JP2010209218A - Antistatic resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic resin composition obtaining a molded article excellent in antistatic property, shock resistance and surface appearance of a molded article. <P>SOLUTION: The antistatic resin composition is obtained by compounding: 5 to 98 mass% of a rubber-reinforced styrene resin (A) obtained by polymerizing an aromatic vinyl compound, or an aromatic vinyl compound and other vinyl monomers (b1) copolymerizable with the aromatic vinyl compound, in the presence of a rubbery polymer (a); 0 to 80 mass% of a styrene resin (B) obtained by polymerizing an aromatic vinyl compound, or an aromatic vinyl compound and other vinyl monomers (b2) copolymerizable with the aromatic vinyl compound; 2 to 50 mass% of a block copolymer and/or its hydrogenated product, having a conjugate diene polymer block [where the total of the components (A), (B) and (C) is 100 mass%]; and an ionic compound (D) that is liquid at normal temperature by 0.01 to 20 parts by mass with respect to total 100 parts by weight of the components (A), (B) and (C). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an antistatic resin composition and a molded article, and more specifically, an antistatic resin composition having excellent antistatic properties, impact resistance, and molded article surface appearance, and the antistatic resin composition. A molded article comprising

  Rubber-reinforced styrene-based resins such as ABS resin are excellent in mechanical properties, physical properties, moldability, etc., so they can be used in a wide range of fields such as the vehicle field, electrical / electronic field, OA / home appliance field, building material field, and sanitary field. Used in. However, because it has the disadvantage of being easily charged, it is used for various parts, sheets, films, etc. used in liquid crystal display devices, semiconductor peripherals, plasma displays, clean rooms, etc. It was difficult to do and the use was limited.

  In order to solve the above problem, for example, a composition in which a surfactant, conductive carbon, metal powder, conductive fiber and the like are blended with a rubber-reinforced styrene resin is known. However, when a surfactant is blended, there is a problem that antistatic properties are difficult to be exhibited and that antistatic durability cannot be obtained. On the other hand, when conductive carbon, metal powder, conductive fiber, or the like is blended, there is a problem that these conductive substances fall off and cause sparks to damage parts and the like.

  A composition in which polyether ester amide is blended with a rubber-reinforced styrene-based resin such as an ABS resin has been disclosed for the purpose of antistatic durability and non-blending of a conductive material, which are the above-mentioned problems (Patent Documents 1 to 3). 3). These compositions have a problem that the antistatic property is not sufficient, although there is no problem of antistatic durability and spark.

  On the other hand, a resin composition in which an ionic compound that is liquid at room temperature is blended with a thermoplastic resin has been proposed (Patent Documents 4 and 5). However, normally, even when an ionic compound that is liquid at room temperature is blended with an ABS resin, there is a problem that antistatic properties are hardly exhibited. An ionic compound that is liquid at room temperature is also called “ionic liquid” or “room temperature molten salt”.

JP 63-23435 A JP-A-4-309547 JP-A-2-292353 Special table 2003-511505 gazette JP-A-10-265673

  An object of the present invention is to provide an antistatic resin composition having excellent antistatic properties, impact resistance, and molded article surface appearance. Another object of the present invention is to provide a molded article comprising the above antistatic resin composition.

  As a result of intensive studies to achieve the above object, the present inventor has formulated a specific rubber component in a composition in which a rubber-reinforced styrene resin and an ionic liquid are blended. The inventors found that an antistatic resin composition excellent in appearance of a molded product can be obtained, and completed the present invention.

  That is, the first gist of the present invention is that an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer (b1) copolymerizable with the aromatic vinyl compound in the presence of the rubbery polymer (a). Polymerizing rubber-reinforced styrene resin (A) 5 to 98% by mass obtained by polymerization, aromatic vinyl compound or aromatic vinyl compound and other vinyl monomer (b2) copolymerizable with aromatic vinyl compound Styrenic resin (B) 0 to 80% by mass, block copolymer having a conjugated diene polymer block and / or hydrogenated product (C) 2 to 50% by mass [in addition, component (A), component (B ) And component (C) is 100% by mass], and ionic compound (D) 0.01 which is liquid at room temperature with respect to a total of 100 parts by weight of component (A), component (B) and component (C). ~ 20 parts by weight blended It consists in antistatic resin composition characterized. And the 2nd summary of this invention exists in the molded article characterized by consisting of said antistatic resin composition.

  According to the antistatic resin composition of the present invention, a molded product having excellent antistatic properties, impact resistance, and molded product surface appearance can be obtained.

  The present invention will be described in detail below. In the present specification, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acrylate” means acrylate and / or methacrylate. Further, the antistatic resin composition of the present invention is simply abbreviated as “composition”.

  Component (A) used in the present invention is an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the rubbery polymer (a). Is a rubber-reinforced styrene resin obtained by polymerizing

  The rubbery polymer (a) used here has a glass transition temperature (Tg) of −10 ° C. or less, such as polybutadiene, polyisoprene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, and the like. Conjugated diene rubber, ethylene / propylene copolymer, ethylene / propylene / nonconjugated diene copolymer, ethylene / butene-1 copolymer, ethylene / butene-1 / nonconjugated diene copolymer, and other olefin rubbers Acrylic rubber, silicone rubber, polyurethane rubber, silicone / acrylic IPN rubber, natural rubber, conjugated diene block copolymer, hydrogenated conjugated diene block copolymer, and the like. Among the conjugated diene rubbers, butadiene rubbers such as polybutadiene, butadiene / styrene copolymers, butadiene / acrylonitrile copolymers are preferable. Among the olefin rubbers, ethylene-α / olefin rubbers such as ethylene / propylene copolymer and ethylene / propylene / non-conjugated diene copolymer are preferable. Acrylic rubbers, conjugated diene block copolymers, and hydrogenated conjugated diene block copolymers are also preferred. In particular, an olefin rubber and a hydrogenated conjugated diene block copolymer are preferable. Two or more of these may be used in combination.

  Examples of the non-conjugated diene compound used in the olefin-based rubber include alkenyl norbornenes, cyclic dienes, and aliphatic dienes, and dicyclopentadiene and 5-ethylidene-2-norbornene are preferable. These non-conjugated diene compounds may be used in combination of two or more. The content of the non-conjugated diene compound unit in the olefin rubber is usually less than 30% by mass, preferably less than 15% by mass.

  The acrylic rubber is not particularly limited, but a (co) polymer of a (meth) acrylic acid alkyl ester compound having 1 to 8 carbon atoms in the alkyl group, or the (meth) acrylic acid alkyl ester compound and the same. A copolymer of a vinyl monomer that can be copolymerized with the monomer is preferred.

  Specific examples of the acrylic acid alkyl ester compound having 1 to 8 carbon atoms in the alkyl group used here include methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, i-butyl acrylate, amyl acrylate, and hexyl. Examples include acrylate, n-octyl acrylate, 2-ethylhexyl acrylate, and cyclohexyl acrylate. Specific examples of the methacrylic acid alkyl ester include methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl methacrylate, i-butyl methacrylate, amyl methacrylate, hexyl methacrylate, n-octyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate and the like. It is done. Among these, n-butyl acrylate and 2-ethylhexyl acrylate are preferable. Moreover, these may use 2 or more types together.

  Examples of the vinyl monomer copolymerizable with the (meth) acrylic acid alkyl ester compound include polyfunctional vinyl compounds, aromatic vinyl compounds, and vinyl cyanide compounds. The polyfunctional vinyl compound refers to a monomer having two or more vinyl groups in one monomer molecule, the function of crosslinking the (meth) acrylic copolymer, and the reaction starting point during graft polymerization. It plays a role. Specific examples of the polyfunctional vinyl monomer include polyfunctional aromatic vinyl compounds such as divinylbenzene and divinyltoluene; (meta) of polyhydric alcohols such as (poly) ethylene glycol dimethacrylate and trimethylolpropane triacrylate (meta ) Acrylic acid ester; diallyl malate, diallyl fumarate, triallyl cyanurate, triallyl cyanurate, diallyl phthalate, allyl methacrylate and the like. Two or more of these polyfunctional vinyl compounds may be used in combination.

  As the aromatic vinyl compound and the vinyl cyanide compound used here, all those described later can be used. Furthermore, as other copolymerizable monomers, acrylamide, methacrylamide, vinylidene chloride, alkyl (carbon number 1 to 6) vinyl ether, alkyl group (meth) acrylic acid alkyl ester having 9 or more carbon atoms, ( And (meth) acrylic acid. Two or more of these may be used in combination.

  A preferable monomer composition of the acrylic rubber is a (meth) acrylic acid alkyl ester compound unit having 1 to 8 carbon atoms in the alkyl group: usually 80 to 99.99 mass%, preferably 90 to 99.95 mass. %, Polyfunctional vinyl compound unit: usually 0.01 to 5% by mass, preferably 0.05 to 2.5% by mass, and other vinyl monomers copolymerizable therewith: usually 0 to 20% by mass Preferably, it is 0-10 mass%. However, the total monomer composition is 100% by mass.

  As the conjugated diene block copolymer, specifically, a copolymer comprising at least one of the following block A or the following block C and at least one of the following block B or the following block A / B, Or it is a polymer by block B or A / B, and the polymerization method is a well-known method with an anionic polymerization method. For example, it can be produced by a method disclosed in Japanese Patent Publication No. 47-28915, Japanese Patent Publication No. 47-3252, Japanese Patent Publication No. 48-2423, Japanese Patent Publication No. 48-20038, and the like. The specific structures are respectively: A: aromatic vinyl compound polymer block, B: conjugated diene polymer block, A / B: aromatic vinyl compound / conjugated diene random copolymer block, C: conjugated diene and aromatic The following structure may be mentioned when the taper block is composed of a copolymer of an aromatic vinyl compound and the aromatic vinyl compound is gradually increased.

[Chemical 1]
AB (1)
A-B-A (2)
A-B-C (3)
A-B1-B2 (4)
(Here, B1 is a conjugated diene polymer block or a copolymer block of a conjugated diene and an aromatic vinyl compound, and the vinyl bond content of the conjugated diene moiety is usually 20% or more, and B2 is a conjugated diene weight. (It is a copolymer block or a copolymer block of a conjugated diene and an aromatic vinyl compound, and the vinyl bond content of the conjugated diene moiety is usually less than 20%.)

[Chemical 2]
A-A / B (5)
AA / B-C (6)
A-A / B-A (7)
B2-B1-B2 (8)
(Here, B1 and B2 have the same meaning as described above.)

[Chemical formula 3]
CB (9)
C-B-C (10)
C-A / B-C (11)
C-A-B (12)

  Moreover, the copolymer which repeats these basic skeletons can be mentioned, Furthermore, the conjugated diene type block copolymer obtained by coupling it may be sufficient. Regarding the structure of the above formula (4), JP-A-2-133406, and for the structure of the above formula (5) and the above formula (6), JP-A-2-305814, It is shown in Japanese Patent No. 72512.

