JP5361136B2 - Antistatic resin composition and molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an antistatic resin composition which is excellent in antistaticity, chemical resistance, molded article surface appearance, and thermal stability, and is little in the amount of eluted ions, and to provide a molded article. <P>SOLUTION: This antistatic resin composition comprising 40 to 98 mass% of an olefinic resin (A), 2 to 60 mass% of a block copolymer (B) comprising an olefin polymer block and a hydrophilic polymer block, and further a lithium salt (C) in an amount of 0.01 to 5 pts.mass based on 100 total pts.mass of (A) and (B) is characterized in that the molded article of the composition has a surface resistivity of &le;1&times;10<SP>11</SP>&Omega;/sq. (measured in a condition of 50%RH at 23&deg;C) and has a sodium ion and potassium ion elution amount of &le;3 &mu;g/cm<SP>2</SP>. Further, a block copolymer comprising an aromatic vinyl compound polymer block and an unsaturated dienic compound polymer block or its hydrogenation product, and a styrenic resin may be contained in prescribed amounts. <P>COPYRIGHT: (C)2008,JPO&amp;INPIT

Description

  The present invention relates to an antistatic resin composition having excellent antistatic properties, chemical resistance, molded article surface appearance, thermal stability, and a small amount of eluted ions, and a molded article 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 a drawback that it is easily charged, various kinds of resins that are used or handled in static electricity, such as liquid crystal display devices, plasma displays, semiconductor peripheral members, clean rooms, etc. It was difficult to use for parts, sheets, films, etc. 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. In addition, as a method for maintaining antistatic properties, Patent Document 3 proposes that a block copolymer composed of a polyolefin block and a hydrophilic polymer block be blended with a polyolefin resin. There was a problem that it was not fully expressed.

  In addition, for the purpose of improving antistatic properties, an electrolyte component such as sodium salt or potassium salt of alkylbenzene sulfonic acid is generally added to the block copolymer during or after the polymerization. When blended, more electrolyte is added because the antistatic effect is not sufficient. Molded articles made of a composition containing such a block copolymer and an olefin resin have a problem of elution of electrolyte components as described above in applications in the liquid crystal field, hard disk field, organic EL field, LED field, etc. Conventionally, a resin composition satisfying both the antistatic property and the amount of eluted ions has not been obtained.

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

  An object of the present invention is to provide an antistatic resin composition having excellent antistatic properties, chemical resistance, molded article surface appearance, thermal stability, and a small amount of eluted ions, and a molded article comprising this antistatic resin composition Is to provide.

As a result of intensive studies to achieve the above object, the present inventors have added a predetermined amount of lithium salt in the composition containing the olefin resin and the block copolymer, and preferably the block copolymer. By using a block copolymer having a low content of sodium and / or potassium or substantially not containing these elements, a molded product having a sufficiently reduced amount of eluted ions to be suitable for the above-mentioned use can be obtained. It has been found that an electrically conductive resin composition can be obtained. Further, by adding a block copolymer containing a polymer block composed of a styrene-based resin and an aromatic vinyl compound and a polymer block composed of a conjugated diene compound or a hydrogenated product thereof to the composition, the antistatic property is further improved. As a result, the present inventors have found that the amount of eluted ions is reduced and completed the present invention.
That is, according to one aspect of the present invention, it contains 40 to 98% by mass of the following component (A) and 2 to 60% by mass of the following component (B) (provided that the components (A) and (B) The total is 100% by mass), and further, a composition containing 0.01 to 5 parts by mass of the following component (C) with respect to 100 parts by mass of the total of the components (A) and (B), The surface resistivity (measured under conditions of 23 ° C. and 50% RH) of the molded product obtained by molding the product is 1 × 10 ¹¹ Ω / □ or less, and the elution amounts of sodium ions and potassium ions (80 ° C., 60 An antistatic resin composition (hereinafter referred to as “first antistatic resin composition”) is provided, which has a measurement under a minute extraction condition of 3 μg / cm ² or less.
(A) Component: Olefin resin.
(B) Component: A block copolymer containing an olefin polymer block and a hydrophilic polymer block.
(C) Component: Lithium salt.
Moreover, according to the other situation of this invention, the following (A) component 7-91 mass%, the following (B) component 2-60 mass%, the following (D) component 2-50 mass%, and the following ( E) 5 to 50% by mass of component (provided that (A) component, (B) component, (D) component and (E) component are 100% by mass in total)), and (A) component above , (B) component, (D) component, and (E) component, it is a composition containing 0.01-5 mass parts of following (C) component, and shape | molds this composition The surface resistivity (measured under conditions of 23 ° C. and 50% RH) of 1 × 10 ¹¹ Ω / □ or less and the elution amount of sodium ions and potassium ions (extraction conditions at 80 ° C. for 60 minutes) in measurement) is antistatic resin composition characterized in that it is 3 [mu] g / cm ² or less (hereinafter, "second antistatic resin sets Things ") is provided.
(A) Component: Olefin resin.
(B) Component: A block copolymer containing an olefin polymer block and a hydrophilic polymer block.
(C) Component: Lithium salt.
Component (D): at least one elastomer selected from 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, and a hydrogenated product thereof.
Component (E): a rubber-reinforced styrene polymer (E-1) obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of a rubbery polymer, and / or the vinyl monomer Styrenic resin comprising a (co) polymer (E-2) as a monomer.
According to a preferred embodiment of the first and second antistatic resin compositions of the present invention, a block copolymer having a total content of sodium and potassium of 0 to 100 ppm is used as the component (B). The Moreover, when the said (B) component contains sodium and / or potassium, it is preferable to contain these with the form of a sulfonate.
As the component (C), at least one selected from the group consisting of lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide and tris (trifluoromethanesulfonyl) methane lithium is preferably used. .
According to still another aspect of the present invention, a molded article made of the antistatic resin composition, for example, a sheet, a film or the like is provided.
Hereinafter, the first antistatic resin composition and the second antistatic resin composition of the present invention are collectively referred to as “the antistatic resin composition of the present invention”.
In the present invention, the elution amount of sodium ions and potassium ions means the sum of the elution amount of sodium ions and the elution amount of potassium ions, and the elution amount of any one of the ions may be 0. The elution amount of both ions may exceed zero.

  According to the present invention, a predetermined amount of a lithium salt is added to an antistatic resin composition in which a block copolymer containing an olefin polymer block and a hydrophilic polymer block is blended with an olefin resin. By using a block copolymer having a low content of sodium and / or potassium as a block copolymer or substantially free of these elements, the content of sodium and potassium is reduced. An antistatic resin composition is obtained that is excellent in chemical properties, surface appearance of the molded product, and thermal stability, and that provides a molded product having an excellent balance between antistatic properties and elution amounts of sodium ions and potassium ions.

  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.

Description of the first antistatic resin composition The component (A) relating to the antistatic resin composition of the present invention is an olefin resin (A). Examples of the olefin resin (A) include olefin resins composed of at least one olefin having 2 to 10 carbon atoms, and are (co) polymers excluding the component (B) described later. This olefin resin (A) can be used individually by 1 type or in combination of 2 or more types.
Examples of olefins used for forming the olefin resin (A) include ethylene and propylene, butene-1, pentene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3- Examples include α-olefins such as methylhexene-1 and cyclic olefins such as norbornene. These can be used individually by 1 type or in combination of 2 or more types. Of these, ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, and norbornene are preferable.
Other monomers that can be used as necessary in the formation of the olefin resin (A) include 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1 Non-conjugated dienes such as 1,6-octadiene and 1,9-decadiene.

As the olefin resin (A), a polymer mainly containing a propylene unit such as polypropylene and a propylene / ethylene copolymer, polyethylene, and an ethylene-norbornene copolymer are preferable, and these may be used alone or in combination. It may be used. The propylene / ethylene copolymer includes a random copolymer, a block copolymer and the like, and any of them can be used, but it is particularly preferable to use a random type from the viewpoint of the appearance of the molded product surface. As the polyethylene, any of high density polyethylene, low density polyethylene, linear low density polyethylene and the like can be used.
As the olefin resin of the present invention, those produced by a known polymerization method can be used, and examples thereof include a high pressure polymerization method, a low pressure polymerization method, and a metallocene catalyst polymerization method.
Furthermore, as the olefin resin used in the present invention, one obtained by decatalyzing a polymerization catalyst or one modified with an acid anhydride, a carboxyl group, an epoxy group or the like can be used.

It does not matter whether the olefin resin (A) 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.
Moreover, it is preferable to use at least 1 type whose melting | fusing point measured based on JISK7121 of an olefin resin (A) is 40 degreeC or more.
When a polypropylene resin is used as the component (A) of the present invention, the melt flow rate measured according to JIS K7210: 1999 (230 ° C., load 2.16 kg) is preferably 0.01 to 500 g / 10 minutes. More preferably, it is 0.05 to 100 g / 10 min. When a polyethylene resin is used, the melt flow rate measured according to JIS K6922-2 (190 ° C., load 2.16 kg) is preferably 0.01 to 500 g / 10 min, more preferably 0.05 to 100 g / 10 min.

