WO2007119339A1 - Antistatic resin composition and molded article - Google Patents

Antistatic resin composition and molded article Download PDF

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Publication number
WO2007119339A1
WO2007119339A1 PCT/JP2007/054895 JP2007054895W WO2007119339A1 WO 2007119339 A1 WO2007119339 A1 WO 2007119339A1 JP 2007054895 W JP2007054895 W JP 2007054895W WO 2007119339 A1 WO2007119339 A1 WO 2007119339A1
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WIPO (PCT)
Prior art keywords
component
mass
resin composition
sodium
antistatic resin
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PCT/JP2007/054895
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French (fr)
Japanese (ja)
Inventor
Masaaki Mawatari
Naoki Nishiyama
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Techno Polymer Co., Ltd.
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Publication date
Priority claimed from JP2007040509A external-priority patent/JP5361135B2/en
Priority claimed from JP2007040510A external-priority patent/JP5361136B2/en
Application filed by Techno Polymer Co., Ltd. filed Critical Techno Polymer Co., Ltd.
Priority to CN2007800172167A priority Critical patent/CN101443404B/en
Publication of WO2007119339A1 publication Critical patent/WO2007119339A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes
    • C08L53/025—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes modified
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof

Definitions

  • the present invention is 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 molding comprising the antistatic resin composition. Related to goods.
  • Polyolefin resins such as polypropylene are excellent in chemical resistance, heat resistance, fluidity, etc., and are therefore widely used in the electrical / electronic field, the consumer electronics field, the vehicle field, the sanitary field, and the like.
  • this resin has a drawback that it is easily charged, it is used in a device that is damaged by static electricity, such as a liquid crystal display device, a plasma display, a peripheral component of a semiconductor, or a clean nore. Or, it was difficult to use for various parts, sheets, films, etc. to be handled.
  • Patent Document 1 and Patent Document 2 propose that a specific antistatic agent is blended, but the antistatic property is not long enough and the antistatic property is sufficient.
  • Patent Document 3 proposes that a block copolymer composed of a polyolefin block and a hydrophilic polymer block is blended with a polyolefin resin. There was a problem that was not fully expressed.
  • electrolyte components such as sodium salt and potassium salt of alkylbenzene sulfonic acid are generally added to the block copolymer during or after polymerization.
  • electrolyte components such as sodium salt and potassium salt of alkylbenzene sulfonic acid are generally added because the antistatic effect is not sufficient.
  • Molded articles composed of such a composition containing a block copolymer and an olefin resin are used for elution of the above electrolyte components in applications in the liquid crystal field, hard disk field, organic EL field, LED field, etc.
  • resin compositions that satisfy both antistatic properties and the amount of eluted ions have not been obtained.
  • Patent Document 1 Japanese Patent Laid-Open No. 4258258
  • Patent Document 2 Japanese Patent Laid-Open No. 2000-313875
  • Patent Document 3 Japanese Patent Laid-Open No. 2001-278985 Disclosure of the invention
  • 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 the antistatic resin composition.
  • the present inventors have added a predetermined amount of lithium salt to the composition containing the olefin resin and the block copolymer.
  • a block copolymer having a low content of sodium and / or potassium or substantially free of these elements may be used, or the block copolymer may be used in combination with other block copolymers.
  • the amount of eluted ions was sufficiently reduced to be suitable for the above-mentioned use.
  • an antistatic resin composition giving a molded product can be obtained. Further, the composition is further blended with a block copolymer containing a polymer block composed of a styrenic resin and an aromatic bur compound and a polymer block composed of a conjugated diene compound, or a hydrogenated product thereof. As a result, the present invention was completed.
  • a composition comprising 40 to 98% by mass of the following (A) component and 2 to 60% by mass of the following (B) component (provided that the above (A) component and (B) )
  • the total of the components is 100% by mass
  • the surface resistivity (measured under the conditions of 23 ° C and 50% RH) of the molded product formed from the composition is ⁇ ⁇ ⁇ ⁇ ⁇
  • an elution amount of sodium ions and potassium ions is 3 ⁇ g / cm 2 or less (hereinafter referred to as “ A first antistatic resin composition ”)" is provided.
  • Component (B) A block copolymer containing an olefin polymer block and a hydrophilic polymer block.
  • the component (B) and A block copolymer (B-1) having a total content of sodium and potassium of 500 to 8000 ppm and a block copolymer (B-2) having a total content of sodium and potassium of 0 to 100 ppm In the range of 1Z99 to 90Z10 in terms of mass ratio of the block copolymer (B-1) to the block copolymer (B-2), and the blending of the block copolymer (B-1)
  • the amount is set to:! To 15% by mass of the total amount of the above component ( ⁇ ) and the above component ( ⁇ ).
  • the component (ii), particularly sodium and / or potassium contained in the block copolymer (B-1) is preferably in the form of a sulfonate.
  • the (ii) component and (ii) component Lithium salt ( ⁇ ) 0.01 to 5 parts by mass is added to a total of 100 parts by mass.
  • the total content of sodium and potassium of the component (ii) is preferably 0 to 100 ppm, and more preferably 0 to lOOppm.
  • the component (B) contains sodium and / or potassium, it is preferable to contain them in the form of a sulfonate.
  • the surface resistivity (measured under conditions of 23 ° C and 50% RH) of ⁇ is less than ⁇ ⁇ ⁇ ⁇ ⁇ / mouth, and the amount of sodium ions and potassium ions dissolved (80 ° C)
  • An antistatic resin composition (hereinafter referred to as “second antistatic resin composition”) is provided, wherein the antistatic resin composition (measured under extraction conditions for 60 minutes) is 3 ⁇ g / cm 2 or less.
  • Component (B) A block copolymer containing an olefin polymer block and a hydrophilic polymer block.
  • Component (D) rubber-reinforced styrene polymer (D_l) obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of a rubbery polymer, and / or the vinyl polymer Styrenic resin composed of monomeric (co) polymer (D-2).
  • the block copolymer (B-1) and the block copolymer (B-2) are used as the component (B).
  • the blending amount of the polymer (B-1) is 1 to 15% by mass of the total amount of the component (A), the component (B), the component (C) and the component (D).
  • sodium and / or potassium contained in the component (B), especially the block copolymer (B_l) is in the form of a sulfonate.
  • Lithium salt (E) 0.01 to 5 parts by mass is added to 100 parts by mass in total of the above components (A), (B), (C) and (D).
  • the total content of sodium and potassium of the component (B) is preferably 0 to:! OOOOppm, more preferably 0 to! OOppm.
  • the component (B) contains sodium and / or potassium, it is preferable to contain them in the form of a sulfonate.
  • the lithium salt (E) when the lithium salt (E) is added, the lithium salt (E) includes lithium perchlorate, lithium trifluoromethanesulfonate, bis ( At least one selected from the group consisting of trifluoromethanesulfonino) imidolithium and tris (trifluoromethanesulfonyl) methane lithium is preferably used.
  • a molded article made of the above antistatic resin composition such as a sheet or a film.
  • the antistatic resin composition of the present invention is collectively referred to as “the antistatic resin composition of 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 even if the elution amount of any one of the ions is zero. However, the elution amount of both ions may exceed zero.
  • a block containing an olefin polymer block and a hydrophilic polymer block a block containing an olefin polymer block and a hydrophilic polymer block.
  • an antistatic resin composition in which a lock copolymer is blended with an olefin resin, a predetermined amount of lithium salt is added, and / or sodium and a plurality of block copolymers are used together as the block copolymer. Since the content of potassium is reduced, it gives a molded product with excellent chemical resistance, molded product surface appearance and thermal stability, and excellent balance between antistatic properties and the elution amount of sodium ions and potassium ions. An antistatic resin composition is obtained.
  • (co) polymerization means homopolymerization and copolymerization
  • (meth) acryl means acryl and / or methacryl, and refers to “(meth) acrylate”.
  • Component (A) relating to the antistatic resin composition of the present invention is an olefin resin (A).
  • the olefin resin (A) include olefin resins having at least one kind of olefins having 2 to 10 carbon atoms, and are (co) polymers excluding the component (B) described later. These olefin-based resins (A) can be used singly or in combination of two or more.
  • olefins used to form the olefin-based resin (A) include ethylene and propylene, butene_1, pentene-1, hexene-1, 1, methylbutene-1, 4, methylpentene_1, 3- Examples include olefins such as methylhexene_1, and cyclic olefins such as norbornene. These can be used alone or in combination of two or more. Of these, ethylene, propylene, butene-1, 1,3-methylbutene-1, 4-methylpentene-1, and norbornene are preferable.
  • olefin resin (A) examples include 4_methyl_1,4_hexagen, 5_methyl_1,4_hexagen, 7-methyl- Non-conjugated gens such as 1, 6-octadiene and 1, 9-decadiene are included.
  • polymers mainly containing propylene units such as polypropylene and propylene / ethylene copolymers, polyethylene and ethylene norbornene copolymers are preferred, and these may be used alone. , May be used in combination.
  • the above The propylene / ethylene copolymer includes a random copolymer and a block copolymer, and any of them can be used. However, it is particularly preferable to use a random type from the viewpoint of the appearance of the molded product surface.
  • the polyethylene any of high density polyethylene, low density polyethylene, straight chain low density polyethylene, and the like can be used.
  • 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 metamouth catalyst polymerization method.
  • 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.
  • the olefin-based resin (A) may or may not have crystallinity, but it is preferable to use at least one resin having a crystallinity of 10% or more by X-ray diffraction at room temperature.
  • melt flow rate measured according to JIS K7210: 1999 is preferably 0.01 to 500 g / 10 Min, more preferably 0.05 ⁇ : lOOg / 10 min.
  • melt flow rate measured according to JIS K6922-2 190 ° C, load 2.16kg
  • it is preferable between 0.01 and 500 g / 10 minutes, more preferably when it is ⁇ or 0.05-: lOOg / 10 minutes.
  • olefin-based resin of the present invention a resin in which various additives such as an antioxidant, a heat stabilizer and a lubricant are mixed can be used, or an unblended resin can be used. Depending on the application to be used, it may be preferable to use the component (A) which does not contain the above-mentioned various additives that are gas components generated from the molded product.
  • the amount of the component (A) constituting the first antistatic resin composition of the present invention is 40 to 98 in a total of 100% by mass of the components (A) and (B) of the present invention. mass 0/0, preferably from 45 to 97 mass 0/0, more preferably 45 to 95 weight 0/0, and particularly preferably 50 to 95 wt%. 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.
  • the amount of component (A) used is Of the total 100% by mass of component (A) and component (B), preferably 60 to 98% by mass, more preferably 65 to 97% by mass, still more preferably 65 to 95% by mass, and particularly preferably 70 to 95% by mass.
  • the amount used is less than 60% by mass, the chemical resistance and the molded product surface appearance tend to be inferior.
  • the amount of component (A) used is 100% by mass of component (A) and component (B), preferably 40 to 70% by mass, Preferably, it is 50 to 65% by mass.
  • 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 (B_a) and a hydrophilic polymer block (B_b), and sodium and / or potassium Those in which the content of is reduced are preferred.
  • the component (B) having a reduced sodium and / or potassium content for example, as the component (B), a block copolymer (B-1) having a high sodium and / or potassium content,
  • the block copolymer (B-1) has a lower sodium and / or potassium content, or a block copolymer (B-2) not containing these elements can be used in combination.
  • the ability to reduce the amount of sodium compound and / or potassium compound used at the time of polymerization, or component (B) produced without using the compound can also be used.
  • the component (B) of the present invention may be a diblock, or may be a multiblock of a triblock or more.
  • the olefin polymer block (Ba) is a (co) polymer of olefins. Examples of olefins used here include ethylene, propylene, butene-1, hexene_1, 3-methylbutene_1, 4-methylpentene_1, 3-methylhexene-1. In addition, cyclic olefins such as norbornene and the like are preferable, and ethylene, propylene, butene-1, 3-methylbutene_1, 4-methylpentene_1, and norbornene are preferable. Or a combination of two or more.
  • Gel of the olefin polymer block (B_a)
  • the number-average molecular weight in terms of polystyrene by permeation chromatography (GPC) is preferably ⁇ or 800 to 20,000, more preferably ⁇ or 1,000 to 10,000, particularly preferably ⁇ or 1,2000 to 6,000. is there.
  • the olefin polymer block ( ⁇ -a) is substantially bonded to the block (BB), and the bond includes 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 selected from the above, and has a structure in which these bonds are alternately and repeatedly bonded through these bonds.
  • the molecular end of the block (B_a) needs to be modified with a functional group having reactivity with the molecular terminal functional groups on the block (B_b).
  • These functional groups include carboxylic acid groups, hydroxyl groups, amino groups, acid anhydride groups, oxazoline groups, and epoxy groups.
  • the component (B_a) 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.
  • a radical catalyst, a metal oxidation catalyst, a Ziegler catalyst, a chidara It can be easily obtained by a method of (co) polymerizing the above olefin in the presence of a Natta catalyst, a meta-catacene catalyst or the like.
  • low molecular weight polyolefin obtained by thermal degradation of 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 mixture of a polyolefin that can be modified at both molecular ends, a polyolefin that can be modified at one end, a polyolefin that does not have a terminal group that can be modified, and a polyolefin. It is also preferred that the main component is polyolefin which can be modified at both ends.
  • the amount of double bonds in the polyolefin obtained by the thermal degradation method is preferably 1 to 40, more preferably 2 to 30, and particularly preferably 4 to 1,000 per 1,000 carbon atoms. There are 20 pieces.
  • the average number of double bonds per molecule is preferably 1. from the viewpoint of the formation of a repeating structure and from the viewpoint of antistatic properties, more preferably from 1.3 to 3, particularly preferably from 1.8 to 2. Two.
  • low molecular weight polyolefins having an average number of terminal double bonds per molecule of 1.5 to 2 can be easily obtained within a range of Mn force of 00 to 6,000 [for example, Masahide Murata Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].
  • a preferred method for imparting a functional group to the polyolefin obtained by these thermal degradation methods has a carbon-carbon double bond at the molecular end obtained by the thermal degradation method (B- In this method, the carbon-carbon unsaturated compound having the functional group described above is added to component a).
  • hydrophilic polymer of the block (B_b) component examples include polyethers, polyether-containing hydrophilic polymers, and anionic polymers.
  • polyether diol examples include polyether diol, polyether diamine, and modified products thereof.
  • polyether-containing hydrophilic polymer examples include polyether ester amide having a polyether diol segment, polyether amide imide having a polyether diol segment, polyether ester having a polyether diol segment, and polyether diamine. And polyether urethane having a segment of polyether diol or polyether diamine.
  • a dicarboxylic acid having a sulfonyl group and the above polyether are essential component units, and preferably 2 to 80, more preferably 3 to 60 sulfonyl groups in one molecule.
  • Anionic polymers having These may be linear or branched.
  • a particularly preferred component (Bb) is a polyether.
  • 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
  • n and n ′ are per hydroxyl group of the divalent hydroxyl group-containing compound.
  • n (OA 1 ) and n ′ (Aio) may be the same or different, and if they are composed of two or more oxyalkylene groups The combination form can be either block or random or a combination of these.
  • n and ⁇ are usually integers:! to 300, preferably 2 to 250, particularly preferably 10 to 100. Also, ⁇ and ⁇ may be the same or different.
  • Examples of the divalent hydroxyl group-containing compound include a compound containing two alcoholic or phenolic hydroxyl groups in one molecule, that is, a dihydroxy compound, specifically, a dihydric alcohol.
  • a dihydroxy compound specifically, a dihydric alcohol.
  • an aliphatic, alicyclic or aromatic divalent alcohol having 2 to 12 carbon atoms a divalent phenol having 6 to 18 carbon atoms and a tertiary amino group-containing diol.
  • aliphatic dihydric alcohol examples include alkylene glycols such as ethylene glycol and propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyldaricol, 1,12-dodecanediol, and the like. .
  • Examples of alicyclic dihydric alcohols include 1, 2_ and 1,3-cyclopentanediol, 1,2-, 1,3- and 1,4-cyclohexanediol, and 1,4-cyclohexane.
  • Xylene dimethanol and the like examples of the aromatic dihydric alcohol include xylene diol and the like.
  • Divalent phenols include monocyclic bivalent phenols such as hydroquinone, catechol, resorcin, urushiol, bisphenol ⁇ ⁇ ⁇ , bisphenol F, bisphenol S, 4, A "-dihydroxydiphenol 2, 2-butane, Examples thereof include bisphenols such as dihydroxybiphenyl and dihydroxydiphenyl ether, and condensed polycyclic divalent phenols such as dihydroxynaphthalene and binaphthol.
  • monocyclic bivalent phenols such as hydroquinone, catechol, resorcin, urushiol, bisphenol ⁇ ⁇ ⁇ , bisphenol F, bisphenol S, 4, A "-dihydroxydiphenol 2, 2-butane, Examples thereof include bisphenols such as dihydroxybiphenyl and dihydroxydiphenyl ether, and condensed polycyclic divalent phenols such as dihydroxynaphthalene and binaphthol.
  • 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 partially represented by the general formula (III): _CHR_CHR'_ [wherein, one of R and R 'is a group represented by the general formula (IV): -CH 0 (A 3 0) R ", and the other is H.
  • X is an integer of 1 to 10
  • R ′′ is H or an alkyl group having 1 to 10 carbon atoms, an aryl group, an anolenoquinaleolinole group, an arylalkyl group or an acyl group
  • a 3 is an alkylene group having 2 to 4 carbon atoms.
  • the remaining alkylene group may be an alkylene group having 2 to 4 carbon atoms
  • m (OA 2 ) And m ′ (A 2 0) may be the same or different
  • m and m ′ are preferably integers of 1 to 300, more preferably 2 to 250, 10 to: 100 power S preferred.
  • M may be the same as or different from m.
  • 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.
  • alkylene oxides 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. These two or more combined systems are used.
  • the bond type may be either random and / or block.
  • Preferred alkylene oxides are ethylene oxide alone and block and / or random additions in combination with ethylene oxide and other alkylene oxides.
  • the addition number of alkylene oxide 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 examples of the polyether diol represented by the general formula (ii) and the production method thereof are as follows:
  • a 4 in the general formula (V) is an alkylene group having 2 to 4 carbon atoms, p is an integer of 1 to 10, R 1 is H or an alkyl group having 1 to 10 carbon atoms, an arylene group, an alkyl aryl. A group, an arylalkyl group or an acyl group. ]
  • alkylene oxide having 2 to 4 carbon atoms used here, all of the above-mentioned ones can be used.
  • the preferred component (B) of the present invention can be obtained by polymerizing the olefin polymer block (B_a) and the hydrophilic polymer block (B_b) by a known method.
  • a known method for example, it is possible to produce the block (B_a) and the block (B_b) by performing a polymerization reaction at 200 to 250 ° C. under reduced pressure.
  • a known polymerization catalyst can be used.
  • a known polymerization catalyst can be used in the polymerization reaction, but preferable ones are tin-based catalysts such as monoptyltin oxide, antimony-based catalysts such as antimony trioxide and antimony dioxide, tetrabutyl titanate and the like. These are one or a combination of two or more selected from titanium-based catalysts, zirconium-based catalysts such as dinoleconium hydroxide, zirconium oxide, zirconyl acetate and the like, and organic organic acid salt catalysts.
  • the component (B), particularly the component (B-1) of the present invention includes a sodium and / or potassium-containing compound (B-11) for the purpose of improving antistatic properties.
  • These compounds have the ability to be contained by the method of polymerization of the component (B), particularly the component (B-1), after polymerization, or a combination thereof.
  • the preferred method is to allow these compounds to exist during polymerization. It is a method of containing.
  • component (B-1-1) examples include sodium and potassium organic acids, sulfonic acids, inorganic acid salts, and halides.
  • component (B-1-1) include sodium or potassium halides such as sodium chloride, potassium chloride, sodium bromide, potassium bromide; sodium perchlorate, Sodium or potassium inorganic acid salts such as potassium perchlorate, sodium or potassium organic acid salts such as sodium acetate, potassium acetate, sodium stearate, potassium stearate; octylsulfonic acid, dodecylsulfonic acid, tetradecylsulfonic acid, Alkyls such as stearinolesulfonic acid, tetracosylsulfonic acid, 2_ethylhexylsulfonic acid, etc.
  • sodium or potassium halides such as sodium chloride, potassium chloride, sodium bromide, potassium bromide
  • sodium perchlorate Sodium or potassium inorganic acid salts such as potassium perchlorate, sodium or potassium organic acid salts such as sodium acetate, potassium acetate, sodium stearate, potassium stearate
  • alkylsulfonic acid having 8 to 24 carbon atoms Sodium or potassium salt of alkylsulfonic acid having 8 to 24 carbon atoms; Sodium or potassium salt of aromatic sulfonic acid such as phenylsulfonic acid or naphthylsulfonic acid; Octylphenylsulfonic acid or dodecylphenylsulfonic acid Sodium salt or potassium salt of alkylbenzene sulfonic acid having 6 to 18 carbon atoms, such as dimethyl naphthyl sulfonic acid, diisopropyl naphthyl sulfonic acid, dibutyl naphthyl sulfone, such as dibutyl phenyl sulfonic acid, dinoyl phenyl sulfonic acid, etc.
  • aromatic sulfonic acid such as phenylsulfonic acid or naphthylsulfonic acid
  • Examples thereof include sodium salt or potassium salt of alkyl naphthalene sulfonic acid having 2 to 18 carbon atoms of alkyl group such as acid; sodium salt or potassium salt such as fluorinated sulfonic acid such as trifluoromethanesulfonic acid, and the like. These are one type alone. It can be used in combination of two or more kinds.
  • Particularly preferred component (B_ 1 _ 1) is a compound in the form of sodium and Z or potassium sulfonate, specifically, sodium salt of sulfonic acid or potassium of sulfonic acid It is a salt compound.
  • the component (B) of the present invention is composed of the component (B-1) and the component (B-2), the component (B-11) is the component (B-1) of the present invention.
  • the component (B-1) of the present invention is 0.1-20 mass parts with respect to a mass part, More preferably, it can be used in the range of 1-: 15 mass parts.
  • the total content of sodium and potassium in the component (B-1) of the present invention is preferably 500-800 Oppm, wherein the component (B-1) is the content of either element May be 0, or may contain both elements.
  • the total content of sodium and potassium in the component (B) is 0 to:! OOOppm 0 to 500 ppm is more preferable 0 to:! OOppm is particularly preferable.
  • the component (B) has a content of either one of sodium and potassium of 0. However, it may contain both elements.
  • the respective contents of sodium and potassium can be calculated from the amount added in the production of the composition of the present invention, or the composition of the present invention can be obtained by fluorescent X-ray analysis, atomic absorption spectrometry, etc. It can also be determined by measuring.
  • ingredients of the present invention (B- a) component / (B- b)
  • the preferred ratio of the components is in the range to 10 to 90/10 to 90 mass 0/0, more preferably 20 to 80 / 20 to 80 mass 0/0, JP Preferably, it is the range of 30-70 / 30-70 mass%.
  • Such a block polymer (B-1) can be produced, for example, by the method described in JP-A-2001-278985 and JP-A-200003-48990, and further, (B — 1)
  • the components are available as 300, 303 of Perezatsu 300 Series, 303, 230 of Pereztat 200 Series, etc.
  • the content of the sodium and / or potassium-containing compound (B-11) contained in the component (B_l) for the purpose of improving antistatic properties is reduced.
  • a component that does not contain the compound (B-1 1 1), and all of those described in the component (B-1) can be used. These can be used alone or in combination of two or more. Can be used in combination.
  • the component (B-2) can be obtained, for example, by reducing the amount of sodium and / or potassium compound (B-11) used during the polymerization of the component, or by performing polymerization without using the compound. It is done.
  • the total content of sodium and strong rhodium in the component (B-2) of the present invention is preferably 0 to:! OOppm, wherein the component (B-2) is any one of the elements
  • the content of may be 0, or may contain both elements.
  • the component (B) is used for the purpose of improving antistatic properties.
  • Component (B) is composed of component (B-1) and component (B-2), or composed of component (B-2) alone, so that component (B) having a low sodium and potassium content can be obtained.
  • component (B) having a low sodium and potassium content can be obtained.
  • the component (B) is 2 to 60% by mass, preferably 3 in the total of 100% by mass of the component (A) and the component (B). ⁇ 55 wt%, more preferably 5 to 55 wt%, particularly preferably 5 to 50 wt%, and if less than 2 wt%, the antistatic property is inferior, If it exceeds 60% by mass, the thermal stability is inferior, and in some cases, the amount of eluted ions may increase.
  • component (B) is a total of 100% by mass of component (A) and component (B), preferably 2 to 40% by mass, more preferably It is 3 to 35% by mass, more preferably 5 to 35% by mass, and particularly preferably 5 to 30% by mass. If it exceeds 40% by mass, the chemical resistance and the surface appearance tend to be inferior. In applications that require excellent antistatic properties and thermal stability, component (B) is a total of 100% by mass of component (A) and component (B), preferably 30-60% by mass, more preferably 35%. ⁇ 50% by weight.
  • component (B) When used as a surface layer of a foamed laminated sheet that has high antistatic properties and a smooth surface, and has a smooth surface, component (B) is a total of 100 masses of component (A) and component (B). %, Preferably 20 to 60% by mass, more preferably 30 to 50% by mass.
  • component (B) is composed of component (B-1) and component (B-2)
  • the ratio used is 1/99 as the mass ratio of component (B-1) to component (B-2). It is preferably in the range of ⁇ 90/10, more preferably 2/98 to 85/15, even more preferably 10/90 to 85/15, and even more ⁇ more preferred ⁇ or 15/85 ⁇ 80/20, specially preferred ⁇ 20/80 to 75/25, especially in this range, the balance between antistatic properties and the amount of ions eluted is excellent.
  • the amount of the component (B-1) used in the first antistatic resin composition of the present invention is 1 to 15 mass with respect to the total of 100% by weight of the components (i) and (ii). %, More preferably 3 to 13% by mass, still more preferably 5 to 10% by mass, and particularly preferably 5 to 9% by mass.
  • the surface resistivity (measured under conditions of 23 ° C. and 50% RH) can be obtained by composing the component ( ⁇ ) from the components ( ⁇ -1) and ( ⁇ -2). ⁇ ⁇ 1 ⁇ / mouth or less, preferably 5 ⁇ ⁇ ⁇ ⁇ / mouth or less, and elution amount of sodium ion and potassium ion (measured under extraction conditions at 80 ° C for 60 minutes) 3 xg / cm 2
  • a molded product that satisfies the following requirements and therefore has a high balance between antistatic properties and eluted ions is obtained.
  • the amount of the above (B_l) component was increased.
  • the elution ions from the molded product increased.
  • a molded body in which the antistatic property and the eluted ions are highly balanced can be used, for example, in the past, with the component (B 1) and the conventional component (B-2). It is obtained by using the component) together.
  • the elution amount of sodium ions and potassium ions is preferably 2 ⁇ g / cm 2 or less, more preferably 1 ⁇ g Zcm 2
  • the ability to reduce the following to S is positive.
  • the component (E) relating 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.
  • lithium salt (E) lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methane lithium, etc. are preferably used.
  • Lithium trifluoromethanesulfonate is preferred. These can be used alone or in combination of two or more. These are Sankonoru manufactured by Sanko Chemical Co., Ltd.
  • the ( ⁇ ) component is preferably used in the range of 0.01 to 5 parts by mass with respect to the total of 100 parts by mass of the ( ⁇ ) and ( ⁇ ) components. To 3 parts by mass, particularly preferably in the range of 0.3 to 2 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 if it exceeds 5 parts by mass, the impact resistance tends to decrease.
  • lithium salt ( ⁇ ) added to the first antistatic resin composition of the present invention, surface resistivity (measured under conditions of 23 ° C and 50% RH) 1 X 10 11 ⁇ / mouth or less 1 x 1 ⁇ ⁇ ⁇ / mouth or less, and sodium ion and potassium ion elution amount (measured under extraction conditions at 80 ° C for 60 minutes) 3 ⁇ g / cm 2 or less, preferably detection Therefore, it is possible to obtain a molded body that satisfies the impossibility requirement and therefore has a highly balanced antistatic property and eluted ions.
  • the blending amount of the component (B) was increased in order to improve antistatic properties, but in this case, the amount of ions eluted from the molded product was increasing.
  • a predetermined amount of lithium salt is blended, and preferably, sodium (N) is used as the component (B).
  • the second antistatic resin composition of the present invention further comprises (C) component and (D) component in the first antistatic resin composition, and the balance between antistatic properties and eluted ions is Improves and increases impact resistance.
  • the above-described olefin-based resins (A) can all be used, and these can be used alone or in combination of two or more.
  • Power S can be.
  • the amount of the component (A) used is the sum of the components (A), (B), (C) and (D) of the present invention. In 100% by mass, 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. . If the amount used is less than 7% by mass, the impact resistance and anti-static property are poor, and if it exceeds 91% by mass, the anti-static property and impact resistance are poor.
  • the amount of component (A) used is 100% by mass of component (A), component (B), component (C) and component (D).
  • 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.
  • the amount of component (A) used is 100% by mass of component (A), component (B), component (C) and component (D).
  • the amount is preferably 7 to 40% by mass, more preferably 10 to 35% by mass.
  • component (A) used is component (A), component (B) In the total 100% by mass of the component (C) and the component (D), preferably 7 to 30% by mass, more preferably 7 to 25% by mass.
  • the amount of component (B) used is 100% by mass in total of the components (A), (B), (C) and (D) of the present invention.
  • 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. If it exceeds mass%, the thermal stability is poor.
  • component (B) is preferably in a total of 100% by mass of component (A), component (B), component (C) and component (D). Is 2 to 40% by mass, more preferably 3 to 35% by mass, even more preferably 5 to 35% by mass, particularly preferably 5 to 30% by mass. There is a tendency for impact properties to be inferior.
  • component (B) is preferably used in a total of 100% by mass of component (A), component (B), component (C) and component (D). Is 30 to 60% by mass, more preferably 35 to 50% by mass.
  • the (B) component When used as the surface layer of a foam laminated sheet with high antistatic properties and a smooth surface, the (B) component contains the components (A), (B), (C ) Component and (D) component in a total of 100% by mass, preferably 20 to 60% by mass, more preferably 30 to 60% by mass, and particularly preferably 40 to 60% by mass.
  • component (B) is composed of component (B-1) and component (B-2)
  • the ratio used is 1/99 as the mass ratio of component (B-1) to component (B-2). It is preferably in the range of ⁇ 90/10, more preferably 2/98 to 85/15, even more preferably 10/90 to 85/15, and even more ⁇ more preferred ⁇ or 15/85 ⁇ 80/20, specially preferred ⁇ 20/80 to 75/25, especially in this range, the balance between antistatic properties and the amount of ions eluted is excellent.
  • the amount of the component (B-1) used in the second antistatic resin composition of the present invention is the total amount of the component ( ⁇ ), the component ( ⁇ ), the component (C) and the component (D). More preferably, it is 3 to 13 mass%, still more preferably 5 to 10 mass%, and particularly preferably 5 to 9 mass%.
  • the surface resistivity (measured under conditions of 23 ° C. and 50% RH) is 1 X 10 "0 / b or less, preferably 5 X 10 1Q Q / m or less, and sodium ion And potassium ion elution (measured under extraction conditions at 80 ° C for 60 minutes) 3 zg / cm 2 or less Therefore, a molded body in which the antistatic property and the eluted ions are highly balanced compared to the conventional one can be obtained.
  • the blending amount of the component (B-1) was increased in order to improve antistatic properties, but in this case, the amount of ions eluted from the molded product was increasing.
  • a molded body in which antistatic properties and eluted ions are highly balanced is, for example, a conventionally used (B-1) component and an unprecedented (B-2) component. It is obtained by using together.
  • component (B_l) and component (B_2) are used in combination as component (B)
  • the elution amount of sodium ions and potassium ions is preferably 2 ag / cm 2 or less, more preferably 1 ⁇ g Zcm 2 or less. It becomes possible to reduce to.
  • the component (B) is used for the purpose of improving antistatic properties. It is preferable that the content of 1) is reduced or the component does not contain the compound (B-1 1 1). The use of the above component (B-2) as the component (B) is preferable.
  • the elution amount of sodium ions and potassium ions is preferably 2 / ig / cm 2 or less, more preferably 1 ⁇ g / cm 2. It is possible to reduce it to 2 or less, and even more preferably to be undetectable.
  • the component (C) of the present invention comprises a block copolymer (C 1) containing a polymer block (C 1) mainly composed of an aromatic bur compound and a polymer block (C 2) mainly composed of a conjugated diene compound. It is at least one polymer selected from the group consisting of a) and its hydrogenated product (Cb), and exhibits properties as an elastomer.
  • aromatic vinyl compound used here examples include styrene, ⁇ -methylstyrene, hydroxystyrene, and the like, preferably styrene and hymethylstyrene, and particularly preferably styrene.
  • Conjugation compounds include butadiene, isoprene, hexagene, 2,3-dimethyl-1,3-butadiene, 1,3-pentane, and the like, preferably butadiene and isoprene. These can be used alone or in combination of two or more.
  • the block (C-2) may be a block in which two or more conjugated gen compounds are used and these are combined in any form of random, block, or taper.
  • (C-2) is a conjugate block of polymer block (C-2) that may contain taper blocks in which the aromatic vinyl compound is gradually increased in the range of 1 to 10 Polymer blocks with different vinyl bond content derived from the product may be copolymerized as appropriate.
  • a preferred structure of the component (C) of the present invention is a polymer represented by the following formulas (VI) to (VIII) or a hydrogenated product thereof.
  • A is a polymer block mainly composed of an aromatic vinyl compound, and if it is a polymer block consisting essentially 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, and more preferably 99% by mass or more of an aromatic bur compound B is a homopolymer of a conjugated Jheny compound or an aromatic vinyl compound.
  • X is the residue of the coupling agent
  • Y is an integer from 1 to 5
  • Z is an integer from 1 to 5, respectively.
  • B is a copolymer of a conjugation compound and another monomer such as an aromatic vinyl compound
  • the content of the other monomer in B is determined based on the conjugation compound and the other conjugation compound. It is preferably 50% by mass or less based on the total with the monomer.
  • Block copolymers comprising an aromatic vinyl compound and a conjugated gen compound are known in the technical field of anion polymerization, such as Japanese Patent Publication Nos. 47-28915 and 47-3252. This is disclosed in Japanese Patent Publication Nos. 48-2423 and 48-20038. Further, a method for producing a polymer block having a tapered block is disclosed in JP-A-60-81217 and the like.
  • the content of vinyl bonds (1, 2_ and 3, 4 — bonds) derived from the conjugate conjugate compound of component (C) of the present invention is preferably in the range of 5 to 80%.
  • (C) Number average component The amount of the lye is preferably ⁇ , 10,000, 000, 000, 000, more preferably 2,000, 000, 500,000, and particularly preferably 20,000, 200,000.
  • the number average molecular weight of the buttocks represented by the above (VI) to (VIII) is in the range of 3,000 to: 150,000
  • the number average molecular weight of the B part is in the range of 5,000 to 200,000. S-preferred.
  • Adjustment of the amount of bull bonds of conjugation compounds can be achieved by using N, N, ⁇ ', N'-tetramethylethylenediamine, trimethylamine, triethinoleamine, diazocyclo (2, 2, 2) octamine, etc.
  • Amines, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether and other ethers, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, alkoxides of potassium and sodium, and the like can be used.
  • a polymer in which a polymer molecular chain is extended or branched via a coupling agent residue using a coupling agent after the polymer is obtained by the above method is also preferably included in the component (C) of the present invention.
  • Power Coupling agents used here include decyl adipate, divinyl benzene, methyl dichlorosilane, silicon tetrachloride, butyl trichloro silicon, tetra black tin, butyl black tri tin, dimethyl black silicon, tetra black germanium, 1 , 2-dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized flax oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate, and the like.
  • the block copolymer itself can be used, or a carbon-carbon double bond of a conjugated gen moiety partially or completely hydrogenated can be used. it can. From the viewpoint of low-temperature impact properties of the obtained composition, it is preferable to use one that is not hydrogenated or has a hydrogenation rate of less than 90%. From that, it is preferable to use a product hydrogenated 90% or more.
  • the hydrogenation reaction of the block copolymer containing the polymer block mainly composed of the aromatic Bürich compound and the polymer block mainly composed of the conjugated compound obtained by the above method is carried out by a known method. And the hydrogenation rate is adjusted by a known method. As a result, the desired polymer can be obtained.
  • Specific methods include JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-63-5401, JP-A-2-133406, There is a method disclosed in Kaihei 1 297413.
  • the block copolymer (C 1a) and its hydrogenated product (C 1b) are other polymers such as a block polymer and / or a graft polymer (however, as the component (D) below) It may be the same as that used, or may not be the same) and may be chemically bonded.
  • the block copolymer (C 1 a) and other polymers chemically bonded to the hydrogenated product (C 1 b) are not necessarily 100% by mass chemically bonded to other polymers.
  • the object of the present invention can be achieved if at least 10% by weight of the polymer is chemically bonded.
