JP2005120351A - Antistatic thermoplastic resin composition and molded article using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a thermoplastic resin composition that gives a molded article excellent in antistatic properties and sliding properties and to provide a molded article produced by using the thermoplastic resin composition. <P>SOLUTION: The antistatic thermoplastic resin composition is produced by blending 100 pts.mass of [A] a rubber-reinforced resin which comprises a rubber-reinforced copolymer resin produced by polymerizing an aromatic vinyl compound, a vinyl cyanide compound and the like in the presence of a butadiene rubbery polymer and/or an acrylic rubbery polymer and has a content of the rubbery polymer of 3-40 mass%, 0.2-20 pts.mass of [B] an alkyl sulfonate, 0.1-10 pts.mass of [C] a polyolefin having a weight-average molecular weight of 500-40,000 and 0.1-20 pts.mass of [D] a combined product of (d) an olefin-based polymer and a (co)polymer of (b-2) a vinyl monomer including an aromatic vinyl compound. Additionally, the composition may contain an aromatic polycarbonate resin or a flame-retardant. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a thermoplastic resin composition that gives a molded article excellent in antistatic properties and sliding properties, and a molded article using the thermoplastic resin composition.

Styrenic resins such as ABS resins are widely used in the electrical / electronic field, the home appliance field, the automobile field, and the like because of their excellent molding processability, physical properties, and mechanical properties. However, this styrenic resin is an electrical insulator and is effective as an insulating material. However, it cannot leak charged electricity, and the surface is dusty. Interference may occur. As a method for improving these drawbacks, a method of kneading an antistatic agent is generally known.
On the other hand, when the above resin is molded and used in electronic equipment casings, etc., in addition to sustained antistatic performance, friction and wear occur during assembly due to contact with metal parts, so slidability is required. The As a method for improving the slidability of the ABS resin, a method is generally known in which a polyolefin wax or the like is blended during melt kneading.
The antistatic property and slidability of styrene resin can be improved considerably by the above-mentioned method. However, in recent years, with the expansion of the field of use, better antistatic property and slidability, especially advanced antistatic properties. Sex is required.

JP-A 61-261359

  An object of the present invention is to provide a thermoplastic resin composition that gives a molded article having excellent antistatic properties and sliding properties, and a molded article using the thermoplastic resin composition.

As a result of diligent research under the above purpose, the present inventor has formulated and modified a specific amount of an alkyl sulfonate as an antistatic agent to a specific styrene resin obtained by blending a low molecular weight polyolefin. By blending a predetermined amount of the polyolefin polymer, it was found that the antistatic property and slidability of the styrene resin were remarkably improved, and the moldability and impact resistance were improved, and the present invention was completed. It was.
Thus, according to the present invention, an antistatic thermoplastic resin composition containing the following components [A] to [D], wherein the component [B] is 0.2 parts per 100 parts by mass of the component [A]. -20 mass parts, component [C] 0.1-10 mass parts, and component [D] 0.1-20 mass parts are mix | blended, The antistatic thermoplastic resin composition characterized by the above-mentioned is provided. Is done.
Component [A] is a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubber polymer (a) comprising a butadiene rubber polymer and / or an acrylic rubber polymer. The rubber-reinforced copolymer resin (A-1) obtained by polymerizing (b-1) or the (co) polymer (A-) of the rubber-reinforced copolymer resin (A-1) and a vinyl monomer. 2) and a rubber-reinforced resin having a content of the rubbery polymer (a) of 3 to 40% by mass.
Component [B] is an alkyl sulfonate.
Component [C] is a low molecular weight polyolefin having a weight average molecular weight of 500 to 40,000.
Component [D] is a combined product of the olefin polymer (d) and the (co) polymer of the vinyl monomer (b-2) containing an aromatic vinyl compound.

The thermoplastic resin composition may further contain 1 to 30 parts by mass of an aromatic polycarbonate resin as the component [E] with respect to 100 parts by mass of the component [A].
The thermoplastic resin composition may further contain 1 to 30 parts by mass of a flame retardant as component [F] with respect to 100 parts by mass of component [A].

Furthermore, according to the present invention, there is provided a molded product characterized by using the thermoplastic resin composition.
Without being bound by theory, according to the present invention, by using the component [C] and the component [D], the component [B] having antistatic performance is converted into the component [C] and the component [D]. It is considered that not only the slidability but also the antistatic property (surface specific resistance) is remarkably improved because of the channel effect.
In the present specification, “(co) polymerization” means homopolymerization and / or copolymerization, and “(meth) acryl” means acrylic and / or methacrylic.

The present invention will be described in detail below.
The rubber reinforced resin [A] according to the present invention comprises an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubber polymer (a) composed of a butadiene rubber polymer and / or an acrylic rubber polymer. A rubber-reinforced copolymer resin (A-1) obtained by polymerizing a vinyl-based monomer (b-1), or the rubber-reinforced copolymer resin (A-1) and a vinyl-based monomer (copolymer). ) A rubber-reinforced resin comprising a mixture with the polymer (A-2) and having a content of the rubbery polymer (a) of 3 to 40% by mass.
The rubber polymer (a) is mainly composed of a butadiene rubber polymer, an acrylic rubber polymer or both, but may contain other rubber polymers as required.
Examples of butadiene-based rubbery polymers include polybutadiene rubber, polyisoprene rubber, polychloroprene rubber, styrene-butadiene random copolymer rubber (styrene content is preferably 5 to 60% by weight), butadiene / acrylate copolymer, and styrene. -Isoprene random copolymer rubber, acrylonitrile-butadiene random copolymer rubber, isobutylene-isoprene random copolymer rubber (butyl rubber), styrene-butadiene block copolymer rubber, styrene-isoprene block copolymer rubber, styrene-isoprene-styrene block copolymer In addition to butadiene rubbers such as rubber and isobutylene-isoprene copolymer rubber, hydrogenated rubbers of the above butadiene rubbers such as SEBS may be mentioned.
Acrylic rubber polymers include acrylic ester rubber, acrylic ester-aromatic vinyl copolymer rubber, acrylic ester-conjugated diene compound copolymer rubber, acrylic ester compound-conjugated diene compound-aromatic vinyl compound Examples thereof include polymer rubber.

The gel content of the rubbery polymer (a) is usually 98% by mass or less, preferably 40 to 98% by mass, more preferably 50 to 95% by mass, and particularly preferably 60 to 90% by mass. . If it exists in this range, when using impact resistance, surface appearance, and a flame retardant, the thermoplastic resin composition which gives the molded article excellent in the flame retardance can be obtained.
In addition, the said gel content rate can be calculated | required by the method shown below. That is, 1 g of a rubbery polymer was put into 100 ml of toluene, allowed to stand at room temperature for 48 hours, and then filtered through a 100 mesh wire mesh (mass was set to ₁ gram) to remove toluene insolubles and the wire mesh at 80 ° C. It is vacuum-dried for 6 hours, weighed (the mass is W ₂ grams), and calculated according to the following formula.
Gel content (%) = [{W ₂ (g) −W ₁ (g)} / 1 (g)] × 100
The gel content is adjusted by appropriately setting the type and amount of the molecular weight adjusting agent, the polymerization time, the polymerization temperature, the polymerization conversion rate, and the like during the production of the rubbery polymer.

The vinyl monomer (b-1) contains an aromatic vinyl compound and a vinyl cyanide compound as essential monomer components, and if necessary, other monomers copolymerizable therewith You may contain a component.
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, vinyltoluene, methyl-α-methylstyrene, brominated styrene, hydroxystyrene, and the like. It can be used alone or in combination of two or more. Of these, styrene and α-methylstyrene are preferred.

Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and the like, and these may be used alone or in combination of two or more. Of these, acrylonitrile is preferred.
The aromatic vinyl compound and the vinyl cyanide compound preferably occupy 30% by mass or more of the entire vinyl monomer (b-1), more preferably 50% by mass or more, and particularly preferably 60% by mass or more. . Further, the use ratio of the aromatic vinyl compound and the vinyl cyanide compound is preferably aromatic vinyl compound / vinyl cyanide compound = 95 to 60% by mass / 5 to 40% by mass when the total of these is 100% by mass. More preferably, it is 90-65 mass% / 10-35 mass%.

  Other monomer components copolymerizable with the above aromatic vinyl compound or vinyl cyanide compound include (meth) acrylic acid ester, maleimide compound, hydroxyl group-containing unsaturated compound, carboxyl group-containing unsaturated compound, acid anhydride Examples thereof include a physical group-containing unsaturated compound, an epoxy group-containing unsaturated compound, and an oxazoline group-containing unsaturated compound, and these can be used alone or in combination of two or more.