  As the olefin resin of the present invention, those containing various additives such as antioxidants, heat stabilizers, lubricants, etc. can be used, or those not added can be used. Depending on the application to be used, it may be preferable to use the component (A) that does not contain the above-mentioned various additives that are generated gas components from the molded product.

The amount of the component (A) constituting the first antistatic resin composition of the present invention is 40 to 98% by mass in a total of 100% by mass of the component (A) and the component (B) of the present invention, Preferably it is 45-97 mass%, More preferably, it is 45-95 mass%, Most preferably, it is 50-95 mass%. If the amount used is less than 40% by mass, the thermal stability is poor, and if it exceeds 98% by mass, the antistatic property is inferior.
In applications where excellent chemical resistance and molded product surface appearance are required, the amount of component (A) used is preferably 100 to 98% by mass, preferably 100 to 98% by mass, of the total of 100% by mass of component (A) and component (B). More preferably, it is 65-97 mass%, More preferably, it is 65-95 mass%, Most preferably, it is 70-95 mass%. When the amount used is less than 60% by mass, the chemical resistance and the molded product surface appearance tend to be inferior. In applications where excellent antistatic properties and thermal stability are required, the amount of the component (A) used is preferably 100 to 70% by mass, more preferably 40 to 70% by mass, in total 100% by mass of the components (A) and (B). Preferably it is 50-65 mass%. When used as a surface layer of a foam laminated sheet having a high antistatic property and a smooth surface, the amount of component (A) used is the amount of component (A) and component (B). The total content is 100% by mass, preferably 40 to 80% by mass, and more preferably 50 to 70% by mass.

The component (B) related to the antistatic resin composition of the present invention is a block copolymer containing an olefin polymer block (Ba) and a hydrophilic polymer block (BB). The component (B) may be a diblock or may be a multiblock of triblock or more. The olefin polymer block (Ba) is a (co) polymer of olefins. Examples of olefins used herein include ethylene and α-olefins such as propylene, butene-1, hexene-1, 3-methylbutene-1, 4-methylpentene-1, 3-methylhexene-1 and the like. Further, there are cyclic olefins such as norbornene, preferably ethylene, propylene, butene-1, 3-methylbutene-1, 4-methylpentene-1, norbornene, and these are one kind alone or two or more kinds. Can be used in combination. In addition, non-conjugated dienes such as 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, 7-methyl-1,6-octadiene, 1,9-decadiene and the like are used as part of the polymer component. It can also be used. The polystyrene-reduced number average molecular weight of the olefin polymer block (Ba) by gel permeation chromatography (GPC) is preferably 800 to 20,000, more preferably 1,000 to 10,000, and particularly preferably. 1,2000-6,000.

The olefin polymer block (Ba) is substantially bonded to the block (Bb), and the bond is selected from an ester bond, an amide bond, an ether bond, a urethane bond, an imide bond, and the like. It has at least one type of bond, and has a structure in which the bonds are alternately and alternately bonded through these bonds.
For this purpose, the molecular end of the block (Ba) needs to be modified with a functional group having reactivity with the functional groups at both ends of the block (Bb). These functional groups include carboxylic acid groups, hydroxyl groups, amino groups, acid anhydride groups, oxazoline groups, epoxy groups and the like.
The component (Ba) of the present invention can be obtained by a polymerization method, a thermal degradation method, or the like, and a polyolefin obtained by the polymerization method can be produced by a known method, for example, a radical catalyst, a metal oxidation catalyst, a Ziegler catalyst. The olefin can be easily obtained by (co) polymerization in the presence of a Ziegler-Natta catalyst, a metallocene catalyst or the like. On the other hand, a low molecular weight polyolefin obtained by a thermal degradation method of a high molecular weight polyolefin can be easily obtained by, for example, the method described in JP-A-3-62804. In view of the ease of modification of the molecular ends, a thermal degradation method is preferred.

The polyolefin obtained by the thermal degradation method is usually a polyolefin which can be modified at both molecular ends, a polyolefin which can be modified at one end and a polyolefin which does not have a modifiable end group, but both ends can be modified. It is also preferable that polyolefin is a main component.
The amount of double bonds in the polyolefin obtained by the thermal degradation method is preferably 1 to 40, more preferably 2 to 30, more preferably 4 to 1,000 per 1,000 carbon atoms from the viewpoint of antistatic properties. There are 20 pieces.
The average number of double bonds per molecule is preferably 1.1 to 5, more preferably 1.3 to 3, particularly preferably 1.8 from the viewpoints of repetitive structure formation and antistatic properties. ~ 2.2.
In the thermal degradation method, a low molecular weight polyolefin having an average number of terminal double bonds per molecule of 1.5 to 2 with an Mn in the range of 800 to 6,000 can be easily obtained [for example, Katsuhide Murata, See Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].

  A preferable method for imparting a functional group to the polyolefin obtained by these thermal degradation methods is the above-mentioned component (Ba) having a carbon-carbon double bond at the molecular end obtained by the thermal degradation method. This is a method of adding a carbon-carbon unsaturated compound having a functional group.

Examples of the hydrophilic polymer of the block (Bb) component include polyethers, polyether-containing hydrophilic polymers, and anionic polymers.
Examples of the polyether include polyether diol, polyether diamine, and modified products thereof.
The polyether-containing hydrophilic polymer includes a polyether ester amide having a polyether diol segment, a polyether amide imide having a polyether diol segment, a polyether ester having a polyether diol segment, and a polyether diamine segment. And polyether urethane having a segment of polyether diol or polyether diamine.
As the anionic polymer, an anionic polymer having a sulfonyl group-containing dicarboxylic acid and the above polyether as essential component units, and preferably having 2 to 80, more preferably 3 to 60 sulfonyl groups in one molecule. Is mentioned. These may be linear or branched. A particularly preferred component (Bb) is a polyether.

Among the polyethers, the polyether diol has the general formula (I):
H- (OA ¹ ) _{n —OE} ¹ —O (A ¹ O) _{n ′} —H, and general formula (II):
_{^{H- (OA 2) m -O-}} E 2 -O- (A 2 O) as represented by m'-H, and the like. In general formula (I), 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 when these are composed of two or more oxyalkylene groups is Either block or random or a combination thereof may be used. n and n ′ are integers of usually 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 (II), E ² is a residue obtained by removing a hydroxyl group from the divalent hydroxyl group-containing compound described in the general formula (I), and A ² is at least partly a general formula (III): —CHR— CHR ′ — [wherein one of R and R ′ is a group represented by the general formula (IV): —CH ₂ O (A ³ O) _X R ″, and the other is H. In the general formula (IV), 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 a carbon number. 2 to 4 alkylene groups. And the remainder may be an alkylene group having 2 to 4 carbon atoms. The 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 (I) can be produced by addition reaction of an alkylene oxide to 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 examples of the alkylene oxide include 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 (II) include the following methods (a) and (b).

  (A) Starting from the above-mentioned divalent hydroxyl group-containing compound, the general formula (V):

［一般式（V）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 4} in the general formula (V) is an alkylene group having 2 to 4 carbon atoms, p is an integer of from 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 (B) component of this invention can be obtained by superposing | polymerizing the said olefin polymer block (Ba) and hydrophilic polymer block (BB) by a well-known method. For example, the block (Ba) and the block (Bb) 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.

The component (B) of the present invention includes sodium and / or potassium-containing compound (B-1) for the purpose of improving antistatic properties. These compounds can be contained by polymerization of the component (B), after polymerization, or by a combination thereof, but a preferred method is a method in which these compounds are present during polymerization.
Examples of the component (B-1) include sodium and potassium organic acids, sulfonic acids, inorganic acid salts, and halides.

Specific preferred examples of component (B-1) include sodium or potassium halides such as sodium chloride, potassium chloride, sodium bromide and potassium bromide; sodium or potassium such as sodium perchlorate and potassium perchlorate Inorganic acid salts, sodium or potassium organic acid salts such as sodium acetate, potassium acetate, sodium stearate, potassium stearate; octylsulfonic acid, dodecylsulfonic acid, tetradecylsulfonic acid, stearylsulfonic acid, tetracosylsulfonic acid Sodium salt or potassium salt of alkylsulfonic acid having 8 to 24 carbon atoms of alkyl group such as 2-ethylhexylsulfonic acid; sodium salt or potassium salt of aromatic sulfonic acid such as phenylsulfonic acid or naphthylsulfonic acid; octyl Phenylsulfone , Sodium salt or potassium salt of alkylbenzenesulfonic acid having 6 to 18 carbon atoms in the alkyl group, such as dodecylphenylsulfonic acid, dibutylphenylsulfonic acid, dinonylphenylsulfonic acid, etc .; dimethylnaphthylsulfonic acid, diisopropylnaphthylsulfonic acid, dibutyl Examples thereof include sodium salts or potassium salts of alkylnaphthalenesulfonic acids having 2 to 18 carbon atoms in the alkyl group such as naphthylsulfonic acid; sodium salts or potassium salts such as fluorinated sulfonic acids such as trifluoromethanesulfonic acid, etc. Can be used singly or in combination of two or more. A particularly preferred component (B-1) is a compound in the form of a sodium and / or potassium sulfonate salt, specifically, a sodium salt compound of sulfonic acid or a potassium salt compound of sulfonic acid. The component (B-1) can be used in an amount of preferably 0.1 to 20 parts by mass, more preferably 1 to 15 parts by mass with respect to 100 parts by mass of the component (B) of the present invention. The total content of sodium and potassium in the component (B) of the present invention is preferably 0 to 1000 ppm, more preferably 0 to 500 ppm, and particularly preferably 0 to 100 ppm. Component (B) may contain either one of sodium or potassium, or may contain both elements. Each content of sodium and potassium can be calculated from the amount added in the production of the composition of the present invention, and the composition of the present invention is measured by X-ray fluorescence analysis, atomic absorption spectrometry, etc. You can also ask for it.

