JP2008127452A - Antistatic resin composition and molded article - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic resin composition providing a molded article having excellent antistatic properties, sustainability of the antistatic properties, impact resistance, chemical resistance and abrasion resistance. <P>SOLUTION: The antistatic resin composition comprises (A) 10-90 mass% aliphatic polyester, (B) 4-80 mass% olefin resin, (C) 3-40 mass% specific aromatic vinyl polymer, and (D) 3-60 mass% block copolymer having (D1) a block of at least one kind selected from the group consisting of a polyamide, a polyester and a polyolefin, and (D2) a hydrophilic polymer block [wherein, the total of the components (A), (B), (C) and (D) is 100 mass%]. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an antistatic resin composition excellent in antistatic properties, antistatic durability, impact resistance, chemical resistance, and abrasion resistance, and a molded article comprising the antistatic resin composition.

Aliphatic polyester is attracting attention as a biodegradable material. Furthermore, for some aliphatic polyesters, plastics using biomass have been developed from those based on conventional petroleum, and measures to combat global warming and to replace petroleum resources that are expected to be depleted in the future. Has also attracted attention.
However, in general, the aliphatic polyester has low impact resistance and its use is greatly restricted. In order to improve such drawbacks, it has been proposed to blend a polyolefin polymer. In Patent Document 1, a composition comprising polylactic acid and a modified olefin compound (Japanese Patent Laid-Open No. 9-316310) is further disclosed in Patent Document 2. Discloses a composition comprising polylactic acid and an ethylene-propylene-diene (EPDM) thermoplastic elastomer (Japanese Patent Laid-Open No. 2002-37987), but the composition obtained by such a method has sufficient impact resistance. There wasn't.

  On the other hand, aliphatic polyesters are easily charged and have limited use in fields where static electricity damage is a concern. Japanese Patent Application Laid-Open No. 10-36650 proposes a method for improving charging property by blending a nonionic surfactant composed of a glycerin fatty acid ester with an aliphatic polyester, particularly polylactic acid. Furthermore, Patent Document 4 proposes blending a specific anionic surfactant with a biodegradable resin (Japanese Patent Laid-Open No. 2005-264159). However, these methods have problems that the antistatic property is not sufficient and the antistatic property cannot be sustained.

In addition, olefin resins such as polypropylene and polyethylene, and styrene resins such as ABS resin are excellent in mechanical performance, physical performance, optical performance, and further excellent in workability.
Widely used in the vehicle field, OA / home appliance field, electric / electronic field, building material field, sanitary field, etc., but it is easily charged like the aliphatic polyester, and its use in fields where electrostatic damage is a concern is limited. It had been.

JP 9-316310 A JP 2002-37987 A JP 10-36650 A JP 2005-264159 A

  An object of the present invention is to provide an antistatic resin composition having excellent antistatic properties, antistatic durability, impact resistance, chemical resistance, and wear resistance. Another object of the present invention is to provide the molded article.

  As a result of intensive studies to achieve the above-mentioned object, the present inventors have mixed anti-static properties by blending a copolymer having a specific block and a specific polymer when mixing an aliphatic polyester and a polyolefin resin. It has been found that an antistatic resin composition having excellent antistatic durability, impact resistance, chemical resistance and abrasion resistance can be obtained. Moreover, it discovered that the antistatic resin composition which is excellent in antistatic property and impact resistance can be obtained by mix | blending a styrene resin with the said composition, and came to complete this invention.

  That is, the gist of the present invention is that the aliphatic polyester (A) is 10 to 90% by mass, the olefin resin (B) is 4 to 80% by mass, and at least one fragrance selected from the following (C1) to (C3). Block copolymer (D) having at least one block (D1) and hydrophilic polymer block (D2) selected from the group consisting of 3 to 40% by mass of an aromatic vinyl polymer (C), polyamide, polyester and polyolefin 3) to 60% by mass (the total of component (A), component (B), component (C) and component (D) is 100% by mass).

  The aromatic vinyl polymer (C1) is an elastomer composed of a block copolymer containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound. The vinyl polymer (C2) is an elastomer obtained by hydrogenating the aromatic vinyl polymer (C1), and the aromatic vinyl polymer (C3) is an aromatic vinyl compound in the presence of an olefin polymer. Is a graft copolymer obtained by polymerizing a vinyl-based monomer containing

  And in the preferable aspect of this invention, the styrene resin (E) which consists of the following (E1) and / or (E2) further is contained, and the ratio is a total of 100 of components (A)-(D). It is 5-100 mass parts with respect to a mass part.

  The styrenic resin (E1) is obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of a rubbery polymer (however, aromatic vinyl polymers (excluding C1 and (C2)). This is a rubber-reinforced styrene resin obtained, and the styrene resin (E2) is obtained by (co) polymerizing a vinyl monomer containing an aromatic vinyl compound in the absence of the rubbery polymer. Styrenic resin.

  According to the present invention, in particular, the antistatic resin composition excellent in antistatic properties, antistatic durability, impact resistance, chemical resistance and abrasion resistance, and the antistatic resin composition. A resin molded product formed by molding is provided.

  The present invention will be described below. In the present specification, “(co) polymerization” means homopolymerization and copolymerization, “(meth) acryl” means acryl and / or methacryl, and “(meth) acrylate” Means acrylate and / or methacrylate.

  The antistatic resin composition of the present invention contains an aliphatic polyester (A), an olefin resin (B), an aromatic vinyl polymer (C), and a block copolymer (D) as essential components. Furthermore, a styrenic resin (E) is contained as an optional component in a preferred embodiment.

<Aliphatic polyester (A)>
The aliphatic polyester used in the present invention is not particularly limited, and (i) an aliphatic polyester obtained by polycondensation of a component mainly composed of an aliphatic diol and an aliphatic dicarboxylic acid or a functional derivative thereof. (A1), (ii) an aliphatic polyester obtained by polycondensation of a component mainly composed of an aliphatic oxycarboxylic acid, and (iii) obtained by polycondensation of a component mainly composed of a lactone compound such as ε-caprolactone. There are aliphatic polyesters, etc., preferably (i) and (ii) above, and particularly preferably a combination system of (i) and (i) / (ii) above. The aliphatic diol used here is represented by the following general formula (1).

In general formula (1), R ¹ represents a divalent aliphatic hydrocarbon group. The number of carbon atoms of R ¹ is usually 2 to 11, preferably 2 to 6. R ¹ includes a cycloalkylene group and may have a branched chain. Preferred R ¹ is “— (CH ₂ ) n—”, where n represents an integer of 2 to 11, preferably an integer of 2 to 6.

  Specific examples of the aliphatic diol include ethylene glycol, trimethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,4- Examples include cyclohexanediol and 1,6-cyclohexanedimethanol. Among these, 1,4-butanediol is particularly preferable from the viewpoint of physical properties of the resulting aliphatic polyester. Two or more of the above aliphatic diols may be used in combination.

  Said aliphatic dicarboxylic acid is represented by the following general formula (2).

In the general formula (2), R ² represents a direct bond or a divalent aliphatic hydrocarbon group. The number of carbon atoms in R ² is usually 2 to 11, preferably 2 to 6. R ² includes a cycloalkylene group and may have a branched chain. Preferred R ² is “— (CH ₂ ) m—”, wherein m represents 0 or an integer of 1 to 11, preferably 0 or an integer of 1 to 6.

  Specific examples of the aliphatic dicarboxylic acid include oxalic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, subvalic acid, dodecanoic acid, etc., and derivatives thereof include these lower alkyl esters and acid anhydrides. As the derivative, a compound in which both of two carboxyl groups are converted into, for example, an ester group is preferable. Among these, succinic acid or adipic acid is preferable from the viewpoint of physical properties of the resulting aliphatic polyester, and succinic acid is particularly preferable. Two or more of the above aliphatic dicarboxylic acids may be used in combination.

  The aliphatic oxycarboxylic acid is not particularly limited as long as it has one hydroxyl group and one carboxylic acid group in the molecule, but the aliphatic oxycarboxylic acid represented by the following general formula (3) is Is preferred.

In general formula (3), R ³ represents a divalent aliphatic hydrocarbon group. The number of carbon atoms of R ³ is usually 1 to 11, preferably from 1 to 16. R ³ includes a cycloalkylene group and may have a branched chain.

  The aliphatic oxycarboxylic acid is preferably a compound having a hydroxyl group and a carboxyl group on one carbon atom, and a compound represented by the following general formula (4) is particularly preferable.

  In general formula (4), z is 0 or an integer of 1 or more, preferably 0 or 1 to 10, and more preferably 0 or 1 to 5.

  Specific examples of the aliphatic oxycarboxylic acid include lactic acid, glycolic acid, 3-hydroxybutyric acid, 4-hydroxybutyric acid, 2-hydroxy-n-butyric acid, 2-hydroxy-3,3-dimethylbutyric acid, and 2-hydroxy-3. -Methylbutyric acid, 2-methyllactic acid, 2-hydroxycaproic acid, a mixture thereof and the like. When optical isomers exist in these, any of D-form, L-form, and racemic form may be sufficient, and the shape may be any of solid, liquid, and aqueous solution. In particular, lactic acid or glycolic acid and an aqueous solution thereof, which have a remarkable increase in polymerization rate during use and are easily available, are preferred. As for lactic acid and glycolic acid, 50%, 70%, and 90% aqueous solutions are generally commercially available, and are easily available.

The aliphatic polyester composed of the aliphatic diol compound (i) and the aliphatic dicarboxylic acid compound may be copolymerized with the aliphatic oxycarboxylic acid compound.
The aliphatic polyester composed of oxycarboxylic acid) may be copolymerized with the aliphatic diol compound and the aliphatic dicarboxylic acid compound. Furthermore, the aliphatic oxycarboxylic acid compound, the aliphatic diol compound, and the aliphatic dicarboxylic acid compound can be copolymerized with the aliphatic polyester composed of the lactone compound (iii).