Examples of (meth) acrylic acid esters include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. These may be used alone or in combination of two or more. They can be used in combination.
Examples of the maleimide compound include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like. These can be used singly or in combination of two or more. Further, in order to introduce a maleimide unit, a method of (co) polymerizing maleic anhydride and then imidizing may be used.

Examples of the hydroxyl group-containing unsaturated compound include 3-hydroxy-1-propene, 4-hydroxy-1-butene, cis-4-hydroxy-2-butene, trans-4-hydroxy-2-butene, and 3-hydroxy-2. -Methyl-1-propene, 2-hydroxyethyl methacrylate, N- (4-hydroxyphenyl) maleimide and the like can be mentioned, and these can be used alone or in combination of two or more.
Examples of the carboxyl group-containing unsaturated compound include acrylic acid and methacrylic acid, and these can be used alone or in combination of two or more.

Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and these can be used alone or in combination of two or more.
Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether, and these can be used alone or in combination of two or more.
Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline and the like, and these can be used singly or in combination of two or more.

The amount of the other monomer used is preferably 70% by mass or less, more preferably 50% by mass or less, particularly when the total amount of the vinyl monomers (b-1) is 100% by mass. Preferably it is 40 mass% or less.
The rubber-reinforced copolymer resin constituting the rubber-reinforced resin [A] according to the present invention (hereinafter sometimes simply referred to as “copolymer resin”) (A-1) is a single type or a combination of two or more types. Can be used. For example, the copolymer resin (A-1) is a rubber-reinforced resin obtained by polymerizing a vinyl monomer (b-1) in the presence of a rubber polymer (a) composed of a butadiene rubber polymer. It may be a copolymer resin (A-1-a), or a vinyl monomer (b-1) is polymerized in the presence of a rubber polymer (a) made of an acrylic rubber polymer. The rubber-reinforced copolymer resin (A-1-b) obtained in this way may be used. Furthermore, the rubber-reinforced copolymer resin (A-1-a) and the rubber-reinforced copolymer resin (A-1-b) may be used. And a mixture of the rubber-reinforced copolymer resin (A-1-a) or (A-1-b) and another rubber-reinforced copolymer resin. .

  The copolymer resin can be produced by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a polymerization method combining these. Of these, emulsion polymerization is particularly preferred.

When manufacturing by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, etc. are used. These can use a well-known thing.
As polymerization initiators, cumene hydroperoxide, diisopropylbenzene hydroperoxide, potassium persulfate, azobisisobutyronitrile, benzoyl peroxide, lauroyl peroxide, t-butylperoxylaurate, t-butylperoxymono And carbonate.

Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, tetraethyl thiuram sulfide, acrolein, methacrolein, allyl alcohol, 2-ethylhexyl thioglycol and the like.
Emulsifiers include higher alcohol sulfates, alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, higher aliphatic carboxylates, rosinates, phosphates and other anions. Surfactant, and also known nonionic surfactants can be used.

  In the emulsion polymerization, the rubber polymer (a) and the vinyl monomer (b-1) are used in the presence of the total amount of the rubber polymer (a). 1) may be added all at once, and polymerization may be carried out, or polymerization may be carried out by dividing or continuously adding. Further, in the presence of a part of the rubber polymer (a), the vinyl monomer (b-1) is added all at once and polymerized, and the remainder of the rubber polymer (a) is added during the polymerization. Alternatively, the vinyl monomer (b-1) may be divided or continuously added for polymerization, and the remainder of the rubbery polymer (a) may be added during the polymerization.

  After the emulsion polymerization, the obtained latex is usually coagulated with a coagulant, washed with water and dried to obtain a copolymer resin powder. As a coagulant in this case, inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, or acids such as sulfuric acid, hydrochloric acid, acetic acid, and the like can be used. Of these, sulfuric acid is preferred.

  The copolymeric resin (A-1) obtained by polymerizing the vinyl monomer (b-1) in the presence of the rubbery polymer (a) by emulsion polymerization usually contains the above-mentioned vinyl monomer. A copolymer obtained by grafting the monomer (b-1) to the rubber polymer (a) and an ungrafted component in which the vinyl monomer (b-1) is not grafted to the rubber polymer (a) ( That is, the (co) polymer of the said vinylic monomers (b-1) is contained.

When producing a copolymer resin by solution polymerization, the solvent that can be used is an inert polymerization solvent used in ordinary radical polymerization, for example, aromatic hydrocarbons such as ethylbenzene and toluene, methyl ethyl ketone, acetone and the like. Examples thereof include ketones, halogenated hydrocarbons such as dichloromethylene and carbon tetrachloride, acetonitrile, dimethylformamide, N-methylpyrrolidone and the like. The polymerization temperature is preferably 80 to 140 ° C, more preferably 85 to 130 ° C, and particularly preferably 90 to 120 ° C.
In the polymerization, a polymerization initiator may be used, or polymerization may be performed by thermal polymerization without using a polymerization initiator. As the polymerization initiator, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, hydroperoxide and the like are preferably used.
Moreover, when using a chain transfer agent, mercaptans, (alpha) -methylstyrene dimer, etc. can be used, for example.

  Moreover, when manufacturing by block polymerization, the polymerization initiator, chain transfer agent, etc. which were demonstrated in solution polymerization can be used.

  In addition to the copolymer resin (A-1) itself, the rubber-reinforced resin [A] according to the present invention comprises at least one of the copolymer resin (A-1) and a vinyl monomer (co). It may be a mixture with the (co) polymer (A-2) obtained by polymerization. In addition, the said copolymer resin (A-1) shall not contain the component [D] demonstrated below.

The vinyl monomer forming the (co) polymer (A-2) may be a single monomer or two or more monomers exemplified for forming the copolymer resin (A-1). They can be used in combination. Preferred monomers are at least two selected from aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid esters, and maleimide compounds, and more preferably aromatic vinyl compounds and vinyl cyanide compounds are essential. It is what. The maleimide compound may be introduced by a method in which maleic anhydride is polymerized and then imidized.
When the aromatic vinyl compound and the cyanidated vinyl compound are used as the vinyl monomer, the ratio of the total amount of these used to the total vinyl monomer used, the aromatic vinyl compound and the vinyl cyanide compound The use ratio is the same as that in the copolymer resin (A-1).
The (co) polymer (A-2) may be a (co) polymer having a single composition or a blend of two or more (co) polymers having different compositions. .

  Examples of the method for producing the (co) polymer include solution polymerization, bulk polymerization, and suspension polymerization. The solution polymerization and bulk polymerization are the same as described in the copolymer resin.

  After obtaining the copolymer resin (A-1) and / or the (co) polymer (A-2) by the above polymerization methods, the amount of monomer finally remaining in the rubber-reinforced resin [A] is: Preferably it is 10,000 ppm or less, More preferably, it is 5,000 ppm or less.

The content of the rubbery polymer (a) contained in the rubber reinforced resin [A] according to the present invention is 3 to 40% by mass, preferably 5 to 35% by mass, more preferably 5%, based on the whole. -30 mass%. When the content of the rubber polymer (a) is less than 3% by mass, the impact resistance of the molded product is not sufficient, while when it exceeds 40% by mass, the surface appearance is inferior.
In the case where the rubber-reinforced resin [A] is a mixture of a copolymer resin (A-1) and a (co) polymer (A-2), the copolymer generally has a rubbery polymer content of 10 to 80% by mass. Resin (A-1) is used, and the proportion of the copolymer resin (A-1) and (co) polymer (A-2) used is such that the content of the rubber polymer (a) in the mixture is in the above range. Selected to enter.

The graft ratio of the rubber-reinforced resin [A] is preferably 20 to 200% by mass, more preferably 30 to 150% by mass, and particularly preferably 40 to 120% by mass. In addition, a graft ratio (mass%) is calculated | required by following Formula.
Graft ratio (mass%) = {(TS) / S} × 100
In the above formula, T represents 1 g of rubber-reinforced resin [A] in 20 ml of acetone (but acetonitrile when rubbery polymer (a) is an acrylic rubbery polymer) and shaken for 2 hours with a shaker. After that, it is the mass (g) of the insoluble matter obtained by centrifuging for 60 minutes with a centrifuge (rotation speed: 23,000 rpm) and separating the insoluble matter and the soluble matter, and S is a rubber-reinforced resin. [A] The mass (g) of the rubbery polymer contained in 1 g.

  In addition, the intrinsic viscosity [η] of the acetone-soluble component of the rubber-reinforced resin [A] according to the present invention (measured at 30 ° C. using methyl ethyl ketone as a solvent) is preferably 0.2 to 1.2 dl / g, More preferably, it is 0.2-1 dl / g, Most preferably, it is 0.3-0.8 dl / g.

