JP2005105052A - Antistatic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic resin composition which enables a volume resistivity value to retain at a lower level by adding only a small amount of an antistatic agent thereto, causes no variation of both a surface resistivity value and the volume resistivity value by humidity, is small in unevenness among lots and has excellent moldability, surface appearance, sustainability and environmental stability. <P>SOLUTION: The antistatic resin composition is obtained by compounding (A) 20-80 pts.wt. of a thermoplastic polymer compound and/or an unvulcanized rubber, (B) 80-20 pts.wt. of an inorganic filler having a surface coated with at least one (co)polymer selected from the group consisting of an polyalkylene ether, polyester, polyamine, polysulfide and polyacrylonitrile and (C) 3-40 pts.wt. of a polar group-having thermoplastic resin excluding the components of (A), based on 100 pts.wt. of (A)+(B). <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an antistatic resin composition, and more specifically, has a high electrostatic dissipation function and excellent dispersibility of the antistatic filler, and has durability, moldability, molding appearance, and environmental stability. The present invention relates to an excellent antistatic resin composition.

Antistatic resins are widely used in industry and are used for various purposes. As this antistatic resin, for example, there is a composition in which each resin is highly filled with a conductive filler such as carbon black, and since it is excellent in economy, it is widely used mainly in the industry. .
By the way, in recent years, antistatic resins and compositions thereof have become widespread in IC chip packaging, and variations in materials have been diversified from general-purpose plastics to engineering plastics. In addition to carbon black, carbon fibers, graphite, metal-coated fillers, metal fibers, and the like are widely used depending on the purpose and function. An antistatic resin composition as a material such as an IC tray used for packaging an IC chip has been studied for weight reduction, thickness reduction, and compactness, and tends to require strength and high rigidity. Furthermore, for the purpose of identifying the type of IC, the tray and the carrier tape are also required to have design properties such as coloring.

In response to such demands, carbon black, which is widely used as an antistatic filler, is economical and can be obtained with a low resistance value. Since there is a problem in material strength and the like, it is usually used in combination with various modifying materials.
Furthermore, in recent years, with regard to electrical characteristics required for polymer materials used in packaging applications such as trays and peripheral devices due to high performance and large capacity of ICs and LSIs, the volume resistivity is 10 ¹⁰ Ω · cm. The characteristic of less than is now required stably, so the level of so-called conventional antistatic area is not enough, and the relatively high volume due to the spread of electrophotographic systems, copiers, printers, etc. using static electricity There is also a demand for a polymer material that allows the specific resistance value to be stably expressed regardless of the influence of the use environment (humid atmosphere, low humidity atmosphere).

Antistatic resin compositions containing an antistatic agent are also widely used and applied to various uses. Antistatic agents can be polymer-alloyed with surfactant-type surfactants that bleed on the surface and so-called polymer-type hydrophilic polymer materials that have hydrophilic segments in their structure. There is something that expresses the function.
The surfactant type is intended to prevent the static electricity by transferring the surfactant contained in the resin composition to the surface. However, the antistatic effect is lost by surface wiping and cleaning, or surface contamination. In addition to sustainability problems, satisfactory volume resistivity cannot be obtained.

  On the other hand, the polymer type imparts permanent antistatic performance to a thermoplastic resin by polymerizing a hydrophilic polymer, and has high industrial utility value. However, if an attempt is made to develop a high antistatic function, the amount of the polymer type antistatic agent required for alloying increases, which may be economically problematic. The polymer antistatic agent generally has many hydrophilic segments, and many have flexibility, so by alloying, the rigidity of the resulting antistatic resin material is reduced, In addition to deformation of a molded product, addition to a polymer material such as a flexible synthetic polymer rubber or elastomer has a problem that the obtained antistatic property is large and difficult to apply.

Furthermore, the antistatic resin composition obtained by using the above-described surfactant type and polymer type antistatic agents both have a volume resistivity of 10 ¹⁰ to 10 ¹² Ω · cm. In most cases, the purpose cannot be sufficiently satisfied.
In addition, there is an antistatic resin composition (for example, Patent Document 1) containing a filler whose surface is pretreated with an antistatic agent, but the volume resistivity is not sufficiently reduced, and the antistatic agent is separated from the filler. There is a problem that bleeds out.

Furthermore, as a polymer type antistatic agent, the terminal group of poly (oligo) ethylene glycol having an alkyl group or an alkyl-substituted phenyl group at one end and having an ethylene oxide group was esterified with a methacryloyl group or an acryloyl group. Methacrylate or acrylate is mentioned (Patent Document 2). As the alkyl group at one end, a linear or branched one having 1 to 25 carbon atoms is used. In the same publication, a filler whose surface is coated with these hydrophilic polymers, or a lithium salt dissolved in the polymer is proposed. Because of the use of chlorine, there are problems of contact equipment corrosion, polymer degradation, environmental stability, and coloring due to chlorine ions.
Further, the same publication (Patent Document 2) also discloses one using lithium trifluoromethanesulfonate. In the invention described in the publication, although the conductivity is good, filling of such a filler necessary for obtaining the desired conductivity requires a high addition amount of 50 to 60% by weight or more, There are problems such as workability due to high filling, deterioration of mechanical properties, deterioration of the surface appearance of molded products, coloring (yellowing), thermal deterioration of materials, and environmental stability.

Japanese Patent Laid-Open No. 56-136849 Japanese Patent Laid-Open No. 11-256144

  The problem to be solved is that the conventional antistatic resin composition cannot keep the volume resistivity value low with the addition of a small amount of antistatic agent, and the surface resistivity value and volume resistivity value due to humidity. Changes, and lot-to-lot variation is large, and there are problems in molding processability, surface appearance, sustainability, and environmental stability.

The present invention comprises (A) 20 to 80 parts by weight of a thermoplastic polymer compound and / or unvulcanized rubber,
(B) 20-80 parts by weight of an inorganic filler whose surface is coated with at least one (co) polymer selected from the group consisting of polyalkylene ether, polyester, polyamine, polysulfide, and polyacrylonitrile [However, (A) + (B) = 100 parts by weight]
(C) thermoplastic resin having a polar group [however, excluding component (A)] 3 to 40 parts by weight,
It is related with the antistatic resin composition characterized by mix | blending.
Here, as the component (C), (C-1) a block copolymer and / or a graft copolymer having a block (α) mainly composed of an olefin component and a block (β) mainly composed of a hydrophilic component, (C -2) At least one selected from the group of polyether ester amides and (C-5) polyurethane elastomers is preferred.
In the antistatic resin composition described above, the present invention further comprises (D) 0.0001 to 20 parts by weight of a metal salt composed of a cation that is an alkali metal or an alkaline earth metal, and an anion [where ( A) + (B) = an antistatic resin composition containing 100 parts by weight].
Here, the component (D) was selected from the group consisting of lithium perchlorate, sodium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, and lithium tris (trifluoromethanesulfonyl) methide. At least one is preferred.
In the antistatic resin composition, the present invention further comprises (E) an organic compound having an ester group and / or an ether group and having a molecular weight of 1,500 or less, based on 100 parts by weight of the component (D). The present invention relates to an antistatic resin composition containing 1,000 parts by weight.
Here, as the component (E), an (E-1)-{O (AO) _n }-group (where A represents an alkylene group having 2 to 4 carbon atoms, and n represents an integer of 1 to 7). And (E-2) an organic compound represented by the following formula (1), and (E-3) the following formula (E), wherein all molecular chain terminals are CH ₃ groups and / or CH ₂ groups: It is preferably at least one selected from the group consisting of organic compounds represented by 2).
R- (Y-Z) _n- Y-R (1)
X- (ZY) _n -ZX (2)
[In the formulas (1) to (2), R is an aliphatic alkoxy group, alicyclic alkoxy group or aromatic alkoxy group, Y is an alkylene dicarboxylic acid residue or aromatic dicarboxylic acid residue having 4 to 12 carbon atoms, X represents a fatty acid residue or a benzene monocarboxylic acid residue, Z represents an alkylene glycol residue having 2 to 18 carbon atoms, and n represents an integer of 0 or more. ]

