WO2007029497A1 - Thermoplastic resin composition, conductive film and conductive sheet - Google Patents

Thermoplastic resin composition, conductive film and conductive sheet Download PDF

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Publication number
WO2007029497A1
WO2007029497A1 PCT/JP2006/316483 JP2006316483W WO2007029497A1 WO 2007029497 A1 WO2007029497 A1 WO 2007029497A1 JP 2006316483 W JP2006316483 W JP 2006316483W WO 2007029497 A1 WO2007029497 A1 WO 2007029497A1
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group
polymer
carbon atoms
conjugated diene
compound
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PCT/JP2006/316483
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French (fr)
Japanese (ja)
Inventor
Motokazu Takeuchi
Fumiaki Miura
Masatoshi Torii
Takumi Miyachi
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Kraton Jsr Elastomers K.K.
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Priority to JP2007534317A priority Critical patent/JP5472561B2/en
Publication of WO2007029497A1 publication Critical patent/WO2007029497A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C08L25/06—Polystyrene
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L15/00—Compositions of rubber derivatives

Definitions

  • the present invention provides impact resistance, low temperature properties, including a modified conjugated diene polymer, a non-rubber modified styrene polymer and a conductive carbon, and in some cases, an impact rubber modified styrene polymer.
  • the present invention relates to a thermoplastic resin composition having an excellent balance of conductivity, and a conductive film and a conductive sheet obtained therefrom. More specifically, in addition to having excellent surface resistance, it is excellent in the balance of various properties such as low temperature characteristics and impact resistance that causes less dropout of conductive carbon, and packaging materials for semiconductors and electronic parts such as IC trays and carrier tapes. And a conductive thermoplastic resin composition, a conductive film and a conductive sheet which are particularly useful for such applications.
  • Styrene-based resins such as polystyrene are inexpensive, excellent in processability, and excellent in transparency and appearance of molded articles, but lack impact resistance, so their use alone is extremely limited. There is. Although the rubber-modified polystyrene produced for the purpose of improving the impact resistance of this polystyrene has a considerable improvement in the impact resistance, its transparency, which is a characteristic of polystyrene, is extremely low.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 61-200151
  • Patent Document 2 Japanese Patent Application Laid-Open No. 4-209615
  • Patent Document 3 Japanese Patent Publication No.
  • the improvement is carried out by a block copolymer which also has a conjugated diene and an aromatic vinyl-vinyl compound having a weight ratio to a vinyl copolymer.
  • Patent Document 8 Japanese Patent Application Laid-Open No. 5-94948
  • I was not able to gain anything.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 61-20151
  • Patent Document 2 Japanese Patent Application Laid-Open No. 4-209615
  • Patent Document 3 Japanese Patent Publication No. 56-54022
  • Patent Document 4 Japanese Patent Application Laid-Open No. 60-65044
  • Patent Document 5 Japanese Patent Application Laid-Open No. 61-252265
  • Patent Document 6 Japanese Patent Application Laid-Open No. 2000-26698
  • Patent Document 7 Japanese Patent Application Laid-Open No. 57-78439
  • Patent Document 8 Japanese Patent Application Laid-Open No. 55-94948
  • the present invention has been made in view of the above problems, and it is possible to remove conductive carbon by blending a modified conjugated diene polymer having a specific functional group with a styrene resin and conductive carbon. It is an object of the present invention to provide a thermoplastic resin composition excellent in balance between impact resistance, low temperature properties and conductivity, and a conductive film and a conductive sheet obtained therefrom.
  • Another object of the present invention is to provide a thermoplastic resin composition which is particularly useful in applications such as IC trays, packaging materials for semiconductors such as carrier tapes, and electronic parts, and conductive films and conductive sheets. .
  • the present invention relates to a modified conjugated gen-based polymer having a group power of (i) an alkoxysilyl group, an amino group, an acid anhydride group, and a carboxyl group (hereinafter referred to as “modification”) (Also referred to as “conjugated polymers”) 2. 5 to 35 parts by weight,
  • the present invention relates to a thermoplastic resin composition containing as a main component.
  • any one of the polymers produced by at least one selected from the group powers of methods (a) to (e) shown below is preferable.
  • R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or carbon It is an organosiloxy group of several 1 to 100.
  • Y is a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or 1 to 6 carbon atoms: It is an organosiloxy group of L00. ]
  • the modified conjugated diene polymers having an alkoxysilyl group and an amino group are at least one selected from the group powers of (f) to (h) below.
  • the modified conjugated diene-based polymer produced by the method is preferred.
  • a conjugated diene-based polymer obtained by polymerizing conjugated diene and an aromatic bi-Louisinated compound in the presence of an organic alkali metal compound having an amino group is represented by the following general formula (2) Modified polymer in which compound is reacted.
  • R 3 is an alkyl group, Ariru group having 6 to 20 carbon atoms, 1 to several 7-2 Ararukiru group or a carbon number of 0 carbon atoms of 1 to 20 carbon atoms: a L00 organosiloxy group, R 3 When there are a plurality of, each R 3 may be the same or different.
  • R 4 is an alkyl group having 1 to 20 carbon atoms, Ariru group having a carbon number of 6-20, a Ararukiru group having 7 to 20 carbon atoms, if R 4 have more than one purpose, each R 4 is different even in the same group group Good.
  • X is a substituent having a polar group containing at least one or more of ⁇ atom and Si atom, and when there are a plurality of X, each X may be the same or different group, and each X is independent It may have a substituent or a cyclic structure.
  • m is 1, 2 or 3 and n is an integer of 0, 1, 2 or 3. The sum of m and n is 1 to 4. ]
  • a conjugated diene polymer obtained by polymerizing an unsaturated monomer having an conjugated group and an amino group and an aromatic vinyl compound in the presence of an organic alkali metal compound is shown by the above general formula (2) The modified polymer which made the compound represented react.
  • R 12 is an alkyl group, Ariru group having 6 to 20 carbon atoms, 1 to Ararukiru group or the number of carbon atoms in the carbon number 7-20 having 1 to 20 carbon atoms: a L00 organosiloxy group, R 12 is When there are two or more, each R 12 may be the same or different.
  • R 13 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of R 13 groups, each R 13 may be the same or different groups May be.
  • Z is a substituent having a polar group containing an N atom, and when there are a plurality of Z, each Z may be the same or different group, and each Z is independent Or a cyclic structure.
  • P is 1, 2 or 3 and q is an integer of 1, 2 or 3. The sum of p and q is 1 to 4. ]
  • an impact resistant rubber modified styrene polymer an impact resistant rubber modified styrene polymer, an acrylonitrile butadiene styrene copolymer, an acrylic ester butadiene styrene copolymer, a methacrylic ester butadiene styrene copolymer At least one selected from the group consisting of a body and a rubber-impact rubber-modified styrene / maleic anhydride copolymer is preferred.
  • non-rubber-modified styrenic polymer at least one selected from polystyrene, a styrene-methyl-styrene copolymer, an acrylonitrile-styrene copolymer, and an acrylonitrile-methacrylic acid ester-styrene copolymer. Is preferred.
  • ketjen black is preferable.
  • the present invention relates to a conductive film and a conductive sheet obtained by molding the above-mentioned thermoplastic resin composition.
  • the thermoplastic resin composition of the present invention has a modified conjugate having at least one group selected from the group consisting of (i) alkoxysilyl group, amino group, acid anhydride group, and carboxyl group. It is a composition in which a gen-based polymer, (iii) a non-rubber-modified styrenic polymer, and (ii) an electrically conductive carbon, and (if necessary) an impact-modified rubber-modified styrenic polymer are blended. It is excellent in the dispersibility of conductive carbon. Such a thermoplastic resin composition is excellent in the balance of impact resistance, transparency, rigidity, and low temperature characteristics in which the conductive carbon does not fall off, and the sheet, film, etc. to which conductivity is imparted.
  • the thermoplastic resin composition useful for the present invention can be obtained.
  • the modified conjugated diene-based polymer used in the thermoplastic resin composition of the present invention can be obtained as a modified compound in (a) in the production methods (a) to (h) described below.
  • Arco In (d) an unsaturated monomer having an amino group, and in (d) a compound represented by the formula (1), (e) Groups of a ketone compound, an ester complex and an aldehyde complex, and at least one selected from an acid anhydride and Z or an acid halide, and an organic alkali metal compound having an amino group in (f)
  • the compound represented by the general formula (2) and the compound represented by the general formula (2) in (g) and the unsaturated monomer having an amino group in (g) are represented in the general formula (7) in (h) Can be obtained by using each of the following compounds.
  • the production methods (a) to (h) will be described below.
  • the modified conjugated diene-based polymer having an alkoxysilyl group used in the thermoplastic resin composition of the present invention can be obtained by reacting an conjugated vinyl-aromatic vinyl compound in an inert organic solvent (a) It can be easily obtained by polymerizing an alkali metal compound as a polymerization initiator, and reacting the resulting conjugated diene polymer with an alkoxysilane compound.
  • alkoxysilyl group is a group in which at least one alkoxy selected from alkyloxy having 1 to 20 carbon atoms, alkyloxy having 6 to 20 carbon atoms, and aralkyloxy having 7 to 20 carbon atoms is bonded to a silicon atom.
  • a silicon atom is bonded to an alkoxy such as methoxy, ethoxy, butoxy, propoxy, pentoxy, neopentoxy, hexyloxy, hexoxy, amioxy, phenoxy, preferably methoxy, ethoxy, amiporti, phenoxy and the like. Other things.
  • conjugated gen examples include, for example, 1,3 butadiene, isoprene, 2,3 dimethyl 1, 3 butadiene, 1,3 pentagen, 2 -methyl- 1,3 -octadiene, 1,3 1 1, 3, 3-cyclohexadiene, 4, 5 Detinolay 1, 3, 3-Octagen, 3, Butyl 1, 3-Octadiene, Myrsen, Cro-prene and the like. Among these, 1,3 butadiene and isoprene are preferable.
  • aromatic vinyl compound examples include styrene, tert-butylstyrene, ⁇ -methylstyrene, ⁇ -methylstyrene, ⁇ ⁇ ⁇ ⁇ -ethylstyrene, divinylbenzene, 1,1-diphenylenostyrene, vinylene naphthalene, vinylene Anthracene, ⁇ , ⁇ , ⁇ , ⁇ ⁇ , ⁇ , ⁇ ⁇ ⁇ ⁇ , ⁇ ⁇ ⁇ ⁇ , etc. may be mentioned. Among these, styrene and tert-butylstyrene are preferred.
  • conjugated gen the above “aromatic vinyl compound”, and other unsaturated compounds such as acrylonitrile and methyl metatalylate are further included.
  • about 5% by weight or less of the total monomers may be polymerized.
  • organic alkali metal compound which is a polymerization initiator
  • organic lithium compounds organic sodium compounds and the like
  • organic lithium compounds are particularly preferable.
  • the amount of the organic alkali metal compound to be used is not particularly limited, and various amounts can be used if necessary. Usually, an amount of 0.02 to 15 parts by weight per 100 parts by weight of the monomer is preferable.
  • alkoxysilane compound which causes an alkoxysilane compound to react with a conjugated diene polymer as long as it can be converted into a modified polymer by reacting with a conjugated polymer,
  • an alkoxysilane compound represented by the following general formula (2) is used.
  • R 3 is an alkyl group, Ariru group having 6 to 20 carbon atoms, 1 to several 7-2 Ararukiru group or a carbon number of 0 carbon atoms of 1 to 20 carbon atoms: a L00 organosiloxy group, R 3 When there are a plurality of, each R 3 may be the same or different.
  • R 4 is an alkyl group having 1 to 20 carbon atoms, Ariru group having a carbon number of 6-20, a Ararukiru group having 7 to 20 carbon atoms, if R 4 have more than one purpose, each R 4 is different even in the same group group Good.
  • X is a substituent having a polar group containing at least one or more of ⁇ atom and Si atom, and when there are a plurality of X, each X may be the same or different group, and each X is independent It may have a substituent or a cyclic structure.
  • n shows the integer of 0, 1, 2 or 3.
  • the sum of m and n is 1 to 4.
  • m is preferably 2 or 3
  • n is preferably 0 or 1.
  • alkoxysilane compound represented by the above general formula (2) examples include tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, methyltrimethoquilysilane, dimethyldimethyoxysilane, dimethyolegetoxysilane, and methyoregetoxyl.
  • the method of modification with the above alkoxysilane compound is as follows: when the polymerization conversion rate of the polymerization reaction for producing a conjugated gen polymer becomes 90% to: LOO%, the above alkoxysilane It is preferred to add the compound into the polymerization system to carry out the modification reaction. The addition may be performed before the polymerization conversion reaches 90%, or the modification reaction may be performed by intermittently or continuously adding an alkoxysilane compound while the polymerization reaction is in progress. .
  • the amount of the above alkoxysilane compound to be used is preferably 0.05 to 5 moles, more preferably 0.1 to 1 mole, with respect to the number of moles of the active point derived from the organic alkali metal compound. 5 times more money.
  • the content of the alkoxysilyl group in the conjugated diene polymer to be obtained is usually 0.000 to 5 mmol / g, preferably 0.001 to: L mmol / g, more preferably 0.003 to 0 It is lm mo lZg.
  • the alkoxysilyl group is usually present at the end of the polymer chain, but may be present at the side chain.
  • the method for introducing an amino group in the modified conjugated diene polymer having an amino group used in the thermoplastic resin composition of the present invention is not particularly limited, and examples thereof include the following (b) It can be easily obtained by the method of (d).
  • (c) It is produced by polymerizing an unsaturated monomer having a conjugated diene, an amino group and an aromatic vinyl compound in the presence of an organic metal compound.
  • R 1 and R 2 each independently represent a hydrogen atom, and an aryl having 1 to 20 carbon atoms] It is a cil group, a C6-C20 aryl group, a C7-C20 aralkyl group or a C1-C100 organosiloxy group.
  • Y is a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or 1 to 6 carbon atoms: It is an organosiloxy group of L00. ]
  • Examples of the organic alkali metal compound having an amino group used in the method (b) include the following general formula (3) or (4).
  • R 5 and R. are both trialkylsilyl groups having 3 to 18 carbon atoms, or one of them is the above trialkylsilyl group, and the other is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, It is an aralkyloxy group having 7 to 20 carbon atoms or an organosiloxy group having 1 to: carbon atoms.
  • R ⁇ 7> in the said General formula (3) and (4) is a C1-C20 alkylene group or alkylidene group.