  • Preferred as other polymers to be combined as block polymerization with the block copolymer (C-1a) and its hydrogenated product (C-1b) are aromatic polycarbonate and Z or polyurethane. More preferably, it is an aromatic polycarbonate.
  • Aromatic polycarbonate block copolymer mixture may, for example, can be force s produced by a method described in JP-A-2001- 220506. Furthermore, it can be obtained as TM-S4L77, TM-H4L77 (trade name) of TM polymer series manufactured by Kuraray.
  • a particularly preferred method for graft polymerizing the other polymer to the block copolymer (C a) and the hydrogenated product (C b) thereof is the block copolymer (C a) and its
  • the bulle monomer includes the following (D) component vinyl monomer (D-b) (however, it may or may not be the same as that used in the following (D) component): Preferably used.
  • D-b component vinyl monomer
  • emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like described later for the component (D) can be used, and solution polymerization and bulk polymerization are more preferable.
  • the component (C) is a total of 100 mass% of the components (A), (B), (C) and (D) of the present invention.
  • 2 to 50% by mass, preferably 5 to 45% by mass, more preferably 7 to 40% by mass, particularly preferably 10 to 35% by mass, and less than 2% by mass has poor impact resistance, and 50% by mass If it exceeds, the impact resistance and surface appearance will be poor.
  • the component (C) is a total of 100% by mass of the components (A), (B), (C) and (D), preferably 15 to 50% by mass, More preferably, it is 20-45 mass%.
  • the component (D) of the present invention is a rubber-reinforced styrene obtained by polymerizing a vinyl monomer (D_b) containing an aromatic vinyl compound in the presence of a rubbery polymer (Da). Resin (D_1) and / or (co) polymer (D-2) of the vinyl monomer. The latter (co) polymer (D-2) is obtained by polymerizing a vinyl monomer (D_b) containing an aromatic vinyl compound in the absence of the rubbery polymer (D_a). .
  • the component (D) of the present invention contains at least one polymer obtained by graft polymerization of a vinyl monomer (D_b) in the presence of the rubbery polymer (D_a) from the viewpoint of impact resistance.
  • the content of the rubber polymer (D_a) is preferably 3 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass, with the component (D) being 100% by mass. .
  • the rubbery polymer (Da) is not particularly limited, but polybutadiene, butadiene 'styrene copolymer, butadiene' acrylonitrile copolymer, ethylene 'propylene copolymer, ethylene' propylene.
  • polybutadiene, butadiene / styrene copolymer, ethylene / propylene copolymer, ethylene / propylene / nonconjugated-gen copolymer, acrylic rubber, silicone rubber, and component (C) are preferred.
  • the butadiene / styrene copolymer used here may be either a block copolymer or a random copolymer.
  • the gel content of the rubbery polymer (D_a) is not particularly limited, but when the component (D_a) is obtained by emulsion polymerization, the gel content is preferably 98% by mass or less, and more preferably 40 to 98% by mass. Within this range, it is possible to obtain an antistatic resin composition that gives a multilayer sheet particularly excellent in impact resistance.
  • the said gel content rate can be calculated
  • 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 (D-b) include styrene, a-methylstyrene, hydroxystyrene, and the like. These may be used alone or in combination of two or more. It can be used in combination. Of these, styrene and monomethylstyrene are preferred.
  • 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.
  • the vinyl-based monomer (D_b) comprises an aromatic bull compound as an essential monomer component, and if necessary, from a vinyl cyanide compound, a (meth) acrylate ester compound and a maleimide compound.
  • One or two or more selected from the group consisting of the above are used as a monomer component, and if necessary, at least one of various other functional group-containing unsaturated compounds is used as a monomer component.
  • various functional group-containing unsaturated compounds include 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 other various functional group-containing unsaturated compounds can be used alone or in combination of two or more.
  • Examples of cyan-vinyl compounds used here include acrylonitrile, methacrylonitrile and the like, and these can be used alone or in combination of two or more.
  • Use of a cyanide bur compound provides chemical resistance. When using a cyanide bur compound, the amount used is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the component (D_b).
  • Examples of the (meth) acrylic acid ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. These can be used alone or in combination of two or more.
  • the amount used thereof is preferably 1 to 80% by mass, more preferably 5 to 80% by mass in the component (Db).
  • maleimide compounds include maleimide, N phenylmaleimide, N cyclohexylmaleimide, and the like. These can be used alone or in combination of two or more.
  • maleic anhydride may be copolymerized and then imidized.
  • heat resistance is imparted.
  • the amount used is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the component (D_b).
  • Examples of the unsaturated acid compound 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. A combination of the above can be used.
  • epoxy group-containing unsaturated compound examples include glycidyl acrylate, glycidyl methacrylate, allyl glycidinole ether, and the like. These may be used alone or in combination of two or more.
  • Hydroxyl-containing unsaturated compounds include 3 hydroxy-1 propene, 4-hydroxy-1-butene, cis 4-hydroxy-2 butene, trans 4-hydroxy-2-butene, 3 hydroxy-2-methyl-1 propene, 2 hydroxyethyl methacrylate, 2 Examples thereof include hydroxychetyl acrylate, N- (4-hydroxyphenyl) maleimide, and the like can be used alone or in combination of two or more.
  • oxazoline group-containing unsaturated compound examples include bruoxazoline and the like, and these can be used alone or in combination of two or more.
  • acid anhydride group-containing unsaturated compound examples include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used alone or in combination of two or more.
  • substituted or unsubstituted amino group-containing unsaturated compounds include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, and phenolic methacrylate.
  • One species can be used alone, or two or more species can be used in combination.
  • the amount of the above other various functional group-containing unsaturated compounds used is the total amount of the functional group-containing unsaturated compounds used in component (D), and is 0.:!-20 Preferred is 0.1% by mass: 10% by mass.
  • the amount of the monomer other than the aromatic vinyl compound in the vinyl monomer (D—b) is 100% by mass when the total of the vinyl monomers (D—b) is 100% by mass.
  • it is 10-95 mass%, More preferably, it is 10-90 mass%, Most preferably, it is 15-80 mass%.
  • More preferred combinations of the monomers constituting the bur monomer (D-b) are styrene / acrylonitrile, styrene / methyl methacrylate, styrene / acrylonitrile / methyl methacrylate, styrene / acrylonitrile / glycidyl methacrylate, Styrene / acrylonitrile / 2-hydroxyxetyl methacrylate, styrene / acrylonitrile / (meth) acrylic acid, styrene / N phenylmaleimide, styrene / methyl methacrylate / cyclohexyl maleimide, etc.
  • the component (D) of the present invention can be produced by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a polymerization method combining these.
  • a known polymerization method for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a polymerization method combining these.
  • the preferred polymerization methods for the polymer obtained by (co) polymerizing the vinyl monomer (Db) in the presence of the rubbery polymer (Da) are emulsion polymerization and solution polymerization.
  • the preferred polymerization method for the polymer obtained by (co) polymerizing the bull monomer (D-b) in the absence of the rubbery polymer (D a) is bulk polymerization or solution polymerization. , Suspension polymerization, and emulsion polymerization.
  • polymerization initiator examples include cumene hydride mouth peroxide, p-menthane hydride mouth peroxide, diisopropylbenzene hydride mouth peroxide, tetramethylbutyl hydride mouth peroxide, tert_butyl hydride mouth peroxide, potassium persulfate, and azobisisobutyronitrile. It is done.
  • chain transfer agent examples include mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, terpinolene, and ⁇ -methylstyrene dimer.
  • mercaptans such as octyl mercaptan, n-dodecyl mercaptan, t-dodecyl mercaptan, n-hexyl mercaptan, terpinolene, and ⁇ -methylstyrene dimer.
  • the emulsifier examples 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.
  • 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.
  • a rosinate such as potassium rosinate can be used.
  • the rubber polymer (Da) and the vinyl monomer (Db) are used in the presence of the entire amount of the rubber polymer (Da).
  • the monomer (D—b) may be polymerized by batch addition or divided or continuously added for polymerization. A part of the rubber polymer (D_a) may be added during the polymerization.
  • the obtained latex is usually coagulated with a coagulant, washed with water and dried to obtain the component (D) powder of the present invention.
  • the latex of two or more components (D) obtained by emulsion polymerization may be appropriately blended and then coagulated.
  • a coagulant inorganic salts such as calcium chloride, magnesium sulfate and magnesium chloride, or acids such as sulfuric acid, hydrochloric acid, acetic acid, citrate and malic acid can be used.
  • the solvent that can be used in the case of producing the component (D) by solution polymerization is an inert polymerization solvent used in ordinary radical polymerization, such as aromatic hydrocarbons such as ethylbenzene and toluene, Mention may be made of ketones such as methyl ethyl ketone and acetone, acetonitrile, dimethylolenolemamide, N-methylpyrrolidone and the like.
  • the polymerization temperature is preferably in the range of 80 to 140 ° C, more preferably 85 to 120 ° C.
  • a polymerization initiator may be used, or polymerization may be performed by thermal polymerization without using a polymerization initiator.
  • organic peroxides such as ketone peroxide, dialkyl peroxide, disilver oxide, peroxyester, hydride peroxide, azobisisoptyronitrile, benzoyl peroxide, Gamma-azobis (cyclohexane-1-carbonitryl) and the like are preferably used.
  • mercaptans for example, mercaptans, terpinolenes, a-methylstyrene dimers, etc. can be used.
  • the polymerization initiator, chain transfer agent, etc. described in the solution polymerization can be used.
  • the amount of monomer remaining in the component (D) obtained by the above polymerization methods is preferably 10000 Oppm or less, more preferably 5, OOOppm or less.
  • the polymer component obtained by polymerizing the bull monomer (Db) in the presence of the rubbery polymer (Da) usually includes the above bull monomer ( D—b) is grafted onto the rubbery polymer (D—a) and grafted onto the rubbery polymer. a copolymer of b).
  • the graft ratio of the component (D) is preferably 20 to 200% by mass, more preferably 30 to: 150% by mass, and particularly preferably 40 to 120% by mass. I can power it.
  • T is (D) component lg is added to 20 ml of acetone (however, if rubber polymer (D_a) uses acrylic rubber, acetonitrile), 2 This is the mass (g) of insoluble matter obtained by centrifuging for 60 minutes in a centrifuge (rotation speed: 23, OOOrpm) after shaking for a while and separating the insoluble matter and the soluble matter. (D) Included in component lg This is the mass (g) of the rubbery polymer.
  • the intrinsic viscosity of the component (D) related to the present invention which is soluble in acetone (wherein the rubbery polymer (D-a) is attalinole rubber) is soluble in viscosity [77] (Measured at 30 ° C using methyl ethyl ketone as the solvent) is preferably 0.2 to: 1.2 dl / g, more preferably ⁇ or 0.2 to: 1. Odl / g, This is preferably 0.3 to 0.8 dl / g.
  • the average particle size of the grafted rubber-like polymer particles dispersed in the component (D) according to the present invention is preferably from f to 500 to 30,000 A, more preferably (preferably from 1,000 to 20, ⁇ , special ( The average particle size can be measured by a known method using an electron microscope.
  • the amount of the component (D) used in the second antistatic resin composition of the present invention is the sum of the components ( ⁇ ), ( ⁇ ), (C), and (D) of the present invention.
  • 100% by mass 5 to 50% by mass, preferably 7 to 50% by mass, more preferably 7 to 38% by mass, and particularly preferably 10 to 30% by mass.
  • the impact resistance and the surface appearance of the molded product are inferior, and if it exceeds 50% by mass, the antistatic property and chemical resistance are inferior.
  • the amount of component (D) used is ( ⁇ ) component, ( ⁇ ) component,
  • the total amount of the component (C) and the component (D) is 100 to 20% by mass, preferably 5 to 20% by mass, more preferably 5 to 15% by mass.
  • the antistatic resin composition of the present invention includes a lithium salt (() and / or a nonionic antistatic agent (F) at the time of producing the antistatic resin composition. Can be added.
  • the lithium salt ( ⁇ ) all the components ( ⁇ ) described above can be used, and these can be used alone or in combination of two or more.
  • the lithium salt ( ⁇ ) is preferably used in the range of 0.01 to 5 parts by mass, more preferably 0.:! To 3 parts by mass, with respect to 100 parts by mass of the antistatic resin composition of the present invention. Parts, particularly preferably in the range of 0.3 to 2 parts by weight. If the amount used is less than 0.01 parts by mass, the effect of improving the antistatic property cannot be obtained, and if it exceeds 5 parts by mass, the impact resistance tends to decrease.
  • the surface resistivity (measured under conditions of 23 ° C and 50% RH) by mixing lithium salt ( ⁇ ) with the second antistatic resin composition of the present invention 1 X 10 11 ⁇ / Mouth, preferably 1 ⁇ 10 9 ⁇ /
  • the amount of sodium ion and potassium ion elution (measured under extraction conditions at 80 ° C for 60 minutes) 3 / g / cm 2 or less, preferably meeting the undetectable requirement.
  • the blending amount of the component (B) was increased in order to improve antistatic properties, but in this case, the amount of ions eluted from the molded product was increasing.
  • a predetermined amount of the lithium salt is blended, and preferably, the content of sodium and / or potassium is low as the component (B), or these elements are substantially contained.
  • Nonionic antistatic agents (F) include polyhydric alcohol ester compounds, amines, amides, etc., and polyhydric alcohol ester compounds include glycerin monostearate, glycerin monomethylene. State, glycerin monopalmitate, glycerin monostearate, glycerin monosteanate, glycerin monooleate, diglycerin monolaurate, diglycerin monomyristate, diglycerin monopalmitate, diglycerin monostearate, diglycerin monostearate Examples include henate, diglycerin monooleate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan monolaurate, etc.
  • 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 jetanolamine, lauryl diisopropanolamine, myristyl diisopropanolamine, panolemityl.
  • Amine compounds such as diisopropanolamine, stearyl diisopropanolamine, oleyldiisopropanolamine, N, N-bishydroxyethylalkyl (alkyl group having 12 to 22 carbon atoms) amine, and lauryldiethanolamide, myristylger Tanololamide, palmityl diethanolamide, behenylethylanolamide, oleyl diethanolamide, lauryl diisopropanolamide, myristyl diisopropanolamide And amide compounds such as palmityl diisopropanolamide, stearyl diisopropanolamide, and oleyl diisopropanolamide. These can be used alone or in combination of two or more. Preferred are the above-described amine compounds, and more preferred are those containing at least 20% by mass of lauryl diethanolamine and stearyl diethanolamine, respectively.
  • 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 with respect to 100 parts by weight of the antistatic resin composition of the present invention. Part by mass, particularly preferably in the range of 0.:! 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 a known weathering (light) agent, antioxidant, heat stabilizer, lubricant, silicone oil, plasticizer, sliding agent, colorant, dye, and foaming agent. Further, processing aids (ultra high molecular weight acrylic polymer, ultra high molecular weight styrene polymer), flame retardant, crystal nucleating agent, and the like can be appropriately blended.
  • a known inorganic or organic filler can be blended with the antistatic resin composition of the present invention.
  • the fillers used here are glass fiber, glass flake, glass fiber milled fiber, glass powder, glass beads, hollow glass bead, carbon fiber, carbon fiber milled fiber, silver, copper, brass, iron.
  • Powders or fibrous materials such as carbon black, tin-coated titanium oxide, tin-coated silica, nickel-coated carbon fiber, talc, carbonated calcium carbonate, carbonated clay whisker, wollastonite, my strength, kaolin , Montmorillonite, hekilite, zinc oxide whisker, potassium titanate whisker, aluminum borate whisker, platy alumina, platy silica, and organically treated smectite, aramid fiber, There are phenol resin, polyester fiber, etc., and these can be used alone or in combination of two or more.
  • those treated with a known coupling agent, surface treating agent, sizing agent, etc. can be used.
  • a known coupling agent silane coupling is used.
  • the inorganic or organic filler is usually used in the range of:! To 200 parts by mass with respect to 100 parts by mass of the antistatic resin composition of the present invention.
  • 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 elastomer 1 PMMA, Methyl methacrylate.
  • Methyl (meth) acrylate copolymer, Ethylene '(Metal ) Acrylic acid copolymer, epoxy resin, phenol resin, urea resin, phenoxy resin, and the like can be appropriately blended.
  • the antistatic resin composition of the present invention can be obtained by melt-kneading the above-described constituent components with various extruders, Banbury mixers, kneaders, continuous kneaders, rolls, and the like. At the time of kneading, the above-described constituent components may be added all at once or kneaded or added separately and kneaded.
  • the antistatic resin composition of the present invention thus prepared includes injection molding, press molding, calendar molding, T-die extrusion molding, inflation molding, lamination molding, vacuum molding, profile extrusion molding, and the like.
  • a molded product can be obtained by a known molding method such as a combined molding method.
  • the antistatic resin composition of the present invention is previously kneaded. It is also possible to obtain a molded product while obtaining the antistatic resin composition of the present invention with the above-mentioned kneader.
  • the thickness is 10
  • the range of ⁇ m to 100 mm is preferable.
  • 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.
  • the antistatic resin composition of the present invention is a two-layer sheet or film with another material, or other It can be a three-layer sheet or film with the material as an intermediate layer.
  • the other materials used here can be made of a known polymer.
  • the adhesion between the layers is excellent. Therefore, such a multilayer sheet or multilayer film is a preferred embodiment in the present invention.
  • a known adhesive layer can be interposed.
  • those containing the inorganic or organic filler can also be used.
  • the thickness of the layer made of the antistatic resin composition of the present invention is preferably 10 / im or more, more preferably 50 / im or more, and particularly preferably for the purpose of stably developing antistatic properties. 80 ⁇ or more.
  • Preferred methods for obtaining such multilayer sheets and films are coextrusion with a T-die and coextrusion with inflation.
  • the sheet thus obtained can be formed into a molded article such as a tray by vacuum forming or the like as necessary.
  • the polypropylene system as the other layer or the intermediate layer is used.
  • a resin with a melt flow rate measured at JIS K7210: 1999, 230.C, load 2.16 kg
  • FIS K6922-2 measured at 190 ° C and 2. 16 kg load
  • a pressure-sensitive adhesive sheet or film is produced using a sheet or film comprising the antistatic resin composition of the present invention as a base material
  • the adhesiveness with the pressure-sensitive adhesive or the adhesiveness with the primer layer is improved.
  • various known treatments such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, UV treatment, ion bombardment are carried out on the surface of the sheet or film comprising the antistatic resin composition of the present invention. Treatment, solvent treatment, etc. can be performed.
  • a primer layer can be formed on the treated surface.
  • 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 zm to about 10 xm.
  • it can be formed by applying as a solvent (including water) solution and drying.
  • the adhesive layer method dry lamination
  • a hot-melt type in which an adhesive layer is formed by a method or a coextrusion method, and any of them can be used.
  • the thickness of the pressure-sensitive adhesive is not particularly limited, but is usually in the range of about:! To 100 ⁇ m.
  • each layer of the multilayer sheet of the present invention is not particularly limited, and may be, for example, foamed or hollow.
  • the foaming agent is not particularly limited, and is known for use in, for example, a foamed polypropylene resin or a foamed polyethylene resin. Any foaming agent can be used.
  • blowing agents include inorganic blowing agents such as carbon dioxide, air and nitrogen, volatile blowing agents such as aliphatic hydrocarbons and halogenated hydrocarbons, azodicarbonamide (ADCA), dinitrosopentamethylenetetraamine And decomposable foaming agents such as azobisisobutyronitrile, hydrazodicarbonamide, and sodium hydrogen carbonate. 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.
  • the amount of foaming agent used is not particularly limited, but in the case of a decomposable foaming agent, it is preferably 0.:! To 10 parts by mass with respect to 100 parts by mass of the resin composition for foam molding.
  • the olefin resin (A) is 40 to 80% by mass
  • the block copolymer (B) is 20 to 60% by mass.
  • the total of component (A) and component (B) is 100% by mass
  • the lithium salt relative to 100 parts by mass of component (A) and component (B).
  • a composition containing 0.01 to 5 parts by mass can be suitably used.
  • the second antistatic resin composition of the present invention is used as the surface layer of the foamed product, 7-30% by mass of the olefin-based resin (8) and 20-60 mass of the block copolymer (B).
  • Molded products obtained in this way are cases such as relay cases, wafer cases, reticle cases, mask cases, liquid crystal trays, chip trays, hard disk (HDD) trays, CCD trays, IC trays, organic Trays such as EL trays, optical pickup-related trays, LED trays, memory trays, etc., carriers such as IC carriers, polarizing films, light guide plates, protective films such as various lenses, underlay sheets when polarizing films are cut, partition plates, etc. Sheets or films used in cleanrooms, internal parts of vending machines, antistatic bags used for liquid crystal panels, hard disks, plasma panels, plastic cardboard, liquid crystal panels, plasma panels, etc. It can be used in the fields of soft cases and other related parts transportation parts.
  • the average particle diameter of the rubber polymer latex used for forming the component (D-1) was measured by a light scattering method.
  • the measuring machine uses the LPA-3100 model manufactured by Otsuka Electronics Co., Ltd. Was used. It was confirmed with an electron microscope that the particle diameter of the dispersion-grafted rubber polymer particles in component (D) was almost the same as the latex particle diameter.
  • Component (C) (Amount of bound styrene, amount of vinyl bond, number average molecular weight, and hydrogenation rate of polymer);
  • Molded product (dimension 2.1mm x 100mm ⁇ disk) is used in accordance with JIS K6911, and the surface resistivity ( ⁇ / port) after standing for 24 hours under 23 ° C, 50 Q / 0 RH conditions is Mitsubishi Chemical The measurement was performed using a Hirester UP MCP-HT450 made by the company. (7) Chemical resistance;
  • the molded product (dimensions 2mm X 40mm X 160mm) is strained 1% and dioctyl phthalate (DO
  • the surface condition of the molded product after applying P) and leaving it to stand at 23 ° C for 72 hours was visually evaluated based on the following evaluation criteria.
  • the surface of the molded product (size 2.1 mm x 100 mm ⁇ disk) was visually evaluated according to the following criteria. ⁇ ; Smooth surface and very good
  • ⁇ The surface is slightly smooth, but the appearance is a problem in practical use.
  • Dupont impact strength (kgf 'cm) was measured according to ASTM D 2794.
  • a molded product having a surface area of 88 cm 2 was immersed in 88 cm 3 of ultrapure water, and the molded product force ion was eluted 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 expressed as xg / cm 2 in terms of the unit area of the molded product.
  • Antistatic property The following standards are used to determine the degree of discoloration between the molded product that was used in the measurement of 1 and the molded product after being left in a 90 ° C atmosphere for 5 days and before being left in a 90 ° C atmosphere. Visually evaluated.
  • Ethylene-norbornene copolymer (glass transition temperature 80 ° C) A9; Novatec HD HB530 (trade name) manufactured by Nippon Polyethylene Co., Ltd. High density polyethylene, melt flow rate 0.3 g / l 0 min A10; Novatec LD HJ560 (produced by Nippon Polyethylene Co., Ltd.) Product name) High density polyethylene, Melt flow rate 7g / l0min
  • a stainless steel autoclave was charged with 80 parts of low molecular weight polypropylene (Mn2, 500) obtained by thermal degradation of high molecular weight polypropylene, then melted at 160 ° C, and 7 parts of maleic anhydride and 12 amino acids. 14 parts of dodecanoic acid was added and reacted at 160 ° C for 1 hour with stirring under nitrogen gas. Thereafter, the reaction was carried out at 200 ° C. for 20 hours to obtain a polyolefin block (Ba).
  • the acid value of (Ba) was 32.1 and Mn was 2,800.
  • a block copolymer (B1-2) having a potassium content of 4000 ppm was obtained in the same manner as in Production Example 1, except that 0.75 part of potassium chloride was used instead of sodium dodecylbenzenesulfonate.
  • a block copolymer (B1-3) having a sodium content of 2000 ppm was obtained in the same manner as in Production Example 1 except that the amount of sodium dodecylbenzenesulfonate was changed to 3.9 parts.
  • the stirrer and the jacketed autoclave were dried and purged with nitrogen, and a cyclohexane solution containing 30 parts of styrene was added.
  • 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.
  • a cyclohexane solution containing 30 parts of styrene was added and polymerized for 1 hour.
  • a portion of the resulting block polymer solution was sampled, and 2, 6-di-tert-butylcatechol was block copolymerized. After adding 0.3 parts to 100 parts, the solvent was removed by heating.
  • the styrene content was 60%
  • the 1,2-bule bond content of the polybutadiene portion was 35%
  • 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 carried out for 3 hours under a hydrogen pressure of 50 ° C. and 50 kgf / cm 2 .
  • 2,6-di-tert-butylcatechol is added in an amount of 0.3 part to 100 parts of the block copolymer, and then the solvent is removed, and the hydrogenation rate of the butadiene part is 100%.
  • 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.
  • 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 devolatilized directly from the unreacted monomer and solvent using a twin-screw, three-stage vented extruder, and the styrene having an intrinsic viscosity of 0.48dlZg. System resin D2 was obtained. (4 3) Production Example 9: Rubber-reinforced styrene resin
  • the stirrer and jacketed autoclave were dried and purged with nitrogen, and cyclohexane and 20 parts of butadiene were added.
  • n-butyllithium was added and isothermal polymerization was performed at 50 ° C.
  • 0.75 parts of tetrahydrofuran and 65 parts of butadiene were added, and the temperature was increased from 50 ° C to 80 ° C.
  • 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 comprises a butadiene block (Bl) having 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-bule content of 35%. It was a polymer with a number average molecular weight of 200,000 consisting of a butadiene block (B2) force with a 1,2-bule content of 10%.
  • component (E) of the present invention the following products manufactured by Sanko Chemical Co., Ltd. were used.
  • Each component is mixed with a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 2. After mixing, the mixture was melt-kneaded using a twin-screw extruder with a vent (cylinder setting temperature 220 ° C) and pelletized. Of the other components, when G1 was used, it was injected from the middle of the extruder. The obtained pellets are sufficiently dried, and then a front and back layer (each thickness of 0.1 mm) made of the pelletized antistatic resin composition and a core made of the composition having the blending ratio shown in Table 2. A three-layer sheet (thickness: 1. Omm) consisting of a material (thickness 0.8 mm) was produced using a multilayer extrusion device with a T-die (processing temperature 190-240 ° C).
  • each component was mixed with a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 3, and then melt-kneaded using a vented twin-screw extruder (cylinder setting temperature 220 ° C) to give pellets. Turned into. Of the other components, when G1 was used, it was injected 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 ⁇ m.
  • the value outside () for the (E1) component is the effect of blending with lithium
  • the «value in () indicates the number of S-base parts as an aqueous solution.
  • the number of (E1) component other than (> is the number of blended parts as lithium soot, and the value in () represents the number of blended parts as an aqueous solution.
  • the value outside () of the (El) component is the E total number of lithium salts, and the number in () is the total number of E as aqueous solution.
  • the value outside () of the (E1) component is the number of parts blended as lithium soot, and the number in () is the number of parts blended as an aqueous solution.
  • Examples 1 to 1-8 and 37 and Comparative Examples 1 to 4 are examples and comparative examples relating to the first antistatic resin composition of the present invention. Excellent antistatic property, chemical resistance, molded product surface appearance, thermal stability and elution ionicity.
  • Comparative Example I-1 is an example in which the amount of eluted ions is larger than 3 ⁇ g / cm 2 .
  • Comparative Example 1-2 is an example in which the antistatic property is higher than 1 ⁇ 10 ” ⁇ / mouth.
  • Comparative Example 1-3 is a large amount of the component (ii) of the present invention that is outside the scope of the invention.
  • Comparative Example 1-4 shows that the amount of component ( ⁇ ) used in the present invention is small outside the range of the invention.
  • the amount of component (ii) used is outside the scope of the invention, and chemical resistance, molded product surface appearance and thermal stability are inferior, and more ions are eluted.
  • Comparative Example 5 is an example in which the amount of eluted ions is larger than S g / cm 2 .
  • Comparative Example 6 is an example in which the antistatic property is higher than IX 10 " ⁇ / mouth.
  • Comparative Example 7 is an example in which the amount of the component (ii) of the present invention is small outside the scope of the invention
  • Comparative Example 1-8 in which the antistatic property, chemical resistance, impact resistance, and molded product surface appearance are inferior, is an example in which the amount of the component (C) of the present invention is small outside the scope of the invention.
  • Comparative Example 1-9 is an example in which the amount of the component (ii) of the present invention is small outside the scope of the invention, and the antistatic property is inferior.
  • This is an example in which the amount of component (D) used is large outside the scope of the invention, and the antistatic property and chemical resistance are inferior From the results described in Table 2, the following is clear.
  • Examples Nos. 20 to 25, Nos. 41 and 1-42 are examples relating to sheets made of the second antistatic resin composition of the present invention, and include antistatic properties, chemical resistance, sheet surface appearance, Excellent impact resistance and elution ionicity, and excellent vacuum formability.
  • Examples 26 to 34 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.
  • a film made of the second antistatic resin composition of the present invention was foamed. This is an example relating to a molded product laminated on a substrate, and is excellent in antistatic property, chemical resistance, surface appearance, thermal stability and elution ionicity.
  • Each component was mixed with a Henschel mixer at the blending ratio shown in Table 4-1 and Table 4-2, then melt-kneaded using a vented twin-screw extruder (cylinder setting temperature 220 ° C) and pelletized. .
  • cylinder setting temperature 220 ° C When the G1 component was used among other components, it was injected from the middle of the extruder. After the obtained pellets are sufficiently dried, injection molding (cylinder setting temperature 220 ° C) is performed using the pellets, and antistatic properties, chemical resistance, impact resistance, molded product surface appearance, and thermal stability. A test piece for evaluation was obtained. The evaluation results are shown in Tables 4-1 and 4-2.
  • Each component was mixed by a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 5, then melt-kneaded using a vented twin-screw extruder (cylinder setting temperature 220 ° C), and pellets Turned into.
  • force was injected in the middle of the extruder.
  • the front and back layers (each having a thickness of 0.1 mm) comprising the pelletized antistatic resin composition, and the core comprising the composition having the blending ratio shown in Table 5 are used.
  • a three-layer sheet (thickness: 1. Omm) consisting of a material (thickness 0.8 mm) was manufactured using a multilayer extrusion device with a T-die (processing temperature 190-240 ° C).
  • Each component was mixed by a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 6, then melt-kneaded using a vented twin-screw extruder (cylinder setting temperature 220 ° C), I was ashamed.
  • the front and back layers (each having a thickness of 30 ⁇ m) composed of the pelletized antistatic resin composition and the composition having the blending ratio shown in Table 6 are mixed with azodicarboxylic acid.
  • a three-layer sheet (thickness 3 mm) consisting of a core material foamed approximately twice as much as an amide-based foaming agent was produced using a multilayer extruder with a T-die (processing temperature 180-200 ° C).
  • the value outside () of the component (E) is the number of parts blended as j-thium soot, and the number in ⁇ ) represents the formula sua as a solution.
  • the value outside () of the component (E) is the number of compounding as a lithium salt, and the number in () is the number of blended parts as a solution.
  • the number IS outside the parentheses of component (E) is the number of blended parts as lithium salt, and the number in (> represents the number of blended parts as port liquid.
  • Examples ⁇ -1 to ⁇ -7 and 11-26, and comparative examples ⁇ - :! to ⁇ -4 are examples and comparative examples relating to the first antistatic resin composition of the present invention. This example is excellent in antistatic property, chemical resistance, molded product surface appearance and elution ionicity.
  • Comparative Example II-1 is an example in which the antistatic property is higher than IX 10 " ⁇ / mouth.
  • Comparative Example II-2 shows that the amount of the component (ii) of the present invention is out of the scope of the invention. This is an example where the amount of component ( ⁇ ) used is small outside the scope of the invention, and the antistatic property is poor.
  • Comparative Example ⁇ -3 shows that the amount of component ( ⁇ ) of the present invention is outside the scope of the invention. This is an example where the amount of component ( ⁇ ) used is small and outside the scope of the invention, and the chemical resistance, the surface appearance of the molded product and the thermal stability are inferior. More examples than the range.
  • Comparison ⁇ _5 to ⁇ _10 ⁇ are examples and comparative examples relating to the second antistatic resin composition of the present invention. These examples are excellent in antistatic properties, chemical resistance, molded product surface appearance, thermal stability, elution ionicity and impact resistance.
  • Comparative Example ⁇ -5 is an example in which the antistatic property is higher than IX 10 " ⁇ / mouth.
  • Comparative Example II-6 is an example in which the amount of the component ( ⁇ ) of the present invention is large. The surface appearance and impact resistance of the molded product are inferior.
  • Comparative Example ⁇ -7 is an example in which the amount of eluted ions is larger than the range of the present invention.
  • Comparative Example ⁇ -8 is the amount of use of the component (C) of the present invention.
  • Comparative example ⁇ -9 is an example in which the amount of component (D) used in the present invention is large outside the scope of the invention, and is antistatic and chemical resistant.
  • Comparative Example 11-10 is an example in which the amount of the component (ii) used in the present invention is small outside the scope of the invention, and the antistatic property is inferior.
  • Examples ⁇ -19 to ⁇ -22, ⁇ -32 and ⁇ -33 are examples relating to the sheet comprising the second antistatic resin composition of the present invention, and are antistatic, chemical resistant, sheet surface Excellent appearance, impact resistance and elution ionicity, and excellent vacuum formability.
  • 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, chemical resistance, surface Excellent appearance, heat stability and elution ionicity.
  • the antistatic resin composition of the present invention is required to have high performance because it has excellent antistatic properties, chemical resistance, appearance of the molded product surface, excellent thermal stability, and few eluted ions. It can be applied as various parts in the vehicle field, electrical / electronic field, bag / home appliance field, sanitary field, etc.

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Abstract

Disclosed is an antistatic resin composition which comprises 40 to 98 mass% of an olefin resin (A) and 2 to 60 mass% of a block copolymer (B) having an olefin polymer block and a hydrophilic polymer block, and which can be molded into an article having a surface resistance (measured under the conditions of 23˚C and 50% RH) of 1x1011 Ω/□ or lower and having the leaching amount of sodium and potassium ions (measured under conditions of 80˚C and extraction for 60 minutes) of 3 μg/cm2 or less. The composition may contain a predetermined amount of a block copolymer having an aromatic vinyl compound polymer block and a conjugated diene compound polymer block or a hydrogenation product of the block copolymer and a predetermined amount of a styrene resin. The component (B) may be a combination of a block copolymer as mentioned above which has higher sodium and potassium contents and a block copolymer as mentioned above which has lower sodium and potassium contents. If required, the composition may contain a lithium salt (E). The composition has excellent antistatic properties, chemical resistance, molded article appearance and thermal stability, and has a reduced leaching amount of ions.

Description

明 細 書  Specification
制電性樹脂組成物および成形品  Antistatic resin composition and molded article
技術分野  Technical field
[0001] 本発明は、制電性、耐薬品性、成形品表面外観、熱安定性に優れ、溶出イオン量 の少ない制電性樹脂組成物、そして、この制電性樹脂組成物からなる成形品に関す る。  [0001] The present invention is 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 molding comprising the antistatic resin composition. Related to goods.
[0002] ポリプロピレン等のポリオレフイン系樹脂は、耐薬品性、耐熱性、流動性等に優れる ため、電気 ·電子分野、 ΟΑ·家電分野、車両分野、サニタリー分野等に広く使用され ている。しかし、この樹脂は、帯電し易い欠点を有していることから、静電気により障 害が発生するもの、例えば、液晶表示装置、プラズマディスプレイ、半導体の周辺部 材、クリーンノレーム内等で使用され又は取扱われる各種パーツ、シート、フィルム等 に使用することは難しかった。かかる欠点を改良する目的から、特許文献 1、特許文 献 2には、特定の帯電防止剤を配合することが提案されているが、制電性の持続性 が無いこと、制電性が充分でない等の問題があった。また、制電性を持続させる方法 として、特許文献 3には、ポリオレフインブロックと親水性ポリマーブロックとからなるブ ロック共重合体をポリオレフイン系樹脂に配合することが提案されているが、制電性が 充分に発現されない問題があった。  [0002] Polyolefin resins such as polypropylene are excellent in chemical resistance, heat resistance, fluidity, etc., and are therefore widely used in the electrical / electronic field, the consumer electronics field, the vehicle field, the sanitary field, and the like. However, since this resin has a drawback that it is easily charged, it is used in a device that is damaged by static electricity, such as a liquid crystal display device, a plasma display, a peripheral component of a semiconductor, or a clean nore. Or, it was difficult to use for various parts, sheets, films, etc. to be handled. For the purpose of improving such drawbacks, Patent Document 1 and Patent Document 2 propose that a specific antistatic agent is blended, but the antistatic property is not long enough and the antistatic property is sufficient. There was a problem such as not. 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 is blended with a polyolefin resin. There was a problem that was not fully expressed.
