity is 0.5% of orthochlorophenol of the sample.
The solution is used and measured with an Ubbelohde 1A viscometer at 25 ° C.

As the ester resin (C6), for example,
Aromatic polyester (polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate, etc.), aliphatic polyester (polybutylene adipate, polyethylene adipate, poly-ε
-Caprolactone etc.) and the like. Of these,
From the viewpoint of the resin physical properties of the elastomer, polybutylene adipate is preferable, and polyethylene terephthalate, polybutylene terephthalate, and polyethylene adipate are more preferable, and polyethylene terephthalate and polybutylene terephthalate are particularly preferable. The intrinsic viscosity of (C6) is not particularly limited, but is preferably 0.1 to 4, more preferably 0.2 to 3.5,
Particularly preferably, it is 0.3 to 3.0.

As the acetal resin (C7), a homopolymer obtained by polymerizing formaldehyde or trioxane,
And a copolymer obtained by copolymerizing formaldehyde or trioxane with a cyclic ether [the above-mentioned alkylene oxide, for example, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), dioxolane, etc.] and the like. Examples of the homopolymer in (C7) include polyoxymethylene homopolymer,
Examples of the copolymer include polyoxymethylene / polyoxyethylene copolymer (polyoxymethylene / polyoxyethylene weight ratio 90/10 to 99/1, block copolymer). (C7) MFR
Is preferably 0.5 to 150, more preferably 1 to 1
00, particularly preferably 2 to 80. MFR is JI
It can be measured according to the SK7210: 1999 B method. The intrinsic viscosity of (C7) is not particularly limited,
Preferably 0.1-4, more preferably 0.2-3.
5, particularly preferably 0.3 to 3.0.

The carbonate resin (C8) includes a polycondensation product of bisphenol and phosgene or carbonic acid diester. Bisphenol has 12 to 12 carbon atoms
20, for example, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-
2,2-butane, dihydroxybiphenyl and the like can be mentioned. Of these, dihydroxybiphenyl is preferred, and bisphenol A, bisphenol F and bisphenol S are more preferred, and bisphenol A is particularly preferred. The MFR of (C8) is preferably 0.5 to 150, more preferably 1 to 1000, and particularly preferably 2 to 80. MFR is JIS K7
210: 1999 It can be measured according to the B method.

As the thermoplastic urethane resin (C9),
The organic polyisocyanate and the polymer diol [Mn
500 to 5,000 (preferably 500 to 4,500,
More preferably 700 to 4,000, particularly preferably 1,000 to 3,000), for example, the polyether (b1), polyester diol [the diol (b0
1) and / or (b1) and a polyester diol obtained by reacting the above dicarboxylic acid or the above lactone], a polymer polyol obtained by polymerizing a vinyl monomer (eg acrylonitrile and / or styrene) in these diols, etc. ], The chain extender and optionally a reaction terminator (monohydric alcohol, primary or secondary monoamine, or mono- or dialkanolamine)
Polyurethane obtained by reacting with a one-shot method or a prepolymer method. The melting point of (C9) is preferably 120 to 270 ° C., more preferably 1
30-260 degreeC, Especially preferably, it is 140-250 degreeC. The melting point is measured by the DSC method (differential scanning calorimetry), the temperature is raised at a temperature rising rate of 10 ° C./min, and the temperature at the peak top is taken as the melting point.

Of these thermoplastic resins (C), (C6), (C7), and more preferably,
(C1), (C2), (C5), particularly preferably (C
1). Further, these thermoplastic resins may be used as a mixed resin in which two or more kinds are mixed. Preferred as the mixed resin is (C1) / (C5) [mixing ratio (weight ratio)
= 95/5 to 20/80], (C1) / (C6) [mixing ratio (weight ratio) = 95/5 to 20/80], (C1) /
(C7) [mixing ratio (weight ratio) = 95/5 to 20/8
0], (C2) / (C5) [mixing ratio (weight ratio) = 95 /
5-20 / 80], (C2) / (C6) [mixing ratio (weight ratio) = 95 / 5-20 / 80] and (C2) / (C7)
[Mixing ratio (weight ratio) = 95/5 to 20/80],
More preferred are (C1) / (C5) [mixing ratio (weight ratio) = 95/5 to 20/80], (C1) / (C6).
[Mixing ratio (weight ratio) = 95/5 to 20/80], (C
1) / (C7) [mixing ratio (weight ratio) = 95/5 to 20 /
80].

Mn of (C) is preferably 20,000 to 5,000,000, more preferably 25,000 to, from the viewpoint of dispersibility of the conductive substance (B) and mechanical strength of the conductive elastomer. It is 1,000,000, particularly preferably 30,000 to 500,000.

When the conductive elastomer of the present invention contains a thermoplastic resin (C), (A), (B) and (C)
The amount of (C) used based on the total weight of is preferably 2 from the viewpoint of the conductivity and mechanical strength of the conductive elastomer.
It is 0 to 80%, more preferably 40 to 70%, and particularly preferably 45 to 60%.

The conductive elastomer of the present invention may contain an antistatic agent (D) and / or a compatibilizing agent (E) for the purpose of further improving the conductivity of the conductive elastomer. Examples of (D) include surfactant (D1) [anionic surfactant (D11), cationic surfactant (D12),
Nonionic surfactant (D13), amphoteric surfactant (D1
4) etc.], salts of alkali metals or alkaline earth metals other than the salts in (D1) (D2), ionic liquids (D3)
And a polymer type antistatic agent (D4).

Among the surfactants (D1), examples of the anionic surfactant (D11) include carboxylates, sulfates, sulfonates and phosphates. The cation constituting (D11) is not particularly limited as long as it forms a salt, and usually includes an alkali metal, an alkaline earth metal, ammonium and the like.

As the carboxylic acid salt, higher fatty acids having 8 to 20 carbon atoms (octanoic acid, lauric acid, stearic acid,
Oleic acid, eicosanoic acid, etc.) salts.

The sulfate ester salt has 8 to 20 carbon atoms.
Higher alcohols (octyl alcohol, cetyl alcohol, lauryl alcohol, stearyl alcohol, eicosyl alcohol, etc.) sulfate esters and higher alkyl ethers [EO of the above higher alcohols (1-
50 mol) adduct], sulfate oil, funnel oil, castor oil, sulfated oil (sulfated oil such as sulfated beef oil, sulfated peanut oil, sulfated McCo whale oil, etc.), sulfated fatty acid ester ( Examples thereof include sulfated butyl oleate, sulfated butyl ricinoleate, etc.), salts of sulfated olefins having 8 to 20 carbon atoms, and the like.

As the sulfonate, an alkylbenzene sulfonate having an alkyl group having 8 to 20 carbon atoms (octyl, lauryl, octadecyl, eicosyl etc.),
C8-20 alkyl (as mentioned above) sulfonates, C10-20 (alkyl) naphthalene (di)
Sulfonate (1-naphthalene sulfonate, 1,4-
Naphthalene disulfonate, 2-methyl-1-naphthalene sulfonate, 2-methyl-1,4-naphthalene disulfonate, etc.), α-olefin sulfonate having 8 to 20 carbon atoms, Igepon T-type sulfonate And carbon number 8
Examples thereof include sulfosuccinate dialkyl esters having ˜20 alkyl groups (such as sodium sulfosuccinate di-2-ethylhexyl ester) and polyvinyl sulfonates (such as salts of polystyrene sulfonic acid). Examples of the phosphoric acid ester salts include phosphoric acid mono- and di-ester salts of higher alcohols having 8 to 20 carbon atoms (as described above).

These anionic surfactants (D11)
May be one kind or a mixture of two or more kinds. Among these, higher fatty acid salts, alkylbenzene sulfonates, alkylsulfonates and mixtures thereof are preferable from the viewpoint of the conductivity of the conductive elastomer, and more preferable are stearates, dodecylbenzenesulfonate and lauryl. Sulfonates and mixtures thereof, particularly preferred are sodium stearate, sodium dodecylbenzene sulfonate, sodium lauryl sulfonate and mixtures thereof.

