JP2009173758A - Flame-retardant antistatic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame-retardant antistatic resin composition giving a molded product with excellent balance between flame retardancy, antistaticity, impact resistance, rigidity and moldability. <P>SOLUTION: The flame-retardant antistatic resin composition comprises a rubber reinforced vinyl resin, a resin, a polymeric antistatic agent, a flame retarder consisting of a compound having a bromine atom, an antimony compound, and a tetrafluoroethylene (co)polymer. The above rubber reinforced vinyl resin consists of a graft copolymer obtained by polymerizing a vinyl monomer not including a hydroxyl group-containing vinyl monomer in the presence of a rubber polymer, or a mixture of the graft copolymer and a (co)polymer obtained by using the vinyl monomer. The above resin is a graft copolymer obtained by polymerizing the vinyl monomer including a hydroxyl group-containing vinyl monomer in the presence of a rubber polymer and/or a (co)polymer obtained by using the vinyl monomer, and contains 1-20 mass% of the hydroxyl group-containing vinyl monomer units. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a flame-retardant and anti-static resin composition that provides a molded article having an excellent balance of flame retardancy, anti-static property, impact resistance, rigidity and molding processability.

In recent years, a thermoplastic resin composition containing a rubber-reinforced resin such as an ABS resin has been widely used as a molding material for casings, holding members, protective members, support members, storage containers, and the like of electronic devices. And in such a composition, in order to suppress generation | occurrence | production of static electricity and to achieve a flame retardance, an antistatic agent, a flame retardant, etc. are mix | blended (refer patent document 1).
In Patent Document 1, (a) a polyamide elastomer is 5 to 50% by weight, (b) an aromatic vinyl compound and, if necessary, a vinyl cyanide compound are copolymerized in the presence or absence of a rubbery polymer. 30 to 94% by weight of a thermoplastic resin, and (c) a vinyl containing a functional group in the copolymerization of an aromatic vinyl compound and, if necessary, a vinyl cyanide compound in the presence or absence of a rubbery polymer. (D) with respect to 100 parts by weight of a total amount of 1 to 20% by weight of a thermoplastic resin obtained by copolymerizing at least one compound (where (a) + (b) + (c) = 100% by weight)) A flame retardant resin composition comprising 3 to 50 parts by weight of a halogenated epoxy oligomer and / or a halogenated epoxy polymer is disclosed.

Japanese Patent Laid-Open No. 5-331352

According to the composition of Patent Document 1, although a molded product excellent in antistatic property and flame retardancy can be obtained, the surface resistivity is less than 5 × 10 ¹¹ Ω, and adhesion of dust and the like is further suppressed. Therefore, it was difficult to obtain a molded product having a good balance of flame retardancy, antistatic property, impact resistance, rigidity and molding processability.
An object of the present invention is to provide a flame-retardant and anti-static resin composition that gives a molded article having an excellent balance of flame retardancy, anti-static property, impact resistance, rigidity and molding processability.

  As a result of intensive studies to solve the above problems, the present inventor has found that a graft copolymer obtained by polymerizing a vinyl monomer not containing a hydroxyl group-containing vinyl monomer in the presence of a rubbery polymer. Contains a rubber-reinforced vinyl resin containing a coal, a resin containing a hydroxyl group-containing vinyl monomer unit, a polymer-type antistatic agent, a flame retardant comprising a bromine-containing compound, an antimony compound, and a tetrafluoroethylene (co) polymer. The present inventors have found that the composition gives a molded article having an excellent balance of flame retardancy, antistatic property and impact resistance, and completed the present invention.

The present invention is shown below.
1. [A] A graft copolymer (A1) obtained by polymerizing a vinyl monomer (a2) not containing a hydroxyl group-containing vinyl monomer in the presence of the rubbery polymer (a1), or A rubber-reinforced vinyl resin comprising the graft copolymer (A1) and a mixture of the (co) polymer (A2) obtained using the vinyl monomer (a2), and [B] rubber A graft copolymer (B1) obtained by polymerizing a vinyl monomer (b2) containing a hydroxyl group-containing vinyl monomer in the presence of a polymeric polymer (b1), and / or the vinyl polymer It is a (co) polymer (B2) obtained using the monomer (b2), and the content of the monomer unit comprising the hydroxyl group-containing vinyl monomer is 1 to 20% by mass. A resin, [C] a polymeric antistatic agent, and [D] a compound having a bromine atom. A flame retardant antistatic resin composition comprising a flame retardant, [E] an antimony compound, and [F] a tetrafluoroethylene (co) polymer, wherein the resin [B], the polymer type Each content of the antistatic agent [C], the flame retardant [D], the antimony compound [E] and the tetrafluoroethylene (co) polymer [F] is 100 masses of the rubber-reinforced vinyl resin [A]. 1 to 20 parts by mass, 5 to 30 parts by mass, 20 to 35 parts by mass, 1 to 15 parts by mass, and 0.05 to 2 parts by mass, respectively, constituting the flame retardant [D]. The ratio Br / Sb between the content of bromine atoms and the content of antimony atoms constituting the antimony compound [E] is 1 to 5, and the combustibility according to the UL94 standard is V-0 or V-1. A flame retardant antistatic resin composition, characterized by
2. Further, [G] contains a silicone compound, and the content of the silicone compound [G] is 0.1 to 8 parts by mass with respect to 100 parts by mass of the rubber-reinforced vinyl resin [A]. The flame-retardant antistatic resin composition as described.
3. 3. The flame-retardant antistatic resin composition according to 1 or 2 above, wherein the molded article containing the flame-retardant antistatic resin composition has a surface resistance value of less than 5 × 10 ¹¹ Ω.

According to the flame-retardant antistatic resin composition of the present invention, it is possible to form a molded product having an excellent balance of flame retardancy, antistatic property, impact resistance, rigidity and molding processability.
When the flame-retardant antistatic resin composition of the present invention further contains a [G] silicone compound, it is excellent in molding processability, without reducing the antistatic and impact resistance, A molded product having an excellent balance of antistatic properties, impact resistance, rigidity, and molding processability, and excellent slidability can be formed.

The present invention will be described in detail below.
In the present invention, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acryl and methacryl.

  The flame retardant antistatic resin composition of the present invention is obtained by polymerizing a vinyl monomer (a2) not containing a hydroxyl group-containing vinyl monomer in the presence of [A] rubbery polymer (a1). The obtained graft copolymer (A1), or a mixture of the graft copolymer (A1) and the (co) polymer (A2) obtained using the vinyl monomer (a2), A vinyl-based monomer comprising a hydroxyl group-containing vinyl monomer in the presence of a rubber-reinforced vinyl resin (hereinafter also referred to as “component [A]”) and [B] a rubbery polymer (b1). A graft copolymer (B1) obtained by polymerizing the body (b2) and / or a (co) polymer (B2) obtained using the vinyl monomer (b2), and A tree having a monomer unit content of the hydroxyl group-containing vinyl monomer of 1 to 20% by mass. (Hereinafter also referred to as “component [B]”), [C] a polymer antistatic agent (hereinafter also referred to as “component [C]”), and [D] a compound having a bromine atom. A flame retardant (hereinafter also referred to as “component [D]”), an [E] antimony compound (hereinafter also referred to as “component [E]”), and a [F] tetrafluoroethylene (co) polymer (hereinafter referred to as “component”). A composition containing the resin [B], the polymer antistatic agent [C], the flame retardant [D], and the antimony compound [E]. And the tetrafluoroethylene (co) polymer [F] are 1 to 20 parts by mass, 5 to 30 parts by mass, respectively, with respect to 100 parts by mass of the rubber-reinforced vinyl resin [A]. 20 to 35 parts by mass, 1 to 15 parts by mass, and 0.05 to 2 parts by mass, and the flame retardant [ The ratio Br / Sb between the content of bromine atoms constituting the antimony compound [E] and the content of antimony atoms constituting the antimony compound [E] is 1 to 5, and the combustibility according to the UL94 standard is V-0. Or it is V-1.

The component [A] is a graft copolymer (A1) obtained by polymerizing a vinyl monomer (a2) not containing a hydroxyl group-containing vinyl monomer in the presence of the rubbery polymer (a1). Or a mixture of the graft copolymer (A1) and the (co) polymer (A2) obtained by using the vinyl monomer (a2). .
In addition, the component [B] is a graft copolymer (b2) obtained by polymerizing a vinyl monomer (b2) containing a hydroxyl group-containing vinyl monomer in the presence of the rubbery polymer (b1). B1) and / or (co) polymer (B2) obtained by using the vinyl monomer (b2), and a monomer unit comprising the hydroxyl group-containing vinyl monomer. A resin having a content of 1 to 20% by mass.

Among the components [A], the rubbery polymer (a1) constituting the graft copolymer (A1), and among the components [B], the rubbery polymer constituting the graft copolymer (B1). (B1) may be the same polymer as each other or different polymers.
The rubbery polymers (a1) and (b1) may be homopolymers or copolymers as long as they are rubbery at room temperature. In addition, these rubbery polymers may be non-crosslinked polymers or crosslinked polymers. Specific examples include diene polymers and non-diene polymers. These may be used alone or in combination.

  Examples of the diene polymer include homopolymers such as polybutadiene, polyisoprene and polychloroprene; styrene / butadiene such as styrene / butadiene copolymer, styrene / butadiene / styrene copolymer, and acrylonitrile / styrene / butadiene copolymer. Styrene / isoprene copolymer, styrene / isoprene / styrene copolymer, styrene / isoprene copolymer rubber such as acrylonitrile / styrene / isoprene copolymer; natural rubber and the like. Each of the above copolymers may be a block copolymer or a random copolymer. The said diene polymer can be used individually by 1 type or in combination of 2 or more types.

