JP2007063302A - Antistatic resin composition and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic resin composition affording a molded product having excellent antistatic properties, heat and chemical resistances and appearance of the molded product. <P>SOLUTION: The antistatic resin composition is characterized as follows. The composition comprises (A) 7-91 mass% of an olefinic resin, (B) 3-30 mass% of a block copolymer containing an olefin polymer block (b1) and a hydrophilic polymer block (b2), (C) 1-50 mass% of a block copolymer containing a polymer block (c1) consisting essentially of an aromatic vinyl compound and a polymer block (c2) consisting essentially of a conjugated diene compound or a hydrogenated substance thereof and (D) 5-40 mass% of a styrenic resin. The component (A) is composed of an olefinic resin (A-1) without containing a cyclic olefin component and an olefinic resin (A-2) containing a cyclic olefin component and having 60-200°C glass transition temperature. The ratio ä(A-1)/(A-2)} of contents of both is (99/1) to (5/95) (mass ratio). <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to an antistatic resin composition having excellent antistatic properties, heat resistance, chemical resistance, and appearance of a molded product, and a molded product comprising the antistatic resin composition.

  Polyolefin resins such as polypropylene are widely used in the electrical / electronic field, OA / home appliance field, vehicle field, sanitary field and the like because of their excellent chemical resistance, heat resistance, fluidity and the like. However, since this resin has the disadvantage that it is easily charged, it causes troubles due to static electricity, for example, various parts and sheets used in liquid crystal display devices, semiconductor peripheral devices, plasma displays, clean rooms, etc. It was difficult to apply to films. For the purpose of improving such drawbacks, Patent Documents 1 and 2 propose that a specific antistatic agent is blended, but there is no antistatic durability and antistatic properties are not sufficient. There was a problem such as. Moreover, as a method for maintaining antistatic properties, Patent Document 3 proposes that a specific polymer is blended with a polyolefin resin, but there is a problem that antistatic properties are not sufficiently exhibited. Further, these antistatic polyolefin resins have low heat resistance and have limited use.

  On the other hand, rubber-reinforced styrene-based resins such as ABS resin are superior in mechanical strength such as impact resistance, moldability, rigidity, and the like, and also in the surface appearance of molded products. Therefore, electrical / electronic field, OA / home appliance field, vehicle field. Although it is widely used in the sanitary field, etc., the chemical resistance is not sufficient depending on the intended use, and further improvement in chemical resistance has been demanded. Further, these styrene resins also have the problem of static electricity damage as described above, and these improvements have been desired. Patent Document 4 proposes that a polyamide elastomer is blended with a styrene resin such as an ABS resin, but there is a problem that the antistatic property is not sufficiently exhibited.

JP-A-4-258647 JP 2000-313875 A Japanese Patent Laid-Open No. 2001-278985 Japanese Patent Laid-Open No. 60-23435

  An object of the present invention is to provide an antistatic resin composition having excellent antistatic properties, heat resistance, chemical resistance, and appearance of a molded product. Another object of the present invention is to provide the molded article.

  As a result of diligent studies to achieve the above object, the present inventors have significantly improved antistatic properties by blending a polymer having a specific block structure with a mixture of an olefin resin and a styrene resin. As the olefin-based resin, by using an olefin-based resin containing a cyclic olefin component such as norbornene at a certain ratio, it is found that heat resistance can be expressed while maintaining excellent antistatic properties, and the present invention is completed. It came to.

That is, according to the present invention,
(A) 7-91 mass% of olefin resin,
(B) 3-30% by mass of a block copolymer containing the olefin polymer block (b1) and the hydrophilic polymer block (b2),
(C) a block copolymer containing a polymer block (c1) mainly composed of an aromatic vinyl compound and a polymer block (c2) mainly composed of a conjugated diene compound and at least selected from the group consisting of hydrogenated products thereof 1 to 50% by mass of one polymer,
(D) A rubber-reinforced styrene resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of the rubbery polymer (a) and / or the vinyl monomer ( Co) polymer 5-40% by mass,
Containing component (A), component (B), component (C), and component (D) (however, the total of component (A), component (B), component (C), and component (D)) Is 100% by mass), and the component (A) is an olefin resin (A-) having a glass transition temperature of 60 to 200 ° C. containing an olefin resin (A-1) not containing a cyclic olefin component and a cyclic olefin component. 2), and the ratio of the content of the two ((A-1) / (A-2)) is 99/1 to 5/95 (mass ratio). Is provided.

According to a preferred embodiment of the present invention, the component (E) further comprises the following component (e-1), component (e-2), component (e-3), and component (e-4). 0.01-30 mass parts is contained with respect to a total of 100 mass parts of the said component (A), a component (B), a component (C), and a component (D) at least 1 sort (s) chosen from the group. An antistatic resin composition is provided.
(E-1) a salt having an anion having a fluorinated alkylsulfonyl group,
(E-2) a boron compound containing a unit represented by the following general formula (1),
(E-3) a compound represented by the following general formula (2),
(E-4) Nonionic surfactant.

Moreover, according to the other situation of this invention, the sheet | seat, film, and other molded article which consist of the said antistatic resin composition of this invention are provided.
According to still another aspect of the present invention, a laminate formed by laminating a sheet or film made of the antistatic resin composition of the present invention on at least one surface of a sheet or film made of an olefin resin. Is provided.

  The antistatic resin composition of the present invention is a composition comprising the component (A), the component (B), the component (C), and the component (D), wherein the specific proportion of the component (A) is a cyclic olefin component. Since it is composed of the olefin resin to be contained, a molded product excellent in antistatic property, heat resistance, chemical resistance, and molded product appearance can be obtained.

 The present invention will be described in detail 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.

Component (A-1) constituting component (A) used in the present invention is a polyolefin-based resin containing olefins having 2 or more carbon atoms as constituent monomer units, and cyclic as constituent monomer units. It differs from the component (A-2) described later in that it does not contain olefin. In the present invention, a preferred component (A-1) is a (co) polymer containing olefins having 2 to 10 carbon atoms as constituent monomer units, and is a known polymerization method such as a high pressure polymerization method or a low pressure polymerization method. Further, all of those obtained by the metallocene catalyst method can be used.
As a preferred embodiment of the component (A-1) according to the present invention, a polymer in which a constituent monomer unit is mainly constituted by at least one selected from olefins having 2 or more carbon atoms; Examples thereof include a polymer mainly composed of constituent monomer units from at least one selected from olefins and at least one selected from compounds copolymerizable with the olefins. These can be used individually by 1 type or in combination of 2 or more types.

  Examples of olefins having 2 or more carbon atoms include ethylene and propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, and 3-ethyl-1. -Pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1 -Α-olefins such as tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene and the like. These can be used alone or in combination of two or more. Of these, ethylene and / or propylene are particularly preferred.

  Examples of compounds copolymerizable with the olefins include 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 1,9-decadiene, and the like. Non-conjugated dienes and the like. These can be used individually by 1 type or in combination of 2 or more types.

Specific examples of the component (A-1) include polyethylene, polypropylene, propylene / ethylene copolymer, polybutene-1, ethylene / butene-1 copolymer, and the like. Of these, polyethylene, polypropylene, and propylene / ethylene copolymers are preferable. Examples of the propylene / ethylene copolymers include random copolymers and block copolymers. These can be used individually by 1 type or in combination of 2 or more types.
The component (A-1) may be crystalline or amorphous, but preferably has a crystallinity of 20% or more by X-ray diffraction at room temperature. is there. Here, for the purpose of controlling crystallinity, a known crystal nucleating agent may be blended with the component (A-1).

In the case of propylene or the component (A-1) mainly composed of propylene, the melting point (conforming to JIS K7121) is preferably 40 ° C. or higher, and the molecular weight is not particularly limited, but from the viewpoint of moldability, the melt flow rate ( (According to JIS K7210) is preferably 0.01 to 500 g / 10 min, more preferably 0.05 to 100 g / 10 min, and those having a molecular weight corresponding to each value are preferable.
In the case of ethylene or ethylene-based component (A-1), the melting point (according to JIS K7121) is preferably 40 ° C. or higher, and the molecular weight is not particularly limited, but from the viewpoint of moldability, the melt flow rate ( (According to JIS K6922) is preferably 0.001 to 500 g / 10 minutes, more preferably 0.01 to 100 g / 10 minutes, and those having a molecular weight corresponding to each value are preferable.

The component (A-2) constituting the component (A) used in the present invention is a polyolefin resin containing a cyclic olefin as a constituent monomer unit.
As the cyclic olefin used for the component (A-2), for example, all known ones such as those described in JP-A-5-310845 can be used. Preferably, norbornene and / or norbornene derivatives having 11 or less carbon atoms are used. It occupies 50% by mass or more of the entire cyclic olefin.
A preferred embodiment of the component (A-2) according to the present invention is a copolymer of at least one selected from the olefins described in the component (A-1) and the cyclic olefin, and has a glass transition. The temperature is 60 to 200 ° C, preferably 70 to 200 ° C, more preferably 70 to 190 ° C, and particularly preferably 75 to 185 ° C. When the glass transition temperature is less than 60 ° C., the effect of improving the heat resistance is small, and when it exceeds 200 ° C., the appearance of the molded product is inferior.
As olefins used here, ethylene and α-olefin are preferable, ethylene is particularly preferable, and in order to obtain a polymer having the glass transition temperature, the cyclic olefin is 40 to Copolymerization is preferably performed in the range of 90% by mass.