  Furthermore, the aliphatic polyesters of (i), (ii) and (iii) include, as other compounds, aromatic dicarboxylic acids such as trifunctional aliphatic oxycarboxylic acid, terephthalic acid, isophthalic acid and naphthalenedicarboxylic acid, An aromatic diol such as bisphenol A and an aromatic oxycarboxylic acid such as hydroxybenzoic acid can be appropriately copolymerized.

  As the catalyst used in the esterification reaction of the aliphatic polyester, all known ones can be used. For example, germanium, titanium, antimony, tin, magnesium, calcium, zinc, and other metal compounds soluble in the reaction system Is mentioned. Among these, germanium compounds are preferable, and specific examples thereof include organic germanium compounds such as tetraalkoxygermanium, and inorganic germanium compounds such as germanium oxide and germanium chloride. Germanium oxide, tetraethoxygermanium or tetrabutoxygermanium is particularly preferred because of its price and availability.

  The usage-amount of a catalyst is 0.001 to 3 weight% normally with respect to the total amount of the monomer amount to be used, Preferably it is 0.005 to 1.5 weight%. The catalyst addition time is not particularly limited as long as it is before the production of the polyester, but it may be added when the raw materials are charged, or may be added at the start of pressure reduction. It is particularly preferred to add at the same time as the aliphatic oxycarboxylic acid when charging the raw materials, or to dissolve the catalyst in the bifunctional aliphatic oxycarboxylic acid and its aqueous solution.

  Conditions such as temperature, time, and pressure when producing the aliphatic polyester are not particularly limited as long as the target aliphatic polyester can be obtained, but the temperature is usually 150 to 260 ° C., preferably 180 to 260 ° C. 230 degreeC, superposition | polymerization time is 1 hour or more normally, Preferably it is 2 to 15 hours, and a pressure reduction degree is 10 mmHg or less normally, Preferably it is 2 mmHg or less.

  The number average molecular weight (Mn) of the aliphatic polyester (A) is usually 1 to 200,000, preferably 2 to 200,000 from the viewpoint of impact resistance, which is the object of the present invention. The ratio (Mw / Mn) of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is usually 3 or more, preferably 4 or more.

  In the present invention, from the viewpoint of further improving impact resistance, which is one of the objects of the present invention, at least one of a diol component and a dicarboxylic component (including a derivative) constituting the aliphatic polyester resin (A) is included. It is preferably derived from a plant, and more preferably both raw materials are derived from a plant.

<Olefin resin (B)>
The olefin resin (B) used in the present invention is usually composed of at least one olefin having 2 to 10 carbon atoms. This olefin resin (B) may use 2 or more types together. Examples of olefins used for forming the olefin resin (B) include ethylene, propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, and 3-methylhexene. Α-olefin such as −1. Two or more of these may be used in combination. Among these, ethylene, propylene, butene-1, 3-methyl-butene-1 or 4-methylpentene-1 is preferable, and ethylene or propylene is particularly preferable.

  Moreover, a cyclic olefin can be used as said olefins. The cyclic olefin is usually used in combination with the above-mentioned 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) occupies 50 mass% or more of the whole cyclic olefin. 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 [2. 2.1] bicyclo [2.2] such as hept-2-ene, 6-isobutylbicyclo [2.2.1] hept-2-ene, 7-methylbicyclo [2.2.1] hept-2-ene .1] hept-2-ene derivatives, tricyclo [4.3.0.1 ^2.5 ] -3-decene, 2-methyltricyclo [4.3.0.1 ^2.5 ] -3-decene, 5-methyl-tricyclo [4.3.0.1 ^2.5] -3-tricyclo decene [ .3.0.1 ^2.5] -3-decene derivatives, tricyclo [4.4.0.1 ^2.5] -3-undecene and the like. Two or more of these may be used in combination. The cyclic olefin having 12 or more carbon atoms can be used alone in addition to the above-mentioned compound having 11 or less carbon atoms.

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

  As the olefin resin (B), a polymer mainly containing ethylene units such as polyethylene and ethylene-norbornene copolymer, and a polymer mainly containing propylene units such as polypropylene and propylene-ethylene copolymer are preferable. A polymer containing mainly is preferred. Two or more of these may be used in combination. A preferable combination when used in 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, but a random type is preferable from surface appearance property. Moreover, as polyethylene, any of high density polyethylene, low density polyethylene, linear low density polyethylene, etc. may be sufficient.

  The olefin resin (B) used in the present invention is produced by a known polymerization method, for example, a high pressure polymerization method, a low pressure polymerization method, a metallocene catalyst polymerization method, etc. Those removed may be modified with an acid anhydride group, a carboxyl group, an epoxy group, or the like.

  It does not matter whether the olefin resin (B) has crystallinity, but it is preferable to use at least one of those having a crystallinity by X-ray diffraction of 10% or more at room temperature. In addition, it is preferable to use at least one of the olefin resins (B) having a melting point of 40 ° C. or higher measured according to JIS K7121.

  When a polypropylene resin is used as the olefin resin (B), the melt flow rate measured according to JIS K7210: 1999 (230 ° C., load 2.16 kg) is usually 0.01 to 500 g / 10 minutes, preferably Is 0.05 to 100 g / 10 min. When a polyethylene resin is used, the melt flow rate measured in accordance with JISK6922-2 (190 ° C., load 2.16 kg) is usually 0.01 to 500 g / 10 minutes, preferably 0.05 to 100 g / 10 minutes.

  Various additives such as an antioxidant, a heat stabilizer, and a lubricant can be blended and used in the olefin resin (B). Depending on the application of the antistatic resin composition of the present invention, an olefin resin (B) that does not contain an additive that becomes a gas component generated from a molded product may be preferable. In addition, a low molecular weight hydrocarbon compound with a small amount or a removed one, and further a catalyst that has been decatalyzed may be preferable.

<Aromatic vinyl polymer (C)>
The aromatic vinyl polymer (C) used in the present invention is at least one aromatic vinyl polymer selected from the following (C1) to (C3).

<Aromatic vinyl polymers (C1) and (C2)>
The aromatic vinyl polymer (C1) is a block copolymer containing a polymer block (Ca) mainly composed of an aromatic vinyl compound and a polymer block (Cb) mainly composed of a conjugated diene compound. The aromatic vinyl polymer (C2) is an elastomer obtained by hydrogenating the aromatic vinyl polymer (C1).

  Examples of the aromatic vinyl compound used in the polymer block (C-a) include styrene, α-methylstyrene, hydroxystyrene, and the like, preferably styrene and α-methylstyrene, and particularly preferably styrene. is there. The conjugated diene compound used for the polymer block (Cb) includes butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and preferably butadiene. Isoprene. Two or more of these may be used in combination. Further, the polymer block (Cb) may be a block in which two or more kinds of conjugated diene compounds are used and bonded in any form of random, block, or taper. Moreover, the polymer block (Cb) may contain 1 to 10 taper blocks in which the aromatic vinyl compound gradually increases, and is derived from the conjugated diene compound of the polymer block (Cb). Polymer blocks having different vinyl bond contents may be appropriately copolymerized.

  A preferred structure of the aromatic vinyl polymer (C1) is a polymer represented by the following structural formulas (5) to (7) or a hydrogenated product (C2) thereof.

  In the structural formulas (5) to (7), A represents a polymer block mainly composed of an aromatic vinyl compound. If the polymer block A is a polymer block substantially composed of an aromatic vinyl compound, the content of the aromatic vinyl compound in the polymer block A which may partially contain a conjugated diene compound is usually 90. It is at least mass%, preferably at least 99 mass%. B represents a homopolymer of a conjugated diene compound or a copolymer of another monomer such as an aromatic vinyl compound and a conjugated diene compound. X represents a residue of the coupling agent, Y represents an integer of 1 to 5, and Z represents an integer of 1 to 5, respectively. When B is a copolymer of another monomer such as an aromatic vinyl compound and a conjugated diene compound, the content of the other monomer in B is the conjugated diene compound and the other monomer. It is preferable that it is 50 mass% or less with respect to the sum total.

  The use ratio of the aromatic vinyl compound and the conjugated diene compound in the aromatic vinyl polymer (C1) is usually 10 to 70/30 to 90% by mass, preferably 15 to 15% as the aromatic vinyl compound / conjugated diene compound. 65 / 35-85 mass%, More preferably, it is 20-60 / 40-80 mass%.

  The block copolymer comprising an aromatic vinyl compound and a conjugated diene compound is known in the technical field of anionic polymerization. For example, Japanese Patent Publication No. 47-28915, Japanese Patent Publication No. 47-3252, Japanese Patent Publication No. 48. No. 2423, and Japanese Patent Publication No. 48-20038. A method for producing a polymer block having a tapered block is disclosed in JP-A-60-81217.

  The vinyl bond content (1,2- and 3,4-bond) content derived from the conjugated diene compound in the aromatic vinyl polymer (C1) is usually in the range of 5 to 80%. The number average molecular weight of the aromatic vinyl polymer (C1) is usually 10,000 to 1,000,000, preferably 20,000 to 500,000, more preferably 20,000 to 200,000. . Among these, the number average molecular weight of the A part represented by the above (5) to (7) is usually in the range of 3,000 to 150,000, and the number average molecular weight of the B part is usually in the range of 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 performed using ethers such as butyl ether, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, alkoxides of potassium and sodium, and the like.

