JP3057363B2 - Conductive elastomer composition and antistatic resin composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a conductive elastomer composition and an antistatic resin composition. More specifically, the present invention relates to a conductive elastomer composition comprising polyetheresteramide and conductive whisker and having a low specific gravity and excellent moldability, and an antistatic resin composition containing polyetheresteramide and conductive whisker. .

[0002]

2. Description of the Related Art Conventionally, as a method of imparting conductivity to an elastomer, a method of blending an electrolyte salt or a surfactant (for example, JP-A-7-10899); There is known a method of blending a toxic substance (for example, JP-A-7-216224).

[0003]

However, in the above-mentioned composition, the compounded electrolyte salt or surfactant bleeds out to the surface of the molded article with the passage of time to impair the appearance, and the conductivity is largely dependent on humidity. There was a problem.
In addition, it is necessary to mix a relatively large amount of a conductive substance, so that there is a problem that the specific gravity becomes large, the molded product becomes heavy, and the fluidity at the time of molding is poor, so that it is difficult to handle. Was.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, by blending a conductive whisker with polyetheresteramide, it is possible to form a resin with a low specific gravity even with a relatively small amount of addition. A conductive elastomer composition having excellent properties is obtained, and further, a polyetheresteramide, a resin composition comprising a conductive whisker and another thermoplastic resin is found to have excellent antistatic properties,
The present invention has been reached.

That is, the present invention comprises a polyetheresteramide (A), a conductive whisker (B) and another thermoplastic resin (C), wherein (C) is a polyolefin resin, a polyacrylic resin, or a polystyrene resin. , A thermoplastic resin selected from a polyamide resin, a polycarbonate resin, a polyacetal resin, a thermoplastic polyurethane resin and a fluororesin, wherein (A) is 2 to 100 parts by weight in total of (A), (B) and (C). 30 parts by weight, (B) 0.01 to 10 parts by weight, (C) 65 to 9
An antistatic resin composition containing 8 parts by weight of a polyetheresteramide (A), a conductive whisker (B) and another thermoplastic resin (C), wherein (A), (B) and (C) )) Per 2 parts by weight per 100 parts by weight of (A)
Parts by weight, (B) 0.01 to 10 parts by weight, (C) 65
A surfactant (D) and / or one or more metal salts (E) selected from alkali metal salts and alkaline earth metal salts. And a polyetheresteramide (A), a conductive whisker (B) and another thermoplastic resin (C), per 100 parts by weight of the total of (A), (B) and (C) (A) 2-30
Parts by weight, (B) 0.01 to 10 parts by weight, (C) 65
To 98 parts by weight, further comprising a compatibilizer (F) or (F) and a surfactant (D) and / or an alkali metal salt and an alkaline earth metal salt. It is a composition comprising at least one kind of metal salt (E).

[0006]

DETAILED DESCRIPTION OF THE INVENTION The polyetheresteramide (A) which can be used in the present invention includes, for example, a number average molecular weight of 200 to 5 having carboxyl groups at both ends described in JP-A-6-287747. , 00
0 (a1) and a number average molecular weight of 300 to 5,
And / or polyalkylene glycol (a2)
And 3) a polyetheresteramide derived from the above. Preferred among these are polyetheresteramides derived from (a1) and (a2).

The polyamide (a1) constituting (A)
Are (1) a lactam ring-opening polymer having 6 to 12 or more carbon atoms, (2) a polycondensate of an aminocarboxylic acid having 6 to 12 or more carbon atoms, or (3) a 4 to 20 carbon atoms.
Is a polycondensate of a dicarboxylic acid with a diamine having 4 to 12 or more carbon atoms. Examples of the lactam of (1) include caprolactam, enantholactam, laurolactam, undecanolactam and the like. Examples of the aminocarboxylic acid (2) include ω-aminocaproic acid, ω-aminoenanthic acid, ω-aminocaprylic acid, ω-aminopelargonic acid, ω-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid And the like. Examples of the dicarboxylic acid (3) include adipic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid, and isophthalic acid. Methylene diamine and the like can be mentioned. Two or more of the above-mentioned amide-forming monomers can be used in combination. Among these, preferred are caprolactam, 12-aminododecanoic acid and adipic acid-hexamethylenediamine, and particularly preferred is caprolactam.