  The conjugated dienes used here include 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 2-methyl-1,3-pentadiene, 1,3- Hexadiene, 4,5-diethyl-1,3-octadiene, 3-butyl-1,3-octadiene, chloroprene and the like can be mentioned. In order to obtain a conjugated diene block copolymer which can be used industrially and has excellent physical properties, 1,3-butadiene, isoprene and 1,3-pentadiene are preferable, and 1,3-butadiene is more preferable. It is.

  Examples of the aromatic vinyl compound used here include styrene, t-butylstyrene, α-methylstyrene, p-methylstyrene, hydroxystyrene, vinylxylene, monochlorostyrene, dichlorostyrene, monobromostyrene, dibromo. Styrene, fluorostyrene, pt-butyl styrene, ethyl styrene, vinyl naphthalene, divinyl benzene, 1,1-diphenyl styrene, N, N-diethyl-p-aminoethyl styrene, N, N-diethyl-p-aminoethyl Examples include styrene and vinyl pyridine. Among these, preferred is styrene or α-methylstyrene, and particularly preferred is styrene.

  The ratio of the aromatic vinyl compound / conjugated diene in the conjugated diene block copolymer is usually 0 to 70/100 to 30, preferably 0 to 60/100 to 40, and more preferably 0 to 50 as a mass ratio. When the aromatic vinyl compound is essential, it is preferably 10-70 / 90-30. Here, when the content of the aromatic vinyl compound exceeds 70% by mass, it becomes resinous and the effect as a rubber component is inferior. Furthermore, the vinyl bond content of the conjugated diene moiety in the conjugated diene block is usually in the range of 5 to 80%.

  The number average molecular weight of the conjugated diene block copolymer is usually 10,000 to 1,000,000, preferably 20,000 to 500,000, and more preferably 20,000 to 200,000. In particular, the number average molecular weight of the A part in the above structural formula is preferably 3,000 to 150,000, and the number average molecular weight of the B part is preferably 5,000 to 200,000.

  Adjustment of the vinyl bond amount of the conjugated diene compound is carried out by using amines such as N, N, N ′, N′-tetramethylethylenediamine, trimethylamine, triethylamine, diazocyclo (2,2,2) octamine, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diester. It can be carried out using ethers such as butyl ether, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, alkoxides of potassium and sodium, and the like.

  Examples of the coupling agent used in the present invention include diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2 -Dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate and the like.

  The hydrogenated conjugated diene block copolymer used in the present invention is such that at least 30% or more, preferably 50% or more, of the carbon-carbon double bonds in the conjugated diene portion of the conjugated diene block copolymer are hydrogenated. Partial hydrogenated or completely hydrogenated, and more preferably 90% or more hydrogenated hydrogenated.

  The hydrogenation reaction of the conjugated diene block copolymer can be carried out by a known method, and the target polymer can be obtained by adjusting the hydrogenation rate 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 gel content of the rubbery polymer (a) used in the present invention is not particularly limited, but is usually 90% by mass or less. The gel content can be determined by the following method.

That is, 1 g of the rubbery polymer (a) is put into 100 ml of toluene and allowed to stand at room temperature for 48 hours. Thereafter, the toluene-insoluble portion and the wire mesh filtered through a 100-mesh wire mesh (mass is W1 gram) are vacuum-dried at a temperature of 80 ° C. for 6 hours and weighed (mass W2 gram). The gel content is obtained by substituting W1 and W2 into the following formula (13). Some ethylene-propylene rubbery polymers have ethylene crystals, and when such rubbery polymers are used, they are dissolved at a temperature of 80 ° C. to obtain the gel content.
[Equation 1]
Gel content = [[W2 (g) -W1 (g)] / 1 (g)] × 100 (13)

  The gel content is determined at the time of production of the rubbery polymer (a) by determining the type of crosslinkable monomer and the amount of use thereof, the type of molecular weight regulator and the amount of use thereof, the polymerization time, the polymerization temperature, the polymerization conversion rate, etc. It can be adjusted by appropriately setting.

  The rubbery polymer (a) used in the present invention can be obtained by a known method such as emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization or the like. Among these, butadiene rubber and acrylic rubber are preferably produced by emulsion polymerization, and ethylene / propylene copolymer, ethylene / propylene / nonconjugated diene copolymer, conjugated diene block copolymer, and The hydrogenated conjugated diene block copolymer is preferably produced by solution polymerization.

  The rubber-reinforced styrene-based resin as component (A) is an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the rubbery polymer (a). It can be obtained by polymerizing the body (b1). As the aromatic vinyl compound used here, all of those described in the rubber polymer (a) can be used. Particularly preferred are styrene and α-methylstyrene. Two or more of these may be used in combination.

  Examples of other vinyl monomers copolymerizable with the aromatic vinyl compound include vinyl cyanide compounds, (meth) acrylic acid ester compounds, maleimide compounds, and other various functional group-containing unsaturated compounds. As other various functional group-containing unsaturated compounds, unsaturated acid compounds, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, substituted or unsubstituted And amino group-containing unsaturated compounds. Two or more of these other vinyl monomers may be used in combination.

  Examples of the vinyl cyanide compound include acrylonitrile and methacrylonitrile. These may be used in combination of two or more. Chemical resistance is imparted by using a vinyl cyanide compound. The usage-amount of a vinyl cyanide compound is 0-60 mass% normally as a ratio in the vinyl monomer whole quantity (b1), Preferably it is 5-50 mass%.

  Examples of the (meth) acrylic acid ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like, and these may be used in combination of two or more. By using the (meth) acrylic acid ester compound, the surface hardness is improved. The usage-amount of a (meth) acrylic acid ester compound is 0-80 mass% normally as a ratio in vinyl monomer whole quantity (b1).

  As said maleimide compound, maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, etc. are mentioned, These may use 2 or more types together. In order to introduce maleimide units, maleic anhydride may be copolymerized and then imidized. Heat resistance is imparted by using a maleimide compound. The usage-amount of a maleimide compound is 1-60 mass% normally as a ratio in the vinyl monomer whole quantity (b1).

  Examples of the unsaturated acid compound include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, and cinnamic acid, and these may be used 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 may be used in combination of two or more.

  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-3- Examples thereof include methyl-1-propene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N- (4-hydroxyphenyl) maleimide, and these may be used in combination of two or more.

  Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline, and these may be used 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 two or more of these may be used in combination.

  Examples of substituted or unsubstituted amino group-containing unsaturated compounds include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, phenylaminoethyl methacrylate, N-vinyldiethylamine, N-acetylvinylamine, and acrylamine. , N-methylacrylamine, acrylamide, N-methylacrylamide, p-aminostyrene and the like, and two or more of these may be used in combination.

  When the above other various functional group-containing unsaturated compounds are used, when the rubber-reinforced styrene resin (A), the styrene resin (B) and another thermoplastic polymer (E) are blended, both phases Solubility can be improved. Preferred monomers for achieving such an effect are an epoxy group-containing unsaturated compound, an unsaturated acid, an acid anhydride group-containing unsaturated compound, and a hydroxyl group-containing unsaturated compound. The amount of the other functional group-containing unsaturated compound used is usually 0.1 to 20% by mass as the total amount of the functional group-containing unsaturated compound with respect to the total of component (A) and component (B). Preferably, it is 0.1-10 mass%.

  The amount of monomers other than the aromatic vinyl compound in the total amount of vinyl monomer (b1) is usually 80% by mass or less, preferably 60% by mass or less, when the total of (b1) is 100% by mass. More preferably, it is 50 mass% or less.

  More preferable (or combination) monomers constituting the vinyl monomer (b1) are styrene alone, styrene / acrylonitrile, styrene / methyl methacrylate, styrene / acrylonitrile / methyl methacrylate, styrene / acrylonitrile / Glycidyl methacrylate, styrene / acrylonitrile / 2-hydroxyethyl methacrylate, styrene / acrylonitrile / (meth) acrylic acid, styrene / N-phenylmaleimide, styrene / methyl methacrylate / cyclohexyl maleimide, and more preferably styrene alone Styrene / acrylonitrile = 65 / 45-90 / 10 (mass ratio), styrene / methyl methacrylate = 80 / 20-20 / 80 (mass ratio), styrene / acrylonitrile / methacrylic acid methyl , And the styrene content of 20 to 80 wt%, the sum of acrylonitrile and methyl methacrylate is any in the range of 20 to 80 wt%.

  The rubber-reinforced styrene resin (A) used in the present invention can be produced by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a polymerization method combining these. In the polymerization method, a rubbery polymer obtained by emulsion polymerization can be produced by emulsion polymerization in the production of component (A), and a rubbery polymer obtained by solution polymerization. In this case, the component (A) is generally and preferably produced by bulk polymerization, solution polymerization and suspension polymerization. However, even in the case of a rubbery polymer produced by solution polymerization, the component (A) can be produced by emulsion polymerization if the rubbery polymer is emulsified by a known method. Even in the case of a rubbery polymer produced by polymerization, the component (A) can be produced by solidification, solution polymerization and suspension polymerization after solidification and isolation.

  In the case of producing by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier and the like are used, and all of these known ones can be used.

  Examples of the polymerization initiator include cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, tetramethylbutyl hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, azobisisobutyronitrile and the like. Can be mentioned. Moreover, it is preferable to use redox systems such as various reducing agents, sugar-containing iron pyrophosphate formulations, sulfoxylate formulations, etc. as polymerization initiation aids.

  Examples of the chain transfer agent include octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, terpinolene and the like.

  Emulsifiers include alkylbenzene sulfonates such as sodium dodecylbenzene sulfonate, aliphatic sulfonates such as sodium lauryl sulfate, higher fatty acid salts such as potassium laurate, potassium stearate, potassium oleate, and potassium palmitate, rosin acid A rosinate such as potassium can be used.

  In the emulsion polymerization, the rubber polymer (a) and the vinyl monomer (b1) are used by adding the vinyl monomer (b1) in the presence of the entire amount of the rubber polymer (a). May be polymerized, or may be polymerized by dividing or continuously adding. Moreover, you may add a part of rubber-like polymer (a) in the middle of superposition | polymerization.

  After emulsion polymerization, the resulting latex is usually coagulated with a coagulant. Then, the powder of a component (A) is obtained by washing with water and drying. At this time, the latex of two or more components (A) obtained by emulsion polymerization may be appropriately blended and then coagulated, and further the component (B) latex may be appropriately blended and then coagulated. . As the coagulant, inorganic salts such as calcium chloride, magnesium sulfate and magnesium chloride, and acids such as sulfuric acid, acetic acid, citric acid and malic acid can be used. Moreover, the powder of a component (A) can also be obtained by spray-drying latex.

  Solvents that can be used when the component (A) is produced by solution polymerization are inert polymerization solvents used in ordinary radical polymerization, such as aromatic hydrocarbons such as ethylbenzene and toluene, methyl ethyl ketone, and acetone. And ketones such as acetonitrile, dimethylformamide, N-methylpyrrolidone and the like.