  A polymer represented by the structural formula (6), that is, a polymer in which a polymer chain is extended or branched via a coupling agent residue, is obtained by the above method, and then a coupling agent is used. Is obtained. The coupling agent used here is diethyl adipate, divinylbenzene, methyldichlorosilane, silicon tetrachloride, butyltrichlorosilicon, tetrachlorotin, butyltrichlorotin, dimethylchlorosilicon, tetrachlorogermanium, 1,2- Examples include dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized linseed oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate, and the like.

  Among the above block copolymers, a polymer preferable from the viewpoint of impact resistance is a polymer having 1 to 10 tapered blocks in which the aromatic vinyl compound gradually increases in the block (Cb) and / or It is a radial block type polymer subjected to a coupling treatment.

  The hydrogenation reaction for obtaining the aromatic vinyl polymer (C2) can be carried out by a known method, and the target polymer can be obtained by adjusting the hydrogenation rate by a known method. Can be obtained. 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. Usually, 50% or more of the carbon-carbon double bonds in the conjugated diene moiety are hydrogenated.

  The aromatic vinyl polymers (C1) and (C2) may be ones in which another polymer is chemically bonded as a block polymer and / or a graft polymer. In this case, 100% by mass of the other polymer that is chemically bonded does not need to be chemically bonded, and at least 10% by mass of the other polymer may be chemically bonded.

  The other polymer bonded as a block polymer to the aromatic vinyl polymers (C1) and (C2) is usually an aromatic polycarbonate and / or polyurethane, preferably an aromatic polycarbonate. The aromatic polycarbonate block copolymer mixture can be produced, for example, by the method described in JP-A-2001-220506. Furthermore, “TM-S4L77”, “TM-H4L77” (trade name) of “TM polymer series” manufactured by Kuraray Co., Ltd. can be obtained.

  In the method of graft polymerization of a vinyl monomer in the presence of the aromatic vinyl polymer (C1) and / or (C2), the vinyl monomer is a vinyl of a block polymer (D) described later. The system monomer (b) is preferably used. As a method for graft polymerization, emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like described later with respect to the block polymer (D) can be used, but solution polymerization or bulk polymerization is preferable.

<Aromatic vinyl polymer (C3)>
The aromatic vinyl polymer (C3) is a graft copolymer obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of an olefin polymer. As the polyolefin-based resin used here, all of those described with respect to the olefin-based resin (B) can be used, but from the viewpoint of impact resistance, preferably a propylene or ethylene homopolymer and copolymer are used. And more preferably a propylene homopolymer and a propylene-based copolymer. Further, as the vinyl monomer (b) containing an aromatic vinyl compound, all of the vinyl monomers (b) of the block polymer (D) described later can be used, but preferably the aromatic vinyl compound and cyan. It contains a vinyl fluoride compound as an essential component and, if necessary, other vinyl monomers copolymerizable therewith.

  The aromatic vinyl compound is preferably styrene and / or α-methylstyrene, and the vinyl cyanide compound is preferably acrylonitrile. In addition, other copolymerizable vinyl monomers include acrylic acid esters such as methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate; methyl methacrylate, ethyl methacrylate, propyl methacrylate, Methacrylic acid esters such as butyl methacrylate; Unsaturated acid anhydrides such as maleic anhydride, itaconic anhydride and citraconic anhydride; Unsaturated acids such as acrylic acid and methacrylic acid; Maleimide, N-methylmaleimide, N-butylmaleimide And maleimide compounds such as N-cyclohexylmaleimide. Two or more of these may be used in combination.

  The content of the olefin resin in the aromatic vinyl polymer (C3) is 100% by mass of the total amount of the olefin resin and the monomer component, and is usually 10 to 60% by mass, preferably 20 to 50% by mass. is there. The mass ratio of the aromatic vinyl compound to the vinyl cyanide compound in the vinyl monomer (b) is usually 30/70 to 98/2, preferably 60/40 as the aromatic vinyl compound / vinyl cyanide compound. ~ 95/5.

  When using other copolymerizable vinyl monomers, the amount used is 100 parts by mass of the total amount of the aromatic vinyl compound and vinyl cyanide compound, usually 50 parts by mass or less, preferably 30 parts by mass or less. More preferably, it is 20 parts by mass or less.

  As a method for producing the aromatic vinyl polymer (C3), known methods such as emulsion polymerization, bulk polymerization, suspension polymerization, and solution polymerization can be used. In particular, solution polymerization is preferable from the viewpoint of quality. . The solution polymerization can be carried out by either a batch polymerization method or a continuous polymerization method, but the continuous polymerization method is preferred from the viewpoint of economy.

  Examples of the solvent that can be used for the solution polymerization include inert solvents mainly composed of aromatic hydrocarbons. Examples of the aromatic hydrocarbon include benzene, toluene, ethylbenzene, xylene, i-propylbenzene, and the like, and toluene is preferable from the viewpoint of economy and quality. In addition, polar solvents such as ketones, esters, ethers, amides, and halogenated hydrocarbons may be used at 30% by mass or less in the solvent, but combined use with aliphatic hydrocarbons is not preferable. The usage-amount of an inert solvent is 50-200 mass parts normally with respect to a total of 100 mass parts of an olefin resin and a vinyl monomer component, Preferably it is 60-180 mass parts. The polymerization temperature is usually 80 to 140 ° C, preferably 90 to 135 ° C, more preferably 100 to 130 ° C.

  When performing graft copolymerization, the olefin resin is used in a proportion of 10 to 60% by mass and the vinyl monomer component 90 to 40% by mass (the total of the olefin resin and the vinyl monomer component is 100% by mass). It is preferable. In addition, it is preferable to perform graft copolymerization by adding a vinyl monomer component after dissolving the olefin resin in the solvent in advance. At this time, the olefin-based resin does not necessarily need to be dissolved uniformly, and may be partially dissolved or swollen. The temperature of the solvent at the time of dissolution is usually 100 ° C. or higher, preferably 105 ° C. or higher, more preferably 110 to 200 ° C., and particularly preferably 110 to 170 ° C. This dissolution is preferably performed over the time range of about 2 to 5 hours. The solubility of the olefin-based resin varies depending on the specifications of the reaction vessel, but usually the solubility is low at a temperature lower than 100 ° C., the graft rate is lowered, and the intended performance cannot be obtained. The polymerization time for carrying out the graft copolymerization is usually 1 to 10 hours, preferably 1.5 to 8 hours, and more preferably 2 to 6 hours. If the polymerization time is too short, the polymerization rate does not increase, and the graft rate may be lowered. If it is too long, the productivity is lowered.

  In graft copolymerization, a polymerization initiator may be used, or polymerization may be performed by thermal polymerization without using a polymerization initiator, but it is preferable to use a polymerization initiator. Any known polymerization initiator can be used as the polymerization initiator, but an organic peroxide effective for the graft reaction is preferably used.

Examples of the organic peroxide include peroxyester compounds, dialkyl peroxide compounds, diacyl peroxide compounds, peroxydicarbonate compounds, peroxyketal compounds, and the like. Examples of peroxyester compounds include cumylperoxyneodecanoate, 1,1,3,3-tetramethylbutylperoxyneodecanoate, t-hexylperoxyneodecanoate, and t-butylperperoxide. Oxyneodecanoate, t-butylperoxyneoheptanoate, t-hexylperoxyvalate, t-butylperoxypivalate, 1,1,3,3-tetramethylbutylperoxy-2-ethylhexano Ate, 2,5-dimethyl-2,5-di (2-ethylhexanoylperoxy) hexane, t-hexylperoxy-2-ethylhexanoate, t-butylperoxy-2-ethylhexanoate, t-hexylperoxyisopropyl monocarbonate, t-butylperoxymaleic acid, t-butylperoxy -3,5,5-trimethylhexanoate, t-butyl peroxylaurate, t-butyl peroxyisopropyl monocarbonate, t-butyl peroxy-2-ethylhexyl monocarbonate, t-hexyl peroxybenzoate, 2 , 5-dimethyl-2,5-di (benzoylperoxy) hexane, t-butylperoxyacetate, t-butylperoxy-3-methylbenzoate, t-butylperoxybenzoate, and the like. Examples of the dialkyl peroxide compound include di (2-t-butylperoxyisopropyl) benzene, dicumyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexane, t- Examples include butylcumyl peroxide, di-t-hexyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di (t-butylperoxy) hexyne-3 and the like. Examples of diacyl peroxide compounds include diisobutyryl peroxide, di (3,5,5-trimethylhexanoyl) peroxide, dilauroyl peroxide, disuccinic acid peroxide, and di- (3-methylbenzoyl) peroxide. Benzoyl (3-methylbenzoyl) peroxide, dibenzoyl peroxide, di (4-methylbenzoyl) peroxide, and the like. Examples of peroxydicarbonate compounds include di-n-propyl peroxydicarbonate, diisopropyl peroxydicarbonate, di (4-t-butylcyclohexyl) peroxydicarbonate, and di (2-ethylhexyl) peroxydi. Carbonate,
Examples include di-sec-butyl peroxydicarbonate. Examples of peroxyketanol compounds include 1,1-di (t-hexylperoxy) -3,3,5-trimethylcyclohexane, 1,1-di (t-hexylperoxy) cyclohexane, 1,1 -Di (t-butylperoxy) -2-methylcyclohexane, 1,1-di (t-butylperoxy) cyclohexane, 2,2-di (t-butylperoxy) butane, n-butyl-4,4 -Di (t-butylperoxy) valate, 2,2-di (4,4-di (t-butylperoxy) cyclohexyl) propane and the like. Two or more of these may be used in combination. Of these, peroxyester compounds are preferred, more preferred are peroxyester compounds having a 10-hour half-life temperature (T ₁₀ ) of 80 to 120 ° C., and particularly preferred is t-butylperoxy. Isopropyl monocarbonate.