As the cationic surfactant (D12),
Quaternary ammonium salt and / or phosphonium salt,
For example, a compound represented by the following general formula may be mentioned.

[0127]

[Chemical 1]

In the formula, J is a nitrogen atom or a phosphorus atom (preferably a nitrogen atom); R ¹ and R ⁴ are C 1-20.
Or an (substituted) phenyl group having 6 to 20 carbon atoms; R ² and R ³ may have an amide bond, an imide bond, an ester bond, an ether bond or a urea bond, and R ² and R 3 ³ is an alkylene group having 1 to 20 carbon atoms which may be bonded to each other to form a ring or (substituted)
Phenylene group; M ^- is anion; v is an integer of 1 to 10 (preferably 1 to 6).

As the anion constituting (D12),
As (D12), those having a heat loss onset temperature in air of 200 ° C. or higher can be used, and examples thereof include a conjugate base of a super strong acid [Hammett's acidity function (−H ₀ ) is at least 12] and other anions. . In this case, the thermal loss starting temperature is 8. of JIS K7120: 1987. It is a value measured according to the TG curve analysis method described in the section. When R ¹ , R ² , R ³ and R ⁴ do not have β hydrogen (for example, tetramethylammonium and trimethylbenzylammonium), Hofmann decomposition cannot occur. Therefore, the conjugate base of superstrong acid and other anions Any of these can be used, but when β is present in R ¹ , R ² , R ³ and R ⁴ (eg, trimethylethylammonium, didecyldimethylammonium), a conjugate base of a super strong acid is preferable.

As anions other than the conjugate base of the super strong acid, halogen (fluorine, chlorine, bromine, etc.) ions, p-
Examples thereof include toluene sulfonate ion and undecafluoropentane sulfonate ion.

Super-strong acids include those derived from protic acids and combinations of protic acids with Lewis acids, and mixtures thereof. As the protic acid as a super strong acid, bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane (carbon number) 1 to 30) sulfonic acid [eg, methanesulfonic acid, dodecanesulfonic acid, etc.], poly (n = 1 to 3)
0) Fluoroalkane (having 1 to 30 carbon atoms) sulfonic acid (trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, heptafluoropropanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid Etc.), boric acid, borofluoric acid, and tetrafluoroboric acid. Of these, borofluoric acid, trifluoromethanesulfonic acid, and bis (pentafluoroethylsulfonyl) imidic acid are preferable from the viewpoint of ease of synthesis.

The protonic acid used in combination with the Lewis acid includes hydrogen halides (hydrogen fluoride, hydrogen chloride, hydrogen bromide, hydrogen iodide, etc.), perchloric acid, fluorosulfonic acid, methanesulfonic acid, trifluoromethane. Examples thereof include sulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid, and mixtures thereof. Of these, hydrogen fluoride is preferable from the viewpoint of the conductivity of the elastomer.

As the Lewis acid, a Group 13 element (boron,
Thallium, etc. fluorides (boron trifluoride, thallium pentafluoride, etc.) and Group 15 elements (phosphorus, antimony,
Arsenic and the like) fluoride (phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, etc.). Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the conductivity of the elastomer. The combination of a protonic acid and a Lewis acid is arbitrary, but as a super strong acid composed of these combinations, tetrafluoroboric acid, hexafluorophosphoric acid, thallium hexafluoride, antimony hexafluoride, thallium hexafluoride sulfonate can be used. , Tetrafluoroboric acid, hexafluorophosphoric acid, chlorotrifluoroboric acid, and the like. These may be used alone or as a mixture of two or more kinds.

Of the anions constituting (D12), the conjugate base of a super strong acid (a super strong acid consisting of a protic acid and a super strong acid consisting of a combination of a protic acid and a Lewis acid) is preferable from the viewpoint of the conductivity of the elastomer. (Conjugated base), more preferably a super strong acid consisting of a protic acid and a conjugate base of a super strong acid consisting of a protonic acid and boron trifluoride and / or phosphorus pentafluoride among Lewis acids.

Of (D12), specific examples of the quaternary ammonium salt include (a) a salt of an anion other than the conjugate base of a super strong acid, and (b) a super strong acid (protonic acid, protonic acid and Lewis acid). Combinations) and salts with a conjugated base are separately exemplified. (A) Salts of superstrong acids with anions other than the conjugate base Quaternary ammonium, such as tetramethylammonium, tetraethylammonium, trimethylbenzylammonium, trimethyldodecylammonium, didecyldimethylammonium and trimethyl-2-ethylhexylammonium, and superstrong acids Anion other than the conjugated base of, for example, fluoride, chloride, bromide,
Salts combining p-toluenesulfonic acid and undecafluoropentanesulfonic acid, etc.

(B1) Salt of Super Strong Acid (Protonic Acid) with Conjugate Base The above quaternary ammonium and a conjugate base of super strong acid (protonic acid) such as methanesulfonic acid, perchloric acid, fluorosulfonic acid, Salts combining trifluoromethanesulfonic acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid and tridecafluorohexanesulfonic acid, etc.

(B2) Salt of super strong acid (combination of protonic acid and Lewis acid) with conjugate base Quaternary ammonium described above and a conjugate base of super strong acid (combination of protonic acid and Lewis acid), for example, tetrafluoro Salts combining boric acid, hexafluorophosphoric acid, thallium hexafluoride, antimony hexafluoride and thallium hexafluoride sulfonate, etc.

Among (D12), specific examples of the phosphonium salt are (c) a salt of an anion other than the conjugate base of a super strong acid,
(D) Examples of the salt of a super strong acid (protonic acid, a combination of a protonic acid and a Lewis acid) with a conjugate base are given separately. (C) Salt of an anion other than the conjugate base of superacid, phosphonium, for example, tetramethylphosphonium, tetraethylphosphonium, trimethylbenzylphosphonium, trimethyldodecylphosphonium, didecyldimethylphosphonium and trimethyl-2-ethylhexylphosphonium, and a conjugate base of superacid Other than anions such as fluoride, chloride, bromide, p-toluenesulfonic acid, and salt combining undecafluoropentanesulfonic acid

(D) Salt of super strong acid (protonic acid) with conjugate base: The above phosphonium and a conjugate base of super strong acid (protonic acid), such as methanesulfonic acid, perchloric acid, fluorosulfonic acid, trifluoromethanesulfone. Acid, pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, and salt combining tridecafluorohexanesulfonic acid, etc.

(D2) Salt of Super Strong Acid (Combination of Protonic Acid and Lewis Acid) with Conjugate Base The above phosphonium and a conjugate base of super strong acid (combination of protonic acid and Lewis acid), for example, tetrafluoroboric acid, Hexafluorophosphoric acid, thallium hexafluoride, antimony hexafluoride, and salts in combination with thallium hexafluoride, etc.

Of the above (a) to (d), from the viewpoint of the conductivity of the elastomer, a conjugate base of a super strong acid (a super strong acid consisting of a protic acid and a super strong acid consisting of a combination of a protic acid and a Lewis acid) is preferable. A conjugate base), and more preferably, a super strong acid consisting of a protic acid and a conjugate base of a super strong acid consisting of a protonic acid and a Lewis acid consisting of boron trifluoride and / or phosphorus pentafluoride. These may be used alone or as a mixture of two or more kinds, or may be a mixture of an anion other than the conjugate base of the super strong acid and the conjugate base of the super strong acid. In the case of a mixture of an anion other than the conjugate base of superacid and the conjugate base of superacid, the ratio (weight ratio) is preferably 95/5 to 5/95, more preferably 70/30 from the viewpoint of the conductivity of the elastomer.
~ 30/70.