  The number average particle size of the rubber component dispersed in the rubber-reinforced resin [A] according to the present invention is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 1, It is in the range of 500 to 8,000. The average particle diameter can be measured by a known method using electron microscopy.

Examples of the alkyl sulfonate [B] related to the present invention include a general formula (R—SO ₃ ) _n M (wherein R is a linear or branched alkyl group, M is a counter ion such as a metal ion, n Are alkane sulfonates and metal salts thereof. The alkyl group is preferably a linear saturated alkyl group. The average carbon number of the alkyl group is preferably 8 to 23, more preferably 12 to 20, and particularly preferably 12 to 18. The alkyl sulfonate [B] is preferably a metal salt, more preferably an alkali metal salt and an alkaline earth metal salt, particularly preferably a sodium salt, a lithium salt and a potassium salt, and most preferably a sodium salt.

  The addition amount of the alkyl sulfonate [B] is 0.2 to 20 parts by mass with respect to 100 parts by mass of the component [A] of the present invention, preferably 0.2 to 5 parts by mass, more preferably 0.8. 5 to 3 parts by mass. If it is less than 0.2 parts by mass, the resulting molded article has insufficient antistatic properties. If the amount exceeds 20 parts by mass, the surface appearance and impact resistance of the molded product are inferior, which is not preferable.

Examples of the low molecular weight polyolefin [C] having a weight average molecular weight of 500 to 40,000 according to the present invention include low molecular weight polyolefins called so-called polyolefin waxes, and specific examples include polyethylene wax and polypropylene wax. The weight average molecular weight of the component [C] is preferably 1,000 to 20,000, more preferably 2,000 to 8,000, and particularly preferably 4,000 to 7,000. When the molecular weight is within the above range, sufficient mold releasability is obtained when a thin molded article is molded with the composition of the present invention, and sufficient slidability is imparted to the molded article.
The low molecular weight polyolefin is obtained by using a Ziegler catalyst or the like by a low pressure polymerization method, obtained by a high pressure method, or by decomposing the high molecular weight polyolefin obtained by the low pressure polymerization method or the high pressure polymerization method. Also included. In addition, the low molecular weight polyolefin includes a partially oxidized product and a modified product obtained by introducing a functional group, but an unmodified product is generally preferable. The low molecular weight polyolefin includes linear and branched ones, but in general, branched ones are preferred.

  Component [C] is added in an amount of 0.1 to 10 parts by weight, preferably 0.1 to 5 parts by weight, more preferably 0.5 to 4 parts by weight per 100 parts by weight of component [A] of the present invention. It is a mass part, Most preferably, it is 0.5-3 mass part, Most preferably, it is 1-2 mass part. If it is less than 0.1 part by mass, the resulting molded article has insufficient antistatic properties and slidability. If it exceeds 10 parts by mass, the impact resistance is inferior, and defective peeling occurs near the surface of the molded product, which is not preferable.

Component [D] related to the present invention is a combined product of an olefin polymer (d) and a (co) polymer of a vinyl monomer (b-2) containing an aromatic vinyl compound.
As the olefin polymer (d), for example, one selected from the group consisting of the following components (d-1), (d-2) and (d-3) can be used.
(D-1); an olefin resin,
(D-2); ethylene-α-olefin rubbery polymer,
(D-3); Hydrogenated product of diene polymer.

  Examples of the olefin resin (d-1) include polyethylene and polypropylene. The olefin resin (d-1) preferably has a crystallinity at room temperature by X-ray diffraction, more preferably has a crystallinity of 20% or higher and a melting point of 40 ° C. or higher. The olefin resin (d-1) needs to have a molecular weight sufficient as a molding resin at room temperature. For example, the melt flow rate measured in accordance with JIS K-6758 is preferably 0.01. It has a molecular weight corresponding to ˜500 g / 10 min, more preferably 0.05 to 100 g / 10 min. The olefin resin (d-1) may be modified with an acid anhydride, a carboxyl group, or the like.

The ethylene-α-olefin-based rubbery polymer (d-2) is mainly composed of an ethylene-α-olefin-based rubbery polymer, but may contain other rubbery polymers as necessary. Good.
Examples of the ethylene-α-olefin rubbery polymer include ethylene-α-olefin copolymer rubber and ethylene-α-olefin-nonconjugated diene copolymer rubber.
Specific examples of the ethylene-α-olefin rubbery polymer include, for example, ethylene / α-olefin having 3 to 20 carbon atoms / non-conjugated diene = 5 to 95/95 to 5/0 to 30% by weight (the three components) Examples thereof include copolymer rubber obtained by copolymerizing monomers having a mixing ratio of 100% by weight in total. Examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-heptene, 1-octene, 1-decene, 1 -Dodecene and the like. Preferred are propylene, 1-butene and 1-octene, and more preferred are propylene and 1-butene. These α-olefins can be used alone or in combination of two or more. The α-olefin has 3 to 20 carbon atoms, preferably 3 to 12, and more preferably 3 to 8. When there are too many carbon atoms, copolymerizability will fall extremely. The ratio of ethylene to α-olefin (ethylene / α-olefin) is preferably 5 to 95/95 to 5, more preferably 40 to 90/60 to 10, particularly preferably 50 to 90/50 to 10, Most preferably, it is 50-85 / 50-15.

  Non-conjugated dienes that may be used in combination include alkenyl norbornenes, cyclic dienes, aliphatic dienes, and the like, preferably dicyclopentadiene and 5-ethylidene-2-norbornene. These non-conjugated dienes can be used alone or in combination of two or more. The content of non-conjugated diene in the ethylene-α-olefin rubbery polymer is 0 to 30% by weight, preferably 0 to 15% by weight. The unsaturated amount of this copolymer rubber is preferably in the range of 0 to 40 in terms of iodine value. If the amount of unsaturation is too large, the weather resistance (light) and hue become incompatible.

  In order to obtain these ethylene-α-olefin rubbery polymers, either homogeneous or heterogeneous catalysts may be used. Examples of the homogeneous catalyst include a metallocene catalyst. Examples of the heterogeneous catalyst include a vanadium catalyst in which a vanadium compound and an organoaluminum compound are combined.

The Mooney viscosity (ML _{1 + 4} , 100 ° C.) of the ethylene-α-olefin rubbery polymer is preferably 60 or less, more preferably 50 or less, and particularly preferably 5 to 40. The glass transition temperature of the ethylene-α-olefin rubber polymer is preferably −110 to −40 ° C., more preferably −70 to −45 ° C.

  Examples of the hydrogenated product of a diene polymer (d-3) include a hydrogenated product of a polymer of a conjugated diene (d-3-1), a conjugated diene and a vinyl monomer (for example, styrene, acrylonitrile, etc.) Block having a random copolymer hydrogenated product (d-3-2), a polymer block (PST-1) mainly composed of an aromatic vinyl compound, and a polymer block (PBD-2) mainly composed of a conjugated diene compound Examples include a hydrogenated copolymer (d-3-3). A preferable hydrogenated product (d-3) of the diene polymer is the component (d-3-3).

  As the aromatic vinyl compound used in the polymer block (PST-1) of the above component (d-3-3), any of those shown in [A] component can be used, but preferably styrene and α-methyl. Styrene, particularly preferably styrene. Examples of the conjugated diene compound used in the polymer block (PBD-2) include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and preferably Butadiene and isoprene. These can be used individually by 1 type or in combination of 2 or more types. Furthermore, the polymer block (PBD-2) may be a block in which two or more conjugated diene compounds are used and bonded in any form of random, block, and tapered blocks. In addition, the polymer block (PBD-2) may contain 1 to 10 taper blocks in which the aromatic vinyl compound gradually increases, and conjugated dienes having different vinyl bond contents derived from the conjugated diene compound. A polymer block or the like may be appropriately copolymerized.

A preferred structure of the component (d-3-3) is a hydrogenated product of a polymer represented by the following formulas (1) to (3).
(AB) _Y (1)
(AB) _Y- X (2)
A- (B-A) _Z (3)
(In the structural formulas (1) to (3), A is a polymer block mainly composed of an aromatic vinyl compound. If the polymer block is substantially composed of an aromatic vinyl compound, a part of the conjugated diene compound is A is a polymer block containing preferably 90% by mass or more, more preferably 99% by mass or more of an aromatic vinyl compound, and B is a homopolymer or aromatic of a conjugated diene compound. A copolymer of another monomer such as a vinyl compound and a conjugated diene compound, X is a residue of a coupling agent, Y represents an integer of 1 to 5, and Z represents an integer of 1 to 5. Represents.)