  The amount of the polymerization initiator used is usually 0.01 to 5 parts by mass, preferably 0.05 to 3 parts by mass, more preferably 0.1 to 0.1 parts by mass with respect to a total of 100 parts by mass of the olefin resin and the vinyl monomer. 2 parts by mass. Further, for example, chain transfer agents such as mercaptans and α-methylstyrene dimer can be used, and an antioxidant may be added if necessary. It may be added before or after the polymerization reaction.

As a polymerization initiator, when solution polymerization is performed using a peroxyester compound having a 10-hour half-life temperature (T ₁₀ ) of 80 to 120 ° C., a temperature (Tr) range that satisfies the following formula (8): It is preferable to carry out the polymerization.

  The graft ratio of the graft copolymer (C3) is usually 20 to 200% by mass, preferably 30 to 150% by mass, and more preferably 40 to 120% by mass. This graft ratio is determined by the following formula (9).

  In formula (9), T represents 1 g of an olefin resin graft copolymer in 200 ml of acetone, shaken with a shaker for 2 hours, and then centrifuged for 60 minutes with a centrifuge (rotation speed: 23,000 rpm). The mass (g) of the insoluble matter obtained by separating the insoluble content and the soluble content, and S is the mass (g) of the polyolefin-based resin contained in 1 g of the olefin-based resin graft copolymer.

  In addition, the intrinsic viscosity [η] of acetone-soluble matter of the graft copolymer (C3) (measured at 30 ° C. using methyl ethyl ketone as a solvent) is usually 0.1 to 1.2 dl / g, preferably 0.8. 2 to 1 dl / g, more preferably 0.2 to 0.8 dl / g.

  The graft copolymer (C3) melt flow rate (MFR) is usually 5 g / 10 min or more, preferably 10 to 200 g / 10 min, as a value measured at 220 ° C. and 10 kg. Moreover, IZOD (Izod) impact strength is 20-200 J / m normally, Preferably it is 90-200 J / m. The flexural modulus is usually 1400 to 3000 MPa, preferably 1500 to 3000 MPa.

  The graft copolymer (C3) obtained by copolymerizing a vinyl monomer component in the presence of an olefin resin usually contains a copolymer obtained by grafting a vinyl monomer component onto an olefin resin and vinyl. An ungrafted component in which the monomer component is not grafted to the olefin resin (that is, a homopolymer and a copolymer of vinyl monomers) is included.

<Block copolymer (D)>
It has at least one block (D1) selected from the group of polyamide, polyester and polyolefin and a hydrophilic polymer block (D2). In the block (D1), polyester and / or polyolefin may be copolymerized in the polyamide block, polyamide and / or polyolefin may be copolymerized in the polyester block, and further in the polyolefin block. Polyamide and / or polyester may be copolymerized.

  Polyamides include (I) polyamides derived from diamine components and dicarboxylic acid components, (II) polyamides by ring-opening polymerization of lactams, (III) polyamides derived from aminocarboxylic acids, copolyamides thereof, and mixtures thereof Any of polyamides may be used.

As the diamine component in the above (I), ethylenediamine, tetramethylenediamine, hexamethylenediamine, decamethylenediamine, 2,3,4, or 2,4,4-
Aliphatic, alicyclic such as trimethylenehexamethylenediamine, 1,3- or 1,4-bis (aminomethyl) cyclohexane, bis (p-aminohexyl) methane, phenyldiamine, m-xylenediamine, p-xylenediamine Examples of the dicarboxylic acid component include aliphatic, alicyclic or aromatic dicarboxylic acids such as adipic acid, suberic acid, sebacic acid, cyclohexanedicarboxylic acid, terephthalic acid, and isophthalic acid. It is done. Examples of the lactam (II) include caprolactam and lauryl lactam. Examples of the aminocarboxylic acid (III) include ω-aminocaproic acid, ω-aminoenanoic acid, aminoundecanoic acid, and 1,2-aminododecanoic acid.

  Examples of the polyester include a polymer obtained from a dicarboxylic acid component having 4 to 20 carbon atoms and / or an ester-forming derivative (I) thereof and a diol component (II), a polymer obtained from a bifunctional oxycarboxylic acid compound, and a caprolactone compound. There are polymers obtained, (I), (II), bifunctional oxycarboxylic acid compounds, copolymers made of a compound selected from the group of caprolactone compounds, and the like. (II) A copolymer composed of a bifunctional oxycarboxylic acid compound is preferred. Here, the carbon number means the total number of carbon atoms constituting a chain or a ring directly connected to the carbon number of the carboxyl group and the carbon number of the carboxyl group.

Examples of the dicarboxylic acid having 4 to 20 carbon atoms include aliphatics having 4 to 20 carbon atoms such as succinic acid, adipic acid, azelaic acid, sebacic acid, α, ω-dodecanedicarboxylic acid, dodecenyl succinic acid, and octadecenyl dicarboxylic acid. Dicarboxylic acid; alicyclic dicarboxylic acid having 8 to 20 carbon atoms such as 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 2,6- C8-12 aromatic dicarboxylic acids such as naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid; sulfonic acids such as 5-sodium sulfoisophthalic acid, 5-potassium sulfoisophthalic acid, and 5-tetrabutylphosphonium sulfoisophthalic acid A substituted aromatic dicarboxylic acid having 8 to 12 carbon atoms in which the group is bonded to an aromatic ring; There are ester-forming derivatives such as methyl esters of dicarboxylic acids. Two or more of these may be used in combination. Among these, terephthalic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, 5-sodium sulfoisophthalic acid, succinic acid or ester-forming derivatives thereof are preferable.

  As the diol component, all those described as the raw material component of the above-mentioned aliphatic polyester (A) can be used, and ethylene glycol or 1,4-butanediol is particularly preferable. Also, lactone compounds such as caprolactone, bifunctional aliphatic oxycarboxylic acids and bifunctional oxycarboxylic acids described as raw material components of the aliphatic polyester (A) can be used.

  The polyester used in the present invention includes (i) a polyester comprising the dicarboxylic acid or its ester-forming derivative and the diol, and (ii) comprising the dicarboxylic acid or its ester-forming derivative, the diol and the bifunctional oxycarboxylic acid. Polyester is preferred.

  Polyolefin refers to a (co) polymer of olefins. As the olefin, all those described for the olefin resin (B) can be used, and among these, ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, or norbornene is preferable. Two or more of these may be used in combination. Further, as a part of the polymer component, non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl 1,6-octadiene, 1,9-decadiene, etc. Can also be used. The number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) of polyolefin is usually 800 to 20,000, preferably 1,000 to 10,000, and more preferably 1,200 to 6,000.

  Polyolefin can be obtained by a polymerization method, a thermal degradation method, or the like. In the case of the polymerization method, the olefin is (co) polymerized in the presence of a catalyst. As the catalyst, for example, a radical catalyst, a metal oxide catalyst, a Ziegler-Natta catalyst, a metallocene catalyst, or the like is used. On the other hand, a low molecular weight polyolefin obtained by thermal degradation of a high molecular weight polyolefin can be easily obtained, for example, according to the method described in JP-A-3-62804. When obtaining the block copolymer (D), it is necessary to modify the molecular ends of the polyolefin. From the viewpoint of ease of modification of the molecular ends, a polyolefin obtained by a thermal degradation method is preferred.

  The polyolefin obtained by the thermal degradation method is usually a mixture of a polyolefin that can be modified at both molecular ends and a polyolefin that does not have a terminal group that can be modified at one end. Preferably it is a component. The amount of double bonds in the polyolefin obtained by the thermal degradation method is usually 1 to 40, preferably 2 to 30, more preferably 4 to 20 per 1,000 carbon atoms from the viewpoint of antistatic properties. It is a piece. The average number of double bonds per molecule is usually 1.1 to 5, preferably 1.3 to 3, and more preferably 1.8 to 2 from the viewpoints of the repetitive structure formation and antistatic properties. .2. In the thermal degradation method, a low molecular weight polyolefin having an Mn of 800 to 6,000 and an average number of terminal double bonds per molecule of 1.5 to 2 can be easily obtained [for example, Katsuhide Murata, Tadahiko Makino, See Journal of the Chemical Society of Japan, page 192 (1975)].

  Examples of a method for imparting a functional group to a polyolefin include a method of adding a carbon-carbon unsaturated compound having a functional group to a polyolefin obtained by a thermal degradation method and having a carbon-carbon double bond at a molecular end. .

  In the block copolymer (D), the bond between at least one block (D1) selected from the group of polyamide, polyester and polyolefin and the hydrophilic polymer block (B2) is an ester bond, an amide bond, an ether It is at least one bond selected from a bond, a urethane bond, an imide bond, and the like. For this reason, the molecular terminal of the block (B1) needs to be modified with a functional group having reactivity with both terminal functional groups of the hydrophilic polymer block (B2) described below. Examples of these functional groups include a carboxyl group, a hydroxyl group, an amino group, an acid anhydride group, an oxazoline group, and an epoxy group.

  Examples of the hydrophilic polymer of the hydrophilic polymer block (B2) include polyethers, polyether-containing hydrophilic polymers, anionic polymers, and the like.

  Examples of the polyether include polyether diol, polyether diamine, and modified products thereof. Examples of the polyether-containing hydrophilic polymer include polyether ester amide having polyether diol segment, polyether ester amide imide, polyether ester, polyether amide having polyether diamine segment, polyether diol, or polyether diamine. Examples thereof include polyether urethane having a segment. As an anionic polymer, the anionic polymer which has dicarboxylic acid which has a sulfonyl group, and said polyether as an essential component unit, and has a sulfonyl group is mentioned. The number of sulfonyl groups in one molecule is usually 2 to 80, preferably 3 to 60. The hydrophilic polymer block (B2) may be linear or branched. As the hydrophilic polymer of the hydrophilic polymer block (B2), polyether is preferable.