  The antistatic resin composition of the present invention can keep the volume specific resistance value low even with the addition of a small amount of an antistatic agent, and the surface specific resistance value and volume specific resistance value do not change with humidity. There is little variation between the two, excellent molding processability and surface appearance, and excellent durability and environmental stability. Utilizing its excellent characteristics, it is suitable for use in office automation equipment, home appliances, electrical / electronics, vehicles, writing instruments, building materials, security, and other parts, housings, packages, etc. can do.

(A) Component Any of the (A) thermoplastic polymer compound and unvulcanized rubber used in the composition of the present invention may be used. Among these, the thermoplastic polymer compound includes a thermoplastic resin and a thermoplastic elastomer. Examples of the thermoplastic resin include polyvinyl chloride, polystyrene resins such as polystyrene and acrylonitrile / butadiene / styrene copolymers (ABS resins); vinyl monomer polymers or copolymers such as acrylate / methacrylate resins; Poly α-olefins such as density polyethylene, medium density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, polybutene-1, poly 4-methylpentene-1, propylene / ethylene block copolymer, propylene / ethylene Copolymers of α-olefins such as random copolymers, or copolymers of α-olefins and other monomers; other polyolefin resins; polyamides such as nylon 6, nylon 66, nylon 12, polyethylene terephthalate, polybutyl Examples include aromatic polyesters such as terephthalate and aliphatic polyesters; liquid crystal polyesters; aromatic polyethers such as polyphenylene oxide; polyacetal resins; polycarbonate resins; sulfone polymers such as polyimide, polysulfone, and polyethersulfone. .

  Thermoplastic elastomers include polar elastomers such as polyurethane, polyester and polyamide, polyolefins, polystyrenes [derivatives based on a copolymer of aromatic vinyl and conjugated diene (for example, styrene-butadiene-styrene copolymer). Polymer (SBS), styrene-isoprene-styrene copolymer (SIS), styrene-ethylene-butadiene-styrene copolymer (SEBS), styrene-ethylene-propylene-styrene copolymer (SEPS), styrene-ethylene Ethylene / propylene / styrene copolymer (SEEPS), styrene / ethylene / butene / styrene copolymer (SEBS), styrene / butadiene / butylene / styrene copolymer (partially hydrogenated styrene / butadiene / styrene copolymer, SBBS) )), Styrene - isobutylene - such as non-polar elastomers such as styrene copolymer (SIBS) can be used.

As unvulcanized rubber, acrylonitrile-butadiene rubber (NBR), ethylene-propylene terpolymer (EPDM), chloroprene rubber (CR), acrylic rubber (AR), styrene-butadiene rubber (SBR), isoprene rubber (IR), Butadiene rubber (BR), butyl rubber (IIR), ethylene-propylene rubber (EPM), fluorine rubber, silicone rubber, urethane rubber and the like are also applicable.
These thermoplastic elastomers and unvulcanized rubbers may contain processing oils such as plasticizers and process oils.

In the present invention, one or more of the above thermoplastic polymer compounds and / or unvulcanized rubbers are appropriately selected according to the purpose. Among these, from the viewpoint of moldability, the thermoplastic polymer compound may be a vinyl monomer polymer or copolymer such as polyvinyl chloride, polystyrene, or ABS resin; polypropylene, crystalline propylene / ethylene copolymer or crystalline propylene. -Crystalline propylene copolymers such as butene-1 copolymer, nylon, polybutylene terephthalate, and the like are preferable, and vinyl monomer polymers or copolymers such as polyvinyl chloride, polystyrene, and ABS resin are particularly preferable. Examples of unvulcanized rubber include NBR, isoprene rubber (IR), butadiene rubber (BR), butyl rubber (IIR), ethylene-propylene rubber (EPM), EPDM, AR, SBR, fluoro rubber, silicone rubber, urethane rubber, and the like. preferable. Also, two or more types of composite resin (PC / ABS alloy) of polycarbonate and acrylonitrile / butadiene / styrene copolymer (ABS resin) and composite resin of polycarbonate and polystyrene (PC / PS alloy) These resins can also be used in combination. In this case, improvement in moldability and mechanical properties is observed.
Furthermore, from the viewpoint of heat resistance, polycarbonate, polyethylene terephthalate, aromatic polyimide, aromatic polyether and the like are preferable.

Component (B) The component (B) is a surface-treated inorganic filler, and the surface of the inorganic filler is at least one selected from the group consisting of polyalkylene ether, polyester, polyamine, polysulfide, and polyacrylonitrile ( Co) polymer is surface-coated or graft-bonded and coated.
The inorganic filler of the present invention is not particularly limited, and known inorganic fillers can be used. Among them, calcium carbonate, talc, mica, glass, calcium silicate, sericite, magnesium hydroxide, water Aluminum oxide, montmorillonite, zeolite, titanium oxide, kaolin and the like can be used satisfactorily. Further, the form of the inorganic filler is not particularly limited, and it can be used from those having a small particle diameter to those having a large aspect ratio such as a fiber shape, a tetrapot shape, and a scale shape.

  The (co) polymer used for the surface treatment of the inorganic filler is a (co) polymer having a segment having one or more of alkylene ether, ester, amine, sulfide, and acrylonitrile as a basic repeating unit. Yes, preferably a polyalkylene ether or polyester. The (co) polymer has an ester group, ether group, hydroxyl group, amine group, carbonyl group, epoxy group, sulfonic acid group which is a polar functional group, an alkyl group which is a nonpolar group, and an alkyl group-substituted phenyl group. , May be contained in the skeleton.

A (co) polymer having a segment having an alkylene ether and / or ester as a basic repeating unit can be obtained by various synthesis methods, and there are various forms thereof. Examples thereof include a chain or branched polymer polyol type and / or a type in which a terminal hydroxyl group is capped with a methyl group, an ethyl group, a t-butyl group, or the like.
As the linear polymer polyol, for example, a linear block copolymer having a hydroxyl group at the end and having at least one compound selected from the group of ethylene glycol, propylene glycol, and butanediol as a constituent component The linear polymer polyol which has as frame | skeleton is mentioned.

  Moreover, as said branched polymer polyol, the content rate of an ethylene oxide type structural component is 10 mol%-50 mol%, for example, saponification degree 30-100%, number average molecular weight 1,000-20,000, ethylene Examples thereof include branched polymer polyols obtained by grafting alkylene oxide to a saponified ethylene / saturated carboxylic acid vinyl ester copolymer having a unit content of 1 to 90% by weight.