  The polymerization temperature is usually in the range of 80 to 140 ° C, preferably 85 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, azobisisobutyronitrile, and benzoyl peroxide are preferably used. Further, when a chain transfer agent is used, for example, mercaptans, terpinolenes, α-methylstyrene dimer and the like can be used.

  Moreover, when manufacturing by block polymerization and suspension polymerization, the polymerization initiator, chain transfer agent, etc. which were demonstrated in solution polymerization can be used. The amount of residual monomer in the component (A) obtained by each polymerization method is usually 10,000 ppm or less, preferably 5,000 ppm or less.

  The polymer monomer obtained by polymerizing the vinyl monomer (b1) in the presence of the rubber polymer (a) contains the above-mentioned vinyl monomer (b1) as the rubber polymer (a ) Includes a copolymer obtained by graft copolymerization and an ungrafted component [(co) polymer of the above vinyl monomer (b1)] which is not grafted to the rubber polymer.

The graft ratio of the rubber-reinforced styrene resin (A) is usually 5 to 100% by mass, preferably 10 to 90% by mass, more preferably 15 to 85% by mass, and particularly preferably 20 to 80% by mass. Graft rate is the type of polymerization initiator, the amount used, the type of chain transfer agent, the amount used, the polymerization method, the contact time between the monomer and the rubber polymer during polymerization, the type of rubber polymer, the polymerization temperature, etc. It can be changed by various factors.
The graft rate can be obtained by the following formula (14).

[Equation 2]
Graft ratio (mass%) = {(TS) / S} × 100 (14)

In the above formula (14), T is a mixture of 1 g of rubber-reinforced styrene resin in 20 ml of acetone, shaken with a shaker for 2 hours, and then centrifuged for 60 minutes with a centrifuge (rotation speed: 23,000 rpm). And S is the mass (g) of the rubbery polymer contained in 1 g of the rubber-reinforced styrene resin.
When only an aromatic vinyl compound is used as the vinyl monomer (b1), methyl ethyl ketone is used as a solvent instead of acetone.

  Further, the intrinsic viscosity [η] of acetone-soluble component of the rubber-reinforced styrene resin (A) used in the present invention (measured at 30 ° C. using methyl ethyl ketone as a solvent) is usually 0.15 to 1.2 dl. / G, preferably 0.2 to 1.0 dl / g, more preferably 0.2 to 0.8 dl / g. The average particle diameter of the grafted rubbery polymer particles dispersed in the rubber-reinforced styrene resin (A) is usually 50 to 3,000 nm, preferably 100 to 2,500 nm, and more preferably 150 to 2,000 nm. . When the rubber particle diameter is less than 50 nm, the impact resistance tends to be inferior, and when it exceeds 3,000 nm, the appearance of the molded product surface tends to be inferior. Further, the refractive index of the copolymer of the rubber polymer and vinyl monomer to be used is substantially matched and / or the particle diameter of the rubber polymer to be dispersed is substantially equal to or less than the wavelength of visible light (usually The component (A) having transparency can be obtained by setting the thickness to 1,500 nm or less, but these transparent resins can also be used as the component (A).

  The rubber-reinforced styrene resin (A) can be used in combination of two or more different rubbery polymers (a). Preferred combination is rubber reinforced styrene resin using butadiene rubber / rubber reinforced styrene resin using ethylene-α / olefin rubber, rubber reinforced styrene resin using butadiene rubber / hydrogenated conjugated diene block Rubber reinforced styrene resin using copolymer, rubber reinforced styrene resin using acrylic rubber / rubber reinforced styrene resin using ethylene-α / olefin rubber, rubber reinforced styrene resin using acrylic rubber This is a rubber-reinforced styrene resin using a resin / hydrogenated conjugated diene block copolymer. A preferred combination ratio is in the range of 5 to 95/5 to 95% by mass.

  The amount of the rubbery polymer in the rubber-reinforced styrene resin (A) is not particularly limited, but is usually 3 to 75% by mass, preferably 5 to 70% by mass, more preferably 6 to 65% by mass, and particularly preferably. Is 10-60 mass%.

  The usage-amount of the said component (A) is 5-98 mass% in the total of 100 mass% of a component (A), a component (B), and a component (C), Preferably it is 8-95 mass%, More preferably, it is 10- It is 90% by mass, particularly preferably 15 to 85% by mass. If the amount used is less than 5% by mass, the impact resistance is inferior.

  Component (B) is a styrenic resin formed by polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer (b2) copolymerizable with the aromatic vinyl compound. As the aromatic vinyl compound and other vinyl monomers copolymerizable with the aromatic vinyl compound, all those described in the component (A) can be used.

  Preferred components (B) include styrene homopolymers, styrene / acrylonitrile copolymers, styrene / methyl methacrylate copolymers, styrene / acrylonitrile / methyl methacrylate copolymers, styrene / maleimide compound copolymers, and the like. And a functional group-containing unsaturated compound.

  A component (B) can be manufactured by the well-known method which combined emulsion polymerization, block polymerization, solution polymerization, suspension polymerization, and these described with the manufacturing method of above-mentioned component (A).

The usage-amount of a component (B) is 0-90 mass% in a total of 100 mass% of a component (A), a component (B), and a component (C). Component (B) is used for the purpose of adjusting the amount of rubber polymer (a) in component (A) + component (B), and the amount of rubber polymer is determined between component (A) and component (B). Is preferably 3 to 50% by mass, more preferably 5 to 40% by mass, and particularly preferably 6 to 30% by mass. If the amount of the rubbery polymer is small, the impact resistance tends to decrease. If the amount is too large, the surface appearance of the molded product tends to be inferior.
In addition, the component (B) is to change the (co) polymer species to give a function to the composition of the present invention and to improve compatibility with other thermoplastic polymers (E). Formulated for purposes.

  The component (C) is a block copolymer (C1) having a conjugated diene polymer block and / or a hydrogenated product (C2) thereof. As the components (C1) and (C2) used here, Examples thereof include conjugated diene block copolymers and hydrogenated conjugated diene copolymers described in the rubbery polymer (a) and functional group-modified products thereof.

  Among these (C) components, preferred are a block copolymer having a hydrogenated conjugated diene block and a functional group-modified product thereof. As the component (C2), the conjugated diene moiety of the component (C1) is used. A hydrogenated product of carbon-carbon double bonds, the hydrogenated product of which hydrogenated 50% or more of the carbon-carbon double bond of the conjugated diene moiety, more preferably a portion hydrogenated of 70% or more Hydrogenated and fully hydrogenated.

  Further, as these functional group-modified products, those modified with a functional group-containing unsaturated compound described as the vinyl monomer of component (A) are preferably used. As a method of modifying with a functional group-containing unsaturated compound, the component (C) is functionalized by allowing the functional group-containing unsaturated compound and, if necessary, an organic peroxide to exist in the solution or molten state of the component (C). A known method such as a method of adding a group-containing unsaturated compound can be used.

  The functional group used here is preferably an acid anhydride group, an epoxy group, a carboxyl group, or an amino group, more preferably an acid anhydride group or an epoxy group, and particularly preferably an acid anhydride group. The addition amount of the group-containing unsaturated compound is usually 0.1 to 10% by mass, preferably 0.5 to 8% by mass, and more preferably 1 to 5% by mass.

  The usage-amount of a component (C) is 2-50 mass% in the total of 100 mass% of a component (A), a component (B), and a component (C), Preferably it is 2-45 mass%, More preferably, it is 3-40. It is 4 to 35% by mass, particularly preferably 4 to 35% by mass. When the content is less than 2% by mass, the antistatic property is inferior.

  The ionic compound (D) that is liquid at room temperature used in the present invention (hereinafter referred to as “ionic liquid”) is basically a salt composed of a liquid cation and an anion near room temperature. It is an ionic compound which has an ionic center of nitrogen atom or an ionic center of phosphorus atom and is liquid at a temperature of 100 ° C. or lower. Examples of the ionic liquid include salts represented by the following general formula (15), but are not limited thereto.

[Chemical formula 4]
N ⁺ A ⁻ (15)

In the general formula (15), N ⁺ represents a cation, a nitrogen cation or a phosphorus cation, and A ⁻ represents an anion.

Examples of the cation (N ⁺ ) include tetraalkylammonium ion, imidazolium ion, pyridium ion, pyrazolium ion, pyrrolium ion, pyrrolinium ion, pyrrolidinium ion, piperidinium ion, and phosphonium ion. From the expression, imidazolium cation, pyridinium cation, pyrrolidinium cation, phosphonium cation, ammonium cation and the like are preferable. These can be used in combination of two or more.

Specific examples of the anion (A ⁻ ) include AlCl ₄ ⁻ , Al ₃ Cl ₈ ⁻ , Al ₂ Cl ₇ ⁻ , PF ₆ ⁻ , BF ₄ ⁻ , SbF ₆ ⁻ , AsF ₆ ⁻ , TaF ₆ ⁻ and BF ₃ Cl. _{^{-, BF 5 Cl -, SbF}} 5 Cl -, BF 3 Br -, BF 5 Br -, SbF 5 Br -, AsF 5 Br -, TaF 5 Br -, BF 5 I -, SbF 5 I -, AsF 5 I _{^{-, TaF 5 I -, CF}} 3 SO 3 -, (CF 3 SO 2) 2 N -, (CF 3 SO 2) 3 C -, Cl -, Br -, RCO 2 - (R is an organic group) and the like Can be mentioned. Two or more of these may be used in combination.

  The ionic liquid that can be suitably used in the present invention is at least one selected from imidazolium salts, pyridinium salts, pyrrolidinium salts, phosphonium salts, ammonium salts, and the like.