The above (a1) is, for example, a compound having 4 to 20 carbon atoms.
Can be obtained by subjecting the amide-forming monomer to ring-opening polymerization or polycondensation in the presence of the dicarboxylic acid component as a molecular weight modifier in a conventional manner. Examples of the dicarboxylic acids having 4 to 20 carbon atoms include aliphatic carboxylic acids such as succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecandioic acid, dodecandioic acid; terephthalic acid, isophthalic acid ,
Aromatic dicarboxylic acids such as phthalic acid and naphthalenedicarboxylic acid; alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and dicyclohexyl-4,4-dicarboxylic acid; sodium 3-sulfoisophthalate and potassium 3-sulfoisophthalate Alkali metal salts of 3-sulfoisophthalic acid; and mixtures of two or more thereof. Of these, preferred are aliphatic dicarboxylic acids, aromatic dicarboxylic acids and alkali metal salts of 3-sulfoisophthalic acid, and particularly preferred are adipic acid, sebacic acid, terephthalic acid, isophthalic acid and
-Sodium sulfoisophthalate.

The number average molecular weight of (a1) is usually from 200 to
It is 5,000, preferably 500-3,000. When the number average molecular weight is less than 200, the heat resistance of the polyetheresteramide itself decreases, and when the number average molecular weight exceeds 5,000, the reactivity decreases, so that much time is required for producing the polyetheresteramide.

The alkylene oxide adduct of bisphenols (a2) can be obtained by adding an alkylene oxide having 2 to 4 carbon atoms to bisphenols. As the bisphenols, bisphenol A (4,4 ′
-Dihydroxydiphenyl-2,2-propane), bisphenol F (4,4'-dihydroxydiphenylmethane), bisphenol S (4,4'-dihydroxydiphenylsulfone), 4,4'-dihydroxydiphenyl-2,2-butane and the like Of these, preferred is bisphenol A. Examples of the alkylene oxide having 2 to 4 carbon atoms include ethylene oxide, propylene oxide, 1,2- or 1,4-butylene oxide, and a mixture of two or more thereof. Of these, particularly preferred is ethylene oxide.

Examples of the polyalkylene glycol (a3) include polyethylene glycol, polypropylene glycol, polybutylene glycol, polyhexamethylene glycol, a block or random copolymer of ethylene oxide and propylene oxide, and a block or random copolymer of ethylene oxide and tetrahydrofuran. Among them, preferred is polyethylene glycol.

The number average molecular weight of each of the above (a2) and (a3) is usually 300 to 5,000, preferably 1,
000 to 3,000, more preferably 1600 to 3,
000. When the number average molecular weight is less than 300, the conductivity of the polyetheresteramide itself becomes insufficient,
If it exceeds 000, the reactivity decreases, so that a great amount of time is required in producing the polyetheresteramide.

The (a2) and / or (a3) constituting the polyetheresteramide (A) are the same as the above (a1)
And (a2) and / or (a3) are usually used in the range of 20 to 80% by weight based on the total weight. If it is less than 20% by weight, the conductivity of (A) itself is poor, and if it exceeds 80% by weight, the heat resistance decreases. Also, (a2) / (a3)
Can vary widely, but the weight ratio is 100/0 to 5
/ 95, particularly preferably 100/0 to 50/50.

Examples of the production method (A) include the following production methods and production methods, but are not particularly limited. Production method: A method in which (a1) is formed by reacting an amide-forming monomer and a dicarboxylic acid, and (a2) and / or (a3) are added thereto, and a polymerization reaction is performed at high temperature and reduced pressure. Production method: An amide-forming monomer and a dicarboxylic acid and (a2) and / or (a3) are simultaneously charged into a reaction vessel, and subjected to a pressure reaction at a high temperature in the presence or absence of water as an intermediate (a1). And then (a1) and (a2) and / or (a3) under reduced pressure
To carry out a polymerization reaction with

In the above-mentioned polymerization reaction, a known esterification catalyst is usually used. Examples of the catalyst include antimony catalysts such as antimony trioxide; tin catalysts such as monobutyltin oxide; titanium catalysts such as tetrabutyl titanate; zirconium catalysts such as tetrabutyl zirconate and zirconyl acetate; acetic acid such as zinc acetate. Metal salt catalysts and the like can be mentioned. These usages are
It is usually 0.1 to 5 parts by weight based on the total weight of (a1), (a2) and / or (a3).