In the component (d-3), the use ratio of the aromatic vinyl compound and the conjugated diene compound is preferably within the range of aromatic vinyl compound / conjugated diene compound = 10 to 70/90 to 30% by mass, and 15 to 65/85. The range of -35 mass% is still more preferable, and the range of 20-60 / 80-40 mass% is especially preferable.
The block copolymer comprising an aromatic vinyl compound and a conjugated diene compound is known in the technical field of anionic polymerization, and includes, for example, Japanese Patent Publication No. 47-28915, Japanese Patent Publication No. 47-3252, Japanese Patent Publication No. 48-. No. 2423, Japanese Patent Publication No. 48-20038, and the like. A method for producing a polymer block having a tapered block is disclosed in JP-A-60-81217.
The vinyl bond (1,2- and 3,4-bond) content derived from the conjugated diene compound of component (d-3) is preferably 5 to 80%, more preferably 5 to 75%, and particularly preferably 5 It is in the range of ˜70%, and if it is in this range, the antistatic property imparting effect is more excellent, which is preferable. The number average molecular weight of the component (d-3) is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and particularly preferably 20,000 to 200,000. Among these, the number average molecular weight of the A part represented by the above formulas (1) to (3) is preferably in the range of 3,000 to 150,000, and the number average molecular weight of the B part is 5,000 to 200,000. A range of 000 is preferred.
Adjustment of the vinyl bond content of the conjugated diene compound is possible by adjusting amines such as N, N, N ′, N′-tetramethylethylenediamine, trimethylamine, triethylamine, diazocyclo (2,2,2) octane, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethylene. It can be carried out using ethers such as butyl ether, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, alkoxides of potassium and sodium, and the like.

The component (d-3) may be obtained by obtaining a polymer by the above method and then extending or branching a polymer molecular chain via a coupling agent residue using a coupling agent. . The coupling agents used here include diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2-dibromo. Examples include ethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate, and the like.
The component (d-3) is obtained by partially or completely hydrogenating a carbon-carbon double bond of a conjugated diene moiety such as the block copolymer. The hydrogenation rate is preferably 30 to 100%, more preferably 50 to 100%. If the hydrogenation rate is low, the effect of imparting antistatic properties tends to be poor.
The hydrogenation reaction of the block copolymer or the like can be performed by a known method, and the adjustment of the hydrogenation rate can also be performed by a known method. Specific methods include JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-63-5401, JP-A-2-133406, JP-A-1 There is a method disclosed in Japanese Patent No. -297413.

  The amount of the olefin polymer (d) used is preferably 10 to 90% by mass, more preferably 20 to 80% by mass in 100% by mass of the component [D].

  The vinyl monomer (b-2) used in component [D] contains an aromatic vinyl compound as an essential component, and, if necessary, other monomer that can be copolymerized with the aromatic vinyl compound. It may contain a body. Other monomers copolymerizable with the aromatic vinyl compound include vinyl cyanide compounds, (meth) acrylic acid esters, maleimide compounds, functional group-containing unsaturated compounds (for example, hydroxyl group-containing unsaturated compounds, carboxyl groups). -Containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, epoxy group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, etc.), etc., each of which is a single type or a combination of two or more types Can be used

  The above aromatic vinyl compound, vinyl cyanide compound, (meth) acrylic acid ester, maleimide compound, hydroxyl group-containing unsaturated compound, carboxyl group-containing unsaturated compound, acid anhydride group-containing unsaturated compound, epoxy group-containing unsaturated compound Examples of the unsaturated compound containing an oxazoline group include the respective compounds shown in the component [A] and preferred compounds.

The amount of the aromatic vinyl compound used in Component [D] is preferably 5% by mass or more, more preferably 10% by mass or more, in 100% by mass of the vinyl monomer (b-2).
When a vinyl cyanide compound is used as the component [D], the amount used thereof is preferably 3 to 60% by mass, more preferably 5 to 50% by mass in 100% by mass of the vinyl monomer (b-2). It is.
When (meth) acrylic acid ester is used in Component [D], the amount used is preferably 3 to 95% by mass, more preferably 5 to 85% in 100% by mass of the vinyl monomer (b-2). % By mass.
When a maleimide compound is used as component [D], the amount used is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, in 100% by mass of the vinyl monomer (b-2). .
When a functional group-containing unsaturated compound is used as the component [D], the amount used is 100% by mass of the vinyl monomer (b-2), preferably 0.05 to 30% by mass, more preferably 0. .1 to 20% by mass.
If the amount of the compound used is less than the above range, the positive effect of the compound cannot be obtained. On the other hand, if it exceeds the above range, the negative effect becomes remarkable, which is not preferable in any case.
A preferred combination of the vinyl monomer (b-2) is an aromatic vinyl compound, and one or two single monomers selected from the group consisting of a vinyl cyanide compound, a (meth) acrylic acid ester and a maleimide compound. It is a combination with the body.
The amount of the vinyl monomer (b-2) used is preferably 10 to 90% by mass and more preferably 20 to 80% by mass in 100% by mass of the component [D].

Examples of the component [D] include the following graft copolymer (D1) and addition copolymer (D2).
(D1): a so-called graft copolymer obtained by polymerizing the vinyl monomer (b-2) in the presence of the olefin polymer (d).
(D2): a so-called addition copolymer obtained by combining an olefin polymer (d) and a (co) polymer of a vinyl monomer (b-2).

The graft copolymer (D1) can be obtained by polymerization by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a combination of these using a radical catalyst. Of these, bulk polymerization and solution polymerization are preferable. In addition, the description regarding the manufacturing method of said component [A] is applicable as it is to manufacture of a graft copolymer (D1).
In the graft copolymer (D1), as the olefin polymer (d), the ethylene-α-olefin rubbery polymer (d-2) and / or the hydrogenated product of the diene polymer (d- 3) is preferably used, and in this case, the graft copolymer (D1) is a so-called rubber-reinforced resin. The number average particle diameter of the rubber component dispersed in the rubber-reinforced resin by a known measurement method using an electron microscope is preferably 500 to 100,000, more preferably 1,000 to 50,000, and particularly preferably 1. , 500 Å to 50,000 範 囲. The content of the component (d-2) and the component (d-3) contained in the rubber-reinforced resin is preferably 3 to 40% by mass, more preferably 5 to 35% by mass, particularly with respect to the whole. Preferably it is 5-30 mass%. If the content is less than 3% by mass, the antistatic property and the sliding property are inferior, and a peeling failure phenomenon occurs. On the other hand, when it exceeds 40 mass%, surface appearance property is inferior.

The addition copolymer (D2) is an olefin polymer (d) obtained by copolymerizing a functional group-containing unsaturated compound and a vinyl monomer (b-2) containing a functional group-containing unsaturated compound as a copolymerization component. For example, a polymer reaction by a method such as heat-melt kneading. Here, the usage-amount of a functional group containing unsaturated compound becomes like this with respect to 100 mass parts of olefin polymer (d) or a vinyl-type monomer (b-2), Preferably 0.01-20 mass parts, Furthermore, Preferably, it is 0.1-10 mass parts.
In the addition copolymer (D2), the olefin resin (d-1) is preferably used as the olefin polymer (d).

The graft copolymer (D1) may be composed only of a graft polymer obtained by grafting a polymer of a vinyl monomer (b-2) to the olefin polymer (d), or the graft polymer. And a polymer of a vinyl monomer (b-2) not grafted to the olefin polymer (d) (that is, an ungrafted polymer), usually in the form of the latter mixture It is.
The graft ratio of the graft copolymer (D1) is determined by the same method as described above for the component [A], preferably 20 to 200% by mass, more preferably 30 to 150% by mass, and particularly preferably 40 to 120%. % By mass.
Further, the intrinsic viscosity [η] of the acetone-soluble component of the graft copolymer (D1) (measured at 30 ° C. using methyl ethyl ketone as a solvent) is preferably 0.2 to 1.2 dl / g, more preferably It is 0.2-1 dl / g, Most preferably, it is 0.3-0.8 dl / g.
In the graft copolymer (D1), the olefin polymer (d) may be composed of any one of the component (d-1), the component (d-2), and the component (d-3). Or, two or more may be mixed. The graft copolymer (D1) may be a mixture of two or more graft copolymers having different structures.