  Examples of the imidazolium salt include 1-ethyl-3-methylimidazolinium bromide, 1-ethyl-3-methylimidazolinium hexafluorophosphate, 1-ethyl-3-methylimidazolinium hexafluoroantimony. Nate, 1-ethyl-3-methylimidazolinium tetrafluoroborate, 1-ethyl-3-methylimidazolinium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolinium bistrifluoromethanesulfonylimide, 1-ethyl -3-methylimidazolinium methane sulfate, 1-ethyl-3-methylimidazolinium tosylate, 1-ethyl-3-methylimidazolinium bis [salicylate (2)] borate, 1-ethyl-3-methyl Imidazolinium cobalt Lacarbonyl, 1-butyl-3-methylimidazolinium chloride, 1-butyl-3-methylimidazolinium hexafluorophosphate, 1-butyl-3-methylimidazolinium hexafluoroantimonate, 1-butyl-3 -Methylimidazolinium tetrafluoroborate, 1-butyl-3-methylimidazolinium trifluoromethanesulfonate, 1-butyl-3-methylimidazolinium bistrifluoromethanesulfonylimide, 1-butyl-3-methylimidazolinium Methanesulfate, 1-butyl-3-methylimidazolinium tosylate, 1-butyl-3-methylimidazolinium bis [salicylate (2)] borate, 1-butyl-3-methylimidazolinium cobalt tetracarbonyl, 1-hex Ru-3-methylimidazolinium chloride, 1-hexyl-3-methylimidazolinium hexafluoroantimonate, 1-hexyl-3-methylimidazolinium tetrafluoroborate, 1-hexyl-3-methylimidazolinium trifluoride L-methanesulfonate, 1-hexyl-3-methylimidazolinium bistrifluoromethanesulfonylimide, 1-hexyl-3-methylimidazolinium methanesulfate, 1-methyl-3-octylimidazolinium chloride, 1-methyl- 3-octylimidazolinium hexafluoroantimonate, 1-methyl-3-octylimidazolinium tetrafluoroborate, 1-methyl-3-octylimidazolinium trifluoromethanesulfonate, 1-methyl-3-octane Tyrimidazolinium bistrifluoromethanesulfonylimide, 1-methyl-3-octylimidazolinium methanesulfate, 1-methyl-N-benzoylimidazolinium chloride, 1-methyl-N-benzoylimidazolinium hexafluorophosphate 1-methyl-N-benzylimidazolinium hexafluoroantimonate, 1-methyl-N-benzylimidazolinium tetrafluoroborate, 1-methyl-N-benzylimidazolinium trifluoromethanesulfonate, 1-methyl-N -Benzylimidazolinium trifluoromethanesulfonate, 1-methyl-N-benzylimidazolinium bistrifluoromethanesulfonylimide, 1-methyl-N-benzylimidazolinium methanesulfate, 1 Methyl-3- (3-phenylpropyl) imidazolinium chloride, 1-methyl-3- (3-phenylpropyl) imidazolinium hexafluorophosphate, 1-methyl-3- (3-phenylpropyl) imidazolinium Hexafluoroantimonate, 1-methyl-3- (3-phenylpropyl) imidazolinium tetrafluoroborate, 1-methyl-3- (3-phenylpropyl) imidazolinium trifluoromethanesulfonate, 1-methyl-3- (3-phenylpropyl) imidazolinium bistrifluoromethanesulfonylimide, 1-methyl-3- (3-phenylpropyl) imidazolinium methanesulfate, 1-2,3-dimethylimidazolinium chloride, 1-butyl- 2,3-dimethylimidazolinini Muhexafluorophosphate, 1-butyl-2,3-dimethylimidazolinium hexafluoroantimonate, 1-butyl-2,3-dimethylimidazolinium tetrafluoroborate, 1-butyl-2,3-dimethylimidazolium Tetrafluoroborate, 1-butyl-2,3-dimethylimidazolinium trifluoromethanesulfonate, 1-butyl-2,3-dimethylimidazolinium bistrifluoromethanesulfonylimide, 1-butyl-2,3-dimethylimidazoli Nitromethane sulfate, 1-ethyl-2,3-dimethylimidazolinium chloride, 1-ethyl-2,3-dimethylimidazolinium hexafluorophosphate, 1-ethyl-2,3-dimethylimidazolinium hexafluoro Antimonate 1-ethyl-2,3-dimethylimidazolium tetrafluoroborate, 1-ethyl-2,3-dimethylimidazolinium trifluoromethanesulfonate, 1-ethyl-2,3-dimethylimidazolinium bistrifluoromethanesulfonylimide 1-ethyl-2,3-dimethylimidazolinium methane sulfate and the like.

  Examples of the pyridinium salt include N-butylpyridinium chloride, N-butylpyridinium hexafluorophosphate, N-butylpyridinium hexafluoroantimonate, N-butylpyridinium tetrafluoroborate, N-butylpyridinium trifluoromethanesulfonate, N-butylpyridinium bistrifluoromethanesulfonylimide, N-butylpyridinium methanesulfate, 3-methyl-N-propylpyridinium chloride, 3-methyl-N-butylpyridinium hexafluorophosphate, 3-methyl-N-butylpyridinium hexa Fluoroantimonate, 3-methyl-N-butylpyridinium tetrafluoroborate, 3-methyl-N-butylpyridinium trifluoromethane Ruhoneito, 3-methyl -N- butylpyridinium bistrifluoromethanesulfonylimide, 3-methyl -N- butyl pyridinium methanesulfonate sulfate and the like.

  Examples of the pyrrolidinium salt include 1-ethyl-1-methylpyrrolidinium bromide, 1-ethyl-1-methylpyrrolidinium hexafluorophosphate, 1-ethyl-1-methylpyrrolidinium hexafluoroantimonate. 1-ethyl-1-methylpyrrolidinium hexafluoroantimonate, 1-ethylpyrrolidinium tetrafluoromethanesulfonate, 1-ethyl-1-methylpyrrolidinium, 1-butyl-1-methylpyrrolidinium Nitrobromide, 1-butyl-1-methylpyrrolidinium hexafluorophosphate, 1-butyl-1-methylpyrrolidinium hexafluoroantimonate, 1-butyl-1-methylpyrrolidinium tetrafluoroborate, 1-butyl -1-methylpyrrolidini Arm trifluoromethanesulfonyl Nate, 1-butyl pyrrolidinium bistrifluoromethanesulfonylimide, 1-butyl pyrrolidinium methanesulfonyl fate like is go up.

  Examples of the ammonium salt include tetra-n-butylammonium chloride and tetra-n-butylammonium bromide.

  Examples of the phosphonium salt include tetra-n-butylphosphonium bromide.

  Of the above ionic liquids, pyridinium salts are preferred. Among the pyridinium salts, preferred are sulfonate compounds and sulfonylimide compounds, and particularly preferred are 3-methyl-N-butylpyridinium trifluoromethanesulfonate and / or 3-methyl-N-butylpyridinium bistrifluoromethanesulfonyl. It is an imide. From the standpoint of antistatic properties, 3-methyl-N-butylpyridinium bistrifluoromethanesulfonylimide is particularly preferable.

  The amount of the ionic liquid (D) used is 0.01 to 20 parts by mass, preferably 0.05 to 15 parts by mass with respect to 100 parts by mass in total of the component (A), the component (B) and the component (C). More preferably, it is 0.1-10 mass parts, Most preferably, it is the range of 0.5-5 mass parts. If the usage-amount of an ionic liquid (D) is less than 0.01 mass part, the antistatic property of the composition obtained will not express. On the other hand, when the usage-amount of an ionic liquid (D) exceeds 20 mass parts, the impact resistance of the obtained composition and the molded article surface appearance are inferior.

  Another thermoplastic resin (E) can be further blended in the composition of the present invention. Component (E) includes polyolefin resin (E1), vinyl chloride resin (E2), acrylic resin (E3), aromatic polyester resin (E4), polyamide resin (E5), polyphenylene ether resin ( E6), polycarbonate resin (E7), polyurethane resin (E8), polyarylene sulfide resin (E9) and the like. Two or more of these thermoplastic resins may be used in combination.

  The polyolefin resin (E1) is composed of at least one olefin having 2 to 10 carbon atoms. Two or more of these polyolefin resins may be used in combination. By blending the polyolefin resin (E1), the chemical resistance may be improved and the weight may be reduced.

  Examples of olefins used to form olefin resins include ethylene and propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylhexene. Α-olefins such as −1. Of these, ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1 are preferable, and ethylene and propylene are particularly preferable. Two or more of these may be used in combination.

  Moreover, a cyclic olefin can be used as said olefins. The cyclic olefin is usually used together with the acyclic olefin. The cyclic olefin is not particularly limited as long as it is an alicyclic compound having one double bond, and examples thereof include compounds exemplified in JP-A-5-310845. Preferred cyclic olefins are compounds having 11 or less carbon atoms.

  As said cyclic olefin, norbornene is preferable and it is preferable that C11 or less norbornene (norbornene and / or a norbornene derivative) accounts for 50 mass% or more of the whole cyclic olefin. Specific examples of norbornenes include bicyclo [2.2.1] hept-2-ene, 6-methylbicyclo [2.2.1] hept-2-ene, and 5,6-dimethylbicyclo [2. 2.1] Hept-2-ene, 1-methylbicyclo [2.2.1] hept-2-ene, 6-ethylbicyclo [2.2.1] hept-2-ene, 6-n-butylbicyclo Bicyclo [2.2.1] hept-2-ene, 6-isobutylbicyclo [2.2.1] hept-2-ene, 7-methylbicyclo [2.2.1] hept-2-ene and the like 2.2.1] hept-2-ene derivatives, tricyclo [4.3.0.12.5] -3-decene, 2-methyltricyclo [4.3.0.12.5] -3-decene , Tricyclo such as 5-methyltricyclo [4.3.0.12.5] -3-decene 4.3.0.12.5] -3-decene derivatives, tricyclo [4.4.0.12.5] -3-undecene and the like. Two or more of these may be used in combination. In addition, a cyclic olefin having 12 or more carbon atoms can be used alone or in combination with the compound having 11 or less carbon atoms.

  Other monomers that can be used as necessary in the formation of the polyolefin-based resin include 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6. -Non-conjugated dienes such as octadiene and 1,9-decadiene.

  The polyolefin resin is preferably a polymer mainly containing a propylene unit such as polypropylene or propylene-ethylene copolymer, polyethylene or ethylene-norbornene copolymer, and more preferably polypropylene or propylene-ethylene copolymer. It is a polymer mainly containing the propylene unit. Two or more of these may be used in combination. A particularly preferred combination is a combination of polypropylene and polyethylene or polyethylene and ethylene-norbornene copolymer.

  In addition, as said propylene-ethylene copolymer, there exist a random copolymer, a block copolymer, etc., and all can be used. It is particularly preferable to use a random type from the surface appearance. As the polyethylene, any of high density polyethylene, low density polyethylene, linear low density polyethylene and the like can be used.

  The polymerization method of the polyolefin resin may be any of a high pressure polymerization method, a low pressure polymerization method, a metallocene catalyst polymerization method, and the like. Further, the polyolefin resin used in the present invention may be one obtained by decatalyzing a polymerization catalyst, one obtained by removing a low molecular weight compound, or one modified with an acid anhydride group, carboxyl group, epoxy group or the like. Good.

  Regardless of the crystallinity of the polyolefin resin, it is preferable to use at least one resin having a crystallinity of 10% or more by X-ray diffraction at room temperature. In addition, it is preferable to use at least one polyolefin resin having a melting point of 40 ° C. or higher measured according to JIS K7121.

  The melt flow rate measured in accordance with JISK7210: 1999 (230 ° C., load 2.16 kg) of the polypropylene resin is usually 0.01 to 500 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes. The melt flow rate measured in accordance with JIS K6922-2 (190 ° C., load 2.16 kg) of polyethylene resin is usually 0.01 to 500 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes. is there.

  As the polyolefin-based resin, those containing various additives such as an antioxidant, a heat stabilizer, and a lubricant can be used, and those not added can also be used. Depending on the application used, polyolefin resins that do not contain the above-mentioned various additives that are generated gas components from molded products, those that have low molecular weight hydrocarbon compounds, those that have been removed, and decatalysts. In some cases, it may be preferable to use the above.