[0003] 又、前記ブロック共重合体には、制電性を向上させる目的から、一般的にアルキル ベンゼンスルホン酸のナトリウム塩、カリウム塩等の電解質成分が重合中または重合 後に添加されるが、ポリオレフイン系樹脂に配合する際には、制電性の発現効果が 十分でないことからより多くの電解質が添加される。このようなブロック共重合体とォレ フィン系樹脂とを含有する組成物からなる成形品は、液晶分野、ハードディスク分野 、有機 EL分野、 LED分野等における用途では、上記のような電解質成分の溶出が 問題となる場合があり、従来、制電性と溶出イオン量の両者を満足させる樹脂組成物 は得られていなかった。  [0003] In addition, for the purpose of improving antistatic properties, electrolyte components such as sodium salt and potassium salt of alkylbenzene sulfonic acid are generally added to the block copolymer during or after polymerization. When blended with a polyolefin resin, more electrolyte is added because the antistatic effect is not sufficient. Molded articles composed of such a composition containing a block copolymer and an olefin resin are used for elution of the above electrolyte components in applications in the liquid crystal field, hard disk field, organic EL field, LED field, etc. In the past, resin compositions that satisfy both antistatic properties and the amount of eluted ions have not been obtained.
[0004] 特許文献 1：特開平 4一 258647号公報  [0004] Patent Document 1: Japanese Patent Laid-Open No. 4258258
特許文献 2：特開 2000— 313875号公報  Patent Document 2: Japanese Patent Laid-Open No. 2000-313875
特許文献 3：特開 2001— 278985号公報 発明の開示 Patent Document 3: Japanese Patent Laid-Open No. 2001-278985 Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0005] 本発明の目的は、制電性、耐薬品性、成形品表面外観、熱安定性に優れ、溶出ィ オン量の少ない制電性樹脂組成物、そして、この制電性樹脂組成物からなる成形品 を提供することにある。  [0005] 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 the antistatic resin composition. Is to provide a molded product consisting of
課題を解決するための手段  Means for solving the problem
[0006] 本発明者等は、上記目的を達成すべく鋭意検討した結果、ォレフィン系樹脂と上 記ブロック共重合体とを含有する組成物において、この組成物にリチウム塩を所定量 添加したり、または、該ブロック共重合体としてナトリウムおよび/またはカリウムの含 有量が低レ、かまたはこれらの元素を実質的に含まないブロック共重合体を用いたり、 もしくは、このブロック共重合体と他のブロック共重合体、例えば、ナトリウムおよび/ またはカリウムの含有量が上記ブロック共重合体よりも高いブロック共重合体とを併用 することにより、溶出イオン量が上記用途に適するように十分低減された成形体を与 える制電性樹脂組成物が得られることを見出した。また、前記組成物にスチレン系榭 脂及び芳香族ビュル化合物からなる重合体ブロックと共役ジェン化合物からなる重 合体ブロックとを含有するブロック共重合またはその水素添加物を配合することで、 更に制電性が向上し、溶出イオン量が少なくなることを見出し、本発明を完成するに 至った。 [0006] As a result of intensive studies to achieve the above object, the present inventors have added a predetermined amount of lithium salt to the composition containing the olefin resin and the block copolymer. Alternatively, as the block copolymer, a block copolymer having a low content of sodium and / or potassium or substantially free of these elements may be used, or the block copolymer may be used in combination with other block copolymers. In combination with a block copolymer of, for example, a block copolymer having a sodium and / or potassium content higher than that of the block copolymer, the amount of eluted ions was sufficiently reduced to be suitable for the above-mentioned use. It has been found that an antistatic resin composition giving a molded product can be obtained. Further, the composition is further blended with a block copolymer containing a polymer block composed of a styrenic resin and an aromatic bur compound and a polymer block composed of a conjugated diene compound, or a hydrogenated product thereof. As a result, the present invention was completed.
すなわち、本発明の一局面によれば、下記 (A)成分 40〜98質量％と下記（B)成 分 2〜60質量％とを含有する組成物（但し、上記 (A)成分及び (B)成分の合計は 10 0質量％)であって、該組成物を成形してなる成形体の表面抵抗率（23°C、 50%RH 条件下で測定）が Ι Χ ΙΟ^ Ω Ζ口以下で、かつ、ナトリウムイオン及びカリウムイオン の溶出量 (80°C、 60分間抽出条件下で測定）が 3 μ g/cm2以下であることを特徴と する制電性樹脂組成物 (以下、「第一の制電性樹脂組成物」 )が提供される。 That is, according to one aspect of the present invention, a composition comprising 40 to 98% by mass of the following (A) component and 2 to 60% by mass of the following (B) component (provided that the above (A) component and (B) ) The total of the components is 100% by mass), and the surface resistivity (measured under the conditions of 23 ° C and 50% RH) of the molded product formed from the composition is Ι Χ ΙΟ ^ Ω And an elution amount of sodium ions and potassium ions (measured under extraction conditions at 80 ° C. for 60 minutes) is 3 μg / cm 2 or less (hereinafter referred to as “ A first antistatic resin composition ")" is provided.
(A)成分:ォレフイン系樹脂、  (A) component: olefin resin,
(B)成分:ォレフィン重合体ブロックと親水性重合体ブロックとを含有するブロック共 重合体。  Component (B): A block copolymer containing an olefin polymer block and a hydrophilic polymer block.
本発明の第一の制電性樹脂組成物の好ましい実施形態によれば、上記成分 (B)と して、ナトリウムおよびカリウムの合計の含有量が 500〜8000ppmのブロック共重合 体（B— 1)と、ナトリウムおよびカリウムの合計の含有量が 0〜100ppmのブロック共 重合体 (B— 2)とを、ブロック共重合体 (B— 1)のブロック共重合体 (B— 2)に対する 質量比にして 1Z99〜90Z10の範囲で含むものが使用され、該ブロック共重合体（ B- 1)の配合量は、上記成分 (Α)と上記成分 (Β)との合計量の:!〜 15質量％とされ る。上記成分 (Β)、とりわけ、上記ブロック共重合体 (B— 1)に含まれるナトリウムおよ び/またはカリウムは、スルホン酸塩の形態であることが好ましレ、。 According to a preferred embodiment of the first antistatic resin composition of the present invention, the component (B) and A block copolymer (B-1) having a total content of sodium and potassium of 500 to 8000 ppm and a block copolymer (B-2) having a total content of sodium and potassium of 0 to 100 ppm In the range of 1Z99 to 90Z10 in terms of mass ratio of the block copolymer (B-1) to the block copolymer (B-2), and the blending of the block copolymer (B-1) The amount is set to:! To 15% by mass of the total amount of the above component (Α) and the above component (Β). The component (ii), particularly sodium and / or potassium contained in the block copolymer (B-1) is preferably in the form of a sulfonate.
また、本発明の第一の制電性樹脂組成物の他の好ましい実施形態によれば、上記 (Α)成分及び (Β)成分に加えて、さらに、上記 (Α)成分及び (Β)成分の合計 100質 量部に対してリチウム塩 (Ε) 0. 01〜5質量部が添加される。この場合、上記（Β)成分 のナトリウムおよびカリウムの合計の含有量は 0〜1000ppmであることが好ましぐ 0〜 lOOppmであることがさらに好ましい。上記（B)成分がナトリウム及び/又はカリウムを 含有する場合、これらをスルホン酸塩の形態で含有することが好ましレ、。  In addition, according to another preferred embodiment of the first antistatic resin composition of the present invention, in addition to the above-mentioned (ii) component and (ii) component, the (ii) component and (ii) component Lithium salt (Ε) 0.01 to 5 parts by mass is added to a total of 100 parts by mass. In this case, the total content of sodium and potassium of the component (ii) is preferably 0 to 100 ppm, and more preferably 0 to lOOppm. When the component (B) contains sodium and / or potassium, it is preferable to contain them in the form of a sulfonate.
また、本発明の他の局面によれば、下記 (A)成分 7〜91質量％と、下記（B)成分 2 〜60質量％と、下記（C)成分 2〜50質量％と、下記（0) 5〜50質量％とを含有する 組成物（但し、上記 (A)成分、（B)成分、（C)成分及び (D)成分の合計は 100質量 %)であって、該組成物を成形してなる成形体の表面抵抗率（23°C、 50%RH条件 下で測定）が Ι Χ ΙΟ^ Ω /口以下で、かつ、ナトリウムイオン及びカリウムイオンの溶 出量（80°C、 60分間抽出条件下で測定）が 3 μ g/cm2以下であることを特徴とする 制電性樹脂組成物 (以下、「第二の制電性樹脂組成物」 )が提供される。 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 (C) component 2-50 mass%, and the following ( 0) a composition containing 5 to 50% by mass (provided that the total of the components (A), (B), (C) and (D) is 100% by mass), The surface resistivity (measured under conditions of 23 ° C and 50% RH) of 成形 is less than Ι Χ ΙΟ ^ Ω / mouth, and the amount of sodium ions and potassium ions dissolved (80 ° C) An antistatic resin composition (hereinafter referred to as “second antistatic resin composition”) is provided, wherein the antistatic resin composition (measured under extraction conditions for 60 minutes) is 3 μg / cm 2 or less.
(A)成分:ォレフイン系樹脂。  Component (A): olefin resin.
(B)成分:ォレフィン重合体ブロックと親水性重合体ブロックとを含有するブロック共 重合体。  Component (B): A block copolymer containing an olefin polymer block and a hydrophilic polymer block.
(C)成分：芳香族ビニル化合物から主としてなる重合体ブロックと共役ジェン化合物 から主としてなる重合体ブロックとを含有するブロック共重合体及びその水素添加物 から選ばれた少なくとも 1種のエラストマ一。  Component (C): 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.
(D)成分:ゴム質重合体の存在下に芳香族ビニル化合物を含むビニル系単量体を 重合して得られるゴム強化スチレン系重合体 (D_ l)、および/または、該ビニル系 単量体の（共)重合体 (D— 2)からなるスチレン系樹脂。 Component (D): rubber-reinforced styrene polymer (D_l) obtained by polymerizing a vinyl monomer containing an aromatic vinyl compound in the presence of a rubbery polymer, and / or the vinyl polymer Styrenic resin composed of monomeric (co) polymer (D-2).
また、本発明の第二の制電性樹脂組成物の好ましい実施形態によれば、上記成分 (B)として、上記ブロック共重合体 (B— 1)と、上記ブロック共重合体 (B— 2)とを、該 ブロック共重合体 (B— 1)の該ブロック共重合体 (B— 2)に対する質量比にして 1/9 9〜90/10の範囲で含むものが使用され、該ブロック共重合体（B— 1)の配合量は 、上記成分 (A)と上記成分 (B)と上記成分 (C)と上記成分 (D)との合計量の 1〜 15 質量％とされる。上記成分 (B)、とりわけ、上記ブロック共重合体 (B_ l)に含まれる ナトリウムおよび/またはカリウムは、スルホン酸塩の形態であることが好ましレ、。 また、本発明の第二の制電性樹脂組成物の他の好ましい実施形態によれば、上記 (A)成分、（B)成分、（C)成分及び (D)成分に加えて、さらに、上記 (A)成分、 (B) 成分、（C)成分及び (D)成分の合計 100質量部に対してリチウム塩 (E) 0. 01〜5質 量部が添加される。この場合、上記（B)成分のナトリウムおよびカリウムの合計の含有 量は 0〜： !OOOppmであることが好ましぐ 0〜： !OOppmであることがさらに好ましレ、。上 記（B)成分がナトリウム及び/又はカリウムを含有する場合、これらをスルホン酸塩の 形態で含有することが好ましい。  According to a preferred embodiment of the second antistatic resin composition of the present invention, as the component (B), the block copolymer (B-1) and the block copolymer (B-2) are used. ) In a range of 1/9 9 to 90/10 as a mass ratio of the block copolymer (B-1) to the block copolymer (B-2). The blending amount of the polymer (B-1) is 1 to 15% by mass of the total amount of the component (A), the component (B), the component (C) and the component (D). Preferably, sodium and / or potassium contained in the component (B), especially the block copolymer (B_l), is in the form of a sulfonate. According to another preferred embodiment of the second antistatic resin composition of the present invention, in addition to the above component (A), component (B), component (C) and component (D), Lithium salt (E) 0.01 to 5 parts by mass is added to 100 parts by mass in total of the above components (A), (B), (C) and (D). In this case, the total content of sodium and potassium of the component (B) is preferably 0 to:! OOOOppm, more preferably 0 to! OOppm. When the component (B) contains sodium and / or potassium, it is preferable to contain them in the form of a sulfonate.
本発明の第一及び第二の制電性樹脂組成物において、リチウム塩 (E)を添加する 場合、リチウム塩 (E)としては、過塩素酸リチウム、トリフルォロメタンスルホン酸リチウ ム、ビス（トリフルォロメタンスルホ二ノレ）イミドリチウムおよびトリス（トリフルォロメタンス ルホニル)メタンリチウムからなる群より選ばれた少なくとも 1種が好ましく用いられる。 本発明の更に他の局面によれば、上記制電性樹脂組成物からなる成形品、例えば 、シート、フィルムなどが提供される。  In the first and second antistatic resin compositions of the present invention, when the lithium salt (E) is added, the lithium salt (E) includes lithium perchlorate, lithium trifluoromethanesulfonate, bis ( At least one selected from the group consisting of trifluoromethanesulfonino) imidolithium and tris (trifluoromethanesulfonyl) methane lithium is preferably used. According to still another aspect of the present invention, there is provided a molded article made of the above antistatic resin composition, such as a sheet or a film.
なお、以下、本発明の第一の制電性樹脂組成物と第二の制電性樹脂組成物を総 称する場合は「本発明の制電性樹脂組成物」という。  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”.
また、本発明において、ナトリウムイオン及びカリウムイオンの溶出量は、ナトリウムィ オンの溶出量とカリウムイオンの溶出量との合計を意味し、何れか一方のイオンの溶 出量が 0であってもよし、両方のイオンの溶出量が 0を超えてもよい。  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 even if the elution amount of any one of the ions is zero. However, the elution amount of both ions may exceed zero.
発明の効果 The invention's effect
本発明によれば、ォレフィン重合体ブロックと親水性重合体ブロックとを含有するブ ロック共重合体をォレフイン系樹脂に配合した制電性樹脂組成物において、リチウム 塩を所定量添加、及び/又は、該ブロック共重合体として複数のブロック共重合体を 併用することなどによりナトリウム及びカリウムの含有量を低減させることとしたので、 耐薬品性、成形品表面外観及び熱安定性に優れ、かつ、制電性とナトリウムイオン 及びカリウムイオンの溶出量のバランスに優れた成形品を与える制電性樹脂組成物 が得られる。 According to the present invention, a block containing an olefin polymer block and a hydrophilic polymer block. In an antistatic resin composition in which a lock copolymer is blended with an olefin resin, a predetermined amount of lithium salt is added, and / or sodium and a plurality of block copolymers are used together as the block copolymer. Since the content of potassium is reduced, it gives a molded product with excellent chemical resistance, molded product surface appearance and thermal stability, and excellent balance between antistatic properties and the elution amount of sodium ions and potassium ions. An antistatic resin composition is obtained.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0008] 以下、本発明を詳しく説明する。尚、本明細書において、「（共)重合」とは、単独重 合及び共重合を意味し、「（メタ）アクリル」とは、アクリル及び/又はメタクリルを意味し 、「（メタ）アタリレート」とは、アタリレート及び/又はメタタリレートを意味する。  [0008] Hereinafter, the present invention will be described in detail. In the present specification, “(co) polymerization” means homopolymerization and copolymerization, and “(meth) acryl” means acryl and / or methacryl, and refers to “(meth) acrylate”. "Means attalate and / or metatalate.
[0009] 第一の制雷件樹脂組成物の説明  [0009] Description of the first lightning control resin composition
本発明の制電性樹脂組成物に関わる成分 (A)はォレフイン系樹脂 (A)である。該 ォレフィン系樹脂（A)としては、例えば、炭素数 2〜： 10のォレフィン類の少なくとも 1 種力 なるォレフィン系樹脂が挙げられ、後述する（B)成分を除く（共)重合体である 。このォレフィン系樹脂 (A)は、 1種単独でまたは 2種以上を組み合わせて用いること ができる。  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 having at least one kind of olefins having 2 to 10 carbon atoms, and are (co) polymers excluding the component (B) described later. These olefin-based resins (A) can be used singly or in combination of two or more.
上記ォレフィン系樹脂 (A)の形成に用いるォレフィン類の例としては、エチレン、及 びプロピレン、ブテン _ 1、ペンテン一 1、へキセン一 1、 3 メチルブテン一 1、 4 メ チルペンテン _ 1、 3—メチルへキセン _ 1等のひーォレフイン、更にノルボルネン等 の環状ォレフィン等が挙げられる。これらは、 1種単独でまたは 2種以上を組み合わ せて用いることができる。また、これらのうち、エチレン、プロピレン、ブテン一 1、 3 メ チルブテン一 1、 4—メチルペンテン一 1及びノルボルネンが好ましい。  Examples of olefins used to form the olefin-based resin (A) include ethylene and propylene, butene_1, pentene-1, hexene-1, 1, methylbutene-1, 4, methylpentene_1, 3- Examples include olefins such as methylhexene_1, and cyclic olefins such as norbornene. These can be used alone or in combination of two or more. Of these, ethylene, propylene, butene-1, 1,3-methylbutene-1, 4-methylpentene-1, and norbornene are preferable.
ォレフィン系樹脂 (A)の形成において必要に応じて用いることのできる他の単量体 としては、 4_メチル _ 1， 4_へキサジェン、 5 _メチル _ 1， 4_へキサジェン、 7- メチルー 1 , 6—ォクタジェン、 1 , 9ーデカジエン等の非共役ジェン等が挙げられる。  Other monomers that can be used as necessary in the formation of the olefin resin (A) include 4_methyl_1,4_hexagen, 5_methyl_1,4_hexagen, 7-methyl- Non-conjugated gens such as 1, 6-octadiene and 1, 9-decadiene are included.
[0010] ォレフィン系樹脂（A)としては、ポリプロピレン、プロピレン.エチレン共重合体等の プロピレン単位を主として含む重合体、ポリエチレン、エチレン ノルボルネン共重合 体が好ましぐこれらは単独で用いてもよいし、組み合わせて用いてもよい。尚、上記 プロピレン 'エチレン共重合体としては、ランダム共重合体、ブロック共重合体等があ りいずれも使用できるが、成形品表面外観の点からランダムタイプを用いることが特 に好ましい。又、ポリエチレンとしては、高密度ポリエチレン、低密度ポリエチレン、直 鎖状低密度ポリエチレン等の何れのものも使用できる。 As the olefin-based resin (A), polymers mainly containing propylene units such as polypropylene and propylene / ethylene copolymers, polyethylene and ethylene norbornene copolymers are preferred, and these may be used alone. , May be used in combination. The above The propylene / ethylene copolymer includes a random copolymer and a block copolymer, and any of them can be used. However, 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, straight chain low density polyethylene, and the like can be used.
本発明のォレフィン樹脂は、公知の重合法で製造されたものが使用でき、例えば高 圧重合法、低圧重合法、メタ口セン触媒重合法等がある。  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 metamouth catalyst polymerization method.
更に、本発明で使用されるォレフイン系樹脂としては、重合触媒を脱触媒したもの、 または、酸無水物、カルボキシル基、エポキシ基等で変性したものを用いることができ る。  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.
[0011] ォレフィン系樹脂 (A)の結晶性の有無は問わないが、室温下、 X線回折による結晶 化度が 10%以上であるものを少なくとも 1種用いることが好ましい。  [0011] The olefin-based resin (A) may or may not have crystallinity, but it is preferable to use at least one resin having a crystallinity of 10% or more by X-ray diffraction at room temperature.
また、ォレフィン系樹脂 (A)の JIS K7121に準拠して測定した融点が 40°C以上で あるものを少なくとも 1種用いることが好ましい。  In addition, it is preferable to use at least one type of olefin resin (A) having a melting point measured according to JIS K7121 of 40 ° C. or higher.
本発明の (A)成分としてポリプロピレン系樹脂を使用する場合、 JIS K7210 : 1999 (230°C、荷重 2. 16kg)に準拠して測定したメルトフローレートは、好ましくは 0. 01 〜500g/10分、より好ましくは 0. 05〜： lOOg/10分であり、ポジエチレン系樹脂を 使用する場合は、 JIS K6922— 2 (190°C、荷重 2. 16kg)に準拠して測定したメルト フローレート ίま、好ましく (ま 0. 01〜500g/10分、より好ましく ίま 0. 05〜： lOOg/10 分である。  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 Min, more preferably 0.05 ~: lOOg / 10 min. When using positive ethylene resin, melt flow rate measured according to JIS K6922-2 (190 ° C, load 2.16kg) Further, it is preferable (between 0.01 and 500 g / 10 minutes, more preferably when it is ί or 0.05-: lOOg / 10 minutes.
[0012] 本発明のォレフィン系樹脂は、酸化防止剤、熱安定剤、滑剤等の各種添加剤を配 合したものを用いることもできるし、未配合のものを用いることもできる。使用される用 途によっては、成形品からの発生ガス成分となる前記各種添加剤を配合していない（ A)成分を用レ、た方が好ましレ、場合もある。  [0012] As the olefin-based resin of the present invention, a resin in which various additives such as an antioxidant, a heat stabilizer and a lubricant are mixed can be used, or an unblended resin can be used. Depending on the application to be used, it may be preferable to use the component (A) which does not contain the above-mentioned various additives that are gas components generated from the molded product.
[0013] 本発明の第一の制電性樹脂組成物を構成する (A)成分の使用量は、本発明の (A )成分、及び（B)成分の合計 100質量％中、 40〜98質量0 /0、好ましくは 45〜97質 量0 /0、更に好ましくは 45〜95質量0 /0、特に好ましくは 50〜95質量％である。その使 用量が 40質量％未満では熱安定性が劣り、 98質量％を超えると制電性が劣る。 優れた耐薬品性と成形品表面外観が要求される用途では、（A)成分の使用量は、 (A)成分及び (B)成分の合計 100質量％中、好ましくは 60〜98質量％、更に好まし くは 65〜97質量％、より更に好ましくは 65〜95質量％、特に好ましくは 70〜95質 量％である。その使用量が 60質量％未満では耐薬品性及び成形品表面外観が劣 る傾向がある。優れた制電性と熱安定性が要求される用途では、（A)成分の使用量 は、（A)成分及び (B)成分の合計 100質量％中、好ましくは 40〜70質量％、更に好 ましくは 50〜65質量％である。高い制電性を有し、平滑な表面を有するシート表面 外観の優れた発泡積層シートの表層として使用される場合は、 （A)成分の使用量は 、（A)成分及び (B)成分の合計 100質量％中、好ましくは 40〜80質量％、更に好ま しくは 50〜70質量％である。 [0013] The amount of the component (A) constituting the first antistatic resin composition of the present invention is 40 to 98 in a total of 100% by mass of the components (A) and (B) of the present invention. mass 0/0, preferably from 45 to 97 mass 0/0, more preferably 45 to 95 weight 0/0, and particularly preferably 50 to 95 wt%. 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 Of the total 100% by mass of component (A) and component (B), preferably 60 to 98% by mass, more preferably 65 to 97% by mass, still more preferably 65 to 95% by mass, and particularly preferably 70 to 95% by 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 that require excellent antistatic and thermal stability, the amount of component (A) used is 100% by mass of component (A) and component (B), preferably 40 to 70% by mass, Preferably, it is 50 to 65% by mass. Sheet surface with high antistatic properties and smooth surface When used as a surface layer of a foam laminated sheet with excellent appearance, 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.
本発明の制電性樹脂組成物に関わる（B)成分は、ォレフィン重合体ブロック（B_a )と親水性重合体ブロック（B_b)とを含有するブロック共重合体であり、ナトリウムお よび/またはカリウムの含有量が低減されたものが好ましい。ナトリウムおよび/また はカリウムの含有量が低減された（B)成分は、例えば、（B)成分として、ナトリウムおよ び/またはカリウムの含有量が高いブロック共重合体 (B— 1)と、該ブロック共重合体 (B— 1)よりもナトリウムおよび/またはカリウムの含有量が低レ、か、これらの元素を含 まないブロック共重合体 (B— 2)を併用することによって構成できる。また、重合時に 用いるナトリウム化合物および/またはカリウム化合物の量を低減させる力、または該 化合物を使用せずに製造された (B)成分も使用できる。  The component (B) related to the antistatic resin composition of the present invention is a block copolymer containing an olefin polymer block (B_a) and a hydrophilic polymer block (B_b), and sodium and / or potassium Those in which the content of is reduced are preferred. The component (B) having a reduced sodium and / or potassium content, for example, as the component (B), a block copolymer (B-1) having a high sodium and / or potassium content, The block copolymer (B-1) has a lower sodium and / or potassium content, or a block copolymer (B-2) not containing these elements can be used in combination. Further, the ability to reduce the amount of sodium compound and / or potassium compound used at the time of polymerization, or component (B) produced without using the compound can also be used.
本発明の（B)成分は、ジブロックでもよいし、トリブロック以上のマルチブロックであ つてもよレ、。上記ォレフィン重合体ブロック（B— a)とは、ォレフィン類の（共）重合体で ある。ここで使用されるォレフイン類の例としては、エチレン、及び、プロピレン、ブテ ン一 1、へキセン _ 1、 3—メチルブテン _ 1、 4—メチルペンテン _ 1、 3—メチルへキ セン一 1等のひ一ォレフイン、更にノルボルネン等の環状ォレフィン等があり、好ましく は、エチレン、プロピレン、ブテン一 1、 3—メチルブテン _ 1、 4—メチルペンテン _ 1 、ノルボルネンであり、これらは 1種単独で、または 2種以上を組み合わせて用いるこ とができる。また他に 4_メチル _ 1、 4_へキサジェン、 5—メチノレ 1， 4—へキサジェ ン、 7 _メチル_ 1， 6—ォクタジェン、 1， 9—デカジエン等の非共役ジェンを重合体 成分の一部として使用することもできる。該ォレフイン重合体ブロック（B_a)のゲル パーミエーシヨンクロマトグラフィー（GPC)によるポリスチレン換算の数平均分子量は 、好ましく ίま 800〜20, 000、更に好ましく ίま 1, 000〜10, 000、特に好ましく ίま 1, 2000〜6, 000である。 The component (B) of the present invention may be a diblock, or may be a multiblock of a triblock or more. The olefin polymer block (Ba) is a (co) polymer of olefins. Examples of olefins used here include ethylene, propylene, butene-1, hexene_1, 3-methylbutene_1, 4-methylpentene_1, 3-methylhexene-1. In addition, cyclic olefins such as norbornene and the like are preferable, and ethylene, propylene, butene-1, 3-methylbutene_1, 4-methylpentene_1, and norbornene are preferable. Or a combination of two or more. In addition, non-conjugated gens such as 4_methyl_1, 4_hexagen, 5-methinole 1,4-hexagen, 7_methyl_1,6-octadiene, 1,9-decadiene are used as polymer components. It can also be used as part. Gel of the olefin polymer block (B_a) The number-average molecular weight in terms of polystyrene by permeation chromatography (GPC) is preferably ί or 800 to 20,000, more preferably ί or 1,000 to 10,000, particularly preferably ί or 1,2000 to 6,000. is there.
[0015] 上記ォレフィン重合体ブロック（Β— a)は、上記ブロック（B— b)とは実質的に結合さ れ、その結合は、エステル結合、アミド結合、エーテル結合、ウレタン結合、イミド結合 等から選ばれた少なくとも 1種の結合であり、これらの結合を介して繰り返し交互に結 合した構造を有する。  [0015] The olefin polymer block (Β-a) is substantially bonded to the block (BB), and the bond includes 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 selected from the above, and has a structure in which these bonds are alternately and repeatedly bonded through these bonds.
このために、上記ブロック（B_a)の分子末端は、上記ブロック（B_b)に分子両末 端官能基と反応性を有する官能基で変性されてレ、る必要がある。これらの官能基とし ては、カルボン酸基、水酸基、アミノ基、酸無水物基、ォキサゾリン基、エポキシ基等 力 Sある。  For this purpose, the molecular end of the block (B_a) needs to be modified with a functional group having reactivity with the molecular terminal functional groups on the block (B_b). These functional groups include carboxylic acid groups, hydroxyl groups, amino groups, acid anhydride groups, oxazoline groups, and epoxy groups.
本発明の（B_a)成分は、重合法及び熱減成法等によって得ることができ、重合法 により得られるポリオレフインは公知の方法で製造でき、例えば、ラジカル触媒、金属 酸化触媒、チーグラー触媒、チーダラ一一ナッタ触媒、メタ口セン触媒等の存在下で 上記ォレフィンを（共）重合させる方法により容易に得ることができる。一方、高分子量 のポリオレフインの熱減成法によって得られる低分子量ポリオレフインは、例えば、特 開平 3— 62804号公報記載の方法等により容易に得ることができる。上記分子末端 の変性のし易さから、好ましいものは熱減成法によるものである。  The component (B_a) 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, a chidara It can be easily obtained by a method of (co) polymerizing the above olefin in the presence of a Natta catalyst, a meta-catacene catalyst or the like. On the other hand, low molecular weight polyolefin obtained by thermal degradation of 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.
[0016] 熱減成法で得られるポリオレフインは、通常、分子両末端が変性可能なポリオレフィ ン、片末端が変性可能なポリオレフイン及び変性可能な末端基を持たなレ、ポリオレフ インの混合物であるが、両末端が変性可能なポリオレフインが主成分であるのもが好 ましい。 [0016] The polyolefin obtained by the thermal degradation method is usually a mixture of a polyolefin that can be modified at both molecular ends, a polyolefin that can be modified at one end, a polyolefin that does not have a terminal group that can be modified, and a polyolefin. It is also preferred that the main component is polyolefin which can be modified at both ends.
熱減成法で得られたポリオレフイン中の二重結合量は、制電性の観点から好ましく は、炭素数 1， 000当たり 1〜40個、更に好ましくは 2〜30個、特に好ましくは 4〜20 個である。  From the viewpoint of antistatic properties, the amount of double bonds in the polyolefin obtained by the thermal degradation method is preferably 1 to 40, more preferably 2 to 30, and particularly preferably 4 to 1,000 per 1,000 carbon atoms. There are 20 pieces.
1分子当たりの二重結合の平均数は、繰り返し構造の形成性の観点及び制電性の 観点から好ましくは、 1.ト 5、さらに好ましくは 1. 3〜3、特に好ましくは 1. 8〜2. 2 である。 熱減成法においては、 Mn力 00〜6, 000の範囲で、 1分子当たりの平均末端二 重結合数が 1. 5〜2個の低分子量ポリオレフインが容易に得られる〔例えば、村田勝 英、牧野忠彦、 日本化学会誌、 192頁（1975)参照〕。 The average number of double bonds per molecule is preferably 1. from the viewpoint of the formation of a repeating structure and from the viewpoint of antistatic properties, more preferably from 1.3 to 3, particularly preferably from 1.8 to 2. Two. In the thermal degradation method, low molecular weight polyolefins having an average number of terminal double bonds per molecule of 1.5 to 2 can be easily obtained within a range of Mn force of 00 to 6,000 [for example, Masahide Murata Tadahiko Makino, Journal of the Chemical Society of Japan, page 192 (1975)].
[0017] これらの熱減成法で得たポリオレフインに官能基を付与する方法として好ましレ、もの は、熱減成法により得られた分子末端に炭素一炭素二重結合を有する (B— a)成分 に、上記した官能基を有する炭素一炭素不飽和化合物を付加させる方法である。  [0017] A preferred method for imparting a functional group to the polyolefin obtained by these thermal degradation methods has a carbon-carbon double bond at the molecular end obtained by the thermal degradation method (B- In this method, the carbon-carbon unsaturated compound having the functional group described above is added to component a).
[0018] 上記ブロック（B_b)成分の親水性ポリマーとしては、ポリエーテル、ポリエーテル含 有親水性ポリマー、およびァニオン性ポリマー等が挙げられる。  [0018] Examples of the hydrophilic polymer of the block (B_b) component include polyethers, polyether-containing hydrophilic polymers, and anionic polymers.
ポリエーテルとしては、ポリエーテルジオール、ポリエーテルジァミン、およびこれら の変性物が挙げられる。  Examples of the polyether include polyether diol, polyether diamine, and modified products thereof.
ポリエーテル含有親水性ポリマーとしては、ポリエーテルジオールのセグメントを有 するポリエーテルエステルアミド、ポリエーテルジオールのセグメントを有するポリエー テノレアミドイミド、ポリエーテルジオールのセグメントを有するポリエーテルエステル、 ポリエーテルジァミンのセグメントを有するポリエーテルアミド、および、ポリエーテル ジオールまたはポリエーテルジァミンのセグメントを有するポリエーテルウレタンが挙 げられる。  Examples of the polyether-containing hydrophilic polymer include polyether ester amide having a polyether diol segment, polyether amide imide having a polyether diol segment, polyether ester having a polyether diol segment, and polyether diamine. And polyether urethane having a segment of polyether diol or polyether diamine.
ァニオン性ポリマーとしては、スルホ二ル基を有するジカルボン酸と上記ポリエーテ ルとを必須成分単位とし、かつ一分子内に好ましくは 2〜80個、更に好ましくは 3〜6 0個のスルホ二ル基を有するァニオン性ポリマーが挙げられる。これらは、直鎖状であ つても、また分岐状であってもよい。特に好ましい（B— b)成分はポリエーテルである  As the anionic polymer, a dicarboxylic acid having a sulfonyl group and the above polyether are essential component units, and preferably 2 to 80, more preferably 3 to 60 sulfonyl groups in one molecule. Anionic polymers having These may be linear or branched. A particularly preferred component (Bb) is a polyether.
[0019] ポリエーテルのうちのポリエーテルジオールとしては、一般式（I)： As the polyether diol in the polyether, the general formula (I):
H- (OA1)— O-E1— O (Α'θ) ,— Hで表されるもの、及び一般式（Π)： H- (OA 1 ) — OE 1 — O (Α'θ), — represented by H, and the general formula (Π):
Η- (OA2) -0-E2-0- (A20) 一 Hで表されるもの等が挙げられる。一般式 (I Η- (OA 2 ) -0-E 2 -0- (A 2 0) 1 General formula (I
m m  m m
)中、 E1は二価の水酸基含有化合物から水酸基を除いた残基、 A1は炭素数 2〜4の アルキレン基、 nおよび n'は前記二価の水酸基含有化合物の水酸基 1個当たりのァ ルキレンオキサイド付加数を表す。 n個の（OA1)と n'個の（Aio)とは同一であっても 異なっていてもよぐまた、これらが 2種以上のォキシアルキレン基で構成される場合 の結合形式はブロックもしくはランダムまたはこれらの組み合わせのいずれでもよレ、。 nおよび ηΊま、通常:!〜 300、好ましくは 2〜250、特に好ましくは 10〜： 100の整数で ある。また、 ηと ηΊま、同一であっても異なっていてもよい。 ), 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 per hydroxyl group of the divalent hydroxyl group-containing compound. Represents the number of alkylene oxide additions. n (OA 1 ) and n ′ (Aio) may be the same or different, and if they are composed of two or more oxyalkylene groups The combination form can be either block or random or a combination of these. n and η are usually integers:! to 300, preferably 2 to 250, particularly preferably 10 to 100. Also, η and ηΊ may be the same or different.
[0020] 上記二価の水酸基含有化合物としては、一分子中にアルコール性またはフエノー ル性の水酸基を 2個含む化合物、即ち、ジヒドロキシィ匕合物が挙げられ、具体的には 、二価アルコール (例えば炭素数 2〜： 12の脂肪族、脂環式、あるいは芳香族二価ァ ルコール）、炭素数 6〜： 18の二価フヱノールおよび第 3級ァミノ基含有ジオール等が 挙げられる。 [0020] Examples of the divalent hydroxyl group-containing compound include a compound containing two alcoholic or phenolic hydroxyl groups in one molecule, that is, a dihydroxy compound, specifically, a dihydric alcohol. (For example, an aliphatic, alicyclic or aromatic divalent alcohol having 2 to 12 carbon atoms), a divalent phenol having 6 to 18 carbon atoms and a tertiary amino group-containing diol.
脂肪族二価アルコールとしては、例えば、エチレングリコール、プロピレングリコール 等のアルキレングリコール、 1， 4 _ブタンジオール、 1， 6—へキサンジオール、ネオ ペンチルダリコール、 1， 12—ドデカンジオール等が挙げられる。  Examples of the aliphatic dihydric alcohol include alkylene glycols such as ethylene glycol and propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyldaricol, 1,12-dodecanediol, and the like. .
脂環式二価アルコールとしては、例えば、 1 , 2 _および 1， 3—シクロペンタンジォ ール、 1 , 2—、 1 , 3—および 1 , 4ーシクロへキサンジオール、 1 , 4ーシクロへキサン ジメタノール等が挙げられ、芳香族二価アルコールとしては、例えば、キシレンジォー ル等が挙げられる。  Examples of alicyclic dihydric alcohols include 1, 2_ and 1,3-cyclopentanediol, 1,2-, 1,3- and 1,4-cyclohexanediol, and 1,4-cyclohexane. Xylene dimethanol and the like, and examples of the aromatic dihydric alcohol include xylene diol and the like.