As the nonionic surfactant (D13),
Polyethylene glycol type [EO (1 to 50 mol) adduct of higher alcohol (same as above), EO (1 to 30 mol) adduct of higher fatty acid (same as above),
EO (1 to 50 mol) adduct of higher alkyl amine (C8 to C18, for example, 1-octylamine, 1-dodecylamine), polypropylene glycol (Mn 1.00)
EO (5-150 mol) adduct of 0 to 3,000); polyhydric alcohol type [polyethylene oxide (polymerization degree n = 3 to 300), fatty acid of glycerin (having 4 to 4 carbon atoms)
30, such as caproic acid, octylic acid, lauric acid, stearic acid, oleic acid) ester, fatty acid of pentaerythritol (as described above) ester, fatty acid of sorbitol or sorbitan (as described above), polyhydric alcohol (carbon number) 3-12, for example, glycerin, sorbitan) alkyl (C1-30) ether, alkanolamine (C2-20) fatty acid (the above) amide, etc.] and the like.

Examples of the amphoteric surfactant (D14) include amino acid type [higher alkyl (8 to 18 carbon atoms) aminopropionate, etc.] betaine type (higher alkyl (8 carbon atoms).
~ 18) dimethyl betaine, higher alkyl (C8 ~
18) Dihydroxyethyl betaine, etc.] and the like. These may be used alone or in combination of two or more.

Examples of the alkali metal or alkaline earth metal salt (D2) other than the salt in (D1) include alkali metal (lithium, sodium, potassium, etc.) or alkaline earth metal (magnesium, calcium, etc.) and a protonic acid. And salt. Examples of the protic acid include those exemplified as those used in combination with the Lewis acid.

Specific examples of (D2) include fluorides (lithium fluoride, sodium fluoride, potassium fluoride, magnesium fluoride, calcium fluoride, etc.), chlorides (lithium chloride, sodium chloride, potassium chloride, chloride). Magnesium, calcium chloride, etc., bromide (lithium bromide, sodium bromide, potassium bromide, magnesium bromide, calcium bromide, etc.), iodide (lithium iodide, sodium iodide, potassium iodide, magnesium iodide, Calcium iodide, etc.), perchlorates (lithium perchlorate, sodium perchlorate, potassium perchlorate,
Magnesium perchlorate, calcium perchlorate, etc.), Fluorosulfonates (lithium fluorosulfonate, sodium fluorosulfonate, potassium fluorosulfonate, magnesium fluorosulfonate, calcium fluorosulfonate, etc.), methanesulfonate ( Lithium methanesulfonate, sodium methanesulfonate, potassium methanesulfonate, magnesium methanesulfonate, calcium methanesulfonate, etc., trifluoromethanesulfonate (lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, potassium trifluoromethanesulfonate) , Magnesium trifluoromethanesulfonate, calcium trifluoromethanesulfonate, etc.), pentafluoroethanesulfonate (pentaflu) Lithium loethanesulfonate, sodium pentafluoroethanesulfonate, potassium pentafluoroethanesulfonate, magnesium pentafluoroethanesulfonate, calcium pentafluoroethanesulfonate, etc.), nonafluorobutanesulfonate (lithium nonafluorobutanesulfonate, Sodium nonafluorobutanesulfonate, potassium nonafluorobutanesulfonate, magnesium nonafluorobutanesulfonate, calcium nonafluorobutanesulfonate, etc., undecafluoropentanesulfonate (lithium undecafluoropentanesulfonate, undecafluoropentane) Sodium sulfonate, potassium undecafluoropentane sulfonate, magnesium undecafluoropentane sulfonate, unde Calcium fluoropentanesulfonate, etc., tridecafluorohexanesulfonate (lithium tridecafluorohexanesulfonate, sodium tridecafluorohexanesulfonate, potassium tridecafluorohexanesulfonate, magnesium tridecafluorohexanesulfonate, and tridecafluorohexanesulfonate) Fluorohexane sulfonate calcium etc.) and the like. Among these, chloride and perchlorate are preferable from the viewpoint of the conductivity of the elastomer, and lithium chloride, potassium chloride, lithium perchlorate, potassium perchlorate and sodium perchlorate are more preferable.

The ionic liquid (D3) is a compound except the above-mentioned (D1) and (D2), has a melting point of room temperature or lower,
At least one of the cations or anions constituting (D3) is an organic ion and has an initial conductivity of 1 to 200.
It is a room temperature molten salt of ms / cm (preferably 10 to 200 ms / cm), and examples thereof include the room temperature molten salt described in WO95 / 15572.

The cation constituting (D3) includes amidinium cation, guanidinium cation and 3
Examples thereof include secondary ammonium cations.

Examples of the amidinium cation include imidazolinium cation [1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, and 1,3-dimethylimidazolinium. Rinium,
1,3-Dimethyl-2,4-diethylimidazolinium and the like]; imidazolium cation [1,3-dimethylimidazolium, 1,3-diethylimidazolium, 1-
Ethyl-3-methylimidazolium, 1,2,3-trimethylimidazolium, etc.]; Tetrahydropyrimidinium cation [1,3-Dimethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3 -Trimethyl-
1,4,5,6-tetrahydropyrimidinium, 1,
2,3,4-tetramethyl-1,4,5,6-tetrahydropyrimidinium, 1,2,3,5-tetramethyl-
1,4,5,6-tetrahydropyrimidinium, etc.];
Dihydropyrimidinium cation [1,3-dimethyl-
1,4- or -1,6-dihydropyrimidinium,
1,2,3-trimethyl-1,4- or -1,6-
Dihydropyrimidinium, 1,2,3,4-tetramethyl-1,4- or -1,6-dihydropyrimidinium] and the like.

As the guanidinium cation, a guanidinium cation having an imidazolinium skeleton [2-
Dimethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3,4-trimethylimidazolinium, 2-diethylamino-1,3-dimethyl-4-ethylimidazolinium, 2-dimethylamino -1-methyl-3,4-diethylimidazolinium and the like]; guanidinium cation having an imidazolium skeleton [2-dimethylamino-1,3,4-trimethylimidazolium, 2-diethylamino-1,3,4 -Trimethylimidazolium, 2-diethylamino-1,3-
Dimethyl-4-ethylimidazolium, 2-dimethylamino-1-methyl-3,4-diethylimidazolium, etc.]; guanidinium cation having a tetrahydropyrimidinium skeleton [2-dimethylamino-1,3,4-
Trimethyl-1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3,4-trimethyl-
1,4,5,6-tetrahydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,
4,5,6-Tetrahydropyrimidinium, etc.]; Guanidinium cation having a dihydropyrimidinium skeleton [2-dimethylamino-1,3,4-trimethyl-
1,4- or -1,6-dihydropyrimidinium,
2-diethylamino-1,3,4-trimethyl-1,4
-Or -1,6-dihydropyrimidinium, 2-diethylamino-1,3-dimethyl-4-ethyl-1,4
-Or -1,6-dihydropyrimidinium, etc.] and the like.

Examples of the tertiary ammonium cation include methyldilauryl ammonium and the like.

The above amidinium cations and guanidinium cations may be used alone or in combination of two or more. Of these, an amidinium cation is preferable, an imidazolium cation is more preferable, and 1 is particularly preferable from the viewpoint of initial conductivity.
-Ethyl-3-methylimidazolium cation.

In the ionic liquid (D3), examples of the organic acid and / or inorganic acid forming the anion include the following. Examples of the organic acid include carboxylic acid, sulfuric acid ester, higher alkyl ether sulfuric acid ester, sulfonic acid and phosphoric acid ester. For example, the organic acids described in (D1) and (D2) above can be used. As the inorganic acid, phosphoric acid, boric acid, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid,
Examples thereof include antimony hexafluoride and arsenic hexafluoride. The above organic acids and inorganic acids may be used alone or in combination of two or more.

Of the above organic acids and inorganic acids, it is preferable from the viewpoint of the initial conductivity of the ionic liquid that the anion constituting the ionic liquid (D3) has a Hammett acidity function (-H ₀ ) of 12 to 100. There is a conjugate base of super strong acid,
Anions other than the conjugate base of superacid and mixtures thereof.