The copolymer of the olefins and the cyclic olefin can be obtained by polymerization by a known method, but is preferably produced by a polymerization method using a metallocene catalyst.
The preferred melt flow rate of the component (A-2) (measured at 260 ° C. and 2.16 kg according to ISO 1133) is 0.1 to 100 ml / 10 minutes, and the component (A-2) is non- It is preferably crystalline.

The mixing ratio of the component (A-1) and the component (A-2) is 99/1 to 5/95 in terms of (A-1) / (A-2) ratio (mass ratio), preferably 90. / 10 to 10/90, more preferably 85/15 to 15/85, and particularly preferably 80/20 to 20/80. When the ratio exceeds 99/1, the heat resistance is inferior, and when it is less than 5/95, the chemical resistance and the appearance of the molded product tend to be inferior.
In the antistatic resin composition of the present invention, the content of the component (A) is 7 to 91 mass when the total of the components (A), (B), (C) and (D) is 100 mass%. %, Preferably 11-86% by mass, more preferably 15-82% by mass, particularly preferably 20-75% by mass. When the amount used is less than 7% by mass, the antistatic property and chemical resistance are inferior, and when it exceeds 91% by mass, the antistatic property tends to be inferior.

 The component (B) of the present invention comprises an olefin polymer block (b1) (also referred to herein as “polymer block (b1)”) and a hydrophilic polymer block (b2) (herein “ A polymer block (also referred to as “polymer block (b2)”). This component (B) imparts antistatic properties to the antistatic resin composition of the present invention. Moreover, this component (B) can be used individually by 1 type or in combination of 2 or more types.

In the component (B), the arrangement of the polymer blocks (b1) and (b2) is not particularly limited, and can have a block structure exemplified by the following (1) to (5). However, m1 is an integer of 1 or more, and m2 and m2 ′ are both integers of 2 or more, and may be the same or different. In each structure, when there are a plurality of polymer blocks (b1) and (b2), the blocks may be the same as or different from each other.
(1) (b1-b2) m1
(2) b1- (b2-b1) m1
(3) b2- (b1-b2) m1
(4) (b1) m2- (b2) m2 ′
(5) b1-b1- (b2-b2-b1-b1) m1
Among these, it is preferable that the embodiments of (1), (2) and (3), that is, the polymer blocks (b1) and (b2) are alternately and alternately arranged.
The component (B) is mainly composed of the block copolymer described above, but other (co) polymers such as polyamide block and polyester block in a proportion of 20% by mass or less in the component (B). Blocks can also be included.
In said aspect (1)-(3), it is preferable that the coupling | bonding form of polymer block (b1) and (b2) is an ester bond, an amide bond, an ether bond, a urethane bond, or an imide bond.

The polymer block (b1) is a block composed of a polymer mainly composed of olefin units, and examples of the compound forming the polymer block (b1) include acyclic olefins having 2 or more carbon atoms, cyclic olefins, and the like. Can be mentioned. Examples of acyclic olefins include ethylene and propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, and other α-olefins. Moreover, norbornene etc. are mentioned as an example of a cyclic olefin. These compounds can be used alone or in combination of two or more.
In addition to the above compounds, the polymer block (b1) includes 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 1,9- It may be a polymer containing a non-conjugated diene such as decadiene as a constituent monomer unit.

  In order to make the bond form of the polymer blocks (b1) and (b2) an ester bond, an amide bond, an ether bond, a urethane bond or an imide bond, both ends of the molecule of the polymer block (b1) are carboxyl groups. , Hydroxyl group, amino group, acid anhydride group, oxazoline group, epoxy group and the like are preferable. Examples of a method for imparting these functional groups include a method in which an unsaturated compound having the above functional group is added to a polymer having a double bond at the molecular end obtained by a thermal degradation method. .

The number average molecular weight in terms of polystyrene by gel permeation chromatography (GPC) of the polymer block (b1) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and still more preferably 1,200. ~ 6,000.
The polymer block (b1) is contained alone or in combination of two or more in the block copolymer (B).

Examples of the hydrophilic polymer of the polymer block (b2) component include polyether (b2-a), polyether-containing hydrophilic polymer (b2-b), and anionic polymer (b2-c).
Examples of the polyether (b2-a) include polyether diol, polyether diamine, and modified products thereof.
Examples of the polyether-containing hydrophilic polymer (b2-b) include polyether ester amide having a polyether diol segment, polyether amide imide having a polyether diol segment, polyether ester having a polyether diol segment, Examples include polyether amides having ether diamine segments, and polyether urethanes having polyether diol or polyether diamine segments.
As the anionic polymer (b2-c), a dicarboxylic acid having a sulfonyl group and a polyether (b2-a) are essential structural units, and preferably 2 to 80, more preferably 3 to 60 in one molecule. Anionic polymers having a number of sulfonyl groups.
These may be linear or branched. Particularly preferred component (b2) is polyether (b2-a).

As the polyether diol in the polyether (b2-a), the general formula (3):
H— (OA ¹ ) _n —O—E ¹ —O— (A ¹ O) _{n ′} —H, and general formula (4):
H- (OA ² ) _m —O—E ² —O— (A ² O) _{m ′} —H are exemplified.
In general formula (3), 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 hydroxyl groups of the divalent hydroxyl group-containing compound. This represents the number of alkylene oxide additions per unit. 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 May be either block or random or a combination thereof. n and n ′ are generally integers of 1 to 300, preferably 2 to 250, particularly 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 12 carbon atoms) Aliphatic, alicyclic, or aromatic dihydric alcohols), C6-C18 dihydric phenols, and tertiary amino group-containing diols.
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, urushiol, bisphenol A, bisphenol F, bisphenol S, 4,4'-dihydroxydiphenyl-2,2-butane, dihydroxybiphenyl, dihydroxydiphenyl ether And condensed polycyclic dihydric phenols such as dihydroxynaphthalene and binaphthol.

In the general formula (4), E ² is a residue obtained by removing a hydroxyl group from the divalent hydroxyl group-containing compound described in the general formula (3), and A ² is at least partly a general formula (5): —CHR— CHR ′ — [wherein one of R and R ′ is a group represented by general formula (6): —CH ₂ O (A ³ O) _X R ″, and the other is H. General formula (6) Wherein x is an integer of 1 to 10, R ″ is H or an alkyl group, aryl group, alkylaryl group, arylalkyl group or acyl group having 1 to 10 carbon atoms, and A ³ is an alkylene group having 2 to 4 carbon atoms. It is. The remaining alkylene group may be an alkylene group having 2 to 4 carbon atoms. m (OA ² ) and m ′ (A ² O) may be the same or different. m and m ′ are preferably integers of 1 to 300, more preferably 2 to 250, and particularly preferably 10 to 100. M and m ′ may be the same or different.

  The polyether diol represented by the general formula (3) 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. Two or more of these combined systems are used. When two or more kinds of alkylene oxide are used in combination, the bonding form may be random and / or block. Preferable alkylene oxides are ethylene oxide alone and block and / or random addition using ethylene oxide in combination with other alkylene oxides. The number of alkylene oxides added is preferably an integer of 1 to 300, more preferably 2 to 250, and particularly 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 (4) include the following methods (a) and (b).

［一般式（７）中のＡ^４は炭素数２〜４のアルキレン基、ｐは１〜１０の整数、Ｒ^１はＨ または炭素数１〜１０のアルキル基、アリール基、アルキルアリール基、アリールアルキル基またはアシル基である。］
で表されるグリシジルエーテルを重合、または炭素数２〜４のアルキレンオキサイドと共重合する方法。 (A) General formula (7): Starting from the above divalent hydroxyl group-containing compound

[A ⁴ in the general formula (7) is an alkylene group having 2 to ⁴ carbon atoms, p is an integer of 1 to 10, R ¹ is H or an alkyl group having 1 to 10 carbon atoms, an aryl group, an alkylaryl group, an aryl An alkyl group or an acyl group; ]
The method of superposing | polymerizing the glycidyl ether represented by these, or copolymerizing with a C2-C4 alkylene oxide.

(A) 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. More specifically, epichlorohydrin or epichlorohydrin and alkylene oxide are added and 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 is as described above, X is Cl, Br or I) is reacted in the presence of an alkali, or the polyether is reacted with a polyalkylene glycol monocarbyl ether having 2 to 4 carbon atoms in the presence of an alkali. Is the method.