The preferred ratio of the (Ba) component / (BB) component in the (B) component 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 in the range of 30-70 / 30-70% by mass.
Such a block polymer (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 is Available from Sanyo Kasei Kogyo Co., Ltd. Pelestat 300 series 300, 303, Pelestat 200 series 230, etc.

The component (B) of the present invention is a component in which the content of the sodium and / or potassium-containing compound (B-1) is reduced or a component not containing the compound (B-1) for the purpose of improving antistatic properties. It is preferable that Such preferable component (B) can be obtained, for example, by reducing the amount of the sodium and / or potassium compound (B-1) used during the polymerization of the component, or by performing polymerization without using the compound. The total content of sodium and potassium in the component (B) of the present invention is preferably 0 to 100 ppm. Here, the component (B-2) has a content of one of the elements of 0. It may be present or both elements may be contained. Thus, by using the component (B) having a low sodium and potassium content, the elution amount of sodium ions and potassium ions is preferably 2 μg / cm ² or less, more preferably 1 μg / cm ² or less, and even more preferably It is possible to reduce the detection level to impossible to detect.

In the first antistatic resin composition of the present invention, the component (B) is 2 to 60% by mass, preferably 3 to 55% by mass, of the total 100% by mass of the component (A) and the component (B). More preferably, it is 5 to 55% by mass, particularly preferably 5 to 50% by mass. If it is less than 2% by mass, the antistatic property is inferior, and if it exceeds 60% by mass, the thermal stability is inferior. May increase.
In applications where excellent chemical resistance and molded product surface appearance are required, component (B) is preferably 2 to 40% by mass, more preferably 2 to 40% by mass, in total of 100% by mass of component (A) and component (B). It is 3-35 mass%, More preferably, it is 5-35 mass%, Most preferably, it is 5-30 mass%, and when it exceeds 40 mass%, there exists a tendency for chemical resistance and surface appearance to be inferior. In applications where excellent antistatic properties and thermal stability are required, the component (B) is preferably 30 to 60% by mass, more preferably 35%, in a total of 100% by mass of the component (A) and the component (B). -50 mass%. When used as a surface layer of a foam laminated sheet having a high antistatic property and a smooth surface having a smooth surface, the component (B) is a total of 100 masses of the component (A) and the component (B). %, Preferably 20 to 60% by mass, more preferably 30 to 50% by mass.

The component (C) related to the antistatic resin composition of the present invention is a lithium salt, and the effect of improving antistatic properties can be obtained by blending this component.
As the lithium salt (C), lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methane lithium and the like are preferably used, and more preferably trifluoromethanesulfonic acid. Lithium. These can be used individually by 1 type or in combination of 2 or more types. These can be obtained as a solution or a master batch as Sankonol 0862-13T, AQ-50T, AQ-75T, or TBX-25 (trade name) manufactured by Sanko Chemical Co., Ltd.
In the first antistatic resin composition of the present invention, the component (C) is used in a range of 0.01 to 5 parts by mass with respect to a total of 100 parts by mass of the component (A) and the component (B). Is more preferable, 0.1 to 3 parts by mass, and particularly preferably 0.3 to 2 parts by mass. If the amount used is less than 0.01 parts by mass, the effect of improving antistatic properties cannot be obtained, and if it exceeds 5 parts by mass, the impact resistance tends to decrease.

According to the present invention, the surface resistivity (measured under conditions of 23 ° C. and 50% RH) is 1 × 10 ¹¹ Ω / □ or less, preferably 1 × 10 ¹⁰ Ω / □ or less, and sodium ions and potassium Elution amount of ions (measured under extraction conditions at 80 ° C. for 60 minutes) 3 μg / cm ² or less, preferably satisfying the undetectable requirement, and thus a molded body with a high balance between antistatic properties and eluted ions Is obtained. In the prior art, the blending amount of the component (B) has been increased in order to improve antistatic properties, but in this case, the amount of ions eluted from the molded product has increased. On the other hand, according to the present invention, a predetermined amount of lithium salt is blended, and preferably, the component (B) has a low content of sodium and / or potassium or substantially does not contain these elements. By using it, a molded body in which antistatic properties and eluted ions are highly balanced can be obtained.

Description of Second Antistatic Resin Composition The second antistatic resin composition of the present invention further comprises (D) component and (E) component in the first antistatic resin composition. Yes, the balance between antistatic properties and eluted ions is improved, and impact resistance is enhanced.
In the second antistatic resin composition of the present invention, as the component (A), all the olefin resins (A) described above can be used, and these can be used alone or in combination of two or more. Can do.
In the second antistatic resin composition of the present invention, the amount of the component (A) used is 100% by mass in total of the components (A), (B), (D) and (E) of the present invention. Among them, 7 to 91% by mass, preferably 10 to 85% by mass, more preferably 15 to 80% by mass, still more preferably 15 to 70% by mass, and particularly preferably 15 to 65% by mass. When the amount used is less than 7% by mass, the impact resistance and the antistatic property are inferior, and when it exceeds 91% by mass, the antistatic property and the impact resistance are inferior.
In applications where excellent chemical resistance and molded product surface appearance are required, the amount of component (A) used is 100% by mass in total of component (A), component (B), component (D) and component (E). Among them, the content is preferably 10 to 85% by mass, more preferably 20 to 80% by mass, and particularly preferably 30 to 75% by mass. If the amount used is less than 30% by mass, the chemical resistance and the molded product surface appearance tend to be inferior. In applications that require excellent antistatic properties and thermal stability, the amount of component (A) used is 100% by mass in total of component (A), component (B), component (D) and component (E). The amount is preferably 7 to 40% by mass, more preferably 10 to 35% by mass. When used as a surface layer of a foam laminated sheet having a high antistatic property and a smooth surface, the amount of the component (A) used is the component (A), the component (B), (D) In total 100 mass% of component and (E) component, Preferably it is 7-30 mass%, More preferably, it is 7-25 mass%.

In the second antistatic resin composition of the present invention, as the component (B), all the components (B) described above can be used, and these can be used alone or in combination of two or more. .
In the second antistatic resin composition of the present invention, the amount of the component (B) used is 100% by mass in total of the components (A), (B), (D) and (E) of the present invention. Among them, 2 to 60% by mass, preferably 3 to 55% by mass, more preferably 5 to 55% by mass, particularly preferably 5 to 50% by mass, and if it is less than 2% by mass, the antistatic property is inferior and 60% by mass. If it exceeds%, the thermal stability is poor.
In applications where excellent chemical resistance and molded product surface appearance are required, component (B) is preferably a total of 100% by mass of component (A), component (B), component (D) and component (E). Is from 2 to 40% by mass, more preferably from 3 to 35% by mass, even more preferably from 5 to 35% by mass, particularly preferably from 5 to 30% by mass. Tend to be inferior. In applications where excellent antistatic properties and thermal stability are required, the component (B) is preferably a total of 100% by mass of the component (A), the component (B), the component (D), and the component (E). It is 30-60 mass%, More preferably, it is 35-50 mass%. When used as a surface layer of a foam laminate sheet having a high antistatic property and a smooth surface having a smooth surface, the component (B) includes the component (A), the component (B), and the component (D). Among the total of 100% by mass of the component and the component (E), it is preferably 20 to 60% by mass, more preferably 30 to 60% by mass, and particularly preferably 40 to 60% by mass.
The component (B) of the present invention is a component in which the content of the sodium and / or potassium-containing compound (B-1) is reduced or a component not containing the compound (B-1) for the purpose of improving antistatic properties. It is preferable that Such preferable component (B) can be obtained, for example, by reducing the amount of the sodium and / or potassium compound (B-1) used during the polymerization of the component, or by performing polymerization without using the compound. The total content of sodium and potassium in the component (B) of the present invention is preferably 0 to 100 ppm. Here, the component (B-2) has a content of one of the elements of 0. It may be present or both elements may be contained. Thus, by using the component (B) having a low sodium and potassium content, the elution amount of sodium ions and potassium ions is preferably 2 μg / cm ² or less, more preferably 1 μg / cm ² or less, and even more preferably It is possible to reduce the detection level to impossible to detect.