The addition copolymer (D2) may be composed only of an addition polymer obtained by adding a polymer of a vinyl monomer (b-2) to the olefin polymer (d), or the addition polymer. And a polymer of the vinyl monomer (b-2) not added to the olefin polymer (d) (that is, a non-added polymer), usually in the form of the latter mixture It is. The addition rate of the polymer of the vinyl monomer (b-2) in the addition copolymer (D2) is preferably 20 to 200% by mass, more preferably 30 to 150% by mass, and particularly preferably 30 to 120% by mass. %. The intrinsic viscosity [η] (measured at 30 ° C. using methyl ethyl ketone as a solvent) of the soluble component obtained by the addition rate measurement is preferably 0.2 to 1.2 dl / g, more preferably 0.2. ˜1 dl / g, particularly preferably 0.3 to 0.8 dl / g The addition rate is a polymer of vinyl monomer (b-2) in place of acetone in the above graft ratio measurement method. However, the addition copolymer can be measured by using a solvent that does not dissolve.
In the addition copolymer (D2), the olefin polymer (d) may be composed of any one of the component (d-1), the component (d-2), and the component (d-3). Or, two or more may be mixed. Further, the addition copolymer (D2) may be a mixture of two or more types of addition copolymers having different structures.

  After obtaining said component [D] by said each polymerization method, the monomer quantity finally remained in this component [D] becomes like this. Preferably it is 10,000 ppm or less, More preferably, it is 5,000 ppm or less.

The addition amount of the component [D] of the present invention is 0.1 to 20 parts by mass, preferably 1 to 20 parts by mass, more preferably 2 to 15 parts by mass with respect to 100 parts by mass of the component [A] of the present invention. Part, particularly preferably 2 to 10 parts by mass, most preferably 3 to 8 parts by mass. If it is less than 0.1 part by mass, the antistatic property and the sliding property of the obtained molded product are not sufficiently improved. If it exceeds 20 parts by mass, the mechanical strength, surface hardness and the like are lowered, which is not preferable.
As the component [D], it is preferable to use a component rich in the same olefin component as that of the component [C]. For example, when polyethylene wax is used as the component [C], an ethylene-rich polymer is used as the olefin polymer (d) of the component [D], and when polypropylene wax is used as the component [C], the component [C] It is preferable to use a propylene-rich polymer as the olefin polymer (d) of D].
Moreover, it is preferable that each addition amount of component [C] and component [D] shall be 0.5 to 5 times the addition amount of component [B]. By using these components in this ratio, it is considered that the component [B] having antistatic performance is likely to appear on the surface of the molded product due to the channel effect of the components [C] and [D].

  The aromatic polycarbonate resin [E] according to the present invention is not particularly limited, and examples thereof include those obtained by interfacial polycondensation between various hydroxyaryl compounds and phosgene, or dihydroxyaryl compounds and carbonate compounds such as diphenyl carbonate. What was obtained by well-known polymerization methods, such as what is obtained by transesterification (melt polycondensation), can be used.

  Examples of the dihydroxyaryl compound used as a raw material for the aromatic polycarbonate resin include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane, 2 , 2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) octane, bis (4-hydroxyphenyl) phenylmethane, 2,2-bis (4-hydroxy-3-methylphenyl) Propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3, 5-dichlorophenyl) propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4 Hydroxyphenyl) cyclohexane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethyl Phenyl sulfide, 4,4'-dihydroxyphenyl sulfide, 4,4'-dihydroxy-3,3'-dimethylphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 4,4'-dihydroxy-3,3'-dimethyl Examples thereof include phenyl sulfoxide, 4,4′-dihydroxyphenyl sulfone, 4,4′-dihydroxy-3,3′-dimethyldiphenyl sulfone, hydroquinone, resorcin and the like. Of these, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) is preferred. Moreover, these can be used individually by 1 type or in combination of 2 or more types. Furthermore, as a component [E] in connection with this invention, it can be used individually by 1 type or in combination of 2 or more types.

The viscosity average molecular weight of the aromatic polycarbonate resin [E] according to the present invention is preferably 13,000 to 32,000, more preferably 17,000 to 31,000, and particularly preferably 18,000 to 30,000. . If the viscosity average molecular weight is less than 13,000, the impact resistance of the molded product tends to be reduced, whereas if the viscosity average molecular weight exceeds 31,000, the moldability tends to be inferior.
When using 2 or more types of aromatic polycarbonate resin from which a viscosity average molecular weight differs, the viscosity average molecular weight at the time of mixing should just be in the said range. When two types of aromatic polycarbonate resins having different viscosity average molecular weights are used, those having a viscosity average molecular weight in the range of 13,000 to 19,000 (E1) and in the range of 20,000 to 32,000 (E2) (E1) / (E2) = 10-50% by mass / 90-50% by mass (however, the total of these is 100% by mass), the balance between impact resistance and fluidity An excellent molded product can be obtained. The above (E1) and (E2) may be the same aromatic polycarbonate resin or different ones.

The viscosity average molecular weight can be calculated by the following formula using the specific viscosity (η _sp ) measured at 20 ° C. and a concentration [0.7 g / 100 ml (methylene chloride)] using methylene chloride as a solvent.
Viscosity average molecular weight = ([η] × 8130) ^1.205
(In the formula, [η] = [(η _sp × 1.12 + 1) ^1/2 −1] /0.56C, where C is the concentration of the polymer solution (g / 100 ml).)

  When the aromatic polycarbonate resin [E] according to the present invention is obtained by interfacial polycondensation, it may contain various chlorine compounds. Since this chlorine compound may adversely affect the thermal stability of the thermoplastic resin composition of the present invention, the chlorine compound content of the aromatic polycarbonate resin is preferably 300 ppm or less in terms of chlorine content, 100 ppm The following is more preferable.

  The addition amount of the aromatic polycarbonate resin [E] is 1 to 30 parts by mass, preferably 5 to 25 parts by mass with respect to 100 parts by mass of the component [A] of the present invention. If it is less than 1 part by mass, the heat resistance of the obtained molded product is not sufficient, and if it exceeds 30 parts by mass, the antistatic property and slidability of the obtained molded product are not sufficiently improved.

In the present invention, the thermoplastic resin composition containing the flame retardant [F] can provide a molded product excellent not only in antistatic property and sliding property but also in flame retardancy.
Although it does not specifically limit as said flame retardant [F], Inorganic flame retardants, such as magnesium hydroxide, an alumina, a calcium borate, a low melting glass, inorganic phosphorus, such as red phosphorus, an organic halogen flame retardant, an organic phosphorus flame retardant And organic flame retardants such as silicone compounds, organometallic compounds, and hindered amine flame retardants. These can be used singly or in combination of two or more.
Moreover, among these, as an example used in combination, a combination of an organic halogen flame retardant and one or more selected from antimony oxide, zinc borate, zinc stannate, iron oxide, etc., an organic phosphorus flame retardant and A combination with a silicone compound, a combination of an organopolysiloxane and an organometallic compound, or the like.

  As the organic halogen-based flame retardant, a compound containing bromine and / or chlorine is preferable, and a halogenated bisphenol compound, a halogenated bisphenol compound and an epihalohydrin, or a halogenated bisphenol compound and a halogenated bisphenol diester. Particularly preferred are halogenated epoxy compounds and halogenated triazine compounds which are reaction products with glycidyl ether.

Examples of the halogenated bisphenol compound include tetrabromobisphenol A, dibromobisphenol A, tetrachlorobisphenol A, dichlorobisphenol A, tetrabromobisphenol F, dibromobisphenol F, tetrachlorobisphenol F, dichlorobisphenol F, tetrabromobisphenol S, dibromo. Bisphenol S, tetrachlorobisphenol S, dichlorobisphenol S, etc. are mentioned. These can be used singly or in combination of two or more.
As said halogenated epoxy compound, what has a structure shown by following General formula (1) is mentioned.

[In the formula, R ¹ represents an isopropylidene group, a methylene group or a sulfone group; R ² and R ³ represent a 2,3-epoxypropyl group or a —CH ₂ CH (OH) CH ₂ OR group (R represents bromine or X is bromine or chlorine, a, b, c and d are integers of 1 to 4, and n is an integer of 0 or more. . ]

  N of the compound represented by the general formula (1) is preferably 15 or less. Moreover, the terminal of the said compound may be an epoxy group, and the epoxy group may be sealed with an allyl group or an alkyl group. The allyl group or alkyl group that seals the end may be modified with a halogen atom such as chlorine or bromine, if necessary. Specific examples of the end-capping group include unsubstituted allyl groups such as phenyl group and naphthyl group, allyl halide groups such as tribromophenyl group, pentabromophenyl group, trichlorophenyl group and pentachlorophenyl group, and stearyl groups. An alkyl group is mentioned. Moreover, the terminal may be the same in one and the other, or may be different. These can be used individually by 1 type or in combination of 2 or more types.