As the alkylene oxide having 2 to 4 carbon atoms used here, all of those described above can be used.
Moreover, the preferable component (B) of this invention can be obtained by superposing | polymerizing the said olefin polymer block (b1) and hydrophilic polymer block (b2) by a well-known method. For example, the polymer block (b1) and the polymer block (b2) 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.

  In addition, known polymerization catalysts can be used in the polymerization reaction, but preferred are tin-based catalysts such as monobutyltin oxide, antimony-based catalysts such as antimony trioxide and antimony dioxide, and titanium-based catalysts such as tetrabutyl titanate. , Zirconium hydroxide, zirconium oxide, zirconium acetate such as zirconyl acetate, or a combination of two or more selected from group IIB organic acid salt catalysts.

For the purpose of further improving the antistatic property which is the object of the present invention, the component (B) can contain at least one salt (F) selected from the group consisting of alkali metals and alkaline earth metals. . These components can be contained before polymerization of component (B), during polymerization of component (B), or after polymerization of component (B). Moreover, it can mix | blend when manufacturing the antistatic resin composition of this invention, and can also be made to contain by the method of combining these.
Examples of the component (F) include alkali metals such as lithium, sodium and potassium and / or alkaline earth metals such as magnesium and calcium, organic acids, sulfonic acids, salts of inorganic acids, halides, and the like.

  Specific preferred examples of component (F) include halides of alkali metals such as lithium chloride, sodium chloride, potassium chloride, lithium bromide, sodium bromide, potassium bromide; lithium perchlorate, sodium perchlorate, Inorganic acid salts of alkali metals such as potassium perchlorate, organic acid salts of alkali metals such as potassium acetate and lithium stearate; octylsulfonic acid, dodecylsulfonic acid, tetradecylsulfonic acid, stearylsulfonic acid, tetracosylsulfonic acid An alkali metal salt of an alkyl sulfonic acid having an alkyl group having 8 to 24 carbon atoms such as 2-ethylhexyl sulfonic acid; an alkali metal salt of an aromatic sulfonic acid such as phenyl sulfonic acid or naphthyl sulfonic acid; octylphenyl sulfonic acid, Dodecylphenylsulfonic acid, dibutylphenylsulfone Alkali metal salts of alkylbenzene sulfonic acids having 6 to 18 carbon atoms in the alkyl group, such as dinonylphenyl sulfonic acid; dimethyl naphthyl sulfonic acid, diisopropyl naphthyl sulfonic acid, dibutyl naphthyl sulfonic acid, etc. Alkali metal salts of 2-18 alkylnaphthalene sulfonic acids; alkali metal salts such as fluorinated sulfonic acids such as trifluoromethane sulfonic acid, etc. are used, and these are used alone or in combination of two or more. be able to. The component (F) can be used in an amount of preferably 0.001 to 10% by mass, more preferably 0.01 to 5% by mass, based on the component (B) of the present invention.

A preferred ratio of the component (b1) / component (b2) in the component (B) of the present invention is in the range of 10 to 90/10 to 90% by mass, more preferably 20 to 80/20 to 80% by mass, particularly. Preferably, it is the range of 30-70 / 30-70 mass%.
Such a block copolymer (B) can be produced, for example, by the method described in JP-A Nos. 2001-278985 and 2003-48990, and the component (B) of the present invention. Can be obtained as 300, 303, 230, etc. of Pelestat 300 series manufactured by Sanyo Chemical Industries.

  The component (B) of the present invention is 3 to 30% by mass, preferably 4 to 25% by mass, more preferably 100% by mass in the total of components (A), (B), (C), and (D). Is used in the range of 5 to 24% by mass, particularly preferably 5 to 23% by mass. If it is less than 3% by mass, the antistatic property is inferior. If it exceeds 30% by mass, the chemical resistance and the appearance of the molded product are inferior.

  Component (C) of the present invention comprises a block copolymer containing a polymer block (c1) mainly comprising an aromatic vinyl compound and a polymer block (c2) mainly comprising a conjugated diene compound, and a hydrogenated product thereof. It is at least one polymer selected from the group.

Examples of the aromatic vinyl compound used herein include styrene, α-methylstyrene, hydroxystyrene, and the like, preferably styrene and α-methylstyrene, and particularly preferably styrene.
Examples of the conjugated diene compound include butadiene, isoprene, hexadiene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, and preferably butadiene and isoprene. These can be used individually by 1 type or in combination of 2 or more types. Furthermore, the block (c2) may be a block in which two or more conjugated diene compounds are used and bonded in any form of random, block, or tapered block. Moreover, (c2) may contain 1 to 10 taper blocks in which the aromatic vinyl compound gradually increases, and the vinyl bond content derived from the conjugated diene compound of the polymer block (c2) is different. A polymer block or the like may be appropriately copolymerized.

A preferred structure of the component (C) of the present invention is a polymer represented by the following formulas (8) to (10) or a hydrogenated product thereof.
(AB) _Y (8)
(AB) _Y- X (9)
A- (B-A) _Z (10)
(In the structural formulas (8) to (10), A is a polymer block mainly composed of an aromatic vinyl compound. If the polymer block is substantially composed of an aromatic vinyl compound, a part of the conjugated diene compound is included. Preferably, it is a polymer block containing 90% by mass or more, more preferably 99% by mass or more of an aromatic vinyl compound, B is a homopolymer of a conjugated diene compound or an aromatic vinyl compound, etc. And X is a residue of the coupling agent, Y is an integer of 1 to 5, and Z is an integer of 1 to 5.)

  In the component (C) of the present invention, the use ratio of the aromatic vinyl compound and the conjugated diene compound is preferably within the range of aromatic vinyl compound / conjugated diene compound = 10 to 70/30 to 90% by mass, more preferably 15 to It is 65 / 35-85 mass%, Most preferably, it is the range of 20-60 / 40-80 mass%.

  The block copolymer composed of 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. 48-2423. And the 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 of the component (C) of the present invention is preferably in the range of 5 to 80%, and the component (C ) Is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, and particularly preferably 20,000 to 300,000. Among these, the number average molecular weight of the A part represented by the above formulas (8) to (10) is 3,000 to 150,000, and the number average molecular weight of the B part is in the range of 5,000 to 200,000. preferable.

Adjustment of the vinyl bond amount of the conjugated diene compound is possible by adjusting amines such as N, N, N ′, N′-tetramethylethylenediamine, trimethylamine, triethylamine, diazocyclo (2,2,2) octane, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diethylene. It can be carried out using ethers such as butyl ether, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, alkoxides of potassium and sodium, and the like.
A polymer in which a polymer molecular chain is extended or branched via a coupling agent residue using a coupling agent after the polymer is obtained by the above method is also preferably included in the component (C) of the present invention. Coupling agents used here include 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, preferred from the viewpoint of impact resistance is a polymer having 1 to 10 tapered blocks in which aromatic vinyl compounds gradually increase in the block (c2), and / or coupling. Processed radial block type.

 In addition, as the component (C), the above block copolymer itself can be used, or one obtained by partially or completely hydrogenating the carbon-carbon double bond of the conjugated diene moiety can be used. From the low temperature impact property of the obtained composition, it is preferable to use a non-hydrogenated one or a hydrogenation rate of less than 90%. From the aspect of the weather resistance (light) of the obtained composition, It is preferable to use a hydrogenated product of 90% or more.

  The hydrogenation reaction of the polymer comprising a polymer block mainly comprising an aromatic vinyl compound unit obtained by the above method and a polymer block mainly comprising a conjugated diene compound can be carried out by a known method, The target polymer can be obtained by adjusting the hydrogenation rate by this method. Specific methods include JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-63-5401, JP-A-2-133406, JP-A-1 There is a method disclosed in Japanese Patent No. 297413.

  Component (C) of the present invention is 1 to 50% by mass, preferably 5 to 50% by mass, in a total of 100% by mass of component (A), component (B), component (C) and component (D) of the present invention. %, More preferably 5 to 45% by mass, particularly preferably 10 to 40% by mass, and if it is less than 1% by mass and exceeds 50% by mass, the appearance of the molded product is inferior. The component (C) improves the compatibility between the component (A) and the component (D), and improves the impact resistance and the appearance of the molded product.

Component (D) of the present invention comprises a rubber-reinforced styrene resin obtained by polymerizing a vinyl monomer (b) containing an aromatic vinyl compound in the presence of the rubbery polymer (a), and / or And a (co) polymer of the vinyl monomer (b). The latter (co) polymer is obtained by polymerizing the vinyl monomer (b) containing an aromatic vinyl compound in the absence of the rubbery polymer (a).
The component (D) of the present invention preferably contains at least one polymer obtained by graft polymerization of the vinyl monomer (b) in the presence of the rubbery polymer (a) from the viewpoint of impact resistance. . The content of the rubber-like polymer (a) is preferably 3 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass, with the component (D) being 100% by mass.