Examples of the vinyl chloride resin (E2) include polyvinyl chloride resins, copolymers of vinyl chloride and other copolymerizable vinyl monomers, blends of acrylonitrile / butadiene copolymers, Examples include chlorinated polyvinyl chloride resin obtained by chlorinating vinyl chloride. Chemical resistance and flame retardancy may be improved by blending the vinyl chloride resin (E2).
Examples of the other copolymerizable vinyl monomers include ethylene, propylene, maleic acid ester, vinyl acetate, (meth) acrylic acid, (meth) acrylic acid ester, and the like. The average degree of polymerization of the vinyl chloride resin is usually 700 to 1800, preferably 1000 to 1500.

  The vinyl chloride resin (E2) can be used by blending a known heat stabilizer, antioxidant, lubricant, plasticizer and the like.

  The acrylic resin (E3) is a resin containing a (meth) acrylic acid ester monomer unit having an ester group of secondary alcohol or tertiary alcohol and carboxylic acid. The scratch resistance may be improved by blending the acrylic resin (E3).

  Here, as the methacrylic acid ester monomer, for example, methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, t-butyl methacrylate, methacrylic acid Isoamyl, lauryl methacrylate, dodecyl methacrylate, phenyl methacrylate, benzyl methacrylate, 2-ethylhexyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, cyclopeptyl methacrylate, cyclooctyl methacrylate, 4-t-butylcyclohexyl methacrylate, 3,3,5-trimethylcyclohexyl methacrylate, tricyclodecanyl methacrylate, dicyclopentadienyl methacrylate, isobornyl methacrylate, methacryl Adamantyl, methacrylic acid esters such as triphenylmethyl methacrylate.

  Also, methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, n-butyl acrylate, isobutyl acrylate, t-butyl acrylate, isoamyl acrylate, lauryl acrylate, dodecyl acrylate, acrylic acid Acrylic esters such as phenyl, benzyl acrylate, glycidyl acrylate, 2-ethylhexyl acrylate, cyclopentyl acrylate, cyclohexyl acrylate, cyclopeptyl acrylate, cyclooctyl acrylate, 4-t-butyl acrylate Cyclohexyl, 3,3,5-trimethylcyclohexyl acrylate, tricyclodecanyl acrylate, dicyclopentadienyl acrylate, isobornyl acrylate, adamantyl acrylate, diphenyl acrylate Le, and a triphenylmethyl acrylic acid.

  Furthermore, other monomers copolymerizable with the (meth) acrylic acid ester can be appropriately copolymerized. Examples of the copolymerizable monomer include ethylene, propylene, 1-butene, 2-butene, 1-pentene, 3-methyl-1-butene, 1-hexene, 4-methyl-1-pentene, and 3-methyl- Branched or straight chain olefins such as 1-pentene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene and 1-eicocene; cyclopentene, cycloheptene, norbornene, 5 Cyclic olefins such as methyl-2-norbornene, tetracyclodecene, 2-methyl-1,4,5,8-dimethanol 1,2,3,4,5,8,8a-octahydronaphthalene; fumaric acid, Α, β- such as maleic anhydride, itaconic acid, itaconic anhydride, bicyclo [2.2.1] -5-heptene-2,3-dicarboxylic anhydride Saturated carboxylic acid; N- phenylmaleimide, N- cyclohexyl maleimide, N-t-butyl maleimide, and the like.

  The structure of acrylic resin is not specifically limited, For example, it can have structures, such as a random copolymer and a graft copolymer. Moreover, the number average molecular weight is 5,000-500,000 normally, Preferably it is 10,000-300,000. The polymerization method of the acrylic resin may be any of radical polymerization, charge transfer radical polymerization, anionic polymerization, group transfer polymerization, and coordination anionic polymerization.

  The aromatic polyester resin (E4) is a polymer obtained from (1) an aromatic dicarboxylic acid and / or an ester-forming derivative thereof and (2) a diol component.

  As the aromatic dicarboxylic acid (1), an aromatic dicarboxylic acid having 8 to 12 carbon atoms can be used, and specifically, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid. Examples include acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, and ester-forming derivatives such as methyl ester of the above dicarboxylic acid. Two or more of these may be used in combination. Among these, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid and ester-forming derivatives thereof are preferable. Chemical resistance may be improved by blending the polyester resin (E4).

  As the diol component (2), an aliphatic diol or alicyclic diol having usually 2 to 11 carbon atoms is used. Specifically, ethylene glycol, trimethylene glycol, 1,3-propanediol, 1,4 -Butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4-cyclohexanediol, 1,6-cyclohexanediol and the like. Two or more of these diol components may be used in combination. Among these, ethylene glycol or 1,4-butanediol is preferable.

  In the production of the aromatic polyester resin (E4), a metal compound such as germanium, titanium, antimony, tin, magnesium, calcium, or zinc is used as a catalyst used for the esterification reaction.

  Preferable examples of the aromatic polyester resin (E4) are polybutylene terephthalate (PBT) and polyethylene terephthalate (PET). The intrinsic viscosity of the aromatic polyester-based resin (E4) is not particularly limited, but in the case of polybutylene terephthalate, the intrinsic viscosity [η] (η) (measured at 25 ° C. using O-chlorophenol as a solvent from the viewpoint of impact resistance. The unit dl / g) is usually 0.5 to 2.0. In the case of polyethylene terephthalate, the intrinsic viscosity [η] (unit dl / g) measured at 25 ° C. in an equal amount mixed solvent of tetrachloromethane / phenol is usually 0.5 to 2.0, preferably 0.8. 5 to 1.5.

  Examples of the polyamide-based resin (E5) include polyamides derived from a diamine component and a dicarboxylic acid component, polyamides derived from ring-opening polymerization of lactams, polyamides derived from aminocarboxylic acids, and copolyamides thereof, and mixed polyamides thereof. Either of them may be used. Chemical resistance and molding processability may be improved by blending the polyamide resin (E5).

  Examples of the diamine component include ethylenediamine, tetramethylenediamine, hexamethylenediamine, 2,3,4- or 4,4,4-trimethylenehexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) Aliphatic, alicyclic or aromatic diamines such as cyclohexane, bis (p-aminohexyl) methane, phenyldiamine, m-xylenediamine, and p-xylenediamine are listed. Examples thereof include aliphatic, alicyclic or aromatic dicarboxylic acids such as acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid. Examples of the lactams include caprolactam and lauryl lactam. Examples of the aminocarboxylic acids include ω-aminocaproic acid, ω-aminoundecanoic acid, 1,2-aminododecanoic acid, and the like. These diamines, dicarboxylic acids, lactams, and aminocarboxylic acids are appropriately selected. Can be used in combination.

  The polyamide resin (E5) is preferably nylon 6 (polycaproamide), nylon 6,6 (polyhexamethylene adipamide), nylon 12 (polydodecamide), nylon 6,10 (polyhexamethylene). Sebacamide), nylon 4,6 (polytetramethylene adipamide) and copolymers or mixtures thereof, more preferably nylon 6, nylon 6,6 and nylon 12.

  The degree of polymerization of the polyamide-based resin (E5) is not particularly limited, but the relative viscosity is usually 1.6 to 6.0, preferably 2.0 to 5.0, from the viewpoint of impact resistance. The relative viscosity is a value measured at 30 ° C. by dissolving 2 g of polymer in 100 ml of formic acid (purity 90% by mass).

  The polyphenylene ether resin (E6) is represented by the following general formula (16). Heat resistance may improve by mix | blending a polyphenylene ether-type resin (E6).

In General Formula (16), R ¹ and R ² each independently represent a hydrogen atom or a hydrocarbon having 1 to 20 carbon atoms which may have a substituent.

Examples of the hydrocarbon group include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, Alkyl groups having 1 to 20 carbon atoms such as cyclohexyl, octyl and decyl; aryl groups having 6 to 20 carbon atoms such as phenyl, 4-methylphenyl, 1-naphthyl and 2-naphthyl; And an aralkyl group having 7 to 20 carbon atoms in total, such as a benzyl group, a 2-phenylethyl group, and a 1-phenylethyl group. When the hydrocarbon group has a substituent, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom, an alkoxy group such as a t-butyloxy group, and a diarylamino group such as a 3-diphenylamino group. Is mentioned. Specific examples of the hydrocarbon group having a substituent include a trifluoromethyl group, a 2-t-butyloxyethyl group, and a 3-diphenylaminopropyl group. In addition, carbon number of a substituent is not included in said total carbon number. In the general formula (16), R ¹ and R ² are preferably a hydrogen atom or a methyl group, and particularly preferably a hydrogen atom.

  Even if the polyphenylene ether resin having a structural unit of the general formula (16) is a homopolymer, structural units derived from monomers that are phenolic compounds other than the phenolic compound corresponding to the general formula (16). It may be a copolymer. Examples of such phenol compounds include polyvalent hydroxyaromatic compounds such as bisphenol A, tetrabromobisphenol A, resorcin, hydroquinone, and novolak resins. The proportion of the structural unit represented by the general formula (16) in such a copolymer is usually 80 mol% or more, preferably 90 mol% or more.

The polyphenylene ether-based resin having the structural unit of the general formula (16) can be produced by oxidative polymerization of a phenol compound represented by the following general formula (17). In General Formula (17), R ¹ and R ² have the same meaning as in General Formula (16).

  When only the phenol compound of the general formula (17) is used as a raw material, the above homopolymer can be produced. Two or more of these phenol compounds may be used in combination. Furthermore, said copolymer can be manufactured by using the phenol compound represented by General formula (17), and a phenol compound other than this.

  The oxidative polymerization can be performed using an oxidative coupling catalyst and using, for example, oxygen or an oxygen-containing gas as an oxidant. The oxidative coupling catalyst is not particularly limited, and any catalyst having a polymerization ability can be used. For example, typical examples include a catalyst containing cuprous chloride and a catalyst containing divalent manganese salts (see, for example, JP-A-60-229923).

  The polyphenylene ether-based resin is used in combination with polystyrene [the component (B)] and / or high-impact polystyrene obtained by polymerizing styrene in the presence of a rubbery polymer (the component (A)). However, a preferred embodiment is a combined system in the range of polyphenylene ether resin / impact polystyrene = 10 to 90/10 to 90 (mass ratio).

  A typical example of the polycarbonate resin (E7) is aromatic polycarbonate. By blending the polycarbonate resin (E7), improvement in impact resistance and heat resistance is expected. The aromatic polycarbonate can be obtained by a known polymerization method such as an interfacial polycondensation method between a dihydroxyaryl compound and phosgene or a transesterification reaction (melt polycondensation) between a dihydroxyaryl compound and a carbonate compound such as diphenyl carbonate. Everything can be used.