The method for producing the ethylene / saturated carboxylic acid vinyl ester copolymer is not particularly limited, and can be produced by a known method such as a high-pressure radical polymerization method.
The vinyl ester of a saturated carboxylic acid that is a raw material for copolymerization with an ethylene monomer is not particularly limited, but is preferably an aliphatic carboxylic acid vinyl ester having about 2 to 4 carbon atoms, such as vinyl acetate, vinyl propionate, Examples thereof include vinyl butyrate and the like, and these can also be used in appropriate mixture. Of these, vinyl acetate is most preferred.

Further, as a copolymer raw material, in addition to ethylene and saturated carboxylic acid vinyl ester, a small amount of alkyl ester of α, β-unsaturated carboxylic acid such as methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, Ethyl methacrylate, butyl methacrylate and the like, and a mixture of two or more thereof can also be used. The ethylene content of the ethylene / saturated carboxylic acid vinyl ester copolymer is usually about 1 to 90% by weight, preferably about 40 to 80% by weight.
The number average molecular weight is usually about 1,000 to 20,000, preferably about 1,000 to 10,000.

The saponification reaction of the ethylene / saturated carboxylic acid vinyl ester copolymer is also not particularly limited. For example, the saponification is performed by heating the ethylene / saturated carboxylic acid vinyl ester copolymer and alcohol in the presence of an alkali catalyst. A method of grafting by introducing an alkylene oxide after removing the alcohol is mentioned.
In addition, as a saponification method, a heterogeneous liquid phase system with an alcohol, an alcohol solution, depending on characteristics due to the molecular weight of the ethylene / saturated carboxylic acid vinyl ester copolymer used, the content of the saturated carboxylic acid vinyl ester A system, a pellet dispersion system in alcohol, and the like can be appropriately employed. The saponification rate varies depending on the saturated carboxylic acid vinyl ester content of the ethylene / saturated carboxylic acid vinyl ester copolymer, and is not particularly limited, but is usually about 30 to 100%, preferably about 50 to 100%.

The method for adding alkylene oxide to the saponified ethylene / saturated carboxylic acid vinyl ester copolymer is not particularly limited, but the saponified product is generally reacted with alkylene oxide in a gaseous state.
Although it does not specifically limit as an alkylene oxide, Usually, a C2-C4 thing is preferable, For example, the copolymer modified material etc. which are ethylene oxide, propylene oxide, butylene oxide, cyclic ether, etc. are mentioned. Of these, ethylene oxide is preferably used. Two or more kinds of alkylene oxides can be used. In this case, block addition or random addition may be performed.
The addition amount of alkylene oxide is not particularly limited, but is usually about 20 to 1,000 parts by weight, preferably about 50 to 500 parts by weight with respect to 100 parts by weight of the saponified product.
An alkylene oxide adduct of a saponified ethylene / saturated carboxylic acid vinyl ester copolymer is obtained by saponifying an ethylene / saturated carboxylic acid vinyl ester copolymer to change a part or all of the saturated carboxylic acid vinyl ester into a vinyl alcohol structure. It is presumed to have a structure in which the main chain has a polyethylene unit and the side chain has a polyoxyalkylene unit.

As the ethylene / saturated carboxylic acid vinyl ester copolymer used in the present invention, an ethylene / vinyl acetate copolymer is particularly preferable from the viewpoint of market availability, price, etc., vinyl acetate unit content 5 to 50% by weight, number average Those having a molecular weight of 1,000 to 5,000 are more preferred because the bulk saponification reaction is easy.
The saponification rate of the ethylene / vinyl acetate copolymer is preferably in the range of 30 to 100% in order to obtain a resin having good compatibility with the resin. The amount of ethylene oxide added to the saponified ethylene / vinyl acetate copolymer is 50 to 1,000% by weight based on the saponified ethylene / vinyl acetate copolymer. It is more preferable in terms of the effect.

As the branched polymer polyol, a branched polymer polyol having a hydroxyl group at the terminal and obtained by grafting alkylene oxide to a trifunctional polyol structure can also be used. Trifunctional polyols having a trifunctional polyol structure include pyrogallol, trihydroxy aromatic compounds such as 1,2,4-trihydroxybenzene, aliphatic triols such as glycerin 1,1,1-tris (hydroxymethyl) ethane, Trialcoholamines such as ethanolamine can be mentioned.
Examples of these polymers include, but are not limited to, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile, halogens such as chloroform, amides such as dimethylformamide, and the like. It can be easily obtained by a polymerization method using a crosslinking agent such as isocyanate in these organic solvents, or a polymerization method in which a trifunctional polyol or alkylene oxide is melt blended with a thermoplastic resin and reacted. The alkylene oxide is not particularly limited, but usually those having about 2 to 4 carbon atoms are preferable. Examples thereof include ethylene oxide, propylene oxide, butylene oxide, and modified copolymer of cyclic ether. .

As the branched polymer polyol, a branched polymer polyol obtained by a reaction of a styrene / maleic anhydride copolymer and a polyalkylene oxide monoalkyl ether can also be used.
For example, the number average molecular weight of the styrene / maleic anhydride copolymer is 1,000 to 400,000, and the copolymerization molar ratio of styrene to maleic anhydride is 1/1 to 1/9. The branched polymer polyol R ¹ O— (CH ₂ —CH—O) _m —H, wherein the number average molecular weight of the alkyl ether is 100 to 5,000, and the polyalkylene oxide monoalkyl ether is represented by the following formula (3):
│ ……… (3)
R ²
(Wherein R ¹ is an alkyl group having 1 to 4 carbon atoms, R ² is a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, and m is an integer of 5 to 100). The polyalkylene oxide monoalkyl ether may be not only a single compound but also two or more kinds (for example, those in which R ² is hydrogen and a methyl group in formula (3)). Among these, polyethylene oxide monomethyl ether is preferable in terms of reactivity.

As the branched polymer polyol, the reaction between the terminal hydroxyl group of polyalkylene oxide monoalkyl ether and the acid anhydride group of styrene / maleic anhydride copolymer results in polystyrene as the main chain and polyalkylene oxide monoalkyl ether as the side chain. Also included are comb polymer polyols. In the above comb polymer polyol, if the number average molecular weight of the polyalkylene oxide monoalkyl ether is less than 100, the antistatic function of the polymer polyol itself is insufficient, while if it exceeds 5,000, the styrene / maleic anhydride copolymer is insufficient. Reactivity with coalescence is poor. When the carbon number of R ^{1 in} the formula (3) exceeds 4, the ionic conductivity is inferior.

As for the content rate of ethylene oxide in the polyether used for these polymers, it is desirable that they are 10 mol%-50 mol%. If it exceeds 50 mol%, crystallization will occur and it will be solid and difficult to handle. On the other hand, if it is less than 10 mol%, the components (C) and (D) will not be sufficiently dissolved, and the electrical characteristics will deteriorate.
Further, as the chain extender, a linear or branched polyether block copolymer type polymer polyol that can be extended by a reaction with an aromatic isocyanate, an aliphatic isocyanate or the like can also be used. Examples of such structures include segmented polyurethane elastomers.