The reduced viscosity (ηSP / C, C = 0.
(5% by weight m-cresol solution, 25 ° C.) is not particularly limited, but is usually 0.5 to 4, preferably 0.6 to 3.
If the reduced viscosity is less than 0.5, the heat resistance of the elastomer composition is poor, and if it exceeds 4, the moldability is reduced.

The conductive whisker (B) used in the present invention includes a metal titanate-based whisker [for example,
Potassium titanate whiskers, sodium titanate whiskers, etc.], metal borate whiskers [eg, magnesium borate, aluminum borate, etc.], metal silicate salt whiskers [eg, calcium silicate whiskers, aluminum silicate whiskers, etc.], metal sulfates Whisker [eg, calcium sulfate whisker], metal carbonate whisker [eg, calcium carbonate whisker], metal oxide whisker [eg, zinc oxide whisker, titanium oxide whisker, magnesium oxide whisker, aluminum oxide whisker, beryllium oxide whisker, etc.] Metal carbide whiskers [eg, silicon carbide whiskers, titanium carbide whiskers, etc.], metal nitride whiskers [eg, aluminum nitride whiskers, silicon nitride whiskers, titanium nitride whiskers, etc.], and other whiskers [ Needle-like or tetrapod-shaped whiskers such example, if such carbon whiskers, and, these whiskers surface silver, copper, and a whisker coated with a metal such as tin. Preferred among these are metal titanate whiskers, metal borate whiskers and metal oxide whiskers, and more preferred are potassium titanate whiskers, titanium oxide whiskers,
Zinc oxide whiskers and aluminum borate whiskers, particularly preferred are potassium titanate whiskers.

The conductivity of (B) is usually 10 ^-6 to 10 ⁶ Ω.
· Cm, and preferably 10 ^-6 ~10 ² Ω · cm.

As the shape of (B), from the viewpoint of reducing the specific gravity of the conductive elastomer composition, the short axis is usually 0.01 to 30 μm, preferably 0.1 to 10 μm, and the long axis is usually 1 to 100 μm. Needles are preferably acicular whiskers of 10 to 50 μm. The ratio (aspect ratio) of the major axis to the minor axis is usually 10 to 1,000, preferably 10 to 1,000.
0 to 500.

When the conductive elastomer composition of the present invention is used for a molding material, the amount of (B) is usually 0.01 to 30 parts by weight, preferably 0.5 to 30 parts by weight, per 100 parts by weight of (A).
10 parts by weight. If it is less than 0.01 part by weight, the conductivity is insufficient, and if it exceeds 30 parts by weight, the moldability becomes poor,
Further, the specific gravity of the elastomer composition is undesirably increased.

The conductivity of the conductive elastomer composition of the present invention is generally 1 × 10 ⁸ to 1 × 10 ⁻⁶ Ω · cm, preferably 1 × 10 ⁶ to 1 × 10 ⁰ Ω · cm, particularly preferably 1 × 10 ⁶ to 1 × 10 ⁰ Ω · cm. ×
It is 10 ⁴ to 1 × 10 ² Ω · cm.

The thermoplastic resin (C) used in the antistatic resin composition of the present invention may be a polyolefin resin (for example, polypropylene, polyethylene, ethylene-vinyl acetate copolymer resin (EVA), ethylene-ethyl acrylate resin). Polyacrylic resin [eg, polymethyl methacrylate etc.]; polystyrene type resin [eg, polystyrene, styrene / acrylonitrile copolymer (AN resin), acrylonitrile / butadiene / styrene copolymer (ABS resin), methacrylic Methyl acrylate / butadiene / styrene copolymer (MBS resin), styrene / methyl methacrylate copolymer (MS resin), etc.]; polyester resins [polyethylene terephthalate, polybutylene terephthalate, polycyclohexane dimethylene terephthalate] Phthalate, polybutylene adipate, polyethylene adipate]; polyamide resin [nylon 66, nylon 69, nylon 612, nylon 6, nylon 11, nylon 12, nylon 4
6, nylon 6/66, nylon 6/12, etc.]; polycarbonate resins; polyacetal resins; thermoplastic polyurethane resins; The melt index (230C, 2.16 kg) of (C) is usually from 0.1 to 100. Preferred of these are:
Polyolefin resins and polystyrene resins are preferred, with polypropylene, polyethylene and ABS resins being particularly preferred.