  Examples of the dihydroxyaryl compound include bis (4-hydroxyphenyl) methane, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) butane, and 2,2-bis (4 -Hydroxyphenyl) octane, bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) propane, 2,2-bis (4-hydroxy-3-tert-butylphenyl) ) Propane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 4,4′-dihydroxyphenyl ether, 4,4′-dihydroxyphenyl sulfide, 4, 4'-dihydroxyphenylsulfone, 4,4'-dihydroxy-3,3'-dimethyldiphenyl Examples include sulfone, hydroquinone, and resorcin. In addition, there are hydroxyaryloxy-terminated polyorganosiloxanes (see, for example, US Pat. No. 3,419,634). Two or more of these may be used in combination. Among these, 2,2-bis (4-hydroxyphenylpropane (bisphenol A)) is preferable.

  The viscosity average molecular weight of the polycarbonate resin is usually 13,000 to 32,000, preferably 17,000 to 31,000, and more preferably 18,000 to 30,000. Two or more polycarbonate resins may be used in combination. In addition, aromatic polycarbonates having different viscosity average molecular weights can be used in combination.

  The viscosity average molecular weight of the above aromatic polycarbonate is usually expressed by the following formula (18) as a specific viscosity (ηsp) measured at 20 ° C. and a concentration [0.7 g / 100 ml (methylene chloride)] using methylene chloride as a solvent. Can be calculated by inserting.

[Equation 3]
Viscosity average molecular weight = ([η] × 8130) ^1.205 (18)

In formula (18), [η] = [(ηsp × 1.12 + 1) _1/2 −1] /0.56C.
C indicates the concentration.

  The polycarbonate resin obtained by interfacial polycondensation may contain various chlorine compounds, which may adversely affect the durability of the composition of the present invention. From this, the chlorine compound content is usually 300 ppm or less, preferably 100 ppm or less, as chlorine atoms.

  The polyurethane resin (E8) is composed of a polymer polyol component (I), an organic diisocyanate (I I), and a chain extender (III). Examples of the polymer polyol component (I) include polyether polyol, polyester polyol, polycarbonate polyol, and polyether ester polyol. The number average molecular weight is usually 1,000 to 7,000. By blending the polyurethane resin (E8), improvement in impact resistance and wear resistance is expected.

  Polyether polyols include polyether diols and glycols (for example, ethylene glycol, propylene glycol, 1, and the like) obtained by ring-opening polymerization of cyclic ethers (for example, ethylene oxide, propylene oxide, trimethylene oxide, tetrahydrofuran, methyltetrahydrofuran, etc.). 4-butanediol, neopentyl glycol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 1,9-nonanediol, 1,10-decane And polyether polyols obtained by polycondensation of diols). Two or more of these may be used in combination.

  The polyester polyol can be produced by known polycondensation by an esterification method or a transesterification method using a polycarboxylic acid, a polyol and other components as required.

  Examples of the polyol used for producing the polyester polyol include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, 1,3-propanediol, 2-methyl-1,3-propanediol, and 2,2-diethyl-1. , 3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,4-butanediol, neopentyl glycol, 1,5-pentanediol, 3-methyl-1,5- Pentanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol, 1, 9-nonanediol, 2-methyl-1,9-nonanediol, 2,8-dimethyl Aliphatic diols having 2 to 15 carbon atoms such as 1,9-nonanediol and 1,10-decanediol; alicyclic diols such as 1,4-cyclohexanediol, cyclohexanedimethanol and cyclooctanedimethanol; Diol having two hydroxyl groups per molecule such as aromatic dihydric alcohol such as, 4-bis (β-hydroxyethoxy) benzene, etc., trimethylolpropane, trimethylolethane, glycerin, 1,2,6-hensantriol, Examples include polyols having 3 or more hydroxyl groups per molecule such as pentaerythritol and diglycerin.

  In producing the polyester polyol, two or more kinds of polyols may be used in combination. Among these, 2-methyl-1,4-butanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol, 2,7-dimethyl-1,8-octanediol C5-C12 aliphatic diols having a methyl group as a side chain, such as 2-methyl-1,9-nonanediol and 2,8-dimethyl-1,9-nonanediol, are preferred.

  Polycarboxylic acids used for the production of polyester polyols include succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dodecanoic acid, methylsuccinic acid, 2-methylglutaric acid, and 3-methylglutaric acid. C4-C12 aliphatic dicarboxylic acids such as acid, trimethyladipic acid, 2-methyloctanoic acid, 3,8-dimethyldecanedic acid, 3,7-dimethyldodecanedic acid; cyclohexanedicarboxylic acid, dimer acid, Cycloaliphatic dicarboxylic acids such as hydrogenated dimer acids; aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, orthophthalic acid, and naphthalenedicarboxylic acid; trifunctional or more polycarboxylic acids such as trimellitic acid and pyromellitic acid; Examples include ester-forming derivatives. Two or more of these polycarboxylic acids may be used in combination. In these, a C6-C12 aliphatic dicarboxylic acid is preferable, and especially adipic acid, azelaic acid, and sebacic acid are preferable.

  Moreover, as a polycarbonate polyol, what is obtained by reaction with carbonate compounds, such as the said polyol and dialkyl carbonate, alkylene carbonate, diaryl carbonate, can be used. As the polyol constituting the polycarbonate diol, the polyol exemplified above as a constituent component of the polyester polyol can be used. Examples of diallyl carbonate include dimethyl carbonate and diethyl carbonate. Examples of the alkylene carbonate include ethylene carbonate, and examples of the diaryl carbonate include diphenyl carbonate.

  Furthermore, as the polyester polycarbonate polyol, those obtained by reacting polyol, polycarboxylic acid and carbonate compound at the same time, or polyester polyol and polycarbonate polyol are respectively synthesized by the above-described method, and then reacted with the carbonate compound. Or what is obtained by making it react with a polyol and polycarboxylic acid can be used.

  As organic diisocyanate (II), 4,4'-diphenylmethane diisocyanate, tolylene diisocyanate, phenylene diisocyanate, xylylene diisocyanate, 1,5-naphthylene diisocyanate, 3,3'-dichloro-4,4'-diphenylmethane diisocyanate, Aromatic diisocyanates such as toluylene diisocyanate; aliphatic or alicyclic diisocyanates such as hexamethylene diisocyanate, isophorone diisocyanate, 4,4′-dicyclohexylmethane diisocyanate, and hydrogenated xylylene diisocyanate. Two or more of these organic diisocyanates may be used in combination. Among these, 4,4′-diphenylmethane diisocyanate is preferable. Further, a tri- or higher functional polyisocyanate compound such as triphenylmethane triisocyanate can be appropriately added.

  As the chain extender (III), a low molecular weight compound having a molecular weight of 300 or less having two or more active hydrogen atoms capable of reacting with an isocyanate group in the molecule is preferable. Examples of the low molecular weight compound include ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, 1,4-bis (β-hydroxyethoxy) benzene, 1,4-cyclohexanediol, bis Diols such as (β-hydroxyethyl) terephthalate and xylylene glycol; hydrazine, ethylenediamine, xylylenediamine, isophoronediamine, piperazine and derivatives thereof, phenylenediamine, tolylenediamine, xylenediamine, adipic acid hydrazine, isophthalic acid dihydrazide Diamines such as; amino alcohols such as aminoethyl ether and aminopropyl alcohol; Two or more of these low molecular compounds may be used in combination. In these, it is preferable to use C2-C10 aliphatic diol, Especially preferably, it is 1, 4- butanediol.

  The logarithmic viscosity of the polyurethane resin (E8) was obtained by dissolving a polyretane resin in an N, N-dimethylformamide solution containing 0.05 mol / l of n-butylamine so as to be 0.5 g / dl. As a value measured in (1), it is usually 0.5 to 2.5 dl / g, preferably 0.9 to 2.0 dl / g.

  An example of a preferred production method of the polyurethane resin (E8) is to melt the molecular polyol component (I), the organic diisocyanate (II) and the chain extender (III) at 240 to 290 ° C. in the presence of Sn catalyst or Ti catalyst. Polymerization method. The usage-amount of a catalyst is 2-50 ppm in conversion of Sn atom or Ti atom with respect to the total amount of molecular polyol component (I), organic diisocyanate (I I), and chain extender (III). In particular, when the melt polymerization is performed by a continuous melt polymerization method using a multi-screw extruder, productivity is increased.

  The polyarylene sulfide resin (E9) is a polymer consisting essentially of arylene groups bonded to each other by sulfide groups, and is represented by the following general formula (19). By blending the polyarylene sulfide resin (E9), heat resistance and chemical resistance may be improved.

  In general formula (19), Ar is a substituted or unsubstituted arylene group, preferably a phenylene group, and n is preferably a number greater than 50.

  The polyarylene sulfide resin (E9) may be linear, branched or cross-linked. Preferred starting compounds and production methods for polyarylene sulfide resins are described, for example, in US Pat. Nos. 3,354,129 and 3,919,177. In the production, it is obtained by reacting a polyhalogenated aromatic compound with a sulfur-containing compound in a polar solvent in the presence of a catalyst.

  Suitable polyhalogenated aromatic compounds include, for example, 1,2-dichlorobenzene, 1,3-dichlorobenzene, 1,4-dichlorobenzene, 2,5-dichlorotoluene, 1,4-dibromobenzene, 2, 5-dibromoaniline and mixtures thereof. When producing a branched polyarylene sulfide-based resin, at least 0.05 mol% of the polyhalogenated aromatic compound is an aromatic trihalogen or tetrahalogen compound such as 1,2,4-trichlorobenzene, 1 3,5-trichlorobenzene or 1,2,4,5-tetrachlorobenzene is preferred.

  Suitable sulfur-containing compounds are alkali metal sulfides such as sodium and potassium sulfide. These alkali metal sulfide hydrates are particularly preferred. Alkali metal sulfides can also be generated from hydrogen sulfide using alkali hydroxides such as lithium hydroxide and sodium hydroxide. Suitable polar solvents include, for example, N-methylpyrrolidone, N-ethylpyrrolidone, N-methylated prolactam, N-ethylcaprolactam and 1,3-dimethylimidazoline. Suitable catalysts include substances such as alkali fluorides, alkali phosphates or alkali carboxylates, and should be used in an amount of 0.02 to 1.0 mole per mole of alkali metal sulfide. Is preferred.

  Two or more of the above components (E) (E1 to E9) may be used in combination. Among the components (E), preferred are polyolefin resin (E1), aromatic polyester resin (E4), polyamide resin (E5), polyphenylene ether resin (E6), polycarbonate resin (E7) and polyurethane. The resin (E8) is more preferable, and the polyolefin resin (E1), the aromatic polyester resin, the polyamide resin (E5), and the polycarbonate resin (E7) are more preferable.

  The component (E) is usually 5 to 500 parts by weight, preferably 5 to 300 parts by weight, and more preferably 10 to 200 parts by weight with respect to 100 parts by weight as the total of the components (A), (B) and (C). When the amount used is less than 5 parts by mass, the effect of blending the component (D) is hardly exhibited, and when it exceeds 500 parts by mass, the antistatic property tends to be inferior. It is in.

  In the composition of the present invention, particularly preferred combinations of the component (A), the component (C) and the component (E) are as described in Table 1 below. In the table, ST represents styrene, AN represents acrylonitrile, and MMA represents methyl methacrylate.