  • R 8 in the general formula (4) is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to carbon atoms: It is. ]
  • Examples of the organic alkali metal compound represented by the above general formula (3) or (4) include 3 lithium 1- [N, N bis (trimethylsilyl)] aminopropane, 2-lithium 1- [N, N bis (Trimethylsilyl)] aminoethane, 3 lyo 2, 2 dimethyl 1 1-[N, N bis (trimethyl silyl)] amino propane, 2, 2, 5, 5- tetramethyl 1 1 (3 lithium)-1-1 2, 5 Disilacyclopentane, 2, 2, 5, 5-Tetramethyl-I 1-(3-Liqui-T, 2-Dimethyl-p-Pill) I 1-Aza-I 2, 5 Disilacyclopentane, 2, 2, 5, 5-Tetramethyl- 1 (2 lyocetyl)-1-2, 2, 5 disilacyclopentane, 3 Lithio 1-[N- (tert-butyl-dimethylsilyl)-N-trimethylsilyl] amino Examples thereof include propane, 3-lithium 1- (N-methyl-N-trimethylsilyl) aminopropane
  • Examples of the unsaturated monomer having an amino group used in the method (c) include the following general formula (5) or (6).
  • R 9 and R 1 C> are both a trialkylsilyl group having 3 to 18 carbon atoms, or one of them is a trialkylsilyl group as described above And the other is an alkyl group having 1 to 20 carbon atoms, a aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to: carbon atoms.
  • R 11 is an alkylene or alkylidene group having 1 to 20 carbon atoms.
  • n in the above general formulas (5) and (6) is 1 to 3.
  • the amount of use of the unsaturated monomer represented by the general formula (5) or (6) is from 0.01 to 1:00 mol, preferably 0. 00 mol, per mol of the organic alkali metal-derived active site. It is added in the proportion of 0.1 to 10 times mol, particularly preferably 1.0 to 3.0 times mol.
  • the reaction time is preferably in the range of 1 second to 2 hours.
  • unsaturated monomers Can be added at any time such as initiation of polymerization, during polymerization, before completion of polymerization, after completion of polymerization, and the like.
  • the aromatic vinyl compound and the organic alkali metal compound used in the above method (C) As the conjugated diene, the aromatic vinyl compound and the organic alkali metal compound used in the above method (C), those used in the above method (a) can be used.
  • Examples of the compound of the above general formula (1) used in the method (d) include N-benzylidenemethylamine, N-benzylideneethylamine, N-benzylidenebutyramine, N-beta Nydridener can be mentioned.
  • the amount of the compound represented by the above general formula (1) to be reacted with the above-mentioned conjugated diene polymer to be modified is not particularly limited, but usually the molar amount of the active site derived from the organic alkali metal compound is The amount is 0.2 to 2 times by mole, preferably 0.3 to 1.5 times by mole, and more preferably 0.4 to 1.3 times by mole.
  • the content of the amino group in the modified conjugated diene polymer to be obtained is usually 0.2 to 5 mmol / g, preferably 0.001 to: L mmol / g, more preferably 0.003 to 0. 0. 1 mmol Zg.
  • the position of the amino group may be present at the end of the polymer chain without particular limitation, and may be present at the side chain.
  • the amino group is preferably a primary amino group and / or a secondary amino group.
  • conjugated diene the aromatic vinyl compound and the organic alkali metal compound used in the above method (d), those used in the above method (a) can be used.
  • the method for producing the modified conjugated diene-based polymer having an alkoxysilyl group and an amino group, which is used for the thermoplastic resin composition of the present invention is not particularly limited, but for example, the following (f) to (h) It can be easily obtained by the method.
  • the conjugated diene polymer obtained by polymerizing the conjugated diene and the aromatic vinyl compound in the presence of the organic alkali metal compound having the amino group is represented by the general formula (2) It is manufactured by setting it as the modified polymer with which the compound represented by these was made to react.
  • R 12 is an alkyl group, Ariru group having 6 to 20 carbon atoms, 1 to Ararukiru group or the number of carbon atoms in the carbon number 7-20 having 1 to 20 carbon atoms: a L00 organosiloxy group, R 12 is When there are two or more, each R 12 may be the same or different.
  • R 13 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of R 13 groups, each R 13 may be the same or different groups May be.
  • Z is a substituent having a polar group containing an N atom, and when there are a plurality of Z, each Z may be the same group or a different group, and each Z may form a cyclic structure even with an independent substituent. It is also good.
  • P is 1, 2 or 3 and q is an integer of 1, 2 or 3. The sum of p and q is 1 to 4. In particular, p is preferably 2 or 3, and q is 1. ]
  • N N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N bis (trimethylsilyl) aminopropyltriethoxysilane, N, N bis (trimethylsilyl) ) Aminopropyldimethylethoxysilane, N, N bis (trimethylsilyl) aminopropyldimethylmethoxysilane, N, N bis (trimethylsilyl) aminopropylmethyl jetoxysilane, N, N bis (trimethylsilyl) amino Propylmethyldimethoxysilane, N, N bis (trimethylsilyl) aminoethyl trimethoxysilane, N, N bis (trimethylsilyl) aminoethyl triethoxysilane, N, N-bis (trimethylsilyl) aminoethyl dimethylethoxysilane, N, N bis ( Trimethyl silyl) Noethyl
  • the content of the alkoxysilyl group and the amino group in the conjugated diene polymer to be obtained is generally in the range of usually 0.000 to 5 mmol Zg, preferably 0.000 to 1: L mmol Zg, more preferably 0. 003-0. I mmol Zg. These groups are usually present at the end of the polymer chain but may be present at the side chain.
  • the process for producing the modified conjugated diene-based polymer having an acid anhydride group and Z or a lupoxyl group to be used in the thermoplastic resin composition of the present invention is not particularly limited. It can be easily obtained by the method (e) shown.
  • a conjugated diene, an esterified compound and an aldehyde compound are added to the conjugated conjugated polymer obtained by polymerizing conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound.
  • the compound is easily prepared by reacting at least one selected group with an acid anhydride and Z or an acid halide.
  • ketone complex is not particularly limited, and examples thereof include acetone, jetyl ketone, n-butyl ethyl ketone, ethyl amyl ketone, isophorone, cyclohexanone, cyclopentanone, and methyl isobutyl.
  • Ketones methyl isopropyl ketone, methyl cyclohexanone, 4-acetodiphenyl, methyl ethyl ketone, benzophenone, cyclohexyl phenyl ketone, 4 methylbenzophenone, 4-octyl penphenone, propiophenone, etc.
  • ester compound is not limited to the structure, but is, for example, ethyl acetate, methyl acetate, propyl acetate, methyl benzoate, methyl toluate, methyl benzoate, phenyl benzoate, benzyl benzoate, ⁇ -petite ratatonate. Etc.
  • aldehyde complex is not limited to the structure thereof, and examples thereof include, but are not limited to, for example, formaldehyde, acetaldehyde, butyraldehyde, ⁇ -octylaldehyde, benzaldehyde, phthalaldehyde, a tolylaldehyde, o Tolualdehyde, cumin aldehyde, p-tri Rucetaldehyde, 4-isopropylbenzaldehyde, aldehydepyridine, ⁇ -naphthaldehyde, furfural and the like can be mentioned.
  • the total amount of the above ketone complex, ester complex and aldehyde compound used is preferably 0.1 to 2 moles, relative to the number of moles of the active point derived from the organic alkali metal compound, More preferably, it is 0.5 to 1. 3-fold moles.
  • acid anhydride is not particularly limited in its structure, but is, for example, propionic acid anhydride, anhydrous acetic acid latanoic acid, caproic acid anhydride, maleic acid anhydride, phthalic acid anhydride, 3-methyl phthalic acid anhydride, Methyl phthalic anhydride, cis-hexahydrophthalic anhydride, trans-hexahydrophthalic anhydride, hexahydro-4 methyl phthalic anhydride, cis 1,2,3,6-tetrahydric phthalic anhydride, 1,2,4 benzene Examples thereof include tricarboxylic acid anhydride and pyromellitic acid dianhydride.
  • acid halide is not limited in its structure, but includes, for example, benzenedicarboxylic acid chloride, phthalic acid chloride, isophthalic acid dichloride, trimellitic acid trichloride and the like.
  • the compound having both an acid anhydride and an acid halide is not limited to the structure, and examples thereof include trimellitic anhydride chloride.
  • the amount of the above acid anhydride and ⁇ ⁇ ⁇ or acid chloride to be used is, in total, preferably 0.05 to 5 moles, more preferably 0 moles, relative to the number of moles of the active point derived from the organic alkali metal compound. 1 to 1.5 times the molar amount.
  • the total content of the acid anhydride group and the ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ or carboxyl group in the conjugated diene polymer to be obtained is usually, in total, from 0. 0001 to 5 mmol Zg, preferably from 0.0001 to: L mmol Zg, and further Preferably, it is 0.0003 to 0.1 mmol / g.
  • conjugated diene the aromatic vinyl compound and the organic alkali metal compound used in the above method (e), those used in the above method (a) can be used.
  • the modified conjugated diene-based polymer having at least one group selected from among alkoxysilyl group, amino group, acid anhydride group, and carboxyl group is selected to be combined with other components. Pellets and crumbs are preferred. Therefore, block copolymers containing one or more selected polymer blocks are preferred, with moderate strength of the following polymer blocks of (A), (B) and (C): I'm sorry.
  • the random copolymer block of (C) may also include a so-called tapered type in which the content of the aromatic vinyl compound changes continuously in one molecule.
  • examples of the above-mentioned “block copolymer containing one or more selected polymer blocks of medium power of (A), and (B) and (C) polymer blocks” include (A) — (B ), (A) Ichi (C), [(A)-(B)] Y ,, [(A)-(C)] Y ,, (A)-(B) — ( ⁇ ) ⁇ (A)- (C)-(A), [(A)-(B) (C)] Y ', [(A)-(B)-(A)] Y', [(A)-(C)-(A) ] Y ', [(A)-(C)-(A) ] Y ', (A)-(B)-(A)-(B), (B)-(A)-(B)-(A), (A)-(C)-(A)-( C), (C)-(A)-(C)-(A), (A)-(B)-
  • At least one or more (A) polymer blocks as an outer block component of the modified conjugated diene-based polymer.
  • aliphatic hydrocarbons eg, butane, pentane, hexane, heptane etc.
  • alicyclic hydrocarbons eg, cyclopentane, cyclohexane, cycloheptane etc.
  • alkyl substituted alicyclic hydrocarbons eg, methylcyclohexene, methylcycloheptane, etc.
  • aromatic hydrocarbons eg, benzene
  • alkyl-substituted aromatic hydrocarbons eg, toluene, xylene, etc.
  • ethers eg, tetrahydrofuran, jetyl ether
  • the vinyl bond content of the conjugated diene of the above “conjugated diene polymer” is less than 80% by weight, preferably 3 to 60% by weight, more preferably 5 to 55% by weight.
  • ethers typically, tertiary Amin acids, may be used polar I ⁇ of such alkali metals alkoxides.
  • the amount of the polar compound to be used is 300 mol or less, preferably 0 to L00 mol, per 1 mol of the organic lithium compound.
  • a coupling agent can also be used for the above block copolymer, if necessary.
  • the coupling agent for example, halogen compound, epoxy compound, carbonyl compound, polyvinyl compound and the like can be mentioned, and specifically, for example, methyldichlorosilane, methyltrichlorosilane, butyltrichlorosilane , Tetrachlorosilane, dibromoethene, bisphenol A diglycidyl ether, bis phenol F diglycidyl ether, epoxidized soybean oil, dibutyl benzene, tetrachloro tin, butyl trichloro tin, tetra black germanium, bis (trichlorosilyl) atane, Examples thereof include jetyl adipate, dimethyl adipate, dimethylterephtalic acid, jetylterephthalic acid, and polyisocyanate.
  • the resulting modified (ii) modified conjugated polymer is, if necessary, removed from the catalyst residue, or a phenolic or amine anti-aging agent is added, and then the modified conjugated diene polymer is removed.
  • the molecular weight of the modified conjugated diene-based polymer having at least one of a silyl group, an amino group, an acid anhydride group and a carboxyl group is not particularly limited, but it is 30,000 in weight average molecular weight by polystyrene conversion in GPC method. -2,000,000, preferably 40,000 to 1,000,000, more preferably 50,000 to 500,000.
  • the impact-modified rubber-modified styrenic polymer used in the thermoplastic resin composition of the present invention comprises polymerizing a styrenic monomer or a mixture of a monomer copolymerizable therewith with the elastomer.
  • a polymerization method suspension polymerization, emulsion polymerization, bulk polymerization, bulk suspension polymerization and the like are generally performed.
  • styrene-based monomer styrene, tert-butylstyrene, ⁇ -methylstyrene, ⁇ -methinolestyrene, ⁇ -ethylstyrene, 1,1-diphenylstyrene, ⁇ , ⁇ -gethyl- ⁇ -aminoethylstyrene, etc. It can be mentioned.
  • a monomer copolymerizable with the styrenic monomer acrylonitrile, acrylic ester, methacrylic ester, maleic anhydride and the like can be mentioned.
  • an elastomer natural rubber, synthetic isoprene rubber, butadiene rubber, styrene butadiene rubber, ⁇ , ⁇ ⁇ ⁇ ⁇ styrene rubber, polybutadiene resin, chloroprene rubber, polybutene rubber, rubber-like ethylene-propylene copolymer, rubber-like butadiene-acrylonitrile co-weight Combination, butyl rubber, various-tolyl rubber, rubbery ethylene-acetate-acetate copolymer, rubbery ethylene-acrylic acid ester copolymer, rubbery atactic polypropylene resin, rubbery ethylene-acrylic acid ionomer, etc. used.
  • an impact-resistant rubber-modified styrene-based polymer an impact-resistant rubber-modified styrene polymer, an acrylonitrile-butadiene-styrene copolymer, an acrylic ester-butadiene styrene copolymer, a methacrylic ester butadiene styrene Copolymers, impact-resistant rubber-modified styrene-maleic anhydride copolymers, etc. may be mentioned, and they may be used alone or in combination of two or more.
  • the “impact resistance” of the (mouth) impact resistant rubber-modified styrenic polymer means that when the polymer itself is used as an IC tray or an embossed carrier tape, it can withstand impact or drop during transportation.
  • the balance between the impact resistance and the rigidity is good even when the (mouth) impact-resistant rubber-modified styrenic polymer is not added. By adding it, it is possible to further improve the balance between impact resistance and rigidity economically.
  • the non-rubber-modified styrenic polymer used in the thermoplastic resin composition of the present invention is a (mouth) impact resistant rubber-modified styrenic polymer and a styrenic polymer other than styrenic thermoplastic elastomers. They are obtained by polymerizing styrenic monomers or monomers copolymerizable therewith in the absence of an elastomer. Examples of the monomer copolymerizable with the styrenic monomer include acrylonitrile, acrylic ester, methacrylic ester, and maleic anhydride.