  Examples of the non-diene polymer include ethylene / α-olefin copolymer rubbers containing ethylene units and units composed of α-olefins having 3 or more carbon atoms; acrylic rubbers; urethane rubbers; silicone rubbers. And silicone rubbers such as silicone / acrylic composite rubbers; polymers obtained by hydrogenating (co) polymers containing units composed of conjugated diene compounds. Each of the above copolymers may be a block copolymer or a random copolymer. The said non-diene polymer can be used individually by 1 type or in combination of 2 or more types. The non-diene polymer is preferably an ethylene / α-olefin copolymer rubber and an acrylic rubber.

The ethylene / α-olefin copolymer rubber includes an ethylene unit and a unit composed of an α-olefin having 3 or more carbon atoms, and includes an ethylene / α-olefin copolymer rubber and an ethylene / α-olefin. -Non-conjugated diene copolymer rubber and the like.
Examples of the α-olefin having 3 or more carbon atoms include propylene, butene-1, pentene-1, 3-methylbutene-1, hexene-1, 3-methylpentene-1, 4-methylpentene-1, 3,3-dimethyl. Examples include butene-1, heptene-1, methylhexene-1, dimethylpentene-1, trimethylbutene-1, ethylpentene-1, octene-1, and propylpentene-1.
Examples of the non-conjugated diene include linear acyclic diene compounds such as 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,6-hexadiene; 5-methyl-1,4- Hexadiene, 3,7-dimethyl-1,6-octadiene, 5,7-dimethylocta-1,6-diene, 3,7-dimethyl-1,7-octadiene, 7-methylocta-1,6-diene, dihydro Branched acyclic diene compounds such as myrcene; 5-methylene-2-norbornene, 5-ethylidene-2-norbornene, 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene, 5-cyclohexylidene -2-norbornene, 5-vinyl-2-norbornene, dicyclopentadiene, 1,4-cyclohexadiene, 1,4-cyclooct Diene, 1,5-cyclooctadiene, tetrahydroindene, methyl tetrahydroindene, dicyclopentadiene, bicyclo [2.2.1] - alicyclic diene compound hepta-2,5-diene and the like, and the like.

Examples of the ethylene / α-olefin copolymer rubber include ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / 1-pentene copolymer, and ethylene / 3-methyl-1-butene copolymer. , Ethylene / 1-hexene copolymer, ethylene-3-methyl-1-pentene copolymer, ethylene-4-methyl-1-pentene copolymer, ethylene-3-ethyl-1-pentene copolymer, ethylene -A 1-octene copolymer, an ethylene / 1-decene copolymer, an ethylene / 1-undecene copolymer, etc. are mentioned.
Examples of the ethylene / α-olefin / non-conjugated diene copolymer rubber include ethylene / propylene / 5-ethylidene-2-norbornene copolymer, ethylene / propylene / dicyclopentadiene copolymer, ethylene / propylene / 5 -Ethylidene-2-norbornene / dicyclopentadiene copolymer, ethylene / propylene / 5-ethylidene-2-norbornene / 5-vinyl-2-norbornene copolymer, ethylene / 1-butene / 5-ethylidene-2-norbornene A copolymer etc. are mentioned.

  The ethylene unit content of the ethylene / α-olefin copolymer rubber is preferably 10 to 90% by mass, more preferably 20 to 80% by mass, and still more preferably based on the total amount of all units. 30 to 70% by mass. The number average molecular weight (Mn) of the ethylene / α-olefin copolymer rubber is preferably 5,000 to 1,000,000, more preferably 30,000 to 300,000. If this Mn is too large, the workability may decrease. Furthermore, the ratio (Mw / Mn) between the weight average molecular weight (Mw) and the number average molecular weight is preferably 10 or less.

  The acrylic rubber (acrylic rubbery polymer) is not particularly limited as long as it is a (co) polymer composed of a monomer containing an alkyl acrylate ester and / or an alkyl methacrylate ester.

The monomer preferably includes an alkyl acrylate ester, and particularly preferably includes an alkyl acrylate ester having 1 to 12 carbon atoms in the alkyl group.
Examples of the alkyl acrylate include methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, amyl acrylate, and n-acrylate Examples include hexyl, n-octyl acrylate, 2-ethylhexyl acrylate, dodecyl acrylate, cyclohexyl acrylate, phenyl acrylate, and benzyl acrylate. Of these compounds, n-butyl acrylate and 2-ethylhexyl acrylate are preferred. Moreover, these alkyl acrylate esters can be used alone or in combination of two or more.

  The acrylic rubbery polymer may be a homopolymer using one of the above alkyl acrylates, or may be a copolymer using two or more. Moreover, the copolymer which uses 1 or more types of the alkyl acrylate ester and 1 or more types of a compound copolymerizable with this acrylate alkyl ester may be sufficient.

  The compound copolymerizable with the alkyl acrylate ester is not particularly limited, and examples thereof include an alkyl methacrylate ester, a monofunctional aromatic vinyl compound, a monofunctional vinyl cyanide compound, a diene compound, and a polyfunctional vinyl compound. Can be mentioned. These may be used alone or in combination.

The rubber polymer (a1) used for forming the component [A] is preferably a diene rubber polymer.
The rubber polymer (b1) used for forming the component [B] is preferably a diene rubber polymer.

  Used to form the rubbery polymer (a1) used for forming the graft copolymer (A1) contained in the component [A] and to form the graft copolymer (B1) contained in the component [B]. The shape of the rubbery polymer (b1) may be the same as or different from each other. When both of the shapes are particles, the volume average particle diameter of each of the rubber polymers (a1) and (b1) is preferably 50 to 3,000 nm, more preferably 100 to 2, 000 nm, more preferably 150 to 800 nm. When the volume average particle size is too small, the impact resistance of the composition of the present invention and a molded article containing the composition tends to be inferior. On the other hand, if it is too large, the surface appearance of the molded product tends to be inferior. The volume average particle diameter can be measured by a laser diffraction method, a light scattering method, or the like.

  When the rubbery polymers (a1) and (b1) are in the form of particles obtained by emulsion polymerization, for example, if the volume average particle diameter is within the above range, for example, JP-A-61-233010 It is also possible to use a material that has been enlarged by a known method such as those described in JP-A-59-93701 and JP-A-56-167704.

The graft copolymer (A1) constituting the component [A] polymerizes a vinyl monomer (a2) not containing a hydroxyl group-containing vinyl monomer in the presence of the rubbery polymer (a1). It was obtained. As the vinyl monomer (a2) used for the formation of the graft copolymer (A1), any of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid esters having no hydroxyl group. Examples thereof include compounds, maleimide compounds, acid anhydrides and the like. These may be used alone or in combination.
As the vinyl monomer (a2), at least two kinds selected from aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds and maleimide compounds, all having no hydroxyl group. It is preferable to contain.

  The aromatic vinyl compound is not particularly limited as long as it is a compound having at least one vinyl bond and at least one aromatic ring. Examples thereof include styrene, α-methyl styrene, o-methyl styrene, p-methyl styrene, vinyl toluene, β-methyl styrene, ethyl styrene, p-tert-butyl styrene, vinyl xylene, vinyl naphthalene and the like. These 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 and methacrylonitrile. These can be used alone or in combination of two or more. Of these, acrylonitrile is preferred.

  Examples of the (meth) acrylate compound include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, Examples thereof include isobutyl (meth) acrylate, tert-butyl (meth) acrylate, hexyl (meth) acrylate, cyclohexyl (meth) acrylate, and phenyl (meth) acrylate. These can be used alone or in combination of two or more. Of these, methyl methacrylate is preferred.

Examples of the maleimide compounds include maleimide, N-methylmaleimide, N-butylmaleimide, N-phenylmaleimide, N- (2-methylphenyl) maleimide, N- (4-hydroxyphenyl) maleimide, N-cyclohexylmaleimide and the like. Can be mentioned. These can be used alone or in combination of two or more. Of these, N-phenylmaleimide is preferred. In addition, as another method for introducing a unit composed of a maleimide compound, for example, a method in which maleic anhydride is copolymerized and then imidized may be used.
Examples of the acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used alone or in combination of two or more.

  In addition to the above compounds, vinyl compounds having a functional group such as an amino group, an epoxy group, an amide group, a carboxyl group, or an oxazoline group can be used as necessary. For example, N, N-dimethylaminomethyl (meth) acrylate, N, N-diethyl-p-aminomethylstyrene, glycidyl (meth) acrylate, 3,4-oxycyclohexyl (meth) acrylate, vinyl glycidyl ether, Examples include methallyl glycidyl ether, allyl glycidyl ether, (meth) acrylamide, (meth) acrylic acid, and vinyl oxazoline. These can be used alone or in combination of two or more.

The vinyl monomer (a2) is preferably a combination of an aromatic vinyl compound and a vinyl cyanide compound (hereinafter referred to as “monomer (a21)”), an aromatic vinyl compound, or cyanide. A combination of a vinyl compound and another compound (such as a (meth) acrylic acid ester compound) (hereinafter referred to as “monomer (a22)”). By using a vinyl cyanide compound, the balance of physical properties such as chemical resistance and heat resistance is improved.
Therefore, the graft copolymer (A1) is preferably obtained using the monomer (a21) as the vinyl monomer (a2) in the presence of the rubbery polymer (a1). Graft copolymer obtained by using the monomer (a22) as the vinyl monomer (a2) in the presence of the rubbery polymer (a1), and the like. .
The said graft copolymer (A1) can be used individually by 1 type or in combination of 2 or more types.