The rubbery polymer (a) is not particularly limited, but polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, hydrogenated products thereof, ethylene / propylene copolymer, ethylene / propylene / non-polymer. Conjugated diene copolymer, ethylene / butene-1 copolymer, ethylene / butene-1 / non-conjugated diene copolymer, acrylic rubber, silicone rubber, silicone / acrylic IPN rubber, and component (C) described above Examples thereof include block copolymers containing a polymer block mainly composed of an aromatic vinyl compound and a polymer block mainly composed of a conjugated diene, and hydrogenated products thereof. These may be used alone or in combination of two or more. Can be used.
Of these, polybutadiene, butadiene / styrene copolymer and hydrogenated product thereof, ethylene / propylene copolymer, ethylene / propylene / nonconjugated diene copolymer, acrylic rubber, and silicone rubber are preferable. As the butadiene / styrene copolymer used here, a block and / or a random copolymer is usually used.

The gel content of the rubber polymer (a) is not particularly limited, but when the component (a) is obtained by emulsion polymerization, the gel content is preferably 98% by mass or less, more preferably 40 to 98. % By mass. Within this range, it is possible to obtain an antistatic resin composition that gives a molded product particularly excellent in the appearance of the molded product.
In addition, the said gel content rate can be calculated | required by the method shown below. That is, 1 g of a rubbery polymer was put into 100 ml of toluene and 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 W ₁ gram) were heated at 80 ° C for 6 hours. It vacuum-drys, weighs (it is set as ₂ mass of mass W), and calculates by following formula (11).

Gel content (% by mass) = [{W ₂ (g) −W ₁ (g)} / 1 (g)] × 100 (11)
The gel content is 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. These may be used alone or in combination of two or more. Can do. Of these, styrene and α-methylstyrene are 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. . Preferably, the vinyl monomer (b) comprises an aromatic vinyl compound as an essential monomer component, and, if necessary, a group consisting of a vinyl cyanide compound, a (meth) acrylic acid ester compound and a maleimide compound. One or more selected from the above are used in combination as a monomer component, and if necessary, at least one of other various functional group-containing unsaturated compounds is used in combination as a monomer component. As other various functional group-containing unsaturated compounds, unsaturated acid compounds, epoxy group-containing unsaturated compounds, hydroxyl group-containing unsaturated compounds, oxazoline group-containing unsaturated compounds, acid anhydride group-containing unsaturated compounds, substituted or unsubstituted And amino group-containing unsaturated compounds. The above various other functional group-containing unsaturated compounds can be used alone or in combination of two or more.

Examples of the vinyl cyanide compound used here include acrylonitrile, methacrylonitrile and the like, and these can be used alone or in combination of two or more. When a vinyl cyanide compound is used, chemical resistance is imparted. When using a vinyl cyanide compound, the usage-amount is in a component (b), Preferably it is 1-60 mass%, More preferably, it is 5-50 mass%.
Examples of (meth) acrylic acid ester compounds include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. These may be used alone or in combination of two or more. Can be used in combination.
Use of a (meth) acrylic acid ester compound is preferable because surface hardness is improved. When the (meth) acrylic acid ester compound is used, the amount used thereof is preferably 1 to 80% by mass, more preferably 5 to 80% by mass in the component (b).
Examples of the maleimide compound include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like, and these can be used alone or in combination of two or more. In order to introduce a maleimide unit, maleic anhydride may be copolymerized and post-imidized. When a maleimide compound is used, heat resistance is imparted. When a maleimide compound is used, the amount used thereof is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the component (b).

Examples of unsaturated acid compounds include acrylic acid, methacrylic acid, ethacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, cinnamic acid, and the like. These may be used alone or in combination of two or more. Can be used.
Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, and allyl glycidyl ether, and these can be used alone or in combination of two or more.

Examples of the 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 include methyl-1-propene, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, N- (4-hydroxyphenyl) maleimide, and these may be used alone or in combination of two or more. it can.
Examples of the oxazoline group-containing unsaturated compound include vinyl oxazoline and the like, and these can be used singly or in combination of two or more.
Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride and the like, and these can be used alone or in combination of two or more.
Examples of 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, etc., and these can be used alone or in combination of two or more.
When the above-mentioned various other functional group-containing unsaturated compounds are used, when the styrenic resin and another polymer are blended, the compatibility between them 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 usage-amount of said other various functional group containing unsaturated compound is the total amount of this functional group containing unsaturated compound used in a component (D), and is 0.1-20 mass with respect to the whole component (D). % Is preferable, and 0.1 to 10% by mass is more preferable.

 The amount of the monomer other than the aromatic vinyl compound in the vinyl monomer (b) is preferably 80% by mass or less when the total of the vinyl monomers (b) is 100% by mass. Preferably it is 60 mass% or less, Most preferably, it is 40 mass% or less. More preferable 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. -Monomers that are polymerized in the presence of rubbery polymer (a) such as hydroxyethyl methacrylate, styrene / acrylonitrile / (meth) acrylic acid, styrene / N-phenylmaleimide, styrene / methyl methacrylate / cyclohexylmaleimide Particularly preferred combinations of the body are styrene / acrylonitrile = 65/45 to 90/10 (mass ratio), styrene / methyl methacrylate = 80/20 to 20/80 (mass ratio), styrene / acrylonitrile / methacrylate. Le methyl, styrene content of 20 to 80 wt%, the sum of acrylonitrile and methyl methacrylate is any in the range of 20 to 80 wt%.

  Component (D) of the present invention can be produced by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a polymerization method combining these. Among these, preferred polymerization methods for the polymer obtained by (co) polymerizing the vinyl monomer (b) in the presence of the rubbery polymer (a) are emulsion polymerization and solution polymerization. On the other hand, the preferred polymerization method of the polymer obtained by (co) polymerizing the vinyl monomer (b) in the absence of the rubbery polymer (a) is bulk polymerization, solution polymerization, suspension polymerization, And emulsion polymerization.

In the case of producing by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, and the like are used, and any known one can be used.
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, etc., 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 A rosin acid salt such as potassium can be used.

  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 emulsion polymerization, the obtained latex is usually coagulated with a coagulant, washed with water and dried to obtain the component (D) powder of the present invention. At this time, the latex of two or more components (D) obtained by emulsion polymerization may be appropriately blended and then coagulated. As the coagulant used here, inorganic salts such as calcium chloride, magnesium sulfate and magnesium chloride, or acids such as sulfuric acid, hydrochloric acid, acetic acid, citric acid and malic acid can be used.

The solvent that can be used in the case of producing the component (D) by solution polymerization is an inert polymerization solvent used in ordinary radical polymerization, such as aromatic hydrocarbons such as ethylbenzene and toluene, methyl ethyl ketone, acetone, and the like. Ketones, acetonitrile, dimethylformamide, N-methylpyrrolidone and the like.
The polymerization temperature is preferably in the range of 80 to 140 ° C, more preferably 85 to 120 ° C.
In the polymerization, a polymerization initiator may be used, or polymerization may be performed by thermal polymerization without using a polymerization initiator. As polymerization initiators, organic peroxides such as ketone peroxide, dialkyl peroxide, diacyl peroxide, peroxy ester, hydroperoxide, azobisisobutyronitrile, benzoyl peroxide, 1, 1′-azobis ( Cyclohexane-1-carbonitrile) is preferably used.
When a chain transfer agent is used, 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 monomer remaining in the component (D) obtained by each polymerization method is preferably 10,000 ppm or less, more preferably 5,000 ppm or less.

The polymer component obtained by polymerizing the vinyl monomer (b) in the presence of the rubber polymer (a) usually contains the rubber monomer (b). The copolymer obtained by graft copolymerization and the ungrafted component [(co) polymer of the above vinyl monomer (b)] not grafted to the rubbery polymer are included in a).
The graft ratio of the component (D) is preferably 20 to 200 mass%, more preferably 30 to 150 mass%, particularly preferably 40 to 120 mass%, and the graft ratio is determined by the following formula (12). Can do.

Graft ratio (% by mass) = {(TS) / S} × 100 (12)
In the above formula (12), T is 1 g of component (D) in 20 ml of acetone (but acetonitrile is used when the rubbery polymer (a) uses an acrylic rubber). It is the mass (g) of insoluble matter obtained by centrifuging for 60 minutes in a centrifuge (rotation speed: 23,000 rpm) after shaking for a while to separate the insoluble matter and the soluble matter. (D) Mass (g) of rubbery polymer contained in 1 g.

In addition, the intrinsic viscosity of the component (D) acetone (however, when the rubbery polymer (a) uses an acrylic rubber, acetonitrile) the intrinsic viscosity [η] (methyl ethyl ketone as a solvent) Used and measured at 30 ° C.) is preferably 0.2 to 1.2 dl / g, more preferably 0.2 to 1.0 dl / g, particularly preferably 0.3 to 0.8 dl / g.
The number average particle diameter of the grafted rubbery polymer particles dispersed in the component (D) according to the present invention is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 1 , 500 to 8,000 cm. The number average particle diameter can be measured by a known method using an electron microscope.