  The halogenated triazine compound is not particularly limited as long as it is a compound having a triazine skeleton, and examples thereof include those having a structure represented by the following general formula (2).

(In the formula, R ⁴ represents a brominated or chlorinated allyl group and / or alkyl group or a hydrogen atom, and Y represents an —O— group or an —NH— group.)

  Such a compound is generally obtained by reacting a triazine skeleton-containing compound such as cyanuric acid or melamine with a hydroxyl group-containing compound such as brominated or chlorinated phenols or alcohols or an amine compound. These can be used individually by 1 type or in combination of 2 or more types.

Moreover, as said organophosphorus flame retardant, a phosphate compound and a phosphazene compound are preferable because the flame retardancy of a molded product can be increased.
As said phosphate compound, what has the structure shown by the following general formula (3) and (4) is mentioned, for example.

(Wherein R ⁵ , R ⁶ , R ⁷ and R ⁸ are an alkyl group, a phenyl group or a xylyl group, and may be the same or different. X is a divalent resorcinol residue. Group, hydroquinone residue or bisphenol A residue, n is 0 to 5 on average.)

(Wherein R ⁹ and R ¹⁰ are a hydrogen atom, a halogen atom or a lower alkyl group, and R ¹¹ is a hydrogen atom, a phenyl group or a group represented by the following formula:

The phenyl group may be substituted with at least one selected from a halogen atom, a hydroxyl group or a lower alkyl group. y and z are integers of 1 to 4, and may be the same or different. R ⁹ and R ¹⁰ may be the same or different. )

  Examples of the flame retardant represented by the general formula (4) include compounds represented by the following formulas (5) to (8).

Of the compounds shown above, those represented by formulas (5) and (6) are preferred.
Examples of the phosphazene compound include compounds having phosphorus and nitrogen as constituent elements and a double bond, and having a propoxyl group, an amino group, or the like bonded to a phosphorus atom. The specific structure is shown by the following general formulas (9) and (10).

(Wherein R ^{12 to} R ²⁰ are an alkyl group, an allyl group, an alkoxyl group, an allyloxyl group, an amino group or a hydroxyl group, and may be the same or different. N ′ is 0. It is an integer of ˜15, preferably 1 to 10. Further, the functional group is further substituted with at least one selected from an alkyl group, an allyl group, an alkoxyl group, an allyloxyl group, an amino group and a hydroxyl group. May be.)

(Wherein R ^{21 to} R ²⁶ are an alkyl group, an allyl group, an alkoxyl group, an allyloxyl group, an amino group, or a hydroxyl group, and may be the same or different. N ″ is 0. It is an integer of ˜15, preferably 1 to 10. Further, the functional group is further substituted with at least one selected from an alkyl group, an allyl group, an alkoxyl group, an allyloxyl group, an amino group and a hydroxyl group. May be.)

  Examples of the phosphazene compound include propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene, fluoroalkylphosphazene and the like. Of these, phenoxyphosphazene is preferred.

  The addition amount of the flame retardant [F] is 1 to 30 parts by mass, preferably 3 to 25 parts by mass, and more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the component [A] of the present invention. is there. If it is less than 1 part by mass, the flame retardancy of the obtained molded product is not sufficient, and if it exceeds 30 parts by mass, the antistatic property and the slidability of the obtained molded product are not sufficiently improved.

When the flame retardant as described above is used in the thermoplastic resin composition of the present invention, a flame retardant aid may be further blended. Examples of the flame retardant aid include antimony compounds such as antimony trioxide, antimony tetroxide, and antimony pentoxide, zinc borate, zinc stannate, iron oxide, polytetrafluoroethylene (PTFE), and the like. When using a halogen flame retardant, the flame retardant aid is preferably an antimony compound, and when using a phosphorus flame retardant, PTFE is preferred.
The PTFE has an effect of preventing dripping (melted liquid dripping) during combustion and achieving a higher combustion level. The weight average molecular weight of PTFE is usually 500,000 or more, preferably 1 million or more. The average particle size of PTFE at the time of kneading with other polymer components is usually 90 to 600 μm, preferably 100 to 500 μm, more preferably 120 to 400 μm. After being kneaded with other polymer components, etc., PTFE is dispersed as a granular material having an average particle diameter of 0.1 to 100 μm or a finer fibrous material. The specific gravity of PTFE is usually 1.5 to 2.5, preferably 2.1 to 2.3. Moreover, a bulk density is 0.5-1 g / ml normally, Preferably it is 0.6-0.9 g / ml. As PTFE, a dispersion type PTFE dispersed in a medium such as water together with a lubricant can also be used.

  Although the compounding quantity of the said flame retardant adjuvant is based on the kind of flame retardant, it is 0.1-50 mass parts normally with respect to 100 mass parts of flame retardants, Preferably it is 1-40 mass parts.

  The thermoplastic resin composition of the present invention further includes, as other polymer components, polyamide resin, polyamide elastomer, polyester elastomer, polyethylene, polypropylene, polyphenylene ether, POM, phenol resin, epoxy resin, LCP, PPS, HIPS, Polystyrene, thermoplastic polyurethane, or the like can be appropriately blended.

Various additives can be blended in the thermoplastic resin composition of the present invention depending on the purpose and application. Examples of additives include fillers, weathering (light) agents, antistatic agents, antioxidants, lubricants, plasticizers, colorants, antibacterial agents, silicone oils, coupling agents and the like.
The blending method of each component [A] to [D] of the present invention is not particularly limited. In particular, when the component (A-2) is used, the component (A-2) may be blended with the component (A-1) in advance, or may be blended with the component (D) in advance. May be.

The thermoplastic resin composition of the present invention can be produced by kneading each component with various extruders, Banbury mixers, kneaders, rolls, feeder ruders, and the like. A preferred production method is a method using an extruder or a Banbury mixer.
Furthermore, when kneading each component, these components may be kneaded together. You may knead | mix and knead | mix and divide multistage with an extruder and a Banbury mixer.
In addition, after knead | mixing with a Banbury mixer, a kneader, etc., it can also pelletize with an extruder.

  With the thermoplastic resin composition of the present invention, a molded product can be obtained by a known molding method such as injection molding, press molding, sheet extrusion molding, vacuum molding, profile extrusion molding, foam molding or the like. Various molded articles obtained by the above molding method can be used for various housings of household electrical appliances, various parts and housings in the electric / electronic field or automobile field, miscellaneous goods, and the like by utilizing their excellent properties.

  EXAMPLES Hereinafter, although an example is given and this invention is demonstrated concretely, this invention is not restrict | limited at all by the following examples. In Examples, parts and% are based on mass unless otherwise specified.

1. Evaluation Methods Various evaluation methods used in this example are as follows.
(1) Average particle diameter of rubbery polymer The average particle diameter of the rubbery polymer particles used for forming the rubber-reinforced resin [A] was measured by dispersing light particles in the latex by a light scattering method. As a measuring instrument, “LPA-3100 type” (trade name) manufactured by Otsuka Electronics Co., Ltd. was used, and the cumulant method was used by integrating 70 times. In addition, it confirmed with the electron microscope that the particle size of the dispersed particle in rubber-reinforced resin [A] was substantially the same as the latex particle size.

(2) Graft ratio of rubber-reinforced resins [A] and [D]
(3) Intrinsic viscosity [η] of acetone-soluble components of rubber-reinforced resins [A] and [D]
Shown above.
(5) Viscosity average molecular weight of polycarbonate resin [E]

(6) Antistatic property After forming a disk with a diameter of 100 mm and a thickness of 2 mm and adjusting the condition for 7 days at 23 ° C. × 50% relative humidity, a 4329A type super insulation resistance meter manufactured by Yokogawa Hewlett-Packard Company was used. Used to measure the surface resistivity.

(7) Sliding property (dynamic friction coefficient)
A Suzuki type sliding tester (ring-on-ring type) was used, and steel (S45C) was used as the mating material. The test piece was a hollow cylindrical press-molded product having an outer diameter of 25.4 mm and an inner diameter of 20.0 mm, and the counterpart material was also of the same shape. The dynamic friction coefficient was measured under the conditions of a load of 0.5 kgf, a peripheral speed of 500 mm / second, and a travel distance of 10 km in an atmosphere of room temperature 23 ° C. and humidity 50% RH. The dynamic friction coefficient was calculated by the following equation.
μ = [3 × F × R × (r ₂ ² −r ₁ ² )] / [P × (r ₂ ³ −r ₁ ³ )] (3)
(Wherein μ represents a dynamic friction coefficient, F represents a force applied to the load cell, P represents a load, R represents an arm length to the load cell, r ₁ represents an inner diameter, and r ₂ represents an outer diameter.)