The antistatic resin composition of the present invention comprises:
(A) is usually 2 to 30 parts by weight, preferably 5 to 25 parts by weight, and (B) is usually 0.01 to 10 parts by weight, preferably 100 to 10 parts by weight, per 100 parts by weight of the total of (A), (B) and (C). Is 0.02 to 5 parts by weight, (C) is usually 65 to 98 parts by weight,
Preferably, it is contained in an amount of 70 to 95 parts by weight. By setting the amount of each component within the above range, an antistatic resin composition having a good balance between mechanical strength and antistatic properties can be obtained.

In the present invention, a surfactant (D) can be added as required for the purpose of further improving the conductivity of the conductive elastomer composition or the antistatic resin composition. Examples of the (D) include anionic, cationic, nonionic or amphoteric surfactants.

Examples of the anionic surfactant include carboxylate salts such as alkali metal salts of higher fatty acids, sulfate salts such as higher alcohol sulfate salts and higher alkyl ether sulfate salts, alkylbenzene sulfonates, and alkyl sulfonates. And sulfonate salts such as paraffin sulfonate salt, and phosphate ester salts such as higher alcohol phosphate ester salt. Examples of the cationic surfactant include quaternary ammonium salts such as an alkyltrimethylammonium salt. As nonionic surfactants, higher alcohol ethylene oxide adducts, fatty acid ethylene oxide adducts, higher alkylamine ethylene oxide adducts, polyethylene glycol type nonionic surfactants such as polypropylene glycol ethylene oxide adducts, polyethylene oxide, Examples include fatty acid esters of glycerin, fatty acid esters of pentaerythritol, fatty acid esters of sorbitol and sorbitan, alkyl ethers of polyhydric alcohols, and polyhydric alcohol-type nonionic surfactants such as aliphatic amides of alkanolamines. Examples of the amphoteric surfactant include amino acid-type amphoteric surfactants such as higher alkylaminopropionate, and betaine-type amphoteric surfactants such as higher alkyldimethylbetaine and higher alkyldihydroxyethylbetaine. Of these, anionic surfactants are preferred from the viewpoints of conductivity and heat resistance, and particularly preferred are sulfonates such as alkylbenzene sulfonates, alkyl sulfonates and paraffin sulfonates.

When (D) is used, the amount added is usually not more than 30 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of the composition. When the content is within the above range, a resin composition having a good balance between mechanical strength and conductivity can be obtained.

In the present invention, for the purpose of further improving the conductivity of the conductive elastomer composition or the antistatic resin composition, at least one metal salt selected from alkali metal salts and alkaline earth metal salts (if necessary) E) can be contained. Examples of (E) include salts of alkali metals and / or alkaline earth metals such as organic acids, inorganic acids, and halogenated acids. Specific examples thereof include lithium acetate, potassium acetate, lithium chloride, sodium chloride, and chloride. Examples include potassium, magnesium chloride, calcium chloride, sodium bromide, potassium bromide, magnesium bromide, potassium perchlorate, potassium sulfate, potassium phosphate, potassium thiocyanate, and the like.
Preferred among these are lithium chloride, sodium chloride, potassium chloride and potassium acetate.

When (E) is used, the amount is usually not more than 3 parts by weight, preferably 0.01 to 2 parts by weight, per 100 parts by weight of the composition. When the content is within the above range, a resin composition having a good balance between mechanical strength and conductivity can be obtained.

In the antistatic resin composition of the present invention,
For the purpose of improving the compatibility between (A) and (C), if necessary, the compatibilizer (F) is added in an amount not exceeding 20 parts by weight, preferably 0.5 to 10 parts by weight, per 100 parts by weight of (C). Parts can be contained.

When (C) is a polyolefin-based resin, the compatibilizer (F) includes the following (F1) and (F
One or more modified low molecular weight polyolefins selected from 2) are used. (F1): a number average molecular weight of 800 to 25,000,
Modified low-molecular-weight polyolefin having an acid value of 5 to 150 (F2); a number-average molecular weight obtained by secondary-modifying a part or all of the (anhydrous) carboxylic acid group of (F1) with an alkanolamine and / or a polyoxyalkylene compound 800 to 28,000 modified low molecular weight polyolefins.