  As described above, the component [A] may be only the graft copolymer (A1), or the graft copolymer (A1) and the vinyl monomer (a2) may be used. It may be a mixture comprising the (co) polymer (A2) obtained. This (co) polymer (A2) can be a single type or a combination of two or more types.

When the component [A] is a mixture of the graft copolymer (A1) and the (co) polymer (A2) of the vinyl monomer (a2), It is not limited.
As the vinyl monomer (a2) used for forming the (co) polymer (A2), the compounds exemplified above can be used. That is, the vinyl monomer (a2) is not an aromatic vinyl compound, a cyanidated vinyl compound, a (meth) acrylic ester compound, a maleimide compound, and an acid anhydride, all having no hydroxyl group. , Vinyl compounds having an amino group, vinyl compounds having an epoxy group, vinyl compounds having an amide group, vinyl compounds having a carboxyl group, vinyl compounds having an oxazoline group, and the like. A (co) polymer comprising a compound can be used as the (co) polymer (A2). Therefore, the (co) polymer (A2) may be either a homopolymer or a copolymer, and may be a combination thereof, but is preferably a copolymer.

  The (co) polymer (A2) is at least two selected from aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds and maleimide compounds, all having no hydroxyl group. A copolymer obtained by using is preferably used.

  A preferred copolymer as the (co) polymer (A2) is obtained by polymerizing components having exactly the same composition as the vinyl monomer (a2) used for forming the graft copolymer (A1). A copolymer obtained by polymerizing the same type of monomer with different compositions, a copolymer obtained by polymerizing different types of monomers with different compositions, and the like.

Examples of the (co) polymer (A2) include acrylonitrile / styrene copolymer, acrylonitrile / α-methylstyrene copolymer, acrylonitrile / styrene / methyl methacrylate copolymer, styrene / methyl methacrylate copolymer, and acrylonitrile. -Styrene and N-phenylmaleimide copolymer etc. are mentioned.
The said (co) polymer (A2) can be used individually by 1 type or in combination of 2 or more types.

  Next, the manufacturing method of the said graft copolymer (A1) and the said (co) polymer (A2) is demonstrated.

  The graft copolymer (A1) can be produced by polymerizing the vinyl monomer (a2) in the presence of the rubbery polymer (a1). As the polymerization method, emulsion polymerization, solution polymerization, bulk polymerization, and bulk-suspension polymerization are preferable.

  In the production of the graft copolymer (A1), the rubbery polymer (a1) and the vinyl monomer (a2) are present in the reaction system in the total amount of the rubbery polymer (a1). Below, the said vinylic monomer (a2) may be added collectively and superposition | polymerization may be started, or superposition | polymerization may be performed dividing | segmenting or adding continuously. Further, in the presence or absence of a part of the rubber polymer (a1), the vinyl monomer (a2) may be added all at once to initiate polymerization, or may be divided or continuously. May be added. At this time, the remainder of the rubber-like polymer (a1) may be added all at once during the reaction, divided or continuously.

  When 100 parts by mass of the graft copolymer (A1) is produced, the amount of the rubbery polymer (a1) used is usually 5 to 80 parts by mass, preferably 10 to 70 parts by mass, and more preferably 15 to 15 parts by mass. 60 parts by mass. Moreover, the usage-amount of the said vinylic monomer (a2) is 20-95 mass parts normally, Preferably it is 30-90 mass parts, More preferably, it is 40-85 mass parts.

  When the rubber-reinforced vinyl resin (A1) is produced by emulsion polymerization, a polymerization initiator, a chain transfer agent (molecular weight regulator), an emulsifier, water and the like are used.

As the polymerization initiator, a redox in which an organic peroxide such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, paramentane hydroperoxide, or the like and a reducing agent such as a sugar-containing pyrophosphate formulation or a sulfoxylate formulation are combined. System initiators; persulfates such as potassium persulfate; peroxides such as benzoyl peroxide (BPO), lauroyl peroxide, tert-butyl peroxylaurate, and tert-butyl peroxymonocarbonate. These can be used alone or in combination of two or more. The usage-amount of the said polymerization initiator is 0.1-1.5 mass% normally with respect to the said vinylic monomer (a2) whole quantity, Preferably it is 0.2-0.7 mass%.
The polymerization initiator can be added to the reaction system all at once or continuously.

Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, tert-dodecyl mercaptan, n-hexyl mercaptan, n-hexadecyl mercaptan, n-tetradecyl mercaptan, tert-tetradecyl mercaptan, and other mercaptans; Examples include α-methylstyrene dimers. These can be used alone or in combination of two or more. The amount of the chain transfer agent used is usually 0.05 to 2.0 mass% with respect to the total amount of the vinyl monomer (a2).
The chain transfer agent can be added to the reaction system all at once or continuously.

  Examples of the emulsifier include anionic surfactants and nonionic surfactants. Anionic surfactants include higher alcohol sulfates; alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate; aliphatic sulfonates such as sodium lauryl sulfate; higher aliphatic carboxylates, aliphatic phosphates, etc. Is mentioned. Examples of nonionic surfactants include polyethylene glycol alkyl ester compounds and alkyl ether compounds. These can be used alone or in combination of two or more. The usage-amount of the said emulsifier is 0.3-5.0 mass% normally with respect to the said vinylic monomer (a2) whole quantity.

Emulsion polymerization can be carried out under known conditions depending on the type of vinyl monomer (a2), polymerization initiator, and the like. The latex obtained by this emulsion polymerization is usually purified by coagulation with a coagulant to form a polymer component in powder form, and then washing and drying the polymer component. Examples of the coagulant include inorganic salts such as calcium chloride, magnesium sulfate, magnesium chloride, and sodium chloride; inorganic acids such as sulfuric acid and hydrochloric acid; organic acids such as acetic acid and lactic acid.
In addition, when making the said graft copolymer (A1) 2 or more types of components [A], after isolating resin from each latex, you may mix, but as another method, each resin There is a method of coagulating a mixture of latexes containing each of the above.

  A known method can be applied to the method for producing the graft copolymer (A1) by solution polymerization, bulk polymerization and bulk-suspension polymerization.

  The graft ratio of the graft copolymer (A1) is usually 10 to 200% by mass, preferably 15 to 150% by mass, and more preferably 20 to 100% by mass. When the graft ratio is in the above range, the molding processability is excellent, and the surface appearance and impact resistance of the molded product containing the flame-retardant antistatic resin composition of the present invention are excellent.

Here, the graft ratio refers to x grams of the rubbery polymer (a1) in 1 gram of the graft copolymer (A1) and 1 gram of the graft copolymer (A1) dissolved in acetone. When the insoluble content is y gram, the value is obtained by the following formula. However, when the rubbery polymer (a1) is an acrylic rubber, acetonitrile is used instead of acetone.
Graft ratio (mass%) = {(y−x) / x} × 100

  The intrinsic viscosity [η] (η) of a component soluble in the acetone of the graft copolymer (A1) (provided that acetonitrile is used when the rubbery polymer (a1) is an acrylic rubber) (Measured at 30 ° C. in methyl ethyl ketone) is usually 0.1 to 1.0 dl / g, preferably 0.2 to 0.9 dl / g, more preferably 0.3 to 0.7 dl / g. When the intrinsic viscosity [η] is within the above range, the molding processability is excellent, and the resulting molded article is excellent in impact resistance.

  The above graft ratio and intrinsic viscosity [η] are the types and amounts of polymerization initiators, chain transfer agents, emulsifiers, solvents, etc. used in producing the above graft copolymer (A1), and further the polymerization time. It can be easily controlled by adjusting the polymerization temperature and the like.

  The (co) polymer (A2) can be produced by polymerizing the vinyl monomer (a2) using a polymerization initiator or the like applied to the production of the graft copolymer (A1). it can. As the polymerization method, solution polymerization, bulk polymerization, emulsion polymerization, suspension polymerization and the like are suitable, and these polymerization methods may be used in combination. The method for producing the (co) polymer (A2) may be a method using a polymerization initiator, a thermal polymerization method not using a polymerization initiator, or a combination thereof. Good.

  The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the (co) polymer (A2) is usually 0.1 to 1.0 dl / g, preferably 0.15 to 0.8 dl / g. is there. When the intrinsic viscosity [η] is within the above range, the molding processability is excellent, and the resulting molded article is excellent in impact resistance. The intrinsic viscosity [η] of the (co) polymer (A2) can be controlled by adjusting the production conditions as in the case of the graft copolymer (A1).

  Component soluble in acetone of the above component [A] (however, acetonitrile is used when the rubbery polymer (a1) used for forming the graft copolymer (A1) is an acrylic rubber). The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) is usually 0.1 to 1.0 dl / g, preferably 0.15 to 0.8 dl / g. When the intrinsic viscosity [η] is within the above range, the physical property balance between molding processability and impact resistance is excellent.

  The component [A] used in producing the flame-retardant antistatic resin composition of the present invention is only the graft copolymer (A1) or the graft copolymer (A1) and (co-polymer). ) Polymer (A2), and in any of these, the content of the rubbery polymer (a1) is preferably 3 to 35 masses when the component [A] is 100 mass%. %, More preferably 5 to 30% by mass. In the above, the component [A] is a mixture of the graft copolymer (A1) and the (co) polymer (A2), but the (co) polymer (A2) is It may be directly mixed with the graft copolymer (A1), or may be mixed separately without directly mixing with the graft copolymer (A1).