  The composition of the present invention includes known weathering (light) agents, antioxidants, heat stabilizers, lubricants, plasticizers, nonionic surfactants, antistatic agents, drip-proofing agents, antifogging agents, Colorants, dyes, foaming agents, processing aids (ultra high molecular weight acrylic polymers, ultra high molecular weight styrene / acrylonitrile copolymers, etc.), flame retardants, crystal nucleating agents, silicone oils, and the like can be appropriately blended.

  Preferred as the antistatic agent used here is a lithium compound, and as the lithium compound, lithium trifluoromethanesulfonate, lithium perchlorate, lithium bis (trifluoromethanesulfonyl) imido and tris (trifluoromethanesulfonyl). Methane lithium is mentioned. Of these, lithium trifluoromethanesulfonate is preferred. Such a lithium compound can be obtained in a solution state, for example, as “Sanconol 0862-13T”, “Sanconol AQ-50T”, “Sanconol AQ-75T” manufactured by Sanko Chemical Co., Ltd.

In the composition of the present invention, sodium, potassium, and the like are mixed in the production process of various polymers from additives added for the purpose of improving antistatic properties. As a result, in the case of, for example, a molded article for parts conveyance made of the composition of the present invention, it is eluted as sodium and potassium ions, and depending on the intended use, undesired results such as corrosion of the conveyance parts may occur. In addition, if these electrolytes are used in a large amount, the change with respect to the antistatic humidity becomes large, which may lead to an undesirable result depending on the intended use. Therefore, the elution amount of sodium and / or potassium ions from the composition of the present invention (over 80 ° C. pure water, 60 minutes) is usually 1.0 μg / cm ² or less, preferably 0.5 μg / cm ^2. Hereinafter, it is more preferably 0.1 μg / cm ² or less. Here, “cm ² ” represents the surface area of the molded product.

  The composition of the present invention can be blended with known inorganic / organic fillers depending on the required performance. The filler used here is glass fiber, glass flake, glass fiber milled fiber, glass bead, hollow glass bead, carbon fiber, carbon fiber milled fiber, carbon nanotube, fullerene, silver, copper, brass, iron, etc. Powder or fibrous substance. Also, carbon black, tin coated titanium oxide, tin coated silica, nickel coated carbon fiber, talc, calcium carbonate, calcium carbonate whisker, wollastonite, mica, kaolin, montmorillonite, hectorite, zinc oxide whisker, potassium titanate whisker, Examples thereof include aluminum borate whisker, plate-like aluminum, plate-like silica, organically treated smectite, aramid fiber, phenol fiber, polyester fiber, kenaf fiber, wood powder, cellulose fiber, and starch. Two or more of these may be used in combination.

  Further, for the purpose of improving the dispersibility of the above filler, those treated with a known coupling agent, surface treatment agent, sizing agent and the like can also be used. Examples of the coupling agent include silane coupling agents, titanate coupling agents, and aluminum coupling agents.

  Said inorganic and organic filler is normally used in 1-200 mass parts with respect to 100 mass parts of compositions of this invention.

  The composition of the present invention can be obtained by melt-kneading the above-described constituent components with various extruders, Banbury mixers, kneaders, continuous kneaders, rolls and the like. In kneading, the respective components may be added together and kneaded, or may be added separately. Moreover, you may add a liquid thing at room temperature like a component (C) to a processing machine from another line. The composition of the present invention thus prepared can be used for injection molding, press molding, calendar molding, T-die extrusion molding, inflation molding, lamination molding, vacuum molding, profile extrusion molding, and a molding method combining these. A molded product can be obtained by a known molding method. In addition, when a kneading machine such as a kneading extruder or a Banbury mixer is attached to calender molding, T-die extrusion molding, inflation molding, etc., the above-mentioned kneading does not obtain the composition of the present invention by kneading in advance. A molded product can be obtained while obtaining the composition of the present invention with an accompanying kneader.

  Molded products include injection molded products (including multicolor molding and in-mold molding), sheet molded products (including multilayer sheets), film molded products (including multilayer films), profile extrusion molded products, and vacuum molded products. Can be mentioned. The composition of the present invention is also suitably used for sheets and films. Furthermore, a laminate using the composition of the present invention as a surface layer on at least one surface of a multilayer sheet or multilayer film is preferred from the viewpoint of antistatic properties.

  When a multilayer sheet or multilayer film is formed using the composition of the present invention, the composition of the present invention is a two-layer sheet or film with another material, or a three-layer sheet or film with another material as an intermediate layer. Etc. As said other material, what consists of a well-known polymer can be used in combination of 2 or more type as needed. Such a multilayer sheet or film is preferably bonded between layers, and therefore, selection and combination of polymers in consideration of bonding is important, but when using materials with insufficient bonding between layers, A known adhesive layer can be interposed.

  Further, for the purpose of improving the rigidity and heat resistance of the sheet or film, it is possible to use the above-mentioned inorganic or organic filler.

  In the above multilayer sheet, the thickness of the layer comprising the composition of the present invention is usually 10 μm or more, preferably 20 μm or more, more preferably 30 μm or more. A preferred method for obtaining such multilayer sheets and films is coextrusion with a T-die or coextrusion with inflation. The sheet thus obtained can be processed by vacuum forming or the like as necessary to obtain a molded product such as a tray.

  When a pressure-sensitive adhesive sheet or film is produced using a sheet or film comprising the composition of the present invention as a base material, it is composed of the composition of the present invention for the purpose of improving the adhesion to the pressure-sensitive adhesive or the primer layer. Various known treatments such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, UV treatment, ion bombardment treatment, solvent treatment and the like can be performed on the surface of the sheet or film.

  Furthermore, a primer layer can be formed directly on the surface of the sheet or film made of the composition of the present invention or on the above-mentioned surface-treated surface. Specifically, a very thin layer (about 0.1 to 10 μm) of a resin such as polyethyleneimine, polyurethane, or acrylic resin is formed on the surface. Usually, it can be formed by applying as a solvent (including water) solution and drying.

  As the adhesive, in addition to emulsion type and organic solvent type that can be coated by screen method, gravure method, mesh method, bar coating method, etc. to form an adhesive layer, it can be adhered by extrusion lamination method, dry lamination method, etc. There is a hot-melt type for forming a layer, and any of them can be used. The thickness of the pressure-sensitive adhesive is not particularly limited, but is usually in the range of about 1 to 100 μm.

  The structure of each layer of the multilayer sheet of the present invention is not particularly limited, and for example, it may be foamed or hollow.

  Since the composition of the present invention described above is excellent in antistatic properties, impact resistance, and molded product surface appearance, it can be applied as various parts in the vehicle field, electrical / electronic field, OA / home appliance field, sanitary field, and the like. In particular, cases such as relay cases, wafer cases, reticle cases, mask cases; liquid crystal trays, chip trays, hard disk (HDD) trays, CCD trays, IC trays, organic EL trays, optical pickup related trays, LED trays, memory trays Trays such as IC carriers; Carriers such as IC carriers; Underlay sheets when polarizing films are cut; Air control curtains; Sheets and films used in clean rooms such as partitions; Vending machine internal parts; Liquid crystal panels, hard disks, Suitable for fields such as anti-static bags used for plasma panels, etc .; soft cases for carrying plastic cardboard, liquid crystal panels, plasma panels, etc .;

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist of the present invention. In the examples, parts and% are based on mass unless otherwise specified. Various measurements in the examples and comparative examples were based on the following methods.

[1] Evaluation method;
Gel content of rubbery polymer; according to the method described above.

Average particle size of rubbery polymer latex;
The average particle diameter of the rubber polymer latex when used in the latex state as the rubber polymer (a) was measured by a light scattering method. As a measuring machine, “LPA-3100 type” manufactured by Otsuka Electronics Co., Ltd. was used, and the Kimmulant method was used with 70 times integration. The particle diameter of the dispersion-grafted rubber polymer particles in the rubber-reinforced styrene resin was confirmed by an electron microscope to be almost the same as the latex particle diameter.

(3) Graft ratio of rubber-reinforced styrene resin; according to the above method.

(4) Intrinsic viscosity [η] of rubber-reinforced styrene resin and acetone-soluble component of styrene resin;
The above method was followed.

(5) Antistatic property;
Using a molded article (dimensions 2.4 mm (thickness) x 76 mm x 127 mm), according to FTMS-101 (US federal test standard), using "STATEC DECAYMETER 406D" manufactured by ETS USA, at 23 ° C and relative humidity of 12% After applying +5 KV to the molded product, it was grounded, and the time (seconds) until it was attenuated to 50 V was measured.

(6) Impact resistance;
In accordance with JISK7211-2, a puncture impact value (J) at 23 ° C. was measured using a sample of 2.4 mm (thickness) × 50 mm × 100 mm.

(7) Surface appearance of molded product;
The surface of the sample for impact resistance evaluation (6) was visually observed and evaluated according to the following criteria.
O: Smooth and good appearance without flow marks.
X: The surface is not smooth and / or there is a flow mark and the appearance is poor.

[2] Antistatic resin composition component:
<Component (A); Rubber Reinforced Styrene Resin>

Production Example 1 (Polymer A1; polybutadiene / styrene / acrylonitrile copolymer):
A crow flask equipped with a stirrer was charged with 95 parts of ion-exchanged water, 0.5 part of potassium rosinate, 0.1 part of tert-dodecyl mercaptan, polybutadiene latex (average rubber particle size 0.3 μm, gel) in a nitrogen stream. (Content 85%) 40 parts (in terms of solid content), 15 parts of styrene and 5 parts of acrylonitrile were added, and the temperature was increased while 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 polymerization for 1 hour, 50 parts of ion exchange water, 0.7 parts of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 part of tert-dodecyl mercaptan and 0.01 part of cumene hydroperoxide for 3 hours. The polymerization was continued over 1 hour, and the polymerization was continued for another hour. Then, 0.2 part of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) was added to complete the polymerization. . The polymerization conversion rate was 99%. The latex of the reaction product was coagulated with an aqueous sulfuric acid solution and washed with water, then neutralized with an aqueous potassium hydroxide solution, further washed with water, and dried to obtain a polymer A1. The graft ratio of this polymer A1 was 78%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.38 dl / g.

Production Example 2 (Polymer A2; acrylic rubber / styrene / acrylonitrile copolymer):
Instead of the polybutadiene latex used in Production Example 1, an acrylic rubber latex (n-butyl acrylate / allyl acrylate = 98.5 / 1.5 parts copolymer, average rubber particle size 0.35 μm, gel content 78% ) Polymer A2 was obtained in the same manner as in Production Example 1 except that 40 parts (in terms of solid content) were used. The polymerization conversion rate was 99%. The latex of the reaction product was coagulated with an aqueous sulfuric acid solution and washed with water, then neutralized with an aqueous potassium hydroxide solution, further washed with water, and dried to obtain an ASA resin (A1). The graft ratio of this polymer A1 was 71%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.38 dl / g.