二価フエノールとしては、ハイドロキノン、カテコール、レゾルシン、ウルシオール等 の単環二価フエノール、ビスフエノール Α、ビスフエノール F、ビスフエノール S、 4、 A" ージヒドロキシジフエ二ルー 2, 2—ブタン、ジヒドロキシビフエニル、ジヒドロキシジフエ ニルエーテル等のビスフエノール、およびジヒドロキシナフタレン、ビナフトール等の 縮合多環二価フエノール等が挙げられる。  Divalent phenols include monocyclic bivalent phenols such as hydroquinone, catechol, resorcin, urushiol, bisphenol ノ ー ル, bisphenol F, bisphenol S, 4, A "-dihydroxydiphenol 2, 2-butane, Examples thereof include bisphenols such as dihydroxybiphenyl and dihydroxydiphenyl ether, and condensed polycyclic divalent phenols such as dihydroxynaphthalene and binaphthol.
[0021] 一般式 (Π)中、 E2は、一般式 (I)で記載した二価の水酸基含有化合物から水酸基 を除いた残基、 A2は、少なくとも一部が一般式 (III)： _ CHR_ CHR'_〔式中、 R、 R'の一方は、一般式（IV)： - CH 0 (A30) R"で表される基、他方は Hである。一 In the general formula (式), 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 partially represented by the general formula (III): _CHR_CHR'_ [wherein, one of R and R 'is a group represented by the general formula (IV): -CH 0 (A 3 0) R ", and the other is H.
2 X  2 X
般式（IV)中、 Xは 1〜10の整数、 R"は Hまたは炭素数 1〜10の、アルキル基、ァリー ル基、ァノレキノレアリーノレ基、ァリールアルキル基またはァシル基、 A3は炭素数 2〜4 のアルキレン基である。〕で表される置換アルキレン基であり、残りは炭素数 2〜4のァ ルキレン基であってもよレ、。 m個の（OA2)と m'個の（A2〇）とは同一であっても異なつ ていてもよい。 mおよび m'は 1〜300の整数であることが好ましぐ更に 2〜250、特 に 10〜： 100力 S好ましレヽ。また mと とは、同一でも異なっていてもよい。 In the general formula (IV), X is an integer of 1 to 10, R ″ is H or an alkyl group having 1 to 10 carbon atoms, an aryl group, an anolenoquinaleolinole group, an arylalkyl group or an acyl group, A 3 is an alkylene group having 2 to 4 carbon atoms.] The remaining alkylene group may be an alkylene group having 2 to 4 carbon atoms, m (OA 2 ) And m ′ (A 2 0) may be the same or different, and m and m ′ are preferably integers of 1 to 300, more preferably 2 to 250, 10 to: 100 power S preferred. M may be the same as or different from m.
[0022] 上記一般式 (I)で示されるポリエーテルジオールは、二価の水酸基含有化合物に アルキレンオキサイドを付加反応することにより製造することができる。アルキレンォキ サイドとしては、炭素数 2〜4のアルキレンオキサイド、例えばエチレンオキサイド、プ ロピレンオキサイド、 1， 2—ブチレンオキサイド、 1， 4—ブチレンオキサイド、 2, 3 - ブチレンオキサイド、および 1 , 3—ブチレンオキサイド並びにこれらの 2種以上の併 用系が用いられる。 2種以上のアルキレンオキサイドを併用するときの結合形式はラ ンダムおよび/またはブロックのいずれでもよレ、。アルキレンオキサイドとして好まし レ、ものは、エチレンオキサイド単独及びエチレンオキサイドと他のアルキレンォキサイ ドとの併用によるブロックおよび/またはランダム付加である。アルキレンオキサイドの 付加数は、前記二価の水酸基含有化合物の水酸基 1個当たり、好ましくは 1〜300、 更に好ましくは 2〜250、特に好ましくは 10〜： 100の整数である。  [0022] 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 alkylene oxides 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. These two or more combined systems are used. When two or more alkylene oxides are used in combination, the bond type may be either random and / or block. Preferred alkylene oxides are ethylene oxide alone and block and / or random additions in combination with ethylene oxide and other alkylene oxides. The addition number of alkylene oxide 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.
[0023] 上記一般式 (Π)で示されるポリエーテルジオールの好ましレ、製造方法としては下記  [0023] Preferred examples of the polyether diol represented by the general formula (ii) and the production method thereof are as follows:
(ァ）、（ィ）の方法等が挙げられる。  (A), the method of (i) etc. are mentioned.
[0024] (ァ）上記二価の水酸基含有化合物を出発物質として、一般式 (V)：  [0024] (a) Starting from the above divalent hydroxyl group-containing compound, the general formula (V):
[0025] [化 1]
Figure imgf000012_0001
[0025] [Chemical 1]
Figure imgf000012_0001
[一般式 (V)中の A4は炭素数 2〜4のアルキレン基、 pは 1〜10の整数、 R1は Hまた は炭素数 1〜： 10のアルキル基、ァリーノレ基、アルキルァリール基、ァリールアルキル 基またはァシル基である。 ] [A 4 in the general formula (V) is an alkylene group having 2 to 4 carbon atoms, p is an integer of 1 to 10, R 1 is H or an alkyl group having 1 to 10 carbon atoms, an arylene group, an alkyl aryl. A group, an arylalkyl group or an acyl group. ]
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 method of polymerizing glycidyl ether represented by the formula (1) or copolymerizing with an alkylene oxide having 2 to 4 carbon atoms.
[0026] (ィ）上記二価の水酸基含有化合物を出発物質として、側鎖にクロロメチル基を有 するポリエーテルを経由する方法。更に具体的には、ェピクロノレヒドリン、またはェピ クロルヒドリンとアルキレンオキサイドを付加共重合し、側鎖にクロロメチル基を有する ポリエーテルを得た後、該ポリエーテルと炭素数 2〜4のポリアルキレングリコールと R 'Χ (R1は上記したもの、 Xは Cl、 Brまたは I)をアルカリ存在下で反応させる力、また は該ポリエーテルと炭素数 2〜4のポリアルキレングリコールモノカルビルエーテルを アルカリ存在下で反応させる方法である。 [0026] (ii) A method in which the above divalent hydroxyl group-containing compound is used as a starting material, and via a polyether having a chloromethyl group in the side chain. More specifically, epicuronohydrin, or epichlorohydrin and alkylene oxide are addition-copolymerized to obtain a polyether having a chloromethyl group in the side chain, and then the polyether and C2-C4. Polyalkylene glycol and R 'Χ (R 1 is as described above, X is Cl, Br or I) in the presence of alkali, or the polyether and polyalkylene glycol monocarbyl ether having 2 to 4 carbon atoms in the presence of alkali. This is a reaction method.
ここで使用される炭素数 2〜4のアルキレンオキサイドとしては、前記したものが全て 使用できる。  As the alkylene oxide having 2 to 4 carbon atoms used here, all of the above-mentioned ones can be used.
また、本発明の好ましい（B)成分は、上記ォレフィン重合体ブロック（B_ a)と親水 性重合体ブロック（B_b)を公知の方法で重合することによって得ることができる。例 えば、ブロック（B_a)とブロック（B_b)を減圧下 200〜250°Cで重合反応を行うこと により製造すること力 Sできる。また、重合反応に際し公知の重合触媒を使用することが できる。  In addition, the preferred component (B) of the present invention can be obtained by polymerizing the olefin polymer block (B_a) and the hydrophilic polymer block (B_b) by a known method. For example, it is possible to produce the block (B_a) and the block (B_b) by performing a polymerization reaction at 200 to 250 ° C. under reduced pressure. In the polymerization reaction, a known polymerization catalyst can be used.
[0027] また、重合反応に際し公知の重合触媒を使用することができるが、好ましいものは、 モノプチルスズオキサイド等のスズ系触媒、三酸化アンチモン、二酸化アンチモン等 のアンチモン系触媒、テトラブチルチタネート等のチタン系触媒、ジノレコニゥム水酸 化物、酸化ジルコニウム、酢酸ジルコニル等のジルコニウム系触媒、 ΠΒ族有機酸塩 触媒から選ばれる 1種または 2種以上の組み合わせである。  In addition, a known polymerization catalyst can be used in the polymerization reaction, but preferable ones are tin-based catalysts such as monoptyltin oxide, antimony-based catalysts such as antimony trioxide and antimony dioxide, tetrabutyl titanate and the like. These are one or a combination of two or more selected from titanium-based catalysts, zirconium-based catalysts such as dinoleconium hydroxide, zirconium oxide, zirconyl acetate and the like, and organic organic acid salt catalysts.
[0028] 本発明の（B)成分、とりわけ（B— 1)成分には、制電性を向上させる目的からナトリ ゥムおよび/またはカリウム含有化合物（B— 1 1)が含まれる。これらの化合物は、 (B)成分、とりわけ（B— 1)成分の重合時、重合後、またはこれを組み合わせた方法 で含有させること力 Sできる力 好ましい方法は、重合時にこれらの化合物を存在させ 含有させる方法である。  [0028] The component (B), particularly the component (B-1) of the present invention includes a sodium and / or potassium-containing compound (B-11) for the purpose of improving antistatic properties. These compounds have the ability to be contained by the method of polymerization of the component (B), particularly the component (B-1), after polymerization, or a combination thereof. The preferred method is to allow these compounds to exist during polymerization. It is a method of containing.
(B— 1— 1)成分としては、ナトリウム、カリウムの有機酸、スルホン酸、無機酸の塩、 及びハロゲン化物等が挙げられる。  Examples of the component (B-1-1) include sodium and potassium organic acids, sulfonic acids, inorganic acid salts, and halides.
[0029] (B— 1— 1)成分の具体的な好ましい例として、塩ィ匕ナトリウム、塩化カリウム、臭化 ナトリウム、臭化カリウム等のナトリウム又はカリウムのハロゲンィ匕物；過塩素酸ナトリウ ム、過塩素酸カリウム等のナトリウム又はカリウムの無機酸塩、酢酸ナトリウム、酢酸力 リウム、ステアリン酸ナトリウム、ステアリン酸カリウム等のナトリウム又はカリウムの有機 酸塩；ォクチルスルホン酸、ドデシルスルホン酸、テトラデシルスルホン酸、ステアリノレ スルホン酸、テトラコシルスルホン酸、 2 _ェチルへキシルスルホン酸等の、アルキル 基の炭素数が 8〜24のアルキルスルホン酸のナトリウム塩またはカリウム塩；フエニル スルホン酸、ナフチルスルホン酸等の芳香族スルホン酸のナトリウム塩またはカリウム 塩；ォクチルフエニルスルホン酸、ドデシルフェニルスルホン酸、ジブチルフエニルス ノレホン酸、ジノユルフェニルスルホン酸等の、アルキル基の炭素数が 6〜18のアルキ ルベンゼンスルホン酸のナトリウム塩またはカリウム塩；ジメチルナフチルスルホン酸、 ジイソプロピルナフチルスルホン酸、ジブチルナフチルスルホン酸等の、アルキル基 の炭素数が 2〜： 18のアルキルナフタレンスルホン酸のナトリム塩またはカリウム塩；トリ フルォロメタンスルホン酸等のフッ化スルホン酸等のナトリウム塩またはカリウム塩等 が挙げられ、これらは、 1種単独で、または 2種以上を併用して用いることができる。特 に好ましレ、（B_ 1 _ 1)成分は、ナトリウムおよび Zまたはカリウムのスルホン酸塩の 形態の化合物であり、具体的には、スルホン酸のナトリウム塩化合物、または、スルホ ン酸のカリウム塩化合物である。 [0029] Specific preferred examples of the component (B-1-1) include sodium or potassium halides such as sodium chloride, potassium chloride, sodium bromide, potassium bromide; sodium perchlorate, Sodium or potassium inorganic acid salts such as potassium perchlorate, sodium or potassium organic acid salts such as sodium acetate, potassium acetate, sodium stearate, potassium stearate; octylsulfonic acid, dodecylsulfonic acid, tetradecylsulfonic acid, Alkyls such as stearinolesulfonic acid, tetracosylsulfonic acid, 2_ethylhexylsulfonic acid, etc. Sodium or potassium salt of alkylsulfonic acid having 8 to 24 carbon atoms; Sodium or potassium salt of aromatic sulfonic acid such as phenylsulfonic acid or naphthylsulfonic acid; Octylphenylsulfonic acid or dodecylphenylsulfonic acid Sodium salt or potassium salt of alkylbenzene sulfonic acid having 6 to 18 carbon atoms, such as dimethyl naphthyl sulfonic acid, diisopropyl naphthyl sulfonic acid, dibutyl naphthyl sulfone, such as dibutyl phenyl sulfonic acid, dinoyl phenyl sulfonic acid, etc. Examples thereof include sodium salt or potassium salt of alkyl naphthalene sulfonic acid having 2 to 18 carbon atoms of alkyl group such as acid; sodium salt or potassium salt such as fluorinated sulfonic acid such as trifluoromethanesulfonic acid, and the like. These are one type alone. It can be used in combination of two or more kinds. Particularly preferred component (B_ 1 _ 1) is a compound in the form of sodium and Z or potassium sulfonate, specifically, sodium salt of sulfonic acid or potassium of sulfonic acid It is a salt compound.
本発明の (B)成分を上記 (B— 1 )成分と上記 (B— 2)成分とから構成する場合、上 記（B— 1 1 )成分は、本発明の（B— 1 )成分 100質量部に対して、好ましくは 0. 1 〜20質量部、更に好ましくは 1〜： 15質量部の範囲で用いることができる。本発明の（ B— 1)成分中のナトリウムおよびカリウムの合計の含有量は、好ましくは、 500-800 Oppmであり、ここにおいて、（B— 1)成分は、いずれか一方の元素の含有量が 0であ つてもよいし、両方の元素を含有してもよい。  When the component (B) of the present invention is composed of the component (B-1) and the component (B-2), the component (B-11) is the component (B-1) of the present invention. Preferably it is 0.1-20 mass parts with respect to a mass part, More preferably, it can be used in the range of 1-: 15 mass parts. The total content of sodium and potassium in the component (B-1) of the present invention is preferably 500-800 Oppm, wherein the component (B-1) is the content of either element May be 0, or may contain both elements.
本発明の制電性樹脂組成物にリチウム塩 (E)を添加する場合、（B)成分中のナトリ ゥムおよびカリウムの合計の含有量は、 0〜： !OOOppmであること力 S好ましく、 0〜500 ppmであることがより好ましぐ 0〜： !OOppmであることが特に好ましぐここにおいて、 (B)成分は、ナトリウムおよびカリウムのいずれか一方の元素の含有量が 0であっても ょレ、し、両方の元素を含有してもよい。  When the lithium salt (E) is added to the antistatic resin composition of the present invention, the total content of sodium and potassium in the component (B) is 0 to:! OOOppm 0 to 500 ppm is more preferable 0 to:! OOppm is particularly preferable. Here, the component (B) has a content of either one of sodium and potassium of 0. However, it may contain both elements.
ナトリウム及びカリウムの各含有量は、本発明の組成物の製造の際の添加量から計 算して求めることもできるし、本発明の組成物を蛍光 X線分析法、原子吸光分析法等 で測定することによって求めることもできる。  The respective contents of sodium and potassium can be calculated from the amount added in the production of the composition of the present invention, or the composition of the present invention can be obtained by fluorescent X-ray analysis, atomic absorption spectrometry, etc. It can also be determined by measuring.
本発明の（B— 1)成分における（B— a)成分/ (B— b)成分の好ましい比率は、 10 〜90/10〜90質量0 /0に範囲であり、更に好ましくは 20〜80/20〜80質量0 /0、特 に好ましくは、 30〜70/30〜70質量％の範囲である。 In (B- 1) ingredients of the present invention (B- a) component / (B- b) The preferred ratio of the components is in the range to 10 to 90/10 to 90 mass 0/0, more preferably 20 to 80 / 20 to 80 mass 0/0, JP Preferably, it is the range of 30-70 / 30-70 mass%.
このようなブロック重合体（B— 1)は、例えば、特開 2001— 278985号公報、特開 2 003— 48990号公報に記載の方法等で製造することができ、更に、本発明の（B— 1 )成分は、三'洋ィ匕成工業ネ土製ペレスタツ卜 300シリーズの 300、 303、ペレスタツ卜 200 シリーズの 230等として入手できる。  Such a block polymer (B-1) can be produced, for example, by the method described in JP-A-2001-278985 and JP-A-200003-48990, and further, (B — 1) The components are available as 300, 303 of Perezatsu 300 Series, 303, 230 of Pereztat 200 Series, etc.
[0031] 本発明の（B_ 2)成分は、前記（B_ l)成分において制電性を向上させる目的から 含有させるナトリウムおよび/またはカリウム含有化合物（B— 1一 1)の含有量が低減 されたもの又は該化合物（B— 1一 1 )を含有しなレ、成分であり、 (B- 1)成分で記載し たものが全て使用でき、これらは、 1種単独でまたは 2種以上を組み合わせて用いる こと力 Sできる。 （B— 2)成分は、例えば、該成分の重合時に用いるナトリウムおよび/ またはカリウム化合物（B— 1一 1)の量を低減させるか、または該化合物を使用せず に重合を行うことによって得られる。本発明の（B— 2)成分中のナトリウムおよび力リウ ムの合計の含有量は、好ましくは、 0〜： !OOppmであり、ここにおいて、（B— 2)成分 は、いずれか一方の元素の含有量が 0であってもよいし、両方の元素を含有してもよ レ、。 [0031] In the component (B_2) of the present invention, the content of the sodium and / or potassium-containing compound (B-11) contained in the component (B_l) for the purpose of improving antistatic properties is reduced. Or a component that does not contain the compound (B-1 1 1), and all of those described in the component (B-1) can be used. These can be used alone or in combination of two or more. Can be used in combination. The component (B-2) can be obtained, for example, by reducing the amount of sodium and / or potassium compound (B-11) used during the polymerization of the component, or by performing polymerization without using the compound. It is done. The total content of sodium and strong rhodium in the component (B-2) of the present invention is preferably 0 to:! OOppm, wherein the component (B-2) is any one of the elements The content of may be 0, or may contain both elements.
本発明の制電性樹脂組成物にリチウム塩 (E)を添加する場合においても、（B)成 分は、制電性を向上させる目的から、ナトリウムおよび/またはカリウム含有化合物（ B— 1 1)の含有量が低減されたもの又は該化合物（B— 1 1)を含有しない成分 であることが好ましい。力かる好ましい（B)成分として、上記成分 (B— 2)を使用する こと力 Sできる。  Even when the lithium salt (E) is added to the antistatic resin composition of the present invention, the component (B) is used for the purpose of improving antistatic properties. ) Or a component that does not contain the compound (B-11). It is possible to use the above component (B-2) as a preferable component (B).
成分 (B)を成分 (B— 1 )と成分 (B— 2)とから構成、又は、成分 (B— 2)単独で構成 することにより、ナトリウム及びカリウムの含有量の低い（B)成分を得ることができ、力べ して、ナトリウムイオン及びカリウムイオンの溶出量を好ましくは 2 z g/cm2以下、より 好ましくは 1 β gZcm2以下、さらにより好ましくは検出不能まで低減させることが可能 となる。 Component (B) is composed of component (B-1) and component (B-2), or composed of component (B-2) alone, so that component (B) having a low sodium and potassium content can be obtained. By virtue of this, it is possible to reduce the elution amount of sodium ions and potassium ions to 2 zg / cm 2 or less, more preferably 1 β gZcm 2 or less, and even more preferably to undetectable. Become.
[0032] 本発明の第一の制電性樹脂組成物において、（B)成分は、（A)成分、及び (B)成 分の合計 100質量％中、 2〜60質量％、好ましくは 3〜55質量％、更に好ましくは 5 〜55質量％、特に好ましくは 5〜50質量％であり、 2質量％未満では制電性が劣り、 60質量％を超えると熱安定性が劣り、場合によっては溶出イオン量が多くなることが ある。 [0032] In the first antistatic resin composition of the present invention, the component (B) is 2 to 60% by mass, preferably 3 in the total of 100% by mass of the component (A) and the component (B). ~ 55 wt%, more preferably 5 to 55 wt%, particularly preferably 5 to 50 wt%, and if less than 2 wt%, the antistatic property is inferior, If it exceeds 60% by mass, the thermal stability is inferior, and in some cases, the amount of eluted ions may increase.
優れた耐薬品性と成形品表面外観が要求される用途では、（B)成分は、（A)成分 及び（B)成分の合計 100質量％中、好ましくは 2〜40質量％、より好ましくは 3〜35 質量％、より更に好ましくは 5〜35質量％、特に好ましくは 5〜30質量％であり、 40 質量％を超えると耐薬品性、表面外観性が劣る傾向がある。優れた制電性と熱安定 性が要求される用途では、（B)成分は、（A)成分及び (B)成分の合計 100質量％中 、好ましくは 30〜60質量％、更に好ましくは 35〜50質量％である。高い制電性を有 し、平滑な表面を有するシート表面外観の優れた発泡積層シートの表層として使用さ れる場合は、（B)成分は、（A)成分及び (B)成分の合計 100質量％中、好ましくは 2 0〜60質量％、更に好ましくは 30〜50質量％である。  In applications where excellent chemical resistance and molded product surface appearance are required, component (B) is a total of 100% by mass of component (A) and component (B), preferably 2 to 40% by mass, more preferably It is 3 to 35% by mass, more preferably 5 to 35% by mass, and particularly preferably 5 to 30% by mass. If it exceeds 40% by mass, the chemical resistance and the surface appearance tend to be inferior. In applications that require excellent antistatic properties and thermal stability, component (B) is a total of 100% by mass of component (A) and component (B), preferably 30-60% by mass, more preferably 35%. ~ 50% by weight. When used as a surface layer of a foamed laminated sheet that has high antistatic properties and a smooth surface, and has a smooth surface, component (B) is a total of 100 masses of component (A) and component (B). %, Preferably 20 to 60% by mass, more preferably 30 to 50% by mass.
(B)成分を上記 (B— 1)成分と (B— 2)成分から構成する場合、使用する比率は、 ( B— 1)成分の（B— 2)成分に対する質量比にして 1/99〜90/10の範囲であること が好ましぐ更に好ましくは 2/98〜85/15、より更に好ましくは 10/90〜85/15 、より更【こ一層好まし <ίま 15/85〜80/20、特 ίこ好まし < ίま 20/80〜75/25であ り、この範囲において特に制電性と溶出イオン量のバランスに優れる。  When component (B) is composed of component (B-1) and component (B-2), the ratio used is 1/99 as the mass ratio of component (B-1) to component (B-2). It is preferably in the range of ~ 90/10, more preferably 2/98 to 85/15, even more preferably 10/90 to 85/15, and even more <more preferred <ί or 15/85 ~ 80/20, specially preferred <<20/80 to 75/25, especially in this range, the balance between antistatic properties and the amount of ions eluted is excellent.
(Β— 1)成分の使用量を増加させると、制電性を向上させる目的からは有効である 力 成形品からの好ましくないナトリウム、カリウム等の溶出量が増える。このこと力 、 本発明の第一の制電性樹脂組成物における（B—1)成分の使用量は、（Α)成分及 び（Β)成分の合計 100重量％に対して 1〜 15質量％が好ましく、より好ましくは 3〜 1 3質量％、さらにより好ましくは 5〜： 10質量％であり、特に好ましくは 5〜9質量％であ る。  (Β-1) Increasing the amount of component used is effective for the purpose of improving antistatic properties. Force Elution amount of undesired sodium, potassium, etc. from molded products increases. For this reason, the amount of the component (B-1) used in the first antistatic resin composition of the present invention is 1 to 15 mass with respect to the total of 100% by weight of the components (i) and (ii). %, More preferably 3 to 13% by mass, still more preferably 5 to 10% by mass, and particularly preferably 5 to 9% by mass.
本発明によれば、（Β)成分を上記（Β— 1)成分と（Β— 2)成分から構成することによ り、表面抵抗率（23°C、 50%RH条件下で測定） Ι Χ ΙΟ1^ /口以下、好ましくは 5 Χ ΙΟ^ Ω /口以下であって、かつ、ナトリウムイオン及びカリウムイオンの溶出量（80 °C、 60分間抽出条件下で測定) 3 x g/cm2以下の要件を満たし、したがって、制電 性と溶出イオンを従来になく高度にバランスさせた成形体が得られる。従来の技術に おいては、制電性を向上させるために上記（B_ l)成分の配合量を上げていた力 こ の場合、成形品からの溶出イオンが増える方向にあった。これに対し、本発明によれ ば、制電性と溶出イオンが高度にバランスさせた成形体が、例えば、従来用いられて レ、た (B 1)成分と従来になレ、（B— 2)成分を併用することで得られる。 (B)成分とし て（B— 1)成分と（B— 2)成分を併用した場合、ナトリウムイオン及びカリウムイオンの 溶出量を好ましくは 2 μ g/cm2以下、より好ましくは 1 μ gZcm2以下にまで低減させ ること力 S可肯 となる。 According to the present invention, the surface resistivity (measured under conditions of 23 ° C. and 50% RH) can be obtained by composing the component (Β) from the components (Β-1) and (Β-2). ^ ΙΟ 1 ^ / mouth or less, preferably 5 ΙΟ ΙΟ ^ Ω / mouth or less, and elution amount of sodium ion and potassium ion (measured under extraction conditions at 80 ° C for 60 minutes) 3 xg / cm 2 A molded product that satisfies the following requirements and therefore has a high balance between antistatic properties and eluted ions is obtained. In the prior art, in order to improve antistatic performance, the amount of the above (B_l) component was increased. In the case of, the elution ions from the molded product increased. On the other hand, according to the present invention, a molded body in which the antistatic property and the eluted ions are highly balanced can be used, for example, in the past, with the component (B 1) and the conventional component (B-2). It is obtained by using the component) together. When component (B-1) and component (B-2) are used together as component (B), the elution amount of sodium ions and potassium ions is preferably 2 μg / cm 2 or less, more preferably 1 μg Zcm 2 The ability to reduce the following to S is positive.
本発明の制電性樹脂組成物に関わる (E)成分はリチウム塩であり、この成分を配合 することにより、制電性を向上させる効果が得られる。  The component (E) relating 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.
リチウム塩 (E)としては、過塩素酸リチウム、トリフルォロメタンスルホン酸リチウム、ビ ス（トリフルォロメタンスルホニル）イミドリチウム、及びトリス（トリフルォロメタンスルホ二 ル)メタンリチウム等が好ましく使用され、更に好ましくはトリフルォロメタンスルホン酸 リチウムである。これらは、 1種単独で、または 2種以上を組み合わせて使用すること ができる。これらは、三光化学工業社製サンコノール 0862— 13T、 AQ— 50T、 AQ — 75Τ、 ΤΒΧ— 25 (商品名）として溶液、マスターバッチとして入手することができる 本発明の第一の制電性樹脂組成物において、（Ε)成分は、 （Α)成分及び (Β)成分 の合計 100質量部に対して、 0. 01〜5質量部の範囲で用いることが好ましぐ更に 好ましくは 0. ：!〜 3質量部、特に好ましくは 0. 3〜2質量部の範囲で使用される。そ の使用量が、 0. 01質量部未満では制電性を向上させる効果が得られず、又 5質量 部を超えると耐衝撃性が低下する傾向にある。  As the lithium salt (E), lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonyl) imide, tris (trifluoromethanesulfonyl) methane lithium, etc. are preferably used. Lithium trifluoromethanesulfonate is preferred. These can be used alone or in combination of two or more. These are Sankonoru manufactured by Sanko Chemical Co., Ltd. 0862-13T, AQ-50T, AQ—75Τ, ΤΒΧ-25 (trade name), which can be obtained as a solution or a masterbatch The first antistatic resin composition of the present invention In the product, the (Ε) component is preferably used in the range of 0.01 to 5 parts by mass with respect to the total of 100 parts by mass of the (Α) and (Β) components. To 3 parts by mass, particularly preferably in the range of 0.3 to 2 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 if it exceeds 5 parts by mass, the impact resistance tends to decrease.
また、本発明の第一の制電性樹脂組成物にリチウム塩 (Ε)を配合することにより、 表面抵抗率（23°C、 50%RH条件下で測定） 1 X 1011 Ω /口以下、好ましくは 1 X 1 Ο^ Ω /口以下であって、かつ、ナトリウムイオン及びカリウムイオンの溶出量（80°C、 60分間抽出条件下で測定) 3 μ g/cm2以下、好ましくは検出不能の要件を満たし、 したがって、制電性と溶出イオンを従来になく高度にバランスさせた成形体が得られ る。従来の技術においては、制電性を向上させるために上記（B)成分の配合量を上 げていたが、この場合、成形品からの溶出イオンが増える方向にあった。これに対し 、本発明によれば、リチウム塩を所定量配合し、好ましくは、上記（B)成分としてナトリ ゥムおよび/またはカリウムの含有量が低いかまたはこれらの元素を実質的に含まな レ、ものを使用することにより、制電性と溶出イオンが高度にバランスされた成形体が 得られる。 In addition, by adding lithium salt (で) to the first antistatic resin composition of the present invention, surface resistivity (measured under conditions of 23 ° C and 50% RH) 1 X 10 11 Ω / mouth or less 1 x 1 Ο ^ Ω / mouth or less, and sodium ion and potassium ion elution amount (measured under extraction conditions at 80 ° C for 60 minutes) 3 μg / cm 2 or less, preferably detection Therefore, it is possible to obtain a molded body that satisfies the impossibility requirement and therefore has a highly balanced antistatic property and eluted ions. In the prior art, the blending amount of the component (B) was increased in order to improve antistatic properties, but in this case, the amount of ions eluted from the molded product was increasing. On the other hand, according to the present invention, a predetermined amount of lithium salt is blended, and preferably, sodium (N) is used as the component (B). By using a product having a low content of sulfur and / or potassium or substantially free of these elements, a molded product having a high balance between antistatic properties and eluted ions can be obtained.
[0034] 二の制 件榭脂組成 の^明  [0034] The second system
本発明の第二の制電性樹脂組成物は、第一の制電性樹脂組成物に更に (C)成分 、及び (D)成分を含むものであり、制電性と溶出イオンのバランスが向上し、そして、 耐衝撃性が高くなる。  The second antistatic resin composition of the present invention further comprises (C) component and (D) component in the first antistatic resin composition, and the balance between antistatic properties and eluted ions is Improves and increases impact resistance.
本発明の第二の制電性樹脂組成物において、（A)成分は、前記したォレフィン系 樹脂 (A)が全て使用でき、これらは 1種単独で、または 2種以上を組み合わせて使用 すること力 Sできる。  In the second antistatic resin composition of the present invention, as the component (A), the above-described olefin-based resins (A) can all be used, and these can be used alone or in combination of two or more. Power S can be.
[0035] 本発明の第二の制電性樹脂組成物において、（A)成分の使用量は、本発明の (A )成分、（B)成分、（C)成分及び (D)成分の合計 100質量％中、 7〜91質量％、好ま しくは 10〜85質量％、より好ましくは 15〜80質量％、更により好ましくは 15〜70質 量％、特に好ましくは 15〜65質量％である。その使用量が 7質量％未満では、耐衝 撃性及び制電性が劣り、 91質量％を超えると制電性及び耐衝撃性が劣る。  [0035] In the second antistatic resin composition of the present invention, the amount of the component (A) used is the sum of the components (A), (B), (C) and (D) of the present invention. In 100% by mass, 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. . If the amount used is less than 7% by mass, the impact resistance and anti-static property are poor, and if it exceeds 91% by mass, the anti-static property and impact resistance are poor.
優れた耐薬品性と成形品表面外観が要求される用途では、 (A)成分の使用量は、 (A)成分、（B)成分、（C)成分及び (D)成分の合計 100質量％中、好ましくは 10〜 85質量％、更に好ましくは 20〜80質量％、特に好ましくは 30〜75質量％である。 その使用量が 30質量％未満では耐薬品性及び成形品表面外観が劣る傾向がある 。優れた制電性と熱安定性が要求される用途では、（A)成分の使用量は、（A)成分 、（B)成分、（C)成分及び (D)成分の合計 100質量％中、好ましくは 7〜40質量％、 更に好ましくは 10〜35質量％である。高い制電性を有し、平滑な表面を有するシー ト表面外観の優れた発泡積層シートの表層として使用される場合は、（A)成分の使 用量は、（A)成分、 （B)成分、 （C)成分及び (D)成分の合計 100質量％中、好ましく は 7〜30質量％、更に好ましくは 7〜25質量％である。  In applications where excellent chemical resistance and molded product surface appearance are required, the amount of component (A) used is 100% by mass of component (A), component (B), component (C) and component (D). 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 of component (A), component (B), component (C) and component (D). The amount is preferably 7 to 40% by mass, more preferably 10 to 35% by mass. When used as the surface layer of a foamed laminated sheet with high antistatic properties and a smooth surface with a smooth surface, the amount of component (A) used is component (A), component (B) In the total 100% by mass of the component (C) and the component (D), preferably 7 to 30% by mass, more preferably 7 to 25% by mass.
本発明の第二の制電性樹脂組成物において、（B)成分は、前記した（B)成分が全 て使用でき、これらは 1種単独で、または 2種以上を組み合わせて使用することができ る。 本発明の第二の制電性樹脂組成物において、（B)成分の使用量は、本発明の (A )成分、（B)成分、（C)成分及び (D)成分の合計 100質量％中、 2〜60質量％、好ま しくは 3〜55質量％、更に好ましくは 5〜55質量％、特に好ましくは 5〜50質量％で あり、 2質量％未満では、制電性が劣り、 60質量％を超えると熱安定性が劣る。 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. it can. In the second antistatic resin composition of the present invention, the amount of component (B) used is 100% by mass in total of the components (A), (B), (C) and (D) 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. If it exceeds mass%, the thermal stability is poor.
優れた耐薬品性と成形品表面外観が要求される用途では、（B)成分は、（A)成分 、（B)成分、（C)成分及び (D)成分の合計 100質量％中、好ましくは 2〜40質量％、 より好ましくは 3〜35質量％、更により好ましくは 5〜35質量％、特に好ましくは 5〜3 0質量％であり、 40質量％を超えると成形品表面外観及び耐衝撃性が劣る傾向があ る。優れた制電性と熱安定性が要求される用途では、 （B)成分は、（A)成分、（B)成 分、（C)成分及び (D)成分の合計 100質量％中、好ましくは 30〜60質量％、更に 好ましくは 35〜50質量％である。高い制電性を有し、平滑な表面を有するシート表 面外観の優れた発泡積層シートの表層として使用される場合は、 （B)成分は、 (A) 成分、（B)成分、（C)成分及び (D)成分の合計 100質量％中、好ましくは 20〜60質 量％、更に好ましくは 30〜60質量％、特に好ましくは 40〜60質量％である。  In applications where excellent chemical resistance and molded product surface appearance are required, component (B) is preferably in a total of 100% by mass of component (A), component (B), component (C) and component (D). Is 2 to 40% by mass, more preferably 3 to 35% by mass, even more preferably 5 to 35% by mass, particularly preferably 5 to 30% by mass. There is a tendency for impact properties to be inferior. For applications that require excellent antistatic properties and thermal stability, component (B) is preferably used in a total of 100% by mass of component (A), component (B), component (C) and component (D). Is 30 to 60% by mass, more preferably 35 to 50% by mass. When used as the surface layer of a foam laminated sheet with high antistatic properties and a smooth surface, the (B) component contains the components (A), (B), (C ) Component and (D) component in a total of 100% by mass, preferably 20 to 60% by mass, more preferably 30 to 60% by mass, and particularly preferably 40 to 60% by mass.
(B)成分を上記 (B— 1)成分と (B— 2)成分から構成する場合、使用する比率は、 ( B— 1)成分の（B— 2)成分に対する質量比にして 1/99〜90/10の範囲であること が好ましぐ更に好ましくは 2/98〜85/15、より更に好ましくは 10/90〜85/15 、より更【こ一層好まし <ίま 15/85〜80/20、特 ίこ好まし < ίま 20/80〜75/25であ り、この範囲において特に制電性と溶出イオン量のバランスに優れる。  When component (B) is composed of component (B-1) and component (B-2), the ratio used is 1/99 as the mass ratio of component (B-1) to component (B-2). It is preferably in the range of ~ 90/10, more preferably 2/98 to 85/15, even more preferably 10/90 to 85/15, and even more <more preferred <ί or 15/85 ~ 80/20, specially preferred <<20/80 to 75/25, especially in this range, the balance between antistatic properties and the amount of ions eluted is excellent.
(Β— 1)成分の使用量を増加させると、制電性を向上させる目的からは有効である 力 成形品からの好ましくないナトリウム、カリウム等の溶出量が増える。このこと力 、 本発明の第二の制電性樹脂組成物における（B—1)成分の使用量は、（Α)成分、（ Β)成分、 （C)成分及び (D)成分の合計量の:!〜 15質量％が好ましぐより好ましくは 3〜： 13質量％、さらにより好ましくは 5〜： 10質量％であり、特に好ましくは 5〜9質量 %である。  (Β-1) Increasing the amount of component used is effective for the purpose of improving antistatic properties. Force Elution amount of undesired sodium, potassium, etc. from molded products increases. For this reason, the amount of the component (B-1) used in the second antistatic resin composition of the present invention is the total amount of the component (Α), the component (Β), the component (C) and the component (D). More preferably, it is 3 to 13 mass%, still more preferably 5 to 10 mass%, and particularly preferably 5 to 9 mass%.