  The component [B] is a (co) polymer (B2) obtained by using a graft copolymer (B1) and / or a vinyl monomer (b2) containing a hydroxyl group-containing vinyl monomer. It is resin which consists of. And the content of the monomer unit which comprises this resin and is formed by the hydroxyl group-containing vinyl monomer is 1 to 20% by mass, preferably 3 to 15% by mass, more preferably 3 to 13%. % By mass. When the content is within the above range, the balance of flame retardancy, antistatic property, impact resistance, rigidity and molding processability is excellent. If the content of the monomer unit is too small, the antistatic property tends to be lowered, and a defective phenomenon such as peeling may occur in the obtained molded product. On the other hand, when there is too much said content, it exists in the tendency for thermal stability and shaping | molding workability to fall.

  The method for producing the graft copolymer (B1) can be the same as the method for producing the graft copolymer (A1).

  When manufacturing 100 mass parts of said graft copolymers (B1), the usage-amount of the said rubber-like polymer (b1) is 3-60 mass parts normally, Preferably it is 5-50 mass parts. Moreover, the usage-amount of the said vinylic monomer (b2) is 40-97 mass parts normally, Preferably it is 50-95 mass parts.

Examples of the hydroxyl group-containing vinyl monomer constituting the vinyl monomer (b2) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2 -Hydroxyalkyl (meth) acrylates such as hydroxybutyl (meth) acrylate, 3-hydroxybutyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate; o-hydroxystyrene, m-hydroxystyrene, p-hydroxystyrene, o Hydroxyl group-containing vinyl aromatic compounds such as hydroxy-α-methylstyrene, m-hydroxy-α-methylstyrene, p-hydroxy-α-methylstyrene, and p-vinylbenzyl alcohol; polyethylene glycol, polypropylene glyco Mono (meth) acrylates of polyalkylene glycols (eg, the number of alkylene glycol units is 2 to 23, for example); N-hydroxymethyl (meth) acrylamide, N- (2-hydroxyethyl) (meth) acrylamide, Examples thereof include hydroxyl group-containing unsaturated amides such as N, N-bis (2-hydroxyethyl) (meth) acrylamide. Of these, hydroxyalkyl (meth) acrylate is preferred.
The said hydroxyl group containing vinyl monomer can be used individually by 1 type or in combination of 2 or more types.
The content ratio of the hydroxyl group-containing vinyl monomer in the vinyl monomer (b2) forming the graft copolymer (B1) is not particularly limited, but is preferably 1 to 20% by mass, more preferably 3 ˜15 mass%. In addition, when the said component [B] consists of a graft copolymer (B1) and a (co) polymer (B2), the hydroxyl in the vinyl-type monomer (b2) which forms a graft copolymer (B1) The content ratio of the group-containing vinyl monomer includes the amount of the hydroxyl group-containing vinyl monomer used during the polymerization of the graft copolymer (B1) and the hydroxyl group in the obtained graft copolymer (B1). The relationship between the content of the vinyl monomer unit and the content of the vinyl monomer unit was determined by experiment, and the graft copolymer (B1) having the target hydroxyl group-containing vinyl monomer unit amount was obtained. The amount of use of the monomer can be selected.

  The vinyl monomer (b2) used for forming the graft copolymer (B1) may include a vinyl monomer having no hydroxyl group. For example, the vinyl monomer (a2) Examples of aromatic vinyl compounds, vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, acid anhydrides, functional groups such as amino groups, epoxy groups, amide groups, carboxyl groups, oxazoline groups The vinyl-type compound etc. which have can be used together.

The vinyl monomer (b2) is preferably a hydroxyalkyl (meth) acrylate, and a combination of an aromatic vinyl compound and a vinyl cyanide compound each having no hydroxyl group (hereinafter referred to as “single amount”). Body (b21) ").
Therefore, the graft copolymer (B1) is preferably obtained using the monomer (b21) as the vinyl monomer (b2) in the presence of the rubbery polymer (b1). Graft copolymer.
The said graft copolymer (B1) can be used individually by 1 type or in combination of 2 or more types.

  The graft ratio of the graft copolymer (B1) is usually 10 to 150%, preferably 15 to 150%, more preferably 20 to 100%. This graft ratio can be measured by the same method as for the graft copolymer (A1).

  The intrinsic viscosity [η] (η) of a component soluble in the acetone of the graft copolymer (B1) (however, acetonitrile is used when the rubbery polymer (b1) is an acrylic rubber). (Measured in methyl ethyl ketone at 30 ° C.) is usually 0.1 to 1.0 dl / g, preferably 0.2 to 0.9 dl / g, more preferably 0.2 to 0.8 dl / g. When the intrinsic viscosity [η] is within the above range, the molding processability is excellent, and the resulting molded article is excellent in impact resistance.

  The above graft ratio and intrinsic viscosity [η] are the types and amounts of polymerization initiators, chain transfer agents, emulsifiers, solvents, etc. used in producing the graft copolymer (B1), and further the polymerization time. It can be easily controlled by adjusting the polymerization temperature and the like.

The component [B] may be a (co) polymer (B2) obtained using the vinyl monomer (b2). As the vinyl monomer (b2), the vinyl monomer (b2) used for forming the graft copolymer (B1) can be used as it is. The vinyl monomer (b2) forming the (co) polymer (B2) has the same composition as the vinyl monomer (b2) used for the formation of the graft copolymer (B1). It may be a copolymer obtained by polymerizing the same, or may be a copolymer obtained by polymerizing the same kind of monomers with different compositions, and further different with different compositions. It may be a copolymer obtained by polymerizing various types of monomers. A preferred vinyl monomer (b2) is the monomer (b21).
The content ratio of the hydroxyl group-containing vinyl monomer in the vinyl monomer (b2) forming the (co) polymer (B2) is not particularly limited, but is preferably 1 to 20% by mass. Preferably it is 3-15 mass%. In addition, when the said component [B] consists of a graft copolymer (B1) and a (co) polymer (B2), in the vinyl-type monomer (b2) which forms a (co) polymer (B2). The content ratio of the hydroxyl group-containing vinyl monomer can be selected by the same method as that for the graft copolymer (B1).

  Examples of the (co) polymer (B2) include polyhydroxyethyl methacrylate, acrylonitrile / styrene / 2-hydroxyethyl (meth) acrylate copolymer, acrylonitrile / α-methylstyrene / 2-hydroxyethyl (meth) acrylate copolymer Examples thereof include (meth) acrylic acid alkyl ester and 2-hydroxyethyl (meth) acrylate copolymer.

  The method for producing the (co) polymer (B2) can be the same as the method for producing the (co) polymer (A2). The polymerization method is preferably solution polymerization.

The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) of the (co) polymer (B2) is usually 0.1 to 1.0 dl / g, preferably 0.2 to 0.8 dl / g. is there. When the intrinsic viscosity [η] is within the above range, the effect of adding the (co) polymer (B2) is more excellent.
The said (co) polymer (B2) can be used individually by 1 type or in combination of 2 or more types.

  As described above, the component [B] may be a mixture of the graft copolymer (B1) and the (co) polymer (B2). In this case, the content ratio of the graft copolymer (B1) and the (co) polymer (B2) is not particularly limited.

  A component soluble in acetone of the above component [B] (however, acetonitrile is used when the rubbery polymer (b1) used for forming the graft copolymer (B1) is an acrylic rubber). The intrinsic viscosity [η] (measured in methyl ethyl ketone at 30 ° C.) is usually 0.1 to 1.0 dl / g, preferably 0.2 to 0.8 dl / g. When the intrinsic viscosity [η] is within the above range, the effect due to the inclusion of the component [B] is more excellent.

  The component [B] used in producing the flame-retardant antistatic resin composition of the present invention is only the graft copolymer (B1), or the graft copolymer (B1), ) Polymer (B2), and in any of these, the content of the rubbery polymer (b1) is preferably 3 to 35 masses when the component [B] is 100 mass%. %, More preferably 5 to 30% by mass. In the above description, the component [B] is a mixture of the graft copolymer (B1) and the (co) polymer (B2), but the (co) polymer (B2) is: It may be mixed directly with the graft copolymer (B1), or may be mixed separately without directly mixing with the graft copolymer (B1).

  Content of the said component [B] contained in the flame-retardant antistatic resin composition of this invention is 1-20 mass parts with respect to 100 mass parts of said components [A], Preferably it is 2-18. Part by mass, more preferably 3 to 15 parts by mass. When the content of the component [B] is within the above range, the balance among flame retardancy, antistatic property, impact resistance, rigidity and molding processability is excellent. In addition, when there is too much content of the said component [B], it exists in the tendency for a flame retardance, impact resistance, molding processability, and thermal stability to be inferior. On the other hand, when the content of the component [B] is too small, the antistatic property tends to be inferior.

  As the components [A] and [B] contained in the flame-retardant antistatic resin composition of the present invention, a rubbery polymer is used so that the content ratio of the components [A] and [B] is in the above range. A mixed resin composition obtained using (a1) and (b1) and the vinyl monomers (a2) and (b2) can also be used.