The above (F1) is a number average molecular weight of 700 to 2 obtained by a polymerization method of propylene and / or ethylene or a thermal degradation method of a high molecular weight polyolefin.
Modification is carried out by reacting an α, β-unsaturated carboxylic acid and / or an anhydride thereof with a low molecular weight polyolefin having a molecular weight of 000 in the presence of an organic peroxide, if necessary, by a solution method or a melting method. Can be obtained by: From the viewpoint of easiness of modification, a low molecular weight polyolefin obtained by a thermal degradation method is preferable. The low-molecular-weight polyolefin obtained by the thermal degradation method is disclosed in, for example, JP-A-3-6.
It can be obtained by the method described in JP-A-2804.

The α, β-unsaturated carboxylic acid or anhydride thereof used in the above modification includes (meth) acrylic acid,
(Anhydride) maleic acid, fumaric acid, (anhydride) itaconic acid and citraconic anhydride. Among these, maleic acid (anhydride) is preferred. These amounts used during the modification are usually 1 to 25 parts by weight, preferably 3 to 20 parts by weight, based on the weight of the low molecular weight polyolefin. The number average molecular weight of (F1) obtained by the above method is usually 800 to 25,000, preferably 1,0.
00 to 20,000. If the number average molecular weight is less than 800, the heat resistance is poor, and if it exceeds 25,000, the effect as a compatibilizer is poor, and the mechanical properties of the resin composition deteriorate. The acid value of (F1) is usually from 5 to 150, preferably from 10 to 100. If the acid value is less than 5, the effect as a compatibilizer is poor, and if it exceeds 150, the hue deteriorates, which causes coloring of the resin composition.

Further, (F2) can be obtained by reacting a part or all of the (anhydrous) carboxylic acid groups of the above (F1) with an alkanolamine and / or a polyoxyalkylene compound to perform secondary modification. . Examples of the alkanolamine include monoethanolamine, monoisopropanolamine, diethanolamine, and diisopropanolamine. Of these, particularly preferred is monoethanolamine.

Examples of the polyoxyalkylene compound include compounds having hydroxyl groups at both terminals such as polyethylene glycol, polypropylene glycol, polyethylene polypropylene glycol, and polytetramethylene ether glycol; alcohols (methanol, ethanol,
Butanol, octanol, lauryl alcohol, 2-
Polyoxyalkylene compounds having a hydroxyl group at one end of a structure in which an alkylene oxide is added to a monovalent hydroxyl group-containing compound such as ethylhexyl alcohol, phenols (phenol, alkylphenol, naphthol, phenylphenol, benzylphenol, etc.); Examples of the compound include a compound in which a hydroxyl group of a compound is replaced with an amino group or an epoxy group. The number average molecular weight of these polyoxyalkylene compounds is usually from 300 to 5,000.
It is. The secondary modification rate is not particularly limited, but may be 10 to 100 of the (anhydrous) carboxylic acid unit of (F1).
It is preferred that mole% is secondary modified. The (F
The number average molecular weight of 2) is usually from 800 to 28,000, preferably from 1,200 to 25,000. If it is less than 800, the heat resistance is poor, and if it exceeds 28,000, the effect as a compatibilizer becomes poor.

The modified low molecular weight polyolefins (F1) and (F2) exemplified above may be used in combination of two or more. A modified low-molecular-weight polyolefin having all of a carboxylic acid group, a hydroxyl group and a polyoxyalkylene group in the molecule may be used.

In the case where (C) is a polyolefin-based resin, a smaller amount of (A) and (B) may be used to provide effective antistatic properties than a polyolefin-based resin, if necessary. Polyamide resin,
At least one polymer or oligomer selected from polyester resins and polyacetal resins (molecular weight: 1,0
(0000 to 5,000) (G).
The amount of the (G) used is preferably 1 to 20 parts by weight, particularly preferably 3 to 20 parts by weight, based on the weight of the polyolefin resin.
15 parts by weight. Within the above range, a resin composition having a better balance between mechanical strength and antistatic property can be obtained.

Preferred as (G) above are polyamide resins, and particularly preferred are at least one polymer or oligomer selected from nylon 6, nylon 66, nylon 12, and nylon 6/12.

The conductive elastomer composition and the antistatic resin composition of the present invention can be obtained by melt-kneading the above components using various known mixers.
Mixers include, for example, extruders, Brabender, kneaders and Banbury mixers.