  Among the polyethers, examples of the polyether diol include those represented by the following general formulas (10) and (11).

In general formula (10), E ¹ is a residue obtained by removing a hydroxyl group from a divalent hydroxyl group-containing compound, A ¹ is an alkylene group having 2 to 4 carbon atoms, and n and n ′ are the above divalent hydroxyl group-containing compounds. This represents the number of alkylene oxide additions per hydroxyl group. n (OA ¹ ) and n ′ (A ¹ O) may be the same or different, and the bond form in the case where these are composed of two or more oxyalkylene groups Can be either block or random or a combination thereof. n and n ′ are generally integers of 1 to 300, preferably 2 to 250, and more preferably 10 to 100. N and n ′ may be the same or different.

  Examples of the divalent hydroxyl group-containing compound include compounds containing two alcoholic or phenolic hydroxyl groups in one molecule, that is, dihydroxy compounds. Specifically, divalent alcohols (for example, having 2 to 2 carbon atoms) 12 aliphatic, alicyclic or aromatic dihydric alcohol), C6-C18 dihydric phenol, tertiary amino group-containing diol, and the like.

  Examples of the aliphatic dihydric alcohol include alkylene glycols such as ethylene glycol and propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, 1,12-dodecanediol, and the like. Examples of the alicyclic dihydric alcohol include 1,2- and 1,3-cyclopentanediol, 1,2-, 1,3- and 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol and the like. Examples of the aromatic dihydric alcohol include xylene diol.

Dihydric phenols include monocyclic dihydric phenols such as hydroquinone, catechol, resorcin, and urushiol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyl, dihydroxydiphenyl ether And the like, and condensed polycyclic dihydric phenols such as dihydroxynaphthalene and binaphthol.

In the general formula (11), E ² is a residue obtained by removing a hydroxyl group from the divalent hydroxyl group-containing compound described in the general formula (10), and A ² is at least partially represented by the following general formula (12). The remaining alkylene group may be an alkylene group having 2 to 4 carbon atoms.

  However, in General Formula (12), one of R and R ′ is a group represented by General Formula (13), and the other is H.

In general formula (13), x is an integer of 1 to 10, R ″ is H or an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an arylalkyl group or an acyl group, and A ³ is 2 to 2 carbon atoms. 4 alkylene group.

In the general formula (11), m (OA ² ) and m ′ (A ² O) may be the same or different. m and m ′ are integers, and are usually 1 to 300, preferably 2 to 250, and more preferably 10 to 100. M and m ′ may be the same or different.

  The polyether diol represented by the general formula (10) can be produced by addition reaction of an alkylene oxide with a divalent hydroxyl group-containing compound. Examples of the alkylene oxide include alkylene oxides having 2 to 4 carbon atoms such as ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,4-butylene oxide, 2,3-butylene oxide, and 1,3-butylene oxide. Can be mentioned. Two or more of these may be used in combination. When two or more kinds of alkylene oxides are used in combination, the bond form may be random and / or block. Preferable alkylene oxides are ethylene oxide alone and block and / or random addition by the combined use of ethylene oxide and other alkylene oxides. The addition number of alkylene oxide is usually 1 to 300, preferably 2 to 250, and more preferably 10 to 100 per hydroxyl group of the divalent hydroxyl group-containing compound.

  Preferred methods for producing the polyether diol represented by the general formula (11) include the following methods (A) and (B).

  (A) A method of polymerizing a glycidyl ether represented by the following general formula (14) or copolymerizing with an alkylene oxide having 2 to 4 carbon atoms using the above divalent hydroxyl group-containing compound as a starting material.

A ⁴ in the general formula (14) is an alkylene group having 2 to ⁴ carbon atoms, p is an integer of 1 to 10, R ¹ is a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an aryl An alkyl group or an acyl group;

(B) A method of using a divalent hydroxyl group-containing compound as a starting material and passing through a polyether having a chloromethyl group in the side chain. Specifically, epichlorohydrin or epichlorohydrin and alkylene oxide are addition copolymerized to obtain a polyether having a chloromethyl group in the side chain, and then the polyether, a polyalkylene glycol having 2 to 4 carbon atoms, and R ¹ X. (R ¹ has the same meaning as above, X is Cl, Br or I) in the presence of an alkali, or the polyether and a polyalkylene glycol monocarbyl ether having 2 to 4 carbon atoms are alkalinized. A method of reacting in the presence. As the alkylene oxide having 2 to 4 carbon atoms used here, all of those described above can be used.

  Moreover, the preferable block copolymer (D) of this invention can be obtained by superposing | polymerizing the said block (D1) and hydrophilic polymer block (D2) by a well-known method. For example, the block (D1) and the hydrophilic polymer block (D2) can be produced by performing a polymerization reaction at 200 to 250 ° C. under reduced pressure. A known polymerization catalyst can be used in the polymerization reaction.

  Polymerization catalysts include tin-based catalysts such as monobutyltin oxide, antimony-based catalysts such as antimony trioxide and antimony dioxide, titanium-based catalysts such as tetrabutyl titanate, zirconium-based catalysts such as zirconium hydroxide, zirconium oxide and zirconyl acetate. , One or a combination of two or more selected from the group of catalysts consisting of organic acid salts of Group IIB metals of the periodic table.

  The block copolymer (D) can contain an alkali metal salt and / or an alkaline earth metal salt (F) for the purpose of improving antistatic properties. The component (F) can be contained before or during the polymerization for obtaining the block copolymer (D), or after the polymerization, the block copolymer (D) can be contained. In addition, the component (F) may be blended when the antistatic resin composition of the present invention is produced, and can also be contained by a method combined with the above method.

  Examples of the component (F) include organic acid salts, sulfonic acid salts, inorganic acid salts, halides and the like of alkali metals such as lithium, sodium and potassium, and alkaline earth metals such as magnesium and calcium.

  Preferred specific examples of component (F) include halides of alkali metals such as lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide; sodium perchlorate, potassium perchlorate, etc. Inorganic acid salts of alkali metals, organic acid salts of alkali metals such as potassium acetate and lithium stearate; octyl sulfonic acid, dodecyl sulfonic acid, tetradecyl sulfonic acid, stearyl sulfonic acid, tetracosyl sulfonic acid, 2-ethylhexyl sulfonic acid Alkali metal salts of alkyl sulfonic acids having 8 to 24 carbon atoms of alkyl groups; Alkali metal salts of aromatic sulfonic acids such as phenyl sulfonic acid and naphthyl sulfonic acid; Octyl phenyl sulfonic acid, dodecyl phenyl sulfonic acid, dibutyl phenyl Sulfonic acid, dinonyl pheny Alkali metal salt of alkylbenzene sulfonic acid having 6 to 18 carbon atoms in alkyl group such as sulfonic acid; alkyl naphthalene having 2 to 18 carbon atoms in alkyl group such as dimethylnaphthylsulfonic acid, diisopropylnaphthylsulfonic acid, dibutylnaphthylsulfonic acid, etc. Alkali metal salts of alkyl naphthalene sulfonic acids having 2 to 18 carbon atoms of alkyl groups such as sulfonic acids; alkali metal salts such as fluorinated sulfonic acids such as trifluoromethanesulfonic acid. Two or more of these may be used in combination. The usage-amount of a component (F) is 30 mass% or less normally with respect to a block copolymer (D), Preferably it is 20 mass% or less, More preferably, it is 10 mass% or less.

  The ratio of the component of the block (D1) / the component of the hydrophilic polymer block (D2) in the block copolymer (D) is usually 10 to 90/10 to 90% by mass, preferably 20 to 80/20 to 80. It is 30 mass%, More preferably, it is 30-70 / 30-70 mass%.

  The block copolymer (D) using a polyolefin as the component of the block (D1) can be produced, for example, by the method described in JP-A Nos. 2001-278985 and 2003-48990. In addition, “Pelestat 300 Series” “300”, “303”, “Pelestat 200 Series” “230”, “201”, etc. manufactured by Sanyo Chemical Industries, Ltd. can be obtained.

  The number average molecular weight of the polyamide in the block copolymer (D) using polyamide as the component of the block (D1) is usually 500 to 20,000, preferably 500 to 10,000, and more preferably 500 to 5,000. Although the molecular weight of such a block copolymer (D) is not specifically limited, As a reduced viscosity ((eta) sp / C), it is 1.0-3.0 normally, Preferably it is 1.2-2.5. The reduced viscosity is a value measured in a formic acid solution under the conditions of a concentration of 0.5 g / 100 ml and a temperature of 25 ° C. A particularly preferred example of such a block copolymer (D) is a polyether ester amide in which a polyamide and a poly (alkylene oxide) glycol block are bonded by an ester bond, and “Pelestat NC6321” manufactured by Sanyo Chemical Industries, Available as “M-140” and “6500” (trade names).

  The molecular weight of the block copolymer (D) using polyester as the component of the block (D1) is not particularly limited, but the reduced viscosity (ηsp / C) is usually 0.3 to 2.5, preferably 0. .5 to 2.5. The reduced viscosity is a value measured using a mixed solvent of phenol / tetrachloroethane = 40/60 mass ratio under the conditions of a concentration of 1.0 g / 100 ml and a temperature of 35 ° C. Particularly preferred examples of such a block copolymer (D) can be obtained, for example, as “TEP004”, “TEP010”, “TEP008” (trade name) manufactured by Takemoto Yushi Co., Ltd.

  A known antioxidant, heat stabilizer and the like can be present during the production of the block copolymer (D) (before polymerization, during polymerization, and after polymerization). Moreover, 2 or more types of block copolymers (D) may be used in combination. When polyolefin is used as the component of the block (D1), the antistatic property is particularly excellent, and when polyester is used, the wear property is particularly excellent. Further, when polyamide is used, the surface appearance of the molded product is particularly excellent.