As a (co) polymer having a segment having an alkylene ether and / or ester as a basic repeating unit, an elastomer skeleton composed of a hard segment and a soft segment can be used in addition to the branched polymer polyol described above. It is. For example, it has a polyester elastomer structure, and is represented by a polyester / polyether type having a polyether structure as a soft segment or a polyester / polyester type having a polyester structure as a soft segment for polybutylene terephthalate as a hard segment. It is an elastomer.
The polyester / polyether type is synthesized by, for example, transesterification and polycondensation using dimethyl terephthalate, 1,4 butanediol, polytetramethylene ether glycol, and the like as starting materials.

Polyamide elastomers can also be used as (co) polymers having segments having alkylene ethers and / or esters as basic repeating units. The polyamide elastomer is a general term for a thermoplastic elastomer having a polyamide constrained phase and a polyether and / or polyester structure as a soft segment. For example, a polyamide elastomer using a PA (polyamide) 12 component as a polyamide constrained phase is prepared by using lauryl lactam, dicarboxylic acid, and polyether diol as raw materials, adding water as a lactam ring-opening catalyst, and reacting under pressure and heating. To obtain a carboxyl telechelic nylon 12 oligomer and then a condensation reaction with a polyether diol. In addition, PA (polyamide) 6 or the like is also used as the polyamide constrained phase.
The polyamide elastomer that can be used in the present invention is basically a polyester block polyamide elastomer or a polyether ester block polyamide elastomer. Polyamide elastomers having various characteristics can be used depending on the type of diol used as a component.

As the (co) polymer having a segment having an alkylene ether and / or ester as a basic repeating unit, an aliphatic polyester can also be used. Industrially, aliphatic polyesters include those synthesized by dehydration polycondensation reaction and dediol reaction using aliphatic dicarboxylic acid and excess diol as starting materials, and those synthesized by ring-opening polymerization of caprolactone. It is done.
The structure of the aliphatic polyester used in the present invention includes a binary condensate of succinic acid and 1,4-butanediol, such as polybutylene succinate and polybutylene succinate adipate, succinic acid and adipic acid, and 1, What consists of a ternary condensate of 4-butanediol is mentioned. In addition, reactive groups and skeletons such as isocyanate groups, urethane groups, and aromatic rings are introduced into the structure, and polylactic acid is used in combination as long as the functionality of the biodegradable function is not impaired. Various copolymers such as polymerized copolyesters can also be used.

As the aliphatic polyester, various high molecular weight types such as polybutylene succinate, polyethylene succinate and copolymers thereof are industrially produced. As the aliphatic polyester, a commercially available product having a biodegradable function can be used. For example, polybutylene succinate adipate manufactured by Showa Polymer Co., Ltd., biodegradable aliphatic polyester, trade name Bionore, polycaprolactone There is a product name CELGREEN PH7 manufactured by Daicel Chemical Industries, Ltd., and a resin can be arbitrarily selected according to the use and characteristics.
In general, it is preferable to use an aliphatic polyester having a glass transition point of 30 ° C. or lower. When it exceeds 30 ° C., sufficient antistatic property may not be obtained.

Polyether-based amide resins can also be used as the (co) polymer having a segment having an alkylene ether and / or ester as a basic repeating unit.
The polyether-based amide resin is one type of high-molecular nonionic surfactant having a polyether segment, and specific examples thereof include polyether ester amide resins and polyether amide imide resins. Specifically, antistatic elastomers obtained by copolymerizing an ether segment and an amide segment, such as an ethylene glycol / amide copolymer, an ethylene glycol / methacrylate copolymer, and an ethylene glycol / ester amide copolymer. Of these, polyether ester amide resins derived from polyamides having carboxyl groups at both ends and alkylene oxide adducts of bisphenols and / or polyoxyalkylene glycols are preferred.

As a (co) polymer having a segment having at least one of amine, sulfide, and acrylonitrile as a basic repeating unit, polysulfide-based thermoplasticity by polycondensation reaction of polyacrylonitrile, triadisodithiol compound and aliphatic dihalide Examples thereof include polyamines and non-proteinaceous aliphatic compounds used as main raw materials for elastomers and polyurea resins.
The glass transition point (Tg) of the (co) polymer used for the surface treatment of the inorganic filler is preferably 40 ° C. or lower, more preferably 25 ° C. or lower. When Tg exceeds 40 ° C., sufficient conductivity cannot be obtained under a normal use environment.
A preferred (co) polymer has a weight average molecular weight of 1,000 to 100,000, more preferably 5,000 to 50,000.

The surface treatment method of the inorganic filler with a (co) polymer having a segment having any one or more of alkyl ether, ester, amine, sulfide, and acrylonitrile as a basic repeating unit is not particularly limited.
For example, a method of treating the surface of the inorganic filler with a water-soluble cationic or anionic polymer surfactant exemplified in JP-A-10-176079 can be used.
Examples of the water-soluble cationic and anionic polymer surfactants include first, second and third amine salt type cationic low molecular weight surfactants, polymer surfactants and quaternary ammonium salt type cationic low molecular surfactants. Or a polymeric surfactant.

In the case of obtaining the component (B) of the present invention, for example, it has a segment having at least one of alkylene ether, ester, amine, sulfide, and acrylonitrile as a basic repeating unit with respect to 100 parts by weight of the inorganic filler. ) The polymer is preferably blended in an amount of 0.5 to 15 parts by weight, more preferably 1 to 10 parts by weight.
When the amount of the (co) polymer is less than 0.5 parts by weight, the conductivity is insufficient. On the other hand, when the amount of the (co) polymer exceeds 15 parts by weight, the electrical properties are good, but the filler In addition to the increased stickiness of the resin, there is a problem in supplyability, and the effect of plasticizing the matrix resin is added, the molding shrinkage ratio is large, deformation occurs, mechanical properties are lowered, and it is not suitable for precise molded products.
When the inorganic filler is coated with the (co) polymer, specifically, for example, the inorganic filler whose surface is treated with a water-soluble cationic or anionic polymer surfactant and the (co) heavy Examples include a method in which the coalescence is dissolved in an organic solvent and mixed using a Henschel mixer or a ribbon mixer.

The average particle diameter of the inorganic filler whose surface thus obtained is coated with the (co) polymer is preferably 0.05 to 10.0 μm, more preferably 0.1 to 3.0 μm, and still more preferably. Is 0.3 to 2.0 μm. When the particle size is less than 0.05 μm or more than 10.0 μm, there is a problem in the productivity of the inorganic filler and the dispersibility in the resin composition.
The component (B) of the present invention optionally contains one or more ionic components that include alkali metal ions such as Li, Na, and K, anions, and the like, which are blended as necessary. It doesn't matter.

  In the composition of the present invention, the use ratio of the (B) surface-treated inorganic filler is such that when the total of the component (A) and the component (B) is 100 parts by weight, the component (A) is 20 to 80 parts by weight, (B 80) -20 parts by weight of component, preferably 30-70 parts by weight of component (A), 70-30 parts by weight of component (B), more preferably 40-60 parts by weight of component (A), 60-40 parts of component (B). Parts by weight. When the blending ratio of the component (B) exceeds 80 parts by weight, the electric characteristics are good, but the workability, the appearance are deteriorated, and the mechanical characteristics are deteriorated. On the other hand, if the component (B) is less than 20 parts by weight, the electrical characteristics are insufficient.