The method for producing the conductive elastomer composition is not particularly limited. For example, a method in which (A) and (B) are blended and kneaded together; a small amount of (A) and (B) are blended and kneaded; A method of kneading the remaining (A);
A method of adding (B) at the production stage of (A) is mentioned. Among these, the method called master batch or master pellet is used. A method is preferred in that an elastomer composition in which (B) is more uniformly dispersed can be obtained.

The method for producing the antistatic resin composition is not particularly limited. For example, (A) and (B) are previously blended and kneaded (corresponding to the production of the conductive elastomer composition). A) blending and kneading a small amount of (C) with the conductive elastomer composition or (A) and (B);
A method of kneading the remaining (C) (master bee method);
(A), (B) and (C) may be a method of collectively blending and kneading. A method is preferable in that a resin composition in which (A) and (B) are more uniformly dispersed is obtained.

The conductive elastomer composition and the antistatic resin composition of the present invention may contain, if necessary, other known resin additives within a range that does not impair the properties of the composition according to the intended use. It can be arbitrarily added. Examples of the additives include pigments, dyes, fillers, nucleating agents, glass fibers, lubricants, plasticizers, release agents, antioxidants, flame retardants, and ultraviolet absorbers.

Since the conductive elastomer composition of the present invention is particularly excellent in conductivity, moldability due to low specific gravity, mechanical strength, etc., for example, housing products for electric / electronic parts, home appliances / OA equipment, various rollers ( It can be suitably used as a molding material for various applications requiring conductivity, such as a molding material such as a charging roller for a copying machine, and a packaging material for LSI and IC. In addition, the antistatic resin composition of the present invention has a good appearance of a molded article, and has excellent antistatic properties, mechanical strength of resin, paintability, printability, and the like.
OA equipment, game equipment, office equipment and other housing products,
It is suitably used as a molding material for various applications requiring antistatic properties such as various plastic containers and automobile parts.

[0043]

EXAMPLES The present invention will be further described with reference to the following examples, but the present invention is not limited to these examples. “Parts” in the examples indicates parts by weight.

[Production of Polyetheresteramide (A)] Production Example 1 83.5 parts of ε-caprolactam, 16.5 parts of terephthalic acid, 0.3 parts of “Irganox 1010” and water 6 were placed in a 3 L stainless steel autoclave. The resulting mixture was purged with nitrogen, heated and stirred at 220 ° C. for 4 hours under pressure and airtight to obtain 96 parts of oxidized 112 polyamide oligomer having carboxyl groups at both ends. Next, 192 parts of a bisphenol A ethylene oxide adduct having a number average molecular weight of 2,000 and 0.5 part of zirconyl acetate were added, and the mixture was added at 245 ° C. and 1 mmH
Polymerization was performed for 5 hours under a reduced pressure of not more than g to obtain a viscous polymer. The polymer was taken out in a strand form on a belt and pelletized to obtain a polyetheresteramide. Reduced viscosity of this product (ηSP / C, m-cresol solvent, 25 ° C., C = 0.5% by weight, and so on)
Was 2.10. This polyetheresteramide is abbreviated as [A-1] below.

Production Example 2 A 3 L stainless steel autoclave was charged with 105 parts of ε-caprolactam, 17.1 parts of adipic acid, 0.3 parts of “Irganox 1010” and 6 parts of water. The mixture was heated and stirred for 4 hours in a sealed state to obtain 117 parts of a polyamide oligomer having an acid value of 110 and having carboxyl groups at both ends. Then, 175 parts of polyoxyethylene glycol having a number average molecular weight of 1,500 and 0.5 parts of zirconyl acetate were added, and the mixture was polymerized at 245 ° C. under a reduced pressure of 1 mmHg or less for 5 hours to obtain a viscous polymer. Hereinafter, the same operation as in Production Example 1 was performed to obtain a polyetheresteramide. This had a reduced viscosity of 2.30. This polyether ester amide is referred to below as [A-2]
Abbreviated.

[Production of Modified Low-Molecular-Weight Polyolefin] Production Example 3 95 parts of low-molecular-weight polypropylene having a number average molecular weight of 12,000 and a density of 0.89, obtained by thermal degradation, and 5 parts of maleic anhydride were mixed under a nitrogen stream for 180 minutes. Xylene 5 in which 1.5 parts of dicumyl peroxide was dissolved.
A 0% solution was added dropwise over 15 minutes, and after the reaction was performed for 1 hour, the solvent was distilled off to obtain an acid-modified low molecular weight polypropylene [F-1]. This had an acid value of 25.7 and a number average molecular weight of 15,000.