  Next, the component [C] is a polymer type antistatic agent, and conventionally known ones can be used. Specifically, polyamide elastomers (including polyether amides, polyether ester amides, polyether amide imides, etc.); polyether ester elastomers; polyester elastomers; polyalkylene oxides such as ethylene oxide / epichlorohydrin copolymers Polymer; Polyalkylbenzenesulfonate; Acrylic copolymer such as polyethylene glycol (meth) acrylate copolymer, methoxypolyethylene glycol (meth) acrylate copolymer; Quaternary ammonium base-containing (meth) acrylate copolymer , Quaternary ammonium base-containing maleimide copolymers, quaternary ammonium base-containing methacrylimide copolymers and other quaternary ammonium base copolymers; solids such as carbobetaine graft copolymers Emissions-based copolymer, waxes, ionomer resins. These antistatic agents can be used alone or in combination of two or more. Of these, polyamide elastomers and polyether ester elastomers are preferred.

  Hereinafter, the polyamide elastomer and the polyether ester elastomer will be described.

  A typical polyamide-based elastomer is a block copolymer containing a hard segment (x1) made of a polyamide component and a soft segment (x2) made of a poly (alkylene oxide) glycol component.

  The polyamide component used for forming the hard segment (x1) is not particularly limited as long as it is a polymer having an acid amide bond (—CO—NH—) in the main chain. This polyamide component is usually produced by a method such as ring-opening polymerization of a lactam compound having a ring structure, polymerization of aminocarboxylic acid, condensation polymerization of dicarboxylic acid and diamine compound. Therefore, homopolyamide, copolyamide and the like are usually used as the polyamide component.

Examples of the lactam compound used in the ring-opening polymerization include ε-caprolactam and ω-laurolactam.
Examples of the aminocarboxylic acid include aminocaproic acid, aminoenanoic acid, aminocaprylic acid, aminobergonic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid, 9-aminononanoic acid, and 12-aminododecanoic acid.

  Examples of the dicarboxylic acid used for polycondensation of dicarboxylic acid and diamine compound include adipic acid, suberic acid, sebacic acid, dodecanedicarboxylic acid, glutaric acid, cyclohexanedicarboxylic acid, terephthalic acid, 2-methylterephthalic acid, isophthalic acid, and naphthalene dicarboxylic acid. An acid etc. are mentioned. Examples of the diamine compound include ethylene diamine, tetramethylene diamine, hexamethylene diamine, nonamethylene diamine, decamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,3,4-trimethylhexamethylene diamine, 2,4,4. -Trimethylhexamethylenediamine, bis (p-aminocyclohexyl) methane, m-xylylenediamine, p-xylylenediamine, paraphenylenediamine, metaphenylenediamine and the like.

  Examples of the polyamide component include nylon 4, 6, 7, 8, 11, 12, 6.6, 6.9, 6.10, 6.11, 6.12, 6T, 6 / 6.6, and 6/12. 6 / 6T, 6T / 6I, and the like can be used. In addition, the terminal of this polyamide component may be sealed with carboxylic acid, amine or the like. Examples of carboxylic acids include aliphatic monocarboxylic acids such as caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, and behenic acid. Examples of the amine include aliphatic primary amines such as hexylamine, octylamine, decylamine, laurylamine, myristylamine, palmitylamine, stearylamine, and behenylamine.

  The number average molecular weight of the polyamide component is preferably 500 to 10,000, more preferably 500 to 5,000. In addition, when using 2 or more types of polyamide components, the measured value when mixed may be in the above range.

As the poly (alkylene oxide) glycol component used for forming the soft segment (x2), a known polymer such as a polymer represented by the following formula (I) is used singly or in combination of two or more. be able to.
HO (CH ₂ CH ₂ O) _m (CH ₂ CH (X) O) _n H (I)
[Wherein, X represents a hydrogen atom (—H) or a substituent —CH ₃ , —CH ₂ Cl, —CH ₂ Br, —CH ₂ I or —CH ₂ OCH ₃ , and n ≧ 0, m ≧ 0. And (n + m) ≧ 20. ]

Specific examples of the poly (alkylene oxide) glycol component include polyethylene glycol, poly (1,2-propylene oxide) glycol, poly (1,3-propylene oxide) glycol, poly (tetramethylene oxide) glycol, poly (hexamethylene). Oxide) glycol, polyethylene oxide, polypropylene oxide, block or random copolymer of ethylene oxide and propylene oxide, block or random copolymer of ethylene oxide and tetrahydrofuran, alkylene oxide adduct of bisphenol A, and the like. Of these, an alkylene oxide adduct of polyethylene glycol and bisphenol A is preferred.
Note that both ends of the poly (alkylene oxide) glycol component may be aminated and / or carboxylated.

  The number average molecular weight of the poly (alkylene oxide) glycol component is preferably 200 to 20,000, more preferably 300 to 10,000, and still more preferably 300 to 4,000. In the case of using two or more kinds of poly (alkylene oxide) glycol components, the measured value when mixed may be within the above range.

The polyamide-based elastomer can be obtained by polymerizing a polyamide component and a poly (alkylene oxide) glycol component under reduced pressure or normal pressure.
Each use ratio of the polyamide component and the poly (alkylene oxide) glycol component is preferably 10 to 95% by mass and 90 to 5% by mass, respectively, when the total is 100% by mass from the viewpoint of antistatic properties. More preferably, they are 20-90 mass% and 80-10 mass%, Most preferably, they are 30-70 mass% and 70-30 mass%. If the proportion of the polyamide component used is less than 10% by mass, the resulting polyamide-based elastomer may not be sufficiently compatible with the above components [A] and [B], whereas if it exceeds 95% by mass, Sexuality may not be sufficient.
In the polymerization, an antimony catalyst, a tin catalyst, a titanium catalyst, a zirconium catalyst, an acetate metal salt catalyst, or the like can be used.

In the polymerization of the polyamide component and the poly (alkylene oxide) glycol component, a dicarboxylic acid, a diamine compound or the like can be used in combination as a polymerization raw material.
Examples of the dicarboxylic acid include aromatic dicarboxylic acid, alicyclic dicarboxylic acid, and aliphatic dicarboxylic acid. Aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid, diphenyl-4,4-dicarboxylic acid, diphenoxyethanedicarboxylic acid, 3 -Sodium sulfoisophthalate and the like. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, dicyclohexyl-4,4-dicarboxylic acid, and the like. Examples of the aliphatic dicarboxylic acid include succinic acid, oxalic acid, adipic acid, sebacic acid, dodecanedicarboxylic acid and the like. Of these, terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, sebacic acid, adipic acid and dodecanedicarboxylic acid are preferred. Moreover, these dicarboxylic acids can be used individually by 1 type or in combination of 2 or more types.

  Examples of the diamine compound include aromatic diamine compounds, alicyclic diamine compounds, and aliphatic diamine compounds. Examples of the aromatic diamine compound include p-phenylenediamine, m-phenylenediamine, diaminodiphenyl ether, diaminodiphenylmethane, and the like. Examples of the alicyclic diamine compound include piperazine, diaminodicyclohexylmethane, cyclohexyldiamine, and the like. Examples of the aliphatic diamine compound include hexamethylene diamine, ethylene diamine, propylene diamine, and octamethylene diamine. Of these, hexamethylenediamine is preferred. Moreover, these diamine compounds can be used individually by 1 type or in combination of 2 or more types.

  Bonding of hard segment (x1) and soft segment (x2) is achieved by polymerization of polyamide component and poly (alkylene oxide) glycol component, or polymerization of polyamide component, poly (alkylene oxide) glycol component and dicarboxylic acid, diamine compound, etc. Depending on the terminal structure of the soft segment (x2), it is usually an ester bond or an amide bond.

  As the polyamide-based elastomer, (1) a polyamide obtained by polymerization of an aminocarboxylic acid having 6 or more carbon atoms or polymerization of a lactam compound, or a diamine compound and dicarboxylate having 6 or more carbon atoms is used. Obtained by using the obtained polyamide, (2) polyethylene glycol having a number average molecular weight of 200 to 20,000, and (3) a dicarboxylic acid having 4 to 20 carbon atoms. Polyether ester amides with respect to 10 to 95% by weight are preferred.

The reduced viscosity η _{sp / c} (measured using a 0.5 g / 100 ml formic acid solution at 25 ° C.) of the polyamide-based elastomer is preferably 0.5 to 3.0 dl / g, more preferably 1.0 to 2.5 dl / g. The polyamide-based elastomer may have a reduced molecular weight due to thermal degradation during the molding process when the flame-retardant antistatic resin composition of the present invention is produced, but it is reduced in the final product (molded product). The viscosity η _{sp / c} is preferably 0.3 dl / g or more.

  The polyamide-based elastomer can be used alone as an antistatic agent, but is composed of a mixture containing an alkali metal salt such as lithium, sodium, or potassium; and a salt such as an alkaline earth metal salt such as magnesium or calcium. It can also be used as [C]. By containing these salts, the antistatic performance can be further improved. The salt may be blended before, during or after the production of the polyamide-based elastomer, and further during the production of the flame-retardant antistatic resin composition of the present invention.

Examples of the salts include halides, inorganic acid salts, and organic acid salts.
The halides are preferably alkali metal halides and alkaline earth metal halides.
The inorganic acid salt is preferably an alkali metal inorganic acid salt.

Examples of the alkali metal halide include lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, and potassium bromide.
Examples of the alkaline earth metal halide include magnesium chloride and calcium chloride.
Examples of alkali metal inorganic acid salts include perchlorates such as lithium perchlorate, sodium perchlorate, and potassium perchlorate.