Component (C) The thermoplastic resin having a polar group (C) used in the composition of the present invention may be anything as long as it has a polar group in the molecular structure other than the component (A) used. . Among them, (C-1) a block copolymer and / or graft copolymer having a block (α) mainly composed of an olefin component and a block (β) mainly composed of a hydrophilic component, and a thermoplastic elastomer are preferable. Examples include (C-2) polyether ester amide resin, (C-3) polyester elastomer, (C-4) aliphatic polyester, (C-5) polyurethane elastomer, and (C-6) polyamide elastomer. . These can be used alone or in combination of two or more.

(C-1) Component A block copolymer and / or graft copolymer having a block (α) mainly composed of an olefin component and a block (β) mainly composed of a hydrophilic component. In the (C-1) copolymer, the block (α) and the block (β) are preferably bonded via at least one bond selected from the group consisting of an ester bond, an amide bond, an ether bond, a urethane bond and an imide bond. Have a combined structure. The (C-1) copolymer is known, and for example, those described in JP-A No. 2001-278985 can be used. As a commercially available product, for example, Pelestat 300 (trademark, manufactured by Sanyo Chemical Industries, Ltd.) can be used.
(C-1) The block (α) mainly comprising an olefin component constituting the copolymer is preferably a polyolefin (α1) having a carbonyl group (preferably a carboxyl group, the same shall apply hereinafter) at both ends of the polymer, and a hydroxyl group. At both ends of the polymer (α2), polyolefin having an amino group at both ends of the polymer (α3), polyolefin having a carbonyl group at one end of the polymer (α4), and polyolefin having a hydroxyl group at one end of the polymer ( α5), a polyolefin having an amino group at one end of the polymer (α6), a polyolefin having a carbonyl group introduced from the main chain of the polymer (α7), or the like can be used. Of these, polyolefins (α1) and (α4) having a carbonyl group are more preferable because of easy modification.

(Α1) is a polyolefin (α0) having a carbonyl group introduced at both ends of a polyolefin (α0) whose main component (content is 50% by weight or more, preferably 75% by weight or more). .
Here, (α0) is obtained by polymerization of one or a mixture of two or more olefins having 2 to 30 carbon atoms (preferably olefins having 2 to 12 carbon atoms, particularly preferably propylene and / or ethylene). By thermal degradation of polyolefins and high molecular weight polyolefins (preferably polyolefins obtained by polymerization of olefins having 2 to 30 carbon atoms, more preferably olefins having 2 to 12 carbon atoms, particularly preferably polypropylene and / or polyethylene) The low molecular weight polyolefin obtained is mentioned.
As (α2), those in which hydroxyl groups are introduced at both ends of (α0) are used.
As (α3), those in which amino groups are introduced at both ends of (α0) are used.
As (α4), a polyolefin (α00) having a carbonyl group introduced at one end is used as a main component (content is 50% by weight or more, preferably 75% by weight or more). .
As (α5), one in which a hydroxyl group is introduced at one end of (α00) is used.
As (α6), one in which an amino group is introduced at one end of (α00) is used.
As (α7), those in which a carbonyl group is introduced in a form branched from the main chain of (α00) are used.

  As the block (β) mainly composed of a hydrophilic component, a polyether-containing hydrophilic polymer, preferably one having a polyether segment, one having a polyether ester segment, one having a polyether amide segment, polyether ester Those having an amide segment can be used.

The volume resistivity of the block (β) (value measured according to ΑSTM D257 described later) is preferably 1 × 10 ⁵ to 1 × 10 ¹¹ Ω · cm, more preferably 1 × 10 ⁶ to 1 × 10 ^9. Ω · cm. When the volume resistivity exceeds 10 ¹¹ Ω · cm, the antistatic property decreases.

(C-2) polyetheresteramide;
The (C-2) polyether ester amide of the present invention is one kind of a polymeric nonionic surfactant having a polyether segment. Specific examples of the (C-2) polyether ester amide include antistatic elastomers having a polyether segment such as a polyethylene glycol / polyamide copolymer and a polyethylene glycol polyester amide copolymer. These can be used alone or in combination of two or more.
A polyether ester amide resin derived from a polyamide having carboxyl groups at both ends and an alkylene oxide adduct of bisphenols and / or a polyoxyalkylene glycol is preferred.

(C-3) polyester elastomer;
The polyester elastomer which is the component (C-3) of the present invention is a multi-block copolymer using polyester as a hard segment in the molecule and polyether or polyester having a low glass transition temperature (Tg) as a soft segment. As the component (C-3), an aromatic crystalline polyester such as polybutylene terephthalate as a hard segment, a polyester / polyether type using a polyether as a soft segment, and an aromatic crystalline polyester as a hard segment And polyester / polyester type using an aliphatic polyester as a soft segment.

The polyester / polyether type is synthesized by, for example, transesterification and polycondensation using dimethyl terephthalate, 1,4 butanediol, polytetramethylene ether glycol, and the like as starting materials. The polyester / polyether type can also be synthesized by transesterification and ring-opening reactions using dimethyl terephthalate, 1,4-butanediol, ε-caprolactone, and the like as starting materials.
As the component (C-3) of the present invention, all ordinary polyester elastomers can be used, and one kind can be used alone, or two or more kinds can be used in combination.

( C-4) aliphatic polyester ;
As the aliphatic polyester which is the component (C-4) of the present invention, those commercially available as biodegradable can also be used. For example, trade names Bionore (polybutylene succinate, polybutylene succinate adipate) sold by Showa Polymer Co., Ltd. and Cell Green (polycaprolactone) sold by Daicel Chemical Industries, Ltd. However, it is possible to arbitrarily select a resin according to the application and characteristics. Industrially, those synthesized by a dehydration polycondensation reaction and a dediol reaction using an aliphatic dicarboxylic acid and an excess diol as starting materials can be mentioned. As such aliphatic polyesters, polybutylene succinate, polyethylene succinate and copolymers thereof are common, and various high molecular weight types are industrially produced.

Examples of the (C-4) aliphatic polyester suitably used in the present invention include polybutylene succinate (binary condensate of succinic acid and 1,4-butanediol), polybutylene succinate adipate (succinic acid and adipine) Acid, and a ternary condensate of 1,4-butanediol).
In the (C-4) aliphatic polyester of the present invention, a reactive group such as an isocyanate group or a urethane group can be introduced into the structure. Furthermore, as the (C-4) aliphatic polyester of the present invention, various copolymers such as a copolyester obtained by copolymerizing polylactic acid or the like can also be used. These can be used alone or in combination of two or more.

(C-5) polyurethane elastomer ;
The polyurethane elastomer (C-5) of the present invention is a thermoplastic elastomer having a urethane group, a polyurethane obtained by a reaction of a long chain glycol and an isocyanate as a soft segment, and a polyurethane comprising a short chain glycol and an isocyanate as a hard segment. And a linear multi-block copolymer, and a crosslinking agent (chain extender) is also used as necessary.
Here, as a general classification according to the kind of long chain glycol, polyethylene oxide, polypropylene oxide, or a copolymer thereof can be cited as a polyether system, and polyadipate, polylactone, polycarbonate, aliphatic system as a polyester system. Examples thereof include polybutadiene and polyisoprene.