<Styrene resin (E)>
It consists of the following (E1) and / or (E2) consisting of the following (E1) and / or (E2).

<Styrenic resins (E1) and (E2)>
The styrene resin (E1) is obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of a rubbery polymer (however, an aromatic vinyl polymer (excluding C1 and (C2)). The styrene resin (E2) is obtained by (co) polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the absence of the above rubbery polymer. It is a styrene resin obtained. From the viewpoint of impact resistance, a styrene resin containing at least one polymer grafted (co) polymerized in the presence of the rubbery polymer (a) is preferable.

  The content of the rubber polymer (a) is usually 3 to 80% by mass, preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on the styrene resin (E) (as 100% by mass). %.

  The rubbery polymer (a) is not particularly limited, but has a glass transition temperature (Tg) of −10 ° C. or less, polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, ethylene / propylene. Copolymer, ethylene / propylene / non-conjugated diene copolymer, ethylene / butene-1 copolymer, ethylene / butene-1 / non-conjugated diene copolymer, acrylic rubber, silicone rubber, silicone / acrylic IPN rubber, A natural rubber etc. are mentioned, These may use 2 or more types together. Of these, polybutadiene, butadiene / styrene copolymer, ethylene / propylene copolymer, ethylene / propylene / nonconjugated diene copolymer, acrylic rubber, silicone rubber, and natural rubber are preferable.

  The gel content of the rubber polymer (a) is not particularly limited, but the gel content when obtained by emulsion polymerization is usually 98% by mass or less, preferably 40 to 98% by mass. In such a gel content range, it is possible to obtain an antistatic resin composition that gives a molded article particularly excellent in impact resistance.

  In addition, said gel content rate can be calculated | required by the method shown below. That is, 1 g of a rubbery polymer was put into 100 ml of toluene, allowed to stand at room temperature for 48 hours, and then the toluene-insoluble matter and the wire mesh filtered through a 100 mesh wire mesh (with a mass of W1 gram) were vacuumed at 80 ° C. for 6 hours. It is dried and weighed (mass W2 gram), and calculated by the following formula (15).

  The gel content can be adjusted by appropriately setting the type and amount of the molecular weight regulator, the polymerization time, the polymerization temperature, the polymerization conversion rate and the like during the production of the rubbery polymer.

  Examples of the aromatic vinyl compound constituting the vinyl monomer (b) include styrene, α-methylstyrene, hydroxystyrene and the like, and two or more of these may be used in combination. Of these, styrene or α-methylstyrene is preferred.

  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 the vinyl monomer (b) of a preferred embodiment of the present invention, an aromatic vinyl compound is an essential monomer component, and if necessary, a vinyl cyanide compound, a (meth) acrylic acid ester compound and a maleimide compound 1 type or 2 types or more selected from the group of these are used together as a monomer component, and also at least 1 sort (s) of other various functional group containing unsaturated compounds is used together as a monomer component as needed. Examples of the functional group-containing unsaturated compound include unsaturated acid compounds, epoxy group-containing unsaturated compounds, substituted or unsubstituted amino group-containing unsaturated compounds, and the like. Two or more of the above functional group-containing unsaturated compounds may be used in combination.

  Examples of the vinyl cyanide compound include acrylonitrile, methacrylonitrile and the like, and these may be used in combination of two or more. When a vinyl cyanide compound is used, chemical resistance is imparted. The usage-amount of the vinyl cyanide compound of a vinyl-type monomer (b) is 1-60 mass% normally, 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. Good. Use of a (meth) acrylic acid ester compound is preferable because surface hardness is improved. The usage-amount of the (meth) acrylic acid ester compound of a vinyl-type monomer (b) is 1-80 mass% normally, Preferably it is 5-80 mass%.

  Examples of the maleimide compound include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like, and two or more of these may be used in combination. In order to introduce a maleimide unit, maleic anhydride may be copolymerized and then imidized. When a maleimide compound is used, heat resistance is imparted. The usage-amount of the maleimide compound of a vinyl-type monomer (b) is 1-60 mass% normally, Preferably it is 5-50 mass%.

  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-2- 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 Methacrylamine, N-methylacrylamine, acrylamide, N-methylacrylamide, p-aminostyrene and the like, and two or more of these may be used in combination.

  When the above functional group-containing unsaturated compound is used, compatibility between the styrenic resin and another polymer can be improved. Preferred monomers for achieving such effects are epoxy group-containing unsaturated compounds, unsaturated acid compounds and hydroxyl group-containing unsaturated compounds.

  The amount of the functional group-containing unsaturated compound used is usually 0.1 to 20% by mass, preferably, based on the total amount of the styrenic resin, as the total amount of the functional group-containing unsaturated compound used in the styrene resin. Is 0.1 to 10% by mass.

  The amount of the monomer other than the aromatic vinyl compound used in the vinyl monomer (b) is usually 80% by mass or less, preferably 100% by mass or less when the total of the vinyl monomers (b) is 100% by mass, preferably It is 60 mass% or less, More preferably, it is 40 mass% or less.

  Preferred combinations of monomers constituting the vinyl monomer (b) are 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 / cyclohexylmaleimide and the like.

  A preferable combination of monomers to be polymerized in the presence of the rubbery polymer (a) and the ratio thereof are styrene / acrylonitrile = 65/45 to 90/10 (mass ratio), styrene / methyl methacrylate = 80/20. 20/80 (mass ratio), styrene / acrylonitrile / methyl methacrylate, styrene content is 20 to 80% by mass, and the total amount of acrylonitrile and methyl methacrylate is 20 to 80% by mass. .

  The styrenic resin (E) can be produced by a known polymerization method such as emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a combination of these. Among these, preferred polymerization methods for the styrene resin (E1) are emulsion polymerization and solution polymerization. On the other hand, preferred polymerization methods for the styrene resin (E2) are bulk polymerization, solution polymerization, suspension polymerization and emulsion polymerization.

  When manufacturing by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, etc. are used, However, These can use a well-known thing.

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

  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 Examples thereof include rosinates such as potassium.

  In the emulsion polymerization, the rubber polymer (a) and the vinyl monomer (b) are used by adding the vinyl monomer (b) in the presence of the total 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 the emulsion polymerization, the obtained latex is usually coagulated with a coagulant, washed with water and dried to obtain a styrene resin (E) powder. At this time, the latex of two or more styrene resins (E) obtained by emulsion polymerization may be appropriately blended and then coagulated. As the coagulant, in addition to inorganic salts such as calcium chloride, magnesium sulfate and magnesium chloride, acids such as sulfuric acid, hydrochloric acid, acetic acid, citric acid and malic acid can be used.

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

  The polymerization temperature is usually 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. Examples of the polymerization initiator include organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, hydroperoxide, azobisisobutyronitrile, and benzoyl peroxide. As the chain transfer agent, for example, mercaptans, terpinolenes, α-methylstyrene dimer, etc. 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 the monomer remaining in the styrenic resin (E) obtained by the above polymerization methods is usually 10,000 ppm or less, preferably 5,000 ppm or less.

  The styrene resin (E1) usually contains a copolymer obtained by graft copolymerization of the vinyl monomer (b) with the rubber polymer (a) and an ungrafted component that is not grafted to the rubber polymer. [(Co) polymer of vinyl monomer (b)] is included. The graft ratio of the styrene-based resin (E1) is usually 20 to 200 mass%, preferably 30 to 150 mass%, more preferably 40 to 120 mass%, and the graft ratio can be obtained by the following formula (8). I can do it.

  In the above formula (16), T represents 1 g of styrene resin (E1) 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). It is the mass (g) of the insoluble matter obtained by separating and separating the insoluble matter and the soluble matter, and S is the mass (g) of the rubbery polymer contained in 1 g of the styrene resin (E1).

  Further, the intrinsic viscosity [η] of acetone-soluble component of styrene resin (E1) (measured at 30 ° C. using methyl ethyl ketone as a solvent) is usually 0.2 to 1.2 dl / g, preferably 0.2. It is -1.0 dl / g, More preferably, it is 0.3-0.8 dl / g. The average particle diameter of the grafted rubbery polymer particles dispersed in the styrene resin (E1) is usually 500 to 30,000, preferably 1,000 to 20,000, and more preferably 1,500 to 8,800. 000. The average particle diameter can be measured by a known method using an electron microscope.

  The antistatic resin composition of the present invention contains the aliphatic polyester (A), the olefin resin (B), the aromatic vinyl polymer (C), and the block copolymer (D) as essential components. In addition, the styrenic resin (E) is contained as an optional component in a preferred embodiment. And the ratio of each component is as follows. And the ratio of each component is as follows by making the total amount of said component (A), (B), (C) and (D) into 100 mass%.

  The ratio of a component (A) is 10-90 mass%, Preferably it is 15-90 mass%, More preferably, it is 20-85 mass%, Most preferably, it is 25-80 mass%. When the proportion of the component (A) is less than 5% by mass, the impact resistance is inferior and is not preferable from the viewpoint of biodegradability, and when it exceeds 90% by mass, the antistatic property and the chemical resistance are inferior.

  The ratio of a component (B) is 4-80 mass%, Preferably it is 5-75 mass%, More preferably, it is 5-70 mass%, Most preferably, it is 10-70 mass%. When the proportion of the component (B) is less than 4% by mass, the chemical resistance is inferior, and when it exceeds 80% by mass, the antistatic property is inferior, and it is not preferable from the viewpoint of biodegradability.