  • non-rubber-modified styrene polymers include polystyrene, styrene OL methyl styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-methacrylic acid ester-styrene copolymer, etc. It can be used as a mixture of species and more.
  • the conductivity is improved by using conductive carbon black such as furnace black, channel black, gas black, acetylene black, arc black, ketjen black as the conductive carbon.
  • conductive carbon black such as furnace black, channel black, gas black, acetylene black, arc black, ketjen black
  • fineness black, ketjen black, and particularly ketjen black which are excellent in conductivity and have a large specific surface area, are preferable.
  • conductive composite carbon blacks combining these conductive carbon blacks may also be used.
  • the specific surface area of conductive carbon black 100 ⁇ l, 500m 2 Zg, especially 500 to 1,500 m 2 about Zg are preferred.
  • the average particle size of conductive carbon black at the time of sale has a close relationship with the ratio of (i) component, and can not be generally specified, but usually 1 ⁇ ⁇ 10/10 ⁇ ⁇ ⁇ , preferably 5 nm to 1 More preferably, it is about 10 to 100 nm.
  • thermoplastic resin composition of the present invention can be produced by any conventionally known compounding method.
  • melt-kneading method using a general mixing machine such as open roll, intensive mixer, internal mixer, co-kneader, continuous kneader with twin-screw rotor, single-screw extruder, twin-screw extruder, etc. After dissolution or dispersal mixing, the method of heating and removing the solvent is used.
  • thermoplastic resin composition of the present invention can be obtained by any known method, for example, extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotational molding, powder slush. It can be processed into a practically useful molded article by molding, steam foam molding, lamination molding, calendar molding, blow molding and the like. If necessary, processing such as foaming, drawing, drawing, bonding, printing, painting, and plating may be performed.
  • thermoplastic resin composition of the present invention other styrene butadiene styrene block copolymer and styrene isoprene styrene block copolymer can be used together in a small amount.
  • thermoplastic elastomers and thermoplastic resins such as ethylene-butyl acetate copolymer, ethylene-acrylic acid ethyl acetate copolymer, atactic polypropylene, 1,2-polybutadiene, ethylene propylene rubber and the like It is possible to use the polymer of In this case, the thermoplastic resin composition of the present invention and the above-mentioned other polymer may be kneaded at an arbitrary ratio and then used as a pellet and / or powder.
  • Stabilizers such as anti-aging agents, heat stabilizers, weathering agents, metal deactivators, ultraviolet light absorbers, light stabilizers, copper inhibitors, anti-fungal / anti-mold agents, dispersants, softeners, plasticizers, foams Coloring agent; metal powder such as ferrite; glass fiber; inorganic fiber such as metal fiber; carbon fiber, organic fiber such as aramid fiber; composite fiber, inorganic whisker such as potassium titanate whisker; Fillers such as glass beads, glass balloons, glass flakes, hyacinthtalcite, kaolin, diatomaceous earth, graphite, pumice, rubble powder, cotton flock, cork powder, barium sulfate, fluorine resin, polymer beads or Mixtures of these; fillers such as polyolefin wax, cellulose powder and rubber powder; low molecular weight polymers etc.
  • Stabilizers such as anti-aging agents, heat stabilizers, weathering agents, metal deactivators, ultraviolet light absorbers, light stabilizers
  • additives such as fillers such as silica, talc, calcium carbonate and carbon black other than conductive carbon, crosslinking agents, and flame retardants such as magnesium hydroxide can also be blended.
  • a rubbery polymer, a thermoplastic resin and the like may be appropriately blended to such an extent that the achievement of the object of the present invention is not impaired.
  • thermoplastic resin composition of the present invention can be formed into a thin film to obtain films and sheets to which conductivity has been imparted.
  • the resin temperature is set to 180 ° C. or more using a known forming method using a T-die method or the like. It can also be molded using multilayer molding with a substrate.
  • the thickness of the film and sheet thus obtained is usually 10 to 1,000 m, preferably 50 to 800 ⁇ m.
  • the conductive film and sheet thus obtained are particularly useful in applications such as IC trays, carrier tapes (embossed carrier tapes), IC containers, top cover tapes, electromagnetic wave shielding sheets and the like.
  • a modified conjugated gen-based polymer was produced by the methods 1) to 12) described below.
  • various measurement depended on the following method.
  • a calibration curve was prepared and determined by infrared absorption spectroscopy.
  • the modified polymer was purified, it was dissolved in an organic solvent, and phenolphthalein was used as an indicator, and it was determined by titration with a potassium hydroxide solution until the color of the solution changed from colorless to pink.
  • Si-OC H present in the modified compound
  • the calibration curve force created by the amount of absorption around 250 cm 1 was also quantified.
  • the alkoxysilyl group present in the modifier is Si—OCH, Si—OC 2 H, Si—OC 2 (CH 2) 2 (CH 2) bond
  • the polymer (Hy-1) is a non-modified conjugated diene-based polymer obtained by polymerizing according to the polymer (I) except that methyltriphenoxysilane is not used.
  • reaction solution is returned to normal temperature and normal pressure and removed from the reaction vessel, then, as in (I-1), after addition of an antioxidant, the reaction solution is stirred into water and the solvent is removed. Removal by steam distillation gave a polymer (II-2) described in Table 1.
  • the amino group content of the obtained polymer (2) was 0. 0092 mmol / g.
  • reaction solution After the reaction, the reaction solution is returned to normal temperature and pressure and withdrawn from the reaction vessel, and then, as in (I-1), after addition of an anti-aging agent, the reaction solution is stirred into water and steam distilled. By removing, a polymer (I-3) described in Table 1 was obtained.
  • the amino group content of the obtained polymer (i-3) is 0. 009. 0 which was 5 mmol Z g
  • the amount of the polymerization initiator, the kind of monomer, the amount of the monomer, the polymerization temperature, the polymerization time, and the copolymer structure as shown in Table 2 (5) was obtained according to the production method of the above 1) by changing etc. Next, 15.9 g of N-benzylidene ethyl amine was added to the active site of the polymer and reacted for 30 minutes. After the reaction, the reaction solution is returned to normal temperature and pressure and withdrawn from the reaction vessel, and then, as in (I-1), after addition of an anti-aging agent, the reaction solution is stirred into water and steam distilled. By removing, a polymer (I-5) described in Table 2 was obtained. The amino group content of the obtained polymer (i-5) is 0.0.05 mmol, g of 0.
  • the polymers (i 9) to (i 12) described in Table 2 or 3 were obtained.
  • the polymer (He 2) is a non-modified conjugated diene obtained by polymerizing according to the polymer (i 12) except that N, N-bis (trimethylsilyl) aminopropylmethyl jetoxysilane is not used. It is a base polymer.
  • isoprene is used, and the other is a polymer.
  • the polymer (I-13) described in Table 3 was obtained in the same manner as in the above.
  • the amount of ethylene glycol jetyl ether, the type of modified compound, and the kind of the modified compound are as shown in Table 4 in accordance with (I), so as to obtain a variable conjugated diene-based polymer having an alkoxysilyl group.
  • the amount was changed to obtain a polymer (i-15).
  • the polymer (He-3) is a non-modified conjugated diene-based polymer obtained by polymerizing according to the polymer (i) except that the methyl jetoxy (t-amino acid) silane is not used. .
  • the second stage vinyl bond of this block polymer contained 12%, and the weight average molecular weight measured by GPC was 100,000. Then, 40.7 g of methyltriphenoxysilane was added to this system and reacted for 30 minutes. After the reaction, the temperature is returned to normal temperature and normal pressure, and the reaction vessel is taken out from the reaction vessel. After adding the antiaging agent as described in (A), stirring into water is carried out and the solvent is removed by steam distillation. The title polymer (i-16) was obtained. The alkoxysilyl group content of the obtained polymer (i-16) was 0.1085 mmol / g.
  • the polymer (4) is a non-modified conjugated diene-based polymer obtained by polymerizing according to the polymer (1) except that methyltriphenoxysilane is not used.
  • Hydrogenated conjugated diene-based polymers having the structures shown in Tables 1 to 4 (D1) to (D16), (D1) to (D4)
  • the surface resistance value was measured using a low resistivity meter according to JIS K7194.
  • a sheet of 15 cm long and 15 cm wide was fixed, and the copy paper was reciprocated 10 times with a 20 mm span thereon, and the change in color of the copy paper due to friction was visually observed and evaluated according to the following criteria.
  • Test pieces were produced in the same manner as in Example 1 using the formulation shown in Tables 5 to 10, and the physical properties were evaluated. The results are shown in Tables 5 to 10 below. [Table 5]
  • thermoplastic resin composition having well-balanced physical properties.
  • thermoplastic resin composition of the present invention is useful in applications such as automotive interior materials, electricity, electronic components, construction materials, etc., and is particularly used as a packaging material for semiconductors and electronic components.
  • the conductive film 'sheets obtained by the present invention are useful for applications such as IC trays and carrier tapes.

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Abstract

Disclosed is a thermoplastic resin composition which does not suffer from fall-off of a conductive carbon by blending a modified conjugated diene polymer with a styrene resin and the conductive carbon. This thermoplastic resin composition has an excellent balance among impact resistance, low temperature characteristics and electrical conductivity. Also disclosed are a conductive film and conductive sheet made of such a thermoplastic resin composition. Specifically disclosed is a thermoplastic resin composition mainly containing (i) 2.5-35 parts by weight of a modified conjugated diene polymer having at least one group selected from the group consisting of an alkoxysilyl group, an amino group, an acid anhydride group and a carboxyl group, (ii) not more than 50 parts by weight of an impact-resistant rubber-modified styrene polymer, (iii) 40-90 parts by weight of a non-rubber modified styrene polymer, and (iv) 1-15 parts by weight of a conductive carbon (with (i) + (ii) + (iii) + (iv) being 100 parts by weight). Also disclosed are a conductive film and conductive sheet obtained by molding such a thermoplastic resin composition.

Description

明 細 書  Specification
熱可塑性樹脂組成物、導電性フィルムおよび導電性シート  Thermoplastic resin composition, conductive film and conductive sheet
技術分野  Technical field
[0001] 本発明は、変性共役ジェン系重合体と非ゴム変性スチレン系重合体および導電性 カーボン、場合によってはさらに耐衝撃性ゴム変性スチレン系重合体を含む、耐衝 撃性、低温特性、導電性のバランスに優れた熱可塑性榭脂組成物、およびこれより 得られる導電性フィルムおよび導電性シートに関する。さら〖こ詳しくは、表面抵抗性 に優れるとともに、導電性カーボンの脱落が少なぐ低温特性および衝撃性などの諸 物性のバランスに優れ、 ICトレー、キャリアテープなどの半導体や電子部品用包装材 料などの用途に特に有用な導電性の熱可塑性榭脂組成物、導電性フィルムおよび 導電性シートに関する。  The present invention provides impact resistance, low temperature properties, including a modified conjugated diene polymer, a non-rubber modified styrene polymer and a conductive carbon, and in some cases, an impact rubber modified styrene polymer. The present invention relates to a thermoplastic resin composition having an excellent balance of conductivity, and a conductive film and a conductive sheet obtained therefrom. More specifically, in addition to having excellent surface resistance, it is excellent in the balance of various properties such as low temperature characteristics and impact resistance that causes less dropout of conductive carbon, and packaging materials for semiconductors and electronic parts such as IC trays and carrier tapes. And a conductive thermoplastic resin composition, a conductive film and a conductive sheet which are particularly useful for such applications.
背景技術  Background art
[0002] ポリスチレンなどのスチレン系榭脂は、安価で加工性に優れ、しかも成形品の透明 性と外観に優れているが、耐衝撃性に欠けるため、単独ではその用途を著しく限定さ れている。このポリスチレンの耐衝撃性を改良する目的で製造されたゴム変性ポリス チレンは、耐衝撃性がかなり改良されるものの、ポリスチレン本来の特性である透明 性が著しく劣る。耐衝撃性と透明性とのバランス向上のために、特許文献 1 (特開昭 6 1— 200151号公報)、特許文献 2 (特開平 4— 209615号公報)、特許文献 3 (特公 昭 56 - 54022号公報）などのような共役ジェンと芳香族ビニルイ匕合物からなるブロッ ク共重合体とポリスチレンとの組成物や、特許文献 4 (特開昭 60— 65044公報)など のようなブロック共重合体とポリスチレンとゴム変性ポリスチレンの組成物や特許文献 5 (特開昭 61— 252265号公報）、特許文献 6 (特開 2000— 26698号公報)などのよ うな分子量や共役ジェンと芳香族ビニルイ匕合物との重量比を規定した共役ジェンと 芳香族ビ-ルイ匕合物力もなるブロック共重合体による改良が行われている。  [0002] Styrene-based resins such as polystyrene are inexpensive, excellent in processability, and excellent in transparency and appearance of molded articles, but lack impact resistance, so their use alone is extremely limited. There is. Although the rubber-modified polystyrene produced for the purpose of improving the impact resistance of this polystyrene has a considerable improvement in the impact resistance, its transparency, which is a characteristic of polystyrene, is extremely low. In order to improve the balance between impact resistance and transparency, Patent Document 1 (Japanese Patent Application Laid-Open No. 61-200151), Patent Document 2 (Japanese Patent Application Laid-Open No. 4-209615), Patent Document 3 (Japanese Patent Publication No. 56 -54022) and the like, a composition of block copolymer consisting of a conjugated diene and an aromatic vinyl compound and polystyrene, and a block such as disclosed in Patent Document 4 (JP-A 60-65044) Compositions of copolymers, polystyrenes and rubber-modified polystyrenes, molecular weights such as those disclosed in Patent Document 5 (JP-A-61-252265), Patent Document 6 (JP-A-2000-26698), etc. The improvement is carried out by a block copolymer which also has a conjugated diene and an aromatic vinyl-vinyl compound having a weight ratio to a vinyl copolymer.
