JP2008248097A - Conductivity imparting agent - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a conductivity imparting agent which imparts semi-conductivity largely surpassing conventional antistatic property without reducing moldability and mechanical properties as a conventional method of imparting conductivity to a thermoplastic resin has such drawbacks that moldability is deteriorated due to the reduction of flowability of a resin composition, a molded article becomes heavy in weight, and impact resistance is lowered, because a large amount of conductive material is necessary to be blended. <P>SOLUTION: The conductivity imparting agent is obtained by reducing a metal salt in a composition comprising the metal salt, and a polymer having a volume resistivity of 1×10<SP>6</SP>-1×10<SP>12</SP>Ωcm and at least one hydrophilic group. A semi-conductive resin composition comprises a thermoplastic resin, and the conductivity imparting agent contained in the thermoplastic resin. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a conductivity imparting agent. More specifically, the present invention relates to a conductivity imparting agent that imparts excellent conductivity to a thermoplastic resin.

  Conventionally, as a method for imparting conductivity to a highly insulating thermoplastic resin, (1) a method of blending a conductive material such as carbon, metal fiber, or metal powder (see, for example, Patent Document 1), (2) A method of containing an ionic salt composed of a nitrogen onium cation and a fluorine-containing organic anion as an antistatic agent in a thermoplastic resin (for example, see Patent Document 2), (3) a polymer solid containing an ionic liquid as an antistatic agent An electrolyte (for example, see Non-Patent Document 1) and the like are known.

JP-A-7-216224 Special table 2003-511505 gazette "Chemistry and Industry", Vol. 54 (2001) No. 3, 281-285, The Chemical Society of Japan Publication

In the method (1), since it is necessary to add a large amount of conductive material, the moldability is deteriorated due to the decrease in fluidity of the resin composition, the molded article becomes heavy, and the impact resistance is decreased. There was a difficulty. In the methods (2) and (3), when the use amount of the antistatic agent is increased for the purpose of further improving the antistatic property, the appearance of the molded product is deteriorated or molded due to the moldability defect of the resin composition. There were problems such as deterioration of the mechanical properties of the product.
An object of the present invention is to provide a conductivity-imparting agent that imparts semiconductivity that greatly exceeds conventional antistatic properties without impairing the moldability and mechanical properties of a thermoplastic resin.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention has a metal salt (A) and a volume resistivity of 1 × 10 ⁶ to 1 × 10 ¹² Ω · cm, and at least one selected from the group consisting of the following (B1) to (B9) In the composition comprising the seed type hydrophilic group-containing polymer (B), the conductivity imparting agent (X) is characterized by further reducing (A).
(B1): Polyether ester amide (B2) derived from a polyamide (b11) and an alkylene oxide adduct (b12) of a bisphenol compound and / or a polyoxyalkylene glycol (b13): a block of a polyolefin (b21) The polyoxyalkylene chain-containing compound (b22) has a structure in which the block is repeatedly and alternately bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond. Block polymer (B3): polyether amide imide (B4): polyether ester (B5): epihalohydrin / alkylene oxide copolymer (B6): acrylamide copolymer (B7): ethylene / unsaturated carboxylic acid (salt) or ethylene (Meth) acrylate / unsaturated carboxylic acid (salt) copolymer (B8): methoxypolyethylene glycol (meth) acrylate copolymer (B9): polyether group-containing ethylene / vinyl acetate copolymer [ethylene / vinyl alcohol copolymer Polymer ethylene oxide adduct]

The conductivity imparting agent of the present invention has the following effects.
(1) A semiconductive resin composition obtained by incorporating the conductivity imparting agent in a thermoplastic resin is excellent in moldability.
(2) A molded product formed by molding the semiconductive resin composition is excellent in mechanical properties.
(3) The molded product has semiconductivity and is excellent in permanent antistatic properties.

Examples of the metal salt (A) in the present invention include Group 8 metals (iron, ruthenium, etc.), Group 9 metals (cobalt, rhodium, etc.), Group 10 metals (nickel, palladium, platinum, etc.) and Transition metals such as Group 11 metals (copper, silver, gold, etc.), halides of Group 12 metals (zinc, cadmium, mercury, etc.), inorganic acids (sulfuric acid, nitric acid, hydrochloric acid, perchloric acid, carbonic acid, phosphoric acid, Thiocyanic acid, etc.) salt, organic acid [carbon number (hereinafter abbreviated as C) 1-15, for example, aliphatic carboxylic acid (formic acid, acetic acid, etc.), fluorinated sulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.] salt, etc. Is mentioned.
Of these, from the viewpoint of conductivity, the group 8 metal, the group 9 metal, the group 10 metal and the group 11 metal salts are preferable, and iron, cobalt, nickel, palladium, platinum, copper are particularly preferable. Silver and gold halides, sulfates and nitrates.

The hydrophilic group-containing polymer (B) in the present invention has a volume specific resistance value of 1 × 10 ⁶ to 1 × 10 ¹² Ω · cm. If the volume resistivity value of (B) is less than 1 × 10 ⁶ Ω · cm, the moldability of the composition described later will be poor, and if it exceeds 1 × 10 ¹² Ω · cm, the conductivity will be poor.
(B) includes the following (B1) to (B9) and a mixture of two or more thereof. (B1): Polyether ester amide (B2) derived from polyamide (b11) and an alkylene oxide (hereinafter abbreviated as AO) adduct (b12) and / or polyoxyalkylene glycol (b13) of a bisphenol compound: polyolefin The block of (b21) and the polyoxyalkylene chain-containing compound (the block of (b22) are alternately alternated through at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond. Block polymer (B3): polyetheramideimide (B4): polyetherester (B5): epihalohydrin / alkylene oxide (hereinafter abbreviated as AO) copolymer (B6): acrylamide copolymer (B7) ): Ethylene / No Japanese carboxylic acid (salt) or ethylene / (meth) acrylate / unsaturated carboxylic acid (salt) copolymer (B8): methoxypolyethylene glycol (meth) acrylate copolymer (B9): polyether group-containing ethylene / vinyl acetate Copolymer [ethylene / vinyl alcohol copolymer ethylene oxide (hereinafter abbreviated as EO) adduct]

  Of these, (B1) to (B3) are preferable from the viewpoint of conductivity, and (B1) and (B2) are more preferable.

Examples of (B1) include polyether ester amides described in JP-A-6-287547 and JP-B-4-5691, that is, polyamide (b11), an AO adduct (b12) of a bisphenol compound and / or Polyether ester amides derived from polyoxyalkylene glycol (b13) can be used.
(B12) and / or (b13) to be reacted with (b11) may be either (b12) or (b13) alone or in combination. The ratio [(b12) / (b13) weight ratio] when used in combination is preferably 1/99 to 99/1, more preferably 5/95 to 95/5, from the viewpoint of dispersibility with respect to the thermoplastic resin.

Examples of the polyamide (b11) include a lactam ring-opening polymer (b111), an aminocarboxylic acid polycondensate (b112), and a dicarboxylic acid and diamine polycondensate (b113).
Among the amide-forming monomers that form these polyamides, the lactam in (b111) includes C6-12, such as caprolactam, enantolactam, laurolactam, and undecanolactam.
As the aminocarboxylic acid in (b112), C6-12, 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 (b113) include aliphatic dicarboxylic acids, aromatic (aliphatic) dicarboxylic acids, alicyclic dicarboxylic acids, amide-forming derivatives thereof [acid anhydrides, lower (C1-4) alkyl esters], and the like. Or a mixture of two or more thereof.

Aliphatic dicarboxylic acids include C4-20, such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, maleic acid, fumaric acid, itaconic acid. Can be mentioned.
Aromatic (aliphatic) dicarboxylic acids include C8-20, such as ortho-, iso- and terephthalic acid, naphthalene-2,6- and -2,7-dicarboxylic acid, diphenyl-4,4'dicarboxylic acid, diphenoxy Examples thereof include alkali metal (sodium, potassium, etc.) salts of ethanedicarboxylic acid and 3-sulfoisophthalic acid.
Examples of the alicyclic dicarboxylic acid include C7 to 14 such as cyclopropanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cyclohexenedicarboxylic acid, and dicyclohexyl-4,4-dicarboxylic acid.
Among the amide-forming derivatives, examples of the acid anhydride include anhydrides of the above dicarboxylic acids, such as maleic anhydride, itaconic anhydride, and phthalic anhydride. Lower (C1-4) alkyl esters include those of the above dicarboxylic acids. Alkyl esters such as dimethyl adipate, ortho-, iso- and dimethyl terephthalate are mentioned.
Examples of the diamine include C6-12, such as hexamethylene diamine, heptamethylene diamine, octamethylene diamine, and decamethylene diamine.

  Two or more of those exemplified as the amide-forming monomer may be used in combination. Of these, caprolactam, 12-aminododecanoic acid and adipic acid / hexamethylenediamine are preferable from the viewpoint of conductivity, and caprolactam is more preferable.

The polyamide (b11) can be obtained by using one or more C4-20 dicarboxylic acids as molecular weight regulators and subjecting the amide-forming monomer to ring-opening polymerization or polycondensation in the presence thereof in the usual manner.
Examples of the C4-20 dicarboxylic acid include those exemplified in the above (b113). Among these, aliphatic dicarboxylic acid, aromatic dicarboxylic acid and alkali 3-sulfoisophthalic acid are preferable from the viewpoint of conductivity. Metal salts, more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and sodium 3-sulfoisophthalate.

The amount of the molecular weight modifier used is preferably 2 to 80%, more preferably 4 to 75% from the viewpoints of conductivity and heat resistance based on the total weight of the amide-forming monomer and the molecular weight modifier.
It is.

  Mn of the polyamide (b11) is preferably 200 to 5,000, more preferably 500 to 5,000 from the viewpoint of heat resistance of the polyetheresteramide (B1) and reactivity with the AO adduct (b12) of a bisphenol compound described later. 3,000.

Examples of the bisphenol compound constituting the AO adduct (b12) of the bisphenol compound include C13-20, such as bisphenol A, -F, and -S. Among these, the dispersibility of the conductivity-imparting agent in the thermoplastic resin. From this viewpoint, bisphenol A is preferred.
As the AO added to the bisphenol compound, C2-4 or more, for example, EO, PO, 1,2-, 2,3- and 1,4-butylene oxide, C5-12 α-olefin epoxidized product Styrene oxide and epihalohydrins (eg epichlorohydrin and epibromohydrin) and mixtures of two or more thereof (random and / or block). Of these, EO is preferable from the viewpoint of conductivity.

  Mn in (b12) is preferably 300 to 5,000, more preferably 500 to 4,000 from the viewpoints of conductivity and mechanical properties.

The volume specific resistance value of the polyalkylene glycol (b13) (value measured in an atmosphere of 23 ° C. and 50% RH by the method described later. The same applies hereinafter) is preferably 10 ¹¹ Ω · from the viewpoint of conductivity. cm, more preferably 10 ¹⁰ Ω · cm, particularly preferably 10 ⁹ Ω · cm. From the viewpoint of mechanical properties, the lower limit is preferably 10 ⁵ Ω · cm, more preferably 10 ⁶ Ω · cm, and particularly preferably 10 ⁷ Ω · cm. cm.
Further, Mn of (b13) is preferably 150 to 20,000, more preferably 300 to 15,000, particularly preferably from the viewpoint of the heat resistance of (B1) and the reactivity of (b13) with (b11). 1,000 to 10,000, most preferably 1,200 to 8,000.

Examples of the method for producing the polyetheresteramide (B1) include the following (1) and (2), but are not particularly limited.
Production Method (1) An amide-forming monomer and a dicarboxylic acid (molecular weight modifier) are reacted to form a polyamide (b11), and an AO adduct (b12) and / or a polyalkylene glycol (b13) of a bisphenol compound is added thereto. And polymerization at high temperature (160 to 270 ° C.) under reduced pressure (0.03 to 3 kPa).
Production Method (2) An amide-forming monomer and a dicarboxylic acid (molecular weight modifier) and a part of (b12) and / or (b13) are simultaneously charged into a reaction vessel, and heated at a high temperature (160 to 270 ° C.) under pressure (0.1 to 1 MPa) to form a polyamide intermediate (b11), and then the remaining (b12) and / or (b13) under reduced pressure (0.03 to 3 kPa) Polymerization method. Of the above production methods, production method (1) is preferred from the viewpoint of reaction control.

In addition to the above, (B1) is produced by replacing the terminal hydroxyl group of (b12) and / or (b13) with an amino group or a carboxyl group and reacting with a polyamide having a carboxyl group or an amino group at the terminal. It may be used.
As a method for substituting the terminal hydroxyl group of (b12) and / or (b13) with an amino group, a known method, for example, a method of reducing a terminal cyanoalkyl group obtained by cyanoalkylating a hydroxyl group to form an amino group [for example, , (B12) and / or (b13) and acrylonitrile are reacted, and the resulting cyanoethylated product is hydrogenated.
As a method of substituting the terminal hydroxyl group of (b12) and / or (b13) with a carboxyl group, a method of oxidizing with an oxidizing agent [for example, a method of oxidizing the hydroxyl group of (b12) and / or (b13) with chromic acid] Etc.

  The ratio of (b12) and / or (b13) based on the total weight of (b11) and (b12) and / or (b13) is preferably 20 to 80% from the viewpoint of the conductivity and heat resistance of (B1). More preferably, it is 30 to 70%.

In the above polymerization reaction, a commonly used known esterification catalyst is used. Examples of the catalyst include antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide, etc.), titanium catalysts (tetrabutyl titanate, etc.), zirconium catalysts (tetrabutyl zirconate, etc.), organic acid metal salts [zirconium organic acid Salts (such as zirconyl acetate) and zinc acetate].
The amount of the catalyst used is usually 0.1 to 5% based on the total weight of (b11) and (b12) and / or (b13), preferably 0.2 to 3% from the viewpoint of reactivity and resin properties. It is.

The reduced viscosity [η _sp / C, C = 0.5 wt% (m-cresol solution, 25 ° C.)] of (B1) is preferable from the viewpoint of the heat resistance of (B1) and the moldability of the resin composition described later. Is 0.5-4, more preferably 0.6-3.

As the block polymer (B2), a block polymer described in the specification of International Publication WO00 / 47652 can be used.
(B2) is at least one selected from the group wherein the block of the polyolefin (b21) and the block of the polyoxyalkylene chain-containing compound (b22) are an ester bond, an amide bond, an ether bond, a urethane bond and an imide bond It has a structure in which the bonds are alternately and alternately connected through the bonds.
The proportion of (b22) based on the total weight of (b21) and (b22) is preferably 20 to 80%, more preferably 30 to 70%, from the viewpoint of the conductivity and heat resistance of (B2).
The block of (b21) constituting (B2) includes a polyolefin (b211) having carbonyl groups at both ends of the polymer, a polyolefin (b212) having hydroxyl groups at both ends of the polymer, and an amino group at both ends of the polymer. Polyolefin (b213) or the like can be used.

As (b211), those having carbonyl groups introduced at both ends of polyolefin (b210) mainly composed of a denatureable polyolefin at both ends are used.
As (b212), those having hydroxyl groups introduced at both ends of (b210) are used.
As (b213), those in which amino groups are introduced at both ends of (b210) are used.
(B210) is usually a mixture of a polyolefin that can be modified at both ends, a polyolefin that can be modified at one end, and a polyolefin that does not have a modifiable end group, but contains a polyolefin that can be modified at both ends as a main component. You can use it if you do.
The content of the polyolefin which can be modified at both ends as the main component of (b210) is preferably 50 to 100%, more preferably 75 to 100%, particularly preferably 80 to 100% based on the weight of (b210). It is.

(B210) means (co) polymerization (polymerization or copolymerization) of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. )) And a degraded polyolefin [a product obtained by mechanically, thermally and chemically degrading a high molecular weight polyolefin (preferably Mn 50,000 to 150,000)] (reduced) Method). From the viewpoint of ease of modification and availability of introduction of a carbonyl group, hydroxyl group or amino group, a degraded polyolefin, particularly a thermally degraded polyolefin, is preferred.
The heat-degraded polyolefin is not particularly limited, but is heat-degraded by heating a high molecular weight polyolefin in an inert gas (usually at 300 to 450 ° C. for 0.5 to 10 hours) (for example, JP-A-3 -62804).
Examples of the high molecular weight polyolefin used in the thermal degradation method include (co) polymers of one or a mixture of two or more C2-30 (preferably 2-12, more preferably 2-10) olefins. Can be used. As the C2-30 olefin, the same as those used for the production of the polyolefin (polymerization method) described later can be used, and among these, ethylene, propylene and C4-12 α-olefin are preferred, and ethylene is more preferred. , Propylene and C4-10 alpha-olefins, particularly preferred are ethylene and propylene.