本発明によれば、表面抵抗率（23°C、 50%RH条件下で測定） 1 X 10" 0 /ロ以 下、好ましくは 5 X 101Q Q /口以下であって、かつ、ナトリウムイオン及びカリウムィォ ンの溶出量 (80°C、 60分間抽出条件下で測定） 3 z g/cm2以下の要件を満たし、し たがって、制電性と溶出イオンを従来になく高度にバランスさせた成形体が得られる 。従来の技術においては、制電性を向上させるために上記（B— 1)成分の配合量を 上げていたが、この場合、成形品からの溶出イオンが増える方向にあった。これに対 し、本発明によれば、制電性と溶出イオンが高度にバランスさせた成形体が、例えば 、従来用いられていた (B— 1)成分と従来にない (B— 2)成分を併用することで得ら れる。 （B)成分として (B_ l)成分と (B_ 2)成分を併用した場合、ナトリウムイオン及 びカリウムイオンの溶出量を好ましくは 2 a g/cm2以下、より好ましくは 1 μ gZcm2以 下にまで低減させることが可能となる。 According to the present invention, the surface resistivity (measured under conditions of 23 ° C. and 50% RH) is 1 X 10 "0 / b or less, preferably 5 X 10 1Q Q / m or less, and sodium ion And potassium ion elution (measured under extraction conditions at 80 ° C for 60 minutes) 3 zg / cm 2 or less Therefore, a molded body in which the antistatic property and the eluted ions are highly balanced compared to the conventional one can be obtained. In the prior art, the blending amount of the component (B-1) was increased in order to improve antistatic properties, but in this case, the amount of ions eluted from the molded product was increasing. On the other hand, according to the present invention, a molded body in which antistatic properties and eluted ions are highly balanced is, for example, a conventionally used (B-1) component and an unprecedented (B-2) component. It is obtained by using together. When component (B_l) and component (B_2) are used in combination as component (B), the elution amount of sodium ions and potassium ions is preferably 2 ag / cm 2 or less, more preferably 1 μg Zcm 2 or less. It becomes possible to reduce to.
本発明の制電性樹脂組成物にリチウム塩 (E)を添加する場合においても、（B)成 分は、制電性を向上させる目的から、ナトリウムおよび/またはカリウム含有化合物（ B- 1 - 1)の含有量が低減されたもの又は該化合物（B— 1一 1)を含有しない成分 であることが好ましい。力、かる好ましい（B)成分として、上記成分 (B— 2)を使用する こと力 Sできる。このようにナトリウム及びカリウムの含有量の低レ、（B)成分を用いること により、ナトリウムイオン及びカリウムイオンの溶出量を好ましくは 2 /i g/cm2以下、よ り好ましくは 1 β g/cm2以下、さらにより好ましくは検出不能まで低減させることが可 能となる。 Even when the lithium salt (E) is added to the antistatic resin composition of the present invention, the component (B) is used for the purpose of improving antistatic properties. It is preferable that the content of 1) is reduced or the component does not contain the compound (B-1 1 1). The use of the above component (B-2) as the component (B) is preferable. Thus, by using the low content of sodium and potassium and component (B), the elution amount of sodium ions and potassium ions is preferably 2 / ig / cm 2 or less, more preferably 1 β g / cm 2. It is possible to reduce it to 2 or less, and even more preferably to be undetectable.
[0037] 本発明の（C)成分は、芳香族ビュル化合物から主としてなる重合体ブロック（C 1 )と共役ジェン化合物から主としてなる重合体ブロック（C 2)とを含有するブロック共 重合体 (C a)及びその水素添加物（C b)からなる群より選ばれる少なくとも 1種の 重合体であり、エラストマ一としての性質を示すものである。  [0037] The component (C) of the present invention comprises a block copolymer (C 1) containing a polymer block (C 1) mainly composed of an aromatic bur compound and a polymer block (C 2) mainly composed of a conjugated diene compound. It is at least one polymer selected from the group consisting of a) and its hydrogenated product (Cb), and exhibits properties as an elastomer.
[0038] ここで使用される芳香族ビエル化合物としては、スチレン、 α—メチルスチレン、ヒド ロキシスチレン等が挙げられ、好ましくはスチレン、 ひーメチルスチレンであり、特に好 ましくはスチレンである。  [0038] Examples of the aromatic vinyl compound used here include styrene, α-methylstyrene, hydroxystyrene, and the like, preferably styrene and hymethylstyrene, and particularly preferably styrene.
また、共役ジェン化合物としては、ブタジエン、イソプレン、へキサジェン、 2, 3—ジ メチル一1 , 3_ブタジエン、 1 , 3 _ペンタジェン等があり、好ましくはブタジエン、イソ プレンである。これらは、 1種単独で、または 2種以上を組み合わせて用いることがで きる。更に、ブロック（C— 2)は、 2種以上の共役ジェン化合物を使用し、それらがラン ダム状、ブロック状、テーパー状のいずれの形態で結合したブロックであってもよい。 また、（C— 2)は、芳香族ビニルイ匕合物が漸増するテーパーブロックを 1〜： 10個の範 囲で含有していてもよぐ重合体ブロック（C— 2)の共役ジェンィ匕合物に由来するビ ニル結合含有量の異なる重合体ブロック等が、適宜共重合してレ、てもよレ、。 Conjugation compounds include butadiene, isoprene, hexagene, 2,3-dimethyl-1,3-butadiene, 1,3-pentane, and the like, preferably butadiene and isoprene. These can be used alone or in combination of two or more. Further, the block (C-2) may be a block in which two or more conjugated gen compounds are used and these are combined in any form of random, block, or taper. In addition, (C-2) is a conjugate block of polymer block (C-2) that may contain taper blocks in which the aromatic vinyl compound is gradually increased in the range of 1 to 10 Polymer blocks with different vinyl bond content derived from the product may be copolymerized as appropriate.
[0039] 本発明の（C)成分の好ましい構造は下記式 (VI)〜 (VIII)で表される重合体または その水素添加物である。 [0039] A preferred structure of the component (C) of the present invention is a polymer represented by the following formulas (VI) to (VIII) or a hydrogenated product thereof.
(A-B) (VI)  (A-B) (VI)
Y  Y
(A-B) —X (VII)  (A-B) —X (VII)
γ  γ
A- (B-A) (VIII)  A- (B-A) (VIII)
z  z
(構造式 (VI)〜 (VIII)中、 Aは芳香族ビニル化合物を主体とする重合体ブロックで 、実質的に芳香族ビニル化合物からなる重合体ブロックであれば、一部共役ジェン 化合物が含まれていてもよい。好ましくは芳香族ビュル化合物を 90質量％以上、更 に好ましくは 99質量％以上含有する重合体ブロックである。 Bは共役ジェンィ匕合物 の単独重合体または芳香族ビニルイヒ合物等の他の単量体と共役ジェンィヒ合物との 共重合体であり、 Xはカップリング剤の残基であり、 Yは 1〜5の整数、 Zは 1〜5の整 数をそれぞれ表す。 Bが芳香族ビニル化合物等の他の単量体と共役ジェン化合物と の共重合体である場合、 B中の当該他の単量体の含有量は、共役ジェン化合物と当 該他の単量体との合計に対して 50質量％以下であること好ましい。 )  (In the structural formulas (VI) to (VIII), A is a polymer block mainly composed of an aromatic vinyl compound, and if it is a polymer block consisting essentially 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, and more preferably 99% by mass or more of an aromatic bur compound B is a homopolymer of a conjugated Jheny compound or an aromatic vinyl compound. X is the residue of the coupling agent, Y is an integer from 1 to 5, and Z is an integer from 1 to 5, respectively. In the case where B is a copolymer of a conjugation compound and another monomer such as an aromatic vinyl compound, the content of the other monomer in B is determined based on the conjugation compound and the other conjugation compound. It is preferably 50% by mass or less based on the total with the monomer.
[0040] 本発明の（C)成分における、芳香族ビニル化合物と共役ジェン化合物の使用割合 は、芳香族ビニルィ匕合物/共役ジェン化合物= 10〜70/30〜90質量％の範囲が 好ましく、更に好ましく ίま 15〜65/35〜85質量0 /0、特に好ましく ίま 20〜60/40〜 80質量％の範囲である。 [0040] In the component (C) of the present invention, the use ratio of the aromatic vinyl compound and the conjugated gen compound is preferably within the range of aromatic vinyl compound / conjugated gen compound = 10 to 70/30 to 90% by mass, more preferably ί or 15 to 65/35 to 85 mass 0/0, in particular in the range of preferably ί or 20-60 / 40-80 mass%.
[0041] 芳香族ビニル化合物と共役ジェン化合物からなるブロック共重合体は、ァニオン重 合の技術分野で公知のものであり、例えば特公昭 47— 28915号公報、特公昭 47— 3252号公報、特公昭 48— 2423号公報、更に特公昭 48— 20038号公報等に開示 されている。また、テーパーブロックを有する重合体ブロックの製造方法については、 特開昭 60— 81217号公報等に開示されている。  [0041] Block copolymers comprising an aromatic vinyl compound and a conjugated gen compound are known in the technical field of anion polymerization, such as Japanese Patent Publication Nos. 47-28915 and 47-3252. This is disclosed in Japanese Patent Publication Nos. 48-2423 and 48-20038. Further, a method for producing a polymer block having a tapered block is disclosed in JP-A-60-81217 and the like.
[0042] 本発明の（C)成分の共役ジェン化合物に由来するビニル結合量（1， 2_及び 3， 4 —結合)含有量は、好ましくは 5〜80%の範囲であり、本発明の（C)成分の数平均分 子量 ίま、好ましく ίま 10, 000〜： 1, 000, 000、更に好ましく ίま 20, 000力ら 500, 00 0、特に好ましくは 20, 000〜200, 000である。これらのうち上記（VI)〜（VIII)で表 した Α部の数平均分子量は 3, 000〜： 150, 000、 B部の数平均分子量は 5, 000〜 200, 000の範囲であること力 S好ましレヽ。 [0042] The content of vinyl bonds (1, 2_ and 3, 4 — bonds) derived from the conjugate conjugate compound of component (C) of the present invention is preferably in the range of 5 to 80%. (C) Number average component The amount of the lye is preferably ί, 10,000, 000, 000, 000, more preferably 2,000, 000, 500,000, and particularly preferably 20,000, 200,000. Among these, the number average molecular weight of the buttocks represented by the above (VI) to (VIII) is 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. S-preferred.
[0043] 共役ジェン化合物のビュル結合量の調整は、 N, N, Ν' , N'—テトラメチルェチレ ンジァミン、トリメチルァミン、トリエチノレアミン、ジァゾシクロ（2, 2, 2)ォクタミン等のァ ミン類、テトラヒドロフラン、ジエチレングリコールジメチルエーテル、ジエチレングリコ ールジブチルエーテル等のエーテル類、チォエーテル類、ホスフィン類、ホスホアミド 類、アルキルベンゼンスルホン酸塩、カリウムやナトリウムのアルコキシド等を用いて 行うことができる。 [0043] Adjustment of the amount of bull bonds of conjugation compounds can be achieved by using N, N, Ν ', N'-tetramethylethylenediamine, trimethylamine, triethinoleamine, diazocyclo (2, 2, 2) octamine, etc. Amines, tetrahydrofuran, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether and other ethers, thioethers, phosphines, phosphoamides, alkylbenzene sulfonates, alkoxides of potassium and sodium, and the like can be used.
上記方法で重合体を得た後、カップリング剤を使用して重合体分子鎖がカップリン グ剤残基を介して延長または分岐された重合体も本発明の（C)成分に好ましく含ま れる力 ここで使用されるカップリング剤としてはアジピン酸ジェチル、ジビニルベン ゼン、メチルジクロロシラン、四塩化珪素、ブチルトリクロ口珪素、テトラクロ口錫、ブチ ノレトリクロ口錫、ジメチルクロ口珪素、テトラクロ口ゲルマニウム、 1, 2—ジブロモェタン 、 1 , 4—クロロメチルベンゼン、ビス（トリクロロシリル）ェタン、エポキシ化アマ二油、ト リレンジイソシァネート、 1 , 2, 4—ベンゼントリイソシァネート等が挙げられる。  A polymer in which a polymer molecular chain is extended or branched via a coupling agent residue using a coupling agent after the polymer is obtained by the above method is also preferably included in the component (C) of the present invention. Power Coupling agents used here include decyl adipate, divinyl benzene, methyl dichlorosilane, silicon tetrachloride, butyl trichloro silicon, tetra black tin, butyl black tri tin, dimethyl black silicon, tetra black germanium, 1 , 2-dibromoethane, 1,4-chloromethylbenzene, bis (trichlorosilyl) ethane, epoxidized flax oil, tolylene diisocyanate, 1,2,4-benzene triisocyanate, and the like.
[0044] 上記ブロック共重合体の内、耐衝撃性の点から好ましいものは、ブロック（C— 2)に 芳香族ビュル化合物が漸増するテーパーブロックを 1〜： 10個の範囲で有する重合 体、及び/又は、カップリング処理されたラジアルブロックタイプのものである。  [0044] Among the above block copolymers, preferred from the viewpoint of impact resistance is a polymer having in the range of 1 to 10 taper blocks in which the aromatic bur compound gradually increases in the block (C-2), And / or coupled radial block type.
[0045] また、 （C)成分として、上記ブロック共重合体そのものを用いることも、また共役ジェ ン部分の炭素一炭素二重結合を部分的にまたは完全に水素添加したものを用いる こと力 Sできる。得られた組成物の低温衝撃性からは、水素添カ卩していないものまたは 水素添加率が 90%未満のものを用いることが好ましぐ得られた組成物の耐候（光） 性の面からは、 90%以上水素添加されたものを用いることが好ましい。  [0045] In addition, as the component (C), the block copolymer itself can be used, or a carbon-carbon double bond of a conjugated gen moiety partially or completely hydrogenated can be used. it can. From the viewpoint of low-temperature impact properties of the obtained composition, it is preferable to use one that is not hydrogenated or has a hydrogenation rate of less than 90%. From that, it is preferable to use a product hydrogenated 90% or more.
[0046] 上記方法で得た芳香族ビュルィヒ合物から主としてなる重合体ブロックと共役ジェン 化合物から主としてなる重合体ブロックとを含有するブロック共重合体の水素添加反 応は、公知の方法で行うことができるし、また、公知の方法で水素添加率を調整する ことにより、 目的の重合体を得ることができる。具体的な方法としては、特公昭 42— 8 704号公報、特公昭 43— 6636号公報、特公昭 63— 4841号公報、特公昭 63— 54 01号公報、特開平 2— 133406号公報、特開平 1 297413号公報に開示されてい る方法がある。 [0046] The hydrogenation reaction of the block copolymer containing the polymer block mainly composed of the aromatic Bürich compound and the polymer block mainly composed of the conjugated compound obtained by the above method is carried out by a known method. And the hydrogenation rate is adjusted by a known method. As a result, the desired polymer can be obtained. Specific methods include JP-B-42-8704, JP-B-43-6636, JP-B-63-4841, JP-B-63-5401, JP-A-2-133406, There is a method disclosed in Kaihei 1 297413.
[0047] 上記ブロック共重合体（C一 a)及びその水素添加物（C一 b)は、他の重合体がブロ ック重合体及び/又はグラフト重合体 (但し、下記（D)成分として使用したものと同一 でもよレ、し、同一でなくてもよい）として化学的に結合したものであってもよい。  [0047] The block copolymer (C 1a) and its hydrogenated product (C 1b) are other polymers such as a block polymer and / or a graft polymer (however, as the component (D) below) It may be the same as that used, or may not be the same) and may be chemically bonded.
上記ブロック共重合体（C一 a)及びその水素添加物（C一 b)に化学的に結合してい る他の重合体は、 100質量％が化学的に結合している必要はなぐ他の重合体の少 なくとも 10質量％が化学的に結合しておれば本発明の目的は達成できる。  The block copolymer (C 1 a) and other polymers chemically bonded to the hydrogenated product (C 1 b) are not necessarily 100% by mass chemically bonded to other polymers. The object of the present invention can be achieved if at least 10% by weight of the polymer is chemically bonded.
[0048] 上記ブロック共重合体（C一 a)及びその水素添加物（C一 b)にブロック重合として結 合される他の重合体として好ましいものは、芳香族ポリカーボネート及び Z又はポリゥ レタンであり、更に好ましくは芳香族ポリカーボネートである。芳香族ポリカーボネート ブロック共重合体混合物は、例えば、特開 2001— 220506号公報に記載の方法で 製造すること力 sできる。更に、クラレ社製 TMポリマーシリーズの TM— S4L77、TM -H4L77 (商品名）等として入手すること力 Sできる。 [0048] Preferred as other polymers to be combined as block polymerization with the block copolymer (C-1a) and its hydrogenated product (C-1b) are aromatic polycarbonate and Z or polyurethane. More preferably, it is an aromatic polycarbonate. Aromatic polycarbonate block copolymer mixture may, for example, can be force s produced by a method described in JP-A-2001- 220506. Furthermore, it can be obtained as TM-S4L77, TM-H4L77 (trade name) of TM polymer series manufactured by Kuraray.
[0049] また、他の重合体を上記ブロック共重合体（C a)及びその水素添加物（C b)に グラフト重合させるために特に好ましい方法は、上記ブロック共重合体（C a)及び その水素添加物（C b)の存在下にビュル系単量体をグラフト重合する方法である。 該ビュル単量体としては下記（D)成分のビニル系単量体 (D— b) (但し、下記（D)成 分で使用したものと同一でもよいし、同一でなくてもよい）が好ましく使用される。ダラ フト重合する方法としては、 （D)成分について後述する乳化重合、溶液重合、塊状 重合、懸濁重合等が全て使用でき、更に好ましくは溶液重合及び塊状重合である。  [0049] In addition, a particularly preferred method for graft polymerizing the other polymer to the block copolymer (C a) and the hydrogenated product (C b) thereof is the block copolymer (C a) and its This is a method of graft polymerization of a bull monomer in the presence of a hydrogenated product (Cb). The bulle monomer includes the following (D) component vinyl monomer (D-b) (however, it may or may not be the same as that used in the following (D) component): Preferably used. As the method for the draft polymerization, emulsion polymerization, solution polymerization, bulk polymerization, suspension polymerization and the like described later for the component (D) can be used, and solution polymerization and bulk polymerization are more preferable.
[0050] 本発明の第二の制電性樹脂組成物において、（C)成分は、本発明の (A)成分、 （ B)成分、 （C)成分及び (D)成分の合計 100質量％中、 2〜50質量％、好ましくは 5 〜45質量％、更に好ましくは 7〜40質量％、特に好ましくは 10〜35質量％であり、 2質量％未満では耐衝撃性が劣り、 50質量％を超えると耐衝撃性及び表面外観性 が劣る。高い制電性を有し、平滑な表面を有するシート表面外観の優れた発泡積層 シートの表層として使用される場合は、（C)成分は、（A)成分、（B)成分、 （C)成分 及び (D)成分の合計 100質量％中、好ましくは 15〜50質量％、更に好ましくは 20 〜45質量％である。 [0050] In the second antistatic resin composition of the present invention, the component (C) is a total of 100 mass% of the components (A), (B), (C) and (D) of the present invention. Among them, 2 to 50% by mass, preferably 5 to 45% by mass, more preferably 7 to 40% by mass, particularly preferably 10 to 35% by mass, and less than 2% by mass has poor impact resistance, and 50% by mass If it exceeds, the impact resistance and surface appearance will be poor. Highly antistatic foam lamination with a smooth surface with a smooth surface When used as a surface layer of a sheet, the component (C) is a total of 100% by mass of the components (A), (B), (C) and (D), preferably 15 to 50% by mass, More preferably, it is 20-45 mass%.
[0051] 本発明の（D)成分は、ゴム質重合体 (D— a)の存在下に芳香族ビニル化合物を含 むビニル系単量体 (D_b)を重合して得られたゴム強化スチレン系樹脂（D_ 1)、お よび/または該ビニル系単量体の（共)重合体 (D - 2)である。後者の（共)重合体（ D- 2)は、ゴム質重合体 (D_a)の非存在下に、芳香族ビニル化合物を含むビニル 系単量体（D_b)を重合して得られるものである。  [0051] The component (D) of the present invention is a rubber-reinforced styrene obtained by polymerizing a vinyl monomer (D_b) containing an aromatic vinyl compound in the presence of a rubbery polymer (Da). Resin (D_1) and / or (co) polymer (D-2) of the vinyl monomer. The latter (co) polymer (D-2) is obtained by polymerizing a vinyl monomer (D_b) containing an aromatic vinyl compound in the absence of the rubbery polymer (D_a). .
本発明の（D)成分は、耐衝撃性の面から、ゴム質重合体 (D_a)の存在下にビニ ル系単量体 (D_b)をグラフト重合させた重合体を少なくとも 1種含むものが好ましい 。ゴム質重合体 (D_a)の含有量は、（D)成分を 100質量％として、好ましくは 3〜8 0質量％、更に好ましくは 5〜70質量％、特に好ましくは 10〜60質量％である。  The component (D) of the present invention contains at least one polymer obtained by graft polymerization of a vinyl monomer (D_b) in the presence of the rubbery polymer (D_a) from the viewpoint of impact resistance. Preferred. The content of the rubber polymer (D_a) is preferably 3 to 80% by mass, more preferably 5 to 70% by mass, and particularly preferably 10 to 60% by mass, with the component (D) being 100% by mass. .
[0052] 上記ゴム質重合体（D— a)としては、特に限定されなが、ポリブタジエン、ブタジェ ン 'スチレン共重合体、ブタジエン 'アクリロニトリル共重合体、エチレン 'プロピレン共 重合体、エチレン 'プロピレン.非共役ジェン共重合体、エチレン'ブテン 1共重合 体、エチレン'ブテン— 1 ·非共役ジェン共重合体、アクリルゴム、シリコーンゴム、シリ コーン ·アクリル系 IPNゴム、上記（C)成分等が挙げられ、これらは 1種単独で、また は 2種以上を組み合わせて用いることができる。  [0052] The rubbery polymer (Da) is not particularly limited, but polybutadiene, butadiene 'styrene copolymer, butadiene' acrylonitrile copolymer, ethylene 'propylene copolymer, ethylene' propylene. Non-conjugated gen copolymer, ethylene 'butene 1 copolymer, ethylene' butene 1 · non-conjugated gen copolymer, acrylic rubber, silicone rubber, silicone · acrylic IPN rubber, component (C) above, etc. These can be used alone or in combination of two or more.
また、これらのうちポリブタジエン、ブタジエン.スチレン共重合体、エチレン 'プロピ レン共重合体、エチレン 'プロピレン '非共役ジェン共重合体、アクリルゴム、シリコー ンゴム、上記（C)成分が好ましい。ここで用いられるブタジエン 'スチレン共重合体は 、ブロック共重合体およびランダム共重合体のいずれであってもよい。  Of these, polybutadiene, butadiene / styrene copolymer, ethylene / propylene copolymer, ethylene / propylene / nonconjugated-gen copolymer, acrylic rubber, silicone rubber, and component (C) are preferred. The butadiene / styrene copolymer used here may be either a block copolymer or a random copolymer.
[0053] 上記ゴム質重合体 (D_a)のゲル含率は、特に限定しないが、乳化重合で（D_a) 成分を得る場合、ゲル含率は、好ましくは 98質量％以下であり、更に好ましくは 40〜 98質量％である。この範囲において、特に耐衝撃性に優れた多層シートを与える制 電性樹脂組成物を得ることができる。  [0053] The gel content of the rubbery polymer (D_a) is not particularly limited, but when the component (D_a) is obtained by emulsion polymerization, the gel content is preferably 98% by mass or less, and more preferably 40 to 98% by mass. Within this range, it is possible to obtain an antistatic resin composition that gives a multilayer sheet particularly excellent in impact resistance.
尚、上記ゲル含率は、以下に示す方法により求めることができる。すなわち、ゴム質 重合体 lgをトルエン 100mlに投入し、室温で 48時間静置したのち、 100メッシュの 金網（質量を Wグラムとする）で濾過したトルエン不溶分と金網を 80°Cで 6時間真空 In addition, the said gel content rate can be calculated | required by the method shown below. That is, the rubber polymer lg was put into 100 ml of toluene and allowed to stand at room temperature for 48 hours. Toluene insoluble matter filtered through wire mesh (weight is W grams) and wire mesh are vacuumed at 80 ° C for 6 hours
1  1
乾燥して秤量 (質量 wグラムとする）し、下記式（1)により算出する。  Dry, weigh (mass w gram), and calculate by the following formula (1).
2  2
[0054] ゲル含率 (質量％) =〔{W (g)— W (g) }/l (g)〕X 100 - (1)  [0054] Gel content (mass%) = [{W (g) — W (g)} / l (g)] X 100-(1)
2 1  twenty one
ゲル含率は、ゴム質重合体の製造時に、分子量調節剤の種類および量、重合時間 、重合温度、重合転化率等を適宜設定することにより調整される。  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.
[0055] 上記ビニル系単量体（D— b)を構成する芳香族ビニル化合物としては、スチレン、 a—メチルスチレン、ヒドロキシスチレン等が挙げられ、これらは 1種単独で、または 2 種以上を組合わせて用いることができる。また、これらのうち、スチレン、 ひ一メチルス チレンが好ましい。 [0055] Examples of the aromatic vinyl compound constituting the vinyl monomer (D-b) include styrene, a-methylstyrene, hydroxystyrene, and the like. These may be used alone or in combination of two or more. It can be used in combination. Of these, styrene and monomethylstyrene are preferred.
[0056] 芳香族ビニル化合物と共重合可能な他のビニル系単量体としては、ビニルシアン 化合物、（メタ）アクリル酸エステルイ匕合物、マレイミド化合物、および、その他の各種 官能基含有不飽和化合物などが挙げられる。好ましくは、ビニル系単量体 (D_b)は 、芳香族ビュル化合物を必須単量体成分とし、これに必要に応じて、シアン化ビニル 化合物、（メタ）アクリル酸エステルイ匕合物及びマレイミド化合物からなる群より選ばれ る 1種又は 2種以上が単量体成分として併用され、更に必要に応じて、その他の各種 官能基含有不飽和化合物の少なくとも 1種が単量体成分として併用される。その他の 各種官能基含有不飽和化合物としては、不飽和酸化合物、エポキシ基含有不飽和 化合物、水酸基含有不飽和化合物、ォキサゾリン基含有不飽和化合物、酸無水物 基含有不飽和化合物、置換または非置換のアミノ基含有不飽和化合物等が挙げら れる。上記その他の各種官能基含有不飽和化合物は 1種単独で、または 2種以上を 組み合わせて使用することができる。  [0056] 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. Etc. Preferably, the vinyl-based monomer (D_b) comprises an aromatic bull compound as an essential monomer component, and if necessary, from a vinyl cyanide compound, a (meth) acrylate ester compound and a maleimide compound. One or two or more selected from the group consisting of the above are used as a monomer component, and if necessary, at least one of various other functional group-containing unsaturated compounds is used as a monomer component. Other various functional group-containing unsaturated compounds include 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 other various functional group-containing unsaturated compounds can be used alone or in combination of two or more.
[0057] ここで使用されるシアンィ匕ビ二ルイ匕合物としては、アクリロニトリル、メタタリロニトリル 等が挙げられ、これらは、 1種単独で、または 2種以上を組み合わせて用いることがで きる。シアン化ビュル化合物を使用すると、耐薬品性が付与される。シアン化ビュル 化合物を使用する場合、その使用量は、（D_b)成分中、好ましくは 1〜60質量％、 さらに好ましくは 5〜50質量％である。  [0057] Examples of cyan-vinyl compounds used here include acrylonitrile, methacrylonitrile and the like, and these can be used alone or in combination of two or more. . Use of a cyanide bur compound provides chemical resistance. When using a cyanide bur compound, the amount used is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the component (D_b).
(メタ）アクリル酸エステルイ匕合物としては、アクリル酸メチル、アクリル酸ェチル、ァク リル酸ブチル、メタクリル酸メチル、メタクリル酸ェチル、メタクリル酸ブチル等が挙げら れ、これらは、 1種単独で、または 2種以上を組み合わせて用いることができる。 Examples of the (meth) acrylic acid ester compound include methyl acrylate, ethyl acrylate, butyl acrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylate and the like. These can be used alone or in combination of two or more.
(メタ)アクリル酸エステル化合物を使用すると、表面硬度が向上するので好ましい。 (メタ）アクリル酸エステル化合物を使用する場合、その使用量は、 （D— b)成分中、 好ましくは 1〜80質量％、さらに好ましくは 5〜80質量％である。  Use of a (meth) acrylic acid ester compound is preferable because surface hardness is improved. When the (meth) acrylic acid ester compound is used, the amount used thereof is preferably 1 to 80% by mass, more preferably 5 to 80% by mass in the component (Db).
マレイミド化合物としては、マレイミド、 N フエニルマレイミド、 N シクロへキシルマ レイミド等が挙げられ、これらは、 1種単独で、または 2種以上を組み合わせて用いる こと力 Sできる。また、マレイミド単位を導入するために、無水マレイン酸を共重合させ、 後イミド化してもよい。マレイミド化合物を使用すると、耐熱性が付与される。マレイミド 化合物を使用する場合、その使用量は、（D_b)成分中、好ましくは 1〜60質量％、 さらに好ましくは 5〜50質量％である。  Examples of maleimide compounds 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 then imidized. When a maleimide compound is used, heat resistance is imparted. When a maleimide compound is used, the amount used is preferably 1 to 60% by mass, more preferably 5 to 50% by mass in the component (D_b).
[0058] 不飽和酸化合物としては、アクリル酸、メタクリル酸、ェタクリル酸、マレイン酸、フマ ル酸、ィタコン酸、クロトン酸、桂皮酸等が挙げられ、これらは、 1種単独で、または 2 種以上を組み合わせて用いることができる。 [0058] Examples of the unsaturated acid compound 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. A combination of the above can be used.
エポキシ基含有不飽和化合物としては、グリシジルアタリレート、グリシジルメタクリレ ート、ァリルグリシジノレエーテル等が挙げられ、これらは、 1種単独で、または 2種以上 を組み合わせて用いることができる。  Examples of the epoxy group-containing unsaturated compound include glycidyl acrylate, glycidyl methacrylate, allyl glycidinole ether, and the like. These may be used alone or in combination of two or more.
[0059] 水酸基含有不飽和化合物としては、 3 ヒドロキシー 1 プロペン、 4ーヒドロキシー 1ーブテン、シス 4ーヒドロキシー 2 ブテン、トランス 4ーヒドロキシー 2 ブテン、 3 ヒドロキシー2—メチルー 1 プロペン、 2 ヒドロキシェチルメタタリレート、 2 ヒ ドロキシェチルアタリレート、 N— (4—ヒドロキシフエニル）マレイミド等が挙げられ、こ れらは、 1種単独で、あるいは 2種以上を組み合わせて用いることができる。 [0059] Hydroxyl-containing unsaturated compounds include 3 hydroxy-1 propene, 4-hydroxy-1-butene, cis 4-hydroxy-2 butene, trans 4-hydroxy-2-butene, 3 hydroxy-2-methyl-1 propene, 2 hydroxyethyl methacrylate, 2 Examples thereof include hydroxychetyl acrylate, N- (4-hydroxyphenyl) maleimide, and the like can be used alone or in combination of two or more.
ォキサゾリン基含有不飽和化合物としては、ビュルォキサゾリン等が挙げられ、これ らは、 1種単独で、または 2種以上を組み合わせて用いることができる。  Examples of the oxazoline group-containing unsaturated compound include bruoxazoline and the like, and these can be used alone or in combination of two or more.
酸無水物基含有不飽和化合物としては、無水マレイン酸、無水ィタコン酸、無水シ トラコン酸等が挙げられ、これらは、 1種単独で、または 2種以上を組み合わせて用い ること力 Sできる。  Examples of the acid anhydride group-containing unsaturated compound include maleic anhydride, itaconic anhydride, citraconic anhydride, and the like. These can be used alone or in combination of two or more.
置換または非置換のアミノ基含有不飽和化合物としては、アクリル酸アミノエチル、 アクリル酸プロピルアミノエチル、メタクリル酸ジメチルアミノエチル、メタクリル酸フエ二 ノレアミノエチノレ、 N ビニルジェチルァミン、 N ァセチルビニルァミン、アタリノレアミ ン、メタクリルアミン、 N メチルアクリルァミン、アクリルアミド、 N メチルアクリルアミ ド、 p アミノスチレン等があり、これらは、 1種単独で、または 2種以上を組み合わせ て用いることができる。 Examples of substituted or unsubstituted amino group-containing unsaturated compounds include aminoethyl acrylate, propylaminoethyl acrylate, dimethylaminoethyl methacrylate, and phenolic methacrylate. There are noreaminoethinole, N-vinyljetylamine, N-acetylethylamine, attalinoleamine, methacrylamine, N-methylacrylamine, acrylamide, N-methylacrylamide, p-aminostyrene, etc. One species can be used alone, or two or more species can be used in combination.
上記その他の各種官能基含有不飽和化合物を使用した場合、スチレン系樹脂と他 のポリマーとをブレンドしたとき、両者の相溶性を向上させる効果が期待できる。かか る効果を達成するために好ましい単量体は、エポキシ基含有不飽和化合物、不飽和 酸化合物、および水酸基含有不飽和化合物である。  When the above-mentioned other functional group-containing unsaturated compounds are used, when a styrene resin and other polymer are blended, an effect of improving the compatibility between them can be expected. Preferred monomers for achieving such effects are epoxy group-containing unsaturated compounds, unsaturated acid compounds, and hydroxyl group-containing unsaturated compounds.
上記その他の各種官能基含有不飽和化合物の使用量は、（D)成分中に使用され る該官能基含有不飽和化合物の合計量で、（D)成分全体に対して 0. ：!〜 20質量％ が好ましぐ 0. 1〜： 10質量％がさらに好ましい。  The amount of the above other various functional group-containing unsaturated compounds used is the total amount of the functional group-containing unsaturated compounds used in component (D), and is 0.:!-20 Preferred is 0.1% by mass: 10% by mass.
[0060] ビニル系単量体（D— b)中の芳香族ビニル化合物以外の単量体の使用量は、ビニ ル系単量体 (D— b)の合計を 100質量％とした場合、好ましくは 10〜95質量％、より 好ましくは 10〜90質量％、特に好ましくは 15〜80質量％である。ビュル系単量体（ D— b)を構成する単量体のより好ましい組み合わせは、スチレン/アクリロニトリル、 スチレン/メタクリル酸メチル、スチレン/アクリロニトリル/メタクリル酸メチル、スチレ ン/アクリロニトリル/グリシジルメタタリレート、スチレン/アクリロニトリル /2—ヒドロ キシェチルメタタリレート、スチレン/アクリロニトリル/ (メタ）アクリル酸、スチレン/ N フエニルマレイミド、スチレン/メタクリル酸メチル/シクロへキシルマレイミド等であ り、特に好ましい組み合わせは、スチレン/アクリロニトリルであり、ゴム質重合体（D a)の存在下に重合される単量体のより好ましい組み合わせは、スチレン/アタリ口 二トリル = 65Z45〜90ZlO (質量比）、スチレン/メタクリル酸メチル = 80Z20〜2 0/80(質量比)、スチレン Zアクリロニトリル Zメタクリル酸メチルで、スチレン量が 20 〜80質量0 /0、アクリロニトリル及びメタクリル酸メチルの合計が 20〜80質量％の範囲 の任意のものであり、特に好ましくはスチレン Zアクリロニトリル 70Z30〜85Zl5(質 量比)である。 [0060] The amount of the monomer other than the aromatic vinyl compound in the vinyl monomer (D—b) is 100% by mass when the total of the vinyl monomers (D—b) is 100% by mass. Preferably it is 10-95 mass%, More preferably, it is 10-90 mass%, Most preferably, it is 15-80 mass%. More preferred combinations of the monomers constituting the bur monomer (D-b) are styrene / acrylonitrile, styrene / methyl methacrylate, styrene / acrylonitrile / methyl methacrylate, styrene / acrylonitrile / glycidyl methacrylate, Styrene / acrylonitrile / 2-hydroxyxetyl methacrylate, styrene / acrylonitrile / (meth) acrylic acid, styrene / N phenylmaleimide, styrene / methyl methacrylate / cyclohexyl maleimide, etc. Styrene / acrylonitrile, and a more preferable combination of monomers polymerized in the presence of the rubbery polymer (D a) is styrene / atari nitrile = 65Z45 ~ 90ZlO (mass ratio), styrene / methacrylic acid Methyl = 80Z20 ~ 2 0/80 (mass ratio), styrene Z acrylonitrile In Z methyl methacrylate, styrene content of 20 to 80 mass 0/0, the sum of acrylonitrile and methyl methacrylate be of any range of 20 to 80 wt%, particularly preferably styrene Z acrylonitrile 70Z30～85Zl5 (Quality (Quantity ratio).