Production Example 4 The acid-modified low-molecular-weight polypropylene obtained in Production Example 3 [F
-1] 95 parts to 100 parts of xylene under a nitrogen stream at 120 ° C
And then add 5 parts of monoethanolamine to 1 part
After dropwise addition over 5 minutes, the reaction was carried out for 1 hour, and then the solvent and unreacted monoethanolamine were distilled off to obtain a modified low molecular weight polypropylene [F-2] having a hydroxyl group. This had a hydroxyl value of 25.2 and a number average molecular weight of 16,000.

Production Example 5 The acid-modified low-molecular-weight polypropylene obtained in Production Example 3 [F
-2] 95 parts and 50 parts of an adduct of 24 moles of ethylene oxide of lauryl alcohol are melted at 180 ° C under a nitrogen stream, and then subjected to an esterification reaction under a reduced pressure of 10 mmHg for 5 hours to obtain a polyoxyalkylene-modified low molecular weight polypropylene [ F-3] was obtained. It has a hydroxyl value of 0.
5, and the number average molecular weight was 18,000. In addition, NMR analysis confirmed that the esterification reaction was performed quantitatively.

Examples 1-4 and Comparative Examples 1-2 After blending (A)-(D) at the ratios shown in Table 1 with a Henschel mixer for 3 minutes, the mixture was heated at 205 ° C. with a vented twin screw extruder. The mixture was melt-kneaded under the conditions of 30 rpm and a residence time of 5 minutes to obtain a conductive elastomer composition of the present invention and a comparative elastomer composition.

[0050]

[Table 1]

(Note) [B-1]: conductive potassium titanate whisker [trade name "Dentol WK200B", manufactured by Otsuka Chemical Co., Ltd., single axis 0.4 to 0.7 μm, long axis 10 to 2]
0 μm] [B-2]: conductive zinc oxide whisker [trade name “Panatetra”, manufactured by Matsushita Amtech Co., Ltd., single axis 0.2 to 3 μm]
m, major axis 2 to 50 μm (tetrapot shape)] [D-1]: sodium dodecylbenzenesulfonate [E-1]: potassium chloride [added during the production of (A)]

Performance Test Example 1 The physical properties of the elastomer compositions of the present invention of Examples 1 to 4 and the comparative elastomer compositions of Comparative Examples 1 and 2 were measured based on the following test methods. Table 2 shows the results.
Shown in (1) Appearance: The injection molded piece was evaluated by observing the surface after leaving it at 23 ° C. and a humidity of 50% RH for 72 hours or more. Evaluation criteria ○: No surface roughness, ×: Surface roughness occurred. (2) Specific gravity: based on ASTM D792. (3) Volume specific resistance value: The injection molded piece was left for at least 48 hours in an atmosphere of 23 ° C. and a humidity of 50% RH in an atmosphere of and then measured with a super insulation meter (manufactured by Toa Denpasha Co., Ltd.).

[0053]

[Table 2]

Examples 5 to 13 and Comparative Examples 3 to 4 (A) to (E) and, if necessary, (F) and / or (G) in the proportions shown in Table 3 were blended with a Henschel mixer and then vented. The mixture was melt-kneaded with a twin-screw extruder to obtain an antistatic resin composition of the present invention and a comparative resin composition.

[0055]

[Table 3]

(Note) [C-1]: Polypropylene resin [trade name “J609H”, manufactured by Grand Polymer Co., Ltd.] [C-2]: ABS resin [trade name “ABS10”, manufactured by Techno Polymer Co., Ltd.] [C-3]: Polycarbonate / ABS resin polymer alloy [trade name “Multilon T-3000”, manufactured by Teijin Chemicals Ltd.] [C-4]: Acrylic resin [trade name “Acripet V
H ", manufactured by Mitsubishi Rayon Co., Ltd.] [C-5]: Polyacetal resin [trade name" Duracon M90 ", manufactured by Polyplastics Co., Ltd.] [G-1]: Nylon 6 [trade name" Ube nylon 101 "
3B ", manufactured by Ube Industries, Ltd.] [G-2]: Polybutylene terephthalate [trade name" Geranex 2000 ", Polyplastics Co., Ltd.]
Made

