WO2007119339A1 - Composition de resine antistatique et article moule - Google Patents

Composition de resine antistatique et article moule 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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English (en)
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/ja
Priority claimed from JP2007040510A external-priority patent/JP5361136B2/ja
Application filed by Techno Polymer Co., Ltd. filed Critical Techno Polymer Co., Ltd.
Priority to CN2007800172167A priority Critical patent/CN101443404B/zh
Publication of WO2007119339A1 publication Critical patent/WO2007119339A1/fr

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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

La présente invention concerne une composition de résine antistatique qui comprend de 40 à 98 % en masse d'une résine d'oléfine (A) et de 2 à 60 % en masse d'un copolymère séquencé (B) ayant une séquence de polyoléfine et une séquence de polymère hydrophile, et qui peut être moulée sous la forme d'un article ayant une résistance de surface (mesurée dans des conditions d'une température de 23 °C et d'une humidité relative (RH) de 50 %) inférieure ou égale à 1 x 1011 Ω/□ et ayant une quantité de lixiviation d'ions de sodium et de potassium (mesurée dans des conditions d'une température de 80 °C et d'extraction pendant 60 minutes) inférieure ou égale à 3 μg/cm2. La composition peut contenir une quantité prédéterminée d'un copolymère séquencé ayant une séquence de polymère de composé vinyle aromatique et une séquence de polymère de composé diène conjugué ou un produit d'hydrogénation du copolymère séquencé et une quantité prédéterminée d'une résine de styrène. Le composant (B) peut être une combinaison d'un copolymère séquencé tel que mentionné ci-dessus ayant des teneurs plus élevées en sodium et potassium et d'un copolymère séquencé tel que mentionné ci-dessus ayant de plus faibles teneurs en sodium et potassium. Si nécessaire, la composition peut contenir un sel de lithium (E). La composition est excellente en termes de propriétés antistatiques, de résistance chimique, d'aspect d'article moulé et de stabilité thermique et a une quantité de lixiviation d'ions réduite.
PCT/JP2007/054895 2006-03-16 2007-03-13 Composition de resine antistatique et article moule WO2007119339A1 (fr)

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CN106217324A (zh) * 2016-08-16 2016-12-14 杨林 一种防静电工作台

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TWI612067B (zh) * 2015-08-24 2018-01-21 Asahi Chemical Ind 氫化嵌段共聚物與使用其之聚丙烯系樹脂組合物及其成型體
CN108699299B (zh) * 2016-02-16 2021-03-12 住友精化株式会社 聚烯烃系树脂组合物和聚烯烃系树脂膜
CN112080075B (zh) * 2020-09-29 2021-06-22 湖南大学 抗静电长玻璃纤维增强热塑性复合材料及其制备方法与应用

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