[0061] 本発明の（D)成分は、公知の重合法、例えば、乳化重合、塊状重合、溶液重合、 懸濁重合およびこれらを組み合わせた重合法で製造することができる。これらのうち 、ゴム質重合体 (D— a)の存在下に、ビニル系単量体 (D— b)を（共)重合して得られ る重合体の好ましい重合法は、乳化重合及び溶液重合である。一方、ゴム質重合体 (D a)の非存在下に、ビュル系単量体 (D— b)を (共)重合して得られる重合体の好 ましい重合法は、塊状重合、溶液重合、懸濁重合、及び乳化重合である。 [0061] The component (D) of the present invention can be produced by a known polymerization method, for example, emulsion polymerization, bulk polymerization, solution polymerization, suspension polymerization, or a polymerization method combining these. Out of these The preferred polymerization methods for the polymer obtained by (co) polymerizing the vinyl monomer (Db) in the presence of the rubbery polymer (Da) are emulsion polymerization and solution polymerization. . On the other hand, the preferred polymerization method for the polymer obtained by (co) polymerizing the bull monomer (D-b) in the absence of the rubbery polymer (D a) is bulk polymerization or solution polymerization. , Suspension polymerization, and emulsion polymerization.
[0062] 乳化重合で製造する場合、重合開始剤、連鎖移動剤、乳化剤等が用いられるが、 これらは公知のものが全て使用できる。 [0062] In the case of production by emulsion polymerization, a polymerization initiator, a chain transfer agent, an emulsifier, and the like are used, and all of these known ones can be used.
重合開始剤としては、クメンハイド口パーオキサイド、 p—メンタンハイド口パーォキサ イド、ジイソプロピルベンゼンハイド口パーオキサイド、テトラメチルブチルハイド口パー オキサイド、 tert_ブチルハイド口パーオキサイド、過硫酸カリウム、ァゾビスイソブチ ロニトリル等が挙げられる。  Examples of the polymerization initiator include cumene hydride mouth peroxide, p-menthane hydride mouth peroxide, diisopropylbenzene hydride mouth peroxide, tetramethylbutyl hydride mouth peroxide, tert_butyl hydride mouth peroxide, potassium persulfate, and azobisisobutyronitrile. It is done.
又、重合開始助剤として、各種還元剤、含糖ピロリン酸鉄処方、スルホキシレート処 方等があり、特にレドックス系を用いることが好ましい。  Further, there are various reducing agents, sugar-containing iron pyrophosphate formulations, sulfoxylate treatments and the like as polymerization initiation assistants, and it is particularly preferable to use a redox system.
連鎖移動剤としては、ォクチルメルカプタン、 n—ドデシルメルカプタン、 t ドデシ ルメルカプタン、 n—へキシルメルカプタン等のメルカプタン類、ターピノーレン類、及 び α—メチルスチレンダイマー等が挙げられる。  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.
乳化剤としては、ドデシルベンゼンスルホン酸ナトリウム等のアルキルベンゼンスル ホン酸塩、ラウリル硫酸ナトリウム等の脂肪族スルホン酸塩、ラウリル酸カリウム、ステ アリン酸カリウム、ォレイン酸カリウム、パルミチン酸カリウム等の高級脂肪酸塩、ロジ ン酸カリウム等のロジン酸塩等を用いることができる。  Examples of the emulsifier 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. A rosinate such as potassium rosinate can be used.
[0063] 尚、乳化重合において、ゴム質重合体（D— a)およびビニル系単量体（D— b)の使 用方法は、ゴム質重合体 (D— a)全量の存在下にビュル系単量体 (D— b)を一括添 カロして重合してもよぐ分割もしくは連続添加して重合してもよい。また、ゴム質重合 体（D_ a)の一部を重合途中で添カ卩してもよい。 [0063] In the emulsion polymerization, the rubber polymer (Da) and the vinyl monomer (Db) are used in the presence of the entire amount of the rubber polymer (Da). The monomer (D—b) may be polymerized by batch addition or divided or continuously added for polymerization. A part of the rubber polymer (D_a) may be added during the polymerization.
[0064] 乳化重合後、得られたラテックスは、通常、凝固剤により凝固させ、水洗、乾燥する ことにより、本発明の（D)成分粉末を得る。この際、乳化重合で得た 2種以上の成分（ D)のラテックスを適宜ブレンドしたあと、凝固してもよレ、。ここで使用される凝固剤とし ては、塩ィ匕カルシウム、硫酸マグネシウム、塩化マグネシウム等の無機塩、または硫 酸、塩酸、酢酸、クェン酸、リンゴ酸等の酸を用いることができる。 [0065] 溶液重合により（D)成分を製造する場合に用いることのできる溶剤は、通常のラジ カル重合で使用される不活性重合溶媒であり、例えば、ェチルベンゼン、トルエン等 の芳香族炭化水素、メチルェチルケトン、アセトン等のケトン類、ァセトニトリル、ジメ チノレホノレムアミド、 N—メチルピロリドン等が挙げられる。 [0064] After emulsion polymerization, the obtained latex is usually coagulated with a coagulant, washed with water and dried to obtain the component (D) powder of the present invention. At this time, the latex of two or more components (D) obtained by emulsion polymerization may be appropriately blended and then coagulated. As the coagulant used here, inorganic salts such as calcium chloride, magnesium sulfate and magnesium chloride, or acids such as sulfuric acid, hydrochloric acid, acetic acid, citrate and malic acid can be used. [0065] The solvent that can be used in the case of producing the component (D) by solution polymerization is an inert polymerization solvent used in ordinary radical polymerization, such as aromatic hydrocarbons such as ethylbenzene and toluene, Mention may be made of ketones such as methyl ethyl ketone and acetone, acetonitrile, dimethylolenolemamide, N-methylpyrrolidone and the like.
重合温度は、好ましくは 80〜： 140°C、さらに好ましくは 85〜： 120°Cの範囲である。 重合に際し、重合開始剤を用いてもよいし、重合開始剤を使用せずに、熱重合で 重合してもよレ、。重合開始剤としては、ケトンパーオキサイド、ジアルキルパーォキサ イド、ジァシルバーオキサイド、パーォキシエステル、ハイド口パーオキサイド、ァゾビ スイソプチロニトリル、ベンゾィルパーオキサイド等の有機過酸化物、 1、 Γ—ァゾビス (シクロへキサン一 1 _カーボ二トリル)等が好ましく用いられる。  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, disilver oxide, peroxyester, hydride peroxide, azobisisoptyronitrile, benzoyl peroxide, Gamma-azobis (cyclohexane-1-carbonitryl) and the like are preferably used.
また，連鎖移動剤を用いる場合、例えば、メルカブタン類、ターピノーレン類、 a - メチルスチレンダイマー類等を用いることができる。  When a chain transfer agent is used, for example, mercaptans, terpinolenes, a-methylstyrene dimers, etc. can be used.
また、塊状重合、懸濁重合で製造する場合、溶液重合において説明した重合開始 剤、連鎖移動剤等を用いることができる。  In the case of production by bulk polymerization or suspension polymerization, the polymerization initiator, chain transfer agent, etc. described in the solution polymerization can be used.
上記各重合法によって得た（D)成分中に残存する単量体量は、好ましくは 10, 00 Oppm以下、さらに好ましくは 5, OOOppm以下である。  The amount of monomer remaining in the component (D) obtained by the above polymerization methods is preferably 10000 Oppm or less, more preferably 5, OOOppm or less.
[0066] また、ゴム質重合体（D— a)の存在下にビュル系単量体（D— b)を重合して得られ る重合体成分には、通常、上記ビュル系単量体 (D— b)がゴム質重合体 (D— a)に グラフト共重合した共重合体とゴム質重合体にグラフトしてレ、なレ、未グラフト成分〔上 記ビュル系単量体 (D— b)の共重合体〕が含まれる。 [0066] In addition, the polymer component obtained by polymerizing the bull monomer (Db) in the presence of the rubbery polymer (Da) usually includes the above bull monomer ( D—b) is grafted onto the rubbery polymer (D—a) and grafted onto the rubbery polymer. a copolymer of b).
上記（D)成分のグラフト率は、好ましくは 20〜200質量％、更に好ましくは 30〜： 15 0質量％、特に好ましくは 40〜120質量％であり、グラフト率は、下記式（2)により求 めること力できる。  The graft ratio of the component (D) is preferably 20 to 200% by mass, more preferably 30 to: 150% by mass, and particularly preferably 40 to 120% by mass. I can power it.
[0067] グラフト率(質量％)={ (丁_ 3) 73} 100' (2) [0067] Graft rate (mass%) = {(Ding_ 3) 73} 100 '(2)
上記式（2)中、 Tは（D)成分 lgをアセトン (ただし、ゴム質重合体 (D_a)がアクリル 系ゴムを使用したものである場合、ァセトニトリル） 20mlに投入し、振とう機により 2時 間振とうした後、遠心分離機（回転数; 23， OOOrpm)で 60分間遠心分離し、不溶分 と可溶分とを分離して得られる不溶分の質量 (g)であり、 Sは (D)成分 lgに含まれる ゴム質重合体の質量 (g)である。 In the above formula (2), T is (D) component lg is added to 20 ml of acetone (however, if rubber polymer (D_a) uses acrylic rubber, acetonitrile), 2 This is the mass (g) of insoluble matter obtained by centrifuging for 60 minutes in a centrifuge (rotation speed: 23, OOOrpm) after shaking for a while and separating the insoluble matter and the soluble matter. (D) Included in component lg This is the mass (g) of the rubbery polymer.
[0068] また、本発明の関わる（D)成分のアセトン（ただし、ゴム質重合体（D— a)がアタリノレ 系ゴムを使用したものである場合、ァセトニトリル）可溶分の極限粘度〔77〕（溶媒とし てメチルェチルケトンを使用し、 30°Cで測定）は、好ましくは 0. 2〜： 1. 2dl/g、更に 好ましく ίま 0. 2〜： 1. Odl/g、特 (こ好ましく ίま 0. 3〜0. 8dl/gである。 [0068] In addition, the intrinsic viscosity of the component (D) related to the present invention, which is soluble in acetone (wherein the rubbery polymer (D-a) is attalinole rubber) is soluble in viscosity [77] (Measured at 30 ° C using methyl ethyl ketone as the solvent) is preferably 0.2 to: 1.2 dl / g, more preferably ί or 0.2 to: 1. Odl / g, This is preferably 0.3 to 0.8 dl / g.
本発明に関わる（D)成分中に分散するグラフト化ゴム質重合体粒子の平均粒系は 、好ましく fま 500〜30, 000A、更 (こ好ましく ίま 1， 000〜20, ΟΟθΑ、特 (こ好ましく は、 1， 500-8, 000Αの範囲である。平均粒径は、電子顕微鏡を用いる公知の方 法で測定できる。  The average particle size of the grafted rubber-like polymer particles dispersed in the component (D) according to the present invention is preferably from f to 500 to 30,000 A, more preferably (preferably from 1,000 to 20, ΟΟθΑ, special ( The average particle size can be measured by a known method using an electron microscope.
[0069] 本発明の第二の制電性樹脂組成物における（D)成分の使用量は、本発明の (Α) 成分、（Β)成分、（C)成分、及び (D)成分の合計 100質量％中、 5〜50質量％、好 ましくは 7〜50質量％、更に好ましくは 7〜38質量％、特に好ましくは 10〜30質量 %であり、 5質量％未満では、制電性、耐衝撃性、及び成形品表面外観が劣り、また 、 50質量％を超えると制電性及び耐薬品性が劣る。高い制電性を有し、平滑な表面 を有するシート表面外観の優れた発泡積層シートの表層として使用される場合は、 ( D)成分の使用量は、（Α)成分、 （Β)成分、 （C)成分及び (D)成分の合計 100質量 %中、好ましくは 5〜20質量％、更に好ましくは 5〜： 15質量％である。  [0069] The amount of the component (D) used in the second antistatic resin composition of the present invention is the sum of the components (Α), (Β), (C), and (D) of the present invention. In 100% by mass, 5 to 50% by mass, preferably 7 to 50% by mass, more preferably 7 to 38% by mass, and particularly preferably 10 to 30% by mass. In addition, the impact resistance and the surface appearance of the molded product are inferior, and if it exceeds 50% by mass, the antistatic property and chemical resistance are inferior. When used as a surface layer of a foam laminated sheet with a high antistatic property and a smooth surface, the amount of component (D) used is (Α) component, (Β) component, The total amount of the component (C) and the component (D) is 100 to 20% by mass, preferably 5 to 20% by mass, more preferably 5 to 15% by mass.
[0070] 本発明の制電性樹脂組成物には、制電性を更に向上させる目的から、制電性樹脂 組成物製造時にリチウム塩 (Ε)及び/又は非イオン系帯電防止剤（F)を配合するこ とができる。  [0070] For the purpose of further improving the antistatic property, the antistatic resin composition of the present invention includes a lithium salt (（) and / or a nonionic antistatic agent (F) at the time of producing the antistatic resin composition. Can be added.
[0071] リチウム塩 (Ε)としては、前記した (Ε)成分が全て使用でき、これらは 1種単独で、ま たは 2種以上を組み合わせて使用することができる。リチウム塩 (Ε)は、本発明の制 電性樹脂組成物 100質量部に対して、 0. 01〜5質量部の範囲で用いることが好まし く、更に好ましくは 0.：!〜 3質量部、特に好ましくは 0. 3〜2質量部の範囲で使用さ れる。その使用量が、 0. 01質量部未満では制電性を向上させる効果が得られず、 又 5質量部を超えると耐衝撃性が低下する傾向にある。  [0071] As the lithium salt (Ε), all the components (Ε) described above can be used, and these can be used alone or in combination of two or more. The lithium salt (Ε) is preferably used in the range of 0.01 to 5 parts by mass, more preferably 0.:! To 3 parts by mass, with respect to 100 parts by mass of the antistatic resin composition of the present invention. Parts, particularly preferably in the range of 0.3 to 2 parts by weight. If the amount used is less than 0.01 parts by mass, the effect of improving the antistatic property cannot be obtained, and if it exceeds 5 parts by mass, the impact resistance tends to decrease.
[0072] 本発明の第二の制電性樹脂組成物にリチウム塩 (Ε)を配合することにより、表面抵 抗率（23°C、 50%RH条件下で測定） 1 X 1011 Ω /口以下、好ましくは 1 Χ 109 Ω / 口以下であって、かつ、ナトリウムイオン及びカリウムイオンの溶出量（80°C、 60分間 抽出条件下で測定） 3 / g/cm2以下、好ましくは検出不能の要件を満たし、したがつ て、制電性と溶出イオンを従来になく高度にバランスさせた成形体が得られる。従来 の技術においては、制電性を向上させるために上記（B)成分の配合量を上げていた が、この場合、成形品からの溶出イオンが増える方向にあった。これに対し、本発明 によれば、リチウム塩を所定量配合し、好ましくは、上記（B)成分としてナトリウムおよ び/またはカリウムの含有量が低レ、かまたはこれらの元素を実質的に含まないものを 使用することにより、制電性と溶出イオンが高度にバランスされた成形体が得られる。 [0072] The surface resistivity (measured under conditions of 23 ° C and 50% RH) by mixing lithium salt (Ε) with the second antistatic resin composition of the present invention 1 X 10 11 Ω / Mouth, preferably 1 Χ 10 9 Ω / The amount of sodium ion and potassium ion elution (measured under extraction conditions at 80 ° C for 60 minutes) 3 / g / cm 2 or less, preferably meeting the undetectable requirement. Thus, it is possible to obtain a molded body in which antistatic properties and eluted ions are highly balanced as never before. In the prior art, the blending amount of the component (B) was increased in order to improve antistatic properties, but in this case, the amount of ions eluted from the molded product was increasing. In contrast, according to the present invention, a predetermined amount of the lithium salt is blended, and preferably, the content of sodium and / or potassium is low as the component (B), or these elements are substantially contained. By using non-contained ones, it is possible to obtain a molded body in which antistatic properties and eluting ions are highly balanced.
[0073] 非イオン系帯電防止剤（F)としては、多価アルコールエステルィヒ合物、アミン類、ァ ミド類等があり、多価アルコールエステル化合物としては、グリセリンモノステアレート 、グリセリンモノミリステート、グリセリンモノパルミテート、グリセリンモノステアレート、グ リセリンモノべへネート、グリセリンモノォレート、ジグリセリンモノラウレート、ジグリセリ ンモノミリステート、ジグリセリンモノパルミテート、ジグリセリンモノステアレート、ジグリ セリンモノべへネート、ジグリセリンモノォレート、ソルビタンモノラウレート、ソルビタン モノミリステート、ソルビタンモノパルミテート、ソルビタンモノステアレート、ソルビタン モノべへネート、ソルビタンモノラウレート等が挙げられ、これらは 1種単独でまたは 2 種以上を組み合わせて用いることができる。特に好ましいものは、グリセリンモノステ ァレート、ジグリセリンモノステアレート、グリセリンモノラウレート、ジグリセリンモノラウ レート、ソルビタンモノステアレート及びこれらを少なくとも 20質量％以上含有するも のである。 [0073] Nonionic antistatic agents (F) include polyhydric alcohol ester compounds, amines, amides, etc., and polyhydric alcohol ester compounds include glycerin monostearate, glycerin monomethylene. State, glycerin monopalmitate, glycerin monostearate, glycerin monosteanate, glycerin monooleate, diglycerin monolaurate, diglycerin monomyristate, diglycerin monopalmitate, diglycerin monostearate, diglycerin monostearate Examples include henate, diglycerin monooleate, sorbitan monolaurate, sorbitan monomyristate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monobehenate, sorbitan monolaurate, etc. Others may be used in combination of two or more. 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.
[0074] アミン類及びアミド類としては、ラウリルジエタノールァミン、ミリスチルジエタノールァ ミン、パルミチルジエタノールァミン、ステアリルジエタノールァミン、ォレイルジェタノ ーノレアミン、ラウリルジイソプロパノールァミン、ミリスチルジイソプロパノールァミン、パ ノレミチルジイソプロパノールァミン、ステアリルジイソプロパノールァミン、ォレイルジィ ソプロパノールァミン、 N, N—ビスヒドロキシェチルアルキル（アルキル基の炭素数 1 2〜22)ァミン等のアミン化合物、およびラウリルジエタノールアミド、ミリスチルジェタ ノーノレアミド、パルミチルジエタノールアミド、ベへ二ルジェタノールアミド、ォレイルジ エタノールアミド、ラウリルジイソプロパノールアミド、ミリスチルジイソプロパノールアミ ド、パルミチルジイソプロパノールアミド、ステアリルジイソプロパノールアミド、ォレイ ルジイソプロパノールアミド等のアミド化合物がある。これらは 1種単独で、または 2種 以上を組み合わせて用いることができる。好ましくは上記アミン化合物であり、更に好 ましくは、ラウリルジエタノールァミン、ステアリルジエタノールアミンをそれぞれ少なく とも 20質量％以上含有するものである。 [0074] Examples of amines and amides include lauryl diethanolamine, myristyl diethanolamine, palmityl diethanolamine, stearyl diethanolamine, oleyl jetanolamine, lauryl diisopropanolamine, myristyl diisopropanolamine, panolemityl. Amine compounds such as diisopropanolamine, stearyl diisopropanolamine, oleyldiisopropanolamine, N, N-bishydroxyethylalkyl (alkyl group having 12 to 22 carbon atoms) amine, and lauryldiethanolamide, myristylger Tanololamide, palmityl diethanolamide, behenylethylanolamide, oleyl diethanolamide, lauryl diisopropanolamide, myristyl diisopropanolamide And amide compounds such as palmityl diisopropanolamide, stearyl diisopropanolamide, and oleyl diisopropanolamide. These can be used alone or in combination of two or more. Preferred are the above-described amine compounds, and more preferred are those containing at least 20% by mass of lauryl diethanolamine and stearyl diethanolamine, respectively.
[0075] また上記した化合物の帯電防止性能を向上させる目的から、公知の添加剤を配合 すること力 Sできる。これらを例示すると炭素数 12〜： 18の高級アルコール、滑剤、シリ 力、ケィ酸カルシウム等がある。また、混和性を向上させる目的で、マスターバッチ化 したものを用いることもできる。  [0075] For the purpose of improving the antistatic performance of the above-mentioned compound, it is possible to add a known additive. Examples of these are higher alcohols having 12 to 18 carbon atoms, lubricants, sili- cal power, calcium silicate, and the like. A master batch can also be used for the purpose of improving miscibility.
上記非イオン系帯電防止剤は、例えば、花王社製エレクトロストリッパー EA、 TS - 3B、 TS _ 6B、 TS _ 5、 TS— 2B (商品名）等として市場より入手できる。  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.
[0076] 上記非イオン系帯電防止剤は、本発明の制電性樹脂組成物 100質量部に対して 0 . 01〜： 10重量部の範囲が好ましぐ更に好ましくは 0.：!〜 8質量部、特に好ましくは 0.：!〜 5質量部の範囲で使用される。その使用量が 0. 01質量部未満では制電性を 向上させる効果が得られず、また、 10質量部を超える成形品の表面外観が劣る傾向 にある。  [0076] The nonionic antistatic agent is preferably in the range of 0.01 to 10 parts by weight with respect to 100 parts by weight of the antistatic resin composition of the present invention. Part by mass, particularly preferably in the range of 0.:! 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.
[0077] 本発明の制電性樹脂組成物には、公知の耐候 (光)剤、酸化防止剤、熱安定剤、 滑剤、シリコーンオイル、可塑剤、摺動剤、着色剤、染料、発泡剤、加工助剤 (超高 分子量アクリル系重合体、超高分子量スチレン系重合体)、難燃剤、結晶核剤等を 適宜配合することができる。  [0077] The antistatic resin composition of the present invention includes a known weathering (light) agent, antioxidant, heat stabilizer, lubricant, silicone oil, plasticizer, sliding agent, colorant, dye, and foaming agent. Further, processing aids (ultra high molecular weight acrylic polymer, ultra high molecular weight styrene polymer), flame retardant, crystal nucleating agent, and the like can be appropriately blended.
又、本発明の制電性樹脂組成物には、公知の無機または有機充填材を配合するこ とができる。ここで使用される充填材としては、ガラス繊維、ガラスフレーク、ガラス繊 維のミルドファイバー、ガラス粉、ガラスビーズ、中空ガラスビーズ、炭素繊維、炭素繊 維のミルドファイバー、銀、銅、黄銅、鉄等の粉体あるいは繊維状物質、カーボンブラ ック、錫コート酸化チタン、錫コートシリカ、ニッケノレコート炭素繊維、タルク、炭酸カル シゥム、炭酸カノレシゥムゥイスカー、ワラストナイト、マイ力、カオリン、モンモリロナイト、 へキトライト、酸化亜鉛ウイスカー、チタン酸カリウムゥイスカー、ホウ酸アルミニウムゥ イスカー、板状アルミナ、板状シリカ、及び有機処理されたスメクタイト、ァラミド繊維、 フエノール樹脂、ポリエステル繊維等があり、これらは 1種単独で、または 2種以上を 組み合わせて用いることができる。 In addition, a known inorganic or organic filler can be blended with the antistatic resin composition of the present invention. The fillers used here are glass fiber, glass flake, glass fiber milled fiber, glass powder, glass beads, hollow glass bead, carbon fiber, carbon fiber milled fiber, silver, copper, brass, iron. Powders or fibrous materials such as carbon black, tin-coated titanium oxide, tin-coated silica, nickel-coated carbon fiber, talc, carbonated calcium carbonate, carbonated clay whisker, wollastonite, my strength, kaolin , Montmorillonite, hekilite, zinc oxide whisker, potassium titanate whisker, aluminum borate whisker, platy alumina, platy silica, and organically treated smectite, aramid fiber, There are phenol resin, polyester fiber, etc., and these can be used alone or in combination of two or more.
更に、上記充填材の分散性を向上させる目的から、公知のカップリング剤、表面処 理剤、集束剤等で処理したものを用いることができ、公知のカップリング剤としては、 シラン系カップリング剤、チタネート系カップリング剤、アルミニウム系カップリング剤等 力 Sある。  Furthermore, for the purpose of improving the dispersibility of the filler, those treated with a known coupling agent, surface treating agent, sizing agent, etc. can be used. As the known coupling agent, silane coupling is used. Agents, titanate coupling agents, aluminum coupling agents, etc.
上記無機または有機充填材は、本発明の制電性樹脂組成物 100質量部に対して 、：!〜 200質量部の範囲で通常使用される。  The inorganic or organic filler is usually used in the range of:! To 200 parts by mass with respect to 100 parts by mass of the antistatic resin composition of the present invention.
[0078] 更に、本発明の制電性樹脂組成物には、他の公知の重合体であるポリアミド樹脂、 ポリアミドエラストマ一、ポリブチレンテレフタレート、ポリエチレンテレフタレート、ポリ ァリレート、液晶ポリエステル等の熱可塑性ポリエステル樹脂、ポリエステルエラストマ 一、 PMMA、メタクリル酸メチル.マレイミド化合物共重合体、ポリフヱニレンエーテル 、ポリフエ二レンスルフイド、芳香族ポリカーボネート、熱可塑性ポリウレタン、 エチレン.（メタ）アクリル酸メチル共重合体、エチレン'（メタ）アクリル酸共重合体、ェ ポキシ樹脂、フエノール樹脂、尿素樹脂、フエノキシ樹脂等を適宜配合することができ る。 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 elastomer 1, PMMA, Methyl methacrylate. Maleimide compound copolymer, Polyphenylene ether, Polyphenylene sulfide, Aromatic polycarbonate, Thermoplastic polyurethane, Ethylene. Methyl (meth) acrylate copolymer, Ethylene '(Metal ) Acrylic acid copolymer, epoxy resin, phenol resin, urea resin, phenoxy resin, and the like can be appropriately blended.
[0079] 本発明の制電性樹脂組成物は、上記各構成成分を、各種押出機、バンバリ一ミキ サー、ニーダー、連続ニーダー、ロール等により溶融混練することにより得ることがで きる。混練に際し、上記各構成成分を一括添加して混練してもよぐ分割して添加し て混練してもよい。このように調製された本発明の制電性樹脂組成物は、射出成形、 プレス成形、カレンダー成形、 Tダイ押出成形、インフレーション成形、ラミネーシヨン 成形、真空成形、異形押出成形等、また、これらを組み合わせた成形法等の公知の 成形法により成形品を得ることができる。又、カレンダー成形、 Tダイ押出成形、イン フレーシヨン成形機等に混練り押出機、バンノ リーミキサー等の混練り機が付帯され ている場合、事前に上記混練によって本発明の制電性樹脂組成物を得ることなぐ 上記付帯の混練り機で本発明の制電性樹脂組成物を得ながら成形品を得ることもで きる。  [0079] 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-described constituent components may be added all at once or kneaded or added separately and kneaded. The antistatic resin composition of the present invention thus prepared includes injection molding, press molding, calendar molding, T-die extrusion molding, inflation molding, lamination molding, vacuum molding, profile extrusion molding, and the like. A molded product can be obtained by a known molding method such as a combined molding method. In addition, when a kneading machine such as a kneading extruder or a banolly 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 previously kneaded. It is also possible to obtain a molded product while obtaining the antistatic resin composition of the present invention with the above-mentioned kneader.
[0080] 本発明の制電性樹脂組成物をシートまたはフィルムに加工する場合の厚みは、 10 μ m〜100mmの範囲が好ましい。 [0080] When the antistatic resin composition of the present invention is processed into a sheet or film, the thickness is 10 The range of μm to 100 mm is preferable.
上記シート及びフィルムは、単層品であってもよぐまた他材料と積層した多層品で あってもよく、粘着剤等を積層したシート及びフィルムであってもよい。更に前記シー ト及びフィルムに公知のガスバリア膜を形成させることもできる。  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.
[0081] 本発明の制電性樹脂組成物を用いて多層シートまたは多層フィルムを成形する場 合、本発明の制電性樹脂組成物は、他材との 2層シートもしくはフィルム、または、他 材を中間層とする 3層シートもしくはフィルム等とすることができる。ここで使用される 他材としては、公知の重合体からなるものを用いることができる力 本発明の (A)成 分、（D)成分等を用レ、ると層間の接着性が優れることから、このような多層シートまた は多層フィルムは、本発明において好ましい態様である。層間の接着が不十分な材 料を用いる場合は、公知の接着層を介在させることができる。また、シート、フィルム の剛性、耐熱性を向上させる目的から、前記無機または有機充填材を配合したもの を用いることもできる。 [0081] When the multilayer sheet or 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 other It can be a three-layer sheet or film with the material as an intermediate layer. The other materials used here can be made of a known polymer. When the components (A) and (D) of the present invention are used, the adhesion between the layers is excellent. Therefore, such a multilayer sheet or multilayer 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. In addition, for the purpose of improving the rigidity and heat resistance of the sheet and film, those containing the inorganic or organic filler can also be used.
上記多層シートにおいて、本発明の制電性樹脂組成物からなる層の厚みは、安定 的に制電性を発現する目的から好ましくは 10 /i m以上、更に好ましくは 50 /i m以上 、特に好ましくは 80 μ ΐη以上である。このような多層シート及びフィルムを得る方法と して好ましい方法は、 Tダイによる共押出、インフレーションによる共押出である。この ようにして得られたシートは、必要に応じて真空成形等でトレィ等の成形品を得ること ができる。  In the multilayer sheet, the thickness of the layer made of the antistatic resin composition of the present invention is preferably 10 / im or more, more preferably 50 / im or more, and particularly preferably for the purpose of stably developing antistatic properties. 80 μΐη or more. Preferred methods for obtaining such multilayer sheets and films are coextrusion with a T-die and coextrusion with inflation. The sheet thus obtained can be formed into a molded article such as a tray by vacuum forming or the like as necessary.
[0082] 本発明の制電性樹脂組成物を 1層とし、ポリプロピレン系樹脂を他層または中間層 とする多層シートを用いて真空成形を行う場合、前記他層または中間層となるポリプ ロピレン系樹脂としては、メルトフローレート (JIS K7210 : 1999に準拠して 230。C、 荷重 2. 16kgで測定）が 1. OgZlO分以下のものを用いることが好ましぐ更に好まし くはメノレトフローレート FIS K6922— 2に準拠して 190°C、 2. 16kg荷重で測定）力 S i . Og/10分以下のポリエチレンを 10〜30%の範囲で併用したものを用いることが好 ましい。  [0082] 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, the polypropylene system as the other layer or the intermediate layer is used. It is preferable to use a resin with a melt flow rate (measured at JIS K7210: 1999, 230.C, load 2.16 kg) of 1. OgZlO or less. According to the rate FIS K6922-2, measured at 190 ° C and 2. 16 kg load) It is preferable to use a combination of polyethylene with a force S i. Og / 10 min.
[0083] 本発明の制電性樹脂組成物からなるシートまたはフィルムを基材として粘着シート またはフィルムを製造する場合、粘着剤との接着性またはプライマー層との接着性を 向上させる目的から、本発明の制電性榭脂組成物からなるシートまたはフィルムの表 面に公知の種々の処理、例えばコロナ放電処理、火炎処理、酸化処理、プラズマ処 理、 UV処理、イオンボンバード処理、溶剤処理等を行うことができる。 [0083] When a pressure-sensitive adhesive sheet or film is produced using a sheet or film comprising the antistatic resin composition of the present invention as a base material, the adhesiveness with the pressure-sensitive adhesive or the adhesiveness with the primer layer is improved. For the purpose of improving, various known treatments such as corona discharge treatment, flame treatment, oxidation treatment, plasma treatment, UV treatment, ion bombardment are carried out on the surface of the sheet or film comprising the antistatic resin composition of the present invention. Treatment, solvent treatment, etc. can be performed.
更に、本発明の制電性樹脂組成物からなるシートまたはフィルムと粘着剤との接着 力を向上させる目的から、本発明の制電性樹脂組成物からなるシートまたはフィルム の表面に直接または上記表面処理した面にプライマー層を形成させることができる。 具体的には、上記表面に、ポリエチレンィミン、ポリウレタン、またはアクリル樹脂等の 樹脂を極薄い、 0.： 1 z m〜： 10 x m程度の厚みの層として形成させる。通常は、溶剤 (水を含む)溶液として塗布し、乾燥することにより形成できる。  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 zm to about 10 xm. Usually, it can be formed by applying as a solvent (including water) solution and drying.
粘着剤としては、スクリーン法、グラビア法、メッシュ法、バー塗工法等で塗工して粘 着層を形成させるェマルジヨンタイプおよび有機溶剤タイプのものの他に、押出ラミネ ート法、ドライラミネート法、共押出法等で粘着層を形成させる熱溶融タイプのもの等 があり、いずれも使用できる。また、粘着剤の厚みは、特に限定しないが、通常:!〜 1 00 μ m程度の範囲である。  In addition to the emulsion type and organic solvent type adhesives that are applied by the screen method, gravure method, mesh method, bar coating method, etc. to form an adhesive layer, the adhesive layer method, dry lamination There is a hot-melt type in which an adhesive layer is formed by a method or a coextrusion method, and any of them can be used. The thickness of the pressure-sensitive adhesive is not particularly limited, but is usually in the range of about:! To 100 μm.
本発明の多層シートの各層の構造は、特に限定されず、例えば、発泡したものであ つても、中空になったものであってもよい。上記他材の層、例えば、上記（A)成分から なる層を発泡させる場合、発泡剤としては特に制限されず、例えば、発泡ポリプロピレ ン系樹脂または発泡ポリエチレン系樹脂に用レ、られている公知の発泡剤を用いるこ とができる。発泡剤の具体例としては、二酸化炭素、空気、窒素などの無機発泡剤、 脂肪族炭化水素、ハロゲン化炭化水素などの揮発性発泡剤、ァゾジカルボンアミド（ ADCA)、ジニトロソペンタメチレンテトラアミン、ァゾビスイソブチロニトリル、ヒドラゾジ カルボンアミド、炭酸水素ナトリウムなどの分解型発泡剤が挙げられる。これらは、単 独で又は 2種以上を混合して用いることができる。これらのうち、成形加工温度と発泡 量の調整が行い易い分解型発泡剤を用いるのが好ましい。また、発泡剤の使用量に は特に制約はないが、分解型発泡剤の場合、発泡成形用樹脂組成物 100質量部に 対して、 0. ：!〜 10質量部であることが好ましい。  The structure of each layer of the multilayer sheet of the present invention is not particularly limited, and may be, for example, foamed or hollow. In the case of foaming the layer of the other material, for example, the layer made of the component (A), the foaming agent is not particularly limited, and is known for use in, for example, a foamed polypropylene resin or a foamed polyethylene resin. Any foaming agent can be used. Specific examples of blowing agents include inorganic blowing agents such as carbon dioxide, air and nitrogen, volatile blowing agents such as aliphatic hydrocarbons and halogenated hydrocarbons, azodicarbonamide (ADCA), dinitrosopentamethylenetetraamine And decomposable foaming agents such as azobisisobutyronitrile, hydrazodicarbonamide, and sodium hydrogen carbonate. 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. The amount of foaming agent used is not particularly limited, but in the case of a decomposable foaming agent, it is preferably 0.:! To 10 parts by mass with respect to 100 parts by mass of the resin composition for foam molding.
本発明の第一の制電性樹脂組成物を上記発泡品の表層として使用する場合、前 記ォレフイン系樹脂 (A) 40〜80質量％、前記ブロック共重合体（B) 20〜60質量％ とを含有し (但し、上記 (A)成分及び (B)成分の合計は 100質量％)、所望により、上 記 (A)成分及び (B)成分の合計 100質量部に対して前記リチウム塩 (E) 0. 01〜5 質量部を含有する組成物を好適に使用することができる。また、本発明の第二の制 電性樹脂組成物を上記発泡品の表層として使用する場合、前記ォレフィン系樹脂（ 八）7〜30質量％、前記ブロック共重合体（B) 20〜60質量％、前記エラストマ一（C) 15〜50質量％、前記スチレン系樹脂（D) 5〜 20質量％とを含有し (但し、上記 (A) 成分、（B)成分、（C)成分及び (D)成分の合計は 100質量％)、所望により、上記 (A )成分、（B)成分、（C)成分及び (D)成分の合計 100質量部に対して、前記リチウム 塩 (E) 0. 0：!〜 5質量部を含有する組成物を好適に使用することができる。 When the first antistatic resin composition of the present invention is used as the surface layer of the foamed product, the olefin resin (A) is 40 to 80% by mass, the block copolymer (B) is 20 to 60% by mass. (Provided that the total of component (A) and component (B) is 100% by mass), and, if desired, the lithium salt relative to 100 parts by mass of component (A) and component (B). (E) A composition containing 0.01 to 5 parts by mass can be suitably used. When the second antistatic resin composition of the present invention is used as the surface layer of the foamed product, 7-30% by mass of the olefin-based resin (8) and 20-60 mass of the block copolymer (B). %, The elastomer (C) 15 to 50% by mass, and the styrene resin (D) 5 to 20% by mass (provided that the components (A), (B), (C) and ( The total amount of the component (D) is 100% by mass), and, if desired, the lithium salt (E) 0 with respect to the total of 100 parts by mass of the components (A), (B), (C) and (D). 0:! To 5 parts by mass of a composition can be preferably used.