In the second antistatic resin composition of the present invention, as the component (C), all the components (C) described above can be used, and these can be used alone or in combination of two or more. .
In the second antistatic resin composition of the present invention, the component (C) is added to the total amount of 100 parts by mass of the component (A), the component (B), the component (D), and the component (E). It is preferably used in the range of 01 to 5 parts by mass, more preferably 0.1 to 3 parts by mass, and particularly preferably 0.3 to 2 parts by mass. If the amount used is less than 0.01 parts by mass, the effect of improving antistatic properties cannot be obtained, and if it exceeds 5 parts by mass, the impact resistance tends to decrease.

According to the present invention, the surface resistivity (measured under conditions of 23 ° C. and 50% RH) is 1 × 10 ¹¹ Ω / □ or less, preferably 1 × 10 ⁹ Ω / □ or less, and sodium ions and potassium Elution amount of ions (measured under extraction conditions at 80 ° C. for 60 minutes) 3 μg / cm ² or less, preferably satisfying the undetectable requirement, and thus a molded body with a high balance between antistatic properties and eluted ions Is obtained. In the prior art, the blending amount of the component (B) has been increased in order to improve antistatic properties, but in this case, the amount of ions eluted from the molded product has increased. On the other hand, according to the present invention, a predetermined amount of lithium salt is blended, and preferably, the component (B) has a low content of sodium and / or potassium or substantially does not contain these elements. By using it, a molded body in which antistatic properties and eluted ions are highly balanced can be obtained.

The component (D) of the present invention comprises a block copolymer (D-) containing a polymer block (D-1) mainly comprising an aromatic vinyl compound and a polymer block (D-2) mainly comprising a conjugated diene compound. It is at least one polymer selected from the group consisting of a) and its hydrogenated product (Db), and exhibits properties as an elastomer.
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. Further, the block (D-2) may be a block in which two or more conjugated diene compounds are used and bonded in any form of random, block, or taper. In addition, (D-2) may contain 1 to 10 taper blocks in which the aromatic vinyl compound gradually increases, and is a vinyl bond derived from the conjugated diene compound of the polymer block (D-2). Polymer blocks having different contents may be appropriately copolymerized.

A preferred structure of the component (D) of the present invention is a polymer represented by the following formulas (VI) to (VIII) or a hydrogenated product thereof.
(AB) _Y (VI)
(AB) _Y- X (VII)
A- (BA) _Z (VIII)
(In the structural formulas (VI) to (VIII), 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 a coupling agent, Y is an integer of 1 to 5, Z is an integer of 1 to 5, and B is an aromatic. In the case of a copolymer of another monomer such as a vinyl compound and a conjugated diene compound, the content of the other monomer in B is the sum of the conjugated diene compound and the other monomer. (It is preferable that it is 50 mass% or less).

In the component (D) 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 (D) of the present invention is preferably in the range of 5 to 80%. The number average molecular weight of the component is preferably 10,000 to 1,000,000, more preferably 20,000 to 500,000, particularly preferably 20,000 to 200,000. Among these, the number average molecular weight of the A part represented by the above (VI) to (VIII) is preferably in the range of 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. .

Adjustment of the vinyl bond amount of the conjugated diene compound is performed by adjusting amines such as N, N, N ′, N′-tetramethylethylenediamine, trimethylamine, triethylamine, diazocyclo (2,2,2) octamine, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol diester. It can be carried out using ethers such as butyl ether, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, alkoxides of potassium and sodium, and the like.
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 (D) 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 the aromatic vinyl compound gradually increases in the block (D-2), and / or It is a radial block type that has been coupled.

  Further, as the component (D), the 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 block copolymer containing the polymer block mainly composed of the aromatic vinyl compound and the polymer block mainly composed of the conjugated diene compound obtained by the above method can be carried out by a known method. The desired polymer can be obtained by adjusting the hydrogenation rate by a known method. Specific methods include JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-63-5401, JP-A-2-133406, JP-A-1 There is a method disclosed in Japanese Patent No. 297413.

The block copolymer (Da) and hydrogenated product (Db) thereof are the same as those used by other polymers as the block polymer and / or graft polymer (the following (E) component) Or may not be the same) and may be chemically bonded.
The other polymer that is chemically bonded to the block copolymer (Da) and its hydrogenated product (Db) does not need to be 100% by mass chemically bonded. The object of the present invention can be achieved if at least 10% by mass of the polymer is chemically bonded.

  Preferred as other polymer bonded as block polymerization to the block copolymer (D-a) and its hydrogenated product (D-b) are aromatic polycarbonate and / or polyurethane, more preferably aromatic. It is a group polycarbonate. An aromatic polycarbonate block copolymer mixture can be manufactured by the method of Unexamined-Japanese-Patent No. 2001-220506, for example. Furthermore, TM-S4L77, TM-H4L77 (trade name) of TM polymer series manufactured by Kuraray Co., Ltd. can be obtained.

  A particularly preferred method for graft polymerizing the other polymer to the block copolymer (Da) and its hydrogenated product (Db) is the block copolymer (Da) and its In this method, a vinyl monomer is graft polymerized in the presence of a hydrogenated product (Db). The vinyl monomer is preferably a vinyl monomer (Eb) of the following component (E) (however, it may or may not be the same as that used in the following component (E)): used. As a method for graft polymerization, emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like described later for the component (E) can be used, and solution polymerization and bulk polymerization are more preferable.

  In the second antistatic resin composition of the present invention, the component (D) is 2% in a total of 100% by mass of the components (A), (B), (D) and (E) of the present invention. -50% by mass, preferably 5-45% by mass, more preferably 7-40% by mass, particularly preferably 10-35% by mass. When the content is less than 2% by mass, the impact resistance is inferior. Impact resistance and surface appearance are inferior. When used as a surface layer of a foam laminate sheet having a high antistatic property and a smooth surface having a smooth surface, the component (D) includes the component (A), the component (B), and the component (D). The total content of the component and the component (E) is preferably 100 to 50% by mass, more preferably 20 to 45% by mass.

The component (E) of the present invention is a rubber-reinforced styrene resin obtained by polymerizing a vinyl monomer (Eb) containing an aromatic vinyl compound in the presence of a rubbery polymer (Ea). (E-1) and / or a (co) polymer (E-2) of the vinyl monomer. The latter (co) polymer (E-2) is obtained by polymerizing a vinyl monomer (Eb) containing an aromatic vinyl compound in the absence of the rubbery polymer (Ea). It is what
The component (E) of the present invention is at least one polymer obtained by graft polymerization of a vinyl monomer (Eb) in the presence of the rubbery polymer (Ea) in terms of impact resistance. The inclusion is preferred. The content of the rubber polymer (Ea) 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 (E) being 100% by mass. is there.

The rubbery polymer (Ea) is not particularly limited, but polybutadiene, butadiene / styrene copolymer, butadiene / acrylonitrile copolymer, ethylene / propylene copolymer, ethylene / propylene / non-conjugated diene copolymer. Examples include polymers, ethylene / butene-1 copolymers, ethylene / butene-1 / non-conjugated diene copolymers, acrylic rubbers, silicone rubbers, silicone / acrylic IPN rubbers, and the above component (D). These can be used alone or in combination of two or more.
Of these, polybutadiene, butadiene / styrene copolymer, ethylene / propylene copolymer, ethylene / propylene / nonconjugated diene copolymer, acrylic rubber, silicone rubber, and component (D) are preferred. The butadiene / styrene copolymer used here may be either a block copolymer or a random copolymer.

The gel content of the rubber polymer (Ea) is not particularly limited, but when the component (Ea) is obtained by emulsion polymerization, the gel content is preferably 98% by mass or less, and more preferably. Is 40-98 mass%. Within this range, it is possible to obtain an antistatic resin composition that gives a multilayer sheet particularly excellent in impact resistance.
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 (1).

Gel content (% by mass) = [{W ₂ (g) −W ₁ (g)} / 1 (g)] × 100 (1)
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 (Eb) include styrene, α-methylstyrene, hydroxystyrene, and the like. These may be used alone or in combination of two or more. Can be used. 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-based monomer (Eb) comprises an aromatic vinyl compound as an essential monomer component, and if necessary, from a vinyl cyanide compound, a (meth) acrylic acid ester compound and a maleimide compound. 1 type or 2 types or more chosen from the group which is comprised 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. 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 the (Eb) component, 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 using a (meth) acrylic acid ester compound, the usage-amount is in the (Eb) component, Preferably it is 1-80 mass%, More preferably, it is 5-80 mass%.
Examples of the maleimide compound include maleimide, N-phenylmaleimide, N-cyclohexylmaleimide, and the like. 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 (Eb).