Short chain glycols include aliphatic glycols such as ethylene glycol, 1,4-butanediol and 1,6-hexanediol, alicyclic glycols such as cyclohexanedimethanol, and hydroquinone bis (2-hydroxyethyl). Aromatic glycols such as ethers are usually used.
On the other hand, 4,4'-diphenylmethane diisocyanate (MDI), 2,4 '& 2,6-toluene diisocyanate (TDI), etc. are used as the isocyanate.
In addition, as the cross-linking agent (chain extender), aromatic diamines such as 3,3-dichloro-4,4-diaminodiphenylmethane (MOCA) are used.
The (C-5) polyurethane elastomer may be used alone or in combination of two or more.

(C-6) polyamide elastomer ;
The polyamide which is the component (C-6) of the present invention is a generic term for amide resins having an amide bond in its repeating unit. For example, nylon 6, nylon 6, 6, nylon 12, etc., polyamide Examples thereof include polyester copolymers and polyamide polyether copolymers.
The polyamide elastomer which is the component (C-6) of the present invention is a general term for a polyamide constrained phase which is a hard segment and a thermoplastic elastomer having a polyether or polyester structure as a soft segment. For example, a polyamide elastomer using a PA12 component as a polyamide (PA) confined phase is obtained by reacting laurolactam, dicarboxylic acid, and polyether diol with water as a lactam ring-opening catalyst under a reaction under pressure and heating. There is a method of obtaining a rick nylon 12 oligomer and then obtaining a thermoplastic elastomer by a condensation reaction with a polyether diol. In addition to this, PA6 or the like is also used as the polyamide constrained phase.

The polyamide elastomer is basically in the form of a polyether block polyamide elastomer or a polyether ester block polyamide elastomer by the above synthesis method. Here, polyamide elastomers having various characteristics can be obtained depending on the kind of diol used in the synthesis method. These can be used alone or in combination of two or more.
Polyamide elastomers are excellent in high temperature characteristics, mechanical characteristics, oil resistance, low temperature characteristics, and the like, and are therefore used in a wide range of applications such as sporting goods as well as machine parts and automobile parts.

  For the purpose of modifying processability and properties, polyamide and polyamide elastomer can be used in the form of other resins, polymer alloys, and polymer blends.

In addition, (C) the thermoplastic resin having a polar group optionally has an ionic component in advance containing an cation component such as an alkali metal such as Li, Na, K, Mg, Ca, an alkaline earth metal, or an ion-dissociable anion. You may contain at least 1 or more types.
Further, the component (C) preferably has a glass transition temperature of 60 ° C. or lower, more preferably 50 ° C. or lower, particularly preferably 40 ° C. or lower, and more preferably 30 ° C. or lower. When the glass transition temperature exceeds 60 ° C., a sufficient antistatic effect cannot be obtained.

  Component (C) is added in an amount of 3 to 40 parts by weight, more preferably 4 to 30 parts by weight, particularly preferably 5 to 20 parts by weight, based on 100 parts by weight of the total amount of components (A) and (B). It is. It is. If this amount is less than 3 parts by weight, it is not possible to obtain anti-static performance with little environmental dependency.

(D) As an alkali metal which is a cation of a component (D) metal salt, Li, Na, K etc. are mentioned. As the cation, Li ⁺ and Na ⁺ having a small ionic radius are preferable, and lithium Li ⁺ is particularly preferable. Examples of the anion which is a constituent element of the metal salt of the present invention include Cl ⁻ , Br ⁻ , F ⁻ , I ⁻ , NO ₃ ⁻ , SCN ⁻ , ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ and BF ₄ ^−. , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ^{− and the} like, but preferred anion species used in the present invention are ClO ₄ ⁻ , CF ₃ SO ₃ ⁻ , (CF ₃ SO ₂ ) ₂ N ⁻ , (CF ₃ SO ₂ ) ₃ C ⁻ . The preferred anionic species has the advantage of promoting the dissociation of the cation and producing an effect with a smaller addition amount.
(D) The metal salt is blended as necessary, but the blending amount is 0.0001 to 20 parts by weight, preferably 0.001 with respect to 100 parts by weight of the total amount of components (A) and (B). It is the range of -10 weight part. If it is less than 0.0001 part by weight, it is difficult to obtain sufficient conductivity, while if it exceeds 20 parts by weight, the mechanical properties, processing properties, and thermal stability of the resin are impaired. In the present invention, it is desirable that the component (D) is dispersed and stabilized in advance in the component (E) described later.

There are many metal salts composed of the above cation and anion, but lithium perchlorate, sodium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, lithium tris (trifluoromethanesulfonyl) methide, Lithium trifluoromethanesulfonate, sodium trifluoromethanesulfonate, bis (trifluoromethanesulfonyl) imidolithium Li · N (CF ₃ SO ₂ ) ₂ , sodium bis (trifluoromethanesulfonyl) imide Na · N (CF ₃ SO ₂ ) ₂ , tris (trifluoromethanesulfonyl) methide lithium _{Li · C (CF 3 SO 2} ) 3, tris (trifluoromethanesulfonyl) methide sodium _{Na · C (CF 3 SO 2} ) 3 to be used, etc. Preferred. Since the specific resistance of the resin composition is lowered only by adding a small amount of these, the above-described effect is further exhibited. The composition of the present invention contains at least one of these metal salts.
Among these, at least one selected from the group consisting of lithium perchlorate, sodium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, and lithium tris (trifluoromethanesulfonyl) methide is preferable.

Component (E) Component (E) is an organic compound having an ester group and / or an ether group and a molecular weight of 1,500 or less, and is used as necessary. This component (E) is effective for improving the solubility, dissociation stability, electrical conductivity, processing stability, and surface appearance of the metal salt in the composition of the present invention. Examples of the component (E) include the following components (E-1 to 3).
(E-1) Component (E-1) The component (E-1) is particularly preferably the one represented by the following general formula (4), wherein R is an alkyl having no hydroxyl group at the end. What is a group is preferable in terms of balance between antistatic properties and bleed.
COO (AO) _n R
│
B (4)
│
COO (AO) _n R
[Wherein, B represents a linear or branched alkylene group having 1 to 9 carbon atoms, a divalent hydrocarbon group containing an aromatic group, or a divalent alicyclic hydrocarbon group; Represents an alkylene group having 2 to 4 carbon atoms, each R independently represents a linear or branched alkyl group having 1 to 9 carbon atoms, and each n is independently an integer of 1 to 7. ]
Specifically, bis [2- (2butoxyethoxy) ethyl] adipate represented by the following chemical formula (5) [in the general formula (4), B is an alkylene group having 4 carbon atoms, and R is a straight chain having 4 carbon atoms. The chain alkyl group, A represents an alkylene group having 2 carbon atoms, and n represents 2. Or bis (2-butoxyethyl) phthalate represented by the following chemical formula (6) [In the above general formula (4), B is a phenyl group, R is a linear alkyl group having 4 carbon atoms, and A is 2 carbon atoms. An alkylene group, n represents 1; ].