(8) Flame retardancy of molded article A vertical combustion test was performed on a test piece having a length of 5 ″, a width of 13 mm, and a thickness of 1/16 ″ by a method defined in the UL94 standard.
(9) Formability The surface of the injection-molded test piece was visually observed and judged according to the following criteria.
○: No peeling and uniform appearance,
X: Peeling or weld is seen or pearly luster is exhibited.
(10) Impact resistance Measured according to ASTM D256 (1/4 inch, with notch), and judged according to the following criteria.
○: 7 KJ / m ² or more,
X: Less than 7 KJ / m ² .

2. Component [A] (rubber reinforced resin)
Production Example 1 (Preparation of rubber-reinforced copolymer resin A-1-a)
In a 7-liter glass flask equipped with a stirrer, 75 parts of ion-exchanged water, 0.5 part of potassium rosinate, 0.1 part of t-dodecyl mercaptan, polybutadiene latex (average particle size: 3500 kg) in a nitrogen stream Gel content: 85%) 40 parts (solid content), 15 parts of polystyrene, and 5 parts of acrylonitrile were added, and the temperature was raised with stirring. When the internal temperature reached 45 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose were dissolved in 20 parts of ion-exchanged water was added. . Thereafter, 0.07 part of cumene hydroperoxide was added to initiate polymerization. After 1 hour of polymerization, 50 parts of ion exchange water, 0.7 part of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, t- 0.05 part of dodecyl mercaptan and 0.01 part of cumene hydroperoxide were continuously added over 3 hours, and further polymerized for 1 hour to obtain 2,2′-methylene-bis (4-ethylene-6-t -Butylphenol) 0.2 part was added to complete the polymerization. The latex of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and then dried to obtain rubber-reinforced resin A-1-a. The graft ratio of this rubber-reinforced copolymer resin A-1-a was 72%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.47 dl / g.
Production Example 2 (Preparation of rubber-reinforced copolymer resin A-1-b)
Acrylic rubbery polymer latex obtained by emulsion polymerization of 99 parts of n-butyl acrylate and 1 part of allyl methacrylate (average particle size: 1200 kg, gel content of 85%) 50 parts (in terms of solid content), 200 parts of water (Total amount), 1 part of sodium dodecylbenzenesulfonate was charged into the reactor, and the temperature was raised to 60 ° C. in a nitrogen stream while stirring. When the temperature reached 60 ° C., an aqueous solution in which 0.2 parts of sodium formaldehyde sulfoxylate was dissolved was charged into the reactor, and immediately thereafter, 38 parts of styrene, 12 parts of acrylonitrile, and 0.6 parts of t-butyl hydroperoxide were mixed. The solution was continuously added over 3 hours and polymerized to obtain a latex of rubber-reinforced copolymer resin A-1-b. The polymerization conversion rate at this time was 96%. This rubber-reinforced copolymer resin A-1-b latex was coagulated with calcium chloride, then washed and dried to obtain a powdery rubber-reinforced copolymer resin A-1-b. The graft rate was 55%.

Production Example 3 (Preparation of copolymer A-2)
Two jacketed polymerization reactors equipped with a ribbon wing with an internal volume of 30 liters were connected and purged with nitrogen, and then 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene were continuously added to the first reaction vessel. . A solution of 0.1 part of t-dodecyl mercaptan and 5 parts of toluene as a molecular weight regulator and a solution of 0.1 part of 1,1′-azobis (cyclohexane-1-carbonitrile) and 5 parts of toluene as a polymerization initiator Supplied. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion was 60%. The obtained polymer solution was continuously removed from the first reaction vessel by the same amount as the styrene, acrylonitrile, toluene, molecular weight regulator, and polymerization initiator supplied by the pump. Supplied to the eye reaction vessel. The polymerization temperature of the second reaction vessel was 130 ° C., the average residence time was 2.0 hours, and the polymerization conversion was 80%. The copolymer solution obtained in the second reaction vessel was directly devolatilized from the unreacted monomer and solvent using a twin-screw, three-stage vented extruder to obtain copolymer A-2. The intrinsic viscosity [η] of the acetone-soluble component was 0.48 dl / g.

Production Example 4 (Preparation of rubber-reinforced resin [A])
The rubber-reinforced copolymer resins (A-1-a) and (A-1-b) and the copolymer (A-2) were mixed at a ratio shown in Table 1 to obtain a rubber-reinforced resin [A].

3. Component [B] (Antistatic agent)
B-1: Alkyl sulfonic acid salt A linear saturated alkyl sulfonic acid sodium salt salt having an average carbon number of 14 (trade name “Electrostopper PC-3”, manufactured by Kao Corporation) was used.
B-2: Stearic acid monoglyceride Trade name “Riquemar S-100” manufactured by Riken Vitamin Co., Ltd. was used.

4). Component [C] (low molecular weight polyolefin)
C-1: Unmodified polyethylene wax having a molecular weight of 6,000 (trade name “Sunwax 171-P”, manufactured by Sanyo Chemical Industries, Ltd.) was used.
C-2: A polyolefin wax having a molecular weight of 900 (trade name “Mitsui High Wax 100P”, manufactured by Mitsui Petrochemical Co., Ltd.) was used.
C-3: High molecular weight polyethylene (trade name “Novatech LJ803”, manufactured by Nippon Polyethylene Co., Ltd.) having a melt flow rate (MFR) of 22 g / 10 min was used.
C-4: Polypropylene wax having a molecular weight of 15,000 (trade name “Biscol 550-P”, manufactured by Sanyo Chemical Industries, Ltd.) was used.

5). Component [D] (modified olefin polymer)
5-1. D-1 (AES resin)
A 20-liter stainless steel autoclave equipped with a ribbon-type stirrer blade, auxiliary agent addition device, thermometer, etc. is added to an ethylene / propylene rubber polymer (ethylene / propylene = 78/22 (%), Mooney viscosity (ML). _{1 + 4} , 100 ° C.) 20 ethylene-propylene copolymer) 20 parts, 56 parts of styrene, 24 parts of acrylonitrile, 110 parts of toluene, the internal temperature is raised to 75 ° C., and the contents of the autoclave are kept for 1 hour. Stir to a homogeneous solution. Thereafter, 0.45 part of t-butylperoxyisopropyl carbonate was added, the internal temperature was further raised, and after reaching 100 ° C., the polymerization reaction was carried out at a stirring speed of 100 rpm while maintaining this temperature. . From 4 hours after the start of the polymerization reaction, the internal temperature was raised to 120 ° C., and the reaction was further continued for 2 hours while maintaining this temperature. The graft ratio of the obtained AES resin was 55%.
After cooling the internal temperature to 100 ° C., 0.2 part of octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenol) -propionate was added, and then the reaction mixture was extracted from the autoclave and steam distilled. Then, unreacted substances and solvent were distilled off, and the volatile matter was substantially degassed by adjusting the cylinder temperature to 220 ° C. and the degree of vacuum to 770 mmHg with an extruder equipped with a 40 mmφ vent to pelletize the AES resin.

5-2. D-2
Uses a copolymer (trade name “Modiper A1401,” manufactured by NOF Corporation, LDEP / AS = 50/50) in which a styrene / acrylonitrile copolymer (AS) is added to a low molecular weight polyethylene (LDEP) main chain. It was.

5-3. D-3
A copolymer (trade name “Modiper A3400”, manufactured by NOF Corporation, PP / AS = 70/30) in which a styrene / acrylonitrile copolymer (AS) is added to a low molecular weight polypropylene (PP) main chain is used. It was.