  The amount of the component (D) used in the antistatic resin composition of the present invention is 100% by mass in total of the component (A), the component (B), the component (C), and the component (D) of the present invention. 5 to 40% by mass, preferably 5 to 35% by mass, more preferably 8 to 35% by mass, particularly preferably 10 to 35% by mass, and if it is less than 5% by mass, the antistatic property is inferior. If it exceeds mass%, the chemical resistance is poor.

（ｅ−３）；下記一般式（２）で表される化合物、

（式中、Ｒ^１は炭化水素基を表わし、Ｒ^２は水素原子または炭化水素基を表し、Ｘは水素原子、炭化水素基、ウレタン基若しくはエステル基を有する炭化水素基または親水基を表わし、ｍは１以上の数を表わし、ｎは２以上の数を表す。）
（ｅ−４）；非イオン界面活性剤。 By incorporating a specific amount of component (E) into the antistatic resin composition of the present invention, the antistatic property can be further improved without impairing the object of the present invention. The component (E) used here is at least one selected from the group consisting of the following component (e-1), component (e-2), component (e-3), and component (e-4). It is a seed.
(E-1); a salt having an anion having a fluorinated alkylsulfonyl group,
(E-2); a boron compound containing a unit represented by the following general formula (1),

(E-3); a compound represented by the following general formula (2),

(In the formula, R ¹ represents a hydrocarbon group, R ² represents a hydrogen atom or a hydrocarbon group, X represents a hydrocarbon group or a hydrophilic group having a hydrogen atom, a hydrocarbon group, a urethane group or an ester group, m represents a number of 1 or more, and n represents a number of 2 or more.)
(E-4); nonionic surfactant.

The component (e-1) of the present invention is a salt having an anion having a fluorinated alkylsulfonyl group, and the antistatic property can be further improved by blending these components.
Component (e-1) means a salt composed of an anion having one or more fluorinated alkylsulfonyl groups and an appropriate cation. Examples of the fluorinated alkylsulfonyl group contained in the anion include a fluorinated lower alkylsulfonyl group such as trifluoromethanesulfonic acid and pentafluoroethanesulfonic acid, particularly a perfluoroalkylsulfonyl group. As an anion constituting the component (e-1), in addition to trifluoromethanesulfonic acid itself, one or more preferably a plurality of trifluoromethanesulfonyl groups such as bis (trifluoromethanesulfonyl) imide and tris (trifluoromethanesulfonyl) methide. Derivatives such as methide and ammonia substituted with hydrogen atoms are exemplified. As a cation which comprises a component (e-1), alkali metals, such as lithium, sodium, and potassium, are mentioned typically. Specific examples of the component (e-1) include lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide lithium, potassium bis (trifluoromethanesulfonyl) imide, sodium bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl). ) Methidolithium, potassium tris (trifluoromethanesulfonyl) methide and sodium tris (trifluoromethanesulfonyl) methide. These can be used individually by 1 type or in combination of 2 or more types. Preferred components (e-1) are lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide and lithium tris (trifluoromethanesulfonyl) methide. These can be used individually by 1 type or in combination of 2 or more types.

[一般式（１３）中、Ｘは炭素数２〜８からなるアルキレン基、芳香族基を含む二価の炭化水素基、または二価の脂環式炭化水素基、Ｒは同一または異なり炭素数１〜９の直鎖または分岐のアルキル基、Ａは同一または異なり炭素数２〜４のアルキレン基を示し、ｎは同一または異なり１〜７の整数である。] The component (e-1) can be used as it is, can also be used as a solution, and can be used in combination with a polymer having an ether bond in advance. A particularly preferable solvent for dissolving the component (e-1) is water or a compound represented by the following formula (13).

[In general formula (13), X is an alkylene group having 2 to 8 carbon atoms, a divalent hydrocarbon group containing an aromatic group, or a divalent alicyclic hydrocarbon group, and R is the same or different. 1 to 9 linear or branched alkyl groups, A is the same or different and represents an alkylene group having 2 to 4 carbon atoms, and n is the same or different and is an integer of 1 to 7. ]

What is preferable as a compound represented by the said General formula (13) is a thing in which R is an alkyl group which does not have a hydroxyl group at the terminal. Particularly preferred is bis [2- (2butoxyethoxy) ethyl] adipate (dibutoxyethoxyethyl adipate) or bis (2-butoxyethyl) phthalate.
The concentration in the case of dissolving the component (e-1) of the present invention is preferably 0.1 to 80% by mass, more preferably 1 to 60% by mass.

  Examples of the polymer having an ether bond include polyethylene glycol, polyethylene oxide, a block copolymer composed of a polyamide block and polyethylene glycol, a block copolymer composed of a polyester block and a polyethylene glycol block, and the component (B) of the present invention. Etc.

  The solution of the component (e-1) of the present invention is Sanconol 0862-20R, 0862-13T, 0862-10T, AQ-50T (trade name), etc., manufactured by Sanko Chemical Industry Co., Ltd. It can be obtained as Sanconol TBX-25 (trade name) manufactured by Photochemical Industries.

  The compounding quantity of the component (e-1) of this invention is 0.01-30 mass parts with respect to a total of 100 mass parts of the component (A) of this invention, (B), (C), and (D), Preferably Is 0.01 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, and particularly preferably 0.1 to 5 parts by mass. If the content is less than 0.01 parts by mass, the effect of improving the antistatic property cannot be obtained, and if it exceeds 30% by mass, the appearance of the molded product is inferior.

  The component (e-2) of the present invention is a boron compound containing a unit represented by the general formula (1).

〔式中、ｑは、０又は１であり、ｑ＝１のとき、Ｔは、−（Ｔ^１）_ｓ−（Ｔ^２）_ｔ−（Ｔ^３）_ｕ−（但し、Ｔ^１及びＴ^３は、互いに同一又は異なって、１つの末端エーテル残基を有し且つ炭素数の合計が１００以下の含酸素炭化水素基であり、Ｔ^２は、

（但し、Ｒ^９は、炭素数１から８２の炭化水素基である。）
又は、

（但し、Ｒ^１０は、炭素数２〜１３の炭化水素基である。）であり、ｓ、ｔ及びｕは、それぞれ、０又は１である。）であり、Ｒ^６、Ｒ^７及びＲ^８は、互いに同一又は異なる有機基であり、ｒは、１０〜１０００である。〕 As the compound containing the unit represented by the general formula (1), an organic boron polymer compound represented by the following general formula (1-1) is preferable. The compound of the general formula (1-1) is a boron atom composed of a semipolar organic boron polymer compound and one or more tertiary amines having a hydroxyl group and having 5 to 82 carbon atoms in total. It is a reaction product of a ratio of one basic nitrogen atom and forms a polymer charge transfer type conjugate.

[In the formula, q is 0 or 1, and when q = 1, T is-(T ¹ ) _s- (T ² ) _t- (T ³ ) _u- (where T ¹ and T ³ are Are oxygen-containing hydrocarbon groups which are the same or different from each other, have one terminal ether residue and have a total number of carbon atoms of 100 or less, and T ² is

(However, R ⁹ is a hydrocarbon group having 1 to 82 carbon atoms.)
Or

^{(Wherein, R 10} is a hydrocarbon group of 2 to 13 carbon atoms.) And, s, t and u are each 0 or 1. R ⁶ , R ⁷ and R ⁸ are the same or different organic groups, and r is 10 to 1000. ]

Examples of R ⁶ , R ⁷ and R ⁸ in the general formula (1-1) include a hydrocarbon group, an alkoxy group, a phenoxy group, a benzyloxy group, and an alkylene glycol group. These groups may have a functional group such as a hydroxyl group, or may have a substituent.

〔式中、Ｒ’は、平均重合度２０のポリブテンの残基である。〕

Specific examples of the charge transfer type conjugate include conjugates represented by the following chemical formulas (1-2) to (1-9). In each chemical formula below, a hydrogen atom or a hydroxyl group is usually bonded to the terminal carbon atom and oxygen atom, respectively.

[Wherein R ′ is a polybutene residue having an average degree of polymerization of 20. ]

The polymer charge transfer type conjugate can be produced by the method described in Japanese Patent No. 2573986.
In addition, as a boron compound (e-2), a commercial item can be used, for example, "High Boron 400N" by Boron International, etc. are suitable.

  The boron compound (e-2) according to the present invention may be added alone to the composition during the production of the antistatic resin composition, or the components (A), (B), (C) described above. , (D) and the like (mixture) composed of a polymer (composition). Examples of the latter include “High Boron MB400N-8LDPE” (master batch using polyethylene as a matrix) manufactured by Boron International.

  The compounding quantity of the component (e-2) of this invention is 0.01-30 mass parts with respect to a total of 100 mass parts of the component (A) of this invention, (B), (C), and (D), Preferably Is 0.05 to 20 parts by mass, more preferably 0.1 to 10 parts by mass, particularly preferably 0.3 to 5 parts by mass, and if it is less than 0.01 parts by mass, the antistatic property cannot be improved. If the amount exceeds 30 parts by mass, the appearance of the molded product is inferior.