Examples of the anion other than the conjugate base of the super strong acid include a halogen (fluorine, chlorine, bromine, etc.) ion, an alkyl (C 1-12) benzenesulfonic acid (p-toluenesulfonic acid, etc.) ion, and a poly ( n
= 1 to 25) Fluoroalkanesulfonic acid (undecafluoropentanesulfonic acid, etc.) ions and the like can be mentioned.

The superacids include those mentioned above, namely those derived from protic acids and combinations of protic and Lewis acids, and mixtures thereof. As the protic acid as the super strong acid, those mentioned above can be mentioned. Further, the protonic acid to be combined with the Lewis acid also includes the above-mentioned ones, and of these, hydrogen fluoride is preferable from the viewpoint of the initial conductivity of the ionic liquid. Examples of the Lewis acid include those mentioned above. Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of the ionic liquid. The combination of the protonic acid and the Lewis acid is arbitrary as described above.

Of the above anions, from the viewpoint of the initial conductivity of the ionic liquid, a conjugate base of a super strong acid (a super strong acid consisting of a protic acid and a super strong acid consisting of a combination of a protic acid and a Lewis acid) is further preferable. Preferred is a super strong acid consisting of a protic acid or a protic acid, and a conjugate base of a super strong acid consisting of boron trifluoride and / or phosphorus pentafluoride.

The amount of (D1), (D2) and / or (D3) used is usually 10% or less based on the total weight of (A), (B) and (C). From 0.001 to 5%, more preferably from 0.
It is 005 to 4%, particularly preferably 0.01 to 3%, most preferably 0.01 to 2%. Within the above range, the balance between mechanical strength and conductivity of the conductive elastomer tends to be further improved.

For the conductive elastomer (D1), (D2)
The method for adding (D3) and (D3) is not particularly limited, but (A) is preferred because of the ease of effective dispersion in the composition.
It is preferable to add (D1), (D2) and / or (D3) in advance during the production (polymerization) of and to disperse them. (D
The timing of adding 1), (D2) and / or (D3) during the production of (A) is not particularly limited and may be before polymerization, during polymerization or after polymerization.

Examples of the polymer type antistatic agent (D4) include polyether ester amides composed of polyoxyalkylene adducts of bisphenol A described in JP-A-7-10989. The amount of (D4) used is based on the total weight of (A), (B) and (C).
Usually 50% or less, preferably 0.5 to 40%, more preferably 1 to 30%, from the viewpoint of resin physical properties of the elastomer,
It is particularly preferably 5 to 20%. Within the above range, the conductivity tends to be further improved.

The compatibilizer (E) is at least one selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group.
Modified vinyl polymers having various functional groups (polar groups) can be used, and examples thereof include the polymers described in JP-A-3-258850. Further, for example, Japanese Patent Laid-Open No. 6-
A modified vinyl polymer having a sulfonyl group described in Japanese Patent No. 345927, a block polymer having a polyolefin portion and an aromatic vinyl polymer portion, and the like can also be used.
(E) is particularly effective in improving the compatibility between (A) and (C) other than (C1).

The amount of the compatibilizer (E) used is (A),
It is usually 20% or less based on the total weight of (B) and (C), preferably from the viewpoint of the resin physical properties of the elastomer.
It is 1 to 15%, more preferably 1 to 10%, and particularly preferably 1.5 to 8%. Within the above range, the balance between mechanical strength and conductivity tends to be further improved.

As a method of adding (D4) and / or (E), from the viewpoint of avoiding the reaction with unreacted (a) and / or (b), (A) obtained by polymerization is added. The method of addition is preferred.

In the conductive elastomer of the present invention, other additives (F) for resins are added to the extent that the effects of the present invention are not impaired.
Can be added if necessary. (F) The total amount used is usually 20 based on the total weight of (A) and (B).
It is 0% or less, preferably 0.05 to 150%. The (F) is added after mixing a resin composition containing (A) to (B) or (A) to (B) and optionally (C), (D) and / or (E). May be (A)
It may be contained in advance. Examples of (F) include a colorant (F1), a filler (F2), and a nucleating agent (F
3), lubricant (F4), plasticizer (F5), release agent (F
6), antioxidants (F7), ultraviolet absorbers (F8), antibacterial agents (F9) and flame retardants (F10).

Examples of the colorant (F1) include pigments and dyes. As the pigment, an inorganic pigment (titanium oxide,
Aureoline, iron oxide, chromium oxide, cadmium sulfide, etc.); organic pigments (azo lake type, monoazo type, disazo type, chelate azo type, benzimidazoline type, phthalocyanine type, quinacridone type, dioxazine type, isoindolinone type, thioindigo type, Perylene-based, quinophthalone-based, anthraquinone-based, etc.).

As the dye, azo type, anthraquinone type, indigoid type, sulfide type, triphenylmethane type,
Examples include pyrazolone, stilbene, diphenylmethane, xanthene, alizarin, acridine, quinoneimine, thiazole, methine, nitro, nitroso, aniline. The amount of (F1) used is usually 5% by weight or less, preferably 0.1 to 3% by weight, based on the total weight of (A) and (B).

Examples of the filler (F2) include fibrous, powdery, and plate-shaped fillers other than (B). Examples of the fibrous filler include glass fiber, silica fiber, silica-alumina fiber, zirconia fiber and aramid fiber. Among these, glass fibers and silica fibers are preferable from the viewpoint of the mechanical strength of the molded product. Examples of the particulate filler include silica, quartz powder, glass beads, and silicates (calcium silicate, aluminum silicate, kaolin, talc, clay, etc.). Examples of the plate-like filler include mica and glass flakes. These fillers may be used alone or in combination of two or more. Of the above-mentioned fillers, fibrous fillers, particularly glass fibers, are preferable from the viewpoint of mechanical strength of the molded product. The amount of (F2) used is usually 150% or less, preferably 5 to 10 based on the total weight of (A) and (B).
It is 0%.

As the nucleating agent (F3), 1,3,2,4-
Di-benzylidene-sorbitol, aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium-bis (4-t-butylphenyl) phosphate, sodium benzoate and the like can be mentioned. The amount of (F3) used is usually 20% or less, preferably 1 to 10%, based on the total weight of (A) and (B).

Examples of the lubricant (F4) include waxes (carnauba wax etc.), higher fatty acids (the above-mentioned ones such as stearic acid), higher alcohols (the above-mentioned ones).
Examples thereof include stearyl alcohol) and higher fatty acid amides (stearic acid amide). (F
The amount of 4) used is usually 20% or less, preferably 1 to 10%, based on the total weight of (A) and (B).

As the plasticizer (F5), aromatic carboxylic acid ester-based [phthalic acid ester (dioctyl phthalate, dibutyl phthalate, etc.)], aliphatic monocarboxylic acid ester-based [methyl acetyl ricinoleate, triethylene glycol dibenzoate, etc.] Etc.], aliphatic dicarboxylic acid ester-based [di (2-ethylhexyl) adipate, adipic acid-propylene glycol-based polyester, etc.], aliphatic tricarboxylic acid ester-based [citric acid esters (such as triethyl citrate)], phosphoric acid Examples thereof include triester type [triphenyl phosphate and the like], epoxy type [epoxidized oil, epoxy fatty acid ester (epoxy butyl stearate, epoxy octyl stearate and the like)], petroleum resin and the like. (F
The amount of 5) used is usually 20% or less, preferably 1 to 10%, based on the total weight of (A) and (B).