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

The polyolefin obtained by the polymerization method can be produced by various methods, and can be easily obtained, for example, by a (co) polymerization reaction in the presence of a radical catalyst, a metal oxide catalyst, a Ziegler catalyst or a Ziegler-Natta catalyst.
Various radical catalysts can be used, for example, organic peroxides (di-t-butyl peroxide, t-butyl peroxybenzoate, decanol peroxide, lauryl peroxide, peroxydicarbonate ester, etc.) , Azo compounds (azonitrile, azoamidine, azoamide compounds), and γ-alumina carriers having molybdenum oxide attached thereto.
Examples of the metal oxide catalyst include those obtained by attaching chromium oxide to a silica-alumina support. Examples of the Ziegler catalyst or Ziegler-Natta catalyst include Al (C ₂ H ₅ ) ₃ —TiCl ₄ .

Mn of (b210) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably 1,200 to 6,000. When Mn is within this range, the conductivity is further improved.
The amount of double bonds in (b210) is preferably 1 to 40, more preferably 2 to 30, and particularly preferably 4 to 20 per 1,000 C. When the amount of the double bond is within this range, the conductivity is further improved.
The average number of double bonds per molecule is preferably 1.1 to 5.0, more preferably 1
. It is 3-3.0, Most preferably, it is 1.5-2.5, Most preferably, it is 1.8-2.2. When the average number of double bonds is within this range, it becomes easier to take a repeating structure, and the conductivity is further improved.
According to the thermal degradation method, a low-molecular-weight polyolefin having an average terminal double bond amount of 1.5 to 2 per molecule in the range of 800 to 6,000 can be easily obtained [Katsuhide Murata, Tadahiko Makino. , Journal of Chemical Society of Japan, page 192 (1975)].

The polyolefin (b211) having a carbonyl group at both ends of the polymer is as follows. Or an anhydride thereof (hereinafter the same shall apply)) Polyolefin (b211-1) having a structure modified with (b211-1) and (b211-2) having a structure secondary modified with lactam or aminocarboxylic acid (b211-2) ), (B210) a polyolefin having a structure modified by oxidation or hydroformylation (b211
-3), polyolefin (b211-4) having a structure obtained by secondary modification of (b211-3) with lactam or aminocarboxylic acid, and a mixture of two or more of these.

(B211-1) can be obtained by modifying (b210) with an α, β-unsaturated carboxylic acid (anhydride).
As α, β-unsaturated carboxylic acid (anhydride) used for modification, monocarboxylic acid, dicarboxylic acid, alkyl (C1-4) ester thereof and anhydride thereof can be used, for example, (meth) acrylic acid (Means acrylic acid or methacrylic acid; the same shall apply hereinafter), methyl (meth) acrylate, butyl (meth) acrylate, maleic acid (anhydride), dimethyl maleate, fumaric acid, itaconic acid (anhydride) , Diethyl itaconate and citraconic acid (anhydride).
Among these, preferred are dicarboxylic acids, their alkyl esters and their anhydrides, more preferred are maleic acid (anhydride) and fumaric acid, and particularly preferred is maleic acid (anhydride).

The amount of α, β-unsaturated carboxylic acid (anhydride) used for modification is preferably 0.5 to 40%, more preferably 1 to 30%, particularly preferably 2 based on the weight of the polyolefin (b210). ~ 20%. When the amount of α, β-unsaturated carboxylic acid (anhydride) is within this range, it becomes easier to take a repeating structure, and filler dispersibility and conductivity are further improved.
The modification with α, β-unsaturated carboxylic acid (anhydride) can be carried out by various methods. For example, the terminal double bond of (b210) can be modified by either solution method or melt method. , Β-unsaturated carboxylic acid (anhydride) can be thermally added (ene reaction). The temperature at which (b210) is reacted with the α, β-unsaturated carboxylic acid (anhydride) is usually 170 to 230 ° C.

(B211-2) can be obtained by secondary modification of (b211-1) with lactam or aminocarboxylic acid.
As the lactam used for the secondary modification, C6-12 (preferably 6-8, more preferably 6) lactam and the like can be used, and examples thereof include caprolactam, enantolactam, laurolactam and undecanolactam.
As the aminocarboxylic acid, C2-12 (preferably 4-12, more preferably 6-12) aminocarboxylic acid and the like can be used. For example, amino acids (glycine, alanine, valine, leucine, isoleucine, phenylalanine, etc.) ), Ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopergonic acid, ω-aminocapric acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.
Of these, caprolactam, laurolactam, glycine, leucine, ω-aminocaprylic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid are preferred, and caprolactam, laurolactam, ω-aminocaprylic acid, 11-amino are more preferred. Undecanoic acid and 12-aminododecanoic acid, particularly preferably caprolactam, laurolactam and 12-aminododecanoic acid.
The amount of lactam or aminocarboxylic acid used for secondary modification is preferably 0.1 to 50, more preferably 0.3 to 20 per carboxyl group of α, β unsaturated carboxylic acid (anhydride). The number is particularly preferably 0.5 to 10, most preferably 1 to 2. When this amount is within this range, it becomes easier to take a repeating structure, and filler dispersibility and conductivity are further improved.

(B211-3) can be obtained by introducing (b210) a carbonyl group by oxidation with oxygen and / or ozone or hydroformylation by the oxo method.
The introduction of the carbonyl group by the oxidation method can be performed by a known method, for example, the method described in US Pat. No. 3,692,877.
Introduction of a carbonyl group by hydroformylation can be carried out by a known method, for example, see Macromolecules, Vol. 31, 5943 page.
(B211-4) can be obtained by secondarily modifying (b211-3) with a lactam or an aminocarboxylic acid.
The lactam and aminocarboxylic acid and preferred ranges thereof are the same as those which can be used in the production of (b211-2). The amount of lactam and aminocarboxylic acid used is the same.

Mn of the polyolefin (b211) having carbonyl groups at both ends of the polymer is preferably 800 to 25,000, more preferably from the viewpoint of heat resistance and reactivity with the polyoxyalkylene chain-containing compound (b22) described later. 1,000 to 20,000, particularly preferably 2,500 to 10,000.
The acid value of (b211) is preferably 4 to 280 (mg KOH / g. In the following, only numerical values will be described), more preferably 4 to 100, particularly from the viewpoint of reactivity with (b22). Preferably it is 5-50.

As the polyolefin (b212) having a hydroxyl group at both ends of the polymer, a polyolefin having a hydroxyl group obtained by modifying (b211) with hydroxylamine and a mixture of two or more of these can be used.
Examples of hydroxylamine that can be used for the modification include C2-10 (preferably 2-6, more preferably 2-4) hydroxylamine, and the like. For example, 2-aminoethanol, 3-aminopropanol, 1-amino- Examples include 2-propanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol and 3-aminomethyl-3,5,5-trimethylcyclohexanol.
Of these, 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol and 6-aminohexanol are more preferable, 2-aminoethanol and 4-aminobutanol are particularly preferable. Is 2-aminoethanol.
The modification with hydroxylamine can be carried out by various methods, for example, by directly reacting (b211) with hydroxylamine. The reaction temperature is usually 120 ° C to 230 ° C.

The amount of hydroxylamine used for modification is preferably 0.1 to 2, more preferably 0.3 to 1.5, particularly preferably per residue of α, β unsaturated carboxylic acid (anhydride). Is 0.5 to 1.2, most preferably 1. When the amount of hydroxylamine is within this range, it becomes easier to take a repeating structure, and the conductivity is further improved.
Mn of (b212) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably from the viewpoint of heat resistance and reactivity with the polyoxyalkylene chain-containing compound (b22) described later. Is 2,500 to 10,000.
The hydroxyl value of (b212) is preferably 4 to 280 (mg KOH / g. In the following, only numerical values are described), more preferably 4 to 100, particularly from the viewpoint of reactivity with (b22). Preferably it is 5-50.

As the polyolefin (b213) having an amino group at both ends of the polymer, a polyolefin having an amino group obtained by modifying (b211) with a diamine (Q1) and a mixture of two or more of these can be used.
As the diamine (Q1) used for this modification, C2-12 (preferably 2-8, more preferably 2-6) diamines can be used, for example, ethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine. And decamethylenediamine.
Of these, ethylenediamine, hexamethylenediamine, heptamethylenediamine and octamethylenediamine are preferable, ethylenediamine and hexamethylenediamine are more preferable, and ethylenediamine is particularly preferable.
The modification with diamine can be carried out by a known method, for example, by reacting (b211) and diamine (Q1) directly. The reaction temperature is usually 120 ° C to 230 ° C.

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

Mn of (b213) is preferably 800 to 25,000, more preferably 1,000 to 20,000, particularly preferably from the viewpoint of heat resistance and reactivity with the polyoxyalkylene chain-containing compound (b22) described later. Is 2,500 to 10,000.
The amine value of (b213) is preferably 4 to 280 (mg KOH / g, hereinafter, only numerical values are described) from the viewpoint of reactivity with (b22), more preferably 4 to 100, and particularly preferably. Is 5-50.

As the polyoxyalkylene chain-containing compound (b22) constituting the block polymer (B2), polyether diol (b221), polyether diamine (b222), and modified products thereof (b223) can be used.
The upper limit of the volume resistivity of (b22) is preferably 10 ¹¹ Ω · cm, more preferably 10 ¹⁰ Ω · cm, particularly preferably 10 ⁹ Ω · cm, from the viewpoint of conductivity, and the lower limit preferable from the viewpoint of mechanical properties. 10 ⁵ Ω · cm, more preferably 10 ⁶ Ω · cm, and particularly preferably 10 ⁷ Ω · cm.
Further, Mn of (b22) is preferably 150 to 20,000, more preferably 300 to 20,000, particularly preferably 1,000 to 15,000, from the viewpoint of heat resistance and reactivity with (b21). Most preferably, it is 1,200 to 8,000.

As the polyether diol (b221), one having a structure obtained by adding AO to the diol (b01) or the dihydric phenol (b02) can be used.
H— (OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _{m ′} —H

The thing shown by is mentioned.
In the formula, E ¹ represents a residue obtained by removing a hydroxyl group from (b01) or (b02), and A ¹ represents C2-12 (preferably 2-8, more preferably 2) which may contain a halogen atom. -4) alkylene group; m and m 'represent an integer of 1 to 300, preferably 2 to 250, particularly preferably 10 to 100, and m and m' may be the same or different. In addition, m (OA ¹ ) and m ′ (A ¹ O) may be the same or different, and the bond form in the case where these are composed of two or more oxyalkylene groups is a block form. , Random or a combination thereof.

  Of these diols (b01) and dihydric phenols (b02), dihydric alcohols and dihydric phenols are preferable from the viewpoint of reactivity, aliphatic dihydric alcohols and bisphenols are more preferable, and ethylene glycol is particularly preferable. And bisphenol A.

The polyether diol (b221) can be produced, for example, by adding AO to the diol (b01) or the dihydric phenol (b02).
As AO, C2-12 (preferably 2-8, more preferably 2-4) AO (EO, PO, 1,2-, 1,4-, 2,3- and 1,3-butylene oxide and A mixture of two or more of these) is used, and other AO or substituted AO may be used in combination as necessary (in the present invention, these are also collectively referred to as AO). Examples of other AO or substituted AO include epoxidized C5-12 α-olefin, styrene oxide and epihalohydrin (such as epichlorohydrin and epibromohydrin). The amount of other AO or substituted AO is preferably 30% or less, more preferably 0 to 25%, and particularly preferably 0 to 20% based on the weight of the total AO.

When two or more kinds of AO are used in combination, the binding form may be either block and / or random.
Preferred as AO is EO alone or a combination of EO and another AO (block and / or random addition), more preferred is a combination of EO and EO / PO, and particularly preferred is EO alone.
The number of added moles of AO is preferably 1 to 300 moles, more preferably 2 to 250 moles, and particularly preferably 10 to 100 moles per hydroxyl group of (b01) or dihydric phenol (b02). When the added mole number of AO is within this range, the volume resistivity value of (b22) tends to be more preferable.

AO can be added by a known method, for example, at a temperature of 100 to 200 ° C. in the presence of an alkali catalyst.
The content of oxyalkylene units of C2-12 (preferably 2-8, more preferably 2-4) in the polyether diol (b221) is preferably 5-99.8% based on the weight of (b221). More preferably, it is 8 to 99.6%, particularly preferably 10 to 98%.
The content of oxyethylene units in the polyoxyalkylene chain is preferably 5 to 100%, more preferably 10 to 100%, particularly preferably 50 to 100%, most preferably 60, based on the weight of the polyoxyalkylene chain. ~ 100%. When the content of the oxyethylene unit is within this range, the volume resistivity value of (b22) tends to be more preferable.

As the polyether diamine (b222), one having a structure in which the hydroxyl group of the polyether diol (b221) is modified to an amino group can be used.

R ″ NH—A ² — (OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _{m ′} —A ² —NHR ”

The thing shown by is mentioned.
Symbols E ¹ , A ¹ , m and m ′ in the formula are the same as those in the formula (b221), and A ² may contain a halogen atom, C 2-12 (preferably 2-8, more preferably Represents an alkylene group of 2 to 4), and A ¹ and A ² may be the same or different. R ″ represents H or a C1-4 (preferably 1 or 2) alkyl group.
(B222) can be easily obtained by changing the hydroxyl group of (b221) to an amino group by a known method.
Various methods can be used as a method for changing the hydroxyl group to an amino group. For example, a method in which the terminal cyanoalkyl group obtained by cyanoalkylating the hydroxyl group of (b221) is reduced to an amino group [for example, (b221) And a method of reacting acrylonitrile and hydrogenating the resulting cyanoethylated product], a method of reacting (b221) with an aminocarboxylic acid or lactam, and a method of reacting a halogenated amine under alkaline conditions.

Examples of the modified product (b223) of (b221) or (b222) include the isocyanate-modified product (terminal isocyanate group) and the epoxy-modified product (terminal epoxy group) of (b221) or (b222).
The isocyanate-modified product can be obtained by reacting (b221) or (b222) with an organic diisocyanate or reacting (b222) with phosgene.
The epoxy-modified product is obtained by reacting (b221) or (b222) with a diepoxide (epoxy resin such as diglycidyl ether, diglycidyl ester, alicyclic diepoxide: epoxy equivalent 85 to 600), or (b221) and epihalohydrin. It can be obtained by reacting with (e.g. epichlorohydrin).

  As the organic diisocyanate, C (excluding carbon in the NCO group, the same shall apply hereinafter) 6-20 (preferably 6-18, more preferably 8-14) aromatic diisocyanate, C2-18 (preferably 4-16, More preferably 6-14) aliphatic diisocyanate, C4-15 (preferably 4-13, more preferably 6-11) alicyclic diisocyanate, C8-15 (preferably 8-13, more preferably 9- 11) Aro-aliphatic diisocyanates, modified products of these diisocyanates, and mixtures of two or more thereof can be used.

  Examples of the aromatic diisocyanate include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 2,4′- or 4,4′-diphenylmethane diisocyanate ( MDI), 4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane and 1,5 -Naphthylene diisocyanate.

  Examples of the aliphatic diisocyanate include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and 2,6-diisocyanatomethylcaproate. Bis (2-isocyanatoethyl) fumarate, bis (2-isocyanatoethyl) carbonate, 2-isocyanatoethyl-2,6-diisocyanatohexanoate and the like.

Examples of the alicyclic diisocyanate include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), cyclohexylene diisocyanate, methylcyclohexylene diisocyanate (hydrogenated TDI), and bis (2-isocyanato). And ethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

Examples of the araliphatic diisocyanate include m- or p-xylylene diisocyanate (XDI) and α, α, α ′, α′-tetramethylxylylene diisocyanate (TMXDI).
Examples of the modified diisocyanate include urethane-modified products, urea-modified products, carbodiimide-modified products, and uretdione-modified products.
Of these organic diisocyanates, aromatic and aliphatic diisocyanates are preferable from the viewpoint of reactivity, TDI, MDI and HDI are more preferable, and HDI is particularly preferable.