5-4. D-4 (grafted copolymer of hydrogenated diene polymer)
5-4-1. Production of component (d-3) (fully hydrogenated styrene-butadiene block copolymer)
The agitator and jacketed autoclave were dried and purged with nitrogen, and a cyclohexane solution containing 20 parts of butadiene was added. Next, 0.025 part of n-butyllithium was added to carry out isothermal polymerization at 50 ° C. When the conversion rate reached 100%, 0.75 parts of tetrahydrofuran and 65 parts of butadiene were added, and the temperature was increased from 50 ° C to 80 ° C. When the conversion reached 100%, 15 parts of styrene was added, and a polymerization reaction was further performed to obtain an A-B1-B2 triblock copolymer before hydrogenation. The A-B1-B2 triblock copolymer had a styrene block (A) content of 15%, a butadiene block (B1) content of 65%, and a butadiene block (B2) content of 20%. . Further, the 1,2-vinyl content in the B1 block was 35%, and the 1,2-vinyl content in the B2 block was 10%. The number average molecular weight of the A-B1-B2 triblock copolymer was 200,000.
Hydrogenation of the A-B1-B2 triblock copolymer was performed according to the following procedure. That is, 1 part of titanocene dichloride was dispersed in cyclohexane in a separate container and reacted with 0.5 part of triethylaluminum at room temperature. The obtained homogeneous solution was added to the above A-B1-B2 triblock copolymer polymer solution, and a hydrogenation reaction was carried out at 50 ° C. under a hydrogen pressure of 50 kgf / cm ² for 2 hours. After 2,6-di-tert-butylcatechol was added, the solvent was removed to obtain a hydrogenated product (d-3) having a hydrogenation rate of approximately 100%. In addition, the amount of bonded styrene, the amount of vinyl bonds, the number average molecular weight, and the hydrogenation rate were measured by the following methods.
-Bonded styrene content;
It was measured on the polymer before hydrogenation. It was determined from a calibration curve by an infrared method based on absorption of a phenyl group at 699 cm ⁻¹ .
・ Number average molecular weight;
It was measured on the polymer before hydrogenation. It calculated | required from the gel permeation chromatography (GPC).
-Vinyl bond amount Measured with polymer before hydrogenation. It calculated | required by the infrared method (Morero method).
-Hydrogenation rate;
Measurements were taken on the polymer after hydrogenation. It was calculated from the spectrum reduction of unsaturated double bonds of 100 MHz ¹ H-NMR spectrum measured at 15% concentration using ethylene tetrachloride as a solvent.

5-4-2. Production of Graft Copolymer (D-4) After replacing a stainless steel autoclave with a ribbon wing with an internal volume of 10 L with nitrogen, the hydrogenated product (d- 3) was charged with 28 parts (solid content), 7 parts of styrene, 10 parts of acrylonitrile, 55 parts of methyl methacrylate, 120 parts of toluene, and 0.1 part of tert-dodecyl mercaptan, and the temperature was increased while stirring. When the internal temperature reaches 50 ° C., 0.5 part of benzoyl peroxide and 0.1 part of dicumyl peroxide are added, the temperature is further increased, and after reaching 80 ° C., the temperature is controlled to be constant at 80 ° C. A polymerization reaction was performed. It took 1 hour from the 6th hour from the start of the reaction, the temperature was raised to 120 ° C., and the reaction was further completed for 2 hours. The conversion was 97%.
After cooling to 100 ° C., 0.2 part of 2,2-methylenebis-4-methyl-6-tert-butylphenol was added, the reaction mixture was extracted from the autoclave, and unreacted substances and solvent were distilled off by steam distillation. The polymer was pelletized to obtain a polymer D-4. The graft ratio of this product was 45%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g.

6). Component [E] (Polycarbonate resin E-1)
An aromatic polycarbonate resin having a viscosity average molecular weight of 22,000 (trade name “NOVAREX 7022PJ”, manufactured by Mitsubishi Engineering Plastics) was used.

7). Ingredient [F] (Flame Retardant)
F-1: Phosphorus flame retardant 1,3-phenylene-bis (dixylenyl phosphate) (trade name “PX-200”, manufactured by Daihachi Chemical Industry Co., Ltd.) was used.
F-2: Brominated epoxy oligomer The trade name “Plasarm EPC-15F” (manufactured by Dainippon Ink & Chemicals, Inc.) was used.

8). Examples 1-15 and Comparative Examples 1-10
Using the above components [A] to [F], they were mixed by a Henschel mixer at the blending ratio shown in Table 1, and then kneaded with a twin-screw extruder (barrel set temperature 280 ° C.) to be pelletized. The sample was dried to a moisture of 0.02% or less with a dehumidifying dryer, and various physical property evaluation test pieces were molded by injection molding (set temperature 260 ° C.). And it evaluated by the said method using the obtained test piece. About flame retardance, Examples 2-5 and Comparative Examples 4-5 were evaluated. The above evaluation results are shown in Table 1.

9. Effects of Examples As shown in Table 1, Comparative Example 1 is an example outside the scope of the present invention that does not contain the component [D] and is inferior in antistatic properties and sliding properties. Comparative Example 2 is an example in which the content of the component [B] is small outside the scope of the present invention, and the antistatic property is inferior. Comparative Examples 3 to 5 are examples outside the scope of the present invention that do not contain the component [C] and are inferior in antistatic properties and sliding properties. Comparative Example 6 is an example outside the scope of the present invention in which stearic acid monoglyceride is used in place of component [B], and the antistatic property and sliding property are inferior. Comparative Example 7 is an example in which the content of the component [B] is larger than the range of the present invention, and the slidability, moldability and impact resistance are inferior. Comparative Example 8 is an example in which the molecular weight of the component [C] is larger than the range of the present invention, and the antistatic property, slidability and moldability are inferior. Comparative Example 9 is an example in which the amount of component [C] added is larger than the range of the present invention, and the moldability and impact resistance are poor. Comparative Example 10 is an example in which the amount of component [D] added is larger than the range of the present invention, and the antistatic property is inferior.

On the other hand, as shown in Table 1, Examples 1 to 15 are examples within the scope of the present invention containing the components [A], [B], [C] and [D] in a predetermined ratio, and the surface A very good antistatic property with a specific resistance of 1 × 10 ¹³ (Ω) or less is achieved, a good sliding property is obtained, and the same result is obtained even when the component [E] and / or the component [F] is contained. was gotten.

According to the present invention, a specific amount of an alkyl sulfonate as an antistatic agent and a predetermined amount of a modified polyolefin polymer are mixed with a specific styrene resin formed by mixing a low molecular weight polyolefin. As a result, a styrenic resin that is remarkably excellent in antistatic property and sliding property, and also excellent in moldability and impact resistance is provided. The same effect is also achieved in a styrene resin having a high heat resistance blended with an aromatic polycarbonate resin or a styrene resin having a high flame retardancy blended with a flame retardant. The antistatic thermoplastic resin composition of the present invention is useful for molding various molded articles used in the fields of home appliances, electric / electronics, automobiles, miscellaneous goods and the like.

Claims (9)

An antistatic thermoplastic resin composition containing the following components [A] to [D], wherein the component [B] is 0.2 to 20 parts by mass and the component [C] with respect to 100 parts by mass of the component [A]. ] 0.1-10 mass parts and component [D] 0.1-20 mass parts are mix | blended, The antistatic thermoplastic resin composition characterized by the above-mentioned.
Component [A] is a vinyl monomer containing an aromatic vinyl compound and a vinyl cyanide compound in the presence of a rubber polymer (a) comprising a butadiene rubber polymer and / or an acrylic rubber polymer. The rubber-reinforced copolymer resin (A-1) obtained by polymerizing (b-1) or the (co) polymer (A-) of the rubber-reinforced copolymer resin (A-1) and a vinyl monomer. 2) and a rubber-reinforced resin having a content of the rubbery polymer (a) of 3 to 40% by mass.
Component [B] is an alkyl sulfonate.
Component [C] is a low molecular weight polyolefin having a weight average molecular weight of 500 to 40,000.
Component [D] is a combined product of the olefin polymer (d) and the (co) polymer of the vinyl monomer (b-2) containing an aromatic vinyl compound.   2. The antistatic thermoplastic resin composition according to claim 1, wherein component [D] is obtained by polymerizing vinyl monomer (b-2) in the presence of olefin polymer (d). Stuff.   2. The antistatic agent according to claim 1, wherein the component [D] is obtained by bonding the olefin polymer (d) and the (co) polymer of the vinyl monomer (b-2). Thermoplastic resin composition. The olefin polymer (d) of the component [D] is at least one selected from the group consisting of the following components (d-1), (d-2) and (d-3). The antistatic thermoplastic resin composition as described.
(D-1); an olefin resin,
(D-2); ethylene-α-olefin rubbery polymer,
(D-3); Hydrogenated product of diene polymer.   The olefin polymer (d) of component [D] is an ethylene-α-olefin rubbery polymer (d-2) and / or a hydrogenated product (d-3) of a diene polymer. The antistatic thermoplastic resin composition as described.   The antistatic thermoplastic resin composition according to claim 3, wherein the olefin polymer (d) of the component [D] is an olefin resin (d-1).   Furthermore, the antistatic thermoplastic resin composition of Claim 1 which contains 1-30 mass parts of aromatic polycarbonate resins as a component [E] with respect to 100 mass parts of component [A].   Furthermore, the antistatic thermoplastic resin composition of Claim 1 or 7 which contains 1-30 mass parts of flame retardants as a component [F] with respect to 100 mass parts of component [A]. A molded article comprising the antistatic thermoplastic resin composition according to any one of claims 1 to 8.