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 and the like, 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, an effect of improving the compatibility between the styrenic resin and other polymer can be expected. 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 above-mentioned various other functional group-containing unsaturated compounds used is the total amount of the functional group-containing unsaturated compounds used in the component (E), and is 0.1 to 20 mass with respect to the total component (E). % 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 (Eb) is preferably 10 to 10% when the total amount of the vinyl monomers (Eb) is 100% by mass. It is 95 mass%, More preferably, it is 10-90 mass%, Most preferably, it is 15-80 mass%. More preferable combinations of monomers constituting the vinyl monomer (Eb) 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 particularly preferred combination is styrene / acrylonitrile. A more preferable combination of monomers polymerized in the presence of the coalescence (Ea) is styrene / acrylonitrile = 65/45 to 90/10 (mass ratio), styrene / methyl methacrylate = 0 / 20-20 / 80 (mass ratio), styrene / acrylonitrile / methyl methacrylate, the amount of styrene is 20-80% by mass, and the total of acrylonitrile and methyl methacrylate is in the range of 20-80% by mass. And particularly preferably styrene / acrylonitrile 70/30 to 85/15 (mass ratio).

  The component (E) 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 (Eb) in the presence of the rubbery polymer (Ea) are emulsion polymerization and solution polymerization. It is. On the other hand, a preferred polymerization method for the polymer obtained by (co) polymerizing the vinyl monomer (Eb) in the absence of the rubbery polymer (Ea) 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.
Examples of the polymerization initiator include cumene hydroperoxide, p-menthane hydroperoxide, diisopropylbenzene hydroperoxide, tetramethylbutyl hydroperoxide, tert-butyl hydroperoxide, potassium persulfate, azobisisobutyronitrile and the like. Can be mentioned.
Moreover, there are various reducing agents, sugar-containing iron pyrophosphate formulations, sulfoxylate formulations and the like as polymerization initiation assistants, and it is particularly preferable to use a redox system.
Examples of the chain transfer agent include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, terpinolene, and α-methylstyrene dimer.
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 (Ea) and the vinyl monomer (Eb) are used in the presence of the total amount of the rubber polymer (Ea). (Eb) may be added all at once for polymerization, or divided or continuously added for polymerization. Moreover, you may add a part of rubber-like polymer (Ea) 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 the component (E) powder of the present invention. At this time, the latex of two or more components (E) 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 (E) by solution polymerization is an inert polymerization solvent used in normal 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) and the like are preferably used.
When a chain transfer agent is used, for example, mercaptans, terpinolenes, α-methylstyrene dimers, 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 (E) 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 (Eb) in the presence of the rubbery polymer (Ea) usually includes the vinyl monomer (Eb). Contains a copolymer obtained by graft copolymerization with a rubber polymer (Ea) and an ungrafted component that is not grafted onto the rubber polymer [copolymer of the above-mentioned vinyl monomer (Eb)]. It is.
The graft ratio of the component (E) is preferably 20 to 200% by mass, more preferably 30 to 150% by mass, particularly preferably 40 to 120% by mass, and the graft rate is determined by the following formula (2). Can do.

Graft ratio (mass%) = {(TS) / S} × 100 (2)
In the above formula (2), T is a shaker by adding 1 g of component (E) to 20 ml of acetone (but acetonitrile if the rubbery polymer (Ea) uses acrylic rubber). The mass (g) of insoluble matter obtained by shaking for 2 hours and then centrifuging for 60 minutes with a centrifuge (rotation speed: 23,000 rpm) to separate the insoluble matter and the soluble matter. Is the mass (g) of the rubbery polymer contained in 1 g of component (E).

In addition, the intrinsic viscosity of the component (E) involved in the present invention (however, when the rubbery polymer (Ea) is an acrylic rubber, acetonitrile) the intrinsic viscosity [η] (as a solvent) (Measured at 30 ° C. using methyl ethyl ketone) 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. is there.
The average particle size of the grafted rubbery polymer particles dispersed in the component (E) according to the present invention is preferably 500 to 30,000, more preferably 1,000 to 20,000, and particularly preferably 1, It is in the range of 500 to 8,000cm. The average particle diameter can be measured by a known method using an electron microscope.

  The amount of the component (E) used in the second antistatic resin composition of the present invention is 100% by mass in total of the components (A), (B), (D) and (E) of the present invention. Among them, 5 to 50% by mass, preferably 7 to 50% by mass, more preferably 7 to 38% by mass, particularly preferably 10 to 30% by mass, and if less than 5% by mass, the antistatic property, impact resistance, In addition, the surface appearance of the molded product is inferior, and if it exceeds 50% by mass, the antistatic property and the chemical resistance are inferior. When used as a surface layer of a foam laminated sheet having a high antistatic property and a smooth surface, the amount of the (E) component used is the (A) component, the (B) component, (D) In total 100 mass% of component and (E) component, Preferably it is 5-20 mass%, More preferably, it is 5-15 mass%.

  The antistatic resin composition of the present invention can be blended with a nonionic antistatic agent (F) at the time of producing the antistatic resin composition for the purpose of further improving the antistatic property.

  Nonionic antistatic agents (F) include polyhydric alcohol ester compounds, amines, amides, etc., and polyhydric alcohol ester compounds include glycerin monostearate, glycerin monomyristate, glycerin monopalmitate, Glycerol monostearate, glycerol monobehenate, glycerol monooleate, diglycerol monolaurate, diglycerol monomyristate, diglycerol monopalmitate, diglycerol monostearate, diglycerol monobehenate, diglycerol monooleate, sorbitan Examples include monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan monolaurate, and the like. It can be used in combination of at least. Particularly preferred are glycerol monostearate, diglycerol monostearate, glycerol monolaurate, diglycerol monolaurate, sorbitan monostearate and those containing at least 20% by mass or more of these.

  Examples of amines and amides include lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyl diethanolamine, lauryl diisopropanolamine, myristyl diisopropanolamine, palmityl diisopropanolamine, stearyl diisopropanolamine, oleyl diisopropanolamine, Amine compounds such as 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, Palmityl di-isopropanol amides, stearyl diisopropanolamine amide, there is an amide compound such as oleyl monoisopropanolamide. These can be used individually by 1 type or in combination of 2 or more types. Preferably, the amine compound is used, and more preferably contains at least 20% by mass of lauryl diethanolamine and stearyl diethanolamine.

Moreover, a known additive can be blended for the purpose of improving the antistatic performance of the above-mentioned compound. Examples thereof include higher alcohols having 12 to 18 carbon atoms, lubricants, silica, calcium silicate and the like. In addition, for the purpose of improving miscibility, a master batch can be used.
The nonionic antistatic agent can be obtained from the market as, for example, Kao Electro Stripper EA, TS-3B, TS-6B, TS-5, TS-2B (trade name), and the like.

  The nonionic antistatic agent is preferably in the range of 0.01 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, particularly preferably 100 parts by weight of the antistatic resin composition of the present invention. It is used in the range of 0.1 to 5 parts by mass. If the amount used is less than 0.01 parts by mass, the effect of improving the antistatic property cannot be obtained, and the surface appearance of the molded product exceeding 10 parts by mass tends to be inferior.

  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, processing aids. An agent (ultra high molecular weight acrylic polymer, ultra high molecular weight styrene polymer), a flame retardant, a crystal nucleating agent, and the like can be appropriately blended.

  In addition, a known inorganic or organic filler can be blended in the antistatic resin composition of the present invention. The filler used here is glass fiber, glass flake, glass fiber milled fiber, glass powder, glass bead, hollow glass bead, carbon fiber, carbon fiber milled fiber, silver, copper, brass, iron, etc. Powder or 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, hextrite, zinc oxide whisker, titanium There are potassium acid whisker, aluminum borate whisker, plate-like alumina, plate-like silica, and organically treated smectite, aramid fiber, phenol resin, polyester fiber, etc., these are used alone or in combination of two or more. Can be used

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 said inorganic or organic filler is normally used in the range of 1-200 mass parts with respect to 100 mass parts of antistatic resin composition of this 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,
An ethylene / (meth) acrylic acid methyl copolymer, an ethylene / (meth) acrylic acid copolymer, an epoxy resin, a phenol resin, a urea resin, a phenoxy resin, or 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 may be added all 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. In addition, when a kneading machine such as a kneading extruder or a Banbury mixer is attached to a calendar molding, T-die extrusion molding, inflation molding machine or the like, the antistatic resin composition of the present invention is obtained in advance by the kneading. It is also possible to obtain a molded product while obtaining the antistatic resin composition of the present invention using the above-mentioned kneader.

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 product, a multilayer product laminated with other materials, or a sheet and film laminated with an adhesive or the like. Furthermore, a known gas barrier film can be formed on the sheet and film.