  The proportion of component (C) is 3 to 40% by mass, preferably 5 to 35% by mass, more preferably 10 to 35% by mass, particularly preferably 10 to 30% by mass, and the proportion of component (C) is 3%. When it is less than mass%, the impact resistance, chemical resistance and wear resistance are inferior, and when it exceeds 40 mass%, the chemical resistance is inferior.

  Component (C) has the effect of improving the compatibility of components (A) and (B), but from the viewpoint of impact resistance, it is preferable to use either component (C1) or (C2). In particular, it is preferable to use the component (C2). On the other hand, when the molded product surface appearance is required, it is preferable to use the component (C3). From the viewpoint of impact resistance and molded product surface appearance, the component (C1) and / or the component (C2). The combined use of 50 to 95% by mass and 5 to 50% by mass of the component (C3) is preferable (here, the total of the components (C1), (C2) and (C3) is 100% by mass).

  The proportion of component (D) used is 3 to 60% by mass, preferably 5 to 60% by mass, more preferably 5 to 50% by mass, particularly preferably 6 to 45% by mass, and the proportion of component (D) used. Is less than 3% by mass, the antistatic property is inferior, and when it exceeds 50% by mass, the wear resistance and impact resistance are inferior.

  The use ratio of the component (E) is 5 to 100 parts by mass, preferably 5 to 85 parts by mass, more preferably 7 to 70 parts by mass, particularly preferably 7 to 60 parts by mass, and the use ratio of the component (E). When the amount is less than 5 parts by mass, the effect of improving the impact resistance cannot be obtained, and when it exceeds 100 parts by mass, the antistatic property is inferior.

  For the purpose of further improving the antistatic property, the antistatic resin composition of the present invention contains a salt (G) having an anion portion having a fluorinated alkylsulfonyl group and a nonionic surfactant (H). I can do it.

  Examples of the salt (G) include lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide lithium, tris (trifluoromethanesulfonyl) methane lithium, and lithium trifluoromethanesulfonate is particularly preferable. Moreover, these may use 2 or more types together. The above salt (G) is “Sanconol 0862-13T”, “AQ-50T”, “AQ-75T”, “TBX-25” (trade name) manufactured by Sanko Chemical Co., Ltd., in the form of a solution or a masterbatch. You can get it.

  The proportion of the salt (G) used is usually 0.01 to 10 parts by mass, preferably 0.05 to 7 parts by mass, as a ratio with respect to 100 parts by mass of the total of the components (A) to (D). Preferably it is 0.05-5 mass parts, Most preferably, it is 0.1-3 mass parts.

  Examples of the nonionic surfactant (H) include polyhydric alcohol esters and nitrogen-containing compounds (amine compounds and amide compounds).

  As said polyhydric alcohol ester, glycerol ester, polyglycerol ester, sorbitan ester, ethylene glycol ester, propylene glycol ester etc. are mentioned.

  Examples of the glycerol monoester include glycerol monolaurate, glycerol monomyristate, glycerol monopalmitate, glycerol monostearate, glycerol monobehenate, and glycerol monooleate. Examples of the polyglycerol ester include diglycerol monolaurate, diglycerol monomyristate, diglycerol monopalmitate, diglycerol monostearate, diglycerol monobehenate, and diglycerol monooleate.

  Examples of the sorbitan ester include sorbitan monooleate, sorbitan monobehenate, sorbitan monostearate, sorbitan monoisostearate, sorbitan monolaurate, sorbitan monopalmitate and the like. Examples of the ethylene glycol ester include ethylene glycol monostearate. Examples of the propylene glycol ester include propylene glycol monostearate.

  Among the above, glycerol monostearate, diglycerol monostearate, glycerol monolaurate, diglycerol monolaurate and sorbitan monostearate are preferable.

  Examples of the amine compound include lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyl diethanolamine, lauryl diisopropanolamine, myristyl diisopropanolamine, palmityl diisopropanolamine, stearyl diisopropanolamine, oleyl diisopropanolamine, N , N-bishydroxyethylalkylamine (however, the alkyl group usually has 12 to 22 carbon atoms).

  Examples of the amide compound include lauryl diethanolamide, myristyl diethanolamide, palmityl diethanolamide, behenyl diethanolamide, oleyl diethanolamide, lauryl diisopropanolamide, myristyl diisopropanolamide, palmityl diisopropanolamide, stearyl diisopropanolamide, oleyl Examples thereof include diisopropanolamide.

  Among the above, amine-based compounds are preferable, and lauryl diethanolamine or stearyl diethanolamine is particularly preferable.

  The use ratio of the nonionic surfactant (H) is usually 0.05 to 20 parts by mass, preferably 0.1 to 10 parts by mass, as a ratio with respect to 100 parts by mass in total of the components (A) to (D). Part, more preferably 0.3 to 5 parts by mass.

  Furthermore, the antistatic resin composition of the present invention includes known weather resistance (light) agents, antioxidants, heat stabilizers, lubricants, silicone oils, plasticizers, sliding agents, colorants, dyes, foaming agents, Hydrolysis inhibitors such as processing aids (ultra high molecular weight acrylic polymers, ultra high molecular weight styrene polymers), flame retardants, crystal nucleating agents, carbodiimide compounds, and the like can be appropriately blended.

  Moreover, a well-known inorganic and organic filler can be mix | blended with the antistatic resin composition of this invention. Fillers include glass fiber, glass flake, glass fiber milled fiber, glass bead, hollow glass bead, carbon fiber, carbon fiber milled fiber, silver, copper, brass, iron, 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, aluminum borate whisker, plate-like alumina, plate-like There are silica, organically treated smectite, aramid fiber, phenol fiber, polyester fiber, kenaf fiber, wood flour, cellulose fiber, starch and the like, and these may be used in combination of two or more. The use ratio of the filler is 1 to 200 parts by mass as a ratio with respect to 100 parts by mass in total of the components (A) to (D).

  In addition, said filler can be used by processing with a well-known coupling agent, a surface treating agent, a sizing agent, etc. for the purpose of improving a dispersibility. Examples of the coupling agent include a silane coupling agent, a titanate coupling agent, and an aluminum coupling agent.

  Furthermore, the antistatic resin composition of the present invention includes other known polymers such as polyamide resin, polybutylene terephthalate, polyethylene terephthalate, polyarylate, and liquid crystalline polyester, as well as polyacetal, polycarbonate, PMMA, methyl methacrylate / maleimide compound copolymer, polyphenylene ether, polyphenylene sulfide, thermoplastic polyurethane, epoxy resin, phenol resin, urea resin, phenoxy resin and the like can be appropriately blended.

  The antistatic resin composition of the present invention can be obtained by melt-kneading each of the above-described constituent components with various extruders, Banbury mixers, kneaders, continuous kneaders, rolls, and the like. At the time of kneading, the respective components may be added together and kneaded, or may be added separately. The antistatic resin composition of the present invention thus prepared is 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. It can be formed into a molded article by a known molding method such as Examples of the molded product include injection molded products, sheet molded products (including multilayer sheets), film molded products (including multilayer films), profile extrusion molded products, and vacuum molded products.

  The resin molded product obtained as described above has excellent antistatic properties, antistatic durability, impact resistance, chemical resistance, and abrasion resistance, so that it can be used in home appliances, building materials, sanitary, In the vehicle field and the like, it can be suitably used as various parts, housings and the like.

  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. Further, various measurements in Examples and Comparative Examples were based on the following methods.

<Evaluation method>

(1) Gel content of rubbery polymer: According to the above method.

(2) Average particle diameter of rubbery polymer latex:
The average particle diameter of the rubbery polymer latex used for forming the styrene resin (E) was measured by a light scattering method. As a measuring instrument, “LPA-3100 type” manufactured by Otsuka Electronics Co., Ltd. was used, and the Mummland method was adopted with 70 times integration. It was confirmed with an electron microscope that the particle diameter of the dispersion-grafted rubber polymer particles in the styrene resin (E) was almost the same as the latex particle diameter.

(3) Graft ratio of styrenic resin (E): According to the above method.

(4) Intrinsic viscosity [η] of the acetone-soluble matter of the aromatic vinyl polymer (C3) and the styrene resin (E): according to the method described above.

(5) Antistatic property:
As a sample, a molded product having dimensions of 2.4 mm × 76 mm × 127 mm was used. Then, according to FTMS-101 (US federal test standard), using “STATIC DECEYMETER 406D” manufactured by ETS USA, applying +5 KV to the molded product at a temperature of 23 ° C. and a relative humidity of 12%, and then grounding and attenuating to 50 V Time (seconds) was measured.

(6) Antistatic sustainability:
The molded product of the above (5) was immersed in distilled water for 10 days, and then sufficiently dried, and the antistatic evaluation of the above (5) was performed.

(7) Impact resistance:
In accordance with ISO 179, a molded product specified in the ISO standard was used, and Charpy impact strength (KJ / m ² ) was measured.

(8) Chemical resistance:
In accordance with ISO 527, a molded product specified in the ISO standard was used, and the tensile strength (MPa) was measured (T0). Further, the prescribed molded article was immersed in a 5% aqueous solution of caustic soda at 23 ° C. for 10 days, then dried, and the tensile strength was measured under the conditions for obtaining T0 (T1). The strength retention was calculated. Based on this retention rate, evaluation was made with a retention rate of 80% or more as O and a retention rate of less than 80% as x.

(9) Abrasion:
Based on JISK7204, a molded product specified in the JIS standard was used, and the Taber abrasion amount (mg) was measured. Measurement was performed under the conditions of a weight of 500 g and a wear wheel CS17 of 1000 times.

<Components of thermoplastic polymer composition>

(1) Aliphatic polyester (A1):
Aliphatic polyester mainly composed of succinic acid / 1,4-butanediol [Mitsubishi Chemical {GSPlaAZ91T] (trade name)]

(2) Aliphatic polyester (A2):
Polylactic acid aliphatic polyester [“LACEAH-100J” (trade name) manufactured by Mitsui Chemicals, Inc.]