In order to accelerate the polyurethane formation reaction, a commonly used catalyst may be used if necessary. As such a catalyst, a metal catalyst, an amine catalyst, and a mixture of two or more thereof can be used.
Examples of metal catalysts include tin catalysts (trimethyltin laurate, trimethyltin hydroxide, dimethyltin dilaurate, dibutyltin diacetate, dibutyltin dilaurate, stannous octoate, dibutyltin maleate, etc.); lead catalysts (lead oleate) , Lead 2-ethylhexanoate, lead naphthenate, lead octenoate, etc.); other metal catalysts (metal naphthenate such as cobalt naphthenate, phenylmercuric propionate, etc.).

  Examples of the amine catalyst include triethylenediamine, tetramethylethylenediamine, tetramethylhexylenediamine, diazabicycloalkene {1,8-diazabicyclo [5,4,0] undecene-7 [manufactured by San Apro Co., Ltd., registered trademark DBU]. Etc.}, dialkylaminoalkylamines (dimethylaminoethylamine, dimethylaminopropylamine, diethylaminopropylamine, dibutylaminoethylamine, dimethylaminooctylamine, dipropylaminopropylamine, etc.) and heterocyclic aminoalkylamines {2- (1- Aziridinyl) ethylamine, 4- (1-piperidinyl) -2-hexylamine, etc.} carbonates and organic acid salts (formate, etc.), etc. In addition, N-methylmorpholine, N-ethylmorpholine, Ethylamine, diethylethanolamine, dimethylethanolamine and the like can be used.

In the present invention, (B2) includes a polymer having a repeating unit represented by the general formula (1).

In general formula (1), n is an integer of 2 to 50, preferably 3 to 40, and more preferably 4 to 30. One of R ¹ and R ² is H, and the other is H or an alkyl group of C1-10 (preferably 1-8, more preferably 1-6). Moreover, y is an integer of 15 to 800, preferably 20 to 500, more preferably 30 to 400.
E ¹ , A ¹ , m and m ′ are the same as above, and X and X ′ are groups selected from the groups represented by the general formulas (2) to (8) and the corresponding (2 ′) to (8 A group selected from the group represented by '), that is, when X is a group represented by the general formula (2), X' is a group represented by the general formula (2 '), and the general formulas (3) to (3) to ( The same relationship applies to 8) and (3 ′) to (8 ′).

In the general formulas (2) to (8) and (2 ′) to (8 ′), R ³ and R ^{3 ′} are C 2 −
3 represents a trivalent hydrocarbon group, R ⁴ represents a C 1 to 11 (preferably 1 to 8, more preferably 1 to 6) divalent hydrocarbon group, and R ⁵ represents H or C 1 to C 1. 10 (preferably 1-8
, More preferably 1-6), and R ⁶ is C 2-22 (preferably 4-4).
18 and more preferably 6-12), E ² represents an organic diisocyanate residue, r is an integer of 1 to 10 (preferably 1 to 8, more preferably 1 to 6), u and v represent 0 or 1, and A ² and R are the same as defined above.
Q, Q ′, T and T ′ are groups represented by the following formula.

However, R ⁵ is H or C1-10 (preferably 1 to 8, more preferably 1 to 6) represents an alkyl group, R ⁷ represents H or a methyl group, t is, R ⁷ is a methyl group 1 for H, 0 or 1 for H.
The polyether segment {(OA ¹ ) _m —O—E ¹ —O— (A ¹ O) _{m ′} } in {} in the repeating unit represented by the general formula (1) depends on the polyether diol (b221). It is a structure to be constructed, and E ¹ , A ¹ , m and m ′ in the formula are the same as described above.

In the general formula (1), the block polymer (B21) in which X is a group represented by the general formula (2) and X ′ is a group represented by the general formula (2 ′) is a polyolefin having the carbonyl group (b211 -1) and polyether diol (b221) can be obtained. R ³ and R ^{3 ′} in general formulas (2) and (2 ′) are formulas formed from unsaturated dicarboxylic acids.

（Ｒ’はＨまたはメチル基、ｔはＲ’がＨのとき１または０、Ｒ’がメチル基のとき１である。）
で示される基であり、例えば、ポリオレフィンのカルボニル変性に、マレイン酸またはフマル酸を用いた場合は、Ｒ³は−ＣＨ₂−ＣＨ＜であり、Ｒ^3'は＞ＣＨ−ＣＨ₂−である。

(R ′ is H or a methyl group, t is 1 or 0 when R ′ is H, and 1 when R ′ is a methyl group.)
For example, when maleic acid or fumaric acid is used for carbonyl modification of polyolefin, R ³ is —CH ₂ —CH <and R ^{3 ′} is> CH—CH ₂ —. .

(B21) can be produced by various methods. For example, polyether diol (b221) is added to polyolefin (b211-1) having a carbonyl group, and polymerization (polycondensation) reaction is usually performed at 200 to 250 ° C. under reduced pressure. It can be manufactured by the method to be performed. It can also be produced using a single or twin screw extruder. Usually, it can manufacture by the method of superposing | polymerizing with 160-250 degreeC and residence time 0.1-20 minutes. Various catalysts can be used for the above polymerization reaction.
Catalysts include antimony catalysts (antimony trioxide, etc.), tin catalysts (monobutyltin oxide, etc.), titanium catalysts (tetrabutyl titanate, etc.), zirconium catalysts (tetrabutyl zirconate, etc.), organic acid metal salts [zirconium organic acid salts (Such as zirconyl acetate) and zinc acetate], and mixtures of two or more thereof.
Of these, preferred are a zirconium catalyst and an organic acid metal salt, and more preferred is zirconyl acetate.
The usage-amount of a catalyst is 0.001 to 5% normally with respect to the total weight of (b211-1) and (b221).

  In the general formula (1), a block polymer (B22) in which X is a group represented by the general formula (3) and X ′ is a group represented by the general formula (3 ′) is a polyolefin having a carbonyl group (b211-1 ) And polyether diamine (b222). The polymerization reaction of (b211-1) and (b222) can be performed by the same method as the polymerization reaction of (b211-1) and (b221).

  In the general formula (1), the block polymer (B23) in which X is a group represented by the general formula (4) and X ′ is a group represented by the general formula (4 ′) is represented by (b211-2) and (b221 ). The polymerization reaction of (b211-2) and (b221) can be performed by the same method as the polymerization reaction of (b211-1) and (b221).

  In the general formula (1), the block polymer (B24) in which X is a group represented by the general formula (5) and X ′ is a group represented by the general formula (5 ′) is represented by (b211-2) and (b222). ). Alternatively, (b222) may be secondarily modified with the lactam or aminocarboxylic acid and then reacted with (b211-1) for production. These polymerization reactions can be performed in the same manner as the polymerization reaction of (b211-1) and (b221).

  In the general formula (1), the block polymer (B25) in which X is a group represented by the general formula (6) and X ′ is a group represented by the general formula (6 ′) is (b211-3) (r = 1) or (b211-4) (when r ≧ 2) and (b221) (when u = 0) or polyetherdiamine (b222) (when u = 1). be able to. The polymerization reaction of (b211-3) or (b211-4) and (b221) or (b222) can be carried out in the same manner as the polymerization reaction of (b21-1) and (b221).

  In the general formula (1), the block polymer (B26) in which X is a group represented by the general formula (7) and X ′ is a group represented by the general formula (7 ′) has hydroxyl groups at both ends of the polymer. Polyolefin (b212) and polyether diol (b221) (when u = 0) or polyether diamine (b222) (when u = 1) are bonded via an organic diisocyanate. It can be obtained by reacting simultaneously or sequentially. For example, (b212) and an organic diisocyanate are reacted to obtain an isocyanate-modified polyolefin, and then this is reacted with (b221) or (b222).

In the general formula (1), the block polymer (B26) in which X is a group represented by the general formula (8) and X ′ is a group represented by the general formula (8 ′) is (b211-3) (v = 0) or (b212) (when v = 1) and (b221) or (b222) are bonded via an organic diisocyanate, and these are reacted simultaneously or sequentially. Obtainable. For example, (b211-3) or (b212) is reacted with an organic diisocyanate to obtain an isocyanate-modified polyolefin, and then reacted with (b221) or (b222). it can.
The reaction between (b212) and an organic diisocyanate, the reaction between (b221) or (b222) and an organic diisocyanate, and the reaction between an isocyanate-modified polyolefin and (b221) or (b222) are the same as the usual urethanization or urea formation reaction. Can be done in a way.

  The equivalent ratio (NCO / OH ratio) of the organic diisocyanate and (b212) and the equivalent ratio of the isocyanate-modified polyolefin and (b221) or (b222) (NCO / OH ratio) in forming the isocyanate-modified polyolefin are: The ratio is preferably 1.8 / 1 to 3/1, more preferably 1.9 / 1 to 2.5 / 1, and particularly preferably 2/1. When the equivalence ratio is within this range, it becomes easier to take a repeated structure, and filler dispersibility and conductivity are further improved. As the organic diisocyanate and the catalyst for promoting the reaction, those described above can be used.

Among the block polymers (B2) having a repeating unit represented by the general formula (1), (B21), (B22), (B23), (B24) are preferable, and (B21) and (B23 are more preferable. Particularly preferred is (B23).
The amount of the polyoxyalkylene chain-containing compound (b22) constituting the block polymer (B2) is preferably 20 to 90% based on the total weight of (b21) and (b22) from the viewpoint of conductivity, and more preferably Preferably it is 25 to 90%, particularly preferably 30 to 70%.
Moreover, Mn of (B2) is preferably 2,000 to 60,000, more preferably 5,000 to 40,000, and particularly preferably 8,000 to 30,000 from the viewpoints of mechanical properties and conductivity. is there.

In the structure of the block polymer (B2), the average number of repeating units (Nn) of the block of the polyolefin (b21) and the block of the polyoxyalkylene chain-containing compound (b22) is preferably 2 from the viewpoint of conductivity. To 50, more preferably 2.3 to 30, particularly preferably 2.7 to 20, and most preferably 3 to 10.
Nn can be determined by Mn and ¹ H-NMR analysis of (B2). For example, the case of (B21) having a structure in which blocks (b211) and (b221) are alternately and repeatedly bonded will be described. In ¹ H-NMR analysis, 4.0 to 4.
A signal attributed to the proton of 1 ppm ester bond {—C (C═O) —OCH ₂ —} and a signal attributed to the proton of polyethylene glycol of 3.2 to 3.7 ppm can be observed. The ratio of these proton integral values is obtained, and Nn can be obtained from this ratio and Mn.

  Both ends of (B2) have a carbonyl group, amino group, hydroxyl group and / or unmodified polyolefin end derived from (b21), and a hydroxyl group, amino group, isocyanate group and / or epoxy group derived from (b22). The unmodified polyolefin means a polyolefin terminal that is not modified at all, that is, an alkyl group or an alkenyl group.

Examples of the polyether amide imide (B3) include polyether amide imides described in JP-B-7-119342 and JP-A-6-172609.
Among these, from the viewpoint of heat resistance, caprolactam, trivalent or tetravalent aromatic polycarboxylic acid capable of forming at least one imide ring by reacting with an amino group and polyethylene glycol or at least 50% by weight Polyether amide imide derived from a mixture of polyethylene glycol and a polyalkylene glycol other than polyethylene glycol, wherein the content of the mixture is 30 to 85% by weight and the reduced viscosity at 30 ° C. is 1.5 to 4. .
The reduced viscosity of (B3) is preferably 1.5 to 4, more preferably 1.7 to 3.5 from the viewpoint of moldability of the resin composition.

Examples of the polyether ester (B4) include polyesters obtained by reacting a polyether diol or copolyether diol with a divalent or higher polyvalent carboxylic acid, for example, a polyether ester described in Japanese Patent Publication No. 58-19696. Can be mentioned.
The melting point of (B4) [measurement is by differential scanning calorimetry (hereinafter abbreviated as DSC method)] is preferably 100 ° C. or higher, more preferably 120 to 210 ° C. from the viewpoint of heat resistance.

Examples of the epihalohydrin / AO copolymer (B5) include an epihalohydrin / AO copolymer described in JP-B-7-84564.
Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin, and epifluorohydrin, and epichlorohydrin is preferable from the viewpoint of reactivity and cost. AO includes C2-4, such as EO, PO, and THF.
(B5) includes a co-polymer of epihalohydrin and a comonomer composed of one or more selected from 1,2-epoxide monomers [especially alkyl (C2-4) glycidyl ether] and AO (especially EO and PO). Mergers are also included.
The weight ratio of epihalohydrin to AO is usually 5/95 to 95/5, and preferably 10/90 to 60/40 from the viewpoint of imparting conductivity.
Among (B5), a copolymer of epichlorohydrin / EO (weight ratio 50/50) is preferable from the viewpoints of resin physical properties and conductivity.
Mn of (B5) is preferably from 30,000 to 100,000, more preferably from 60,000 to 90,000, from the viewpoints of resin physical properties and moldability.

Examples of the acrylamide copolymer (B6) include an acrylamide copolymer comprising 65 to 99 mol% of ethylene units, 0 to 15 mol% of acrylate units, and 1 to 35 mol% of acrylamide units described in JP-A-4-198308. Coalesce is mentioned.
Mn of (B6) is preferably 1,000 to 150,000, more preferably 3,000 to 100,000, from the viewpoint of the balance between the heat resistance of (B6) and the moldability of the resin composition.

Examples of the ethylene / unsaturated carboxylic acid (salt) or ethylene / (meth) acrylate / unsaturated carboxylic acid (salt) copolymer (B7) include ethylene / unsaturated carboxylic acid described in JP-A-8-269276. Or the ionomer by which the one part or all part of the carboxyl group of the random copolymer of ethylene / (meth) acrylate / unsaturated carboxylic acid was neutralized with the alkali metal is mentioned.
The melt flow rate (hereinafter abbreviated as MFR, measurement conditions are 190 ° C., 2.16 kg) of (B7) is preferably 1 to 20, more preferably 1.5 to 15 from the viewpoint of moldability of the resin composition. .

As the methoxypolyethylene glycol (meth) acrylate copolymer (B8), methoxypolyethylene glycol (Mn is preferably 250 to 4,950, more preferably 750 to 2,950) (meth) acrylate and a vinyl monomer described later. A copolymer may be mentioned.
Mn of methoxypolyethylene glycol (meth) acrylate is preferably 300 to 5,000, more preferably 800 to 3,000, from the viewpoint of conductivity. Preferred as the monomer to be copolymerized are (meth) acrylic acid, alkyl (C1-20) (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, etc.].
Mn of (B8) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000 from the viewpoint of physical properties of the resin. The methoxypolyethylene glycol (meth) acrylate unit and vinyl monomer in (B8) The weight ratio of the unit is preferably 20/80 to 80/20, more preferably 30/70 to 60/40 from the viewpoint of conductivity.

Examples of the polyether group-containing ethylene / vinyl acetate copolymer (B9) include those obtained by hydrolyzing an ethylene / vinyl acetate copolymer to give an ethylene / vinyl alcohol copolymer with EO addition.
The weight ratio of ethylene units to vinyl acetate units in the ethylene / vinyl acetate copolymer is preferably 20/80 to 80/20, more preferably 30/70 to 60/40, from the viewpoint of conductivity. The hydrolysis rate of the unit [vinyl acetate unit before hydrolysis / vinyl alcohol unit after hydrolysis] (mol%) is preferably 30 to 100 mol%, more preferably 40 to 80 mol% from the viewpoint of conductivity. is there. Further, the number of moles of EO added per vinyl alcohol unit is preferably 5 to 30, more preferably 10 to 20, from the viewpoint of conductivity.
Mn of (B9) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000 from the viewpoint of resin physical properties.

The conductivity-imparting agent (X) of the present invention is characterized in that (A) is reduced in the composition comprising the metal salt (A) and the hydrophilic group-containing polymer (B).
The weight ratio [(A) / (B)] of (A) and (B) is preferably 1/99 to 40/60, more preferably 5/95 to 30/70, from the viewpoint of conductivity and mechanical properties. is there.

  As a method for producing a composition comprising a metal salt (A) and a hydrophilic group-containing polymer (B), it is preferable to disperse (A) in (B) in advance from the viewpoint of uniform dispersion. A method in which (A) is contained during the production of is more preferred. There is no particular limitation on the timing of containing (A) during the production of (B), and any of before, during and after polymerization is preferable, but it is preferable to contain it in the raw material before polymerization.