The component (e-3) of the present invention is a polymer antistatic agent represented by the general formula (2).
That is, the component (e-3) of the present invention has a structure similar to a phenol resin in which an alkylene oxide or the like is addition-polymerized to a hydroxyl group of a condensation product of a phenol and a formaldehyde having or not having a hydrocarbon group as a substituent. It is a high molecular weight compound.

In the general formula (2), R ¹ is a hydrocarbon group, preferably an alkylene group having 2 to 4 carbon atoms. The part of (R ¹ —O) _{m in} the general formula (2) can be obtained by addition polymerization of alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide, α-olefin oxide, styrene oxide, and the like. When the portion of (R ¹ —O) _m is formed by adding alkylene oxide or the like, R ¹ is determined by the alkylene oxide or the like to be added. The polymerization form such as alkylene oxide to be added is not particularly limited, and may be homopolymerization of one kind of alkylene oxide, random copolymerization of two or more kinds of alkylene oxide, block copolymerization, random / block copolymerization, or the like. . R ¹ is most preferably an ethylene group, and when R ¹ is two or more groups, one is preferably an ethylene group. The degree of polymerization m is a number of 1 or more, preferably 1 to 300, more preferably 1 to 200, and most preferably 5 to 100.

R ² represents a hydrogen atom or a hydrocarbon group. Examples of the hydrocarbon group include an alkyl group, an alkenyl group, an aryl group, a cycloalkyl group, and a cycloalkenyl group. Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tertiary butyl, pentyl, isopentyl, secondary pentyl, neopentyl, tertiary pentyl, hexyl, secondary hexyl, heptyl, secondary Heptyl, octyl, 2-ethylhexyl, secondary octyl, nonyl, secondary nonyl, decyl, secondary decyl, undecyl, secondary undecyl, dodecyl, secondary dodecyl, tridecyl, isotridecyl, secondary tridecyl, tetradecyl, secondary tetradecyl, Hexadecyl, secondary hexadecyl, stearyl, icosyl, docosyl, tetracosyl, triacontyl, 2-butyloctyl, 2-butyldecyl, 2-hexyloctyl, 2-hexyldecyl, 2-octyldecyl, 2-hexyldecyl, 2 Octyldodecyl, 2-decyltetradecyl, 2-dodecyl-hexadecyl, 2-hexadecyl octadecyl, 2-tetradecyl-octadecyl, monomethyl branched - include isostearyl.

  Examples of the alkenyl group include vinyl, allyl, propenyl, butenyl, isobutenyl, pentenyl, isopentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tetradecenyl, oleyl and the like. Examples of the aryl group include phenyl, toluyl, xylyl, cumenyl, mesityl, benzyl, phenethyl, styryl, cinnamyl, benzhydryl, trityl, ethylphenyl, propylphenyl, butylphenyl, pentylphenyl, hexylphenyl, heptylphenyl, octylphenyl, nonyl Examples include phenyl, decylphenyl, undecylphenyl, dodecylphenyl, phenylphenyl, benzylphenyl, styrenated phenyl, p-cumylphenyl, α-naphthyl, and β-naphthyl groups. Examples of the cycloalkyl group and cycloalkenyl group include cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl, methylcyclohexyl, methylcycloheptyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, methylcyclopentenyl, methylcyclohexenyl, methylcycloheptenyl group, and the like. Is mentioned. Among these, a hydrocarbon group having 3 to 36 carbon atoms is preferable, and an alkyl group or alkenyl group having 3 to 24 carbon atoms is most preferable from the viewpoint of miscibility with the resin and compatibility.

X represents a hydrocarbon group having a hydrogen atom, a hydrocarbon group, a urethane group or an ester group, or a hydrophilic group. Examples of the hydrocarbon group include the above alkyl groups, alkenyl groups, aryl groups, cycloalkyl groups, cycloalkenyl groups and the like, and alkyl groups having 1 to 4 carbon atoms are most preferable. As the hydrophilic group, sulfate group represented by -SO ₃ M, phosphate groups represented by _-PO 3 _{M 2,} carboxylate group represented by -CH 2 COOM and the like.

  M represents a hydrogen atom, a metal atom or ammonium. Examples of the metal atom include alkali metal atoms such as lithium, sodium and potassium, alkaline earth metal atoms such as magnesium and calcium (however, since alkaline earth metal atoms are usually divalent, 1/2), etc. Examples of ammonium include ammonia, methylamine, dimethylamine, ethylamine, diethylamine, (iso) propylamine, di (iso) propylamine, monoethanolamine, N-methylmonoethanolamine, N-ethylmonoethanolamine, diethanolamine. , Triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine, 2-amino-2-methyl-1,3-propanediol, aminoethylethanolamine, N, N, N ′, N′-tetrakis (2 -Hydroxy Ammonium propyl) ethylenediamine, and the like. n represents the number of repetitions of the phenol formaldehyde condensate and is a number of 2 or more, preferably 5 to 200, more preferably 5 to 100, and most preferably 5 to 50.

  The manufacturing method of a component (e-3) is not specifically limited, What is necessary is just to follow the manufacturing method of a normal phenol-formaldehyde condensate. That is, it can be obtained by subjecting substituted phenol and formaldehyde to dehydration condensation in the presence of an acid catalyst and then adding alkylene oxide such as ethylene oxide. Thereafter, a hydrophilic group, a hydrocarbon group or the like may be introduced as the group represented by X as necessary.

Moreover, the component (F) described in the component (B) can be present in the component (e-3) of the present invention.
A compound such as component (e-3) of the present invention can be obtained as Adecanol AS-113 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd.

  The compounding amount of the component (e-3) of the present invention is 0.01 to 30 parts by mass with respect to a total of 100 parts by mass of the components (A), (B), (C) and (D) of the present invention, Preferably it is 0.1-30 mass parts, More preferably, it is 1-25 mass parts, Most preferably, it is 3-20 mass parts, If it is less than 0.01 mass part, antistatic property cannot be improved, and 30 masses If it exceeds the part, the appearance of the molded product is inferior.

  Examples of the nonionic surfactant that is the component (e-4) of the present invention include a polyhydric alcohol ester (e-4-1) and a nitrogen-containing compound (e-4-2). Or in combination of two or more. As the polyhydric alcohol ester (e-4-1), glycerol monolaurate, glycerol monomyristate, glycerol monopalmitate, glycerol monostearate, glycerol monobehenate, glycerol monooleate, diglycerol monolaurate, Diglycerol monomyristate, diglycerol monopalmitate, diglycerol monostearate, diglycerol monobehenate, diglycerol monooleate, sorbitan monostearate, sorbitan monobehenate, sorbitan monolaurate, etc. These can be used alone or in combination of two or more. Particularly preferred are glycerin monolaurate, diglycerin monolaurate, sorbitan monostearate and those containing at least 20% by mass of these.

  Examples of the nitrogen-containing compound (e-4-2) include lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyl diethanolamine, lauryl diisopropanolamine, myristyl diisopropanolamine, palmityl diisopropanolamine, stearyl diisopropanolamine, Amines such as oleyl diisopropanolamine, N, N-bishydroxyethylalkyl (alkyl group having 12 to 22 carbon atoms) amine, and lauryl diethanolamide, myristyl diethanolamide, palmityl diethanolamide, behenyl diethanolamide, oleyl diethanolamide , Lauryl diisopropanolamide, myristyl diisopropanolamide, Le palmityl diisopropanolamine amide, stearyl diisopropanol amide, there are amides such as oleyl monoisopropanolamide. These can be used alone or in combination of two or more. Preferred are the above amine compounds, and more preferred are those containing 20% by mass or more of lauryl diethanolamine and stearyl diethanolamine, respectively.

Moreover, a known additive can be mix | blended with the above-mentioned compound from the objective of improving antistatic performance. Examples thereof include higher alcohols having 12 to 18 carbon atoms, lubricants, silica, calcium silicate and the like. Moreover, what was masterbatched can be used in order to improve miscibility.
A compound such as the component (e-4) of the present invention can be obtained as Kao's electro stripper TS-5, EA, TS-3B, TS-2B, TS-13B, TS-7B (trade name) and the like. it can.
The compounding amount of the component (e-4) of the present invention is 0.01 to 30 parts by mass with respect to a total of 100 parts by mass of the components (A), (B), (C) and (D) of the present invention, Preferably it is 0.05-20 mass parts, More preferably, it is 0.1-10 mass parts, Most preferably, it is 0.5-5 mass parts. If it is less than 0.01 part by mass, the antistatic property cannot be improved, and if it exceeds 30% by mass, the appearance of the molded product is inferior.