[0003] さらに、これらのポリスチレン系榭脂糸且成物を ICトレー、キャリアテープなどの半導 体や電子部品用包装材料などに用いる場合は、導電性を付与しなければならな 、。 導電性を付与するための方法力 従来力 種々開示されている。例えば、その最も 一般的な方法として、特許文献 7 (特開昭 57— 78439号公報)などのように、導電性 付与のために導電性カーボンをポリスチレンと共役ジェンと芳香族ビ-ルイ匕合物から なるブロック共重合体中に含有させる方法が知られている。しかし、導電性カーボン は、榭脂組成物中で凝集しやすぐ静電防止用ケース材料に適用するには多量に 添加する必要がある。導電性カーボンの凝集を極力防ぐには、特許文献 8 (特開昭 5 5— 94948号公報）などのように、アイオノマー、エチレン 酢酸ビュル共重合体を 添加する方法がある力 必ずしも十分に満足し得るものではな力つた。 [0003] Furthermore, in the case of using these polystyrene-based resin yarn composites for semiconductors such as IC trays and carrier tapes, and packaging materials for electronic parts, etc., conductivity must be imparted. Methods for Providing Conductivity Conventional Forces Various disclosures. For example, the most As a general method, as in Patent Document 7 (Japanese Patent Application Laid-Open No. 57-78439), a block comprising conductive carbon, polystyrene, a conjugated diene, and an aromatic vinyl compound to impart conductivity is provided. Methods are known for incorporation in copolymers. However, conductive carbon needs to be added in large amounts in order to coagulate in the resin composition and to be applied to the antistatic case material immediately. In order to prevent the aggregation of conductive carbon as much as possible, there is a method of adding an ionomer or ethylene acetate / buul copolymer as in Patent Document 8 (Japanese Patent Application Laid-Open No. 5-94948) and the like. I was not able to gain anything.
[0004] 特許文献 1：特開昭 61 - 200151号公報 Patent Document 1: Japanese Patent Application Laid-Open No. 61-20151
特許文献 2：特開平 4 - 209615号公報  Patent Document 2: Japanese Patent Application Laid-Open No. 4-209615
特許文献 3：特公昭 56 - 54022号公報  Patent Document 3: Japanese Patent Publication No. 56-54022
特許文献 4：特開昭 60— 65044公報  Patent Document 4: Japanese Patent Application Laid-Open No. 60-65044
特許文献 5：特開昭 61— 252265号公報  Patent Document 5: Japanese Patent Application Laid-Open No. 61-252265
特許文献 6：特開 2000 - 26698号公報  Patent Document 6: Japanese Patent Application Laid-Open No. 2000-26698
特許文献 7：特開昭 57— 78439号公報  Patent Document 7: Japanese Patent Application Laid-Open No. 57-78439
特許文献 8：特開昭 55— 94948号公報  Patent Document 8: Japanese Patent Application Laid-Open No. 55-94948
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problem that invention tries to solve
[0005] 本発明は、上記問題に鑑みなされたもので、特定の官能基を有する変性共役ジェ ン系重合体をスチレン系榭脂と導電性カーボンに配合することにより、導電性カーボ ンの脱落がなぐ耐衝撃性、低温特性および導電性のバランスに優れる熱可塑性榭 脂組成物、およびこれより得られる導電性フィルムおよび導電性シートを提供すること を目的とする。 The present invention has been made in view of the above problems, and it is possible to remove conductive carbon by blending a modified conjugated diene polymer having a specific functional group with a styrene resin and conductive carbon. It is an object of the present invention to provide a thermoplastic resin composition excellent in balance between impact resistance, low temperature properties and conductivity, and a conductive film and a conductive sheet obtained therefrom.
また、本発明は、 ICトレー、キャリアテープなどの半導体や電子部品用包装材料な どの用途に特に有用な熱可塑性榭脂組成物、および導電性フィルムおよび導電性 シートを提供することを目的とする。  Another object of the present invention is to provide a thermoplastic resin composition which is particularly useful in applications such as IC trays, packaging materials for semiconductors such as carrier tapes, and electronic parts, and conductive films and conductive sheets. .
課題を解決するための手段  Means to solve the problem
[0006] 本発明は、（ィ)アルコキシシリル基、アミノ基、酸無水物基、およびカルボキシル基 の群力 選ばれた少なくとも 1種の基を有する変性共役ジェン系重合体 (以下、「変 性共役ジェン系重合体」ともいう） 2. 5〜35重量部、 The present invention relates to a modified conjugated gen-based polymer having a group power of (i) an alkoxysilyl group, an amino group, an acid anhydride group, and a carboxyl group (hereinafter referred to as “modification”) (Also referred to as “conjugated polymers”) 2. 5 to 35 parts by weight,
(口）耐衝撃性ゴム変性スチレン系重合体 0〜50重量部、  (Mouth) Impact resistant rubber modified styrene polymer 0 to 50 parts by weight,
(ハ)非ゴム変性スチレン系重合体 40〜90重量部、ならびに  (C) 40 to 90 parts by weight of a non-rubber-modified styrene polymer,
(二)導電性カーボン 1〜15重量部 [ただし、（ィ） + (口） + (ハ） + (二） = 100重量 部]  (2) 1 to 15 parts by weight of conductive carbon [where (i) + (mouth) + (ha) + (2) = 100 parts by weight]
を主成分とする熱可塑性榭脂組成物に関する。 The present invention relates to a thermoplastic resin composition containing as a main component.
ここで、上記 (ィ)変性共役ジェン系重合体は、次に示す方法 (a)〜(e)の群力も選 ばれた少なくとも 1種で製造された重合体の 、ずれかが好ま ヽ。  Here, as the (i) modified conjugated diene-based polymer, any one of the polymers produced by at least one selected from the group powers of methods (a) to (e) shown below is preferable.
(a)共役ジェンと芳香族ビニル化合物を有機アルカリ金属化合物の存在下で重合 し、得られた共役ジェン系重合体にアルコキシシランィ匕合物を反応させることにより 製造された重合体。  (a) A polymer produced by polymerizing a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound, and reacting the resulting conjugated diene polymer with an alkoxysilane compound.
(b)共役ジェンと芳香族ビ-ルイ匕合物を、アミノ基を有する有機アルカリ金属化合 物の存在下で重合することにより製造された重合体。  (b) A polymer produced by polymerizing a conjugated diene and an aromatic bi-Lewi complex in the presence of an organic alkali metal compound having an amino group.
(c)共役ジェンとアミノ基を有する不飽和単量体と芳香族ビニル化合物とを有機ァ ルカリ金属化合物の存在下で重合することにより製造された重合体。  (c) A polymer produced by polymerizing an unsaturated monomer having a conjugated gene and an amino group and an aromatic vinyl compound in the presence of an organic metal compound.
(d)共役ジェンと芳香族ビニル化合物を有機アルカリ金属化合物の存在下で重合 し、得られた共役ジェン系重合体に下記一般式（1)で表される化合物を反応させる ことにより製造された重合体。  (d) manufactured by polymerizing a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound, and reacting the resulting conjugated diene polymer with a compound represented by the following general formula (1) Polymer.
R1R2C = N-Y- - - - (1) R 1 R 2 C = NY----(1)
[上記一般式（1)中、 R1および R2はそれぞれ独立に水素原子、炭素数 1〜20のアル キル基、炭素数 6〜20のァリール基、炭素数 7〜20のァラルキル基または炭素数 1 〜 100のオルガノシロキシ基である。また、 Yは水素原子、炭素数 3〜18のトリアルキ ルシリル基、炭素数 1〜20のアルキル基、炭素数 6〜20のァリール基、炭素数 7〜2 0のァラルキル基または炭素数 1〜： L00のオルガノシロキシ基である。 ] [In the above general formula (1), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or carbon It is an organosiloxy group of several 1 to 100. Y is a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or 1 to 6 carbon atoms: It is an organosiloxy group of L00. ]
(e)共役ジェンと芳香族ビニルイ匕合物を有機アルカリ金属化合物の存在下で重合 し、得られた共役ジェン系重合体に、ケトンィ匕合物、エステルイ匕合物およびアルデヒ ド化合物の群力 選ばれた少なくとも 1種を反応させた後、酸無水物および Zまたは 酸ハライドと反応させることにより製造された重合体。 ここで、上記 (ィ)変性共役ジェン系重合体のうち、アルコキシシリル基とアミノ基を 有する変性共役ジェン系重合体は、下記 (f)〜 (h)の群力も選ばれた少なくとも 1種 の方法により製造された変性共役ジェン系重合体が好ましい。 (e) The conjugated diene-based polymer obtained by polymerizing a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound, the group power of a ketone complex, an ester complex and an aldehyde compound. A polymer produced by reacting at least one selected species with an acid anhydride and Z or an acid halide. Here, among the above (i) modified conjugated gen polymers, the modified conjugated diene polymers having an alkoxysilyl group and an amino group are at least one selected from the group powers of (f) to (h) below. The modified conjugated diene-based polymer produced by the method is preferred.
(f)共役ジェンと芳香族ビ-ルイ匕合物を、アミノ基を有する有機アルカリ金属化合物 の存在下で重合し、得られた共役ジェン系重合体に下記一般式（2)で表される化合 物を反応させた変性重合体。  (f) A conjugated diene-based polymer obtained by polymerizing conjugated diene and an aromatic bi-Louisinated compound in the presence of an organic alkali metal compound having an amino group is represented by the following general formula (2) Modified polymer in which compound is reacted.
R3 Si (OR4) X …… (2) R 3 Si (OR 4 ) X ...... (2)
(.4— m— n) m n  (.4-m-n) m n
[式中、 R3は炭素数 1〜20のアルキル基、炭素数 6〜20のァリール基、炭素数 7〜2 0のァラルキル基または炭素数 1〜： L00のオルガノシロキシ基であり、 R3が複数ある 場合は、各 R3は同じ基でも異なる基でもよい。 R4は炭素数 1〜20のアルキル基、炭 素数 6〜20のァリール基、炭素数 7〜20のァラルキル基であり、 R4が複数ある場合 は、各 R4は同じ基でも異なる基でもよい。 Xは少なくとも Ο原子、 Si原子のいずれか 1 つ以上含む極性基を有する置換基であり、 Xが複数ある場合は、各 Xは同じ基でも異 なる基でもよく、また、各 Xは独立の置換基でも環状構造を形成していてもよい。 mは 1、 2または 3であり、 nは 0、 1、 2または 3の整数を示す。 mと nの和は 1〜4である。 ]Wherein, R 3 is an alkyl group, Ariru group having 6 to 20 carbon atoms, 1 to several 7-2 Ararukiru group or a carbon number of 0 carbon atoms of 1 to 20 carbon atoms: a L00 organosiloxy group, R 3 When there are a plurality of, each R 3 may be the same or different. R 4 is an alkyl group having 1 to 20 carbon atoms, Ariru group having a carbon number of 6-20, a Ararukiru group having 7 to 20 carbon atoms, if R 4 have more than one purpose, each R 4 is different even in the same group group Good. X is a substituent having a polar group containing at least one or more of Ο atom and Si atom, and when there are a plurality of X, each X may be the same or different group, and each X is independent It may have a substituent or a cyclic structure. m is 1, 2 or 3 and n is an integer of 0, 1, 2 or 3. The sum of m and n is 1 to 4. ]
(g)共役ジェンとアミノ基を有する不飽和単量体と芳香族ビニル化合物とを有機ァ ルカリ金属化合物の存在下で重合し、得られた共役ジェン系重合体に上記一般式（ 2)で表される化合物を反応させた変性重合体。 (g) A conjugated diene polymer obtained by polymerizing an unsaturated monomer having an conjugated group and an amino group and an aromatic vinyl compound in the presence of an organic alkali metal compound is shown by the above general formula (2) The modified polymer which made the compound represented react.
(h)共役ジェンと芳香族ビ-ルイ匕合物を有機アルカリ金属化合物の存在下で重合 し、得られた共役ジェン系重合体に下記一般式 (7)で表される化合物を反応させた 変性重合体。  (h) A conjugated diene polymer obtained by polymerizing a conjugated diene and an aromatic bi-loyl compound in the presence of an organic alkali metal compound, and reacting the compound represented by the following general formula (7) with the obtained conjugated polymer Modified polymer.
R12 Si (OR13) Z …… (7) R 12 Si (OR 13 ) Z ...... (7)
(4-p-q) p q  (4-p-q) p q
[式中、 R12は炭素数 1〜20のアルキル基、炭素数 6〜20のァリール基、炭素数 7〜 20のァラルキル基または炭素数 1〜： L00のオルガノシロキシ基であり、 R12が複数あ る場合は、各 R12は同じ基でも異なる基でもよい。 R13は炭素数 1〜20のアルキル基、 炭素数 6〜20のァリール基、炭素数 7〜20のァラルキル基であり、 R13が複数ある場 合は、各 R13は同じ基でも異なる基でもよい。 Zは N原子を含む極性基を有する置換 基であり、 Zが複数ある場合は、各 Zは同じ基でも異なる基でもよぐまた、各 Zは独立 の置換基でも環状構造を形成していてもよい。 Pは 1、 2または 3であり、 qは 1、 2また は 3の整数を示す。 pと qの和は 1〜4である。 ] Wherein, R 12 is an alkyl group, Ariru group having 6 to 20 carbon atoms, 1 to Ararukiru group or the number of carbon atoms in the carbon number 7-20 having 1 to 20 carbon atoms: a L00 organosiloxy group, R 12 is When there are two or more, each R 12 may be the same or different. R 13 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of R 13 groups, each R 13 may be the same or different groups May be. Z is a substituent having a polar group containing an N atom, and when there are a plurality of Z, each Z may be the same or different group, and each Z is independent Or a cyclic structure. P is 1, 2 or 3 and q is an integer of 1, 2 or 3. The sum of p and q is 1 to 4. ]
また、（口）耐衝撃性ゴム変性スチレン系重合体としては、耐衝撃性ゴム変性スチレ ン重合体、アクリロニトリル ブタジエン スチレン共重合体、アクリル酸エステル ブタジエン スチレン共重合体、メタクリル酸エステル ブタジエン スチレン共重合 体、および耐衝撃性ゴム変性スチレン 無水マレイン酸共重合体の群力 選ばれた 少なくとも 1種が好ましい。  Further, as the (mouth) impact resistant rubber modified styrene polymer, an impact resistant rubber modified styrene polymer, an acrylonitrile butadiene styrene copolymer, an acrylic ester butadiene styrene copolymer, a methacrylic ester butadiene styrene copolymer At least one selected from the group consisting of a body and a rubber-impact rubber-modified styrene / maleic anhydride copolymer is preferred.
さらに、（ハ）非ゴム変性スチレン系重合体としては、ポリスチレン、スチレン ーメ チルスチレン共重合体、アクリロニトリル スチレン共重合体、およびアクリロニトリル ーメタクリル酸エステルースチレン共重合体の群力 選ばれた少なくとも 1種が好まし い。  Further, (iii) as the non-rubber-modified styrenic polymer, at least one selected from polystyrene, a styrene-methyl-styrene copolymer, an acrylonitrile-styrene copolymer, and an acrylonitrile-methacrylic acid ester-styrene copolymer. Is preferred.
さらに、（二）導電性カーボンとしては、ケッチェンブラックが好ましい。  Furthermore, as (2) conductive carbon, ketjen black is preferable.