As the releasing agent (F6), a lower (C1-4) alcohol ester of a higher fatty acid (the above-mentioned) (butyl stearate or the like), a fatty acid (C4-4) is used.
0) polyhydric alcohol esters (such as hydrogenated castor oil),
Examples thereof include glycol esters of fatty acids (the ones mentioned above) (such as ethylene glycol monostearate) and liquid paraffin. The amount of (F6) used is (A) and (B)
It is usually 10% or less, preferably 0.1 to 5%, based on the total weight of

As the antioxidant (F7), phenol type [monocyclic phenol [2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, etc.], polycyclic phenol [1,3,5- Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,1,3-tris (2-methyl-4-)
Hydroxy-5-t-butylphenyl) butane, tetrakis [methylene-3- (3 ', 5'-di-t-butyl-
4'-hydroxyphenyl) propionate] methane [trade name "Irganox 1010", manufactured by Ciba-Geigy Co., Ltd., etc.], bisphenol [2,2'-methylenebis (4-methyl-6-t-butylphenol),
4,4'-butylidene bis (3-methyl-6-t-butylphenol), 4,4'-thiobis (3-methyl-6)
-T-butylphenol) and the like]]; sulfur-based [dilauryl-3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, laurylstearyl-3,3'-thiodipropionate, Dimyristyl-
3,3′-thiodipropionate, distearyl-β,
β'-thiodibutyrate, dilauryl sulfide, etc.]; phosphorus-based [triphenylphosphite, triisodecylphosphite, diphenylisodecylphosphite, phenyldiisodecylphosphite, tris (2,
4-di-t-butylphenyl) phosphite, 2,2-
Methylenebis (4,6-di-t-butylphenyl) octylphosphite, 4,4'-butylidene-bis (3
-Methyl-6-t-butylphenylditridecyl) phosphite, cyclic neopentanetetraylbis (octadecylphosphite), cyclic neopentanetetraylbis (2,6-di-t-butyl-4-methylphenyl) ) Phosphite), cyclic neopentanetetraylbis (2,4-di-t-butylphenyl) phosphite, diisodecylpentaerythritol diphosphite]; amine-based [octylated diphenylamine, Nn-butyl-p- Aminophenol, N, N
-Diisopropyl-p-phenylenediamine, N, N-
Bis (1-ethyl-3-methylpentyl) -p-phenylenediamine, N, N-diphenyl-p-phenylenediamine, N-phenyl-α-naphthylamine, phenyl-β-naphthylamine, phenothiazine, etc.] and the like. The amount of (F7) used is usually 5% or less, preferably 0.1 to 3 based on the total weight of (A) and (B).
%.

As the ultraviolet absorber (F8), benzotriazole type [2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxyphenyl) benzotriazole, etc.], benzophenone type ( 2-hydroxybenzophenone, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, etc.), salicylic acid system (phenyl salicylate, pt-butylphenyl salicylate, p-octylphenyl salicylate, etc.) , Acrylate-based (2-ethylhexyl-2-cyano-3,3 ′, 1-diphenyl acrylate, etc.) and the like. (F
The amount of 8) used is usually 5% or less, preferably 0.1 to 3%, based on the total weight of (A) and (B).

As the antibacterial agent (F9), a quaternary ammonium salt [trimethoxysilyl-propyloctadecyl ammonium chloride, etc.], a pyridine compound [2,
3,5,6-Cytochloro-4- (methylsulfonyl)
-Pyridine], organic acid (ester) [benzoic acid, sorbic acid, paraoxybenzoic acid ester, etc.], halogenated phenol [2,4,6-tribromophenol sodium salt, 2,4,6-trichlorophenol sodium salt, Parachlorometaxylenol, etc.], organic iodine [4-chlorophenyl-3-iodopropargyl formal, 5-chloro-2-methyl-4-isothiazoline-3
-ON, etc.] and the like. The amount of (F9) used is
Usually 3% or less based on the total weight of (A) and (B),
It is preferably 0.05 to 1%.

Examples of the flame retardant (F10) include phosphorus, triazine, halogen and inorganic flame retardants. Phosphorus compounds include phosphorus oxides (phosphorus trioxide, phosphorus tetraoxide, phosphorus pentoxide, etc.); phosphoric acid compounds (phosphoric acid, phosphorous acid, hypophosphorous acid, metaphosphoric acid, pyrophosphoric acid, polyphosphoric acid, etc.); Phosphate [ammonium phosphate (monoammonium phosphate, diammonium phosphate,
Ammonium polyphosphate, etc.), melamine phosphate (melamine monophosphate, melamine diphosphate, melamine polyphosphate, etc.), metal phosphate (lithium phosphate, sodium phosphate, potassium phosphate, calcium phosphate, magnesium phosphate, etc.), etc. ]; Phosphate ester [aliphatic phosphate ester [trimethyl phosphate, triethyl phosphate, tributyl phosphate, tri (2-ethylhexyl) phosphate, tributoxyethyl phosphate, monoisodecyl phosphate, 2-acryloyloxyethyl acid phosphate, 2-methacryloyl] Oxyethyl acid phosphate, etc.], aromatic phosphate ester [triphenyl phosphate, tricresyl phosphate, trixylenyl phosphate , Tris (isopropylphenyl) phosphate, tris (phenylphenyl) phosphate, trinaphthyl phosphate, cresyl diphenyl phosphate, xylenyl diphenyl phosphate, diphenyl (2-ethylhexyl) phosphate,
Di (isopropylphenyl) phenyl phosphate, diphenyl-2-acryloyloxyethyl phosphate, diphenyl-2-methacryloyloxyethyl phosphate, etc.], aromatic di (phosphate ester) [resorcinol bis (diphenyl phosphate), resorcinol bis (diquinoyl) Silenyl phosphate), resorcinol bis (dicresyl phosphate), hydroquinone bis (diphenyl phosphate), hydroquinone bis (dixylenyl phosphate), hydroquinone bis (dicresyl phosphate), bisphenol A bis (diphenyl phosphate), Bisphenol A / bis (dixylenyl phosphate), bisphenol A / bis (dicresyl phosphate), etc.], aromatic poly (trivalent or its Or more) (phosphate ester) [poly (resorcinol phenyl phosphate), poly (resorcinol cresyl phosphate), poly (resorcinol xylenyl phosphate), poly (hydroquinone phenyl phosphate), poly (hydroquinone cresyl phosphate) ), Poly (hydroquinone
Xylenyl phosphate), poly (bisphenol A.
Phenyl phosphate), poly (bisphenol A.cresyl phosphate), poly (bisphenol A.xylenyl phosphate), etc.] and the like.

Examples of the triazine-based compound include melamine derivatives [melamine, methylolmelamines and the like]; cyanuric acid, isocyanuric acid or its derivatives [cyanuric acid, methylcyanurate, diethylcyanurate, trimethylcyanurate, triethylcyanurate, isocyanuric acid, Methyl isocyanurate, N, N'-diethyl isocyanurate, trismethyl isocyanurate, trisethyl isocyanurate, bis (2-carboxyethyl) isocyanurate, 1,3,5-tris (2-carboxyethyl) isocyanurate, tris (2,3-epoxypropyl) isocyanurate and the like]; a salt of melamine (derivative) (melamine cyanurate and the like) and (iso) cyanuric acid (derivative) and the like] and the like.

Examples of the halogen system include bromides of aliphatic or alicyclic hydrocarbons (hexabromocyclododecane etc.); bromides of aromatic compounds (hexabromobenzene, ethylenebispentabromodiphenyl, decabromodiphenyl ether, octabromo). Diphenyl ether, 2,3-dibromopropyl pentabromophenyl ether, etc.); brominated bisphenol and its derivatives [tetrabromobisphenol A, tetrabromobisphenol A bis (2,3-dibromopropyl ether), tetrabromobisphenol A (2-bromo Ethyl ether), tetrabromobisphenol A diglycidyl ether, tetrabromobisphenol A diglycidyl ether and tribromophenol adduct, etc.]; brominated bisphenol derivative Rigomers [tetrabromobisphenol A polycarbonate oligomer, tetrabromobisphenol A diglycidyl ether and brominated bisphenol adduct epoxy oligomer, etc.]; brominated aromatic compounds [tetrabromophthalerodiol, tetrabromophthalate ester, tetrabromophthalate disodium , Poly (pentabromobenzyl polyacrylate), pentabromophenol, bromophenoxyethanol, brominated phenol (novolac type), dibromocresyl glycidyl ether, brominated aromatic triazine, vinyl bromide, tribromophenol, dibromophenol, dibromometacresol , Dibromoneopentyl glycol, ethylene bis tetrabromophthalimide, ethylene bis dibromo norborna Dicarboximide, bis (2,4,6-tribromophenoxy) ethane, brominated acrylic resin, etc.]; chlorine compounds [chlorinated paraffin, chlorinated naphthalene, perchloropentadecane, tetrachlorophthalic anhydride, chlorinated Aromatic compounds, chlorinated alicyclic compounds, etc.] and the like.