  As a method for reducing the metal salt (A), (1) a composition comprising (A) and (B) is brought into contact with a reducing agent solution (a composition in which the composition is pelletized and immersed in the reducing agent solution). (2) A method of containing a composition comprising (A) and (B) in a thermoplastic resin (C) described later and then contacting with the reducing agent solution (same as above) ) And the like. Among these, the method (1) is preferable from the viewpoint of semiconductivity.

Examples of the solvent for dissolving the reducing agent include a water-soluble solvent having permeability to the inside of the hydrophilic group-containing polymer. Specifically, for example, water, methanol, ethanol, acetone, 2-propanol, dimethyl sulfoxide, N-methyl-2-pyrrolidone, N, N-dimethylformamide, ethylene glycol, diethylene glycol, glycerin, tetrahydrofuran and the like can be used. .
Of these, from the viewpoint of the permeability of the reducing agent solution to (B), water-soluble and polar solvents (water, methanol, ethanol, acetone, 2-propanol, dimethyl sulfoxide, N-methyl-2-pyrrolidone are preferred. N, N-dimethylformamide and the like.
Examples of the reducing agent include inorganic reducing agents [hypophosphites (such as sodium hypophosphite), hydrooxyborohydrides (potassium borohydride, sodium borohydride, lithium borohydride, zinc borohydride, hydrogen Triethylborohydride), sulfites (such as ammonium sulfite), thiosulfates (such as ammonium thiosulfate), hydrazine compounds (hydrazine, hydrazine sulfate, etc.), diborane, ferrous chloride, tin chloride, hydrogen peroxide, etc.], Organic reducing agents [aldehyde compounds (formaldehyde, acetaldehyde, etc.), phosphorus-containing compounds (tris-2-carboxyethylphosphine, etc.), dimethylamine borane, organic acids (C1-15, such as formic acid, oxalic acid, succinic acid, lactic acid, citric acid Acid, ascorbic acid, isoascorbic acid, gallic acid, hydroxylamine, catechol Lumpur, pyrogallol, hydroquinone, metol, amidol), etc.] and derivatives thereof.

  The reducing agent concentration (mol / L) in the reducing agent solution is preferably 0.005 to 4, more preferably 0.01 to 2, from the viewpoints of reducing effect and resin physical properties. In the reducing agent solution, various chelating agents (ethylenediaminetetraacetic acid (EDTA), nitrilotriacetic acid (NTA), etc.), pH buffering agents (phosphoric acid, boric acid, etc.), stabilizers (lead compounds, pyrophosphoric acid) Etc.) may be included.

The reduction of the metal salt can be confirmed by determining the state change (color change, gloss generation, etc.) on the surface of the resin composition with an electron microscope or visual inspection.
In addition, after treating the resin composition with a reducing agent, it is desirable to remove the solvent of the reducing agent solution by heating, drying under reduced pressure, or the like from the viewpoint of resin physical properties.

Conductivity imparting agent of the present invention a volume resistivity of (X) (Ω · cm) is preferred from the viewpoint of conductivity ^{1 × 10 1 ~1 × 10 4} , more preferably ¹ × 10 1 ~1 × 10 ³ , particularly preferably 1 × 10 ¹ to 1 × 10 ² .

The semiconductive resin composition of the present invention comprises the above-described conductivity imparting agent (X) in the thermoplastic resin (C).
(C) includes polyphenylene ether resin (C1); vinyl resin [polyolefin resin (C2) [for example, polypropylene, polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate copolymer resin], polyacrylic resin (C3) [for example, polymethyl methacrylate], polystyrene resin (C4) [consisting of a vinyl group-containing aromatic hydrocarbon alone or a vinyl group-containing aromatic hydrocarbon, (meth) acrylic ester, (meth) acrylonitrile, and butadiene Copolymers having at least one selected from the group as structural units, such as polystyrene, styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methyl methacrylate / butadiene / Styrene Polyester resin (C5) [for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polybutylene adipate, polyethylene adipate]; Polyamide resin (C6) [for example, nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 46, nylon 6/66, nylon 6/12]; polycarbonate resin (C7
) [For example, polycarbonate, polycarbonate / ABS alloy resin]; polyacetal resin (C8); biodegradable resin (C9), and a mixture of two or more thereof.

  Of these, (C1), (C2), (C3), (C4) are preferable from the viewpoint of the mechanical properties of the molded product described later and the dispersibility of the conductivity-imparting agent (X) of the present invention in (C). ) And (C7), more preferably (C2), (C4) and (C7).

  The content of (X) based on the total weight of the conductivity-imparting agents (X) and (C) of the present invention is preferably 1 to 30%, more preferably 5 to 15% from the viewpoint of conductivity and mechanical properties. It is.

  Examples of the polyphenylene ether resin (C1) include those represented by the following general formula (9).

In general formula (9), p is an integer of 50 or more, R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are H, a halogen atom, a C1-12 hydrocarbon group, a C2-12 substituted hydrocarbon group, and an alkoxy group. Represents a cyano group, a phenoxy group or a nitro group. R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ may be the same or different. In addition, (C1) is a single polymer of the general formula (9) or a copolymer of two or more structural units or a blend of two or more polymers. Also good.

Specific examples of (C1) include poly (2,6-dimethyl-1,4-phenylene) ether, poly (2,6-diethyl-1,4-phenylene) ether, poly (2-methyl-6-ethyl). -1,4-phenylene) ether, poly (2-methyl-6-propyl-1,4-phenylene) ether, poly (2,6-dipropyl-1,4-phenylene) ether, poly (2-ethyl-6) -Propyl-1,4-phenylene) ether, poly (2,6-dimethoxy-1,4-phenylene) ether, poly (2,6-dichloromethyl-1,4-phenylene) ether, poly (2,6-phenylene) Dibromo-1,4-phenylene) ether, poly (2,6-diphenyl-1,4-phenylene) ether, poly (2,6-dichloro-1,4-phenylene) ether, poly (2,6) Dibenzyl-1,4-phenylene) ether, poly (2,5-dimethyl-1,4-phenylene) ether.
Also, (C1) includes those obtained by grafting the above styrene and / or its derivative monomer (modified polyphenylene ether) to (C1).

The intrinsic viscosity [η] of (C1) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and conductivity. [Η] is measured using a Ubbelohde 1A viscometer at 30 ° C. for a 0.5 wt% chloroform solution of the polymer.
The glass transition temperature (hereinafter abbreviated as Tg) of (C1) is preferably 190 to 240 ° C., more preferably 210 to 230 ° C. from the viewpoint of moldability. Tg is measured by a differential scanning calorimetry (DSC) method.

  As the vinyl resins [(C2) to (C4)], those obtained by (co) polymerizing the following vinyl monomers by various polymerization methods (radical polymerization method, Ziegler catalyst polymerization method, metallocene catalyst polymerization method, etc.) Is mentioned.

Examples of vinyl monomers include unsaturated hydrocarbons (aliphatic hydrocarbons, aromatic ring-containing hydrocarbons, alicyclic hydrocarbons, etc.), acrylic monomers, other unsaturated mono- and dicarboxylic acids and their derivatives, and carboxylic acids of unsaturated alcohols. Examples include acid esters, alkyl ethers of unsaturated alcohols, halogen-containing vinyl monomers, and combinations (random and / or block) of two or more thereof.

Aliphatic hydrocarbons include C2-30 olefins [ethylene, propylene, C4 ~
30 α-olefins (1-butene, 4-methyl-1-pentene, 1-pentene, 1-
Octene, 1-decene, 1-dodecene, etc.)], C4-30 dienes [alkadienes (butadiene, isoprene, etc.), cycloalkadienes (cyclopentadiene, etc.), etc.].

Examples of the aromatic ring-containing hydrocarbon include C8-30 styrene and its derivatives, such as o.
-, M- and p-alkyl (C1-10) styrene (vinyl toluene, etc.), α-alkyl (C1-10) styrene (α-methylstyrene, etc.) and halogenated styrene (chlorostyrene, etc.).

Acrylic monomers include C3-30, such as (meth) acrylic acid and its derivatives.
Examples of derivatives of (meth) acrylic acid include alkyl (C1-20) (meth) acrylate [methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth)
Acrylate etc.], mono- and di-alkyl (C1-4) aminoalkyl (C2-4) (meth) acrylate [methylaminoethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate etc.], (meth) acrylonitrile and (Meth) acrylamide is mentioned.

  Other unsaturated mono- and dicarboxylic acids include C2-30 (preferably 3-20, more preferably 4-15) unsaturated mono- and dicarboxylic acids such as crotonic acid, maleic acid, fumaric acid and itacon. Examples thereof include C5-30, such as mono- and dialkyl (C1-20) esters, acid anhydrides (maleic anhydride, etc.) and acid imides (maleic imide, etc.).

Examples of carboxylic acid esters of unsaturated alcohols include carboxylic acids (C2-4, such as acetic acid, propionic acid) esters (vinyl acetate, etc.) of unsaturated alcohols [C2-6, such as vinyl alcohol, (meth) allyl alcohol]. It is done.
Examples of the alkyl ether of the unsaturated alcohol include alkyl (C1-20) ethers of the above unsaturated alcohol (such as methyl vinyl ether and ethyl vinyl ether). Halogen-containing vinyl monomers include C2-12, such as vinyl chloride, vinylidene chloride and chloroprene.

Examples of the polyolefin resin (C2) include polypropylene, polyethylene, propylene-ethylene copolymer [copolymerization ratio (weight ratio) = 0.1 / 99.9 to 99.9 / 0.1], propylene and / or ethylene. And other α-olefin (C4-12) copolymers (random and / or block addition) [copolymerization ratio (weight ratio) = 99 / 1-5 / 95], ethylene / vinyl acetate Copolymer (EVA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40], ethylene / ethyl acrylate copolymer (EEA) [copolymerization ratio (weight ratio) = 95 / 5-60 / 40 ].
Among these, preferred are polypropylene, polyethylene, propylene-ethylene copolymer, propylene and / or a copolymer of ethylene and one or more of C4-12 α-olefin [copolymerization ratio (weight ratio) = 90. / 10 to 10/90, random and / or block addition].

The MFR of (C2) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of imparting resin physical properties and conductivity. The MFR is measured according to JIS K6758 (in the case of polypropylene: 230 ° C., load 2.16 kgf, in the case of polyethylene: 190 ° C., load 2.16 kgf).
The crystallinity of (C2) is preferably 0 to 98%, more preferably 0 to 80%, and particularly preferably 0 to 70% from the viewpoint of conductivity.
The crystallinity is measured by a method such as X-ray diffraction, infrared absorption spectrum, etc. [Refer to “Solid Structure of Polymers—Lecture of Polymer Experiments 2” (Hatsugoro Minamishino), page 42, published by Kyoritsu Shuppan 1958).

  Examples of the polyacrylic resin (C3) include one or more (co) polymers [poly (meth) acrylic acid methyl ester, such as the above-mentioned acrylic monomers [alkyl (C1-20) (meth) acrylate, (meth) acrylonitrile, etc.], Poly (meth) butyl acrylate, etc.] and copolymers with one or more of the above-mentioned vinyl monomers copolymerizable with one or more of these monomers [acrylic monomer / vinyl monomer copolymerization ratio (weight ratio) is a resin physical property In view of the above, preferably 5/95 to 95/5, more preferably 50/50 to 90/10] [however, those included in (C2) are excluded] are included.

The MFR of (C3) is preferably 0.5 to 150, more preferably 1 to 100 from the viewpoint of resin physical properties. The MFR is measured according to JIS K7210 (1994) (230 ° C in the case of polyacrylic resin, load 1.2 kgf).

As the polystyrene resin (C4), a vinyl group-containing aromatic hydrocarbon alone or a vinyl group-containing aromatic hydrocarbon, and at least one selected from the group consisting of (meth) acrylic acid ester, (meth) acrylonitrile and butadiene Examples thereof include a copolymer as a structural unit.
Examples of vinyl group-containing aromatic hydrocarbons include C8-30 styrene and its derivatives,
For example, o-, m-, and p-alkyl (C1-10) styrene (vinyl toluene, etc.), α-alkyl (C1-10) styrene (α-methylstyrene, etc.) and halogenated styrene (chlorostyrene, etc.) can be mentioned. .
Specific examples of (C4) include polystyrene, polyvinyltoluene, 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) / (5-40) / (40-70)].

  The MFR of (C4) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and conductivity. MFR is measured according to JIS K6871 (1994) (230 ° C. in the case of polystyrene resin, load 1.2 kgf).

  Examples of the polyester resin (C5) include aromatic ring-containing polyesters (polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, etc.) and aliphatic polyesters (polybutylene adipate, polyethylene adipate, poly-ε-caprolactone, etc.).

  The intrinsic viscosity [η] of (C5) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and conductivity. [Η] is measured with a Ubbelohde 1A viscometer at 25 ° C. for a 0.5 wt% orthochlorophenol solution of the polymer.

  As the polyamide resin (C6), a lactam ring-opening polymer (C61), a dehydration polycondensation product of diamine and dicarboxylic acid (C62), a self-polycondensation product of aminocarboxylic acid (C63), and a poly (condensation) combination thereof. Examples thereof include copolymer nylon having two or more types of monomer units.

Examples of the lactam in (C61) include those exemplified in the above (b111), and examples of (C61) include nylon 4, nylon 5, nylon 6, nylon 8, nylon 12, and the like.
Examples of the diamine and dicarboxylic acid in (C62) include those exemplified in the above (b113). Examples of (C62) include nylon 66 obtained by polycondensation of hexanemethylenediamine and adipic acid, and the weight of hexamethylenediamine and sebacic acid. Examples thereof include nylon 610 by condensation.
Examples of the aminocarboxylic acid in (C63) include those exemplified in the above (b112). Examples of (C63) include nylon 7 by polycondensation of aminoenanthate, nylon 11 by polycondensation of ω-aminoundecanoic acid, Nylon 12 and the like by polycondensation of 12-aminododecanoic acid.

In the production of (C6), a molecular weight modifier may be used, and examples of the molecular weight modifier include the dicarboxylic acid and / or diamine exemplified in (b113).
Of the dicarboxylic acids as molecular weight modifiers, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and more preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and It is sodium 3-sulfoisophthalate. Of the diamines as molecular weight regulators, hexamethylene diamine and decamethylene diamine are preferable.

The MFR of (C6) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and conductivity. The MFR is measured according to JIS K7210 (1994) (in the case of polyamide resin, 230 ° C., load 0.325 kgf).

Polycarbonate resins (C7) include bisphenols (C12-20, such as bisphenol A, -F and -S, 4,4'-dihydroxydiphenyl-2,2-butane) and dihydroxybiphenyl polycarbonates such as bisphenol and phosgene. Or the condensate with a carbonic acid diester is mentioned. Of the above bisphenols, bisphenol A is preferred from the viewpoint of the dispersibility of (A).
The MFR of (C7) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and conductivity. MFR is measured according to JIS K7210 (1994) (in the case of polycarbonate resin, 280 ° C., load 2.16 kgf).

Examples of the polyacetal resin (C8) include formaldehyde or trioxane homopolymer (polyoxymethylene homopolymer), and a copolymer of formaldehyde or trioxane and a cyclic ether [the above-mentioned AO (EO, PO, dioxolane, etc.)] (polyoxy). And methylene / polyoxyethylene copolymer [polyoxymethylene / polyoxyethylene (weight ratio) = 90/10 to 99/1 block copolymer, etc.].
The MFR of (C8) is preferably 0.5 to 150, more preferably 1 to 100, from the viewpoint of resin physical properties and conductivity. The MFR is measured according to JIS K7210 (1994) (in the case of polyacetal resin, 190 ° C., load 2.16 kgf).
The intrinsic viscosity [η] of (C8) is preferably from 0.1 to 4, more preferably from 0.2 to 3.5, particularly preferably from 0.3 to 3, from the viewpoints of resin physical properties and conductivity.

  Examples of the biodegradable resin (C9) include polyhydroxybutyrate, polylactic acid, polycaprolactone, polybutylene succinate, adipate-modified polybutylene succinate, carbonate-modified polybutylene succinate, terephthalate-modified polybutylene succinate, polyethylene succinate And polyvinyl alcohol.