Performance Test Example 2 The antistatic resin compositions of the present invention of Examples 5 to 13 and the resin compositions of Comparative Examples 3 and 4 were molded using an injection molding machine to prepare test pieces. Various physical properties were measured on the basis of the test methods described above. Table 4 shows the results. (1) Izod impact strength: based on ASTM D256. (2) Flexural modulus: according to ASTM D790. (3) Surface specific resistance: Injection molded piece was 23 ° C and humidity was 50
After conditioning for 48 hours or more in% RH atmosphere,
It was measured with a super insulation meter (manufactured by Toa Denpasha). (4) Compatibility: Evaluated by bending the molded product and observing the fracture surface. Evaluation criteria ○: good, ×: poor compatibility, delamination

[0058]

[Table 4]

As is evident from Table 2, the conductive elastomer composition of the present invention has excellent appearance, low specific gravity, and low volume resistivity, and thus has excellent conductivity. Further, as is apparent from Table 4, the antistatic resin composition of the present invention is excellent in antistatic properties and mechanical strength of the resin.

[0060]

Industrial Applicability The conductive elastomer composition of the present invention has excellent conductivity and a relatively small content of a conductive compound, so that it has low specific gravity and excellent moldability. Because of the above effects, the conductive elastomer composition of the present invention is useful as a housing product for home appliances and OA equipment, and as a molding material requiring various conductivity such as various rollers (such as a charging roller for a copying machine). . Further, the antistatic resin composition of the present invention has excellent antistatic properties and mechanical strength. Due to the above effects, the antistatic resin composition of the present invention is useful as a molding material for home appliances / OA equipment, game equipment, housing products for office equipment, various plastic containers, automobile parts, and the like.

Continued on the front page (51) Int.Cl. ⁷ Identification code FI C08L 33/00 C08L 33/00 59/00 59/00 69/00 69/00 75/04 75/04 77/00 77/00 77/12 77/12 H01B 1/20 H01B 1/20 Z // (C08K 13/04 7:04 3:10)

Claims (5)

(57) [Claims] 1. A polyetheresteramide (A), a conductive whisker (B) and another thermoplastic resin (C), wherein (C) is a polyolefin resin, a polyacrylic resin, a polystyrene resin, or a polyamide resin. A thermoplastic resin selected from a resin, a polycarbonate resin, a polyacetal resin, a thermoplastic polyurethane resin and a fluororesin, wherein (A) is 2 to 30 parts by weight per 100 parts by weight in total of (A), (B) and (C) , (B) 0.01 to
An antistatic resin composition containing 10 parts by weight and 65 to 98 parts by weight of (C). 2. A composition comprising a polyetheresteramide (A), a conductive whisker (B) and another thermoplastic resin (C), wherein (A), (B) and (C) per 100 parts by weight in total. 2) to 30 parts by weight, and (B) 0.01 to 1 part by weight.
0 parts by weight, an antistatic resin composition containing 65 to 98 parts by weight of (C), further comprising at least one selected from surfactants (D) and / or alkali metal salts and alkaline earth metal salts The composition which mix | blended the metal salt (E) of. 3. A composition comprising a polyetheresteramide (A), a conductive whisker (B) and another thermoplastic resin (C), wherein (A), (A), (B) and (C) per 100 parts by weight in total. 2) to 30 parts by weight, and (B) 0.01 to 1 part by weight.
0 parts by weight and 65 to 98 parts by weight of (C) in the antistatic resin composition, further comprising a compatibilizer (F) or (F) and a surfactant (D) and / or an alkali metal salt; A composition comprising one or more metal salts (E) selected from alkaline earth metal salts. 4. A polyamide (a) having carboxyl groups at both terminals and having a number average molecular weight of 200 to 5,000.
A polyetheresteramide derived from 1) and an alkylene oxide adduct (a2) and / or a polyalkylene glycol (a3) of a bisphenol having a number average molecular weight of 300 to 5,000. A composition as described. 5. (B) is selected from metal oxide whiskers, metal titanate whiskers, metal borate whiskers, metal silicate whiskers, metal carbonate whiskers, metal carbide whiskers, and metal nitride whiskers. The composition according to any one of claims 1 to 4, which is at least one selected from the group consisting of conductive whiskers having a short axis of 0.01 to 30 µm and a long axis of 1 to 100 µm.