COO (CH ₂ CH ₂ O) ₂ (CH ₂ ) ₃ CH ₃
│
(CH ₂ ) ₄ (5)
│
COO (CH ₂ CH ₂ O) ₂ (CH ₂ ) ₃ CH ₃

COOCH ₂ CH ₂ O (CH ₂ ) ₃ CH ₃
│
Ph (6)
│
COOCH ₂ CH ₂ O (CH ₂ ) ₃ CH ₃

  The component (E-1) is, for example, an alcohol obtained by adding 1 to 7 moles of an alkylene oxide having 2 to 4 carbon atoms to 1 mole of a linear or branched aliphatic alcohol having 1 to 9 carbon atoms, A dibasic acid can be used as a raw material, and can be produced by a general ester compound production method.

Examples of the alcohol include 1 to 7 mol of ethylene oxide, 1 to 4 mol of propylene oxide, or 1 to 3 mol of butylene oxide in 1 mol of propanol, and 1 to 6 mol of ethylene oxide or 1 to 3 mol of propylene oxide in 1 mol of butanol. 1 mol of hexanol, 1-2 mol of ethylene oxide, 1 mol of ethylene oxide to 1 mol of pentanol, 1 to 3 mol of propylene oxide, or 1 to 2 mol of butylene oxide, 1 mol of ethylene oxide to 1 mol of octanol, propylene oxide Examples include hydroxyl compounds obtained by adding 1 to 3 moles, 1 to 3 moles of butylene oxide, 1 mole of nonanol, 1 to 4 moles of ethylene oxide, 1 to 2 moles of propylene oxide, or 1 to 2 moles of butylene oxide, respectively. Among these compounds, 2- (2-butoxyethoxy) ethanol in which 2 mol of ethylene oxide is added to 1 mol of butanol, and 2-butoxyethanol in which 1 mol of ethylene oxide is added to 1 mol of butanol are in balance with processability. Good for.
Examples of the dibasic acid include carboxylic acids such as adipic acid, sebacic acid, phthalic acid, and succinic acid, and carboxylic acid anhydrides thereof.

(E-2), (E-3) Component (E-2) Organic compounds represented by the following formula (1), (E-3) Organic compounds represented by the following formula (2) can also be used.
R- (Y-Z) _n- Y-R (1)
X- (ZY) _n -ZX (2)
[In the formulas (1) to (2), R is an aliphatic alkoxy group, alicyclic alkoxy group or aromatic alkoxy group, Y is an alkylene dicarboxylic acid residue or aromatic dicarboxylic acid residue having 4 to 12 carbon atoms, X represents a fatty acid residue or a benzene monocarboxylic acid residue, Z represents an alkylene glycol residue having 2 to 12 carbon atoms, and n represents an integer of 0 or more. ]

  Said (E-2) and (E-3) component can be manufactured with the manufacturing method of a general ester compound. That is, it is produced by condensation using a polybasic acid component and a polyhydric alcohol component, and a monohydric alcohol component and / or a monovalent carboxylic acid component.

  As the polybasic acid component, for example, adipic acid, sebacic acid, succinic acid, maleic acid, fumaric acid, glutaric acid, azelaic acid, dodecanedicarboxylic acid and the like, preferably an aliphatic dicarboxylic acid having 4 to 12 carbon atoms, etc. , Aromatic dicarboxylic acids such as phthalic acid, isophthalic acid and terephthalic acid, and anhydrides thereof. A polybasic acid component can be used as these 1 type, or 2 or more types of mixtures.

Examples of the polyhydric alcohol component include ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, 1,2-butanediol, 1,3-butanediol, 2-methyl-1,3- Propanediol, 1,4-butanediol, 1,5-pentanediol, 2,2-dimethyl-1,3-propanediol (neopentyl glycol), 2,2-diethyl-1,3-propanediol (3, 3-dimethylolpentane), 2-n-butyl-2-ethyl-1,3-propanediol (3,3-dimethylolheptane), 3-methyl-1,5-pentane-diol-1,6-hexane Diol, 2,2,4-trimethyl-1,3-pentanediol, 2-ethyl-1,3-hexanediol, 2-methyl-1,8-octa Diol, 1,9-nonanediol, 1,10-decanediol, 1,12-aliphatic glycols having 2 to 18 carbon atoms such as octadecane diol, and diethylene glycol, polyalkylene glycols such as dipropylene glycol.
The polyhydric alcohol component can be used as one kind or a mixture of two or more kinds.

  As monohydric alcohol components, carbon such as octanol, isooctanol, 2-ethylhexanol, nonanol, isononanol, 2-methyloctanol, decanol, isodecanol, undecanol, dodecanol, tridecanol, tetradecanol, hexadecanol, octadecanol, etc. Aliphatic alcohols such as aliphatic alcohols of number 8 to 18, cyclohexanol, benzyl alcohol, 2-phenylethanol, 1-phenylethanol, 2-phenoxyethanol, 3-phenyl-1-propanol, 2-hydroxyethylbenzyl Aromatic alcohols such as ether can be mentioned. A monohydric alcohol component can be used as a 1 type, or 2 or more types of mixture.

  Examples of the monovalent carboxylic acid component include caprylic acid, nonanoic acid, capric acid, undecylic acid, lauric acid and the like, and can be used as one kind or a mixture of two or more kinds.

  It should be noted that the polyester compounds of the components (E-2) and (E-3) include 3 such as glycerin, diglycerin, trimethylolpropane, pentaerythritol, dipentaerythritol, trimellitic acid, pyromellitic acid as necessary. Polyhydric alcohols and polybasic acids with higher or higher valences may be used as modifiers.

  In addition, the polyester compounds (E-2) and (E-3) include, as necessary, compounds having a carboxylic acid group and an alcohol group, or a carboxylic acid residue and an alcohol residue in the molecule, such as caprolactone, 1 , 2-hydroxystearic acid, ricinoleic acid, lanolin-derived fatty acid, oxybenzoic acid and the like can be incorporated and used as part of the polybasic acid and polyhydric alcohol.

The synthesis reaction of these polyester compounds (E-2) and (E-3) is carried out by using an acid catalyst such as paratoluenesulfonic acid, phosphoric acid, tetraisopropyl titanate, tetrabutyl titanate, dibutyltin oxide. Since it is promoted by a metal catalyst such as dioctyl oxide and zinc chloride, it is usually good to carry out in the presence of these catalysts. The amount of catalyst used is usually in the range of 0.005 to 0.2%.
Usually, the reaction is carried out by heating to 100 to 250 ° C, preferably 130 to 250 ° C.

  The number average molecular weight (Mn) of the polyester compounds (E-2) and (E-3) used in the present invention is preferably 100 to 4,000, preferably 200 to 1,000. For stability of performance, it is usually preferable to dissolve the (D) component in the (E) component, and the solubility is good when it is less than 100, but the migration by contact with the other resin of the (E) component, It causes problems such as gas generation during processing due to deterioration of thermal stability and volatile characteristics. On the other hand, when it exceeds 4,000, the viscosity of the dissolved solution is remarkably increased, so that the blending workability is deteriorated.