When a multilayer sheet or a multilayer film is molded using the antistatic resin composition of the present invention, the antistatic resin composition of the present invention is a two-layer sheet or film with another material, or the other material is an intermediate layer. A three-layer sheet or a film can be used. As the other material used here, a material made of a known polymer can be used, but since the adhesiveness between layers is excellent when the component (A), the component (E), etc. of the present invention are used, Such a multilayer sheet or film is a preferred embodiment in the present invention. In the case of using a material having insufficient adhesion between layers, a known adhesive layer can be interposed. Moreover, what mixed the said inorganic or organic filler can also be used from the objective of improving the rigidity and heat resistance of a sheet | seat and a film.
In the multilayer sheet, the thickness of the layer made of the antistatic resin composition of the present invention is preferably 10 μm or more, more preferably 50 μm or more, and particularly preferably 80 μm or more for the purpose of stably developing antistatic properties. . A preferable method for obtaining such a multilayer sheet and film is coextrusion by T-die or coextrusion by inflation. The sheet thus obtained can be formed into a molded article such as a tray by vacuum forming or the like as necessary.

  When vacuum forming is performed using a multilayer sheet having the antistatic resin composition of the present invention as one layer and a polypropylene resin as another layer or an intermediate layer, as the polypropylene resin as the other layer or intermediate layer, It is preferable to use a melt flow rate (measured at 230 ° C. under a load of 2.16 kg in accordance with JIS K7210: 1999) of 1.0 g / 10 min or less, more preferably a melt flow rate (according to JIS K692-2). It is preferable to use a combination of 10% to 30% of polyethylene having a 1.0 g / 10 min or less (measured at 190 ° C. and 2.16 kg load).

In the case of producing a pressure-sensitive adhesive sheet or film using a sheet or film comprising the antistatic resin composition of the present invention as a base material, for the purpose of improving the adhesiveness to the pressure-sensitive adhesive or the primer layer, the control of the present invention is used. Various known treatments such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, UV treatment, ion bombardment treatment, solvent treatment and the like can be performed on the surface of the sheet or film made of the electrically conductive resin composition.
Furthermore, for the purpose of improving the adhesive force between the sheet or film comprising the antistatic resin composition of the present invention and the pressure-sensitive adhesive, either directly or on the surface of the sheet or film comprising the antistatic resin composition of the present invention. A primer layer can be formed on the treated surface. Specifically, a resin such as polyethyleneimine, polyurethane, or acrylic resin is formed on the surface as a very thin layer having a thickness of about 0.1 μm to 10 μm. Usually, it can be formed by applying as a solvent (including water) solution and drying.

In addition to emulsion type and organic solvent type adhesives that can be applied by screen method, gravure method, mesh method, bar coating method, etc. to form an adhesive layer, extrusion lamination method, dry lamination method, co-extrusion method There is a hot-melt type that forms an adhesive layer with the like, and any of them can be used. Moreover, although the thickness of an adhesive is not specifically limited, Usually, it is the range of about 1-100 micrometers.
The structure of each layer of the multilayer sheet of the present invention is not particularly limited, and for example, it may be foamed or hollow. When foaming the layer of the other material, for example, the layer made of the component (A), the foaming agent is not particularly limited. For example, a known foaming agent used for a foamed polypropylene resin or a foamed polyethylene resin. Can be used. Specific examples of the blowing agent include inorganic blowing agents such as carbon dioxide, air and nitrogen, volatile blowing agents such as aliphatic hydrocarbons and halogenated hydrocarbons, azodicarbonamide (ADCA), dinitrosopentamethylenetetraamine, Examples include decomposable foaming agents such as azobisisobutyronitrile, hydrazodicarbonamide, and sodium bicarbonate. These can be used alone or in admixture of two or more. Of these, it is preferable to use a decomposable foaming agent that allows easy adjustment of the molding temperature and the amount of foaming. Moreover, there is no restriction | limiting in particular in the usage-amount of a foaming agent, However, In the case of a decomposition-type foaming agent, it is preferable that it is 0.1-10 mass parts with respect to 100 mass parts of resin compositions for foam molding.
When the first antistatic resin composition of the present invention is used as a surface layer of the foamed product, 40 to 80% by mass of the olefin resin (A) and 20 to 60% by mass of the block copolymer (B) (However, the total of the component (A) and the component (B) is 100% by mass), and the lithium salt (C) with respect to the total of 100 parts by mass of the component (A) and the component (B). The composition containing 0.01-5 mass parts can be used conveniently. Moreover, when using the 2nd antistatic resin composition of this invention as a surface layer of the said foaming goods, the said olefin resin (A) 7-30 mass%, the said block copolymer (B) 20-60 mass %, The elastomer (D) 15 to 50% by mass, and the styrenic resin (E) 5 to 20% by mass (provided that the components (A), (B), (D) and (E) ) Component is 100% by mass), and the lithium salt (C) is 0.01% with respect to a total of 100 parts by mass of the component (A), component (B), component (D) and component (E). A composition containing ˜5 parts by mass can be suitably used.

  The molded product thus obtained includes cases such as a relay case, wafer case, reticle case, mask case, liquid crystal tray, chip tray, hard disk (HDD) tray, CCD tray, IC tray, organic EL tray, optical Used in clean rooms such as pickup-related trays, LED trays, memory trays, carriers such as IC carriers, polarizing films, light guide plates, protective films such as various lenses, underlay sheets when polarizing films are cut, and partition plates Sheets or films, vending machine internal parts, anti-static bags used for liquid crystal panels, hard disks, plasma panels, plastic cardboard, liquid crystal panels, soft cases for transporting plasma panels, etc. Can be used in the field of materials That.

  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. Various measurements in the examples and comparative examples were based on the following methods.

[1] 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 rubber-like polymer latex used for forming the component (E-1) was measured by a light scattering method. The measuring machine used was LPA-3100 manufactured by Otsuka Electronics Co., Ltd., and the Mummant method was used with 70 times integration. It was confirmed with an electron microscope that the particle diameter of the dispersion-grafted rubber polymer particles in the component (E) was almost the same as the latex particle diameter.
(3) Graft ratio of component (E): According to the method described above.
(4) The intrinsic viscosity [η] of the acetone-soluble component of component (E);
(5) Component (D) (polymer bound styrene content, vinyl bond content, number average molecular weight, and hydrogenation rate);
(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;
(6-1) Antistatic property-1
Using a molded article (dimensions: 2.4 mm × 76 mm × 127 mm), +5000 V was applied under conditions of 23 ° C. and humidity of 12% RH using STATIC DECAY METER 406D manufactured by ETS USA according to FTMS-101 (US federal test standard). After that, the time (second) until grounding and decaying to 50V was measured.
(6-2) Antistatic-2
Using a molded product (a disk with dimensions of 2.1 mm x 100 mmφ), the surface resistivity (Ω / □) after standing for 24 hours under 23 ° C and 50% RH conditions in accordance with JIS K6911 Measurement was performed using MCP-HT450.
(7) Chemical resistance;
A 1% strain was applied to the molded product (dimensions 2 mm × 40 mm × 160 mm), dioctyl phthalate (DOP) was applied, and the surface state of the molded product after being left at 23 ° C. for 72 hours was visually evaluated based on the following evaluation criteria. .
○: No change Δ; Microcrack generation ×; Large crack generation or breakage (8) Surface appearance;
The surface of the molded product (a disk having dimensions of 2.1 mm × 100 mmφ) was visually evaluated according to the following criteria.
◎: Very good smooth surface ○: Good appearance with smooth surface Δ: The surface is slightly smooth but the appearance is practically no problem ×: The surface is not smooth and the appearance is bad (9) Impact resistance;
(9-1) Impact resistance-1
In accordance with ISO 179, Charpy impact strength (KJ / m ² ) was measured using a molded product specified in the ISO standard.
(9-2) Impact resistance-2
Using a molded product (dimensions 2.4 mm × 100 mm × 100 mm), DuPont impact strength (kgf · cm) was measured in accordance with ASTM-D2794.
(10) A molded product having a surface area of 88 cm ² was immersed in 88 cm ³ of eluted ion ultrapure water, and ions were eluted from the molded product at 80 ° C. for 60 minutes. Using this extracted water, the total amount of sodium ions and potassium ions was measured by ion chromatography. The result was converted to a unit area of the molded product and expressed as μg / cm ² .
(11) thermal stability;
Antistatic property-1 Visually observe the degree of discoloration of the molded product after being left in a 90 ° C atmosphere for 5 days and the molded product before being left in a 90 ° C atmosphere based on the following criteria. evaluated.
○: No discoloration or little discoloration ×: Large discoloration