  Among (C9), as polyhydroxybutyrate, for example, biogreen [manufactured by Mitsubishi Gas Chemical Co., Ltd.]]; as polylactic acid, for example, Lacia [manufactured by Mitsui Chemicals, Inc.]]; as polycaprolactone, for example, Cell Green [manufactured by Daicel Chemical Industries, Ltd.]; Polybutylene succinate, for example, Bionore [manufactured by Showa Polymer Co., Ltd.]; Polyethylene succinate, for example, Lunare SE (manufactured by Nippon Shokubai Co., Ltd.)] Examples of polyvinyl alcohol include Poval [manufactured by Kuraray Co., Ltd.].

  The resin composition of the present invention includes a conductive improver (D), a compatibilizing agent (E), and other resin additives (F) as necessary, as long as the effects of the present invention are not impaired. At least one additive selected may be included.

The conductivity improver (D) includes one or more selected from the group consisting of alkali metal or alkaline earth metal salts (D1), surfactants (D2) and ionic liquids (D3). It is.
(D1) includes alkali metal (lithium, sodium, potassium, etc.) and / or alkaline earth metal (magnesium, calcium, etc.) organic acids (C1-12 mono- and di-carboxylic acids such as formic acid, acetic acid, Propionic acid, oxalic acid, succinic acid; salts of C1-20 sulfonic acids such as methanesulfonic acid, p-toluenesulfonic acid; thiocyanic acid, and inorganic acids (hydrohalic acids such as hydrochloric acid, hydrobromic acid; A salt of perchloric acid; sulfuric acid; nitric acid; phosphoric acid) can be used.

Specific examples of (D1) include halides [fluorides (lithium fluoride, -sodium, -potassium, -magnesium, -calcium, etc.), chlorides (lithium chloride, -sodium, -potassium, -magnesium, and -calcium). Etc.), bromides (such as lithium bromide, -sodium, -potassium, -magnesium and -calcium) and iodides (such as lithium iodide, -sodium, -potassium, -magnesium and -calcium) etc.], perchlorates (Such as lithium perchlorate, -sodium, -potassium, -magnesium and -calcium), fluorinated sulfonates (such as lithium fluorosulfonate, -sodium, -potassium, -magnesium and -calcium), methanesulfonate ( Lithium methanesulfonate, -sodium, Potassium, -magnesium and -calcium), trifluoromethanesulfonate (lithium trifluoromethanesulfonate, -sodium, -potassium, -magnesium and -calcium etc.), pentafluoroethanesulfonate (lithium pentafluoroethanesulfonate, -Sodium, -potassium, -magnesium and -calcium), nonafluorobutane sulfonate (such as lithium nonafluorobutane sulfonate, -sodium, -potassium, -magnesium and -calcium), undecafluoropentane sulfonate ( Undecafluoropentanesulfonate lithium, -sodium, -potassium, -magnesium and -calcium, etc.), tridecafluorohexanesulfonate (tridecafluorohexanes) Lithium fonate, -sodium, -potassium, -magnesium and -calcium), acetates (lithium acetate, -sodium, -potassium, -magnesium and -calcium etc.), sulfates (sodium sulfate, -potassium, -magnesium and -Calcium etc.), phosphate (sodium phosphate, -potassium, -magnesium, -calcium etc.), thiocyanate (potassium thiocyanate etc.), etc. are mentioned.
Among these, from the viewpoint of conductivity, preferred are halides, perchlorates, trifluoromethanesulfonates, acetates, and more preferred are lithium chloride, -potassium and -sodium, lithium perchlorate, -potassium and -Sodium, lithium trifluoromethanesulfonate,-potassium and-sodium, potassium acetate.

The amount of (D1) used is based on the total weight of the conductivity-imparting agents (X) and (C) from the viewpoint of the conductivity improvement effect and from the viewpoint of giving a resin molded article having a good appearance without being deposited on the resin surface. , Preferably 0.001 to 3%, more preferably 0.01 to 2.5%, particularly preferably 0.1 to 2%, and most preferably 0.15 to 1%.
Although there is no particular limitation on the method of containing (D1), it is preferable to disperse in advance in the hydrophilic group-containing polymer (B) from the viewpoint of ease of effective dispersion in the composition.
Further, when (D) is dispersed in (B), it is particularly preferable that (D1) is contained and dispersed in advance during the production (polymerization) of (B). There is no particular limitation on the timing at which (D1) is contained during the production of (B), and any of the timing before polymerization, during polymerization, and immediately after polymerization may be used.

(D2) includes nonionic, anionic, cationic and amphoteric surfactants, and mixtures thereof.
Nonionic surfactants include, for example, EO addition type nonionic surfactants [for example, higher alcohol (C8-18, the same hereinafter), higher fatty acid (C8-24, same hereinafter) or higher alkylamine (C8-24). ) EO adduct (molecular weight 158 or more and Mn 200,000 or less); higher fatty acid ester of polyalkylene glycol (molecular weight 150 or more and Mn 6,000 or less) which is an EO adduct of glycol; polyhydric alcohol (C2-18) EO adduct of higher fatty acid ester (molecular weight of 250 or more and Mn of 30,000 or less); EO adduct of higher fatty acid amide (molecular weight 200) And Mn 30,000 or less); And polyhydric alcohol (as described above) EO adduct of alkyl (C3-60) ether (molecular weight of 120 or more and Mn30,000 or less)], and polyhydric alcohol (C3-60) type nonionic surfactant [For example, fatty acid (C3-60) ester of polyhydric alcohol, alkyl (C3-60) ether of polyhydric alcohol and fatty acid (C3-60) alkanolamide].

  As the anionic surfactant, compounds other than the above (D1) can be used, for example, carboxylates such as higher fatty acid salts; sulfates such as higher alcohol sulfates and higher alkyl ether sulfates; alkylbenzene sulfones. Examples thereof include sulfonates such as acid salts, alkyl sulfonates, and paraffin sulfonates; and phosphate ester salts such as higher alcohol phosphate salts.

Cationic surfactants include quaternary ammonium salt types [eg, tetraalkyl (C4-100) ammonium salts (eg, lauryltrimethylammonium chloride, didecyldimethylammonium chloride, dioctyldimethylammonium bromide and stearyltrimethylammonium bromide), Alkyl (C3-80) benzylammonium salts (eg lauryldimethylbenzylammonium chloride (benzalkonium chloride), alkyl (C2-60) pyridinium salts (eg cetylpyridinium chloride), polyoxyalkylene (C2-4) trialkylammonium salts (Eg, polyoxyethylenetrimethylammonium chloride) and sapamine type quaternary ammonium salts (eg, stearamide ester) Rudiethylmethyl ammonium methosulfate)]; and amine salt forms [eg higher aliphatic amines (C12-60, eg laurylamine, stearylamine, cetylamine, hardened tallow amine and rosinamine) inorganic acids (eg hydrochloric acid, sulfuric acid, nitric acid and Phosphoric acid) salts or organic acids (C2-22, such as acetic acid, propionic acid, lauric acid, oleic acid, benzoic acid, succinic acid, adipic acid and azelaic acid) salts, ethylene oxide adducts of aliphatic amines (C1-30) Inorganic acids (above) or organic acids (above) and tertiary amines (C3-30, eg triethanolamine monostearate and stearamide ethyl diethyl methylethanolamine) Thing) salt or organic acid (above thing) salt] It is.

Examples of amphoteric surfactants include amino acid-type amphoteric surfactants such as higher alkylaminopropionates, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine.
Examples of amphoteric surfactants include amino acid type amphoteric surfactants [for example, propionates of higher alkylamines (C8-24)], betaine type amphoteric surfactants [for example, higher alkyl (C12-18) dimethylbetaines, higher alkyldihydroxys. Ethyl betaine], sulfate ester type amphoteric surfactants [for example, sulfates of higher alkylamines (C8-24) and hydroxyethyl imidazoline sulfate esters], sulfonate type amphoteric surfactants (for example, pentadecyl sulfotaurine salts) And imidazoline sulfonate) and phosphate ester type amphoteric surfactants [for example, phosphate ester salts of glycerol higher fatty acid (C8-24) esterified products].

These may be used alone or in combination of two or more.
Salts in the above anionic and amphoteric surfactants include metal salts, such as salts of alkali metals (lithium, sodium, potassium, etc.), alkaline earth metals (calcium, magnesium, etc.) and group IIB metals (zinc, etc.); And ammonium salts [alkylamine (C1-20) and alkanolamine (C2-12, such as mono-, di- and triethanolamine) salts] and quaternary ammonium salts.
Of these, anionic surfactants are preferred from the viewpoint of conductivity, sulfonates are more preferred, alkylbenzene sulfonates (such as sodium dodecylbenzene sulfonate), alkyl sulfonates and paraffin sulfones are particularly preferred. Acid salt.

The amount of (D2) used is preferably 0.001 to 5%, more preferably 0.01 to 3%, particularly preferably 0.001% based on the total weight of the conductivity-imparting agents (X) and (C). 1 to 2.5%.
The method of containing (D2) is also not particularly limited, but it is preferable to disperse in (B) in advance in order to effectively disperse it in the resin composition. Further, when (D2) is dispersed in (B), it is particularly preferable that (D2) is previously contained and dispersed during the production (polymerization) of (B). There is no particular limitation on the timing at which (D2) is contained during the production of (B), and any time before polymerization, during polymerization, or immediately after polymerization may be used.

(D3) is a compound other than the above (D1) and (D2), has a melting point of room temperature or lower, and at least one of cations or anions constituting (D3) is an organic ion, and has an initial conductivity of 1 to 1. A room temperature molten salt of 200 ms / cm (preferably 10 to 200 ms / cm), for example, a room temperature molten salt described in WO95 / 15572. Examples of the cation constituting (D3) include an amidinium cation, a guanidinium cation, and a tertiary ammonium cation.

Examples of the amidinium cation include an imidazolinium cation [1,2,3,4-tetramethylimidazolinium, 1,3,4-trimethyl-2-ethylimidazolinium, 1,3-dimethylimidazolinium. 1,3-dimethyl-2,4-diethylimidazolinium, etc.], 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.], and 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].

Examples of the guanidinium cation include 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, etc.], guanidinium cation having an imidazolium skeleton [2-dimethyl Amino-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.], tetrahydropyrimidiniu Guanidinium cation having a 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.], and guanidinium having a dihydropyrimidinium skeleton Cation [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 methyl dilauryl ammonium.

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

In (D3), examples of the organic acid or inorganic acid constituting the anion include the following.
Examples of the organic acid include carboxylic acid, sulfate ester, higher alkyl ether sulfate ester, sulfonic acid and phosphate ester.
Examples of the inorganic acid include super strong acids (for example, borofluoric acid, tetrafluoroboric acid, perchloric acid, hexafluorophosphoric acid, hexafluoroantimonic acid and hexafluoroarsenic acid), phosphoric acid and boric acid. It is done.
The organic acid and inorganic acid may be used alone or in combination of two or more.
Among the organic and inorganic acids, Hamett acidity function initial conductivity standpoint preferred from of the anion constituting the (D3) of (D3) (-H ₀₎ is 12 to 100, the superacid conjugate base , Acids that form anions other than the conjugate bases of super strong acids, and mixtures thereof.

  Examples of the anion other than the conjugate base of the super strong acid include halogen (for example, fluorine, chlorine and bromine) ions, alkyl (C1-12) benzenesulfonic acid (for example, p-toluenesulfonic acid and dodecylbenzenesulfonic acid) ions and poly (n = 1-25) Fluoroalkanesulfonic acid (for example, undecafluoropentanesulfonic acid) ion.

Super strong acids include those derived from protonic acids and combinations of protonic acids and Lewis acids, and mixtures thereof.
Examples of the protonic acid as the super strong acid include bis (trifluoromethylsulfonyl) imidic acid, bis (pentafluoroethylsulfonyl) imidic acid, tris (trifluoromethylsulfonyl) methane, perchloric acid, fluorosulfonic acid, alkane (C1 -30) sulfonic acid [eg methane sulfonic acid, dodecane sulfonic acid etc.], poly (n = 1-30) fluoroalkane (C1-30) sulfonic acid (eg trifluoromethane sulfonic acid, pentafluoroethane sulfonic acid, heptafluoropropane) Sulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid and tridecafluorohexanesulfonic acid), borofluoric acid and tetrafluoroboric acid.
Of these, borofluoric acid, trifluoromethanesulfonic acid and bis (pentafluoroethylsulfonyl) imidic acid are preferred from the viewpoint of ease of synthesis.

Examples of the protonic acid used in combination with the Lewis acid include hydrogen halides (for example, hydrogen fluoride, hydrogen chloride, hydrogen bromide and hydrogen iodide), perchloric acid, fluorosulfonic acid, methanesulfonic acid, and trifluoromethanesulfonic acid. , Pentafluoroethanesulfonic acid, nonafluorobutanesulfonic acid, undecafluoropentanesulfonic acid, tridecafluorohexanesulfonic acid and mixtures thereof.
Of these, hydrogen fluoride is preferred from the viewpoint of the initial conductivity of (D3).
Examples of the Lewis acid include boron trifluoride, phosphorus pentafluoride, antimony pentafluoride, arsenic pentafluoride, tantalum pentafluoride, and mixtures thereof. Of these, boron trifluoride and phosphorus pentafluoride are preferable from the viewpoint of the initial conductivity of (D3).
The combination of the protonic acid and the Lewis acid is arbitrary, but as the super strong acid comprising these combinations, for example, tetrafluoroboric acid, hexafluorophosphoric acid, hexafluorotantalic acid, hexafluoroantimonic acid, tantalum hexafluoride Examples include sulfonic acid, tetrafluoroboric acid, hexafluorophosphoric acid, chloroboron trifluoride, arsenic hexafluoride, and mixtures thereof.

  Among the above anions, (D3) from the viewpoint of the initial conductivity, a super strong acid conjugate base (a super strong acid consisting of a proton acid and a super strong acid consisting of a combination of a proton acid and a Lewis acid), more preferably It is a conjugate base of a super strong acid consisting of a super strong acid consisting of a proton acid and a proton acid and boron trifluoride and / or phosphorus pentafluoride.

The amount of (D3) used is preferably 10% or less based on the total weight of the conductivity-imparting agents (X) and (C), preferably from the viewpoint of good appearance and conductivity effect of the molded product, and mechanical properties. 0.001 to 5%, more preferably 0.01 to 3%.
The method of adding (D3) is also not particularly limited, but it is preferable to disperse in (B) in advance from the viewpoint of effective dispersion in the resin. Further, when (D3) is dispersed in (B), it is particularly preferable that (D3) is contained and dispersed in advance during the production (polymerization) of (B). There is no particular limitation on the timing at which (D3) is contained during the production of (B), and any time before polymerization, during polymerization, or immediately after polymerization may be used.

  The production method of (D3) includes, for example, an amidinium cation and / or guanidinium cation dimethyl carbonate salt obtained by quaternization with dimethyl carbonate, etc. Acid or inorganic acid] to perform acid exchange, or after amidinium cation and / or guanidinium cation is hydrolyzed to form monoamidoamine, the monoamidoamine is converted to acid (same as above) The method of neutralizing with is mentioned.

As the compatibilizer (E), a modified vinyl polymer having at least one functional group (polar group) selected from the group consisting of a carboxyl group, an epoxy group, an amino group, a hydroxyl group and a polyoxyalkylene group is used. Examples thereof include polymers described in JP-A-3-258850. Further, for example, a modified vinyl polymer having a sulfonyl group described in JP-A-6-345927, a block polymer having a polyolefin portion and an aromatic vinyl polymer portion, and the like can be used.
The use amount of (E) is preferably 0.1 to 15%, more preferably 1 to 10%, particularly preferably 1 to 10%, based on the total weight of the conductivity-imparting agents (X) and (C), from the viewpoint of resin physical properties. Preferably it is 1.5 to 8%.
The method of containing (E) is not particularly limited, but it is preferable to disperse it in advance in the hydrophilic group-containing polymer (B) from the viewpoint of easy dispersion or dissolution in the composition. .
In addition, when (E) is dispersed or dissolved in (B), it is particularly preferable to contain (E) in advance during the production (polymerization) of (B). There is no particular limitation on the timing of incorporating (E) during the production of (B), and any of the timing before polymerization, during polymerization, and immediately after polymerization may be used.