[0085] このようにして得られた成形品は、リレーケース、ウェハーケース、レチクルケース、 マスクケース等のケース類、液晶トレイ、チップトレイ、ハードディスク（HDD)トレイ、 C CDトレイ、 ICトレイ、有機 ELトレイ、光ピックアップ関連トレイ、 LEDトレイ、メモリトレイ 等のトレィ類、 ICキャリア一等のキャリア一類、偏光フィルム、導光板、各種レンズ等 の保護フィルム、偏光フィルム切断時の下敷きシート、仕切り板等のクリーンノレーム内 で使用されるシートまたはフィルム類、 自動販売機内部部材、液晶パネル、ハードデ イスク、プラズマパネル等に使用される制電バッグ、プラスチックダンボール、液晶パ ネル、プラズマパネル等の搬送用ソフトケース、その他各種部品搬送用関連部材等 の分野に使用することができる。 [0085] Molded products obtained in this way are cases such as relay cases, wafer cases, reticle cases, mask cases, liquid crystal trays, chip trays, hard disk (HDD) trays, CCD trays, IC trays, organic Trays such as EL trays, optical pickup-related trays, LED trays, memory trays, etc., carriers such as IC carriers, polarizing films, light guide plates, protective films such as various lenses, underlay sheets when polarizing films are cut, partition plates, etc. Sheets or films used in cleanrooms, internal parts of vending machines, antistatic bags used for liquid crystal panels, hard disks, plasma panels, plastic cardboard, liquid crystal panels, plasma panels, etc. It can be used in the fields of soft cases and other related parts transportation parts.
実施例  Example
[0086] 以下に実施例を挙げ、本発明を更に詳細に説明するが、本発明の主旨を超えない 限り、本発明は力かる実施例に限定されるものではなレ、。尚、実施例中において部 および％は、特に断らない限り質量基準である。また、実施例、比較例中の各種測定 は、下記の方法に拠った。  [0086] Hereinafter, the present invention will be described in more detail with reference to examples. However, the present invention is not limited to the powerful 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. Further, various measurements in Examples and Comparative Examples were based on the following methods.
[0087] 〔1〕評価方法  [0087] [1] Evaluation method
(1)ゴム質重合体のゲル含率；前記の方法に従った。  (1) Gel content of rubbery polymer: according to the method described above.
(2)ゴム質重合体ラテックスの平均粒子径；  (2) Average particle diameter of rubbery polymer latex;
(D— 1)成分の形成に用いるゴム質重合体ラテックスの平均粒子径は、光散乱法で 測定した。測定機は、大塚電子社製 LPA— 3100型を使用し、 70回積算でミュムラ ント法を用いた。尚、（D)成分中の分散グラフト化ゴム質重合体粒子の粒子径は、ラ テックス粒子径とほぼ同じであることを電子顕微鏡で確認した。 The average particle diameter of the rubber polymer latex used for forming the component (D-1) was measured by a light scattering method. The measuring machine uses the LPA-3100 model manufactured by Otsuka Electronics Co., Ltd. Was used. It was confirmed with an electron microscope that the particle diameter of the dispersion-grafted rubber polymer particles in component (D) was almost the same as the latex particle diameter.
(3) (D)成分のグラフト率；前記の方法に従った。  (3) Graft ratio of component (D): According to the method described above.
(4) (D)成分のアセトン可溶分の極限粘度〔 〕；前記の方法に従った。  (4) The intrinsic viscosity [] of the acetone-soluble component (D);
(5) (C)成分 (重合体の結合スチレン量、ビニル結合量、数平均分子量、および水素 添加率）；  (5) Component (C) (Amount of bound styrene, amount of vinyl bond, number average molecular weight, and hydrogenation rate of polymer);
(5_ 1)結合スチレン量；  (5_ 1) bound styrene content;
水素添加前の重合体で測定した。 δθ^π 1のフエニル基の吸収に基づいた赤外法 による検量線から求めた。 It was measured on the polymer before hydrogenation. It was obtained from a calibration curve by the infrared method based on the absorption of the phenyl group of δθ ^ π 1 .
(5— 2)数平均分子量； (5-2) Number average molecular weight;
水素添加前の重合体で測定した。ゲルパーミエーシヨンクロマトグラフィー（GPC)か ら求めた。 It was measured on the polymer before hydrogenation. It was determined from gel permeation chromatography (GPC).
(5— 3)ビュル結合量  (5-3) Bulle coupling amount
水素添加前の重合体で測定した。赤外法 (モレロ法）により求めた。 It was measured on the polymer before hydrogenation. Obtained by infrared method (Morello method).
(5— 4)水素添加率； (5-4) Hydrogenation rate;
水素添加後の重合体で測定した。四塩ィ匕エチレンを溶媒として用い、 15%濃度で測 定した 100MHzの1 Η— NMRスペクトルの不飽和二重結合物のスペクトル減少から 算出した。 Measurements were taken on the polymer after hydrogenation. It was calculated from the spectrum reduction of the unsaturated double bond in the 100 MHz 1- NMR spectrum measured at 15% concentration using tetrasalt ethylene as a solvent.
(6)制電性； (6) Antistatic property;
(6— 1)制電性ー 1  (6— 1) Antistatic-1
成形品（寸法 2.4mm X 76mm X 127mm)を用い、 FTMS— 101 (米国連邦試験基 準）に従レヽ、米国 ETS社製 STATIC DECAY METER 406Dを用レ、、 23°C、湿 度 12%RH条件下で、 + 5000V印加した後、接地し、 50Vまで減衰するまでの時間Using a molded product (dimensions 2.4mm x 76mm x 127mm) according to FTMS-101 (US federal test standard), using STATIC DECAY METER 406D manufactured by ETS, USA, 23 ° C, humidity 12% RH Under the conditions, after applying + 5000V, grounding and decaying to 50V
(秒)を測定した。 (Seconds) was measured.
(6— 2)制電性ー 2  (6-2) Antistatic-2
成形品（寸法 2.1mm X 100mm φの円盤）を用レヽ、 JIS K6911に準拠し、 23°C、 50 Q/0RH条件下に 24時間放置後の表面抵抗率（ Ω /口）を三菱化学社製ハイレスター UP MCP— HT450を用い測定した。 (7)耐薬品性； Molded product (dimension 2.1mm x 100mm φ disk) is used in accordance with JIS K6911, and the surface resistivity (Ω / port) after standing for 24 hours under 23 ° C, 50 Q / 0 RH conditions is Mitsubishi Chemical The measurement was performed using a Hirester UP MCP-HT450 made by the company. (7) Chemical resistance;
成形品（寸法 2mm X 40mm X 160mm)に 1 %歪みをかけ、ジォクチルフタレート（DOThe molded product (dimensions 2mm X 40mm X 160mm) is strained 1% and dioctyl phthalate (DO
P)を塗布し、 23°Cで 72時間放置したあとの成形品の表面状態を、下記評価基準に 基づき目視評価した。 The surface condition of the molded product after applying P) and leaving it to stand at 23 ° C for 72 hours was visually evaluated based on the following evaluation criteria.
〇；変化無し  ○: No change
△;微小なクラック発生  Δ: Micro cracks generated
X；大きなクラック発生又は破断  X: Large crack occurrence or breakage
(8)表面外観；  (8) Surface appearance;
成形品（寸法 2.1mm X 100mm φの円盤）の表面を、下記基準で目視評価した。 ◎;平滑な面で非常に良好 The surface of the molded product (size 2.1 mm x 100 mm φ disk) was visually evaluated according to the following criteria. ◎; Smooth surface and very good
〇；平滑な面で外観良好 ○: Appearance is smooth and smooth
△；面が若干平滑でなレ、が外観は実用上問題なレ、  △: The surface is slightly smooth, but the appearance is a problem in practical use.
X；面が平滑でなく外観が悪い X: The surface is not smooth and the appearance is poor
(9)耐衝撃性；  (9) Impact resistance;
(9 1)耐衝撃性一 1  (9 1) Impact resistance 1
ISO 179に準拠して、同 ISO規格に規定の成形品を用レ、、シャルピー衝撃強さ（KJ /m2)を測定した。 In accordance with ISO 179, a molded product prescribed in the ISO standard was used, and Charpy impact strength (KJ / m 2 ) was measured.
(9 2)耐衝撃性一 2 (9 2) Impact resistance 1 2
成形品（寸法 2.4mm X 100mm X 100mm)を用い、 ASTM D 2794に準拠して、デ ュポン式衝撃強さ（kgf ' cm)を測定した。 Using a molded product (dimensions 2.4 mm X 100 mm X 100 mm), Dupont impact strength (kgf 'cm) was measured according to ASTM D 2794.
(10)溶出イオン  (10) Eluted ions
超純水 88cm3に、表面積 88cm2の成形品を浸漬し、 80°C、 60分間成形品力 ィォ ンを溶出させた。この抽出水を用い、ナトリウムイオン量およびカリウムイオン量の合 計をイオンクロマトグラフで測定した。結果は、成形品の単位面積当たりに換算し x g /cm2で示した。 A molded product having a surface area of 88 cm 2 was immersed in 88 cm 3 of ultrapure water, and the molded product force ion was eluted 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 expressed as xg / cm 2 in terms of the unit area of the molded product.
(11)熱安定性;  (11) thermal stability;
制電性ー 1の測定で用いたと同様の成形品を、 90°C雰囲気中に 5日間放置した後 の成形品と 90°C雰囲気中に放置する前の成形品の変色の程度を下記基準で目視 評価した。 Antistatic property-The following standards are used to determine the degree of discoloration between the molded product that was used in the measurement of 1 and the molded product after being left in a 90 ° C atmosphere for 5 days and before being left in a 90 ° C atmosphere. Visually evaluated.
〇；変色しないか、変色の程度が少ない  ○: No discoloration or little discoloration
X；変色の程度が大きい  X: Large degree of discoloration
[0089] 〔2〕制電性樹脂組成物の成分 [0089] [2] Components of antistatic resin composition
(1) (A)成分;ォレフィン系樹脂  (1) Component (A): olefin resin
本発明の（A)成分のォレフィン系樹脂として下記のものを用いた。 A1 ;日本ポリプロ社製ノバテック PP FY6C (商品名）  The following were used as the olefin resin of the component (A) of the present invention. A1; Novatech PP FY6C (trade name) manufactured by Nippon Polypro Co., Ltd.
ホモタイプポリプロピレン、メルトフローレート 2. 4g/l0分 A2 ;日本ポリプロ社製ノノ テック PP MA3AH (商品名）  Homotype polypropylene, melt flow rate 2.4 g / l 0 min A2; Nontech PP MA3AH (trade name) manufactured by Nippon Polypro
ホモタイプポリプロピレン、メルトフローレート lOg/10分 A3 ;日本ポリプロ社製ノバテック PP EG6D (商品名）  Homotype polypropylene, melt flow rate lOg / 10min A3; Novatec PP EG6D (trade name) manufactured by Nippon Polypro
ランダムタイプポリプロピレン、メルトフローレート 1. 9g/l0分 A4 ;日本ポリプロ社製ノノくテック PP MG3ATB (商品名）  Random type polypropylene, melt flow rate 1.9 g / l 0 min A4; Nonokuku Tech PP MG3ATB (trade name) manufactured by Nippon Polypro
ランダムタイプポリプロピレン、メルトフローレート lOg/10分 A5 ;日本ポリプロ社製ノノくテック PP EA9BT (商品名）  Random type polypropylene, melt flow rate lOg / 10min A5; Nonoku Tech PP EA9BT (trade name) manufactured by Nippon Polypro
ホモタイプポリプロピレン、メルトフローレート 0. 5g/10分 A6 ;日本ポリエチレン社製ハーモレックス NF464N (商品名） メタ口セン系ポリエチレン、メルトフローレート 2. Og/10分 A7 ;日本ポリエチレン社製ノバテック LD LF122 (商品名）  Homotype polypropylene, melt flow rate 0.5 g / 10 min A6; Harmolex NF464N (trade name) manufactured by Nippon Polyethylene Co., Ltd. Metaguchisen polyethylene, melt flow rate 2. Og / 10 min A7; Novatec LD LF122 manufactured by Nippon Polyethylene (Product name)
低密度ポリエチレン、メルトフローレート 0. 3g/10分 A8 ;ポリプラスチックス社製 TOPAS 8007X10 (商品名）  Low density polyethylene, melt flow rate 0.3 g / 10 min A8; TOPAS 8007X10 (trade name) manufactured by Polyplastics
エチレン—ノルボルネン共重合体（ガラス転移温度 80°C) A9 ;日本ポリエチレン社製ノバテック HD HB530 (商品名） 高密度ポリエチレン、メルトフローレート 0. 3g/l0分 A10 ;日本ポリエチレン社製ノバテック LD HJ560 (商品名） 高密度ポリエチレン、メルトフローレート 7g/l0分  Ethylene-norbornene copolymer (glass transition temperature 80 ° C) A9; Novatec HD HB530 (trade name) manufactured by Nippon Polyethylene Co., Ltd. High density polyethylene, melt flow rate 0.3 g / l 0 min A10; Novatec LD HJ560 (produced by Nippon Polyethylene Co., Ltd.) Product name) High density polyethylene, Melt flow rate 7g / l0min
[0090] (2) (B)成分 [0090] (2) Component (B)
(2— 1) (B— 1)成分 (2- 1 1)製造例 1；ナトリウム化合物含有ポリプロピレン ポリエチレングリコールブ ロック共重合体 (2— 1) (B— 1) component (2-1) Production Example 1; Sodium compound-containing polypropylene Polyethylene glycol block copolymer
ステンレス製オートクレープに、高分子量ポリプロピレンの熱減成法で得られた低分 子量ポリプロピレン（Mn2， 500) 80部を仕込んだ後、 160°Cで溶融し、無水マレイン 酸 7部及び 12 アミノドデカン酸 14部をカ卩え、窒素ガス通気下、攪拌しながら 160°C で 1時間反応させた。その後、 200°Cで 20時間反応を行レ、、ポリオレフインブロックを 得た（B— a)を得た。 （B— a)の酸価は 32. 1、 Mnは 2， 800であった。 A stainless steel autoclave was charged with 80 parts of low molecular weight polypropylene (Mn2, 500) obtained by thermal degradation of high molecular weight polypropylene, then melted at 160 ° C, and 7 parts of maleic anhydride and 12 amino acids. 14 parts of dodecanoic acid was added and reacted at 160 ° C for 1 hour with stirring under nitrogen gas. Thereafter, the reaction was carried out at 200 ° C. for 20 hours to obtain a polyolefin block (Ba). The acid value of (Ba) was 32.1 and Mn was 2,800.
上記（B_ a) 64部、ポリエチレングリコール（Mn2， 000) 36部、ドデシルベンゼンス ルホン酸ナトリウム 8部、酸化防止剤〔商品名「ィルガノックス 1010」、チバガイギ一社 製〕 0. 3部及び酢酸ジルコニル 0. 5部をステンレス製オートクレーブに加え、 230°C 、 ImmHg以下の減圧下の条件で 4時間重合させ、ナトリウム含有量 4000ppmのポ リマーを得た。このポリマーをベルト状で取り出し、ペレット化しブロック共重合体（B1 —1)を得た。ブロック共重合体（B1— 1)の Mnは 25, 000であった。また、この Mnと — NMR分析より、ブロック共重合体（B1— 1)の平均繰り返し数は 5. 0であった。 (2- 1 - 2)製造例 2；カリウム化合物含有ポリプロピレン ポリエチレングリコールブ ロック共重合体 (B_a) 64 parts, polyethylene glycol (Mn2,000) 36 parts, sodium dodecylbenzenesulfonate 8 parts, antioxidant (trade name “Ilganox 1010”, manufactured by Ciba-Gaigi Co., Ltd.) 0.3 part and zirconyl acetate 0.5 part was added to a stainless steel autoclave and polymerized for 4 hours under a reduced pressure of 230 ° C. and ImmHg or less to obtain a polymer having a sodium content of 4000 ppm. This polymer was taken out in the form of a belt and pelletized to obtain a block copolymer (B1-1). The Mn of the block copolymer (B1-1) was 25,000. Further, from this Mn and —NMR analysis, the average number of repeats of the block copolymer (B1-1) was 5.0. (2-1-2) Production Example 2: Potassium Compound-containing Polypropylene Polyethylene Glycol Block Copolymer
ドデシルベンゼンスルホン酸ナトリウムの代わりに塩化カリウム 0. 75部を用いた以外 は製造例 1と同様にして、カリウム含有量 4000ppmのブロック共重合体 (B1— 2)を 得た。 A block copolymer (B1-2) having a potassium content of 4000 ppm was obtained in the same manner as in Production Example 1, except that 0.75 part of potassium chloride was used instead of sodium dodecylbenzenesulfonate.
(2- 1 - 3)製造例 3；ナトリウム化合物含有ポリプロピレン ポリエチレングリコールブ ロック共重合体  (2-1-3) Production Example 3; Sodium Compound-containing Polypropylene Polyethylene Glycol Block Copolymer
ドデシルベンゼンスルホン酸ナトリウムの使用量を 3. 9部に変えた以外は製造例 1と 同様にして、ナトリウム含有量 2000ppmのブロック共重合体（B1 - 3)を得た。 A block copolymer (B1-3) having a sodium content of 2000 ppm was obtained in the same manner as in Production Example 1 except that the amount of sodium dodecylbenzenesulfonate was changed to 3.9 parts.
(2- 2) (B— 2)成分 (2-2) Component (B-2)
(2_ 2_ 1)製造例 4；ポリプロピレン—ポリエチレングリコールブロック共重合体 ドデシルベンゼンスルホン酸ナトリウムを用いなかった以外は製造例 1と同様にして、 ナトリウム化合物を含有しないブロック共重合体 (B2— 1)を得た。  (2_ 2_ 1) Production Example 4; Polypropylene-polyethylene glycol block copolymer A block copolymer containing no sodium compound (B2-1) in the same manner as in Production Example 1 except that sodium dodecylbenzenesulfonate was not used. Got.
(3) (C)成分 (3 1)製造例 5：スチレン一ブタジエンラジアルテレブロック共重合体 撹拌機およびジャケット付きオートクレープを乾燥、窒素置換し、窒素気流中でシクロ へキサンとテトラヒドロフラン 2. 75部投入した。スチレン 25部をカ卩え、 60°Cに昇温し たのち、 n—ブチルリチウム 0. 175部を含むシクロへキサン溶液を添カ卩し、重合反応 を 60分間行った（1段目）。次いで、スチレン 3部、ブタジエン 20部の混合物を添加し 60分間重合反応を行った（2段目）、また、スチレン 3部、ブタジエン 20部の混合物を 添加し 60分間重合反応を行った（3段目）、更にブタジエン 29部を添加し転化率 10 0%になるまで重合し完結した。カップリング剤として四塩化珪素 0. 1部を添カ卩したの ち、カップリング反応を完結させた。重合終了後、 2, 6—ジ— tert—プチルカテコー ルを上記で得られた共重合体 100部に対して 0. 3部添加し、その後、溶媒を除去し てテーパーブロックを有するカップリングタイプのスチレン一ブタジエンブロック共重 合体 C1を得た。このもののスチレン含有量は 31%、数平均分子量は 200, 000であ つに。 (3) Component (C) (3 1) Production Example 5: Styrene-Butadiene Radial Teleblock Copolymer A stirrer and jacketed autoclave were dried and purged with nitrogen, and 2.75 parts of cyclohexane and tetrahydrofuran were added in a nitrogen stream. After adding 25 parts of styrene and raising the temperature to 60 ° C, a cyclohexane solution containing 0.175 part of n-butyllithium was added and the 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 was added to 100 parts of the copolymer obtained above, and then the solvent was removed to produce a coupling type having a taper block. A styrene-butadiene block copolymer C1 was obtained. It has a styrene content of 31% and a number average molecular weight of 200,000.
[0092] (3 - 2)製造例 6：完全水素添加スチレン ブタジエンブロック共重合体  [0092] (3-2) Production Example 6: Fully Hydrogenated Styrene Butadiene Block Copolymer
撹拌機及びジャケット付きオートクレープを乾燥、窒素置換し、スチレン 30部を含む シクロへキサン溶液を投入した。次いで、 n ブチルリチウムを添加し、 70°Cで 1時間 重合したのち、ブタジエン 40部を含むシクロへキサン溶液を加えて 1時間重合した。 その後スチレン 30部を含むシクロへキサン溶液を添加し 1時間重合し、得られたプロ ック重合体溶液の一部をサンプリングし、 2, 6 ジ—tert—ブチルカテコールをブロ ック共重合体 100部に対して 0. 3部添カ卩し、その後、溶媒を加熱除去した。このもの の、スチレン含量は 60%、ポリブタジエン部分の 1 , 2—ビュル結合量は 35%、数平 均分子量は 74， 000であった。残りのブロック共重合体溶液にチタノセンジクロライド とトリェチルアルミニウムをシクロへキサン中で反応させた溶液を加え、 50°C、 50kgf /cm2の水素圧下、 3時間水素化反応を行った。 2, 6—ジ—tert—ブチルカテコー ルをブロック共重合体 100部に対して 0. 3部添加し、その後、溶媒を除去し、ブタジ ェン部分の水素添カ卩率 100%の重合体 C2を得た。 The stirrer and the jacketed autoclave were dried and purged with nitrogen, and a cyclohexane solution containing 30 parts of styrene was added. 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. Then, a cyclohexane solution containing 30 parts of styrene was added and polymerized for 1 hour. A portion of the resulting block polymer solution was sampled, and 2, 6-di-tert-butylcatechol was block copolymerized. After adding 0.3 parts to 100 parts, the solvent was removed by heating. Of these, the styrene content was 60%, the 1,2-bule 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 carried out for 3 hours under a hydrogen pressure of 50 ° C. and 50 kgf / cm 2 . 2,6-di-tert-butylcatechol is added in an amount of 0.3 part to 100 parts of the block copolymer, and then the solvent is removed, and the hydrogenation rate of the butadiene part is 100%. Got.
[0093] (4) (D)成分  [0093] (4) Component (D)
(4一 1)製造例 7 ;ABS樹脂 撹拌機を備えた内容積 7Lのガラス製フラスコに窒素気流中で、イオン交換水 75部 、ロジン酸カリウム 0· 5部、 tert—ドデシルメルカプタン 0· 1部、ポリブタジエンラテツ タス（平均粒子径； 2000 A、ゲル含率； 85%) 30部（固形分）、ブタジエン スチレン ランダム重合体ラテックス（平均粒子径； 6000 A、スチレン含量 25%) 10部（固形分 )、スチレン 15部、アクリロニトリル 5部をカ卩え、撹拌しながら昇温した。内温が 45°Cに 達した時点で、ピロリン酸ナトリウム 0. 2部、硫酸第一鉄 7水和物 0. 01部、およびブ ドウ糖 0. 2部をイオン交換水 20部に溶解した溶液をカ卩えた。その後、クメンハイド口 パーオキサイド 0. 07部を加えて重合を開始した。 1時間重合させた後、更にイオン 交換水 50部、ロジン酸カリウム 0. 7部、スチレン 30部、アクリロニトリル 10部、 tert— ドデシルメルカプタン 0. 05部およびクメンハイド口パーオキサイド 0. 01部を 3時間か けて連続的に添加し、更に 1時間重合を継続させた後、 2、 2' ーメチレン一ビス (4 ーェチルー 6 tert ブチルフエノール） 0. 2部を添加し重合を完結させた。反応生 成物のラテックスを硫酸水溶液で凝固、水洗した後、乾燥してゴム強化スチレン系榭 脂 D1を得た。この樹脂 D1のグラフト率は 68%、アセトン可溶分の極限粘度〔77〕は、 0. 45dl/gであった。 (4-1) Production Example 7: ABS resin In a 7 L glass flask equipped with a stirrer, in a nitrogen stream, ion exchange water 75 parts, potassium rosinate 0.5 parts, tert-dodecyl mercaptan 0 parts, polybutadiene latex (average particle size; 2000 A, gel content: 85%) 30 parts (solid content), butadiene styrene random polymer latex (average particle size: 6000 A, styrene content 25%) 10 parts (solid content), styrene 15 parts, acrylonitrile 5 parts The temperature was raised while stirring. When the internal temperature reached 45 ° C, 0.2 parts of sodium pyrophosphate, 0.01 parts of ferrous sulfate heptahydrate, and 0.2 parts of sugar were dissolved in 20 parts of ion-exchanged water. The solution was added. Thereafter, 0.07 part of cumene hydride peroxide was added to initiate polymerization. After polymerizing for 1 hour, add 50 parts of ion-exchanged water, 0.7 parts of potassium rosinate, 30 parts of styrene, 10 parts of acrylonitrile, 0.05 part of tert-dodecyl mercaptan and 0.01 part of cumene hydride peroxide for 3 hours. However, the polymerization was continuously added, and the polymerization was further continued for 1 hour. Then, 0.2 part of 2,2′-methylene bis (4-ethyl-6-tertbutylphenol) was added to complete the polymerization. The latex of the reaction product was coagulated with an aqueous sulfuric acid solution, washed with water, and dried to obtain a rubber-reinforced styrene resin D1. The graft ratio of this resin D1 was 68%, and the intrinsic viscosity [77] of the acetone-soluble component was 0.45 dl / g.
(4 2)製造例 8 ; AS樹脂 (4 2) Production Example 8: AS resin
内容積 30Lのリボン翼を備えたジャケット付き重合反応容器を 2基連結し、窒素置 換した後、 1基目の反応容器にスチレン 75部、アクリロニトリル 25部、トルエン 20部を 連続的に添加した。分子量調節剤として tert—ドデシルメルカブタン 0. 12部および トルエン 5部の溶液、および重合開始剤として、 1、 1' ーァゾビス（シクロへキサン一 1—カーボ二トリル) 0. 1部、およびトルエン 5部の溶液を連続的に供給した。 1基目 の重合温度は、 110°Cにコントロールし、平均滞留時間 2. 0時間、重合転化率 57% であった。得られた重合体溶液は、 1基目の反応容器の外部に設けたポンプにより、 スチレン、アクリロニトリル、トルエン、分子量調節剤、および重合開始剤の供給量と 同量を連続的に取り出し 2基目の反応容器に供給した。 2基目の反応容器の重合温 度は、 130°Cで行レ、、重合転化率は 75%であった。 2基目の反応容器で得られた共 重合体溶液は、 2軸 3段ベント付き押出機を用いて、直接未反応単量体と溶剤を脱 揮し、極限粘度〔 〕0. 48dlZgのスチレン系樹脂 D2を得た。 [0095] (4 3)製造例 9 ;ゴム強化スチレン系樹脂 Two jacketed polymerization reactors equipped with ribbon wings with an internal volume of 30 L were connected and replaced with nitrogen, and then 75 parts of styrene, 25 parts of acrylonitrile and 20 parts of toluene were continuously added to the first reactor. . Tert-dodecyl mercabtan as a molecular weight regulator 0.12 parts and a solution of 5 parts of toluene, and 1, 1′-azobis (cyclohexane 1-carbonitryl) 0.1 part as a polymerization initiator and toluene 5 Part of the solution was fed continuously. The polymerization temperature of the first group was controlled at 110 ° C., the average residence time was 2.0 hours, and the polymerization conversion rate was 57%. The obtained polymer solution was continuously taken out from the first reaction vessel by the same amount as the styrene, acrylonitrile, toluene, molecular weight regulator, and polymerization initiator supplied by the pump. To the reaction vessel. The polymerization temperature of the second reaction vessel was 130 ° C, and the polymerization conversion was 75%. The copolymer solution obtained in the second reaction vessel was devolatilized directly from the unreacted monomer and solvent using a twin-screw, three-stage vented extruder, and the styrene having an intrinsic viscosity of 0.48dlZg. System resin D2 was obtained. (4 3) Production Example 9: Rubber-reinforced styrene resin
(4- 3 1)ゴム質重合体 (D3a)の製造  (4- 3 1) Production of rubbery polymer (D3a)
撹拌機及びジャケット付きオートクレープを乾燥、窒素置換し、シクロへキサンとブタ ジェン 20部溶液を投入した。次いで、 n ブチルリチウムを添カ卩し、 50°Cで等温重合 を行った。転化率 100%になった時点で、テトラヒドロフラン 0. 75部、ブタジエン 65 部を添カ卩し、 50°Cから 80°Cに昇温重合を行った。転化率 100%となった時点でスチ レン 15部を加え、更に重合反応を行い、水素添加前 A— B1— B2トリブロック共重合 体を得た。得られたブロック重合体は、スチレンブロック（A)の含量 15%、ブタジエン ブロック（B1)含量 65%、ブタジエンブロック（B2)含量 20%、 1 , 2 ビュル含量 35 %のブタジエンブロック（Bl)、 1， 2—ビュル含量 10%のブタジエンブロック（B2)力 らなる数平均分子量 200, 000の重合体であった。  The stirrer and jacketed autoclave were dried and purged with nitrogen, and cyclohexane and 20 parts of butadiene were added. Next, 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 comprises a butadiene block (Bl) having 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-bule content of 35%. It was a polymer with a number average molecular weight of 200,000 consisting of a butadiene block (B2) force with a 1,2-bule content of 10%.
別の容器でチタノセンジクロライド 1部をシクロへキサンに分散させ、室温でトリェチ ルアルミニウム 0. 5部と反応させた。得られた均一溶液を上記ポリマー溶液に加え、 50°Cで、 50kgf/cm2の水素圧下、水素添加率がほぼ 100%になるまで水素化反 応を行い、ゴム質重合体 D3aを得た。 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 above polymer solution, and a hydrogenation reaction was performed at 50 ° C. under a hydrogen pressure of 50 kgf / cm 2 until the hydrogenation rate was almost 100%, to obtain a rubbery polymer D3a. .
[0096] (4- 3- 2)ゴム強化スチレン系樹脂（D3)の製造 [0096] (4- 3- 2) Manufacture of rubber-reinforced styrene resin (D3)
リボン翼を備えたステンレス製オートクレープを窒素置換したのち、窒素気流中で、 予めトノレェンを溶媒として均一溶液にした上記重合体 D3aを 28部（固形分）、スチレ ン 10. 8咅 アタリロニトリノレ 7. 2咅、メチノレメタタリレート 54咅、トノレェン 120咅 およ び tert ドデシルメルカプタン 0. 1部を仕込み、撹拌しながら昇温した。内温が 50°C に到達した時点で、ベンゾィルパーオキサイド 0· 5部、ジクミルパーオキサイド 0· 1部 を添加し、更に昇温し、 80°Cに達した後、 80°C—定に制御しながら重合反応を行わ せた。反応開始後 6時間目から 1時間を要して 120°Cまで昇温し、更に 2時間反応を 行って終了した。転化率は、 97%であった。  After substituting a stainless steel autoclave equipped with a ribbon blade with nitrogen, in a nitrogen stream, 28 parts (solid content) of the above polymer D3a that had been made into a homogeneous solution in advance using toluene as a solvent, styrene 10.8 咅 Atalilonitrino The mixture was charged with 7.2 parts of methanol, 54 parts of methinoremethalate, 120 parts of tonolene and 0.1 part of tert-dodecyl mercaptan, and the temperature was increased while stirring. When the internal temperature reaches 50 ° C, add 0.5 part of benzoyl peroxide and 0.1 part of dicumyl peroxide, further increase the temperature and reach 80 ° C. The polymerization reaction was carried out with constant control. 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%.
100。Cまで冷却後、 2， 2—メチレンビス _4_6 _tert ブチルフエノール 0. 2部を 添加した後、反応混合物をオートクレープより抜き出し、水蒸気蒸留により未反応物 と溶媒を留去するとともに、ベント付き押出機を用いて重合体をペレット化し、重合体 D3を得た。このもののグラフト率は 45%、アセトン可溶分の極限粘度〔 〕は 0. 45dl gであった。 100. After cooling to C, 0.2 parts 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, and a vented extruder was used. Was used to pelletize the polymer to obtain polymer D3. The graft ratio of this product is 45%, and the intrinsic viscosity [] of acetone-soluble component is 0.45dl. g.
[0097] (4一 4)製造例 10 ;ゴム強化スチレン系樹脂  [0097] (4-1-4) Production Example 10: Rubber-reinforced styrene resin
ゴム質重合体 D3aの代わりにエチレン.プロピレン系ゴム（商品名「EP84」、 JSR社 製） 19部を用い、スチレン Zアクリロニトリル Zメチルメタタリレートの代わりにスチレン 57部、アクリロニトリル 24部を用いた以外、製造例 9と同様の方法で重合反応を行い 、エチレン.プロピレン系ゴムの含有量 20%、グラフト率 55%、アセトン可溶分の極限 粘度〔 〕 0. 45dlZgである重合体 D4を得た。  19 parts of ethylene / propylene rubber (trade name “EP84”, manufactured by JSR) was used in place of rubber polymer D3a, and 57 parts of styrene and 24 parts of acrylonitrile were used in place of styrene Z acrylonitrile Z methyl methacrylate. Except for the above, a polymerization reaction was carried out in the same manner as in Production Example 9 to obtain a polymer D4 having an ethylene / propylene rubber content of 20%, a graft ratio of 55%, and an intrinsic viscosity [] of acetone-soluble component of 0.45 dlZg. It was.
[0098] (5) (E)成分  [0098] (5) Component (E)
本発明の (E)成分として三光化学工業社製の下記のものを用いた。  As the component (E) of the present invention, the following products manufactured by Sanko Chemical Co., Ltd. were used.
E1 ;サンコノーノレ AQ— 50T (商品名）トリフルォロメタンスルホン酸リチウムの 50%水 溶液。  E1; Sancononole AQ— 50T (trade name) 50% aqueous solution of lithium trifluoromethanesulfonate.
E2 ;サンコノール 0862— 20T (商品名）トリフルォロメタンスルホン酸リチウムの 20% アジピン酸ジブチキシエトキシェチル溶液。  E2; Sanconol 0862-20T (trade name) A solution of lithium trifluoromethanesulfonate in 20% dibutoxyethoxyethyl adipate.
(6)その他成分；  (6) Other ingredients;
制電性を向上させるその他の成分として下記のものを用いた。  The following were used as other components for improving antistatic properties.
F1 ;非イオン系帯電防止剤；花王社製エレクトロストリッパー TS— 5 (商品名）グリセリ ンエステノレ  F1: Nonionic antistatic agent; Kao's electro stripper TS-5 (trade name) Glycerin Estenole
G1；酸化亜鉛ウイスカー；松下電器産業株式会社製パナテトラ WZ— 05F1 (商品名 )  G1; Zinc oxide whisker; Panatetra WZ—05F1 (trade name) manufactured by Matsushita Electric Industrial Co., Ltd.
[0099] 実施例 I-：!〜 1_19及び1_35〜1_40、比較例 I-：!〜 1-10  [0099] Example I-:! To 1_19 and 1_35 to 1_40, Comparative Example I-:! To 1-10
表 1— 1及び表 1— 2記載の配合割合で各構成成分をヘンシェルミキサーにより混 合した後、ベント付き二軸押出機 (シリンダー設定温度 220°C)を用いて溶融混練し、 ペレット化した。尚、その他成分のうち前記 G1を用いた場合、押出機途中から注入し た。得られたペレットを十分に乾燥したのち、このペレットを用いて射出成形（シリンダ 一設定温度 220°C)し、制電性、耐薬品性、耐衝撃性、成形品表面外観、及び熱安 定性の評価用試験片を得た。評価結果を表 1一 1及び表 1一 2に示した。  Each component was mixed with a Henschel mixer at the blending ratio shown in Table 1-1 and Table 1-2, then melt-kneaded using a vented twin-screw extruder (cylinder setting temperature 220 ° C) and pelletized. . Of the other components, when G1 was used, it was injected from the middle of the extruder. After the obtained pellets are sufficiently dried, injection molding (cylinder set temperature 220 ° C) is performed using these pellets, and antistatic properties, chemical resistance, impact resistance, molded product surface appearance, and thermal stability. A test piece for evaluation was obtained. The evaluation results are shown in Table 1-11 and Table 1-12.
[0100] 実施例 1-20〜卜 25、 1-41及び 1-42 [0100] Examples 1-20 to 25, 1-41, and 1-42
表 2記載の制電性樹脂組成物の配合割合で各構成成分をヘンシェルミキサーによ り混合した後、ベント付き二軸押出機 (シリンダー設定温度 220°C)を用いて溶融混 練し、ペレット化した。尚、その他成分のうち前記 G1を用いた場合、押出機途中から 注入した。得られたペレットを十分に乾燥した後、このペレット化された制電性樹脂組 成物からなる表裏層（各々の厚み 0. 1mm)と、表 2記載の配合割合の組成物からな るコア材（厚み 0. 8mm)とからなる三層シート（肉厚 1. Omm)を Tダイ付き多層押出 装置で製造した (加工温度 190〜240°C)。 Each component is mixed with a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 2. After mixing, the mixture was melt-kneaded using a twin-screw extruder with a vent (cylinder setting temperature 220 ° C) and pelletized. Of the other components, when G1 was used, it was injected from the middle of the extruder. The obtained pellets are sufficiently dried, and then a front and back layer (each thickness of 0.1 mm) made of the pelletized antistatic resin composition and a core made of the composition having the blending ratio shown in Table 2. A three-layer sheet (thickness: 1. Omm) consisting of a material (thickness 0.8 mm) was produced using a multilayer extrusion device with a T-die (processing temperature 190-240 ° C).