次に、本発明は、以上の熱可塑性榭脂組成物を成形してなる導電性フィルムおよ び導電性シートに関する。  Next, the present invention relates to a conductive film and a conductive sheet obtained by molding the above-mentioned thermoplastic resin composition.
発明の効果  Effect of the invention
[0007] 本発明の熱可塑性榭脂組成物は、上記 (ィ)アルコキシシリル基、アミノ基、酸無水 物基、およびカルボキシル基の群カゝら選ばれた少なくとも 1種の基を有する変性共役 ジェン系重合体と (ハ）非ゴム変性スチレン系重合体と (二)導電性カーボン、さらに必 要に応じて (口)耐衝撃性ゴム変性スチレン系重合体を配合した組成物であり、非常 に導電性カーボンの分散性に優れている。このような熱可塑性榭脂組成物は、導電 性カーボンの脱落が無ぐ耐衝撃性、透明性、剛性、低温特性のバランスに優れ、ひ V、ては、導電性を付与したシート'フィルムなどに有用な熱可塑性榭脂組成物を得る ことができる。  The thermoplastic resin composition of the present invention has a modified conjugate having at least one group selected from the group consisting of (i) alkoxysilyl group, amino group, acid anhydride group, and carboxyl group. It is a composition in which a gen-based polymer, (iii) a non-rubber-modified styrenic polymer, and (ii) an electrically conductive carbon, and (if necessary) an impact-modified rubber-modified styrenic polymer are blended. It is excellent in the dispersibility of conductive carbon. Such a thermoplastic resin composition is excellent in the balance of impact resistance, transparency, rigidity, and low temperature characteristics in which the conductive carbon does not fall off, and the sheet, film, etc. to which conductivity is imparted. The thermoplastic resin composition useful for the present invention can be obtained.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0008] 以下、本発明について詳細に説明する。 Hereinafter, the present invention will be described in detail.
(ィ)変性共役ジェン系重合体  (I) Modified conjugated gen polymer
本発明の熱可塑性榭脂組成物に用いられる変性共役ジェン系重合体は、以下に 記載する製造方法 (a)〜 (h)にお 、て、それぞれ変性ィ匕合物として、 (a)ではアルコ キシシラン化合物を、（b)ではアミノ基を有する有機アルカリ金属化合物を、（C)では アミノ基を有する不飽和単量体を、（d)では式（1)で表される化合物を、（e)ではケト ン化合物、エステルイ匕合物およびアルデヒドィ匕合物の群力 選ばれた少なくとも 1種 と酸無水物および Zまたは酸ノ、ライドを、 (f)ではアミノ基を有する有機アルカリ金属 化合物と一般式 (2)で表される化合物を、（g)ではアミノ基を有する不飽和単量体と 一般式 (2)で表される化合物を、（h)では一般式 (7)で表される化合物を、それぞれ 、用いることにより得ることができる。以下に、製造方法 (a)〜(h)について説明する。 The modified conjugated diene-based polymer used in the thermoplastic resin composition of the present invention can be obtained as a modified compound in (a) in the production methods (a) to (h) described below. Arco In (d), an unsaturated monomer having an amino group, and in (d) a compound represented by the formula (1), (e) Groups of a ketone compound, an ester complex and an aldehyde complex, and at least one selected from an acid anhydride and Z or an acid halide, and an organic alkali metal compound having an amino group in (f) The compound represented by the general formula (2) and the compound represented by the general formula (2) in (g) and the unsaturated monomer having an amino group in (g) are represented in the general formula (7) in (h) Can be obtained by using each of the following compounds. The production methods (a) to (h) will be described below.
[0009] 本発明の熱可塑性榭脂組成物に用いられるアルコキシシリル基を有する変性共役 ジェン系重合体は、（a)不活性有機溶媒中、共役ジェンと芳香族ビニルイ匕合物を、有 機アルカリ金属化合物を重合開始剤として重合し、得られた共役ジェン系重合体に アルコキシシラン化合物を反応させることにより容易に得ることができる。 The modified conjugated diene-based polymer having an alkoxysilyl group used in the thermoplastic resin composition of the present invention can be obtained by reacting an conjugated vinyl-aromatic vinyl compound in an inert organic solvent (a) It can be easily obtained by polymerizing an alkali metal compound as a polymerization initiator, and reacting the resulting conjugated diene polymer with an alkoxysilane compound.
上記「アルコキシシリル基」としては、炭素数 1〜20のアルキルォキシ、炭素数 6〜2 0のァリールォキシ、炭素数 7〜20のァラルキルォキシから選ばれる少なくとも 1つの アルコキシが珪素原子と結合した基で、具体的にはメトキシ、エトキシ、ブトキシ、プロ ポキシ、ペンチ口キシ、ネオペンチ口キシ、へキシロキシ、アミ口キシ、フエノキシ、好ま しくはメトキシ、エトキシ、アミ口キシ、フエノキシなどのアルコキシと珪素原子が結合し たものが挙げられる。  The above "alkoxysilyl group" is a group in which at least one alkoxy selected from alkyloxy having 1 to 20 carbon atoms, alkyloxy having 6 to 20 carbon atoms, and aralkyloxy having 7 to 20 carbon atoms is bonded to a silicon atom. Specifically, a silicon atom is bonded to an alkoxy such as methoxy, ethoxy, butoxy, propoxy, pentoxy, neopentoxy, hexyloxy, hexoxy, amioxy, phenoxy, preferably methoxy, ethoxy, amiporti, phenoxy and the like. Other things.
[0010] 上記「共役ジェン」としては、例えば、 1, 3 ブタジエン、イソプレン、 2, 3 ジメチ ルー 1 , 3 ブタジエン、 1, 3 ペンタジェン、 2—メチルー 1, 3—ォクタジェン、 1, 3 一へキサジェン、 1, 3 シクロへキサジェン、 4, 5 ジェチノレー 1, 3—ォクタジェン 、 3 ブチル 1, 3—ォクタジェン、ミルセン、クロ口プレンなどが挙げられる。この中 で、 1, 3 ブタジエン、イソプレンが好ましい。  Examples of the above-mentioned “conjugated gen” include, for example, 1,3 butadiene, isoprene, 2,3 dimethyl 1, 3 butadiene, 1,3 pentagen, 2 -methyl- 1,3 -octadiene, 1,3 1 1, 3, 3-cyclohexadiene, 4, 5 Detinolay 1, 3, 3-Octagen, 3, Butyl 1, 3-Octadiene, Myrsen, Cro-prene and the like. Among these, 1,3 butadiene and isoprene are preferable.
[0011] 上記「芳香族ビニル化合物」としては、スチレン、 tert ブチルスチレン、 α—メチ ルスチレン、 ρ—メチルスチレン、 ρ ェチルスチレン、ジビニルベンゼン、 1, 1—ジフ ェニノレスチレン、ビニノレナフタレン、ビニノレアントラセン、 Ν, Ν ジェチノレー ρ ァミノ ェチルスチレン、ビュルピリジンなどが挙げられる。この中で、スチレンおよび tert— プチルスチレンが好ましい。なお、この場合、上記「共役ジェン」と上記「芳香族ビ- ル化合物」と、さらにアクリロニトリル、メチルメタタリレートなどの他の不飽和化合物を 、全モノマーに対し 5重量％以下程度カ卩えて重合させてもよい。 [0011] Examples of the above-mentioned "aromatic vinyl compound" include styrene, tert-butylstyrene, α-methylstyrene, ρ-methylstyrene, ス チ レ ン -ethylstyrene, divinylbenzene, 1,1-diphenylenostyrene, vinylene naphthalene, vinylene Anthracene, Ν, Ν, チ, ミ ノ, ェ, ピ リ ジ ン, ピ リ ジ ン, etc. may be mentioned. Among these, styrene and tert-butylstyrene are preferred. In this case, the above “conjugated gen”, the above “aromatic vinyl compound”, and other unsaturated compounds such as acrylonitrile and methyl metatalylate are further included. About 5% by weight or less of the total monomers may be polymerized.
[0012] 重合開始剤である上記「有機アルカリ金属化合物」としては、有機リチウム化合物、 有機ナトリウム化合物などが挙げられ、特に有機リチウム化合物が好ましい。有機ァ ルカリ金属化合物の使用量については特に限定はなぐ必要に応じて種々の量を使 用できるが、通常はモノマー 100重量部あたり 0. 02〜15重量部の量で、好ましくはExamples of the above-mentioned “organic alkali metal compound” which is a polymerization initiator include organic lithium compounds, organic sodium compounds and the like, and organic lithium compounds are particularly preferable. The amount of the organic alkali metal compound to be used is not particularly limited, and various amounts can be used if necessary. Usually, an amount of 0.02 to 15 parts by weight per 100 parts by weight of the monomer is preferable.
0. 03〜5重量部の量で用いられる。 It is used in an amount of 0.03 to 5 parts by weight.
[0013] 共役ジェン系重合体にアルコキシシランィ匕合物を反応させるアルコキシシランィ匕合 物としては、共役ジェン系重合体に反応させて、変性重合体とすることができる限り、 その構造には限定はないが、以下の一般式 (2)で表されるアルコキシシランィ匕合物 が用いられる。  As an alkoxysilane compound which causes an alkoxysilane compound to react with a conjugated diene polymer, as long as it can be converted into a modified polymer by reacting with a conjugated polymer, There is no limitation, but an alkoxysilane compound represented by the following general formula (2) is used.
R3 Si (OR4) X …… (2) R 3 Si (OR 4 ) X ...... (2)
(4— m— nリ m n  (4-m-n ri m n
[式中、 R3は炭素数 1〜20のアルキル基、炭素数 6〜20のァリール基、炭素数 7〜2 0のァラルキル基または炭素数 1〜： L00のオルガノシロキシ基であり、 R3が複数ある 場合は、各 R3は同じ基でも異なる基でもよい。 R4は炭素数 1〜20のアルキル基、炭 素数 6〜20のァリール基、炭素数 7〜20のァラルキル基であり、 R4が複数ある場合 は、各 R4は同じ基でも異なる基でもよい。 Xは少なくとも Ο原子、 Si原子のいずれか 1 つ以上含む極性基を有する置換基であり、 Xが複数ある場合は、各 Xは同じ基でも異 なる基でもよく、また、各 Xは独立の置換基でも環状構造を形成していてもよい。 mはWherein, R 3 is an alkyl group, Ariru group having 6 to 20 carbon atoms, 1 to several 7-2 Ararukiru group or a carbon number of 0 carbon atoms of 1 to 20 carbon atoms: a L00 organosiloxy group, R 3 When there are a plurality of, each R 3 may be the same or different. R 4 is an alkyl group having 1 to 20 carbon atoms, Ariru group having a carbon number of 6-20, a Ararukiru group having 7 to 20 carbon atoms, if R 4 have more than one purpose, each R 4 is different even in the same group group Good. X is a substituent having a polar group containing at least one or more of Ο atom and Si atom, and when there are a plurality of X, each X may be the same or different group, and each X is independent It may have a substituent or a cyclic structure. m is
1、 2または 3であり、 nは 0、 1、 2または 3の整数を示す。 mと nの和は 1〜4である。特 に、 mは 2または 3で、 nは 0または 1が好ましい。 ] It is 1, 2 or 3 and n shows the integer of 0, 1, 2 or 3. The sum of m and n is 1 to 4. In particular, m is preferably 2 or 3, and n is preferably 0 or 1. ]
[0014] 上記一般式（2)で表されるアルコキシシラン化合物としては、テトラエトキシシラン、 テトラメトキシシラン、メチルトリエトキシシラン、メチルトリメトキリシラン、ジメチルジメト キシシラン、ジメチノレジェトキシシラン、メチノレジェトキシ（t アミ口キシ）シラン、メチ ルトリフエノキシシラン、ジメチルジフエノキシシラン、 1—トリメチルシリル一 2—ジメトキ シ一 1—ァザ 2—シラシクロペンタン、 1 トリメチルシリル 2—ジェトキシ 1—ァ ザ一 2—シラシクロペンタン、 γ グリシドキシプロピルトリメトキシシラン、 γ—グリシド  Examples of the alkoxysilane compound represented by the above general formula (2) include tetraethoxysilane, tetramethoxysilane, methyltriethoxysilane, methyltrimethoquilysilane, dimethyldimethyoxysilane, dimethyolegetoxysilane, and methyoregetoxyl. (T-amino-oxy) silane, methyltriphenoxysilane, dimethyldiphenoxysilane, 1-trimethylsilyldi-2-dimethoxydi-yl 1-aza 2-silacyclopentane, 1trimethylsilyl 2-jetoxy 1-azadi 2-Silacyclopentane, γ glycidoxypropyl trimethoxysilane, γ-Glycid
、 γーグリシドキシプロピルトリエトキシシラン、 γ—メタクリロキシプロピルメチルジメト キシシラン、 γ—メタクリロキシプロピルメトリメトキシシラン、トリメチルシロキシトリフエノ キシシラン、トリメチノレシ口キシトリメトキシシラン、トリメチノレシロキシトリエトキシシラン、 トリメチルシロキシトリブトキシシラン、および 1, 1, 3, 3—テトラメチル一 1—フエノキシ ジシロキサンなどが挙げられる。 Γ-Glycidoxypropyltriethoxysilane, γ-methacryloxypropylmethyl dimetho Xysilane, .gamma.-methacryloxypropylmethymethoxysilane, trimethylsiloxytriphenyloxysilane, trimethyrene xylotrimethoxysilane, trimethyallyloxytriethoxysilane, trimethylsiloxytributoxysilane, and 1,1,3,3-tetramethylsilane 1-Phenoxydisiloxane and the like.
[0015] 上記アルコキシシランィ匕合物による変性方法は、共役ジェン系重合体を製造する ための重合反応の重合転ィ匕率が 90%〜： LOO%になった時点で、上記アルコキシシ ラン化合物を重合系内に添加して変性反応を行うことが好ま 、。重合転化率が 90 %に到達する以前に添加しても良いし、また、重合反応が進行中に、間欠的または 連続的にアルコキシシランィ匕合物を添加して変性反応を行ってもよい。  [0015] The method of modification with the above alkoxysilane compound is as follows: when the polymerization conversion rate of the polymerization reaction for producing a conjugated gen polymer becomes 90% to: LOO%, the above alkoxysilane It is preferred to add the compound into the polymerization system to carry out the modification reaction. The addition may be performed before the polymerization conversion reaches 90%, or the modification reaction may be performed by intermittently or continuously adding an alkoxysilane compound while the polymerization reaction is in progress. .
[0016] 上記アルコキシシランィ匕合物の使用量は、有機アルカリ金属化合物由来の活性点 のモル数に対して、好ましくは、 0. 05〜5倍モル、さらに好ましくは、 0. 1〜1. 5倍モ ルである。  The amount of the above alkoxysilane compound to be used is preferably 0.05 to 5 moles, more preferably 0.1 to 1 mole, with respect to the number of moles of the active point derived from the organic alkali metal compound. 5 times more money.