  The antistatic resin composition of the present invention includes known weather resistance (light) agents, antioxidants, thermal stabilizers, lubricants, silicone oils, surfactants, plasticizers, sliding agents, colorants, dyes, foams. An agent, a processing aid (ultra high molecular weight acrylic polymer, ultra high molecular weight styrene polymer), flame retardant, crystal nucleating agent 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. The filler used here is glass fiber, glass flake, glass fiber milled fiber, glass bead, hollow glass bead, carbon fiber, carbon fiber milled fiber, silver, copper, brass, iron powder or the like Fibrous material, 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 There are whisker, aluminum borate whisker, plate-like alumina, plate-like silica, and organically treated smectite, aramid fiber, phenol fiber, polyester fiber, etc., and these should be used alone or in combination of two or more. Can do.
Furthermore, for the purpose of improving the dispersibility of the filler, those treated with a known coupling agent, surface treatment agent, sizing agent, etc. can be used. As the known coupling agent, a silane coupling agent can be used. , Titanate coupling agents, aluminum coupling agents, and the like.
The inorganic / organic filler is usually used in the range of 1 to 200 parts by mass with respect to 100 parts by mass of the antistatic resin composition of the present invention.

  Further, the antistatic resin composition of the present invention includes other known polymers such as polyamide resin, polyamide elastomer, polybutylene terephthalate, polyethylene terephthalate, polyarylate, liquid crystal polyester, and other thermoplastic polyester resins, polyester elastomers, PMMA, methyl methacrylate / maleimide compound copolymer, polyphenylene ether, polyphenylene sulfide, aromatic polycarbonate, 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 the above-described constituent components with various extruders, Banbury mixers, kneaders, continuous kneaders, rolls, and the like. At the time of kneading, the above components of the present invention may be added together and kneaded, or may be added separately and kneaded. The antistatic resin composition of the present invention thus prepared includes injection molding, press molding, calender molding, T-die extrusion molding, inflation molding, lamination molding, vacuum molding, profile extrusion molding, and combinations thereof. A molded product can be obtained by a known molding method such as a molding method.

The thickness when processing the antistatic resin composition of the present invention into a sheet or film is preferably in the range of 10 μm to 100 mm.
The sheet and film may be a single layer sheet or film, may be multilayered with other materials, or may be a sheet or film laminated with an adhesive or the like. Furthermore, a known gas barrier film can be formed on the sheet or film.

When forming a multilayer sheet or film using the antistatic resin composition of the present invention, two layers in which the sheet or film made of the antistatic resin composition of the present invention is laminated on one side of a sheet or film made of another material A sheet or a two-layer film, or a three-layer sheet or a three-layer film obtained by laminating a sheet or film made of the antistatic resin composition of the present invention on both surfaces of an intermediate layer made of another material can be used. As other materials used here, known polymers can be used, and the component (A-1) and / or (A-2) and the component (D) of the present invention are preferably used for them. . Further, for the purpose of improving the rigidity and heat resistance, those containing the inorganic and organic fillers can be used.
The thickness of the antistatic resin composition of the present invention laminated on the two-layered and multilayered sheets and films is preferably 10 μm or more, more preferably 50 μm or more, particularly preferably for the purpose of stably developing antistatic properties. The thickness is 80 μm or more. As a method for obtaining such a multilayer sheet and film, a particularly preferable method is coextrusion by T-die and coextrusion by inflation. The sheet and film thus obtained can be formed into a molded product such as a tray by vacuum forming or the like as necessary.

  The molded products thus obtained include cases such as relay cases, wafer cases, reticle cases, and ask cases, trays such as liquid crystal trays, chip trays, memory trays, CCD trays, IC trays, IC carriers, etc. It can be used in the fields of carriers, protective sheets for film cutting, sheets such as sheets in a clean room, and vending machine internal members.

  EXAMPLES The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to such examples as long as the gist of the present invention is not exceeded. In the examples, parts and% are based on mass unless otherwise specified. In addition, various measurements in Examples and Comparative Examples were performed according to the following methods.

[1] Evaluation method (1) Gel content of rubbery polymer: According to the above method.
(2) Number average particle diameter of rubbery polymer latex;
The number average particle size of the rubbery polymer latex used for forming the component (D) was measured by a light scattering method. The measuring machine used was LPA-3100 manufactured by Otsuka Electronics Co., Ltd., and the Mummrant method was used with 70 integrations. It was confirmed with an electron microscope that the particle diameter of the dispersion-grafted rubber polymer particles in component (D) was almost the same as the latex particle diameter.
(3) Graft ratio of component (D): According to the method described above.
(4) Intrinsic viscosity [η] of the acetone-soluble component (D); according to the method described above.
(5) Component (C) (bonded styrene content, vinyl bond content, number average molecular weight, and hydrogenation rate of the polymer);
(5-1) Amount of bound styrene;
It was measured on the polymer before hydrogenation. It was determined from a calibration curve by an infrared method based on absorption of a phenyl group at 699 cm ⁻¹ .
(5-2) Number average molecular weight;
It was measured on the polymer before hydrogenation. It calculated | required from the gel permeation chromatography (GPC).
(5-3) Vinyl bond amount Measured with the polymer before hydrogenation. It calculated | required by the infrared method (Morero method).
(5-4) Hydrogenation rate;
Measurements were taken on the polymer after hydrogenation. Using ethylene tetrachloride as a solvent, was calculated from the spectrum decrease of ¹ H-NMR unsaturated double bond of the spectrum of 100MHz was measured at 15% strength.

(6) Antistatic property;
A sheet having a thickness of 0.6 mm was allowed to stand under conditions of 23 ° C. and 50% RH for 24 hours, and then the surface resistivity was measured with an applied voltage of 500 V using Hiresta UP MCP-HT450 manufactured by Mitsubishi Chemical Corporation.
(7) heat resistance;
A sheet having a thickness of 0.6 mm was left in a bath at 800 ° C. for 1 hour, and then its deformation state was visually evaluated according to the following evaluation criteria.
○: No change.
X: Deformation such as warping and curling was observed.
(8) Chemical resistance;
A sheet of 0.6 mm thickness was strained by 1%, and gauze with gasoline was attached to the sheet. After sealing, the surface state after being allowed to stand at 23 ° C. for 72 hours was visually evaluated based on the following evaluation criteria.
○: No change.
X: Crack generation.
(9) Visual appearance of the sheet having a molded product appearance thickness of 0.6 mm was visually evaluated according to the following evaluation criteria.
◯: Good with a smooth appearance.
X: Unevenness is seen on the surface and it is not smooth.

[2] Antistatic resin composition component (1) The following were used as the olefin resin of component (A).
Component (A-1); Olefin resin A1-1 not containing a cyclic olefin component; Novatec PP MG2T (trade name) manufactured by Nippon Polypro Co., Ltd.
A1-2: Nippon Polypro Co., Ltd. Novatec PP EA9BT (trade name)
A1-3; Kernel KF271 (trade name) manufactured by Japan Polyethylene Corporation
A1-4; Novatec LD LF122 (trade name) manufactured by Nippon Polyethylene
Component (A-2); Olefin resin A2-1 containing cyclic olefin component; treated by Polyplastics Co., Ltd. TOPAS 6013 (trade name)
A2-2: Polyplastics company TOPAS 6015 (trade name)

(2) Component (B);
As the component (B) of the present invention, the following polymer manufactured by Sanyo Chemical Industries, Ltd. was used.
B1; Pelestat 303 (trade name) (a block copolymer mainly composed of polypropylene and polyethylene glycol)
B2; Pelestat 230 (trade name) (block copolymer mainly composed of polyolefin and polyethylene glycol)

(3) Component (C)
(3-1) Production Example 1 A styrene-butadiene-styrene block copolymer stirrer and a jacketed autoclave were dried and purged with nitrogen, and cyclohexane and 0.08 part of tetrahydrofuran were added in a nitrogen stream. Thereafter, the temperature was raised, and when the internal temperature reached 70 ° C., a cyclohexane solution containing 0.052 part of n-butyllithium was added, followed by addition of 15.5 parts of styrene and polymerization for 60 minutes (first stage). Next, a mixture of 3 parts of styrene and 20 parts of butadiene was added and polymerized for 60 minutes (second stage). Further, a mixture of 3 parts of styrene and 20 parts of butadiene was added and polymerized for 60 minutes (third stage). Further, a mixture of 3 parts of styrene and 20 parts of butadiene was added and polymerized for 60 minutes (fourth stage) to polymerize three tapered blocks. Next, 15.5 parts of styrene was polymerized for 60 minutes (5th stage). The polymerization conversion rate was 100%.
During the polymerization, the internal temperature was controlled to 70 ° C. After the completion of the polymerization, 0.3 part of 2,6-di-tert-butylcatechol was added, and then the solvent was removed to obtain a block copolymer C1 having three tapered blocks in which polystyrene gradually increases in the polybutadiene block part. It was. This had a number average molecular weight of 128,000 and a styrene content of 40%.