得られた三層シートを用い、前記評価法に従い、制電性、耐薬品性、耐衝撃性、表 面外観、溶出イオン、及び熱安定性を測定した。評価結果を表 2に示した。  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 above evaluation methods. The evaluation results are shown in Table 2.
また、上記三層シートを用いて真空成形（ヒーター温度 400°C、予熱時間 30〜45 秒）を行ったところ、表面外観に優れるトレイ成形品が得られた。  When the above three-layer sheet was used for vacuum forming (heater temperature 400 ° C, preheating time 30 to 45 seconds), a tray molded product excellent in surface appearance was obtained.
[0101] 実施例 1-26〜卜 34 [0101] Examples 1-26 to 卜 34
表 3記載の制電性樹脂組成物の配合割合で各構成成分をヘンシェルミキサーによ り混合した後、ベント付き二軸押出機 (シリンダー設定温度 220°C)を用いて溶融混 練し、ペレット化した。尚、その他成分のうち前記 G1を用いた場合、押出機途中から 注入した。得られたペレットを十分に乾燥した後、このペレット化された制電性樹脂組 成物をインフレーション（170°C)し、厚み 50 μ mのフィルムを得た。  Each component was mixed with a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 3, and then melt-kneaded using a vented twin-screw extruder (cylinder setting temperature 220 ° C) to give pellets. Turned into. Of the other components, when G1 was used, it was injected 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.
得られたフィルムを用い、前記評価法に従い、制電性、表面外観、溶出イオン、及 び熱安定性を測定した。評価結果を表 3に示した。  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.
[0102] 実施例 1-43〜1-46 [0102] Examples 1-43 to 1-46
表 3記載の制電性樹脂組成物の配合割合で各構成成分をヘンシェルミキサーによ り混合した後、ベント付き二軸押出機 (シリンダー設定温度 220°C)を用いて溶融混 練し、ペレツトイ匕した。得られたペレットを十分に乾燥した後、このペレット化された制 電性樹脂組成物からなる表裏層（各々の厚み 30 μ m)と、表 3記載の配合割合の組 成物にァゾジカルボンアミド系発泡剤を配合して約 2倍に発泡させたコア材とからな る三層シート（肉厚 3mm)を Tダイ付き多層押出装置 (加工温度 180〜200°C)で製 造した。  Each component was mixed with a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 3, then melt-kneaded using a vented twin-screw extruder (cylinder setting temperature 220 ° C), I was jealous. After the obtained pellets are sufficiently dried, azodicarboxylic acid 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) consisting of a core material foamed approximately twice as much as an amide-based foaming agent was produced using a multilayer extruder with a T-die (processing temperature 180-200 ° C).
得られた三層シートを用い、前記評価法に従い、制電性、耐薬品性、表面外観、溶 出イオン、及び熱安定性を測定した。評価結果を表 3に示した。 例実施 Using the obtained three-layer sheet, the antistatic property, chemical resistance, surface appearance, dissolved ions, and thermal stability were measured according to the evaluation methods. The evaluation results are shown in Table 3. Example implementation
配合 ( 評価結果 Formulation (Evaluation result
第一の制 First system
鼋性榭脂  Dwarf oil
組成物  Composition
第二の制 Second system
電性樹脂  Electric resin
組成物  Composition
Figure imgf000046_0001
Figure imgf000046_0001
'表中、（E1 )成分の（ ）の外の数値は、リチウム堪としての配合部效であり、（ 〕 の «値は水溶液としての S台部数を表 'In the table, the value outside () for the (E1) component is the effect of blending with lithium, and the «value in () indicates the number of S-base parts as an aqueous solution.
[0104] [表 1-2] [0104] [Table 1-2]
Figure imgf000048_0001
Figure imgf000048_0001
*表中、 (E1 )成分の（ >の外の数慷は、リチウム堍としての配合部数でぁリ、（ ）内の数値は水溶液としての配合部数を表す。 * In the table, the number of (E1) component other than (> is the number of blended parts as lithium soot, and the value in () represents the number of blended parts as an aqueous solution.
Figure imgf000050_0001
Figure imgf000050_0001
*表中、（El )成分の（ ）の外の数値は、リチウム塩としての E合部数でぁリ、 ( )内の数値は水溶液としての E合部数である。 * In the table, the value outside () of the (El) component is the E total number of lithium salts, and the number in () is the total number of E as aqueous solution.
星0 実施例 0 stars Example
制霣性樹脂組成物の配合割合 (部) 三層シートのコア材 評価結果 Mixing ratio of anti-resin composition (Part) Core material of three-layer sheet Evaluation results
Figure imgf000052_0001
Figure imgf000052_0001
*表中、（E1 )成分の（ ）の外の数値は、リチウム埴としての配合部数であ人 ( )内の数値は水溶液としての配合部数を表 1 * In the table, the value outside () of the (E1) component is the number of parts blended as lithium soot, and the number in () is the number of parts blended as an aqueous solution.
表 1 1及び表 1 2に記載された結果から、以下のことが明らかである。 From the results described in Tables 11 and 12, it is clear that:
実施例ト 1〜1-8およびト 37、ならびに、比較例ト 1〜ト 4は、本発明の第一の制電 性樹脂組成物に関する実施例及び比較例であり、これらの実施例は、制電性、耐薬 品性、成形品表面外観、熱安定性及び溶出イオン性に優れる。これに対し、比較例 I -1は、溶出イオン量が 3 μ g/cm2よりも多い例である。比較例 1-2は、制電性が 1 X 1 0" Ω /口よりも高い例である。比較例 1-3は、本発明の (Α)成分の使用量が発明の 範囲外で多ぐ（Β)成分の使用量が発明の範囲外で少ない例であり、制電性が劣る 。比較例 1-4は、本発明の (Α)成分の使用量が発明の範囲外で少なぐ（Β)成分の 使用量が発明の範囲外で多い例であり耐薬品性、成形品表面外観及び熱安定性が 劣り、更に溶出イオンが多い。 Examples 1 to 1-8 and 37 and Comparative Examples 1 to 4 are examples and comparative examples relating to the first antistatic resin composition of the present invention. Excellent antistatic property, chemical resistance, molded product surface appearance, thermal stability and elution ionicity. On the other hand, Comparative Example I-1 is an example in which the amount of eluted ions is larger than 3 μg / cm 2 . Comparative Example 1-2 is an example in which the antistatic property is higher than 1 × 10 ”Ω / mouth. Comparative Example 1-3 is a large amount of the component (ii) of the present invention that is outside the scope of the invention. This is an example in which the amount of component (ぐ) used is small outside the scope of the invention, and the antistatic property is inferior Comparative Example 1-4 shows that the amount of component (Α) used in the present invention is small outside the range of the invention. This is an example in which the amount of component (ii) used is outside the scope of the invention, and chemical resistance, molded product surface appearance and thermal stability are inferior, and more ions are eluted.
実施 ί列 Ι_9〜Ι_19、 I一 35〜1_36及び I一 38〜1_40、並びに、 i 較 ί列 I一 5〜I_10fま、 本発明の第二の制電性樹脂組成物に関する実施例及び比較例であり、これらの実 施例は、制電性、耐薬品性、成形品表面外観、熱安定性、溶出イオン性、及び耐衝 撃性に優れる。これに対し、比較例ト 5は、溶出イオン量が S g/cm2よりも多い例 である。比較例ト 6は、制電性が I X 10" Ω /口よりも高い例である。比較例ト 7は、 本発明の (Α)成分の使用量が発明の範囲外で少ない例であり、制電性、耐薬品性、 耐衝撃性、及び成形品表面外観が劣る、比較例 1-8は、本発明の（C)成分の使用量 が発明の範囲外で少ない例であり、耐衝撃性が劣る。比較例 1-9は、本発明の（Β)成 分の使用量が発明の範囲外で少ない例であり、制電性が劣る。比較例 1-10は、本発 明の（D)成分の使用量が発明の範囲外で多い例であり、制電性、耐薬品性が劣る。 表 2に記載された結果から、以下のことが明らかである。 Implementation 比較 _9 to Ι_19, I 1 35 to 1_36 and I 1 38 to 1_40, and i comparison 列 row I 1 5 to I_10f Examples and Comparative Examples relating to the second antistatic resin composition of the present invention These examples are excellent in antistatic property, chemical resistance, molded article surface appearance, thermal stability, elution ionicity, and impact resistance. On the other hand, Comparative Example 5 is an example in which the amount of eluted ions is larger than S g / cm 2 . Comparative Example 6 is an example in which the antistatic property is higher than IX 10 "Ω / mouth. Comparative Example 7 is an example in which the amount of the component (ii) of the present invention is small outside the scope of the invention, Comparative Example 1-8, in which the antistatic property, chemical resistance, impact resistance, and molded product surface appearance are inferior, is an example in which the amount of the component (C) of the present invention is small outside the scope of the invention. Comparative Example 1-9 is an example in which the amount of the component (ii) of the present invention is small outside the scope of the invention, and the antistatic property is inferior. This is an example in which the amount of component (D) used is large outside the scope of the invention, and the antistatic property and chemical resistance are inferior From the results described in Table 2, the following is clear.
実施例ト 20〜卜 25、ト 41及び 1-42は、本発明の第二の制電性樹脂組成物からな るシートに関する実施例であり、制電性、耐薬品性、シート表面外観、耐衝撃性、及 び溶出イオン性に優れ、また、真空成形性に優れる。  Examples Nos. 20 to 25, Nos. 41 and 1-42 are examples relating to sheets made of the second antistatic resin composition of the present invention, and include antistatic properties, chemical resistance, sheet surface appearance, Excellent impact resistance and elution ionicity, and excellent vacuum formability.
表 3に記載された結果から、以下のことが明らかである。  From the results described in Table 3, the following is clear.
実施例ト 26〜ト 34は、本発明の第一の制電性樹脂組成物からなるフィルムに関 する実施例であり、制電性、フィルム表面外観、及び溶出イオン性に優れる。また、 実施例ト 43〜ト 46は、本発明の第二の制電性樹脂組成物からなるフィルムを発泡 基材に積層した成形品に関する実施例であり、制電性、耐薬品性、表面外観、熱安 定性および溶出イオン性に優れる。 Examples 26 to 34 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. In Examples 43 to 46, a film made of the second antistatic resin composition of the present invention was foamed. This is an example relating to a molded product laminated on a substrate, and is excellent in antistatic property, chemical resistance, surface appearance, thermal stability and elution ionicity.
[0108] 実施例 II-:！〜 11-18及び II_26〜II_31、比較例 II-：！〜 II- 10  [0108] Example II-! ~ 11-18 and II_26 ~ II_31, Comparative Example II-! ~ II-10
表 4—1及び表 4— 2記載の配合割合で各構成成分をヘンシェルミキサーにより混 合した後、ベント付き二軸押出機 (シリンダー設定温度 220°C)を用いて溶融混練し、 ペレット化した。尚、その他成分のうち前記 G1成分を用いた場合、押出機途中から 注入した。得られたペレットを十分に乾燥したのち、このペレットを用いて射出成形（ シリンダー設定温度 220°C)し、制電性、耐薬品性、耐衝撃性、成形品表面外観、及 び熱安定性の評価用試験片を得た。評価結果を表 4—1及び表 4— 2に示した。  Each component was mixed with a Henschel mixer at the blending ratio shown in Table 4-1 and Table 4-2, then melt-kneaded using a vented twin-screw extruder (cylinder setting temperature 220 ° C) and pelletized. . When the G1 component was used among other components, it was injected from the middle of the extruder. After the obtained pellets are sufficiently dried, injection molding (cylinder setting temperature 220 ° C) is performed using the pellets, and antistatic properties, chemical resistance, impact resistance, molded product surface appearance, and thermal stability. A test piece for evaluation was obtained. The evaluation results are shown in Tables 4-1 and 4-2.
[0109] 実施例 Iト 19〜H_22、 Iト 32及び Iト 33 [0109] Examples I to 19 to H_22, I to 32 and I to 33
表 5記載の制電性樹脂組成物の配合割合で各構成成分をヘンシェルミキサーによ り混合した後、ベント付き二軸押出機 (シリンダー設定温度 220°C)を用いて溶融混 練し、ペレット化した。尚、その他成分のうち前記 G1成分を用いた場合、押出機途中 力 注入した。得られたペレットを十分に乾燥した後、このペレット化された制電性樹 脂組成物からなる表裏層（各々の厚み 0. 1mm)と、表 5記載の配合割合の組成物か らなるコア材（厚み 0. 8mm)とからなる三層シート（肉厚 1. Omm)を Tダイ付き多層 押出装置で製造した (加工温度 190〜240°C)。  Each component was mixed by a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 5, then melt-kneaded using a vented twin-screw extruder (cylinder setting temperature 220 ° C), and pellets Turned into. In addition, when the G1 component was used among other components, force was injected in the middle of the extruder. After the obtained pellets are sufficiently dried, the front and back layers (each having a thickness of 0.1 mm) comprising the pelletized antistatic resin composition, and the core comprising the composition having the blending ratio shown in Table 5 are used. A three-layer sheet (thickness: 1. Omm) consisting of a material (thickness 0.8 mm) was manufactured using a multilayer extrusion device with a T-die (processing temperature 190-240 ° C).
得られた三層シートを用い、前記評価法に従い、制電性、耐薬品性、耐衝撃性、表 面外観、溶出イオン、及び熱安定性を測定した。評価結果を表 5に示した。  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 above evaluation methods. The evaluation results are shown in Table 5.
また、上記三層シートを用いて真空成形（ヒーター温度 400°C、予熱時間 30〜45 秒）を行ったところ、表面外観に優れるトレイ成形品が得られた。  When the above three-layer sheet was used for vacuum forming (heater temperature 400 ° C, preheating time 30 to 45 seconds), a tray molded product excellent in surface appearance was obtained.
[0110] 実施例 Π-23〜Π-25 [0110] Examples Π-23 to Π-25
表 6記載の制電性樹脂組成物の配合割合で各構成成分をヘンシェルミキサーによ り混合した後、ベント付き二軸押出機 (シリンダー設定温度 220°C)を用いて溶融混 練し、ペレツトイ匕した。得られたペレットを十分に乾燥した後、このペレット化された制 電性樹脂組成物をインフレーション（170°C)し、厚み 50 μ mのフィルムを得た。 得られたフィルムを用い、前記評価法に従い、制電性、表面外観、溶出イオン、及 び熱安定性を測定した。評価結果を表 6に示した。 [0111] 実施例 II-34〜II-37 Each component was mixed by a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 6, then melt-kneaded using a vented twin-screw extruder (cylinder setting temperature 220 ° C), I was jealous. 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 6. [0111] Examples II-34 to II-37
表 6記載の制電性樹脂組成物の配合割合で各構成成分をヘンシェルミキサーによ り混合した後、ベント付き二軸押出機 (シリンダー設定温度 220°C)を用いて溶融混 練し、ペレツトイ匕した。得られたペレットを十分に乾燥した後、このペレット化された制 電性樹脂組成物からなる表裏層（各々の厚み 30 μ m)と、表 6記載の配合割合の組 成物にァゾジカルボンアミド系発泡剤を配合して約 2倍に発泡させたコア材とからな る三層シート（肉厚 3mm)を Tダイ付き多層押出装置 (加工温度 180〜200°C)で製 造した。  Each component was mixed by a Henschel mixer at the blending ratio of the antistatic resin composition shown in Table 6, then melt-kneaded using a vented twin-screw extruder (cylinder setting temperature 220 ° C), I was jealous. After the obtained pellets are sufficiently dried, the front and back layers (each having a thickness of 30 μm) composed of the pelletized antistatic resin composition and the composition having the blending ratio shown in Table 6 are mixed with azodicarboxylic acid. A three-layer sheet (thickness 3 mm) consisting of a core material foamed approximately twice as much as an amide-based foaming agent was produced using a multilayer extruder with a T-die (processing temperature 180-200 ° C).
得られた三層シートを用い、前記評価法に従い、制電性、耐薬品性、表面外観、溶 出イオン、及び熱安定性を測定した。評価結果を表 6に示した。  Using the obtained three-layer sheet, the antistatic property, chemical resistance, surface appearance, dissolved ions, and thermal stability were measured according to the evaluation methods. The evaluation results are shown in Table 6.
[0112] [表 4-1] [0112] [Table 4-1]
〔〗〔^〕421 実施例 [〗 [^] 421 Example
I第一の制 I first system
| «性樹脂  | «Sexic Resin
組成物  Composition
|第二の制 | Second system
I電性鄉  I electric fence
組成物  Composition
Figure imgf000056_0001
Figure imgf000056_0001
'表中、（E)成分の（ ）の外の数値は jチウム塲としての配合部数であり、 < )内の数值は溶液としての配合 suaを表す。 'In the table, the value outside () of the component (E) is the number of parts blended as j-thium soot, and the number in <) represents the formula sua as a solution.
Figure imgf000057_0001
Figure imgf000057_0001
*表中、（E)成分の（ ）の外の ¾脑は リチウム塩としての配合 ffl数でぁリ、〔 ）Λの数 ffiは港液としての SB合部数を表す。 * In the table, ¾) outside () of component (E) is the number of blends ffl as lithium salt, and the number of () Λ represents the number of SB parts as port solution.
¾a0114
Figure imgf000059_0001
¾a0114
Figure imgf000059_0001
*表中、（E)成分の（ ）の外の数値は、リチウム塩としての配合都数であり、（ ）内の数使は溶液としての配合部数である。 * In the table, the value outside () of the component (E) is the number of compounding as a lithium salt, and the number in () is the number of blended parts as a solution.
^s0115
Figure imgf000061_0001
^ s0115
Figure imgf000061_0001
*表中，（E)成分の（ ）の外の数 ISは、リチウム塩としての配合部数であり、 ( >内の数値は港液としての配合部数を表す。 * In the table, the number IS outside the parentheses of component (E) is the number of blended parts as lithium salt, and the number in (> represents the number of blended parts as port liquid.
表 4 1及び表 4 2に記載された結果から、以下のことが明らかである。 From the results described in Tables 41 and 42, the following is clear.
実施例 Π-1〜Π-7及び 11-26、並びに、比較例 Π-：!〜 ΙΙ-4は、本発明の第一の制電 性樹脂組成物に関する実施例および比較例であり、これらの実施例は、制電性、耐 薬品性、成形品表面外観および溶出イオン性に優れる。  Examples Π-1 to Π-7 and 11-26, and comparative examples Π- :! to ΙΙ-4 are examples and comparative examples relating to the first antistatic resin composition of the present invention. This example is excellent in antistatic property, chemical resistance, molded product surface appearance and elution ionicity.
これに対し、比較例 II-1は、制電性が I X 10" Ω /口よりも高い例である。比較例 II -2は、本発明の (Α)成分の使用量が発明の範囲外で多ぐ （Β)成分の使用量が発 明の範囲外で少ない例であり、制電性が劣る。比較例 ΙΙ-3は、本発明の (Α)成分の 使用量が発明の範囲外で少なぐ（Β)成分の使用量が発明の範囲外で多い例であ り耐薬品性、成形品表面外観及び熱安定性が劣る。比較例 Π-4は、溶出イオン量が 本発明の範囲より多い例である。  On the other hand, Comparative Example II-1 is an example in which the antistatic property is higher than IX 10 "Ω / mouth. Comparative Example II-2 shows that the amount of the component (ii) of the present invention is out of the scope of the invention. This is an example where the amount of component (Β) used is small outside the scope of the invention, and the antistatic property is poor.Comparative Example ΙΙ-3 shows that the amount of component (Α) of the present invention is outside the scope of the invention. This is an example where the amount of component (Β) used is small and outside the scope of the invention, and the chemical resistance, the surface appearance of the molded product and the thermal stability are inferior. More examples than the range.
実施 ί列 Π_8〜ΙΙ一 18及び II一 27〜11一 31、並びに、 ]；匕較 ί列 ΙΙ_5〜ΙΙ_10ίま、本発明の 第二の制電性樹脂組成物に関する実施例及び比較例であり、これらの実施例は、制 電性、耐薬品性、成形品表面外観、熱安定性、溶出イオン性および耐衝撃性に優れ る。  Implementation ί_8 to の 1 18 and II 1 27-11 3131, and]; Comparison ί_5 to ΙΙ_10ί are examples and comparative examples relating to the second antistatic resin composition of the present invention. These examples are excellent in antistatic properties, chemical resistance, molded product surface appearance, thermal stability, elution ionicity and impact resistance.
これに対し、比較例 ΙΙ-5は、制電性が I X 10" Ω /口よりも高い例である。比較例 II -6は、本発明の（Ε)成分の使用量が多い例であり成形品表面外観及び耐衝撃性が 劣る。比較例 ΙΙ-7は、溶出イオン量が本発明の範囲より多い例である。比較例 Π-8は 、本発明の（C)成分の使用量が発明の範囲外で少ない例であり、耐衝撃性が劣る。 比較例 Π-9は、本発明の（D)成分の使用量が発明の範囲外で多い例であり、制電性 及び耐薬品性が劣る。比較例 11-10は、本発明の（Β)成分の使用量が発明の範囲外 で少ない例であり、制電性が劣る。  In contrast, Comparative Example 例 -5 is an example in which the antistatic property is higher than IX 10 "Ω / mouth. Comparative Example II-6 is an example in which the amount of the component (Ε) of the present invention is large. The surface appearance and impact resistance of the molded product are inferior.Comparative Example ΙΙ-7 is an example in which the amount of eluted ions is larger than the range of the present invention.Comparative Example Π-8 is the amount of use of the component (C) of the present invention. Comparative example Π-9 is an example in which the amount of component (D) used in the present invention is large outside the scope of the invention, and is antistatic and chemical resistant. Comparative Example 11-10 is an example in which the amount of the component (ii) used in the present invention is small outside the scope of the invention, and the antistatic property is inferior.
表 5に記載された結果から、以下のことが明らかである。  From the results described in Table 5, the following is clear.
実施例 Π-19〜Π-22、 Π-32及び Π-33は、本発明の第二の制電性樹脂組成物から なるシートに関する実施例であり、制電性、耐薬品性、シート表面外観、耐衝撃性及 び溶出イオン性に優れ、また、真空成形性に優れる。  Examples Π-19 to Π-22, Π-32 and Π-33 are examples relating to the sheet comprising the second antistatic resin composition of the present invention, and are antistatic, chemical resistant, sheet surface Excellent appearance, impact resistance and elution ionicity, and excellent vacuum formability.
表 6に記載された結果から、以下のことが明らかである。  From the results described in Table 6, the following is clear.
実施例 Π-23〜Π-25は、本発明の第一の制電性樹脂組成物からなるフィルムに関 する実施例であり、制電性、フィルム表面外観および溶出イオン性に優れる。また、 実施例 Π-34〜Π-37は、本発明の第二の制電性樹脂組成物からなるフィルムを発泡 基材に積層した成形品に関する実施例であり、制電性、耐薬品性、表面外観、熱安 定性および溶出イオン性に優れる。 Examples Π-23 to Π-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. Also, Examples Π-34 to Π-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, chemical resistance, surface Excellent appearance, heat stability and elution ionicity.
産業上の利用可能性 Industrial applicability
本発明の制電性樹脂組成物は、従来にない優れた制電性、耐薬品性、成形品表 面外観、熱安定性に優れ、溶出イオンが少ないことから、高度な性能が要求される、 車両分野、電気 ·電子分野、 ΟΑ·家電分野、サニタリー分野等の各種部品として適 用できる。  The antistatic resin composition of the present invention is required to have high performance because it has excellent antistatic properties, chemical resistance, appearance of the molded product surface, excellent thermal stability, and few eluted ions. It can be applied as various parts in the vehicle field, electrical / electronic field, bag / home appliance field, sanitary field, etc.

Claims

請求の範囲 The scope of the claims
[1] 下記 (A)成分 40〜98質量％と下記 (B)成分 2〜60質量％とを含有する組成物 (伹 し、上記 (A)成分及び (B)成分の合計は 100質量％)であって、該組成物を成形し てなる成形体の表面抵抗率（23°C、 50%RH条件下で測定）が 1 X 10" Ω Ζ口以下 で、かつ、ナトリウムイオン及びカリウムイオンの溶出量（80°C、 60分間抽出条件下で 測定)が 3 μ gZcm2以下であることを特徴とする制電性樹脂組成物。 [1] A composition containing 40 to 98% by mass of the following (A) component and 2 to 60% by mass of the following (B) component (wherein the total of the above (A) component and (B) component is 100% by mass) And the molded product formed from the composition has a surface resistivity (measured under conditions of 23 ° C and 50% RH) of 1 X 10 "Ω or less, and sodium ions and potassium ions. The antistatic resin composition is characterized in that the elution amount (measured under extraction conditions at 80 ° C. for 60 minutes) is 3 μgZcm 2 or less.
(A)成分:ォレフイン系樹脂、  (A) component: olefin resin,
(B)成分:ォレフィン重合体ブロックと親水性重合体ブロックとを含有するブロック共 重合体。  Component (B): A block copolymer containing an olefin polymer block and a hydrophilic polymer block.
[2] 上記（B)成分は、ナトリウムおよびカリウムの合計の含有量が 500〜8000ppmのブ ロック共重合体（B— 1)と、ナトリウムおよびカリウムの合計の含有量が 0〜： !OOppm のブロック共重合体（B— 2)とを、ブロック共重合体（B— 1)のブロック共重合体（B— 2)に対する質量比にして 1/99〜90/10の範囲で含み、該ブロック共重合体（B— 1)の配合量が上記成分 (A)と上記成分 (B)との合計量の 1〜： 15質量％である請求 項 1に記載の制電性樹脂組成物。  [2] The component (B) is composed of a block copolymer (B-1) having a total content of sodium and potassium of 500 to 8000 ppm, and a total content of sodium and potassium of 0 to:! OOppm Block copolymer (B-2) in a mass ratio of block copolymer (B-1) to block copolymer (B-2) in the range of 1/99 to 90/10, The antistatic resin composition according to claim 1, wherein the blending amount of the copolymer (B-1) is 1 to 15 mass% of the total amount of the component (A) and the component (B).
[3] 上記ブロック共重合体 (B—1)に含まれるナトリウムおよび Zまたはカリウム力 スルホ ン酸塩の形態である請求項 2に記載の制電性樹脂組成物。  [3] The antistatic resin composition according to claim 2, which is in the form of sodium and Z or potassium strength sulfonate contained in the block copolymer (B-1).
[4] さらに、上記 (A)成分及び (B)成分の合計 100質量部に対してリチウム塩 (E) 0. 01 〜5質量部を含有する請求項 2または 3に記載の制電性樹脂組成物。  [4] The antistatic resin according to claim 2 or 3, further comprising 0.01 to 5 parts by mass of a lithium salt (E) with respect to 100 parts by mass in total of the component (A) and the component (B). Composition.
[5] 上記リチウム塩 (E) 、過塩素酸リチウム、トリフルォロメタンスルホン酸リチウム、ビス  [5] Lithium salt (E) above, lithium perchlorate, lithium trifluoromethanesulfonate, bis
(トリフルォロメタンスルホ二ノレ）イミドリチウムおよびトリス（トリフルォロメタンスルホニル )メタンリチウムからなる群より選ばれた少なくとも 1種である請求項 4に記載の制電性 樹脂組成物。  5. The antistatic resin composition according to claim 4, which is at least one selected from the group consisting of (trifluoromethanesulfoninole) imidolithium and tris (trifluoromethanesulfonyl) methanelithium.
[6] さらに、上記 (A)成分及び (B)成分の合計 100質量部に対してリチウム塩 (E) 0. 01 [6] Further, the lithium salt (E) is added to 100 parts by mass of the total of the components (A) and (B).
〜5質量部を含有する請求項 1に記載の制電性樹脂組成物。 The antistatic resin composition according to claim 1, which contains ˜5 parts by mass.
[7] 上記（B)成分のナトリウムおよびカリウムの合計の含有量が 0〜： !OOOppmである請求 項 6記載の制電性樹脂組成物。 [7] The antistatic resin composition according to [6], wherein the total content of sodium and potassium of the component (B) is 0 to:! OOOOppm.
[8] 上記リチウム塩 (E) 1 過塩素酸リチウム、トリフルォロメタンスルホン酸リチウム、ビス (トリフルォロメタンスルホ二ノレ）イミドリチウムおよびトリス（トリフルォロメタンスルホニル[8] Lithium salt (E) 1 Lithium perchlorate, lithium trifluoromethanesulfonate, bis (Trifluoromethanesulfoninole) imidolithium and tris (trifluoromethanesulfonyl)
)メタンリチウムからなる群より選ばれた少なくとも 1種である請求項 6又は 7記載の制 電性樹脂組成物。 8. The antistatic resin composition according to claim 6 or 7, which is at least one selected from the group consisting of methane lithium.
[9] 上記（B)成分が、ナトリウム及び/又はカリウムをスルホン酸塩の形態で含有すること を特徴とする請求項 6〜8の何れ力、 1項に記載の制電性樹脂組成物。  [9] The antistatic resin composition according to any one of claims 6 to 8, wherein the component (B) contains sodium and / or potassium in the form of a sulfonate.
[10] 下記 (A)成分 7〜91質量％と、下記（B)成分 2〜60質量％と、下記（C)成分 2〜50 質量％と、下記 (D) 5〜50質量％とを含有する組成物 (但し、上記 (A)成分、 （B)成 分、（C)成分及び (D)成分の合計は 100質量％)であって、該組成物を成形してな る成形体の表面抵抗率（23°C、 50%RH条件下で測定）が 1 Χ 10" Ω Ζ口以下で、 かつ、ナトリウムイオン及びカリウムイオンの溶出量（80°C、 60分間抽出条件下で測 定）が 3 μ gZcm2以下であることを特徴とする制電性樹脂組成物。 [10] The following (A) component 7 to 91 mass%, the following (B) component 2 to 60 mass%, the following (C) component 2 to 50 mass%, and the following (D) 5 to 50 mass% A composition containing the above composition (provided that the total of the components (A), (B), (C) and (D) is 100% by mass), and is formed by molding the composition. Surface resistivity (measured under conditions of 23 ° C and 50% RH) of 1 Χ 10 "Ω or lower and elution amount of sodium ions and potassium ions (measured under extraction conditions at 80 ° C for 60 minutes) The antistatic resin composition is characterized in that it is 3 μgZcm 2 or less.
(A)成分:ォレフイン系樹脂。  Component (A): olefin resin.
(B)成分:ォレフィン重合体ブロックと親水性重合体ブロックとを含有するブロック共 重合体。  Component (B): A block copolymer containing an olefin polymer block and a hydrophilic polymer block.
(C)成分：芳香族ビュル化合物から主としてなる重合体ブロックと共役ジェン化合物 力 主としてなる重合体ブロックとを含有するブロック共重合体及びその水素添加物 力 選ばれた少なくとも 1種のエラストマ一。  Component (C): a block copolymer containing a polymer block mainly composed of an aromatic bur compound and a conjugate polymer compound and a main polymer block, and a hydrogenated product thereof. At least one selected elastomer.
(D)成分:ゴム質重合体の存在下に芳香族ビニル化合物を含むビニル系単量体を 重合して得られるゴム強化スチレン系重合体 (D— l)、および/または、該ビニル系 単量体の（共)重合体 (D— 2)からなるスチレン系樹脂。  Component (D): A rubber-reinforced styrene polymer (D-l) 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 composed of a monomeric (co) polymer (D-2).
[11] 上記成分（B)は、ナトリウムおよびカリウムの合計の含有量が 500〜8000ppmのブ ロック共重合体（B— 1)と、ナトリウムおよびカリウムの合計の含有量が 0〜： !OOppm のブロック共重合体（B— 2)とを、ブロック共重合体（B— 1)のブロック共重合体（B— 2)に対する質量比にして 1Z99〜90Z10の範囲で含み、該ブロック共重合体（Β— 1)の配合量が上記成分 (Α)と上記成分 (Β)と上記成分 (C)と上記成分 (D)との合計 量の 1〜 15質量％である請求項 10に記載の制電性樹脂組成物。  [11] The above component (B) is composed of a block copolymer (B-1) having a total content of sodium and potassium of 500 to 8000 ppm, and a total content of sodium and potassium of 0 to:! OOppm Block copolymer (B-2) in a mass ratio of block copolymer (B-1) to block copolymer (B-2) in the range of 1Z99 to 90Z10, The amount of Β-1) is 1 to 15 mass% of the total amount of the component (Α), the component (Β), the component (C), and the component (D). Electric resin composition.
[12] 上記ブロック共重合体 (B—1)に含まれるナトリウムおよび Ζまたはカリウム力 スルホ ン酸塩の形態である請求項 11に記載の制電性樹脂組成物。 12. The antistatic resin composition according to claim 11, wherein the antistatic resin composition is in the form of sodium and sodium or potassium strength sulfonate contained in the block copolymer (B-1).
[13] さらに、上記 (A)成分、 （B)成分、（C)成分及び (D)成分の合計 100質量部に対し てリチウム塩 (E) 0. 01〜5質量部を含有する請求項 11または 12に記載の制電性樹 脂組成物。 [13] The lithium salt (E) is further contained in an amount of 0.01 to 5 parts by mass with respect to 100 parts by mass in total of the component (A), the component (B), the component (C) and the component (D). The antistatic resin composition according to 11 or 12.
[14] 上記リチウム塩 (E) 、過塩素酸リチウム、トリフルォロメタンスルホン酸リチウム、ビス  [14] Lithium salt (E), lithium perchlorate, lithium trifluoromethanesulfonate, bis
(トリフルォロメタンスルホ二ノレ）イミドリチウムおよびトリス（トリフルォロメタンスルホニル )メタンリチウムからなる群より選ばれた少なくとも 1種である請求項 13に記載の制電 性樹脂組成物。  14. The antistatic resin composition according to claim 13, which is at least one selected from the group consisting of (trifluoromethanesulfonolinole) imidolithium and tris (trifluoromethanesulfonyl) methanelithium.
[15] さらに、上記 (A)成分、 （B)成分、（C)成分及び (D)成分の合計 100質量部に対し てリチウム塩 (E) 0. 01〜5質量部を含有する請求項 10に記載の制電性樹脂組成物  [15] The lithium salt (E) is further contained in an amount of 0.01 to 5 parts by mass with respect to a total of 100 parts by mass of the components (A), (B), (C) and (D). The antistatic resin composition according to 10,
[16] 上記（B)成分のナトリウムおよびカリウムの合計の含有量が 0〜： !OOOppmである請求 項 15記載の制電性樹脂組成物。 16. The antistatic resin composition according to claim 15, wherein the total content of sodium and potassium of the component (B) is 0 to:! OOOOppm.
[17] 上記 (E)成分が、過塩素酸リチウム、トリフルォロメタンスルホン酸リチウム、ビス（トリフ ノレォロメタンスルホ二ノレ）イミドリチウムおよびトリス（トリフルォロメタンスルホニル）メタ ンリチウムからなる群より選ばれた少なくとも 1種である請求項 15又は 16記載の制電 性樹脂組成物。 [17] The component (E) is selected from the group consisting of lithium perchlorate, lithium trifluoromethanesulfonate, lithium bis (trifluoromethanesulfonolinole) imide and tris (trifluoromethanesulfonyl) methane lithium. The antistatic resin composition according to claim 15 or 16, wherein the antistatic resin composition is at least one kind.
[18] 上記（B)成分が、ナトリウム及び/又はカリウムをスルホン酸塩の形態で含有すること を特徴とする請求項 15〜： 17の何れ力 1項に記載の制電性樹脂組成物。  [18] The antistatic resin composition according to any one of [15] to [17], wherein the component (B) contains sodium and / or potassium in the form of a sulfonate.
[19] 請求項 1乃至 18の何れか 1項に記載の制電性樹脂組成物からなる成形品。 [19] A molded article comprising the antistatic resin composition according to any one of [1] to [18].
[20] 請求項 1乃至 18の何れ力 1項に記載の制電性榭脂組成物からなるシートまたはフィ ノレム。 [20] A sheet or a finalem comprising the antistatic resin composition according to any one of [1] to [18].
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WO2017141886A1 (en) * 2016-02-16 2017-08-24 住友精化株式会社 Polyolefin-based resin composition and polyolefin-based resin film
CN112080075B (en) * 2020-09-29 2021-06-22 湖南大学 Antistatic long glass fiber reinforced thermoplastic composite material and preparation method and application thereof

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WO2008041690A1 (en) * 2006-10-02 2008-04-10 Idemitsu Unitech Co., Ltd. Antistatic composition and molding thereof
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