Moreover, according to various uses, the other resin additive (F) can be arbitrarily added to the resin composition of this invention in the range which does not inhibit the effect of this invention.
(F) includes nucleating agent (F1), lubricant (F2), pigment (F3), dye (F4), mold release agent (F5), antioxidant (F6), flame retardant (F7), ultraviolet absorber Examples thereof include at least one selected from the group consisting of (F8), antibacterial agent (F9), dispersant (F10), plasticizer (F11), conductive material (F12), and filler (F13).

As the nucleating agent (F1), organic nucleating agents [for example, 1,3,2,4-di-benzylidene-sorbitol, aluminum-mono-hydroxy-di-pt-butylbenzoate, sodium-bis (4-t -Butylphenyl) phosphate and sodium benzoate] and inorganic nucleating agents (eg graphite, carbon black, magnesium oxide, calcium silicate, magnesium silicate, talc, kaolin, calcium carbonate, magnesium carbonate, sodium carbonate, potassium carbonate, zinc oxide, Alumina, barium sulfate and calcium sulfate).
Lubricants (F2) include waxes (eg carnauba wax, paraffin wax and polyolefin wax), higher fatty acids (C8-24, eg stearic acid, oleic acid, linoleic acid and linolenic acid), higher alcohols (C8-18, eg stearyl). Alcohols, lauryl alcohol, myristyl alcohol, cetyl alcohol, cetostearyl alcohol and behenyl alcohol) and higher fatty acid amides (C8-24, such as stearic acid amide, oleic acid amide, linoleic acid amide and linolenic acid amide).

Examples of the pigment (F3) include inorganic pigments [white pigments (titanium oxide, lithopone, lead white, zinc white, etc.), cobalt compounds (aureolin, cobalt green, etc.), iron compounds (iron oxide, bitumen, etc.), chromium compounds (oxidation). Chromium, lead chromate, etc.) and sulfides (cadmium sulfide, ultramarine, etc.)], organic pigments [azo pigments (azo lakes, monoazos, disazos, chelate azos, etc.), polycyclic pigments (benzoimidazolones) Phthalocyanine, isoindolinone, anthraquinone, etc.).
Examples of the dye (F4) include azo, indigoid, sulfide, alizarin, acridine, thiazole, nitro, and aniline.
As the release agent (F5), lower fatty acid (C1-4) alcohol ester of higher fatty acid (above) (for example, butyl stearate), polyvalent fatty acid (C2-18) (divalent to tetravalent or higher) ) Alcohol esters (eg hydrogenated castor oil), glycol (C2-8) esters of fatty acids (C2-18) (eg ethylene glycol monostearate) and liquid paraffin.

  Antioxidants (F6) include phenolic {eg monocyclic phenols [eg 2,6-di-t-butyl-p-cresol and butylated hydroxyanisole], bisphenols [eg 2,2′-methylenebis (4- Methyl-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl) -6-tert-butylphenol and 4,4′-thiobis (3-methyl) -6-tert-butylphenol] and polycyclic phenols [ For example, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-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]}; sulfur-based [eg, dilauryl 3,3'-thiodipropionate, distearyl 3,3'-thiodipropionate, lauryl stearyl 3,3'-thiodipropionate, dimyristyl 3,3'- Thiodipropionate, distearyl β, β′-thiodibutyrate and dilauryl sulfide]; phosphorus systems [eg triphenyl phosphite, triisodecyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (2 , 4-di-t-butylphenyl) phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, 4,4′-butylidene-bis (3-methyl-6-t) -Butylphenylditridecyl) phosphite, cyclic neopentanetetri Bis (octadecyl phosphite), cyclic neopentanetetrayl bis (2,6-di-t-butyl-4-methylphenyl) phosphite, cyclic neopentanetetrayl bis (2,4-di-t-butyl) Phenyl) phosphite and diisodecylpentaerythritol diphosphite]; and amine systems such as 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 and phenothiazine.

  The flame retardant (F7) includes a halogen-containing flame retardant (F71), a nitrogen-containing flame retardant (F72), a sulfur-containing flame retardant (F73), a silicon-containing flame retardant (F74), and a phosphorus-containing flame retardant (F75). 1 type or 2 types or more of flame retardants chosen from these are included.

  Examples of the halogen-containing flame retardant (F71) include hexachloropentadiene, hexabromodiphenyl, octabromodiphenyl oxide, tribromophenoxymethane, decabromodiphenyl, decabromodiphenyl oxide, tetrabromobisphenol A, tetromophthalimide, hexabromobutene, Hexabromocyclododecane, etc .;

Examples of the nitrogen-containing flame retardant (F72) include a salt of urea compound, guanidine compound or triazine compound (melamine, guanamine, etc.) and cyanuric acid or isocyanuric acid;
Examples of the sulfur-containing flame retardant (F73) include sulfuric ester, organic sulfonic acid, sulfamic acid, organic sulfamic acid, and salts, esters and amides thereof;
Examples of the silicon-containing flame retardant (F74) include polyorganosiloxane;

  Examples of the phosphorus-containing flame retardant (F75) include phosphorus-containing acids and esters thereof (C2-20) such as phosphoric acid, phosphate, halogen-containing phosphate, phosphorous acid, phosphonate, and ammonium phosphate.

Examples of the phosphate include phosphates and condensed phosphates (di- and polyphosphates).
Examples of the phosphate include trialkyl (alkyl group is C1-12) phosphate [trimethyl-, triethyl-, tributyl- and trioctylphosphate etc.], trialkoxy (alkoxy group is C1-6) phosphate [triethoxy- and tributoxyphosphate etc. ], Triaryl phosphate [triphenyl phosphate and the like], alkyl (alkyl group is C1-10) aryl phosphate [tricresyl-, cresyldiphenyl-, octyldiphenyl-, diisopropylphenyl- and resorcinol-bis (di-2,6- Dimethylphenyl) phosphate, etc.].

  Examples of the condensed phosphate include trialkyl (alkyl group is C1-12) poly (n = 2-30) phosphate, phenyl resorcinol poly (n = 2-30) phosphate, resorcinol poly (n = 2-30) phosphate [resorcin bis. Phosphate, cresyl resorcinol polyphosphate, etc.], hydroquinone poly (n = 2-30) phosphate [hydroquinone bisphosphate, hydroquinone polyphosphate, etc.], bisphenol A bisphosphate, trioxybenzene triphosphate and the like.

  Examples of the halogen-containing phosphate include tris halogenated alkyl (alkyl group is C2-4) phosphate [trischloroethyl phosphate, trisdichloropropyl phosphate, tris-β-chloropropyl phosphate, tris (tribromoneopentyl) phosphate, etc.], And tris-halogenated aryl phosphate [tris (tribromophenyl) phosphate, tris (dibromophenyl) phosphate, etc.].

Examples of the phosphonate include phosphonates and condensed phosphonates.
As phosphonates, trialkyl (alkyl group is C1-12) phosphonate [trimethylphosphonate, triethylphosphonate, tributylphosphonate, trioctylphosphonate, etc.], trialkoxy (alkoxy group is C1-6) phosphonate [triethoxyphosphonate, tributoxyphosphonate Etc.], triaryl phosphonate [triphenyl phosphonate etc.], alkyl (alkyl group is C1-10) aryl phosphonate [tricresyl phosphonate, cresyl diphenyl phosphonate, octyl diphenyl phosphonate, diisopropyl phenyl phosphonate, resorcinol bis (di-2) , 6-dimethylphenyl) phosphonate and the like.

  As the condensed phosphonate, trialkyl (alkyl group is C1-12) poly (n = 2 to 30) phosphonate, phenyl resorcinol poly (n = 2 to 30) phosphonate, resorcinol poly (n = 2 to 30) phosphonate [resorcinbis Phosphate, cresyl resorcinol polyphosphonate, etc.], hydroquinone poly (n = 2-30) phosphonate [hydroquinone bisphosphonate, hydroquinone polyphosphonate, etc.], bisphenol A bisphosphonate, trioxybenzene triphosphonate and the like.

  Examples of the halogen-containing phosphonate include tris halogenated alkyl (alkyl group is C2-4) phosphonate [trischloroethyl phosphonate, tris dichloropropyl phosphonate, tris-β-chloropropyl phosphonate, tris (tribromoneopentyl) phosphonate, etc.], And tris-halogenated aryl phosphonate [tris (tribromophenyl) phosphonate, tris (dibromophenyl) phosphonate, etc.].

  As said ammonium phosphate, what is marketed normally for flame retardants can be used. These may be used in combination with a melamine compound (for example, melamine alone), a pentaerythritol compound (for example, pentaerythritol, dipentaerythritol), an amide (for example, nylon 6, nylon 66) or the like, if necessary.

  These flame retardants may be used in combination with a flame retardant aid [anti-drip agent (for example, polytetrafluoroethylene), metal oxide (for example, zinc oxide), etc.] as necessary.

  Of these flame retardants, (F72) is preferred from the viewpoint of flame retardancy and the absence of environmental pollution such as dioxin generation during incineration.

  Examples of the ultraviolet absorber (F8) include benzotriazoles [for example, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole and 2- (2′-hydroxy-4′-octoxyphenyl) benzotriazole], Benzophenone series [eg 2-hydroxy-4-methoxybenzophenone and 2,2′-dihydroxy-4-methoxybenzophenone], salicylate series [eg phenyl salicylate and ethylene glycol monosalicylate] and acrylate series [eg 2-ethylhexyl 2-cyano-3,3′1-diphenyl acrylate].

  Examples of the antibacterial agent (F9) include benzoic acid, paraoxybenzoic acid ester, sorbic acid, halogenated phenol (for example, 2,4,6-tribromophenol sodium salt), organic iodine (for example, 4-chlorophenyl-3-iodopropargyl). Formal), nitrile (eg, 2,4,5,6-tetrachloroisophthalonitrile), thiocyano (eg, methylene bisthianocyanate), N-haloalkylthioimide (eg, N-tetrachloroethyl-thio-tetrahydrophthalimide), copper agent (Eg 8-oxyquinoline copper), benzimidazole (eg 2-4-thiazolylbenzimidazole), benzothiazole (eg 2-thiocyanomethylthiobenzothiazole), trihaloallyl (eg 3-bromo-2,3-diiodo- 2-propenyl Til carbonate), triazoles (eg azaconazole), organic nitrogen sulfur compounds (eg Suraoff 39), quaternary ammonium compounds (eg trimethoxysilyl-propyloctadecylammonium chloride) and pyridine compounds [eg 2,3,5,6- Cytochloro-4- (methylsulfonyl) -pyridine].

  As the dispersant (F10), a dispersant of Mn 1,000 to 100,000, for example, naphthalene sulfonic acid formalin condensate (Mn 1,000 to 10,000), polystyrene sulfonate metal [for example, alkali metals (for example, sodium and potassium) ] Salt (Mn 1,000-100,000), polyacrylic acid metal [for example, alkali metal (same as above)] salt (Mn 2,000-50,000), carboxymethyl cellulose and polyvinyl alcohol.

Examples of the plasticizer (F11) include mono- and diesters (F111) containing a polyoxyalkylene chain, polyester polyol (F112), polyether polyol (F113), aromatic carboxylic acid ester [C10-28, for example, phthalate ester ( For example, dioctyl phthalate and dibutyl phthalate, di2-ethylhexyl phthalate, etc.)], aliphatic monocarboxylic acid ester [C3-30, such as methylacetylricinoleate and triethylene glycol dibenzoate], aliphatic dicarboxylic acid ester [C8 or more and Mn2 , 000 or less, such as di (2-ethylhexyl) adipate and adipic acid-propylene glycol-based polyester (Mn 200 to 2000)], aliphatic tricarboxylic acid ester [for example, citrate ester Le (e.g. triethyl citrate), and a phosphoric acid triester [e.g. triphenyl phosphate] and petroleum resins.
Of these (F11), (F111), (F112) and (F113) are preferable from the viewpoint of the effect of reducing the crystallinity of (B) and increasing the conductivity.

Mono- and diesters (F111) containing a polyoxyalkylene chain are obtained by reacting a polyether diol (b221) or copolyether diol with a monocarboxylic acid, represented by any of the following formulas: Diesters are included.

R—CO— (OA ² ) _x —O—B ² —O— (A ² O) _y —OC—R (F1111)

R—CO— (OA ² ) _x —O—OC—R (F1112)

R—CO— (OA ² ) _x —O—B ² —O— (A ² O) _y —H (F1113)

R—CO— (OA ² ) _x —O—H (F1114)

In the formula, B ² represents a diol (b220) or a residue obtained by removing a hydroxyl group from a dihydric phenol, and A ² represents C 2-12 (preferably 2-8, more preferably a halogen atom). 2-4) represents an alkylene group. X and y are each an integer of 1 to 300, preferably 2 to 250, and more preferably 8 to 150. X and y may be the same or different. p (OA ² ) and q (A ² O) may be the same or different, and the bond form in the case where they are composed of two or more oxyalkylene groups is block or random. Or any combination thereof may be used.
Of the (F111) represented by the above formula, (F1111) and (F1112) are preferable from the viewpoint of the effect of reducing the crystallinity of (B) and increasing the conductivity.

  In the above formula, R is a C1-24 monovalent hydrocarbon group, and specific examples include aliphatic, aromatic and alicyclic hydrocarbon groups.

  Aliphatic saturated hydrocarbon groups include C1-24 alkyl groups such as methyl, ethyl, n- and i-propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl groups, dodecyl, tridecyl, tetradecyl. , Pentadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, heneicosyl, docosyl, tricosyl, tetracosyl, 2-propyl-1-pentyl, 2-ethyl-1-hexyl, 4-methyl-3-heptyl and 6-methyl-2- Heptyl group; aliphatic unsaturated hydrocarbon group includes C2-24 alkenyl group or alkynyl group such as ethenyl, 1-, 2- and i-propenyl, butenyl, pentenyl, hexenyl, heptenyl, nonenyl, decenyl, undecenyl, Dodecenyl, tri Cenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, eicosenyl, henecocenyl, dococenyl, tricocenyl, tetracocenyl, ethynyl, 2-propynyl, pentynyl, hexynyl, 3-methyl-3-butenyl and 4-methyl-3-pentenyl groups Etc.

Examples of the aromatic hydrocarbon group include C6-24, such as phenyl group, alkyl (C1-10) aryl group (o-, m- and p-methylphenyl, m, p-dimethylphenyl, 2,6-dimethylphenyl, o-, m- and p-ethylphenyl, pn-butylphenyl,
p-octylphenyl and p-nonylphenyl groups), aralalkyl (C1-20 alkyl) (eg benzyl and phenethyl groups), substituted aralkylalkyl (C1-20 alkyl) groups (o-, m- and p) -Methylbenzyl, pn-butylphenethyl group, etc.); Examples of the alicyclic hydrocarbon group include C4-20, such as a cyclopentyl group and a cyclohexyl group.

Polyester polyol (F112) includes low molecular weight (usually C2 or more and Mn300 or less) polyol (2 to 8 or more) and polyvalent (2 to 3 or more) carboxylic acids or ester-forming derivatives thereof. And polycondensate polyol obtained by the ring-opening polymerization of lactone, polycarbonate polyol obtained by the reaction of ethylene carbonate and polyol (1,6-hexanediol, etc.), and the like. Both ends of (F112) may be either OH groups or COOH groups.
Of these (F112), preferred are a condensed polyester polyol and a polylactone polyol from the viewpoint of the effect of reducing the crystallinity of (B) and increasing the conductivity.

The low molecular weight polyol constituting the condensed polyester polyol includes a dihydric to octahydric or higher polyhydric alcohol, and an AO low mole (1 to 8) of the polyhydric alcohol or a dihydric to octahydric or higher polyhydric phenol. 10) Additives are mentioned.
The polyhydric alcohol includes the following.
Dihydric alcohols (C2-20 or higher), such as C2-12 aliphatic dihydric alcohols [(di) alkylene glycols such as EG, diethylene glycol, PG, dipropylene glycol, BD, HD, NPG and 3-methylpentane Diol, dodecanediol, etc.]; C6-10 alicyclic divalent alcohol [1,4-cyclohexanediol, cyclohexanedimethanol, etc.]; C8-20 aromatic ring-containing dihydric alcohol [xylylene glycol, bis (hydroxyethyl) Benzene etc.]; trihydric to octahydric or higher polyhydric alcohols such as (cyclo) alkane polyols and their intramolecular or intermolecular dehydrates [glycerin, trimethylolpropane, pentaerythritol, sorbitol and dipentaerythritol ( Under each GR, TMP, PE, and SO and DPE hereinafter), 1,2, 6-hexanetriol, erythritol, cyclohexanetriol,
Mannitol, xylitol, sorbitan, diglycerin and other polyglycerols, etc.], saccharides and derivatives thereof [for example, sucrose, glucose, fructose, mannose, lactose, and glycosides (methylglucoside, etc.)].