  (E) The addition amount of a component is 100-5,000 weight part with respect to 100 weight part of (D) component, Preferably it is the range of 200-1000 weight part. If it is less than 100 parts by weight, it is difficult to obtain sufficient conductivity, processing characteristics and surface appearance improvement, and the solubility and dissociation stability of the component (D) become insufficient. On the other hand, when it exceeds 5,000 parts by weight, the viscosity of the resulting composition is remarkably lowered, making the molding process difficult, and causing bleed out, resulting in a decrease in physical properties.

In the antistatic resin composition of the present invention, other inorganic fillers, stabilizers, colorants, reinforcing rubbers, elastomer components, plasticizers, dispersants, UV absorbers, etc., unless the object of the present invention is impaired. Additives such as additives, antioxidants, flame retardants, stabilizers, reinforcing agents, lubricants, foaming agents, weathering (light) agents, metal powders and the like can be optionally blended depending on the purpose.
The antistatic resin composition of the present invention can be produced without any problem using ordinary equipment and equipment used for mixing and kneading ordinary thermoplastic resins. Specifically, components (A) to (E) and other components are charged into a premixer such as a tumbler or a Henschel mixer and mixed uniformly. Thereafter, the mixture is supplied to an extruder, melted and kneaded, extruded from a die, and pelletized by a pelletizer. As the extruder, a single shaft with a vent, a biaxial different direction, and a biaxial same direction extruder are desirable. Further, instead of the extruder, a kneader such as a super mixer, a Banbury mixer, a kneader, a tumbler, or a kneader may be used.

EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention, this invention is not limited by these Examples. In the examples, parts and% are based on weight unless otherwise specified.
Various components used in Examples and Comparative Examples are as follows.

(A) a thermoplastic polymer compound;
(A-1) Polypropylene resin: manufactured by Idemitsu Petrochemical Co., Ltd., trade name random PP, F-730NV (“PP” in the table)
(A-2) ABS resin: manufactured by Techno Polymer Co., Ltd., trade name Techno ABS 170 ("ABS" in the table)
(B) component;
Coated with polyalkylene ether on the surface of calcium carbonate: manufactured by Pfematech Co., Ltd., trade name: AFF-EML33re11, average particle size: 1.0 μm (“Filler (1)” in the table)
What does not coat the surface of calcium carbonate with an alkylene ether polymer: manufactured by Co., Ltd., trade name NS400, average particle size 1.17 μm (“Filler (2)” in the table)
(C) component;
(C-1) Block copolymer and / or graft copolymer having block (α) mainly composed of olefin component and block (β) mainly composed of hydrophilic component: Pelestat 300 (trade name), Sanyo Chemical Industries, Ltd. (C-2) Polyetheresteramide: Perestat NC6321 (trade name), Sanyo Chemical Industries, Ltd. (C-5) Polyurethane elastomer: Pandex T-8180N
(D) component;
(D-1) Bis (trifluoromethanesulfonyl) imidolithium: Li · N (CF ₃ SO ₂ ) ₂
(D) component and (E) component;
(D-2) 20% by weight of bis (trifluoromethanesulfonyl) imidolithium as component (D) dissolved in component (E) bis [2- (2butoxyethoxy) ethyl] adipate: Sanconol 0862-20R
(D-3) 18% by weight of bis (trifluoromethanesulfonyl) imidolithium as component (D) dissolved in component (E) bis [2- (2butoxyethoxy) ethyl] adipate: Sanconol 0862-18

Examples 1-9, Comparative Examples 1-4
Preparation of composition pellets;
In accordance with the formulation of Tables 1 and 2, (A) thermoplastic resin, (B) component, and (C) to (E) components were pre-dry blended with a tumbler mixer, and 47 to 180 mm in the same direction biaxial extruder. Melted and mixed at 0 ° C. The string-shaped resin melt mixture that came out of the die of the extruder was cooled in a water tank and passed through a cutter to prepare pellets of the antistatic resin composition.

Preparation of test specimens for evaluation;
The sample pellets prepared above were used for injection molding by an injection molding machine with a clamping pressure of 80 ton / cm ² to form a test piece plate of width 6 × length 6 × thickness 0.3 (cm). The molding conditions were a cylinder temperature of 180 to 220 ° C and a mold temperature of 40 to 60 ° C.

Evaluation The following evaluation was performed on the above test pieces. The results are shown in Tables 1 and 2.
Surface resistivity, volume resistivity Using the test piece prepared above, Mitsubishi Chemical Co., Ltd. was allowed to stand for 24 hours in the specified environment (23 ° C humidity 10%, 23 ° C humidity 50%, 23 ° C humidity 85%). The measurement was carried out according to ASTM D257 (applied voltage: 500 V) with Hiresta.

The antistatic resin composition of the present invention takes advantage of its excellent characteristics, and is an OA equipment field, a home appliance field, an electric / electronic field, a vehicle field, a writing instrument field, a building material field, a security field, and parts in these fields, and It can be suitably used for other various parts, housings, packages, and the like.

Claims (6)

(A) 20-80 parts by weight of a thermoplastic polymer compound and / or unvulcanized rubber,
(B) 80-20 parts by weight of an inorganic filler whose surface is coated with at least one (co) polymer selected from the group consisting of polyalkylene ether, polyester, polyamine, polysulfide, and polyacrylonitrile [(A) + (B) = 100 parts by weight]
(C) a thermoplastic resin having a polar group [however, excluding component (A)] 3 to 40 parts by weight,
An antistatic resin composition comprising: (C) component is
(C-1) a block copolymer and / or a graft copolymer having a block (α) mainly composed of an olefin component and a block (β) mainly composed of a hydrophilic component,
The antistatic resin composition according to claim 1, which is at least one selected from the group consisting of (C-2) polyether ester amide and (C-5) polyurethane elastomer.   Further, (D) 0.0001 to 20 parts by weight of a metal salt composed of an anion or an alkaline earth metal cation and an anion [provided (A) + (B) = 100 parts by weight] The antistatic resin composition according to claim 1 or 2   The component (D) is at least one selected from the group consisting of lithium perchlorate, sodium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, and lithium tris (trifluoromethanesulfonyl) methide. The antistatic resin composition according to any one of claims 1 to 3.   The organic compound having a molecular weight of 1,500 or less and further having (E) an ester group and / or an ether group is blended in an amount of 100 to 5,000 parts by weight with respect to 100 parts by weight of the component (D). Antistatic resin composition. (E) component has (E-1)-{O (AO) _n }-group (Here, A is a C2-C4 alkylene group, n shows the integer of 1-7), And all of the molecular chain terminals are CH ₃ and / or CH ₂ groups, (E-2) an organic compound represented by the following formula (1), and (E-3) represented by the following formula (2). The antistatic resin composition according to claim 5, which is at least one selected from the group consisting of organic compounds.
R- (Y-Z) _n- Y-R (1)
X- (ZY) _n -ZX (2)
[In the formulas (1) to (2), R is an aliphatic alkoxy group, alicyclic alkoxy group or aromatic alkoxy group, Y is an alkylene dicarboxylic acid residue or aromatic dicarboxylic acid residue having 4 to 12 carbon atoms, X represents a fatty acid residue or a benzene monocarboxylic acid residue, Z represents an alkylene glycol residue having 2 to 18 carbon atoms, and n represents an integer of 0 or more. ]