Production Example 3 (Polymer A3; Hydrogenated Conjugated Diene Block Copolymer / Styrene / Acrylonitrile / Methyl Methacrylate Copolymer):
Hydrogenated butadiene block copolymer [Taftec H1041 (trade name) manufactured by Asahi Kasei Chemicals Co., Ltd., styrene / butadiene / styrene = 15/70/15 parts block in a nitrogen stream in a stainless steel autoclave equipped with a ribbon type stirring blade Complete hydrogenated copolymer, gel content 0%], 28 parts, methyl methacrylate 51 parts, styrene 11 parts, acrylonitrile 10 parts, toluene 120 parts charged, dissolved by stirring to obtain a homogeneous solution, t -0.5 part of butyl peroxyisopropyl carbonate and 0.1 part of t-dodecyl mercaptan were added, the temperature was raised while continuing the stirring, and after reaching 110 ° C, the temperature was kept constant and the stirring speed was adjusted to 200 rpm. For 6 hours. The polymerization conversion was 91%. After cooling to 100 ° C., 0.2 part of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) was added, the reaction mixture was extracted from the autoclave, and unreacted product and solvent were removed by steam distillation. After being distilled off and finely pulverized, the volatile matter was substantially devolatilized by an extruder with a 40 mmφ vacuum vent (220 ° C, 700 mmHg vacuum) to obtain pellets of polymer A3. The content of the hydrogenated butadiene block copolymer was 31%, the graft ratio was 51%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.26.

Production Example 4 (Polymer A4; ethylene / propylene rubber polymer / styrene / acrylonitrile copolymer):
An ethylene / propylene rubber polymer (63% ethylene, non-conjugated diene component is 5-ethylidene-2-norbornene, iodine value 14, Mooney viscosity (ML _{1 + 4} , 100 ° C., gel content 0%], 30 parts of styrene, 45 parts of styrene, 25 parts of acrylonitrile, 140 parts of toluene, the internal temperature was raised to 75 ° C., and the contents of the autoclave were stirred for 1 hour. A homogeneous solution was obtained. Thereafter, 0.50 part of t-butylperoxyisopropyl monocarbonate 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 the 4th hour 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. After cooling the internal temperature to 100 ° C., 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added. The polymerization conversion rate was 95%. The reaction mixture is extracted from the autoclave, unreacted substances and solvent are distilled off by steam distillation, and the volatile matter is substantially devolatilized by adjusting the cylinder temperature to 220 ° C and the degree of vacuum of 770 mmHg with an extruder with a vacuum vent of 40 mmφ. And pelletized to obtain a polymer A4. The graft ratio of this polymer was 75%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g.

Production Example 5 (Polymer A5; Butadiene Rubber Polymer / Styrene Copolymer):
Instead of the ethylene / propylene rubber polymer used in Production Example 4, polybutadiene c [BR51 (trade name) manufactured by JSR, high cis type, Mooney viscosity (ML _{1 + 4} , 100 ° C.) 33, gel content 0% The polymer 5 was obtained in the same manner as in Production Example 4 except for changing to 15 parts and 85 parts of styrene. The polymerization conversion was 91%, the grafting rate was 68%, and the intrinsic viscosity [η] of methyl ethyl ketone soluble matter was 0.39 dl / g.

<Component (B); Styrene resin>
Production Example 6 (polymer B1; styrene / acrylonitrile copolymer):
Two stainless steel autoclaves equipped with ribbon blades 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 0.14 part of tert-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 Was fed continuously. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion rate was 57%. The obtained polymer solution was continuously taken out from the first reaction vessel by the same amount as the styrene, acrylonitrile, toluene, molecular weight regulator, and polymerization initiator supplied by the pump. To the reaction vessel. The polymerization temperature of the second reaction vessel was 130 ° C., and the polymerization conversion was 75%. 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, and the intrinsic viscosity [η] 0.45 dl / g of polymer B1 was obtained.

Production Example 7 (polymer B2; styrene / acrylonitrile / methacrylic acid copolymer):
Polymer B2 was obtained in the same manner as in Production Example 6 except that styrene / acrylonitrile / methacrylic acid = 70/20/10 parts were used instead of styrene and acrylonitrile used in Production Example 6. The intrinsic viscosity [η] of this polymer was 0.46 dl / g.

<Ingredient (C)>
C1: Completely hydrogenated block copolymer consisting of styrene / butadiene / styrene = 15/70/15 parts [Tuftec H1031 (trade name) manufactured by Asahi Kasei Chemicals Corporation]
C2: Partially hydrogenated block copolymer comprising styrene / butadiene / styrene = 15/70/15 parts [Tuftec P1500 (trade name) manufactured by Asahi Kasei Chemicals Corporation]
C3: maleic anhydride modified of completely hydrogenated block copolymer consisting of styrene / butadiene / styrene = 15/70/15 [Tuftec M1913 (trade name) manufactured by Asahi Kasei Chemicals Corporation, acid value 10 mg CH ₃ ONa / g]

<Component (D)>
D1: 1-butyl-3-methylpyridinium bistrifluoromethanesulfonylimide [CIL-312 (trade name) manufactured by Nippon Carlit Co., Ltd.]
D2; 1-butyl-3-methylpyridinium trifluoromethanesulfonate [CIL-313 (trade name) manufactured by Nippon Carlit Co., Ltd.]

<Ingredient (E)>

<Component (E1); Olefin resin>
E1: Homotype polypropylene [Novatech PPEA9 (trade name) manufactured by Nippon Polypro Co., Ltd.]

<Ingredient (E4); aromatic polyairster resin>
E4: Polybutylene terephthalate [Duranex 800EP (trade name) manufactured by Polyplastics Co., Ltd.]

<Component (E5); Polyamide resin>
E5: Polyamide 6
[Unitika A1030BRL (trade name)]

<Component (E6); Polyphenylene ether resin>
Production Example 8 (Polymer E6):
To a glass container equipped with an oxygen gas-containing gas introduction pipe, a stirring blade and a gas discharge pipe, 7 parts of toluene, 1.8 parts of 2,6-dimethylphenol, and copper chloride / di-n-butylamine as a catalyst were added. The temperature was raised to ° C. Thereafter, oxygen was bubbled through the polymerization system to initiate the polymerization reaction. After reacting for 120 minutes, a polymer slurry was obtained while adding methanol to the polymer solution. Ethylenediaminetetraacetic acid potassium and hydroquinone were added, and the slurry was left until the slurry became white while maintaining the internal temperature at 50 ° C. After recovering the polymer, it was washed with methanol and dried to obtain a polymer E6. The intrinsic viscosity (chloroform, measured at 25 ° C.) of the polymer was 0.46 dl / g.

<Component (E7); Aromatic polycarbonate resin>
E7; Bisphenol A type polycarbonate [Panlite L-1225WP (trade name) manufactured by Teijin Chemicals Ltd.]

<Component (E8); Thermoplastic polyurethane resin>

Production Example 9 (Polymer E8):
Dibutyltin acetate as a tin-based urethane catalyst in terms of tin atoms is converted into a polymer diol (polymer diol composed of 3-methyl-1,5-pentanediol / 1,9-nonanediol / adipic acid, number average molecular weight 5,000). Add 4.4 ppm (component I), 1,4-butanediol (component II) and 4,4′-diphenyl diisocyanate (component III) heated and melted at 50 ° C. (component I): (component II): component (III) = 1: 3.0: 4.08 A biaxial screw type extruder rotating in the coaxial direction rotating at a ratio of 0.03 was continuously supplied by a metering pump to carry out a polymerization reaction. The resulting polyurethane melt was continuously extruded in water as a strand, pelletized, and dried to obtain a polymer E8. The logarithmic viscosity of this product was 1.15 dl / g.

Examples 1-15 and Comparative Examples 1-5:
After mixing with a Henschel mixer at the blending ratio shown in Table 2, the mixture was melt-kneaded and pelletized using a twin-screw extruder (appropriately set within the range of the cylinder set temperature of 220 to 260 ° C.). After sufficiently drying the obtained pellets, use an injection molding machine (set as appropriate in the range of 200 to 250 ° C. of cylinder setting temperature) to obtain a test piece for evaluating antistatic properties, impact resistance and molded product surface appearance. Obtained and evaluated by the evaluation method. The evaluation results are shown in Table 2.

  Examples 1 to 15 are molded products made of the composition of the present invention, and are excellent in antistatic properties, impact resistance, and molded product surface appearance.

  Comparative Example 1 is an example in which the amount of component (C) used is small outside the scope of the present invention, and the antistatic property is poor.

  Comparative Example 2 is an example in which the amount of component (C) used is large outside the scope of the invention, and the impact resistance and the molded product surface appearance are poor.

  Comparative Example 3 is an example in which the amount of component (A) used is small outside the scope of the invention, and the impact resistance is poor.

  Comparative Example 4 is an example in which the amount of component (D) used is small outside the scope of the invention, and the antistatic property is poor.

  The comparative example 5 is an example with much usage-amount of a component (D) outside the range of invention, and impact resistance and molded article surface property are inferior.

Claims (7)

  A rubber-reinforced styrene-based resin obtained by polymerizing an aromatic vinyl compound or an aromatic vinyl compound and another vinyl monomer copolymerizable with the aromatic vinyl compound in the presence of the rubber polymer (a) ( A) 5 to 98% by mass, styrene resin (B) 0 to 80 obtained by polymerizing aromatic vinyl compound or aromatic vinyl compound and other vinyl monomer (b2) copolymerizable with aromatic vinyl compound 2% to 50% by mass of a block copolymer having a conjugated diene polymer block and / or a hydrogenated product (C) thereof [total of component (A), component (B) and component (C) is 100% by mass % By mass], and a total of 100 parts by weight of the component (A), component (B) and component (C) is blended with 0.01 to 20 parts by weight of an ionic compound (D) which is liquid at room temperature An antistatic resin composition characterized by the above.   The antistatic resin composition according to claim 1, wherein the component (C) is modified with a functional group.   The rubber polymer (a) is a polybutadiene rubber polymer, an acrylic rubber polymer, an ethylene-α / olefin rubber polymer, a conjugated diene block copolymer, and a hydrogenated conjugated diene block copolymer. 3. The antistatic resin composition according to claim 1, wherein the antistatic resin composition is at least one selected from a coalesced rubber polymer.   The antistatic resin composition according to any one of claims 1 to 3, wherein the ionic liquid (D) is a compound having a pyridinium-based cation component.   The other thermoplastic resin (E) is blended in an amount of 5 to 500 parts by mass with respect to a total of 100 parts by mass of the component (A), the component (B), and the component (C). Antistatic resin composition.   The other thermoplastic polymer (E) is one or more selected from the group of polyolefin resins, aromatic polyester resins, polyamide resins, polyphenylene ether resins, polycarbonate resins and polyurethane resins. The antistatic resin composition according to claim 5.   A molded article comprising the antistatic resin composition according to claim 1.