  The polyhydric phenol includes C6-18 dihydric phenol, such as monocyclic dihydric phenol (hydroquinone, catechol, resorcinol, urushiol, etc.), bisphenol (bisphenol A, -F, -C, -B, -AD and -S, dihydroxybiphenyl, 4,4'-dihydroxydiphenyl-2,2-butane, etc.), and condensed polycyclic dihydric phenols [dihydroxynaphthalene (eg, 1,5-dihydroxynaphthalene), binaphthol, etc.]; Octavalent or higher polyhydric phenols such as monocyclic polyphenols (pyrogallol, phloroglucinol, and mono- or dihydric phenols (phenol, cresol, xylenol, resorcinol, etc.) aldehydes or ketones (formaldehyde, glutaraldehyde) , Lyoxal, acetone) low condensates (eg phenol or cresol novolac resins, resole intermediates, polyphenols obtained by the condensation reaction of phenol and glyoxal or glutaraldehyde, and polyphenols obtained by the condensation reaction of resorcin and acetone) .

Examples of the polycarboxylic acid or ester-forming derivative thereof include C2-20 dicarboxylic acids such as aliphatic dicarboxylic acids (succinic acid, adipic acid, azelaic acid, sebacic acid,
Fumaric acid, maleic acid, etc.), alicyclic dicarboxylic acids (1,3- and 1,4-cyclohexanedicarboxylic acid, dimer acids, etc.), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, phthalic acid, etc.); trivalent Or more polycarboxylic acids (trimellitic acid, pyromellitic acid, etc.); anhydrides of these polycarboxylic acids (succinic anhydride, maleic anhydride, phthalic anhydride, trimellitic anhydride, etc.); Acid halides of divalent carboxylic acids (adipic acid dichloride, etc.); lower alkyl (C1-4) esters of these polycarboxylic acids (dimethyl succinate, dimethyl phthalate, etc.); and mixtures of two or more of these Can be mentioned.

  Specific examples of the condensed polyester polyol include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexa Methylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate Diol, Polyneopentyl terephthalate diol, Polyethylene Terephthalate diol, polyhexamethylene isophthalate diol.

Examples of the lactone constituting the polylactone polyol include C4 to 12, for example, ε-caprolactone, γ-butyrolactone, γ-valerolactone, and combinations of two or more thereof. Specific examples of the polylactone polyol include polycaprolactone diol, polyvalerolactone diol, and polycaprolactone triol.

  The polyether polyol (F113) includes an AO adduct having an active hydrogen atom-containing compound as an initiator, and examples of the initiator include polyvalent (divalent to octavalent or higher) alcohols, polyvalent (2 Valent to octavalent or higher) phenols and primary or secondary amino group-containing compounds.

Among the initiators, examples of the polyhydric alcohol include the divalent to octavalent polyhydric alcohols, and examples of the polyhydric phenol include the divalent to octavalent polyhydric phenols.
Examples of the primary or secondary amino group-containing compound include alkyl (C1-12) amine and (poly) alkylene polyamine (C2-6 of alkylene group, 1 to 4 of alkylene group, 2 to 2 of amino group). 5) and the like.

  AO includes C2-4 or more AO, such as EO, PO, BO, tetrahydrofuran (THF), α-olefin oxide, styrene oxide, epihalohydrin (such as epichlorohydrin), and combinations of two or more thereof (random and (Or block).

Among specific examples of polyether polyol (F113), polyhydric alcohol AO adducts include, for example, polyethylene glycol (hereinafter abbreviated as PEG), polypropylene glycol (hereinafter abbreviated as PPG), polyoxyethylene / polyoxypropylene, poly Tetramethylene glycol (hereinafter abbreviated as PTMG), PO PO2 mole adduct of GR and EO6 mole adduct of sorbit; AO adduct of polyhydric phenol having bisphenol skeleton, such as EO or PO adduct of bisphenol A [EO 2 mol adduct of bisphenol A, EO 20 mol adduct of bisphenol A, 2 mol adduct of bisphenol A, PO 5 mol adduct of bisphenol A, etc.] and EO or PO adduct of resorcin [EO 2 mol adduct of resorcin PO6 mol adduct] resorcinol; the AO adduct of primary or secondary amino group-containing compounds, for example EO2 mol adduct of monoethanolamine, PO2 mol adduct of diethanolamine.
Among these (F113), AO adducts of PEG, PPG, PTMG, and bisphenol A are preferable from the viewpoint of the effect of lowering the crystallinity of (B).
Mn of (F11) is preferably 150 to 8,000, more preferably 150 to 5,000, and particularly preferably 150 to 3,000, from the viewpoints of compatibility and conductivity.

  Examples of the conductive substance (F12) are compounds other than the above (D1) and (D3), and examples thereof include carbon nanotubes, carbon black, and white carbon.

  Examples of the filler (F13) include inorganic fillers (eg, calcium carbonate, talc, clay, silicic acid, silicate, asbestos, mica, glass fiber, glass balloon, carbon fiber, metal fiber, ceramic whisker and titanium whisker). And organic fillers [for example, urea, calcium stearate and organic crosslinked fine particles (for example, epoxy-based and urethane-based)].

The total amount of (F) used is preferably 45% or less based on the total weight of the conductivity-imparting agents (X) and (C), and is preferably 0 from the viewpoint of the effect of each additive and the mechanical properties of the molded product. 0.001 to 40%, more preferably 0.01 to 35%, particularly preferably 0.05 to 30%.
Of (F), (F9), (F10), (F11) and (F13) are each usually 10% or less, preferably 1 to 5%; (F7) is usually 20% or less, preferably 1 to 10%. (F3), (F4) and (F12) are usually 5% or less, preferably 0.1 to 3%; (F1), (F2), (F5), (F6) and (F8) are usually 3% Hereinafter, it is preferably 0.05 to 1%.

The semiconductive resin composition of the present invention is obtained by melt-mixing the conductivity-imparting agents (X) and (C) of the present invention and (D), (E) and / or (F) as necessary. Is obtained. As a method of melt mixing, generally, a method in which pellets or powdery components are mixed with an appropriate mixer such as a Henschel mixer, and then melt mixed with an extruder to be pelletized can be applied.
There is no particular limitation on the order of adding each component during melt mixing. For example, (1) (X), (C), and if necessary, (D), (E) and / or (F) are melted together. (2) A part of (X) and (C) is previously melt-mixed to prepare a high concentration composition (masterbatch resin composition) of the conductivity-imparting agent (X), and then the rest (C) and a method of melt-mixing (D), (E) and / or (F) as necessary.
The concentration of the conductivity-imparting agent of the present invention in the masterbatch resin composition in the method (2) is preferably 40 to 80% by weight, more preferably 50 to 70% by weight.
Among these, the method (2) is a method called a master batch method or a master pellet method, which is a preferable method from the viewpoint of efficient dispersion of the conductivity-imparting agent of the present invention into (C).

  The molded product of the present invention can be obtained by molding the semiconductive resin composition. Examples of the molding method include injection molding, compression molding, calendar molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding, film molding (casting method, tenter method, inflation method, etc.). Depending on the method, it can be formed by any method.

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

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

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

Example 1
In a stainless steel autoclave, 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, an antioxidant [trade name “Irganox 1010”, manufactured by Ciba Specialty Chemicals Co., Ltd., tetrakis [methylene-3- (3 ′ 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, and so on. ] 0.3 parts and 6 parts of water were charged, the inside of the autoclave was purged with nitrogen, then heated and stirred at 220 ° C. under pressure (0.3 to 0.5 MPa) for 4 hours, and an acid having carboxyl groups at both ends. 96 parts of polyamide having a value of 112 were obtained.
Next, 192 parts of an EO adduct of bisphenol A with Mn of 2,000, 72 parts of cobalt (II) chloride hexahydrate (A-1) and 0.5 part of zirconyl acetate were added, and 245 ° C. and 0.13 kPa or less were added. Polymerization was performed for 5 hours under reduced pressure to obtain a viscous polymer.
The obtained polymer was taken out as a strand on the belt and pelletized to obtain a hydrophilic group-containing polymer (B1-1). The volume resistivity value of (B1-1) was 1 × 10 ⁸ Ω · cm.
Next, sodium borohydride was dissolved in water to prepare a 1 mol / l reducing agent solution. (B1-1) was immersed in the reducing agent solution for 30 minutes. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the electroconductivity imparting agent (X1). The volume resistivity value of (X1) was 7 × 10 ¹ Ω · cm.

Example 2
In Example 1, hydrophilic group containing polymer (B1-2) was obtained like Example 1 except having used 32 parts of (A-1). The volume resistivity value of (B1-2) was 1 × 10 ⁹ Ω · cm. The volume resistivity of the conductivity-imparting agent (X2) was 5 × 10 ² Ω · cm.

Example 3
A stainless steel autoclave was charged with 104 parts of 12-aminododecanoic acid, 21 parts of adipic acid, 0.3 part of an antioxidant and 6 parts of water, and the inside of the autoclave was purged with nitrogen and pressurized at 220 ° C. (0.3 to 0). 0.5 MPa) under heating and stirring for 4 hours, 120 parts of polyamide having an acid value of 126 having carboxyl groups at both ends were obtained.
Next, 270 parts of polyoxyalkylene glycol of Mn 2,000, 98 parts of nickel nitrate (II) hexahydrate (A-2) and 0.5 parts of zinc acetate were added, and the mixture was subjected to 240 ° C. and reduced pressure of 0.13 kPa or less. For 6 hours to obtain a viscous polymer.
The obtained polymer was taken out as a strand on a belt and pelletized to obtain a hydrophilic group-containing polymer (B1-3). The volume resistivity value of (B1-3) was 2 × 10 ⁸ Ω · cm.
Next, sodium hypophosphite was dissolved in methanol to prepare a 1 mol / l reducing agent solution. (B1-3) was immersed in the reducing agent solution for 30 minutes. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the electroconductivity imparting agent (X3). The volume resistivity value of (X3) was 8 × 10 ¹ Ω · cm.

Example 4
A stainless steel autoclave was charged with 49 parts of ε-caprolactam, 51 parts of succinic acid, 0.3 part of an antioxidant and 6 parts of water, and the autoclave was purged with nitrogen and pressurized at 220 ° C. (0.3 to 0.5 MPa). The mixture was heated and stirred under sealing for 4 hours to obtain 94 parts of polyamide having an acid value of 510 having carboxyl groups at both ends.
Next, 43 parts of an EO adduct of bisphenol A of Mn300, 43 parts of polyoxyalkylene glycol of Mn150, 45 parts of (A-1) and 0.5 part of antimony trioxide were added and reduced pressure at 245 ° C. and 0.13 kPa or less. Polymerization was carried out for 5 hours under a viscous polymer.
The obtained polymer was taken out as a strand on a belt and pelletized to obtain a hydrophilic group-containing polymer (B1-4). The volume resistivity value of (B1-4) was 1 × 10 ¹² Ω · cm.
Next, sodium borohydride was dissolved in water to prepare a 1 mol / l reducing agent solution. (B1-4) was immersed in the reducing agent solution for 30 minutes. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the electroconductivity imparting agent (X4). The volume resistivity value of (X4) was 8 × 10 ³ Ω · cm.

Example 5
A stainless steel autoclave was charged with 97 parts of 12-aminododecanoic acid, 3 parts of adipic acid, 0.3 part of antioxidant and 6 parts of water, and the inside of the autoclave was purged with nitrogen and pressurized at 220 ° C. (0.3 to 0). 0.5 MPa) The mixture was heated and stirred for 4 hours in a sealed state to obtain 95 parts of polyamide having an acid value of 22 having carboxyl groups at both ends.
Next, 48 parts of an EO adduct of bisphenol A of Mn 5,000, 190 parts of polyoxyalkylene glycol of Mn 20,000, 60 parts of (A-2), 1.5 parts of lithium trifluoromethanesulfonate, and 0. 5 parts were added and polymerized at 240 ° C. under reduced pressure of 0.13 kPa or less for 12 hours to obtain a viscous polymer.
The obtained polymer was taken out as a strand on a belt and pelletized to obtain a hydrophilic group-containing polymer (B1-5). The volume resistivity value of (B1-5) was 2 × 10 ⁶ Ω · cm.
Next, sodium hypophosphite was dissolved in methanol to prepare a 1 mol / l reducing agent solution. (B1-5) was immersed in the reducing agent solution for 30 minutes. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the electroconductivity imparting agent (X5). The volume resistivity value of (X5) was 8 × 10 ² Ω · cm.

Example 6
Low molecular weight polypropylene (Mn 2,500, density 0.89, 10.5 double bonds per 1,000 C, average double bonds per molecule) obtained by a stainless steel autoclave 1.9 parts, content of polyolefin which can be modified at both ends (95%) and 85 parts of maleic anhydride and 15 parts of maleic anhydride were melted at 200 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 200 ° C. for 20 hours. I let you.
Then, excess maleic anhydride was distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polypropylene (b21-1). (B21-1) had an acid value of 39.8 and Mn of 2,800.
Next, in a stainless steel autoclave, 50 parts of (b21-1), 50 parts of polyethylene glycol (b22-1) (Mn2,800, volume resistivity 1 × 10 ⁷ Ω · cm), 25 parts of (A-2) Then, 0.3 part of an antioxidant and 0.5 part of zirconyl acetate were charged and polymerized at 230 ° C. under a reduced pressure of 0.13 kPa or less for 3 hours to obtain a viscous polymer.
The obtained polymer was taken out as a strand on a belt and pelletized to obtain a hydrophilic group-containing polymer (B2-1). Mn of (B2-1) was 22,000, and the average number of repetitions (Nn) determined from the Mn and ¹ H-NMR analysis was 3.9. The volume resistivity value of (B2-1) was 2 × 10 ⁸ Ω · cm.
Next, sodium borohydride was dissolved in water to prepare a 1 mol / l reducing agent solution. (B2-1) was immersed in the reducing agent solution for 30 minutes. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the electroconductivity imparting agent (X6). The volume resistivity value of (X6) was 7 × 10 ¹ Ω · cm.

Example 7
In a stainless steel autoclave, 51 parts of (b21-1), 34 parts of (b22-1), 18 parts of EO / THF-random copolymer (EO / THF = weight ratio 40/60, Mn3,000), (A- 1) 26 parts, 1.0 part of lithium chloride, 0.3 part of antioxidant and 0.5 part of tetrabutyl titanate were added and polymerized at 230 ° C. under a reduced pressure of 0.13 kPa or less for 5 hours to obtain a viscous polymer. Got.
The obtained polymer was taken out in a strand form on a belt and pelletized to obtain a hydrophilic group-containing polymer (B2-2). Mn of (B2-2) was 30,000, Nn was 5.3, and the volume resistivity value was 8 × 10 ⁶ Ω · cm.
Next, sodium hypophosphite was dissolved in water to prepare a 1 mol / l reducing agent solution. (B2-2) was immersed in the reducing agent solution for 30 minutes. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the electroconductivity imparting agent (X7). The volume resistivity value of (X7) was 5 × 10 ¹ Ω · cm.