[0017] 得られる共役ジェン系重合体中のアルコキシシリル基の含量は、通常、 0. 0001〜 5mmol/g、好ましくは、 0. 001〜： Lmmol/g、さらに好ましくは、 0. 003〜0. lm mo lZgである。なお、アルコキシシリル基は、通常、重合体鎖末端に存在するが、 側鎖に存在してもよい。  The content of the alkoxysilyl group in the conjugated diene polymer to be obtained is usually 0.000 to 5 mmol / g, preferably 0.001 to: L mmol / g, more preferably 0.003 to 0 It is lm mo lZg. The alkoxysilyl group is usually present at the end of the polymer chain, but may be present at the side chain.
[0018] また、本発明の熱可塑性榭脂組成物に用いられるアミノ基を有する変性共役ジェ ン系重合体は、アミノ基を導入する方法は特に限定はないが、例えば以下に示す (b )〜（d)の方法により容易に得ることができる。  The method for introducing an amino group in the modified conjugated diene polymer having an amino group used in the thermoplastic resin composition of the present invention is not particularly limited, and examples thereof include the following (b) It can be easily obtained by the method of (d).
(b)共役ジェンと芳香族ビ-ルイ匕合物を、アミノ基を有する有機アルカリ金属化合 物の存在下で重合することにより製造される。  (b) It is produced by polymerizing conjugated diene and an aromatic bi-Lewi complex in the presence of an organic alkali metal compound having an amino group.
(c)共役ジェンとアミノ基を有する不飽和単量体と芳香族ビニル化合物とを有機ァ ルカリ金属化合物の存在下で重合することにより製造される。  (c) It is produced by polymerizing an unsaturated monomer having a conjugated diene, an amino group and an aromatic vinyl compound in the presence of an organic metal compound.
(d)共役ジェンと芳香族ビニル化合物を有機アルカリ金属化合物の存在下で重合 し、得られた共役ジェン系重合体に下記一般式（1)で表される化合物を反応させる こと〖こより製造される。  (d) polymerizing conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound, and reacting the compound represented by the following general formula (1) with the conjugated diene polymer obtained; Ru.
R1R2C = N-Y- - - - (1) R 1 R 2 C = NY----(1)
[上記一般式（1)中、 R1および R2はそれぞれ独立に水素原子、炭素数 1〜20のアル キル基、炭素数 6〜20のァリール基、炭素数 7〜20のァラルキル基または炭素数 1 〜 100のオルガノシロキシ基である。また、 Yは水素原子、炭素数 3〜18のトリアルキ ルシリル基、炭素数 1〜20のアルキル基、炭素数 6〜20のァリール基、炭素数 7〜2 0のァラルキル基または炭素数 1〜： L00のオルガノシロキシ基である。 ] [In the above general formula (1), R 1 and R 2 each independently represent a hydrogen atom, and an aryl having 1 to 20 carbon atoms] It is a cil group, a C6-C20 aryl group, a C7-C20 aralkyl group or a C1-C100 organosiloxy group. Y is a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or 1 to 6 carbon atoms: It is an organosiloxy group of L00. ]
[0019] 上記 (b)の方法で使用するアミノ基を有する有機アルカリ金属化合物としては、下 記一般式 (3)または (4)が挙げられる。  Examples of the organic alkali metal compound having an amino group used in the method (b) include the following general formula (3) or (4).
[0020] [化 1]  [Formula 1]
ー Li
Figure imgf000010_0001
ー Li
Figure imgf000010_0001
[0021] [上記一般式（3)中、 R5および R。は両方とも炭素数 3〜18のトリアルキルシリル基で あるか、またはどちらか一方が上記トリアルキルシリル基であり、他方が炭素数 1〜20 のアルキル基、炭素数 6〜20のァリール基、炭素数 7〜20のァラルキル基若しくは 炭素数 1〜： L00のオルガノシロキシ基である。また、上記一般式（3)および (4)中の R 7は、炭素数 1〜20のアルキレン基またはアルキリデン基である。さらに、上記一般式 (4)中の R8は炭素数 1〜20のアルキル基、炭素数 6〜20のァリール基、炭素数 7〜 20のァラルキル基または炭素数 1〜： L00のオルガノシロキシ基である。 ] [In the above general formula (3), R 5 and R. Are both trialkylsilyl groups having 3 to 18 carbon atoms, or one of them is the above trialkylsilyl group, and the other is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, It is an aralkyloxy group having 7 to 20 carbon atoms or an organosiloxy group having 1 to: carbon atoms. Moreover, R <7> in the said General formula (3) and (4) is a C1-C20 alkylene group or alkylidene group. Furthermore, R 8 in the general formula (4) is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to carbon atoms: It is. ]
[0022] 上記一般式（3)または (4)で表される有機アルカリ金属化合物としては、 3 リチォ — 1— [N, N ビス（トリメチルシリル）]ァミノプロパン、 2—リチォ 1— [N, N ビス (トリメチルシリル）]アミノエタン、 3 リチォ 2, 2 ジメチル一 1— [N, N ビス（トリ メチルシリル）]ァミノプロパン、 2, 2, 5, 5—テトラメチルー 1一（3 リチォプロピル） — 1—ァザ一 2, 5 ジシラシクロペンタン、 2, 2, 5, 5—テトラメチル一 1— (3—リチ ォ一 2, 2 ジメチループ口ピル）一 1—ァザ一 2, 5 ジシラシクロペンタン、 2, 2, 5, 5—テトラメチルー 1 （2 リチォェチル）ー1ーァザ 2, 5 ジシラシクロペンタン、 3 リチォ 1— [N— (tert ブチル—ジメチルシリル）—N トリメチルシリル]ァミノ プロパン、 3 リチォ 1—(N—メチル N トリメチルシリル）ァミノプロパン、 3 リ チォ— 1— (N ェチル—N トリメチルシリル）ァミノプロパンなどが挙げられる。 また、上記 (b)の方法で使用する共役ジェンと芳香族ビ-ルイ匕合物は、上記 (a)の 方法で使用するものが使用可能である。 Examples of the organic alkali metal compound represented by the above general formula (3) or (4) include 3 lithium 1- [N, N bis (trimethylsilyl)] aminopropane, 2-lithium 1- [N, N bis (Trimethylsilyl)] aminoethane, 3 lyo 2, 2 dimethyl 1 1-[N, N bis (trimethyl silyl)] amino propane, 2, 2, 5, 5- tetramethyl 1 1 (3 lithium)-1-1 2, 5 Disilacyclopentane, 2, 2, 5, 5-Tetramethyl-I 1-(3-Liqui-T, 2-Dimethyl-p-Pill) I 1-Aza-I 2, 5 Disilacyclopentane, 2, 2, 5, 5-Tetramethyl- 1 (2 lyocetyl)-1-2, 2, 5 disilacyclopentane, 3 Lithio 1-[N- (tert-butyl-dimethylsilyl)-N-trimethylsilyl] amino Examples thereof include propane, 3-lithium 1- (N-methyl-N-trimethylsilyl) aminopropane, and 3-lithium-1- (N-ethyl-N-trimethylsilyl) aminopropane. Further, as the conjugated diene and aromatic bi-Louisium compound used in the above method (b), those used in the above method (a) can be used.
[0023] (c)の方法で使用するアミノ基を有する不飽和単量体としては、下記一般式（5)ま たは（6)が挙げられる。 Examples of the unsaturated monomer having an amino group used in the method (c) include the following general formula (5) or (6).
[0024] [化 2] [Formula 2]
Figure imgf000011_0001
Figure imgf000011_0001
[0025] [上記一般式（5)および (6)中、 R9および R1C>は、両方とも炭素数 3〜18のトリアルキ ルシリル基である力、またはどちらか一方が上記トリアルキルシリル基であり、他方が 炭素数 1〜20のアルキル基、炭素数 6〜20のァリール基、炭素数 7〜20のァラルキ ル基若しくは炭素数 1〜： L00のオルガノシロキシ基である。また、上記一般式 (6)中、 R11は、炭素数 1〜20のアルキレン基またはアルキリデン基である。さらに、上記一般 式（5)および（6)中の n，は 1〜3である。 ] [In the general formulas (5) and (6), R 9 and R 1 C> are both a trialkylsilyl group having 3 to 18 carbon atoms, or one of them is a trialkylsilyl group as described above And the other is an alkyl group having 1 to 20 carbon atoms, a aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or an organosiloxy group having 1 to: carbon atoms. Further, in the general formula (6), R 11 is an alkylene or alkylidene group having 1 to 20 carbon atoms. Furthermore, n in the above general formulas (5) and (6) is 1 to 3. ]
[0026] 上記一般式（5)または（6)で表される不飽和単量体としては、 p— [N, N ビス（トリ メチルシリル）ァミノ]スチレン、 p— [N, N ビス（トリメチルシリル）アミノメチル]スチレ ン、 p— {2— [N, N—ビス（トリメチルシリル）ァミノ]ェチル }スチレン、 m—[N, N ビ ス（トリメチルシリル）ァミノ]スチレン、 ρ— (N—メチル—N トリメチルシリルァミノ）ス チレン、 p— (N—メチルー N トリメチルシリルアミノメチル)スチレンなどが挙げられ る。  As unsaturated monomers represented by the above general formula (5) or (6), p- [N, N bis (trimethylsilyl) amino] styrene, p- [N, N bis (trimethylsilyl) Aminomethyl] styrene, p- {2- (N, N-bis (trimethylsilyl) amino} ethyl} styrene, m- [N, N bis (trimethylsilyl) amino] styrene, 、-(N-methyl-N trimethylsilyl) And mino) styrene, p- (N-methyl-N-trimethylsilylaminomethyl) styrene and the like.
一般式（5)または（6)で表される不飽和単量体の使用量は、有機アルカリ金属由 来の活性点のモル数に対して 0. 01〜： L00倍モル、好ましくは 0. 01〜10倍モル、 特に好ましくは 1. 0〜3. 0倍モルの割合で添加する。  The amount of use of the unsaturated monomer represented by the general formula (5) or (6) is from 0.01 to 1:00 mol, preferably 0. 00 mol, per mol of the organic alkali metal-derived active site. It is added in the proportion of 0.1 to 10 times mol, particularly preferably 1.0 to 3.0 times mol.
また、反応時間は、 1秒〜 2時間の範囲で行うのが好ましい。さらに、不飽和単量体 は、重合の開始時、重合途中、重合終了前、重合終了後などの任意の時に添加する ことができる。 The reaction time is preferably in the range of 1 second to 2 hours. Furthermore, unsaturated monomers Can be added at any time such as initiation of polymerization, during polymerization, before completion of polymerization, after completion of polymerization, and the like.
上記 (C)の方法で使用する共役ジェン、芳香族ビニル化合物および有機アルカリ 金属化合物は、上記 (a)の方法で使用するものが使用可能である。  As the conjugated diene, the aromatic vinyl compound and the organic alkali metal compound used in the above method (C), those used in the above method (a) can be used.
[0027] (d)の方法で使用する上記一般式（1)の化合物としては、 N—べンジリデンメチル ァミン、 N—べンジリデンェチルァミン、 N—べンジリデンプチルァミン、 N—べンジリ デンァ-リンなどが挙げられる。上記一般式（1)で表される化合物を上記共役ジェン 系重合体と反応させて変性する場合の使用量は特に限定がないが、通常、有機ァ ルカリ金属化合物由来の活性点のモル数に対し 0. 2〜3倍モル、好ましくは 0. 3〜1 . 5倍モル、さらに好ましくは 0. 4〜1. 3倍モルの割合で添加する。 Examples of the compound of the above general formula (1) used in the method (d) include N-benzylidenemethylamine, N-benzylideneethylamine, N-benzylidenebutyramine, N-beta Nydridener can be mentioned. The amount of the compound represented by the above general formula (1) to be reacted with the above-mentioned conjugated diene polymer to be modified is not particularly limited, but usually the molar amount of the active site derived from the organic alkali metal compound is The amount is 0.2 to 2 times by mole, preferably 0.3 to 1.5 times by mole, and more preferably 0.4 to 1.3 times by mole.
[0028] 得られる変性共役ジェン系重合体中のアミノ基の含量は、通常、 0. 0001~ 5mm ol/g、好ましくは、 0. 001〜： Lmmol/g、さらに好ましくは、 0. 003〜0. lmmol Zgである。なお、ァミノ基の位置は特に限定はなぐ重合体鎖末端に存在してもよく 、側鎖に存在してもよい。アミノ基は、第 1級ァミノ基および/または第 2級ァミノ基が 好ましい。 The content of the amino group in the modified conjugated diene polymer to be obtained is usually 0.2 to 5 mmol / g, preferably 0.001 to: L mmol / g, more preferably 0.003 to 0. 0. 1 mmol Zg. The position of the amino group may be present at the end of the polymer chain without particular limitation, and may be present at the side chain. The amino group is preferably a primary amino group and / or a secondary amino group.
なお、上記 (d)の方法で使用する共役ジェン、芳香族ビニル化合物および有機ァ ルカリ金属化合物は、上記 (a)の方法で使用するものが使用可能である。  As the conjugated diene, the aromatic vinyl compound and the organic alkali metal compound used in the above method (d), those used in the above method (a) can be used.
[0029] 本発明の熱可塑性榭脂組成物に用いられるアルコキシシリル基とアミノ基を有する 変性共役ジェン系重合体の製法は特に限定はないが、例えば以下に示す (f)〜(h) の方法により容易に得ることができる。 The method for producing the modified conjugated diene-based polymer having an alkoxysilyl group and an amino group, which is used for the thermoplastic resin composition of the present invention, is not particularly limited, but for example, the following (f) to (h) It can be easily obtained by the method.
(f)上記共役ジェンと上記芳香族ビ-ルイ匕合物を、上記アミノ基を有する有機アル カリ金属化合物の存在下で重合し、得られた共役ジェン系重合体に上記一般式 (2) で表される化合物を反応させた変性重合体とすることにより製造される。  (f) The conjugated diene polymer obtained by polymerizing the conjugated diene and the aromatic vinyl compound in the presence of the organic alkali metal compound having the amino group is represented by the general formula (2) It is manufactured by setting it as the modified polymer with which the compound represented by these was made to react.