(3-2) Production Example 2; Styrene-Butadiene Radial Teleblock Copolymer A stirrer and a jacketed autoclave were dried and purged with nitrogen, and 2.75 parts of cyclohexane and tetrahydrofuran were added in a nitrogen stream. After adding 25 parts of styrene and raising the temperature to 60 ° C., a cyclohexane solution containing 0.175 part of n-butyllithium was added, and a polymerization reaction was carried out for 60 minutes (first stage). Next, a mixture of 3 parts of styrene and 20 parts of butadiene was added and a polymerization reaction was carried out for 60 minutes (second stage). Further, a mixture of 3 parts of styrene and 20 parts of butadiene was added and a polymerization reaction was carried out for 60 minutes (third stage). Further, 29 parts of butadiene was added and polymerization was completed until the conversion rate reached 100%. After adding 0.1 part of silicon tetrachloride as a coupling agent, the coupling reaction was completed. After completion of the polymerization, as in Production Example 1, 2,6-di-tert-butylcatechol was added, and then the solvent was removed to obtain a coupling type styrene-butadiene block copolymer C2 having a tapered block. This had a styrene content of 31% and a number average molecular weight of 200,000.

(3-3) Production Example 3: Completely Hydrogenated Styrene-Butadiene Block Copolymer A stirrer and a jacketed autoclave were dried and purged with nitrogen, and cyclohexane and 20 parts of butadiene were charged in a nitrogen stream. Next, 0.025 part of n-butyllithium was added to carry out isothermal polymerization at 50 ° C. When the conversion rate reached 100%, 0.75 part of tetrahydrofuran and 65 parts of butadiene were added, and the temperature was increased from 50 ° C to 80 ° C. When the conversion rate reached 100%, 15 parts of styrene was added, and a polymerization reaction was further performed to obtain an A-B1-B2 triblock copolymer before hydrogenation. A part of the obtained block polymer solution was sampled, 0.3 part of 2,6-di-tert-butylcatechol was added to 100 parts of the block copolymer, and then the solvent was removed by heating. A number average molecular weight of 200,000 comprising a styrene block of 15% (A block), a butadiene block having a 1,2-vinyl content of 35% (B1 block), and a butadiene block having a 1,2-vinyl content of 10% (B2 block). It was a polymer.
In a separate container, 1 part of titanocene dichloride was dispersed in cyclohexane and reacted with 0.5 part of triethylaluminum at room temperature. The obtained homogeneous solution was added to the polymer solution, and a hydrogenation reaction was performed at 50 ° C. under a hydrogen pressure of 50 kgf / cm ² for 2 hours. In the same manner as in Production Example 1, 2,6-di-tert-butylcatechol was added, and then the solvent was removed to obtain a hydrogenated polymer C3 having a hydrogenation rate of approximately 100%.

(4) Component (D)
(4-1) Production Example 4: Rubber Reinforced Styrenic Resin In a 7 L glass flask equipped with a stirrer, in a nitrogen stream, 75 parts of ion exchange water, 0.5 part of potassium rosinate, tert-dodecyl mercaptan 0 0.1 part, 40 parts (solid content) of polybutadiene latex (average particle size: 3500 kg, gel content: 85%), 15 parts of styrene, and 5 parts of acrylonitrile were added, and the temperature was increased while stirring. When the internal temperature reached 45 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose were dissolved in 20 parts of ion-exchanged water was added. It was. 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 part of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 part of tert-dodecyl mercaptan and 0.01 part of cumene hydroperoxide were added for 3 hours. Then, the polymerization was continued for another hour, and 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, and dried to obtain a rubber-reinforced styrene resin D1. The graft ratio of this polymer D1 was 68%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g.

(4-2) Production Example 5: Styrenic resin Two jacketed polymerization reaction vessels equipped with a ribbon wing with an internal volume of 30 L were connected and purged with nitrogen, and then the first reaction vessel was charged with 75 parts of styrene and acrylonitrile 25 Part and 20 parts of toluene were continuously added. 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 Was fed continuously. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion 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 provided in the second reactor. 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 had an intrinsic viscosity [η] of 0.48. Styrene resin D2 was obtained.

(5) Component (E);
The following were used as the component (E) of the present invention.
Ingredient (e-1)
e1-1; Sankonol 0862-10T (trade name) manufactured by Sanko Chemical Co., Ltd.
A solution containing 10% of tris (trifluoromethanesulfonyl) methide lithium in an organic solvent.
e1-2; Sankonol AQ-50T (trade name) manufactured by Sanko Chemical Co., Ltd.
An aqueous solution containing 50% of tris (trifluoromethanesulfonyl) methide lithium in water as a solvent.
Ingredient (e-2)
e2: High Boron MB400N-8LDPE (trade name) manufactured by Boron International
7% organic boron compound content.
Ingredient (e-3)
e3: Adecanol AS-113 (trade name) manufactured by Asahi Denka Kogyo Co., Ltd.
Polymer antistatic agent content 65%.
Ingredient (e-4)
e4; Kao Electro Stripper TS-5
Stearyl monoglyceride 100%.

Examples 1-16, Comparative Examples 1-5
The components listed in Table 1 were mixed at a blending ratio shown in Table 1 using a Henschel mixer, and then melt-kneaded using a twin-screw extruder (cylinder setting temperature 220 ° C.) to be pelletized. The obtained pellets were sufficiently dried to obtain the antistatic resin composition of the present invention.
By coextrusion (at a temperature of 200 ° C.), a 100 μm-thick layer made of the above antistatic resin composition was formed on the front and back surfaces of a 400 μm-thick core layer made of the polymer shown in Table 1, and a wall thickness of 0.6 mm A three-layer sheet was obtained. This sheet was cut into antistatic evaluation test pieces, heat resistance evaluation test pieces, chemical resistance evaluation test pieces, and molded product appearance evaluation test pieces.

From the results described in Table 1, the following is clear.
The molded products of Examples 1 to 16 of the present invention are excellent in antistatic properties, heat resistance, chemical resistance, and molded product appearance.
On the other hand, Comparative Example 1 is an example in which the amount of the component (A-2) used in the present invention is small outside the scope of the invention and the amount of the component (A-1) used is large outside the scope of the invention. Inferior. Comparative Example 2 is an example in which the amount of the component (A-1) of the present invention is small outside the scope of the invention and the amount of the component (A-2) is large outside the scope of the invention. Product appearance is inferior. Comparative Example 3 is an example in which the amount of the component (A) used in the present invention is small outside the scope of the invention, and is inferior in heat resistance, chemical resistance, and molded product appearance. Comparative Example 4 is an example in which the amount of the component (B) used in the present invention is small outside the scope of the invention, and the antistatic property is inferior. Comparative Example 5 is an example in which the amount of the component (B) used in the present invention is large outside the scope of the invention, and the chemical resistance and the appearance of the molded product are inferior.

Since the antistatic resin composition of the present invention is a thermoplastic resin composition having unprecedented excellent antistatic properties, heat resistance, chemical resistance, and appearance of a molded product, high performance is required. It can be used as a molding material for various parts in the vehicle field, electrical / electronic field, OA / home appliance field, sanitary field, and the like.

Claims (5)

(A) 7-91 mass% of olefin resin,
(B) 3-30% by mass of a block copolymer containing the olefin polymer block (b1) and the hydrophilic polymer block (b2),
(C) a block copolymer containing a polymer block (c1) mainly composed of an aromatic vinyl compound and a polymer block (c2) mainly composed of a conjugated diene compound and at least selected from the group consisting of hydrogenated products thereof 1 to 50% by mass of one polymer,
(D) A rubber-reinforced styrene resin obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of the rubbery polymer (a) and / or the vinyl monomer ( Co) polymer 5-40% by mass,
Containing component (A), component (B), component (C), and component (D) (however, the total of component (A), component (B), component (C), and component (D)) Is 100% by mass), and the component (A) is an olefin resin (A-) having a glass transition temperature of 60 to 200 ° C. containing an olefin resin (A-1) not containing a cyclic olefin component and a cyclic olefin component. 2), and the ratio of the content of the two ((A-1) / (A-2)) is 99/1 to 5/95 (mass ratio). . Furthermore, as the component (E), at least one selected from the group consisting of the following component (e-1), component (e-2), component (e-3) and component (e-4) 2. The antistatic property according to claim 1, comprising 0.01 to 30 parts by mass with respect to a total of 100 parts by mass of (A), component (B), component (C) and component (D). Resin composition.
(E-1) a salt having an anion having a fluorinated alkylsulfonyl group,
(E-2) a boron compound containing a unit represented by the following general formula (1),

(E-3) a compound represented by the following general formula (2),

(In the formula, R ¹ represents a hydrocarbon group, R ² represents a hydrogen atom or a hydrocarbon group, X represents a hydrocarbon group or a hydrophilic group having a hydrogen atom, a hydrocarbon group, a urethane group or an ester group, m represents a number of 1 or more, and n represents a number of 2 or more.)
(E-4) Nonionic surfactant. A molded article comprising the antistatic resin composition according to claim 1. The molded article according to claim 3, which is a sheet or a film. The laminated body formed by laminating | stacking the sheet | seat or film which consists of an antistatic resin composition of Claim 1 or 2 on the surface of at least one of the sheet | seat or film which consists of olefin resin.