Example 8
Low molecular weight polypropylene obtained by a thermal degradation method (Mn 3,400, density 0.89, 7.0 double bonds per 1,000 C, average of double bonds per molecule, and stainless steel autoclave) 1.8 parts, 90 parts of polyolefin capable of modifying both ends) and 10 parts of maleic anhydride were melted at 200 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 200 ° C. for 20 hours. Went.
Then, excess maleic anhydride was distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polypropylene (b21-2). (B21-2) had an acid value of 27.5 and Mn3,600.
Next, 97 parts of (b21-2) and 5 parts of ethanolamine were melted at 180 ° C. in a nitrogen gas atmosphere in a stainless steel autoclave and reacted at 180 ° C. for 2 hours. Then, excess ethanolamine was distilled off under reduced pressure at 180 ° C. for 2 hours to obtain a modified polypropylene (b21-3) having a hydroxyl group. (B21-3) had a hydroxyl value of 26.7, an amine value of 0.01, and Mn of 3,700.
Next, an isocyanate-modified polyethylene glycol (b22-3) obtained by reacting polyethylene glycol (b22-2) (Mn3,200, volume resistivity 1 × 10 ⁷ Ω · cm) with MDI in a stainless steel autoclave. Biaxial extrusion of 43 parts (NCO content 3.0%, volume resistivity 1 × 10 ⁷ Ω · cm), 57 parts of modified polypropylene (b21-3) having a hydroxyl group and 25 parts of silver nitrate (A-3) A hydrophilic group-containing polymer (B2-3) was obtained by kneading in a machine at 200 ° C. for a residence time of 30 seconds, taking it into a strand, and pelletizing it. Mn of (B2-3) was 50,000, Nn was 7.2, and the volume resistivity value was 4 × 10 ⁸ Ω · cm.
Next, sodium hypophosphite was dissolved in methanol to prepare a 1 mol / l reducing agent solution. (B2-3) was immersed in the reducing agent solution for 30 minutes. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the electroconductivity imparting agent (X8). The volume resistivity value of (X8) was 8 × 10 ² Ω · cm.

Example 9
Example 4 except that polyethylene glycol diamine (b22-4) (Mn 2,800, volume resistivity 2 × 10 ⁷ Ω · cm) was used instead of (b22-1) in Example 6.
In the same manner as described above, a hydrophilic group-containing polymer (B2-4) was obtained. Mn of (B2-4) was 20,000, Nn was 3.9, and the volume resistivity value was 4 × 10 ⁸ Ω · cm.
Next, hydrazine was dissolved in water to prepare a 1 mol / l reducing agent solution. (B2-4) was immersed in the reducing agent solution for 30 minutes. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the electroconductivity imparting agent (X9). The volume resistivity value of (X9) was 7 × 10 ² Ω · cm.

Example 10
In a stainless steel autoclave, 66 parts of acid-modified polypropylene (b21-2) and 34 parts of 12-aminododecanoic acid were melted at 200 ° C. under stirring in a nitrogen gas atmosphere, at 200 ° C. for 3 hours, 1.3 kPa or less. The reaction was carried out under reduced pressure to obtain 96 parts of acid-modified polypropylene (a21-4). The acid value of (b21-4) was 17.7, and Mn was 5,700.
Next, 60 parts of (b21-4), 27 parts of (b22-1), 22 parts of (A-1), 0.3 part of antioxidant and 0.5 part of zinc acetate were charged into a stainless steel autoclave, 230 Polymerization was carried out for 8 hours under reduced pressure of 0.13 kPa at 0 ° C. to obtain a viscous polymer.
The obtained polymer was taken out as a strand on the belt and pelletized to obtain a hydrophilic group-containing polymer (B2-5). Mn of (B2-5) was 29,000, Nn was 3.6, and the volume resistivity value was 1 × 10 ⁸ Ω · cm.
Next, sodium borohydride was dissolved in water to prepare a 1 mol / l reducing agent solution. (B2-5) was immersed in the reducing agent solution for 30 minutes. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the electroconductivity imparting agent (X10). The volume resistivity value of (X10) was 7 × 10 ¹ Ω · cm.

Example 11
Low molecular weight polypropylene (Mn 19,000, density 0.89, average number of double bonds per 1,000 C, 1,000 double bonds per molecule) obtained by a stainless steel autoclave 1.7 parts, content of polyolefin which can be modified at both ends (90%) 250 parts and maleic anhydride 10 parts were melted at 220 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 220 ° C. for 29 hours. Went.
Thereafter, excess maleic anhydride was distilled off under reduced pressure at 220 ° C. for 3 hours to obtain acid-modified polypropylene (b21-5). (B21-5) had an acid value of 5.5 and Mn of 19,200.
Next, 135 parts of acid-modified polypropylene (b21-5) and 10 parts of bis (2-aminoethyl) ether were melted at 200 ° C. under stirring in a nitrogen gas atmosphere and reacted at 200 ° C. for 2 hours. Thereafter, excess bis (2-aminoethyl) ether was distilled off under reduced pressure at 200 ° C. for 2 hours to obtain a modified polypropylene (b21-6) having amino groups at both ends. The amine value of (b21-6) was 5.8, and Mn was 19,400.
Next, in a stainless steel autoclave, 50 parts of (b21-6), 40 parts of polyethylene glycol (b22-5) (Mn 20,000, volume resistivity 1 × 10 ⁸ Ω · cm), 5.2 parts of dodecanedioic acid , 23 parts of copper (II) sulfate (A-4), 0.3 part of antioxidant and 0.5 part of zinc acetate were charged and polymerized for 15 hours at 230 ° C. under a reduced pressure of 0.13 kPa or less. A polymer was obtained.
The obtained polymer was taken out as a strand on the belt and pelletized to obtain a hydrophilic group-containing polymer (B2-6). Mn of (B2-6) was 58,000, Nn was 1.5, and the volume resistivity value was 2 × 10 ⁹ Ω · cm.
Next, sodium hypophosphite was dissolved in methanol to prepare a 1 mol / l reducing agent solution. (B2-6) was immersed in the reducing agent solution for 30 minutes. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the electroconductivity imparting agent (X11). The volume resistivity value of (X11) was 8 × 10 ² Ω · cm.

Example 12
In a stainless steel autoclave, low molecular weight polypropylene obtained by a thermal degradation method (Mn 800, density 0.89, 10.8 double bonds per 1,000 C, average number of double bonds per molecule 1) 8 parts, content of polyolefin which can be modified at both ends (95%) 80 parts and maleic anhydride 45 parts were melted at 200 ° C. in a nitrogen gas atmosphere (sealed) and reacted at 200 ° C. for 20 hours. It was.
Then, excess maleic anhydride was distilled off under reduced pressure at 200 ° C. for 3 hours to obtain acid-modified polypropylene (b21-7). (B21-7) had an acid value of 112 and Mn of 1,000.
Next, in a stainless steel autoclave, 50 parts of (b21-7), 15 parts of polyethylene glycol (b22-6) (Mn300, volume resistivity 1 × 10 ⁶ Ω · cm), 16 parts of (A-2), oxidized 0.3 parts of an inhibitor and 0.5 parts of zirconyl acetate were charged and polymerized at 230 ° C. under a reduced pressure of 0.13 kPa or less for 3 hours to obtain a viscous polymer.
The obtained polymer was taken out in a strand form on a belt and pelletized to obtain a hydrophilic group-containing polymer (B2-7). Mn of (B2-7) was 6,000, and the average number of repetitions (Nn) determined from the Mn and 1H-NMR analysis was 4.6. The volume resistivity value of (B2-7) was 2 × 10 ¹⁰ Ω · cm.
Next, sodium borohydride was dissolved in water to prepare a 1 mol / l reducing agent solution. (B2-7) was immersed in the reducing agent solution for 30 minutes. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the electroconductivity imparting agent (X12). The volume resistivity value of (X12) was 9 × 10 ³ Ω · cm.

Comparative Example 1
In Example 1, the electroconductivity imparting agent (ratio X1) was obtained like Example 1 except not using (A-1). The volume resistivity value of (Ratio X1) was 3 × 10 ⁹ Ω · cm.

Comparative Example 2
In Example 3, the electroconductivity imparting agent (ratio X2) was obtained like Example 3 except not using sodium hypophosphite. The volume resistivity value of (Ratio X2) was 2 × 10 ⁹ Ω · cm.

Comparative Example 3
In Example 6, the electroconductivity imparting agent (ratio X3) was obtained like Example 6 except not using (A-2). The volume resistivity value of (Ratio X3) was 2 × 10 ⁹ Ω · cm.

Comparative Example 4
In Example 7, the electroconductivity imparting agent (ratio X4) was obtained like Example 7 except using potassium acetate (ratio A-1) instead of (A-1). The volume resistivity value of (Ratio X4) was 3 × 10 ⁹ Ω · cm.

Comparative Example 5
(B2-5) in Example 10 was used as a conductivity-imparting agent (ratio X5). The volume resistivity value of (Ratio X5) was 1 × 10 ⁸ Ω · cm.

Examples 13-27, Comparative Examples 6-12
According to the composition shown in Table 1, (X1) to (X12) or (Ratio X1) to (Ratio X5) and the thermoplastic resin (C-1) or (C-2) are optionally added to an antistatic property improving agent. After blending with (D-1) or (D-2) and compatibilizer (E-1) for 3 minutes with a Henschel mixer, using a twin screw extruder with a vent, 220 ° C., 100 rpm, residence time 5 minutes It melt-kneaded on condition, and obtained the resin composition (Examples 13-27 and Comparative Examples 6-12), respectively.

Example 28
After blending 10 parts of the hydrophilic group-containing polymer (B2-1) and 88 parts of the thermoplastic resin (C-2) with 2 parts of the antistatic property improver (D-1) for 3 minutes using a Henschel mixer, The resin composition (C-3) was obtained by melt-kneading in a twin screw extruder with a vent at 220 ° C., 100 rpm, and a residence time of 5 minutes.
Next, sodium borohydride was dissolved in water to prepare a 1 mol / l reducing agent solution. (C-3) was contacted with the reducing agent solution for 1 hour. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the resin composition (Example 28).

Comparative Example 13
After blending 2 parts of metal salt (A-1) and 88 parts of thermoplastic resin (C-2) with 2 parts of antistatic improver (D-1) for 3 minutes using a Henschel mixer, 2 with vent It melt-kneaded on the conditions of 220 degreeC, 100 rpm, and residence time 5 minutes with the axial extruder, and the resin composition (ratio C-3) was obtained.
Next, sodium borohydride was dissolved in water to prepare a 1 mol / l reducing agent solution. (Ratio C-3) was contacted with the reducing agent solution for 1 hour. Then, it dried at 100 degreeC under pressure reduction for 4 hours, and obtained the resin composition (comparative example 13).

（Ｃ−１）：ＡＢＳ樹脂[商品名「セビアン−Ｖ３２０」、ダイセルポリマー（株）製]
（Ｃ−２）：ポリプロピレン樹脂[商品名「サンアロマーＰＭ７７１Ｍ」、サンアロマー
（株）製]
（Ｄ−１）：ドデシルベンゼンスルホン酸ナトリウム
（Ｄ−２）：塩化リチウム
（Ｅ−１）：相溶化剤[商品名「エポフレンド」、ダイセル化学（株）製、変性ビニル重
合体]

(C-1): ABS resin [trade name “Cebian-V320”, manufactured by Daicel Polymer Co., Ltd.]
(C-2): Polypropylene resin [trade name “Sun Aroma PM771M”, Sun Aroma
Manufactured by]
(D-1): Sodium dodecylbenzenesulfonate (D-2): Lithium chloride (E-1): Compatibilizer [trade name “Epofriend”, manufactured by Daicel Chemical Industries, Ltd., modified vinyl heavy
Combined]

<Performance evaluation>
Using the above resin composition, injection molding machines [PS40E5ASE, Nissei Plastic Industry (
Co., Ltd.], cylinder temperature [240C for (C-1), 2 for (C-2)
20 [deg.] C.] and a mold temperature of 50 [deg.] C. to prepare test pieces, and the impact strength, antistatic properties and moldability were evaluated according to the following methods. The results are shown in Table 2.

[1] Mechanical properties (1) Impact strength Conforms to ASTM D256 (with notch, 3.2 mm thickness) Method A.
[2] Antistatic property (1) Volume specific resistance value For a test piece (100 × 100 × 2 mm), a superinsulator [DSM-8103 (electrode SME-8310 for flat plate sample), Toa Denpa Kogyo Co., Ltd. . ] In an atmosphere of 23 ° C. and humidity 50% RH (according to ASTM D257).
(2) Volume resistivity value after washing with water The surface of a test piece (100 × 100 × 2 mm) leaning diagonally was washed with 100 ml of ion-exchanged water (23 ° C.) at a flow rate of 100 ml / min, and then circulated at 80 ° C. Dry in a dryer for 3 hours. The test piece obtained by repeating the washing-drying operation 10 times was measured in the same manner as (1).
[3] Moldability Molding was performed under the same conditions as molding with a single thermoplastic resin, and the surface condition of the molded product was compared with that of a single thermoplastic resin according to the following criteria.
○: The surface of the molded product is equivalent to a molded product of a single thermoplastic resin.
X: The surface of the molded product is uneven as compared with a molded product of a single thermoplastic resin.

  As is clear from Tables 2 and 3, the resin compositions of the present invention (Examples 13 to 28) were compared with the comparative resin compositions (Comparative Examples 6 to 13) in mechanical properties and permanent charge prevention. It can be seen that it is excellent in properties and moldability.

  The semiconductive resin composition of the present invention is excellent in moldability and gives a molded article having a very high level of permanent antistatic property (semiconductive) and mechanical properties. Various molding methods [injection molding, compression Molding, calender molding, slush molding, rotational molding, extrusion molding, blow molding, foam molding and film molding (casting method, tenter method, inflation method, etc.)], semi-conductivity and antistatic properties are required. Extremely useful as various molding materials for housing products for home appliances / OA equipment, game equipment and office equipment, various plastic containers such as IC trays, various packaging films, flooring sheets, artificial turf, mats, and automotive parts It is.

Claims (8)

Metal salt (A) and a volume specific resistance value of 1 × 10 ⁶ to 1 × 10 ¹² Ω · cm, containing at least one hydrophilic group selected from the group consisting of (B1) to (B9) below A conductivity-imparting agent (X) obtained by reducing (A) in a composition comprising a polymer (B).
(B1): Polyether ester amide (B2) derived from polyamide (b11) and an alkylene oxide adduct (b12) and / or polyoxyalkylene glycol (b13) of a bisphenol compound: a block of polyolefin (b21) A structure in which the block of the polyoxyalkylene chain-containing compound (b22) is alternately and repeatedly bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond. Block polymer (B3): polyether amide imide (B4): polyether ester (B5): epihalohydrin / alkylene oxide copolymer (B6): acrylamide copolymer (B7): ethylene / unsaturated carboxylic acid (salt) Or Ethile / (Meth) acrylate / unsaturated carboxylic acid (salt) copolymer (B8): methoxypolyethylene glycol (meth) acrylate copolymer (B9): polyether group-containing ethylene / vinyl acetate copolymer [ethylene / vinyl alcohol Copolymer ethylene oxide adduct] The conductivity imparting agent (X) according to claim 1, wherein the weight ratio of (A) to (B) is from 1/99 to 40/60. A semiconductive resin composition comprising the thermoplastic resin (C) containing the conductivity imparting agent (X) according to claim 1 or 2. Metal salt (A) and a volume specific resistance value of 1 × 10 ⁶ to 1 × 10 ¹² Ω · cm, containing at least one hydrophilic group selected from the group consisting of (B1) to (B9) below In the resin composition obtained by containing the composition comprising the polymer (B) in the thermoplastic resin (C), (A) is reduced, and the conductive material comprising the reduced (A) and (B). A semiconductive resin composition containing the property-imparting agent (X).
(B1): Polyether ester amide (B2) derived from polyamide (b11) and an alkylene oxide adduct (b12) and / or polyoxyalkylene glycol (b13) of a bisphenol compound: a block of polyolefin (b21) A structure in which the block of the polyoxyalkylene chain-containing compound (b22) is alternately and repeatedly bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, an imide bond and a urethane bond. Block polymer (B3): polyether amide imide (B4): polyether ester (B5): epihalohydrin / alkylene oxide copolymer (B6): acrylamide copolymer (B7): ethylene / unsaturated carboxylic acid (salt) Or Ethile / (Meth) acrylate / unsaturated carboxylic acid (salt) copolymer (B8): methoxypolyethylene glycol (meth) acrylate copolymer (B9): polyether group-containing ethylene / vinyl acetate copolymer [ethylene / vinyl alcohol Copolymer ethylene oxide adduct] The semiconductive resin composition according to claim 3 or 4, wherein the content of the conductivity imparting agent (X) is 1 to 30% based on the total weight of (X) and (C). The semiconductive resin composition according to any one of claims 3 to 5, further comprising at least one additive selected from the group consisting of an antistatic property improver, a compatibilizing agent, and other resin additives. object. A molded product obtained by molding the semiconductive resin composition according to claim 3. A molded article obtained by coating and / or printing the molded article according to claim 7.