Organic acid salts include carboxylates of alkali metals such as potassium acetate and lithium stearate; octyl sulfonic acid, dodecyl sulfonic acid, tetradecyl sulfonic acid, stearyl sulfonic acid, tetracosyl sulfonic acid, 2-ethylhexyl sulfonic acid, etc. An alkali metal salt of an alkyl sulfonic acid having an alkyl group having 8 to 24 carbon atoms; an alkali metal salt of an aromatic sulfonic acid such as phenyl sulfonic acid or naphthyl sulfonic acid; octyl phenyl sulfonic acid, dodecyl phenyl sulfonic acid, Alkali metal salts of alkylbenzene sulfonic acid having an alkyl group having 6 to 18 carbon atoms, such as dibutylphenyl sulfonic acid and dinonylphenyl sulfonic acid; dimethyl naphthyl sulfonic acid, diisopropyl naphthyl sulfonic acid, dibutyl naphthyl sulfonic acid, etc. Alkali metal salts of alkyl naphthalene sulfonic acids having an alkyl group having 2 to 18 carbon atoms; alkali metal salts of fluorinated sulfonic acids such as trifluoromethane sulfonic acid; alkali metal salts of tris (trifluoromethanesulfonyl) methane .
The said salts can be used individually by 1 type or in combination of 2 or more types.
The amount of the salt is preferably 0.001 to 10 parts by mass, more preferably 0.01 to 5 parts by mass with respect to 100 parts by mass of the polyamide-based elastomer.

  On the other hand, representative examples of polyether ester elastomers are block copolymers containing a hard segment (y1) composed of a polyester component and a soft segment (y2) composed of a poly (alkylene oxide) glycol component. .

  As a polyester component used for formation of a hard segment (y1), any of aliphatic polyester, alicyclic polyester, and aromatic polyester may be sufficient. This polyester component is usually produced by a reaction between an acid component containing a dicarboxylic acid and / or an ester-forming derivative of a dicarboxylic acid and a diol component containing a diol compound and / or an ester-forming derivative of a diol compound. Therefore, homopolyester, copolyester, etc. are usually used as the polyester component.

Among the acid components, dicarboxylic acids include terephthalic acid, isophthalic acid, orthophthalic acid, 2,6-naphthalenedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylether dicarboxylic acid, 4,4 ′. -Aromatic dicarboxylic acids such as diphenylmethane dicarboxylic acid, 4,4′-diphenylsulfone dicarboxylic acid, and 4,4′-diphenylisopropylidenedicarboxylic acid. These substitution products (alkyl group substitution products such as methyl isophthalic acid) and derivatives (alkyl ester compounds such as dimethyl terephthalate and dimethyl 2,6-naphthalenedicarboxylate) can also be used.
Furthermore, oxyacids and their ester-forming derivatives such as p-oxybenzoic acid and p-hydroxyethoxybenzoic acid can also be used.
The said acid component can be used individually by 1 type or in combination of 2 or more types.

Examples of the diol component include aliphatic glycols such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, and neopentyl glycol; and alicyclic glycols such as 1,4-cyclohexanedimethanol. In addition, these substitution bodies and derivatives can also be used. A cyclic ester compound such as ε-caprolactone can also be used.
Furthermore, long-chain diol compounds (polyethylene glycol, polytetramethylene glycol, etc.), alkylene oxide addition polymers of bisphenols, etc. (ethylene oxide addition polymers of bisphenol A, etc.), etc. can be used as necessary. .
The said diol component can be used individually by 1 type or in combination of 2 or more types.

  Examples of the polyester component include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexane-1,4-dimethyl terephthalate, polyneopentyl terephthalate, polyethylene isophthalate, polyethylene naphthalate, polybutylene naphthalate, poly Hexamethylene naphthalate or the like can be used. Also, a copolyester can be used.

The average molecular weight of the polyester component is not particularly limited, but is preferably 0.3 to 2.5 dl / g, more preferably 0.5 to 2.5 dl / g, as a reduced viscosity η _{sp / c serving} as an index of the average molecular weight. g.

  The soft segment (x2) can be applied as it is to the poly (alkylene oxide) glycol component used for forming the soft segment (y2).

  The polyether ester elastomer can be used alone as an antistatic agent, but includes an organic sulfonic acid compound, a phenol compound, a mixture containing salts that are components that can be used in combination with the polyamide elastomer, and the like. By doing so, further excellent antistatic properties can be imparted.

Although it does not specifically limit as said organic sulfonic-acid type compound, The carbon number of carbon number of an alkyl group is 8-24, the alkylbenzene sulfonate of an alkyl group is carbon number 6-18, The carbon number of an alkyl group is. 2-18 alkyl naphthalene sulfonates are preferred. Specific examples include tetradecyl sulfonate, dodecyl phenyl sulfonate, dimethyl naphthyl sulfonate, sodium tetradecyl sulfonate, sodium dodecyl phenyl sulfonate, sodium dimethyl naphthyl sulfonate, tetrabutyl dodecyl phenyl sulfonate. Examples thereof include phosphonium.
The said organic sulfonic acid type compound can be used individually by 1 type or in combination of 2 or more types.

The phenolic compound is not particularly limited, and may be a compound containing only one phenol skeleton (—C ₆ H ₅ OH) or a compound containing two or more.
Examples of the phenol compound include 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) -propionyloxy) -1,1-dimethylethyl] -2,4. , 8,10-tetraoxaspiro (5,5) undecane (molecular weight 741), 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxybenzyl) Examples include benzene (molecular weight 775), tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -isocyanurate (molecular weight 784), and the like. Of these, compounds having a molecular weight in the range of 700 to 1,200 are more preferred.
Although some of the above compounds are used as antioxidants, these antioxidants can be used as they are.
The said phenolic compound can be used individually by 1 type or in combination of 2 or more types.

  The polyether ester elastomer can impart excellent antistatic properties by combining an organic sulfonic acid compound and a phenol compound. The preferred configuration is as follows. That is, when the total of these three components is 100% by mass, the organic sulfonic acid compound is 4 to 30% by mass, preferably 10 to 30% by mass, and the phenolic compound is 0.1 to 3.5% by mass. The content is preferably 0.2 to 2% by mass, and the remainder is a polyether ester elastomer.

Moreover, when using the said salts, it can be set as the usage method similar to the case of a polyamide-type elastomer.
In addition, the compounding amount of the salt to the polyamide-based elastomer and / or the polyether ester-based elastomer is preferably 0.001 to 10 with respect to 100 parts by mass in total of the polyamide-based elastomer and / or the polyether ester-based elastomer. Part by mass, more preferably 0.01 to 5 parts by mass.

  In the flame-retardant antistatic resin composition of the present invention, the content of the component [C] is 5 to 30 parts by mass, preferably 10 to 25 parts by mass with respect to 100 parts by mass of the component [A]. More preferably, it is 11-25 mass parts. When the content is within the above range, the balance of flame retardancy, antistatic property, impact resistance, rigidity and molding processability is excellent.

The said component [D] is a flame retardant which consists of a compound which has a bromine atom.
Examples of the component [D] include brominated ethylene, hexabromocyclododecane, decabromodiphenyl oxide, tetrabromobisphenol A, bis (dibromopropyl) tetrabromobisphenol A, bis (dibromopropyl) tetrabromobisphenol S, brominated epoxy. Compounds, brominated alkyltriazine compounds, brominated bisphenol epoxy resins, brominated bisphenol phenoxy resins, brominated bisphenol polycarbonate resins, brominated polystyrene resins, brominated crosslinked polystyrene resins, brominated bisphenol cyanurate resins, brominated Examples include polyphenylene ether. These can be used alone or in combination of two or more.

  In the flame-retardant antistatic resin composition of the present invention, the content of the component [D] is 20 to 35 parts by mass, preferably 20 to 32 parts by mass with respect to 100 parts by mass of the component [A]. More preferably, it is 21-30 mass parts. When the content is within the above range, the balance of flame retardancy, antistatic property, impact resistance, rigidity and molding processability is excellent.

In addition to the above component [D], the flame retardant antistatic resin composition of the present invention includes other flame retardants such as phosphate esters, compounds obtained by modifying them with various substituents, and various condensed phosphorus compounds. Phosphorus flame retardants such as acid ester compounds, phosphazene derivatives containing phosphorus element and nitrogen element may be included.
The content of the other flame retardant is preferably 1 to 10 parts by mass, more preferably 1 to 5 parts by mass with respect to 100 parts by mass of the component [A].

The said component [E] is a component which maintains or improves the flame retardance provision effect by the said component [D].
Although it will not specifically limit as said component [E] if it is a compound containing antimony, Usually, an antimony oxide and / or an antimonate are used.
Examples of the antimony oxide include antimony trioxide (Sb ₂ O ₃ ), antimony tetraoxide (Sb ₂ O ₄ ), and antimony pentoxide (Sb ₂ O ₅ ). These can be used alone or in combination of two or more.
Examples of the antimonate include sodium antimonate, magnesium antimonate, and ammonium antimonate. These can be used alone or in combination of two or more.

In the flame-retardant antistatic resin composition of the present invention, the content of the component [E] is 1 to 15 parts by mass, preferably 3 to 13 parts by mass with respect to 100 parts by mass of the component [A]. More preferably, it is 4-12 mass parts. When this content is within the above range, the flame retardancy is more excellent.
In addition, in the flame-retardant antistatic resin composition of the present invention, there is the following relationship between the contents of the components [D] and [E] in order to impart particularly excellent flame retardancy. . That is, the ratio Br / Sb between the content of bromine atoms constituting the component [D] and the content of antimony atoms constituting the component [E] is 1 to 5, preferably 1.5 to 4 .5, more preferably 1.5-4.