(g)上記共役ジェンと上記アミノ基を有する不飽和単量体と上記芳香族ビ-ルイ匕合 物とを上記有機アルカリ金属化合物の存在下で重合し、得られた共役ジェン系重合 体に上記一般式 (2)で表される化合物を反応させた変性重合体とすることにより製造 される。  (g) A conjugated diene-based polymer obtained by polymerizing the above-mentioned conjugated diene, the above-mentioned unsaturated monomer having an amino group, and the above-mentioned aromatic bi-Louisinated compound in the presence of the above-mentioned organic alkali metal compound. It is manufactured by setting it as the modified polymer which made the compound represented by the said General formula (2) react.
(h)上記共役ジェンと上記芳香族ビ-ルイ匕合物を上記有機アルカリ金属化合物の 存在下で重合し、得られた共役ジェン系重合体に下記一般式（7)で表される化合物 を反応させた変性重合体とすることにより製造される。 (h) the conjugated diene and the aromatic bi-Louisium compound, It manufactures by making it the modified | denatured polymer which made the compound represented by following General formula (7) react with the conjugated-gene polymer which superposed | polymerized in presence and was obtained.
R12 Si (OR13) Z …… (7) R 12 Si (OR 13 ) Z ...... (7)
(4-p-q) p q  (4-p-q) p q
[式中、 R12は炭素数 1〜20のアルキル基、炭素数 6〜20のァリール基、炭素数 7〜 20のァラルキル基または炭素数 1〜： L00のオルガノシロキシ基であり、 R12が複数あ る場合は、各 R12は同じ基でも異なる基でもよい。 R13は炭素数 1〜20のアルキル基、 炭素数 6〜20のァリール基、炭素数 7〜20のァラルキル基であり、 R13が複数ある場 合は、各 R13は同じ基でも異なる基でもよい。 Zは N原子を含む極性基を有する置換 基であり、 Zが複数ある場合は、各 Zは同じ基でも異なる基でもよぐまた、各 Zは独立 の置換基でも環状構造を形成していてもよい。 Pは 1、 2または 3であり、 qは 1、 2また は 3の整数を示す。 pと qの和は 1〜4である。特に pは 2または 3で、 qは 1が好ましい。 ] Wherein, R 12 is an alkyl group, Ariru group having 6 to 20 carbon atoms, 1 to Ararukiru group or the number of carbon atoms in the carbon number 7-20 having 1 to 20 carbon atoms: a L00 organosiloxy group, R 12 is When there are two or more, each R 12 may be the same or different. R 13 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of R 13 groups, each R 13 may be the same or different groups May be. Z is a substituent having a polar group containing an N atom, and when there are a plurality of Z, each Z may be the same group or a different group, and each Z may form a cyclic structure even with an independent substituent. It is also good. P is 1, 2 or 3 and q is an integer of 1, 2 or 3. The sum of p and q is 1 to 4. In particular, p is preferably 2 or 3, and q is 1. ]
上記一般式（7)で表されるアルコキシシラン化合物としては、 N, N—ビス（トリメチ ルシリル）ァミノプロピルトリメトキシシラン、 N, N ビス（トリメチルシリル）ァミノプロピ ルトリエトキシシラン、 N, N ビス（トリメチルシリル）ァミノプロピルジメチルエトキシシ ラン、 N, N ビス（トリメチルシリル）ァミノプロピルジメチルメトキシシラン、 N, N ビ ス（トリメチルシリル）ァミノプロピルメチルジェトキシシラン、 N, N ビス（トリメチルシリ ル）ァミノプロピルメチルジメトキシシラン、 N, N ビス（トリメチルシリル）アミノエチル トリメトキシシラン、 N, N ビス（トリメチルシリル）アミノエチルトリエトキシシラン、 N, N —ビス（トリメチルシリル）アミノエチルジメチルエトキシシラン、 N, N ビス（トリメチル シリル）アミノエチルジメチルメトキシシラン、 N, N ビス（トリメチルシリル）アミノエチ ルメチルジェトキシシラン、 N, N ビス（トリメチルシリル）アミノエチルメチルジメトキ シシラン、 N—メチル N トリメチルシリルアミノプロピルトリメトキシシラン、 N—メチ ル一 N トリメチルシリルアミノプロピルトリエトキシシラン、 N -メチル N トリメチル シリルアミノプロピルジメチルエトキシシラン、 N—メチルー N トリメチルシリルアミノ プロピルジメチルメトキシシラン、 N—メチルー N トリメチルシリルアミノプロピルメチ ルジェトキシシラン、 N—メチルー N トリメチルシリルアミノプロピルメチルジメトキシ シラン、 N, N ジメチルァミノプロピルトリメトキシシラン、 N, N ジメチルァミノプロピ ルトリエトキシシラン、 N, N ジメチルァミノプロピルジメチルエトキシシラン、 N, N— ジメチルァミノプロピルジメチルメトキシシラン、 N, N ジメチルァミノプロピルメチル ジエトキシシラン、 N, N ジメチルァミノプロピルメチルジメトキシシラン、 N— (1, 3 ージメチルブチリデン） 3 （トリエトキシシリル） 1 プロパンァミン、 N— (1—メチ ルェチリデン）—3— (トリエトキシシリル）— 1—プロパンァミン、 N ェチリデン— 3— (トリエトキシシリル） 1 プロパンァミン、 N— (1 メチルプロピリデン） 3 （トリエ トキシシリル）— 1—プロパンァミン、 N— (4— N, N ジメチルァミノべンジリデン）—3 - (トリエトキシシリル）— 1—プロパンァミン、 N— (1, 3 ジメチルブチリデン）—3— (トリメトキシシリル）— 1—プロパンァミン、 N— (1—メチルェチリデン） - 3- (トリメトキ シシリル）一 1—プロパンァミン、 N ェチリデン一 3— (トリメトキシシリル）一 1—プロ パンァミン、 N— (1—メチルプロピリデン） 3 (トリメトキシシリル）一 1—プロパンァ ミン、 N— (4-N, N ジメチルァミノべンジリデン） 3— (トリメトキシシリル）一 1—プ 口パンァミン、 N— (1, 3 ジメチルブチリデン）ー3 （メチルジメトキシシリル） 1 プロパンァミン、 N— (1—メチルェチリデン） 3 （メチルジメトキシシリル） 1ープ 口パンァミン、 N ェチリデン— 3— (メチルジメトキシシリル）— 1—プロパンァミン、 N 一（1 メチルプロピリデン） 3 （メチルジメトキシシリル） 1 プロパンァミン、 N 4—N, N ジメチルァミノべンジリデン） 3 （メチルジメトキシシリル） 1 プロ パンァミン、 N— (1, 3 ジメチルブチリデン） 3 （メチルジェトキシシリル） 1 プロパンァミン、 N— (1—メチルェチリデン） 3 （メチルジェトキシシリル） 1ープ 口パンァミン、 N ェチリデン— 3— (メチルジェトキシシリル）— 1—プロパンァミン、 N 1 メチルプロピリデン） 3 （メチルジェトキシシリル） 1 プロパンァミン、 N 一（4—N, N ジメチルァミノべンジリデン） 3 （メチルジェトキシシリル） 1ープ 口パンァミン、 N— (1, 3 ジメチルブチリデン）—3 (ジメチルメトキシシリル）— 1— プロパンァミン、 N— (1—メチルェチリデン） 3 （ジメチルメトキシシリル） 1ープ 口パンァミン、 N ェチリデン— 3— (ジメチルメトキシシリル）— 1—プロパンァミン、 N - (1—メチルプロピリデン）—3 (ジメチルメトキシシリル）— 1—プロパンァミン、 N — (4— N, N ジメチルァミノべンジリデン）—3 (ジメチルメトキシシリル）— 1—プロ パンァミン、 N— (1, 3 ジメチルブチリデン） 3 （ジメチルエトキシシリル） 1 プロパンァミン、 N— ( 1—メチルェチリデン） 3 （ジメチルエトキシシリル） 1ープ 口パンァミン、 N ェチリデン— 3— (ジメチルエトキシシリル）— 1—プロパンァミン、 N 一（1 メチルプロピリデン） 3 （ジメチルエトキシシリル） 1 プロパンァミン、 N 一（4—N, N ジメチルァミノべンジリデン） 3 （ジメチルエトキシシリル） 1ープ 口パンァミンなどが挙げられる。 As the alkoxysilane compound represented by the above general formula (7), N, N-bis (trimethylsilyl) aminopropyltrimethoxysilane, N, N bis (trimethylsilyl) aminopropyltriethoxysilane, N, N bis (trimethylsilyl) ) Aminopropyldimethylethoxysilane, N, N bis (trimethylsilyl) aminopropyldimethylmethoxysilane, N, N bis (trimethylsilyl) aminopropylmethyl jetoxysilane, N, N bis (trimethylsilyl) amino Propylmethyldimethoxysilane, N, N bis (trimethylsilyl) aminoethyl trimethoxysilane, N, N bis (trimethylsilyl) aminoethyl triethoxysilane, N, N-bis (trimethylsilyl) aminoethyl dimethylethoxysilane, N, N bis ( Trimethyl silyl) Noethyldimethylmethoxysilane, N, N bis (trimethylsilyl) aminoethyl methyl jetoxysilane, N, N bis (trimethylsilyl) aminoethylmethyl dimethoxysilane, N-methyl N trimethylsilylaminopropyltrimethoxysilane, N-methyl N-trimethylsilylaminopropyltriethoxysilane, N-methyl-N-trimethylsilylaminopropyldimethylethoxysilane, N-methyl-N-trimethylsilylamino propyldimethylmethoxysilane, N-methyl-N-trimethylsilylaminopropylmethyljetoxysilane, N-methyl-N-trimethylsilylaminopropyl Methyldimethoxysilane, N, N dimethylaminopropyltrimethoxysilane, N, N dimethylaminopropyl Lutriethoxysilane, N, N dimethylaminopropyldimethylethoxysilane, N, N- dimethylaminopropyldimethylmethoxysilane, N, N dimethylaminopropylmethyl diethoxysilane, N, N dimethylaminopropylmethyldimethoxysilane, N-(1, 3-Dimethylbutylidene) 3 (triethoxysilyl) 1 propaneamine, N-(1-methylethylidene)-3-(triethoxysilyl)-1 -propaneamine, N ethylidene-3-(triethoxysilyl) 1) Propaneamine, N- (1 methyl propylidene) 3 (triethoxysilyl) 1-propaneamine, N-(4- N, N dimethylaminobenzylidene) 3-(triethoxysilyl) 1-propanamine, N-() 1,3 Dimethylbutylidene)-3-(trimethoxysilyl)-1-propanamine, N-(1 Methylethylidene)-3- (trimethoxysilyl) 1 -propaneamine, N-ethylidene 1-3- (trimethoxysilyl) 1-propanamine, N-(1-methylpropylidene) 3 (trimethoxysilyl) 1 -propaneamine , N- (4-N, N dimethylaminobenzylidene) 3- (trimethoxysilyl) 1-bis panamine, N-(1, 3 dimethylbutylidene)-3 (methyldimethoxysilyl) 1 propaneamine, N-( 1-methylethylidene) 3 (methyldimethoxysilyl) 1-port panamine, N ethylidene-3- (methyldimethoxysilyl) -1 -propanamine, N mono (1 methylpropylidene) 3 (methyldimethoxysilyl) 1 propanamine, N 4 —N, N Dimethylaminobenzylidene) 3 (Methyldimethoxysilyl) 1 Propanamine, N — (1, 3 Dimethyl) Butylidene) 3 (Methyl jetxyl silyl) 1 Propanphamine, N-(1-Methylethylidene) 3 (Methyl jetxyl silyl) 1 -P Panamide, N Ethylidene-3-(Methyl jetoxysilyl)-1-Propanamine, N 1 Methyl propylidene) 3 (Methyl jetoxy silyl) 1 Propanphamine, N (4-N, N Dimethyl amino benzylidene) 3 (Methyl jetoxy silyl) 1 -Pan panamine, N-(1, 3 Dimethyl butylidene)- 3 (dimethyl methoxy silyl)-1-propanphamine, N-(1- methyl ethylidene) 3 (dimethyl methoxy silyl) 1-port panamine, N ethylidene-3-(dimethyl methoxy silyl)-1-propanamine, N-(1- Methyl propylidene)-3 (Dimethyl methoxy silyl)-1-Propanamine, N-(4- N, N Roh base Njiriden) -3 (dimethylmethoxysilyl) - 1-pro Panamin, N-(1, 3-dimethyl-butylidene) 3 (dimethylethoxy silyl) 1 Propanphamine, N- (1-Methylethylidene) 3 (dimethylethoxysilyl) 1-p-panpanamine, N ethylidene- 3- (dimethylethoxysilyl) -1 -propanamine, N mono (1 methyl propylidene) 3 (dimethylethoxysilyl) 1 Propanphamine, N- (4-N, N-dimethylaminobenzylidene) 3 (dimethylethoxysilyl) 1-propane Panamine, etc. may be mentioned.
[0031] 得られる共役ジェン系重合体中のアルコキシシリル基とアミノ基との含量は、それぞ れ、通常、 0. 0001〜5mmolZg、好ましくは、 0. 001〜： LmmolZg、さらに好まし くは、 0. 003-0. ImmolZgである。なお、これらの基は、通常、重合体鎖末端に 存在するが、側鎖に存在してもよい。  The content of the alkoxysilyl group and the amino group in the conjugated diene polymer to be obtained is generally in the range of usually 0.000 to 5 mmol Zg, preferably 0.000 to 1: L mmol Zg, more preferably 0. 003-0. I mmol Zg. These groups are usually present at the end of the polymer chain but may be present at the side chain.
[0032] 次に、本発明の熱可塑性榭脂組成物に用いられる酸無水物基および Zまたは力 ルポキシル基を有する変性共役ジェン系重合体の製法は特に限定はな 、が、例え ば以下に示す (e)の方法により容易に得ることができる。  Next, the process for producing the modified conjugated diene-based polymer having an acid anhydride group and Z or a lupoxyl group to be used in the thermoplastic resin composition of the present invention is not particularly limited. It can be easily obtained by the method (e) shown.
(e)共役ジェンと芳香族ビニルイ匕合物を、有機アルカリ金属化合物の存在下で重 合し、得られた共役ジェン系重合体に、ケトンィ匕合物、エステルイ匕合物およびアルデ ヒド化合物の群力 選ばれた少なくとも 1種を反応させた後、酸無水物および Zまた は酸ハライドと反応させることにより容易に製造される。  (e) A conjugated diene, an esterified compound and an aldehyde compound are added to the conjugated conjugated polymer obtained by polymerizing conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound. The compound is easily prepared by reacting at least one selected group with an acid anhydride and Z or an acid halide.