Examples of inorganic materials include aluminum hydroxide, magnesium hydroxide, antimony trioxide, antimony tetroxide, antimony pentoxide, sodium antimonate, boric acid, zinc borate, barium borate, and boron oxide. The amount of (F10) used is usually 30% or less, preferably 0.1-20, based on the total weight of (A) and (B).
%.

The conductive elastomer of the present invention is prepared by adding (A) and (B) and, if necessary, (C), (D), (E) and / or (F), and melt-mixing them. can get. A usual method is used as a method for melt mixing. That is, in general, pellets, powders or liquids (A) and (B), and (C) if necessary,
A method in which (D), (E) and / or (F) are mixed in an appropriate mixer, for example, a Henschel mixer, and then melt-mixed (melting temperature is usually 140 to 350 ° C.) in an extruder to form pellets. Can be applied. The order of addition of the components during melt mixing is not particularly limited, but, for example, (A) and (B) and, if necessary, (C), (D), (E) and / or (F) may be added. A method of blending and melting and mixing all at once, a small amount of (A) and (B), and (C) if necessary,
(D), (E) and / or (F) are blended and melt mixed, and then the remaining (A) is blended and melt mixed,
A small amount of (B) and (C), and if necessary,
Examples include a method in which (D), (E) and / or (F) are blended and melt mixed, and then the remaining (C) and (A) are blended and melt mixed. Among these methods, the method is called a masterbatch method or a master pellet method. Of these methods, (A) and (B),
And, from the viewpoint of uniformly melt-mixing (C), (D), (E) and / or (F) if necessary, the methods of and are.

Examples of the method for molding the conductive elastomer of the present invention include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (cast method, tenter method, inflation method, etc.). For example, single-layer molding, multi-layer molding, foam molding or the like can be used for any desired method. The molded product using the conductive elastomer of the present invention has excellent mechanical strength and conductivity, and also has good coatability and printability.

Examples of the method for coating the molded article include, but are not limited to, air spray coating, airless spray coating, electrostatic spray coating, dip coating, roller coating, brush coating, and electrodeposition coating. Not something. Examples of the paint include polyester melamine resin paints, epoxy melamine resin paints, acrylic melamine resin paints, acrylic urethane resin paints, acrylic resin paints, urethane resin paints and other paints that are generally used for painting plastics. Coating film thickness (dry film thickness)
Can be appropriately selected depending on the purpose, but is usually 10
˜50 μm.

As a method for printing on the molded body,
Any printing method generally used for printing plastics can be used, and examples thereof include gravure printing, flexographic printing, screen printing, and offset printing. As the printing ink, those commonly used for printing plastics can be used. Further, the conductive elastomer of the present invention can be used as a coating material which is added to an ordinary coating material or a solvent (for example, xylene or toluene) to impart conductivity.

The conductive elastomer of the present invention has a conductivity of
Since it is particularly excellent in low specific gravity, moldability, mechanical strength, etc., various molding methods [injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, film molding (casting method, tenter method, inflation method) Law, etc.)
Etc.], the resulting molded article, or a molded article further coated or printed as necessary, has various uses,
For example, housing products for electric / electronic parts, home appliances / OA equipment / game equipment, various rollers (charge rollers for copying machines, etc.), various plastic containers such as IC trays, LS
I, IC packaging materials (films, etc.), floor sheet,
It can be suitably used as a molding material for various uses such as artificial turf, mats, automobile parts, and electromagnetic wave shielding materials that require conductivity.

[0183]

EXAMPLES The present invention will be further described below with reference to examples, but the present invention is not limited thereto. In the following, “part” means “part by weight”.

Production Example 1 Polypropylene obtained by the thermal degradation method (Mn: 2,500, density 0.89, amount of double bonds per 1,000 carbons: 10.5, was added to a stainless steel autoclave. The average number of double bonds per molecule: 1.90) 85 parts and maleic anhydride 15 parts were charged, and the mixture was kept under nitrogen gas atmosphere for 20
It was melted at 0 ° C. and reacted at 200 ° C. for 20 hours. Then, unreacted maleic anhydride was distilled off under reduced pressure to obtain acid-modified polypropylene (a1). The acid value of (a1) was 39.8, and Mn was 2,800.

Production Example 2 Polypropylene was used as an ethylene / propylene copolymer (ethylene content: 2% by weight, Mn: 2,000, density: 0.8).
9, double bond amount per 1000 carbon atoms: 11.8
The acid-modified ethylene / propylene copolymer (a1) was obtained in the same manner as in Production Example 1, except that the average number of double bonds per molecule was 1.92. The acid value of (a1) was 42.3 and Mn was 2,200.

Production Example 3 85 parts of polypropylene were mixed with polypropylene (Mn: 10,
000, density 0.89, double bond amount per 1000 carbon atoms: 13.0, average number of double bonds per molecule: 1.80) 90 parts of maleic anhydride charge amount of 1 part
An acid-modified polypropylene (a1) was obtained in the same manner as in Production Example 1 except that 0 part was used. The acid value of (a1) is 5.
0 and Mn were 10,200.

Production Example 4 85 parts of polypropylene were mixed with polypropylene (Mn: 1,5
00, density 0.89, amount of double bonds per 1000 carbon atoms: 13.9, average number of double bonds per molecule:
1.95) Acid-modified polypropylene (a1) was obtained in the same manner as in Production Example 1 except that the amount of maleic anhydride charged to 80 parts was changed to 20 parts. The acid value of (a1) is 55.
3, Mn was 1,600.

Production Example 5 (a1) 87 parts and 1 were added to a stainless steel autoclave.
13 parts of 2-aminododecanoic acid was charged, melted at 200 ° C., and reacted at 200 ° C. for 2 hours under the condition of 10 mmHg or less to obtain an acid-modified polypropylene (a2). (A
The acid value of 2) was 32.1 and Mn was 3,100.

Production Example 6 (a1) 97 parts, ε in a stainless steel autoclave
-Caprolactam (3 parts) and water (3 parts) were charged, melted at 200 ° C under a nitrogen gas atmosphere, and reacted at 200 ° C for 2 hours to obtain an acid-modified polypropylene (a2). (A2
) Had an acid value of 4.5 and Mn of 11,000.

Production Example 7 The acid-modified polypropylene (a2) was prepared in the same manner as in Production Example 5 except that 87 parts of (a1) was replaced with 83 parts of (a1) and the charged amount of 12-aminododecanoic acid was replaced with 17 parts. Obtained.
The acid value of (a2) was 50.0 and Mn was 1,800.

Production Example 8 94 parts of (a1) and 6 parts of ethanolamine were charged into a stainless steel autoclave, and the mixture was kept under a nitrogen gas atmosphere for 1 hour.
It was melted at 80 ° C. and reacted at 180 ° C. for 2 hours. After that, unreacted ethanolamine was depressurized at 180 ° C. for 2
It was distilled off over time to obtain a hydroxyl group-containing acid-modified polypropylene (a3). The hydroxyl value of (a3) is 3
7.6, the amine value was 0.01, and Mn was 2,900.

Production Example 9 An acid-modified polypropylene (a) having a hydroxyl group was prepared in the same manner as in Production Example 8 except that 94 parts of (a1) was replaced with 97 parts of (a1) and the charged amount of ethanolamine was replaced with 3 parts.
3) was obtained. The hydroxyl value of (a3) was 5.0, the amine value was 0.00, and Mn was 10,000.

Production Example 10 An acid-modified polypropylene (a) having a hydroxyl group was prepared in the same manner as in Production Example 8 except that 94 parts of (a1) was replaced with 93 parts of (a1) and the charged amount of ethanolamine was replaced with 7 parts.
3) was obtained. The hydroxyl value of (a3) was 50.0, the amine value was 0.01, and Mn was 1,900.