  The above-mentioned component [F] is a tetrafluoroethylene (co) polymer, a fire type generated when the resin composition or a molded product containing the resin is burned, a dripping of the melt, that is, flame retardancy. It is a component that improves

As the component [F], an ethylene / tetrafluoroethylene copolymer obtained by using a homopolymer of polytetrafluoroethylene, and tetrafluoroethylene and an olefin monomer such as ethylene and propylene. Examples thereof include copolymers such as coalescence. These can be used alone or in combination of two or more. Of these, polytetrafluoroethylene is preferred.
The weight average molecular weight of the component [F] is preferably 1,000,000 or more. Moreover, the average particle diameter of the said component [F] becomes like this. Preferably it is 600 micrometers or less, More preferably, it is 400 micrometers or less.

  In the flame-retardant antistatic resin composition of the present invention, the content of the component [F] is 0.05 to 2 parts by mass, preferably 0.1 to 100 parts by mass of the component [A]. -1.5 mass parts, More preferably, it is 0.1-1 mass part. When this content is within the above range, excellent flame retardancy can be obtained without reducing antistatic properties and rigidity.

1-5. Additive The flame-retardant antistatic resin composition of the present invention may contain an additive depending on the purpose, application and the like.
Examples of the additive include silicone compounds, antioxidants, ultraviolet absorbers, plasticizers, weathering agents, anti-aging agents, fillers, antibacterial agents, fungicides, and coloring agents.

  The silicone compound (hereinafter also referred to as “component [G]”) is a component that improves sliding properties, and polyorganosiloxanes such as polydimethylsiloxane and polymethylphenylsiloxane can be used. The polyorganosiloxane may have a functional group such as a hydroxyl group, a carboxyl group, a thiol group, an epoxy group, an amino group, a vinyl group, a (meth) acryl group, or an alkoxysilyl group. A preferable silicone compound is a polyorganosiloxane having no functional group.

  In the flame-retardant antistatic resin composition of the present invention, the content of the component [G] is preferably 0.1 to 8 parts by mass, more preferably 100 parts by mass of the component [A]. It is 0.5-7 mass parts, More preferably, it is 1-5 mass parts. When this content is within the above range, excellent slidability can be obtained without reducing flame retardancy, antistatic properties, impact resistance, rigidity and molding processability.

Examples of the antioxidant include hindered amines; hydroquinones; hindered phenols; phosphorus compounds; sulfur-containing compounds. These can be used alone or in combination of two or more.
Examples of hindered phenols include 2,6-di-tert-butyl-p-cresol, 2,6-di-tert-butylphenol, 2,4-dimethyl-6-tert-butylphenol, tert-butylhydroxyanisole, 3 -(3 ', 5'-di-tert-butyl-4'-hydroxyphenyl) -N-octadecylpropionate, 2,2'-methylenebis- (4-methyl-6-tert-butylphenol), 4,4 '-Butylidenebis- (3-methyl-6-tert-butylphenol), 4,4'-thiobis- (3-methyl-6-tert-butylphenol), tetrakis- [methylene-3- (3', 5'-di- -Tert-butyl-4'-hydroxyphenyl) propionate] methane, 1,1,3-tris (2-methyl-4-hydroxy) -5-tert-butylphenyl) butane, tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 2-tert-butyl-6- (3-tert-butyl-2-hydroxy-5) -Methylbenzyl) -4-methylphenyl acrylate and the like.
Examples of the phosphorus compound include pentaerythritol diphosphite and alkyldiaryl phosphite.
Content of the said antioxidant is 0.2-5 mass parts normally with respect to a total of 100 mass parts of said component [A] and [B].

Examples of the ultraviolet absorber include benzophenones, benzotriazoles, salicylic acid esters, metal complex salts and the like. These can be used alone or in combination of two or more.
Content of the said ultraviolet absorber is 0.01-5 mass parts normally with respect to a total of 100 mass parts of said component [A] and [B].

Examples of the plasticizer include dimethyl phthalate, diethyl phthalate, dibutyl phthalate, diisobutyl phthalate, dioctyl phthalate, butyl octyl phthalate, di- (2-ethylhexyl) phthalate, diisooctyl phthalate, diisodecyl phthalate, and the like; dimethyl adipate, Diisobutyl adipate, di- (2-ethylhexyl) adipate, diisooctyl adipate, diisodecyl adipate, octyl decyl adipate, di- (2-ethylhexyl) azelate, diisooctyl azelate, diisobutyl azelate, dibutyl sebacate, di- ( 2-ethylhexyl) fatty acid esters such as sebacate and diisooctyl sebacate; trimellitic acid isodecyl ester, trimellitic acid octyl ester Trimellitic acid esters such as tellurium, trimellitic acid n-octyl ester, trimellitic acid isononyl ester; di- (2-ethylhexyl) fumarate, diethylene glycol monooleate, glyceryl monoricinolate, trilauryl phosphate, tristearyl phosphate , Tri- (2-ethylhexyl) phosphate and the like. These can be used alone or in combination of two or more.
Content of the said plasticizer is 0.5-10 mass parts normally with respect to a total of 100 mass parts of said component [A] and [B].

Examples of the weathering agent include organic phosphorus compounds, organic sulfur compounds, and organic compounds containing a hydroxyl group. These can be used alone or in combination of two or more.
Content of the said weathering agent is 0.01-5 mass parts normally with respect to a total of 100 mass parts of said component [A] and [B].

Antiaging agents include naphthylamine compounds, diphenylamine compounds, p-phenylenediamine compounds, quinoline compounds, hydroquinone derivative compounds, monophenol compounds, bisphenol compounds, trisphenol compounds, polyphenol compounds, thiobisphenols. Compounds, hindered phenol compounds, phosphite compounds, imidazole compounds, nickel dithiocarbamate salts, phosphate compounds and the like. These can be used alone or in combination of two or more.
Content of the said anti-aging agent is 0.05-5 mass parts normally with respect to a total of 100 mass parts of said component [A] and [B].

Examples of the filler include carbon black, silica, talc, titanium oxide, clay, and calcium carbonate. These can be used alone or in combination of two or more.
Content of the said filler is 1-30 mass parts normally with respect to a total of 100 mass parts of said component [A] and [B].

As antibacterial agents, zeolite-based antibacterial agents such as silver-based zeolite and silver-zinc-based zeolite, silica gel-based antibacterial agents such as complexed silver-silica gel, glass-based antibacterial agents, calcium phosphate-based antibacterial agents, zirconium phosphate-based antibacterial agents, Inorganic antibacterial agents such as silicate antibacterial agents such as silver-magnesium aluminate, titanium oxide antibacterial agents, ceramic antibacterial agents, whisker antibacterial agents; formaldehyde releasing agents, halogenated aromatic compounds, road propargyl Derivatives, thiocyanato compounds, isothiazolinone derivatives, trihalomethylthio compounds, quaternary ammonium salts, biguanide compounds, aldehydes, phenols, pyridine oxide, carbanilide, diphenyl ether, carboxylic acids, organometallic compounds, etc .; inorganic / organic hybrids Antibacterial agent; natural antibacterial agent And the like. These can be used alone or in combination of two or more.
Content of the said antibacterial agent is 0.01-5 mass parts normally with respect to a total of 100 mass parts of said component [A] and [B].

As the colorant, any of inorganic pigments, organic pigments, and dyes may be used. Moreover, you may use combining these.
Content of the said coloring agent is 0.1-10 mass parts normally with respect to a total of 100 mass parts of said component [A] and [B].

  In the flame-retardant antistatic resin composition of the present invention, the ratio of the total amount of the rubber polymer (a1) derived from the component [A] and the rubber polymer (b1) derived from the component [B] is The amount is preferably 3 to 35% by mass, more preferably 5 to 30% by mass, and still more preferably 5 to 25% by mass with respect to the entire composition. If it is the said ratio, it is excellent in the balance of a flame retardance, antistatic property, impact resistance, rigidity, and moldability.

  In the flame-retardant antistatic resin composition of the present invention, the content of the monomer unit composed of the hydroxyl group-containing vinyl monomer derived from the component [B] is the sum of the components [A] and [B]. Preferably it is 0.1-2.3 mass% with respect to quantity, More preferably, it is 0.1-1.7 mass%, More preferably, it is 0.2-1.5 mass%. If it is the said ratio, it is excellent in the balance of a flame retardance, antistatic property, impact resistance, rigidity, and moldability.

The flame-retardant antistatic resin composition of the present invention is excellent in antistatic properties, and the surface resistance value (temperature 23 ° C., relative humidity 50%) of the molded product containing the flame-retardant antistatic resin composition of the present invention is: Preferably, it is less than 5 × 10 ¹¹ Ω, more preferably 3 × 10 ¹¹ to 1 × 10 ¹⁰ Ω, and still more preferably 1 × 10 ¹¹ to 1 × 10 ¹⁰ Ω.
Moreover, in the flame-retardant antistatic resin composition of this invention, the combustibility according to UL94 specification is V-0 or V-1, and it is excellent in a flame retardance.

  The flame-retardant antistatic resin composition of the present invention can be prepared by kneading raw material components with various extruders, Banbury mixers, kneaders, rolls, feeder ruders, etc. Can do. The kneading temperature is selected depending on the types of the components [A] and [B], and is usually 180 to 300 ° C, preferably 200 to 280 ° C. The method of using the raw material components is not particularly limited, and the respective components may be mixed and kneaded in a lump, or may be mixed and mixed in multiple stages.