[2] Component (1) (A) component of antistatic resin composition; Olefin resin The following were used as the olefin resin of the component (A) of the present invention.
A1: Novatec PP FY6C (trade name) manufactured by Nippon Polypro Co., Ltd.
Homotype polypropylene, melt flow rate 2.4 g / 10 min A2; Novatec PP MA3AH (trade name) manufactured by Nippon Polypro
Homotype polypropylene, melt flow rate 10 g / 10 min A3; Novatec PP EG6D (trade name) manufactured by Nippon Polypro
Random type polypropylene, melt flow rate 1.9g / 10min A4; Novatec PP MG3ATB (trade name) manufactured by Nippon Polypro
Random type polypropylene, melt flow rate 10 g / 10 min A5; Novatec PP EA9BT (trade name) manufactured by Nippon Polypro
Homotype polypropylene, melt flow rate 0.5 g / 10 min A6; Novatec HD HB530 (trade name) manufactured by Nippon Polyethylene
High density polyethylene, melt flow rate 0.3 g / 10 min A7; Novatec LD HJ560 (trade name) manufactured by Nippon Polyethylene
High density polyethylene, melt flow rate 7g / 10min A8; Harmolex NF464N (trade name) manufactured by Nippon Polyethylene
Metallocene polyethylene, melt flow rate 2.0 g / 10 min A9; TOPAS 8007X10 (trade name) manufactured by Polyplastics
Ethylene-norbornene copolymer (glass transition temperature 80 ° C)
A10: Novatec LD LF122 (trade name) manufactured by Japan Polyethylene Corporation
Low density polyethylene, melt flow rate 0.3g / 10min

(2) Component (B-1) Production Example 1: Polypropylene-polyethylene glycol block copolymer Low molecular weight polypropylene (Mn 2,500) 80 obtained by heat degradation of high molecular weight polypropylene in a stainless steel autoclave Then, the mixture was melted at 160 ° C., 7 parts of maleic anhydride and 14 parts of 12-aminododecanoic acid were added, and the mixture was reacted at 160 ° C. for 1 hour with stirring under nitrogen gas. Then, reaction was performed at 200 degreeC for 20 hours, and the polyolefin block (Ba) was obtained. The acid value of (Ba) was 32.1, and Mn was 2,800.
A stainless steel autoclave containing 64 parts of (B-a), 36 parts of polyethylene glycol (Mn2,000), 0.3 part of an antioxidant (trade name “Irganox 1010”, manufactured by Ciba Geigy) and 0.5 part of zirconium acetate. In addition, the polymer was polymerized for 4 hours under conditions of 230 ° C. and reduced pressure of 1 mmHg or less to obtain a polymer containing neither sodium nor potassium.
This polymer was taken out as a belt and pelletized to obtain a block polymer (B1). The Mn of the block polymer (B1) was 25,000. Moreover, from this Mn and ¹ H-NMR analysis, the average repeat number of the block polymer (B1) was 5.0.
(B-2) Production Example 2 When adding sodium compound-containing polypropylene-polyethylene glycol block copolymer (Ba) component, polyethylene glycol, and antioxidant to the autoclave, 8 parts of sodium dodecylbenzenesulfonate was added simultaneously. Except for the above, polymerization was carried out in the same manner as in Production Example 1 to obtain a polymer having a sodium content of 4,000 ppm. Furthermore, it pelletized by the method similar to manufacture example 1, and obtained block polymer B2.

(3) (C) component The following were manufactured by Sanko Chemical Co., Ltd. as the (C) component of the present invention.
C1: Sanconol AQ-50T (trade name) 50% aqueous solution of lithium trifluoromethanesulfonate.
C2: Sanconol 0862-20T (trade name) 20% dibutoxyethoxyethyl adipate solution of lithium trifluoromethanesulfonate.

(4) Component (4-1) Production Example 3: Styrene-butadiene radial teleblock copolymer stirrer and jacketed autoclave were dried and purged with nitrogen, and 2.75 parts of cyclohexane and tetrahydrofuran were added in a nitrogen stream. did. 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 to conduct a polymerization reaction for 60 minutes (second stage), and a mixture of 3 parts of styrene and 20 parts of butadiene was added to conduct a polymerization reaction for 60 minutes (3). In the second stage), 29 parts of butadiene was further added and polymerization was completed until the conversion reached 100%. After adding 0.1 part of silicon tetrachloride as a coupling agent, the coupling reaction was completed. After completion of the polymerization, 0.3 part of 2,6-di-tert-butylcatechol is added to 100 parts of the block copolymer obtained above, and then the solvent is removed to couple the coupling type having a tapered block. A styrene-butadiene block copolymer D1 was obtained. This had a styrene content of 31% and a number average molecular weight of 200,000.

(4-2) Production Example 4: A fully hydrogenated styrene-butadiene block copolymer stirrer and a jacketed autoclave were dried and purged with nitrogen, and a cyclohexane solution containing 30 parts of styrene was charged. Next, n-butyllithium was added and polymerized at 70 ° C. for 1 hour, and then a cyclohexane solution containing 40 parts of butadiene was added and polymerized for 1 hour.
Thereafter, a cyclohexane solution containing 30 parts of styrene was added, and a part of the block polymer solution obtained by polymerization for 1 hour was sampled, and 2,6-di-tert-butylcatechol was added to 100 parts of the block copolymer. 3 parts were added, and then the solvent was removed by heating. The styrene content was 60%, the 1,2-vinyl bond content of the polybutadiene portion was 35%, and the number average molecular weight was 74,000. A solution obtained by reacting titanocene dichloride and triethylaluminum in cyclohexane was added to the remaining block copolymer solution, and a hydrogenation reaction was performed at 50 ° C. under a hydrogen pressure of 50 kgf / cm ² for 3 hours. 0.3 part of 2,6-di-tert-butylcatechol was added to 100 parts of the block copolymer, and then the solvent was removed to obtain a polymer D2 having a butadiene part hydrogenation rate of 100%.

(5) (E) component (5-1) Production Example 5: ABS resin A glass flask having an internal volume of 7 L equipped with a stirrer, in a nitrogen stream, 75 parts of ion-exchanged water, 0.5 part of potassium rosinate, tert-dodecyl mercaptan 0.1 part, polybutadiene latex (average particle size: 2000 kg, gel content: 85%) 30 parts (solid content), butadiene-styrene random polymer latex (average particle size: 6000 kg, styrene content 25%) ) 10 parts (solid content), 15 parts of styrene and 5 parts of acrylonitrile were added, and the temperature was raised with stirring. When the internal temperature reached 45 ° C., a solution in which 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate and 0.2 parts of glucose were dissolved in 20 parts of ion-exchanged water was added. 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 for 3 hours. Then, the polymerization was continued for another hour, and 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 E1. The graft ratio of this resin E1 was 68%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g.

(5-2) Production Example 6: AS 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 75 parts of styrene and 25 parts of acrylonitrile were added to the first reaction vessel. 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 the intrinsic viscosity [η] 0.48 dl / g of styrene resin E2 was obtained.

(5-3) Production Example 7; rubber-reinforced styrene resin
(5-3-1) Production of rubber-like polymer (E3a) A stirrer and a jacketed autoclave were dried and purged with nitrogen, and cyclohexane and butadiene 20 parts solution were added. Subsequently, n-butyllithium was added and isothermal polymerization was performed at 50 ° C. When the conversion rate reached 100%, 0.75 parts of tetrahydrofuran and 65 parts of butadiene were added, and the temperature was increased from 50 ° C to 80 ° C. When the conversion reached 100%, 15 parts of styrene was added, and a polymerization reaction was further performed to obtain an A-B1-B2 triblock copolymer before hydrogenation. The resulting block polymer had a styrene block (A) content of 15%, a butadiene block (B1) content of 65%, a butadiene block (B2) content of 20%, and a 1,2-vinyl content of 35%. And a polymer having a number average molecular weight of 200,000 consisting of a butadiene block (B2) having a 1,2-vinyl content of 10%.
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 carried out at 50 ° C. under a hydrogen pressure of 50 kgf / cm ² until the hydrogenation rate was almost 100%, to obtain a rubber polymer E3a.

(5-3-2) Production of Rubber Reinforced Styrene Resin (E3) After substituting a stainless steel autoclave equipped with a ribbon blade with nitrogen, the polymer E3a previously made into a homogeneous solution using toluene as a solvent in a nitrogen stream was prepared. 28 parts (solid content), 10.8 parts of styrene, 7.2 parts of acrylonitrile, 54 parts of methyl methacrylate, 120 parts of toluene, and 0.1 part of tert-dodecyl mercaptan were charged and heated with stirring. When the internal temperature reaches 50 ° C., 0.5 part of benzoyl peroxide and 0.1 part of dicumyl peroxide are added, and the temperature is further increased. After reaching 80 ° C., the temperature is controlled to be constant at 80 ° C. A polymerization reaction was performed. It took 1 hour from the 6th hour after the start of the reaction, the temperature was raised to 120 ° C., and the reaction was further completed for 2 hours. The conversion was 97%.
After cooling to 100 ° C, 0.2 part of 2,2-methylenebis-4-6-tert-butylphenol was added, the reaction mixture was extracted from the autoclave, unreacted substances and solvent were distilled off by steam distillation, The polymer was pelletized using a tipped extruder to obtain a polymer E3. The graft ratio of this product was 45%, and the intrinsic viscosity [η] of the acetone-soluble component was 0.45 dl / g.