Production Example 11 70 parts of (a1) and 30 parts of ethylenediamine were charged into a stainless steel autoclave, and the mixture was kept under a nitrogen gas atmosphere for 1 hour.
It was melted at 80 ° C. and reacted at 180 ° C. for 2 hours. Then, excess ethylenediamine was distilled off under reduced pressure at 180 ° C. for 2 hours to obtain an acid-modified polypropylene (a4) having an amino group. (A4) amine value 5.0, Mn
Was 10,000.

Production Example 12 The procedure of Production Example 11 was repeated except that 70 parts of (a1) was replaced with 60 parts of (a1) and the charged amount of ethylenediamine was replaced with 40 parts.
) Got. The amine value of (a4) was 50.0 and Mn was 1,700.

Production Example 13 In an autoclave made of stainless steel, (a1) 45 parts, M
Polyethylene glycol in which n is 3,300 (b1
) (Volume resistivity value: 1 × 10 ⁷ Ω · cm) 55 parts,
Antioxidant (“Irganox 1010”, manufactured by Ciba-Gaiki, 0.3 part) and zirconyl acetate 0.
5 parts were charged and the mixture was polymerized for 3 hours under reduced pressure of 230 ° C. and 1 mmHg or less to obtain a viscous polymer. This polymer was taken out in a strand form on a belt and pelletized to obtain a block polymer (A1).
Mn of (A1) was 20,000 and Nn was 3.3.

Production Example 14 58 parts of (a1), M were added to a stainless steel autoclave.
α, ω-diamino polyethylene glycol (b2) in which n is 1,500 (volume specific resistance value: 3 × 10 ⁷ Ω ·
cm) 42 parts, antioxidant 0.3 parts and tetrabutyl zirconate 0.5 parts were charged and polymerized for 3 hours at 230 ° C. under a reduced pressure of 1 mmHg or less to obtain a viscous polymer. Then, the same operation as in Production Example 13 was performed to obtain a block polymer (A2). Mn of (A2) is 27,000,
Nn was 8.7.

Production Example 15 In an autoclave made of stainless steel, 51 parts (a2),
(B1) 49 parts, an antioxidant of 0.3 part and zinc acetate of 0.5 part were charged and polymerized at 230 ° C. under a reduced pressure of 1 mmHg or less for 4 hours to obtain a viscous polymer. Less than,
A block polymer (A3
) Got. Mn of (A3) was 26,000 and Nn was 4.1.

Production Example 16 Into a stainless steel autoclave, (a2) 75 parts, M
polyethylene glycol in which n is 8,000 (b1
) (Volume resistivity: 1 × 10 ⁹ Ω · cm) 25 parts,
0.3 part of antioxidant and 0.5 part of zirconyl acetate were charged and polymerized for 4 hours under reduced pressure of 230 ° C. and 1 mmHg or less to obtain a viscous polymer. Thereafter, the same operation as in Production Example 13 was carried out to obtain a block polymer (A3).
Mn of (A3) was 60,000 and Nn was 3.2.

Production Example 17 Into a stainless steel autoclave, (a2) 65 parts, M
Polyethylene glycol in which n is 1,200 (b1
) (Volume resistivity: 2 × 10 ⁵ Ω · cm) 35 parts,
Charge 0.3 parts of antioxidant and 0.5 parts of zinc acetate, and 2
Polymerization was carried out at 30 ° C. under a reduced pressure of 1 mmHg or less for 4 hours to obtain a viscous polymer. Thereafter, the same operation as in Production Example 13 was carried out to obtain a block polymer (A3). (A3
), Mn was 8,000, and Nn was 2.7.

Production Example 18 Into a stainless steel autoclave, (a2) 46 parts, M
α, ω-diamino polyethylene glycol (b2) in which n is 1,200 (volume specific resistance value: 8 × 10 ⁶ Ω ·
cm) 54 parts, antioxidant 0.3 parts and tetrabutyl zirconate 0.5 parts were charged and polymerized for 4 hours under a reduced pressure of 230 ° C. and 1 mmHg or less to obtain a viscous polymer. Thereafter, the same operation as in Production Example 13 was carried out to obtain a block polymer (A4). Mn of (A4) is 35,000,
Nn was 8.1.

Production Example 19 Isocyanate-modified polyethylene glycol (b3) obtained by reacting (b1) and MDI (NCO content:
3.0%, volume resistivity value: 1 × 10 ⁷ Ω · cm) 50
And 50 parts of (a3) were kneaded with a twin-screw extruder at 200 ° C. for a residence time of 30 seconds, taken out on a strand and pelletized to obtain a block polymer (A5). Mn of (A5) was 32,000 and Nn was 5.4.

Production Example 20 Isocyanate-modified polyethylene glycol (b3) obtained by reacting (b1) and MDI (NCO content:
1.2%, volume resistivity value: 1 × 10 ⁹ Ω · cm) 26
Part and 74 parts of (a3) were kneaded by a twin-screw extruder at 200 ° C. for a residence time of 30 seconds, taken out on a strand and pelletized to obtain a block polymer (A5). Mn of (A5) was 45,000 and Nn was 2.5.

Production Example 21 Isocyanate-modified polyethylene glycol (b3) obtained by reacting (b1) and MDI (NCO content:
7.0%, volume resistivity: 2 × 10 ⁵ Ω · cm) 35
Part and 65 parts of (a3) were kneaded with a twin-screw extruder at 200 ° C. for a residence time of 30 seconds, taken out onto a strand and pelletized to obtain a block polymer (A5). Mn of (A5) was 15,000, and Nn was 4.8.

Production Example 22 Isocyanate-modified polyethylene glycol (b3) obtained by reacting (b2) and MDI (NCO content:
1.3%, volume resistivity: 5 × 10 ⁸ Ω · cm) 25
Part and 75 parts of (a4) were kneaded with a twin-screw extruder at 200 ° C. for a residence time of 30 seconds, taken out onto a strand and pelletized to obtain a block polymer (A6). Mn of (A6) was 47,000 and Nn was 2.5.

Production Example 23 Into a stainless steel autoclave, (a4) 57 parts, M
α, ω-diepoxy polyethylene glycol (b3) in which n is 1,700 (volume specific resistance value: 1 × 10 ⁷ Ω
(Cm) 43 parts, 0.3 part of antioxidant and 0.5 part of zirconyl acetate were charged and polymerized for 4 hours at 230 ° C. under reduced pressure of 1 mmHg or less to obtain a viscous polymer. Thereafter, the same operation as in Production Example 13 was carried out to obtain a block polymer (A7). Mn of (A7) is 17,000, Nn
Was 5.0.

Production Example 24 ε-caprolactam 2 was placed in a stainless steel autoclave.
4 parts, terephthalic acid 2 parts, antioxidant 0.3 parts and water 2
Part, charged with nitrogen, heated and stirred at 220 ° C. under pressure and closed for 4 hours, and acid value having carboxyl groups at both ends 11
34 parts of polyamide oligomer 2 of 2 were obtained. To this, 66 parts of polyethylene glycol having a Mn of 2,000 (volume specific resistance: 5 × 10 ⁷ Ω · cm) and 0.5 part of tetrabutyl zirconate were added, and the conditions were 230 ° C. and a reduced pressure of 1 mmHg or less. Polymerization was carried out for 5 hours to obtain a viscous polymer. Hereinafter, the same operation as in Production Example 13 was performed to obtain a polymer type antistatic agent (D4). Mn of (D4) is 30,0
00 and Nn were 6.1.