The flame-retardant antistatic resin composition of the present invention is formed by known molding methods such as injection molding, press molding, extrusion molding, coextrusion molding, sheet extrusion molding, profile extrusion molding, foam molding, vacuum molding, compression molding, and the like. A molded product having a predetermined shape can be obtained.
The molded article is suitable as various members and parts used for electronics products, optical products, home appliances, OA equipment, semiconductor-related products, vehicles, building materials, and the like. For example, housings, containers, support members, covers, trays, etc. for computers, music players, AV equipment, copiers, printers, fax machines, personal computers, word processors, portable communication devices, game machines, and composite devices thereof It can be used as cards, belts, cassettes, cartridges, connectors, pallets and the like.
The molded product can be used after being subjected to secondary processing such as painting, plating, sputtering, and welding.

  The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples as long as the gist of the present invention is not exceeded. In the following, parts and% are: Unless otherwise noted, it is based on mass.

1. Raw material component 1-1. Ingredient [A]
(1) A-1
A graft copolymer obtained by emulsion polymerization of styrene and acrylonitrile in the presence of polybutadiene rubber. This graft copolymer has a graft ratio of 55%, a polybutadiene rubber content of 40%, a styrene unit amount of 45%, and an acrylonitrile unit amount of 15%. The intrinsic viscosity of the acetone-soluble component (measured in methyl ethyl ketone at 30 ° C.) is 0.45 dl / g.
(2) A'-2
An acrylonitrile / styrene copolymer having a styrene unit amount of 75% and an acrylonitrile unit amount of 25%. The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) is 0.51 dl / g.

1-2. Ingredient [B]
(1) B-1
It is a terpolymer having a 2-hydroxyethyl methacrylate unit amount of 10%, a styrene unit amount of 67.2% and an acrylonitrile unit amount of 22.8%. The intrinsic viscosity (measured in methyl ethyl ketone at 30 ° C.) is 0.55 dl / g.
(2) B-2
It is a graft copolymer obtained by solution polymerization of 2-hydroxyethyl methacrylate, styrene and acrylonitrile in the presence of polybutadiene rubber. This graft copolymer has a graft ratio of 54%, a polybutadiene rubber content of 10%, a 2-hydroxyethyl methacrylate unit amount of 11%, a styrene unit amount of 59.2%, and an acrylonitrile unit amount of 20.8%. It is. The intrinsic viscosity of the acetone-soluble component (measured in methyl ethyl ketone at 30 ° C.) is 0.45 dl / g.

1-3. Ingredient [C]
(1) Polyamide-based elastomer “Pelestat M-140” (trade name) manufactured by Sanyo Kasei Co., Ltd. was used.
(2) Polyetherester antistatic agent “TEP004” (prototype name) manufactured by Takemoto Yushi Co., Ltd. was used.
1-4. Ingredient [D]
Brominated epoxy resin flame retardant “Plasarm EC-20” (trade name) manufactured by Dainippon Ink & Chemicals, Inc. was used.
1-5. Ingredient [D ′]
1,3-phenylenebisdixylenyl phosphate (trade name “aromatic condensed phosphate ester PX-200”) manufactured by Daihachi Chemical Co., Ltd. was used.
1-6. Ingredient [E]
Sb ₂ O ₃ “Firecut AT-3” (trade name) manufactured by Suzuhiro Chemical Co., Ltd. was used.
1-7. Ingredient [F]
PTFE “FUROMIX” (trade name) manufactured by Nitto Chemical Industries, Ltd. was used.
1-8. Ingredient [F ']
Chlorinated polyethylene “Elastolene 353YB” (trade name) manufactured by Showa Denko KK was used.
1-9. Ingredient [G]
Dimethylpolysiloxane “SH200-12500CS” (trade name) manufactured by Toray Dow Corning Silicone was used.

2. Production of Flame Retardant Antistatic Resin Composition and Its Evaluation Examples 1-12 and Comparative Examples 1-9
After supplying said component (A) and (B) to the Henschel mixer in the ratio of Table 1-Table 3, and mixing for 3 minutes at room temperature, a 50 mm diameter extruder "NVC50" (model) by Nakatani Machinery Co., Ltd. Name) was used for melt kneading (cylinder temperature 230 ° C.). Thereafter, this was used as a cylindrical pellet (a flame-retardant antistatic resin composition).

About the obtained flame-retardant antistatic resin composition, the test piece of the shape and magnitude | size according to an evaluation item was produced on the following conditions, and the evaluation shown below was performed. The results are shown in Tables 1 to 3.
<Molding conditions>
・ Molding equipment: JSW injection molding machine “J-100E” (model name)
Molding temperature: NH (200 ° C), H1 (200 ° C), H2 (200 ° C), H3 (200 ° C)
-Screw rotation speed: 80rpm
・ Injection speed: 50%
・ Injection pressure: 30%
-Holding pressure: 15%
-Cooling time: 25 seconds-Mold temperature: 50 ° C

(1) Surface resistance value In accordance with JIS K6911, the surface resistance value of a disk-shaped test piece (diameter: 100 mm, thickness: 2 mm) was measured using a “Hyrestar UPMCP-HT450” (model name) manufactured by Mitsubishi Chemical Corporation. The measurement was performed at 23 ° C. and a humidity of 50%.
(2) Flame retardance In accordance with the combustion test of UL94 standard, it evaluated using the test piece of thickness 1.5mm.
(3) Charpy impact strength Measured according to ISO 179.
(4) Tensile strength Measured according to ISO 527.
(5) Flexural strength Measured according to ISO 178.
(6) Bending modulus Measured according to ISO 178.
(7) Deflection temperature under load Measured according to ISO 75 (Under Load).
(8) Rockwell hardness Measured according to ISO 2039.
(9) Melt mass flow rate (MFR)
According to ISO 2039, the measurement was performed under conditions of a temperature of 220 ° C. and a load of 98 N.

From Tables 1 to 3, the following is clear.
Comparative Example 1 is an example in which the content of the component [B] is small outside the scope of the present invention, the surface resistance value is large, and the antistatic property is inferior. Comparative Example 2 is an example in which the content of the component [B] is large outside the scope of the present invention, and the flame retardancy, impact resistance and fluidity are inferior. Comparative Example 3 is an example using a flame retardant outside the scope of the present invention, inferior in flame retardancy, low bending modulus and inferior in rigidity. Comparative Example 4 is an example in which the content of the component [F] is small outside the scope of the present invention, and is inferior in flame retardancy. Comparative Example 5 is an example in which the content of the component [C] is small outside the scope of the present invention, the surface resistance value is large, the antistatic property is inferior, and the moldability is also inferior. Comparative Example 6 is an example in which the content of component [C] is large outside the scope of the present invention, and the flame retardancy and bending modulus are inferior. Comparative Example 7 is an example in which the content of the component [D] is small outside the scope of the present invention, and is inferior in flame retardancy. Comparative Example 8 is an example in which the content of the component [D] is large outside the scope of the present invention, the impact resistance is inferior, the surface resistance value is large, and the antistatic property is inferior. Comparative Example 9 is an example having a composition outside the scope of the present invention using chlorinated polyethylene in place of polytetrafluoroethylene, and is inferior in flame retardancy.
On the other hand, Examples 1-12 are all examples of the flame-retardant antistatic resin composition of the present invention, and the intended performance of the present invention is obtained.

  The flame-retardant antistatic resin composition of the present invention is a member, part, etc. used for electronics products, optical products, home appliances, OA equipment, semiconductor-related products, vehicles, building materials, etc., for example, housings, containers, support members, etc. , Covers, trays, cards, belts, cassettes, cartridges, connectors, pallets and the like.

Claims (3)

[A] A graft copolymer (A1) obtained by polymerizing a vinyl monomer (a2) not containing a hydroxyl group-containing vinyl monomer in the presence of the rubbery polymer (a1), or A rubber-reinforced vinyl resin comprising the graft copolymer (A1) and a mixture of the (co) polymer (A2) obtained using the vinyl monomer (a2);
[B] Graft copolymer (B1) obtained by polymerizing vinyl monomer (b2) containing a hydroxyl group-containing vinyl monomer in the presence of rubbery polymer (b1), and / or And (co) polymer (B2) obtained using the vinyl monomer (b2), and the content of the monomer unit comprising the hydroxyl group-containing vinyl monomer is 1 to 20 A resin that is mass%,
[C] a polymeric antistatic agent;
[D] a flame retardant comprising a compound having a bromine atom;
[E] an antimony compound;
[F] tetrafluoroethylene (co) polymer;
A flame retardant antistatic resin composition comprising:
Each content of the resin [B], the polymer antistatic agent [C], the flame retardant [D], the antimony compound [E] and the tetrafluoroethylene (co) polymer [F] 1 to 20 parts by mass, 5 to 30 parts by mass, 20 to 35 parts by mass, 1 to 15 parts by mass, and 0.05 to 2 parts by mass with respect to 100 parts by mass of the rubber-reinforced vinyl resin [A]. The ratio Br / Sb between the content of bromine atoms constituting the flame retardant [D] and the content of antimony atoms constituting the antimony compound [E] is 1 to 5, and conforms to the UL94 standard. A flame-retardant antistatic resin composition, wherein the combustibility is V-0 or V-1.   Furthermore, it contains [G] a silicone compound, and the content of the silicone compound [G] is 0.1 to 8 parts by mass with respect to 100 parts by mass of the rubber-reinforced vinyl resin [A]. The flame-retardant antistatic resin composition described in 1. The flame-retardant antistatic resin composition according to claim 1 or 2, wherein the molded article containing the flame-retardant antistatic resin composition has a surface resistance value of less than 5 × 10 ¹¹ Ω.