(5-4) Production Example 8; rubber-reinforced styrene resin
Except for using 19 parts of ethylene / propylene rubber (trade name “EP84”, manufactured by JSR) instead of rubber polymer E3a, 57 parts of styrene and 24 parts of acrylonitrile instead of styrene / acrylonitrile / methyl methacrylate, Polymerization reaction was carried out in the same manner as in Production Example 8, and a polymer E4 having an ethylene / propylene rubber content of 20%, a graft ratio of 55%, and an acetone-soluble intrinsic viscosity [η] of 0.45 dl / g was obtained. Obtained.

(6) Other components;
The following were used as other components for improving antistatic properties.
F1; nonionic antistatic agent; electro stripper TS-5 (trade name) manufactured by Kao Corporation glycerin ester F2; zinc oxide whisker; Panatetra WZ-05F1 (trade name) manufactured by Matsushita Electric Industrial Co., Ltd.

Examples 1-18 and 26-31, Comparative Examples 1-10
Each component was mixed by a Henschel mixer at the blending ratios shown in Table 1-1 and Table 1-2, and then melt-kneaded using a vented twin screw extruder (cylinder setting temperature 220 ° C.) to form a pellet. In addition, when the said F2 component was used among other components, it inject | poured from the middle of the extruder. The pellets obtained are sufficiently dried and then injection molded (cylinder setting temperature 220 ° C.) using the pellets to evaluate antistatic properties, chemical resistance, impact resistance, molded product surface appearance, and thermal stability. A test piece was obtained. The evaluation results are shown in Table 1-1 and Table 1-2.

Examples 19-22, 32 and 33
Each component was mixed by a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 2, and then melt-kneaded using a vented twin-screw extruder (cylinder setting temperature 220 ° C.) to be pelletized. In addition, when the said F2 component was used among other components, it inject | poured from the middle of the extruder. After sufficiently drying the obtained pellets, the front and back layers (each thickness 0.1 mm) made of this pelletized antistatic resin composition, and the core material made of the composition of the blending ratio shown in Table 2 ( A three-layer sheet (thickness: 1.0 mm) comprising a thickness of 0.8 mm was produced by a multilayer extrusion apparatus with a T-die (processing temperature 190 to 240 ° C.).
Using the obtained three-layer sheet, the antistatic property, chemical resistance, impact resistance, surface appearance, eluted ions, and thermal stability were measured according to the evaluation methods. The evaluation results are shown in Table 2.
Moreover, when vacuum forming (heater temperature 400 ° C., preheating time 30 to 45 seconds) was performed using the above three-layer sheet, a tray molded product excellent in surface appearance was obtained.

Examples 23-25
Each component was mixed by a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 3, and then melt-kneaded using a twin-screw extruder with a vent (cylinder setting temperature 220 ° C.) to form a pellet. In addition, when the said F2 component was used among other components, it inject | poured from the middle of the extruder. After the obtained pellets were sufficiently dried, the pelletized antistatic resin composition was subjected to inflation (170 ° C.) to obtain a film having a thickness of 50 μm.
Using the obtained film, the antistatic property, surface appearance, eluted ions, and thermal stability were measured according to the evaluation method. The evaluation results are shown in Table 3.

Examples 34-37
Each component was mixed by a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 3, and then melt-kneaded using a twin-screw extruder with a vent (cylinder setting temperature 220 ° C.) to form a pellet. After sufficiently drying the obtained pellets, an azodicarbonamide-based foaming agent is added to the front and back layers (each having a thickness of 30 μm) made of the pelletized antistatic resin composition and the composition having the blending ratio shown in Table 3. A three-layer sheet (thickness 3 mm) composed of a core material that was foamed approximately twice as a mixture was produced with a multilayer extrusion apparatus with a T-die (processing temperature 180-200 ° C.).
Using the obtained three-layer sheet, antistatic properties, chemical resistance, surface appearance, eluted ions, and thermal stability were measured according to the evaluation methods. The evaluation results are shown in Table 3.

From the results described in Table 1-1 and Table 1-2, the following is clear.
Examples 1 to 7 and 26, and Comparative Examples 1 to 4 are examples and comparative examples relating to the first antistatic resin composition of the present invention. These examples are antistatic and chemical resistant. Excellent in surface properties, molded product surface appearance and elution ionicity.
On the other hand, Comparative Example 1 is an example in which the amount of the component (C) used in the present invention is small outside the scope of the invention, and the antistatic property is poor. Comparative Example 2 is an example in which the amount of component (A) used in the present invention is large outside the scope of the invention, and the amount of component (B) used is small outside the scope of the invention, and the antistatic property is poor. 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 the amount of the component (B) used is large outside the scope of the invention. Stability is inferior. Comparative Example 4 is an example in which the amount of eluted ions is greater than the range of the present invention.
Examples 8 to 18 and 27 to 31 and Comparative Examples 5 to 10 are examples and comparative examples relating to the second antistatic resin composition of the present invention, and these examples are antistatic, Excellent chemical resistance, molded product surface appearance, thermal stability, elution ionicity and impact resistance.
On the other hand, Comparative Example 5 is an example in which the amount of the component (C) of the present invention used is small outside the scope of the invention, and the antistatic property is inferior. Comparative Example 6 is an example in which the amount of component (C) used in the present invention is large outside the scope of the invention, and the molded product surface appearance and impact resistance are poor. Comparative Example 7 is an example in which the amount of eluted ions is greater than the range of the present invention. Comparative Example 8 is an example in which the amount of the component (D) used in the present invention is small outside the scope of the invention, and the impact resistance is poor. Comparative Example 9 is an example in which the amount of the component (E) used in the present invention is large outside the scope of the invention, and the antistatic property and chemical resistance are poor. Comparative Example 10 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.
From the results described in Table 2, the following is clear.
Examples 19-22, 32, and 33 are examples relating to sheets made of the second antistatic resin composition of the present invention, and are antistatic, chemical resistance, sheet surface appearance, impact resistance, and eluted ions. Excellent in vacuum formability.
From the results described in Table 3, the following is clear.
Examples 23 to 25 are examples relating to the film made of the first antistatic resin composition of the present invention, and are excellent in antistatic property, film surface appearance and elution ionicity. Examples 34 to 37 are examples relating to molded articles obtained by laminating a film made of the second antistatic resin composition of the present invention on a foamed base material, and antistatic properties, chemical resistance, surface appearance, Excellent thermal stability and elution ionicity.

  The antistatic resin composition of the present invention is superior in antistatic properties, chemical resistance, molded product surface appearance, thermal stability, and has low elution ions, which requires high performance. It can be applied as various parts in the vehicle field, electric / electronic field, OA / home appliance field, sanitary field, and the like.

Claims (6)

A multilayer molded article in which a sheet or film made of an antistatic resin composition is laminated with another material,
The antistatic resin composition comprises the following (A) component 7 to 91% by mass, the following (B) component 2 to 60% by mass, the following (D) component 2 to 50% by mass, and the following (E) component: 5 to 50% by mass (provided that the total of the components (A), (B), (D) and (E) is 100% by mass), and further the component (A), (B ) Component, (D) component, and (E) component, a composition containing 0.01 to 5 parts by mass of the following component (C), and formed by molding the composition. The surface resistivity (measured under conditions of 23 ° C. and 50% RH) of the molded body is 1 × 10 ¹¹ Ω / □ or less, and the elution amounts of sodium ions and potassium ions (measured under extraction conditions at 80 ° C. for 60 minutes) Ri der There 3μg / cm ² or less,
It said other material is a multilayer molded article, characterized in der Rukoto polypropylene resin composition.
(A) Component: Olefin resin (however, excluding component (B)).
(B) Component: A block copolymer containing an olefin polymer block and a hydrophilic polymer block.
(C) Component: Lithium salt.
Component (D): at least one elastomer selected from 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, and a hydrogenated product thereof.
Component (E): a rubber-reinforced styrene polymer (E-1) obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of a rubbery polymer, and / or the vinyl monomer Styrenic resin comprising a (co) polymer (E-2) as a monomer. The multilayer molded article according to claim 1, wherein the total content of sodium and potassium of the component (B) is 0 to 1000 ppm. The component (C) is at least one selected from the group consisting of lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide lithium and tris (trifluoromethanesulfonyl) methane lithium. Or the multilayer molded article of 2. The multilayer molded article according to any one of claims 1 to 3, wherein the component (B) contains sodium and / or potassium in the form of a sulfonate. The multilayer molded article according to claim 1 , wherein the polypropylene resin composition has a melt flow rate (measured at 230 ° C and a load of 2.16 kg in accordance with JIS K7210: 1999) of 1.0 g / 10 min or less. The polypropylene resin composition is a combination of 10 to 30% of polyethylene having a melt flow rate (measured at 190 ° C. under a load of 2.16 kg according to JIS K6922-2) of 1.0 g / 10 min or less. The multilayer molded article according to claim 5 .