Production Example 25 A stainless steel autoclave was charged with 37 parts of 12-aminododecanoic acid, 2 parts of adipic acid and 0.3 parts of an antioxidant, and after nitrogen substitution, heated and stirred at 220 ° C. under pressure and sealing for 4 hours. 42 parts of a polyamide oligomer having a carboxyl group at both ends and an acid value of 107 was obtained. Mn is 2,0
Polyethylene glycol of 00 (volume resistivity value:
5 × 10 ⁷ Ω · cm) 58 parts, and zirconyl acetate 0.
5 parts was added, and the mixture was polymerized for 5 hours at 230 ° C. under reduced pressure of 1 mmHg or less to obtain a viscous polymer. Hereinafter, the same operation as in Production Example 13 is carried out, and a polymeric antistatic agent (D4)
Got (D4) has Mn of 32,000 and Nn of 6.
It was 4.

Examples 1 to 20 and Comparative Examples 1 to 10 Based on the formulations shown in Tables 1 and 2, each component was blended for 3 minutes with a Henschel mixer, and then 240 with a vented twin-screw extruder. ℃, 100 rpm, residence time 5
Melt kneading under the condition of minutes, the conductive elastomer of the present invention (Examples 1 to 20) and a comparative resin composition (Comparative Examples 1 to 1).
10) was obtained.

[0210]

[Table 1]

[0211]

[Table 2]

The conductive substances in Table 1 and Table 2,
The thermoplastic resin, alkali or alkaline earth metal salt and surfactant are as follows. B: Potassium titanate whisker {trade name: Dentol WK200B, manufactured by Otsuka Chemical Co., Ltd., minor axis 0.4 to 0.7
μm, major axis 10 to 20 μm} B: Titanium oxide whisker {trade name: FT-1000,
Ishihara Sangyo Co., Ltd., minor axis 0.05-0.1, major axis 3-
6} B: Carbon black {Product name: Ketjen Black EC, manufactured by Lion Corporation, primary volume average particle diameter 0.02
5 μm} C1: polypropylene {trade name: J609H, manufactured by Grand Polymer Co., Ltd., MFR9 (JIS K7210:
1999 method B, temperature 230 ° C, load 2.16kg
f), melting point 160-165 ° C. (DSC method)} C2: ABS resin {trade name: ABS110, Techno Polymer Co., Ltd. MFR25 (JIS K7210: 19)
99 B method, temperature 220 ° C, load 1.00 kgf)} C5: Polyamide {trade name: Novamid 1012C
2, Mitsubishi Engineering Plastics Co., Ltd.} C6: Polyester {Product Name: Novadour 5010
R5, manufactured by Mitsubishi Engineering Plastics Co., Ltd.
Melting point: 224 ° C. (DSC method)} C7: polyacetal {trade name: Iupital F25,
Mitsubishi Engineering Plastics Co., Ltd., MFR
16 (JIS K7210: 1999 B method, temperature 19
0 ° C, load 2.16 kgf, melting point: 165 ° C, (DSC
Method)) D1: Sodium dodecylbenzene sulfonate D2: Lithium chloride D2: Potassium acetate D1, D2 and D2 were added to the block polymer at the same time {simultaneously with the hydrophilic polymer (b)}.

Performance Test The conductive elastomers of the present invention (Examples 1 to 20) and comparative resin compositions (Comparative Examples 1 to 10) were tested using an injection molding machine at a cylinder temperature of 240 ° C. and a mold temperature of 50 ° C. A piece was prepared, and using this, impact strength, flexural modulus, surface resistivity, volume resistivity, surface resistivity after washing with water, primary adhesion, water resistance and coating efficiency were evaluated. .
Also, using a compression molding machine, temperature 200 ℃, pressure 20 kg
/ Cm ² and a time of 30 seconds, a test piece was prepared, and the surface resistivity value was evaluated using the test piece. These results are shown in Table 3.
Shown in.

[0214]

[Table 3]

Each test was carried out by the following method. (1) Impact strength: measured by ASTM D256-81 (notched, 3.2 mm thick) Method A. (2) Flexural modulus: ASTM D790-81 test piece (10 × 4 × 100 mm), distance between fulcrums 60 mm

(3) Surface specific resistance value: test piece (100 ×
(100 × 2 mm) and a super insulation meter [manufactured by Toa Denpa Kogyo KK, the same applies hereinafter] in an atmosphere of 23 ° C. and a humidity of 50% RH (according to ASTM D257-78). (4) Volume resistivity: test piece (100 × 100 × 2 m
m) was measured by a super insulation meter in an atmosphere of 23 ° C. and a humidity of 50% RH (in accordance with ASTM D257-78). (5) Surface resistivity after washing with water: test piece (100 × 10
(0 × 2 mm) is washed with running water at 23 ° C.
It was dried at 0 ° C. for 3 hours. The operation of washing with water and drying was repeated 10 times, and the measurement was carried out with an ultra-insulator under an atmosphere of 23 ° C. and a humidity of 50% RH (in accordance with ASTM D257-78).

(6) Coating test: Test piece (100 ×
(100 × 2 mm) is grounded, and electrostatic coating is performed using an electrostatic atomizing electrostatic coating machine combined with airflow [Turbo near G minibell type automatic electrostatic coating machine manufactured by Nippon Lansburgh Co., Ltd.] (applied voltage = −90 KV). , Discharge rate = 100 cc / min, rotation speed = 2
4,000 rpm, atomizing head diameter = 70 mm, two-component urethane paint: using Hi Urethane # 5000 manufactured by NOF CORPORATION. After baking the coated plate at 80 ° C for 2 hours,
The following tests were conducted. Primary adhesion: Regarding the coating surface of the coated plate JIS K540
0 (1990) cross-cut tape method test was conducted. Water resistance: After the coated plate was immersed in warm water at 50 ° C. for 240 hours, a JISK 5400 (1990) cross-cut tape method test was performed. Coating efficiency: Obtained according to the following formula. Coating efficiency = (weight of test piece after coating-weight of test piece before coating) × 100 ÷ (absolute dry weight of coated coating material)

As is clear from Table 3, the electroconductive elastomer of the present invention is excellent in electroconductivity and paintability.

[0219]

EFFECT OF THE INVENTION The conductive elastomer of the present invention has excellent conductivity and contains a relatively small amount of a conductive substance, so that it has a low specific gravity and excellent moldability. In addition, it is extremely useful because it has excellent mechanical strength and has excellent paintability.

Continued front page    F-term (reference) 4J002 AA012 AA051 AA071 AC022                       BB002 BC012 BC032 BC042                       BP001 CB002 CF032 CF052                       CG012 CH023 CK022 CL022                       CL042 CL052 DA016 DA066                       DB016 DE046 EG017 EN137                       EV187 EV257 FA040 FD010                       FD020 FD050 FD070 FD090                       FD107 FD116 FD130 FD160                       FD180 FD208 FD313 FD317                       GQ02                 4J031 AA12 AA19 AA34 AA47 AA53                       AA55 AB01 AC03 AC05 AC07                       AC08 AD01 AE03 AF25 CF03                 5G301 DA02 DA18 DA22 DA23 DA24                       DA42 DA43 DD10

Claims (8)

[Claims] 1. A block polymer (A) having a structure in which a block of a polyolefin (a) and a block of a hydrophilic polymer (b) having a volume resistivity value of 1 × 10 ⁵ to 1 × 10 ¹¹ are repeatedly and alternately bonded. And a conductive substance (B). 2. (b) is a polyether group-containing polymer,
The conductive elastomer according to claim 1, which is at least one polymer selected from the group consisting of a polymer containing a cationic group and a polymer containing an anionic group. 3. The electrically conductive elastomer according to claim 1, wherein (B) is at least one electrically conductive substance selected from the group consisting of the following (1) to (3). (1) Metals of Groups 6 to 14 of the Periodic Table of Elements or alloys thereof (2) Oxides, carbides, nitrides or salts of the above (1) (3) Carbon 4. The electrically conductive elastomer according to claim 1, further comprising a thermoplastic resin (C) different from (A). 5. The conductive elastomer according to claim 4, wherein (C) is a thermoplastic resin containing a polyolefin resin. 6. The conductive elastomer according to claim 1, further comprising an antistatic agent (D) and / or a compatibilizing agent (E). 7. A molded body obtained by molding the conductive elastomer according to claim 1. 8. A molded article obtained by coating or printing the molded body according to claim 7.