(3) Olefin resin (B1):
Random type polypropylene, melt flow rate 0.8 g / 10 min [Nippon Polypro "NOVATEC PPEG8" (trade name)]

(4) Olefin resin (B2):
Homotype polypropylene, melt flow rate 2.4 g / 10 min [Nippon Polypro's “NOVATEC PPFY6C” (trade name)]

(5) Olefin resin (B3):
Block type polypropylene, melt flow rate 2.5 g / 10 min [Nippon Polypro "NOVATEC PPBC6C" (trade name)]

(6) Olefin resin (B4):
Metallocene polyethylene, melt flow rate 2.0 g / 10 min [Nippon Polyethylene “Harmolex NF464N” (trade name)]

(7) Aromatic vinyl polymer (C1):
Styrene-butadiene-styrene block copolymer, 35% styrene content [“TR2500” (trade name) manufactured by JSR Corporation]

(8) Aromatic vinyl polymer (C2) -1:
Hydrogenated product of styrene-butadiene-styrene block copolymer, styrene content 30% [Asahi Kasei Chemicals "Tuftec H1041" (trade name)]

(9) Aromatic vinyl polymer (C2) -2:
Partial hydrogenation product of styrene-butadiene-styrene block copolymer, 67% styrene content ["Tuftec P2000" (trade name) manufactured by Asahi Kasei Chemicals Corporation]

(10) Aromatic vinyl polymer (C3):
The polypropylene resin graft copolymer obtained in Production Example 1 described later was used.

(11) Block copolymer (D1):
Polyamide-polyethylene glycol block copolymer (sodium compound-containing product, sodium content 1120 ppm) [“Pelestat M-140” (trade name) manufactured by Sanyo Chemical Industries, Ltd.]

(12) Block copolymer (D2):
Polyester-polyethylene glycol block copolymer (sodium compound-containing product, sodium content 12350 ppm) [TEP004 (trade name) manufactured by Takemoto Yushi Co., Ltd.]

(13) Block copolymer (D3):
Polypropylene-polyethylene glycol block copolymer (sodium compound-containing product, sodium content 4540 ppm) [“Pelestat 303” (trade name) manufactured by Sanyo Chemical Industries, Ltd.]

(14) Block copolymer (D4):
Polyolefin-polyethylene glycol block copolymer (a sodium compound-free product) [“Pelestat 201” (trade name) manufactured by Sanyo Chemical Industries, Ltd.]

(15) Styrenic resin (E1):
The rubber-reinforced styrene resin obtained in Production Example 2 described later was used.

(16) Styrene resin (E2):
The styrene resin obtained in Production Example 3 described later was used.

(17) Salt (G) having an anion portion having a fluorinated alkylsulfonyl group:
50% aqueous solution of lithium trifluoromethanesulfonate [“Sanconol AQ-50T” (trade name) manufactured by Sanko Chemical Industries, Ltd.]

Production Example 1 (Production of polypropylene resin graft copolymer):
After replacing the stainless steel autoclave with a ribbon-type stirring blade with nitrogen, 40 parts of polypropylene ("Novatech PPMA3" (trade name) manufactured by Nippon Polypro Co., Ltd., melt flow rate 11 g / 10 min) and 140 parts of toluene were charged in a nitrogen stream. Then, the internal temperature was raised to 120 ° C. and the dissolution operation was performed by stirring for 2 hours while maintaining this temperature. Thereafter, the internal temperature was raised to 95 ° C., 45 parts of styrene, 15 parts of acrylonitrile and 0.5 part of tert-butylperoxyisopropyl monocarbonate were added as a polymerization initiator, and the internal temperature was raised again to 120 ° C. The reaction was carried out for 3 hours while maintaining this temperature. Thereafter, the internal temperature was cooled to 100 ° C., 0.2 part of octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenol) -propionate was added, and then the reaction mixture was extracted from the autoclave, Distillation was performed to distill off the unreacted monomer and the solvent. The resulting polypropylene resin graft copolymer had a graft rate of 40.8% and an intrinsic viscosity [η] of 0.225 dl / g.

Production Example 2 (Production of rubber-reinforced styrene resin):
In a nitrogen flask, a glass flask equipped with a stirrer was charged with 75 parts of ion-exchanged water, 0.5 part of potassium rosinate, 0.1 part of tert-dodecyl mercaptan, polybutadiene latex (average particle size; 2000 kg, gel content; 90%) 30 parts (solid content), styrene / butadiene copolymer latex (styrene content 25%, average particle size 6000Å), 10 parts (solid content), styrene 15 parts, acrylonitrile 5 parts, and the temperature is increased while stirring. did. 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-exchanged water, 0.7 parts of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 parts of tert-dodecyl mercaptan, 0.01 parts of cumene hydroperoxide were further added. The polymerization was continuously added over a period of time, and the polymerization was further continued for 1 hour. Then, 0.2 part of 2,2′-methylene-bis (4-ethyl-6-tert-butylphenol) was added to complete the polymerization. . The reaction product latex was coagulated with an aqueous sulfuric acid solution, washed with water, washed and neutralized with an aqueous potassium hydroxide solution, further washed with water, and dried to obtain a rubber-reinforced styrene resin. The graft ratio of this polymer was 68%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g.

Production Example 3 (Production of styrene resin):
Two jacketed polymerization reaction vessels 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 0.12 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 are continuously added. Supplied to. 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] 0.48. The styrenic resin was obtained.

Examples 1-24 and Comparative Examples 1-7:
After mixing with a Henschel mixer at the blending ratio shown in Tables 1 to 3, the mixture was melt-kneaded using a twin-screw extruder (cylinder setting temperature 210 ° C.) and pelletized. After the obtained pellets are sufficiently dried, the test for evaluating antistatic property, durability of antistatic property, impact resistance, chemical resistance, and wear resistance with an injection molding machine (cylinder setting degree 200 ° C). Pieces were obtained and evaluated by the method described above. The evaluation results are shown in Tables 4-6.

  From the results described in Tables 1 to 6, the following is clear. That is, Examples 1 to 7 and Comparative Examples 1 to 4 are Examples and Comparative Examples of resin compositions not containing a styrene resin (E). These examples are excellent in antistatic properties, antistatic durability, impact resistance, chemical resistance, and wear resistance. On the other hand, in Comparative Example 1, the amount of component (A) used is large outside the range defined by the present invention, and the amount of components (B), (C) and (D) used is defined by the present invention. There are few examples outside, and antistatic property, impact resistance and chemical resistance are inferior. Comparative Example 2 is an example in which the amount of the component (D) used is small outside the range specified in the present invention, and the antistatic property is inferior. The comparative example 3 is an example with much usage-amount of a component (D) outside the range prescribed | regulated by this invention, and impact resistance and abrasion resistance are inferior. Comparative Example 4 is an example in which the amount of the component (C) used is small outside the range specified in the present invention, and the impact resistance, chemical resistance and wear resistance are inferior.

  On the other hand, Examples 8 to 24 and Comparative Examples 5 to 7 are Examples and Comparative Examples of resin compositions containing a styrene resin (E). These examples are excellent in antistatic properties, antistatic durability, impact resistance, chemical resistance, and wear resistance. By containing the styrene resin (E), the antistatic property and the impact resistance are particularly excellent. Comparative Example 5 is an example in which the amount of component (D) used is small outside the range defined in the present invention, and the impact resistance, chemical resistance and wear resistance are poor. Comparative Example 6 is an example in which the amount of the component (D) used is small outside the range defined in the present invention, and the antistatic property is inferior. The comparative example 7 is an example with much usage-amount of a component (D) outside the range prescribed | regulated by this invention, and impact resistance and abrasion resistance are inferior.

Claims (6)

Aliphatic polyester (A) 10 to 90% by mass, olefinic resin (B) 4 to 80% by mass, and at least one aromatic vinyl polymer (C) selected from the following (C1) to (C3) 3 to 40% by mass, block copolymer (D) having at least one block (D1) selected from the group of polyamide, polyester and polyolefin, and hydrophilic polymer block (D2) 3 to 60% by mass (components) An antistatic resin composition comprising (A), component (B), component (C), and component (D) in a total of 100% by mass).
The aromatic vinyl polymer (C1) is an elastomer composed of a block copolymer containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene compound. The vinyl polymer (C2) is an elastomer obtained by hydrogenating the aromatic vinyl polymer (C1), and the aromatic vinyl polymer (C3) is an aromatic vinyl compound in the presence of an olefin polymer. Is a graft copolymer obtained by polymerizing a vinyl-based monomer containing Furthermore, the styrene-type resin (E) which consists of the following (E1) and / or (E2) is contained, The ratio is 5-100 mass parts with respect to a total of 100 mass parts of component (A)-(D). The antistatic resin composition according to claim 1.
The styrenic resin (E1) is obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of a rubbery polymer (however, aromatic vinyl polymers (excluding C1 and (C2)). This is a rubber-reinforced styrene resin obtained, and the styrene resin (E2) is obtained by (co) polymerizing a vinyl monomer containing an aromatic vinyl compound in the absence of the rubbery polymer. Styrenic resin.   The antistatic resin composition according to claim 1 or 2, wherein the aliphatic polyester (A) is a polylactic acid resin.   The antistatic resin composition according to claim 1 or 2, wherein the aliphatic polyester (A) is an aliphatic polyester mainly obtained from 1,4-butanediol and succinic acid.   The antistatic resin body composition according to claim 4, wherein the aliphatic polyester (A) is an aliphatic polyester copolymer obtained by copolymerizing lactic acid as another component.   A resin molded product comprising the antistatic resin composition according to any one of claims 1 to 5.