[0033] 上記「ケトンィ匕合物」としては、その構造に限定はないが、例えばアセトン、ジェチル ケトン、 n—ブチルェチルケトン、ェチルアミルケトン、イソホロン、シクロへキサノン、シ クロペンタノン、メチルイソブチルケトン、メチルイソプロピルケトン、メチルシクロへキ サノン、 4ーァセトジフエニル、メチルェチルケトン、ベンゾフエノン、シクロへキシルフ ェニルケトン、 4 メチルベンゾフエノン、 4ーォクチルペンゾフエノン、プロピオフエノ ンなどが挙げられる。  The structure of the above “ketone complex” is not particularly limited, and examples thereof include acetone, jetyl ketone, n-butyl ethyl ketone, ethyl amyl ketone, isophorone, cyclohexanone, cyclopentanone, and methyl isobutyl. Ketones, methyl isopropyl ketone, methyl cyclohexanone, 4-acetodiphenyl, methyl ethyl ketone, benzophenone, cyclohexyl phenyl ketone, 4 methylbenzophenone, 4-octyl penphenone, propiophenone, etc. .
[0034] 上記「エステル化合物」としては、その構造に限定はな 、が、例えば酢酸ェチル、 酢酸メチル、酢酸プロピル、安息香酸メチル、トルィル酸メチル、安息香酸フエニル、 安息香酸ベンジル、 γ プチ口ラタトンなどが挙げられる。  The above-mentioned “ester compound” is not limited to the structure, but is, for example, ethyl acetate, methyl acetate, propyl acetate, methyl benzoate, methyl toluate, methyl benzoate, phenyl benzoate, benzyl benzoate, γ-petite ratatonate. Etc.
[0035] 上記「アルデヒドィ匕合物」としては、その構造に限定はな 、が、例えばホルムアルデ ヒド、ァセトアルデヒド、ブチルアルデヒド、 η—ォクチルアルデヒド、ベンズアルデヒド、 フタルアルデヒド、 a トリルアルデヒド、 o トルアルデヒド、クミンアルデヒド、 p トリ ルァセトアルデヒド、 4 イソプロピルべンズアルデヒド、アルデヒドピリジン、 α—ナフ トアルデヒド、フルフラールなどが挙げられる。 The above “aldehyde complex” is not limited to the structure thereof, and examples thereof include, but are not limited to, for example, formaldehyde, acetaldehyde, butyraldehyde, η-octylaldehyde, benzaldehyde, phthalaldehyde, a tolylaldehyde, o Tolualdehyde, cumin aldehyde, p-tri Rucetaldehyde, 4-isopropylbenzaldehyde, aldehydepyridine, α-naphthaldehyde, furfural and the like can be mentioned.
[0036] 上記ケトンィ匕合物、エステルイ匕合物およびアルデヒド化合物の使用量は合計で、有 機アルカリ金属化合物由来の活性点のモル数に対して、好ましくは、 0. 1〜2倍モル 、さらに好ましくは 0. 5〜1. 3倍モルである。  The total amount of the above ketone complex, ester complex and aldehyde compound used is preferably 0.1 to 2 moles, relative to the number of moles of the active point derived from the organic alkali metal compound, More preferably, it is 0.5 to 1. 3-fold moles.
[0037] 上記「酸無水物」としては、その構造に限定はないが、例えば無水プロピオン酸、無 水ラタ酸、無水カプロン酸、無水マレイン酸、無水フタル酸、 3—メチル無水フタル酸 、 4 メチル無水フタル酸、シス一へキサヒドロ無水フタル酸、トランス一へキサヒドロ 無水フタル酸、へキサヒドロー 4 メチル無水フタル酸、シス 1, 2, 3, 6—テトラヒド 口無水フタル酸、 1, 2, 4 ベンゼントリカルボン酸無水物、ピロメリット酸二無水物な どが挙げられる。  The above “acid anhydride” is not particularly limited in its structure, but is, for example, propionic acid anhydride, anhydrous acetic acid latanoic acid, caproic acid anhydride, maleic acid anhydride, phthalic acid anhydride, 3-methyl phthalic acid anhydride, Methyl phthalic anhydride, cis-hexahydrophthalic anhydride, trans-hexahydrophthalic anhydride, hexahydro-4 methyl phthalic anhydride, cis 1,2,3,6-tetrahydric phthalic anhydride, 1,2,4 benzene Examples thereof include tricarboxylic acid anhydride and pyromellitic acid dianhydride.
上記「酸ハライド」としては、その構造に限定はないが、例えばベンゼンジカルボン 酸クロライド、フタル酸クロライド、イソフタル酸ジクロライド、トリメリト酸トリクロライドなど が挙げられる。  The above-mentioned "acid halide" is not limited in its structure, but includes, for example, benzenedicarboxylic acid chloride, phthalic acid chloride, isophthalic acid dichloride, trimellitic acid trichloride and the like.
また、酸無水物と酸ハライドの両方を有する化合物としては、その構造に限定はな いが、例えば無水トリメリト酸クロライドなどが挙げられる。  Further, the compound having both an acid anhydride and an acid halide is not limited to the structure, and examples thereof include trimellitic anhydride chloride.
[0038] 上記酸無水物および Ζまたは酸クロリドの使用量は、有機アルカリ金属化合物由来 の活性点のモル数に対して、合計で、好ましくは、 0. 05〜5倍モル、さらに好ましく は 0. 1〜1. 5倍モルである。 The amount of the above acid anhydride and お よ び or acid chloride to be used is, in total, preferably 0.05 to 5 moles, more preferably 0 moles, relative to the number of moles of the active point derived from the organic alkali metal compound. 1 to 1.5 times the molar amount.
[0039] 得られる共役ジェン系重合体中の酸無水物基および Ζまたはカルボキシル基の含 量は、通常、合計で、 0. 0001〜5mmolZg、好ましくは、 0. 001〜： LmmolZg、さ らに好ましくは、 0. 003〜0. lmmol/gである。 The total content of the acid anhydride group and the カ ル ボ キ シ ル or carboxyl group in the conjugated diene polymer to be obtained is usually, in total, from 0. 0001 to 5 mmol Zg, preferably from 0.0001 to: L mmol Zg, and further Preferably, it is 0.0003 to 0.1 mmol / g.
また、上記 (e)の方法で使用する共役ジェン、芳香族ビニル化合物および有機ァ ルカリ金属化合物は、上記 (a)の方法で使用するものが使用可能である。  In addition, as the conjugated diene, the aromatic vinyl compound and the organic alkali metal compound used in the above method (e), those used in the above method (a) can be used.
[0040] (ィ）アルコキシシリル基、アミノ基、酸無水物基、およびカルボキシル基の群力も選 ばれた少なくとも 1種の基を有する変性共役ジェン系重合体は、その他の成分と配 合するためペレットやクラムが好ましい。そのため、以下の (A)、 （B)および (C)の重 合体ブロックの中力 選ばれた 1以上の重合体ブロックを含むブロック共重合体が好 ましい。 (I) The modified conjugated diene-based polymer having at least one group selected from among alkoxysilyl group, amino group, acid anhydride group, and carboxyl group is selected to be combined with other components. Pellets and crumbs are preferred. Therefore, block copolymers containing one or more selected polymer blocks are preferred, with moderate strength of the following polymer blocks of (A), (B) and (C): I'm sorry.
(A)芳香族ビ-ルイ匕合物が 80重量％以上である芳香族ビニル化合物重合体プロ ック  (A) Aromatic vinyl compound polymer block containing 80% by weight or more of aromatic vinyl compound
(B)共役ジェン重合体ブロック  (B) Conjugated Gen-polymer Block
(C)芳香族ビ-ルイ匕合物と共役ジェンのランダム共重合体ブロック  (C) A random copolymer block of an aromatic bi-Louis compound and a conjugated diene
[0041] 上記 (C)のランダム共重合体ブロックにお 、ては、芳香族ビニル化合物含量が連 続的に一分子中で変化するいわゆるテーパータイプも含まれて良い。  The random copolymer block of (C) may also include a so-called tapered type in which the content of the aromatic vinyl compound changes continuously in one molecule.
また、上記「 (A)と、 (B)および (C)の重合体ブロックの中力 選ばれた 1以上の重 合体ブロックを含むブロック共重合体」の例としては、（A)— (B)、 (A)一（C)、 [ (A) - (B) ] Y，、 [ (A) - (C) ] Y，、 (A) - (B)— (Α)ゝ (A) - (C)— (A)、 [ (A) - (B) (C) ] Y' , [ (A) - (B) - (A) ] Y' , [ (A) - (C) - (A) ] Y'、 (A) - (B) - (A) - (B)、 (B)― (A)― (B)― (A)、 (A)― (C)― (A)― (C)、 (C)― (A)― (C)― (A ) , (A) - (B) - (C) - (A)などが挙げられる（ただし、 xは 2〜8の整数であり、 Y'は カップリング剤の残基である)。  In addition, examples of the above-mentioned “block copolymer containing one or more selected polymer blocks of medium power of (A), and (B) and (C) polymer blocks” include (A) — (B ), (A) Ichi (C), [(A)-(B)] Y ,, [(A)-(C)] Y ,, (A)-(B) — (Α) ゝ (A)- (C)-(A), [(A)-(B) (C)] Y ', [(A)-(B)-(A)] Y', [(A)-(C)-(A) ] Y ', (A)-(B)-(A)-(B), (B)-(A)-(B)-(A), (A)-(C)-(A)-( C), (C)-(A)-(C)-(A), (A)-(B)-(C)-(A), etc. (where x is an integer from 2 to 8 and , Y 'is the residue of the coupling agent).
ペレット形状にする場合は、変性共役ジェン系重合体の外側のブロック成分として 少なくとも 1つ以上の (A)重合体ブロックを含むことが好ましい。  When forming into a pellet form, it is preferable to include at least one or more (A) polymer blocks as an outer block component of the modified conjugated diene-based polymer.
[0042] また、上記 (a)で使用される不活性有機溶媒としては、脂肪族、脂環式、アルキル 置換脂環式、芳香族およびアルキル置換芳香族の炭化水素、エーテルおよびそれ らの混合物が挙げられる。具体的には、脂肪族炭化水素 (例えば、ブタン、ペンタン、 へキサン、ヘプタンなど）、脂環式炭化水素（例えば、シクロペンタン、シクロへキサン 、シクロヘプタンなど）、アルキル置換脂環式炭化水素（例えば、メチルシクロへキサ ン、メチルシクロヘプタンなど）、芳香族炭化水素（例えば、ベンゼン）、アルキル置換 芳香族炭化水素（例えば、トルエン、キシレンなど）、ならびにエーテル (例えば、テト ラヒドロフラン、ジェチルエーテル、ジー n—ブチルエーテルなど）が含まれる。  In addition, as the inert organic solvent used in the above (a), aliphatic, alicyclic, alkyl-substituted alicyclic, aromatic and alkyl-substituted aromatic hydrocarbon, ether and mixtures thereof Can be mentioned. Specifically, aliphatic hydrocarbons (eg, butane, pentane, hexane, heptane etc.), alicyclic hydrocarbons (eg, cyclopentane, cyclohexane, cycloheptane etc.), alkyl substituted alicyclic hydrocarbons (Eg, methylcyclohexene, methylcycloheptane, etc.), aromatic hydrocarbons (eg, benzene), alkyl-substituted aromatic hydrocarbons (eg, toluene, xylene, etc.), and ethers (eg, tetrahydrofuran, jetyl ether) , N-butyl ether etc.).
[0043] また、上記「共役ジェン系重合体」における上記「共役ジェン」および上記「芳香族 ビ-ルイ匕合物」の組成比については特に限定はないが、通常、共役ジェン 5〜99重 量％と芳香族ビニル化合物 95〜1重量％、好ましくは 5〜95重量％と 95〜5重量％ 、さらに好ましくは共役ジェン 30〜92重量％と芳香族ビ-ルイ匕合物 70〜8重量。 /0、 最も好ましくは共役ジェン 40〜80重量％と芳香族ビ-ルイ匕合物 60〜20重量％ (た だし、共役ジェン +芳香族ビニルイ匕合物 = 100重量％)の範囲とすることができる。 上記「共役ジェン系重合体」の共役ジェンのビニル結合含有量は 80重量％未満、 好ましくは 3〜60重量％、さらに好ましくは 5〜55重量％である。 There are no particular restrictions on the composition ratio of the above “conjugated gen” and the above “aromatic bi-phenylene compound” in the above “conjugated gen-based polymer”, but usually the conjugated gen 5 to 99 % And an aromatic vinyl compound 95 to 1% by weight, preferably 5 to 95% by weight and 95 to 5% by weight, more preferably 30 to 92% by weight of a conjugated diene and an aromatic vinyl compound 70 to 8% . / 0 , Most preferably, it can be in the range of 40 to 80% by weight of conjugated diene and 60 to 20% by weight of aromatic bi-Louis compound (but, conjugated gen + aromatic vinyl compound = 100% by weight). The vinyl bond content of the conjugated diene of the above "conjugated diene polymer" is less than 80% by weight, preferably 3 to 60% by weight, more preferably 5 to 55% by weight.
ビニル結合含有量を調節するのに、通常、エーテル類、第 3級ァミン類、アルカリ金 属アルコキシドなどの極性ィ匕合物を使用することができる。 For adjusting the vinyl bond content, typically, ethers, tertiary Amin acids, may be used polar I匕合of such alkali metals alkoxides.
例えば、ジェチルエーテル、エチレングリコールジメチルエーテル、プロピレングリコ ーノレジェチノレエーテノレ、プロピレングリコーノレェチノレプロピノレエーテノレ、テトラヒドロフ ラン、ジォキサン、 1, 2—ジメトキシベンゼン、トリエチノレアミン、 N, N, Ν' , Ν，一テト ラメチルエチレンジァミン、カリウム tert アミルォキシド、カリウム tert ブチル ォキシドなどが挙げられ、これらの化合物は単独または 2種以上の混合物として使用 できる。力かる極性ィ匕合物の使用量は、有機リチウム化合物 1モルに対して 300モル 以下、好ましくは 0〜： L00モルである。  For example, gethyl ether, ethylene glycol dimethyl ether, propylene glycol noreletino ree tenole, propylene glycono reetino repro pinore ene nore, tetrahydrofuran, dioxane, 1, 2-dimethoxybenzene, triethinoleamine, N And N, Ν ', Ν, tetraethyl ethylenediamine, potassium tert amyl oxide, potassium tert butyl oxide and the like, and these compounds can be used alone or as a mixture of two or more. The amount of the polar compound to be used is 300 mol or less, preferably 0 to L00 mol, per 1 mol of the organic lithium compound.
[0044] 上記ブロック共重合体には、必要であれば、カップリング剤も使用できる。カップリン グ剤としては、例えば、ハロゲンィ匕合物、エポキシィ匕合物、カルボニル化合物、ポリビ 二ルイ匕合物などが挙げられ、具体的には、例えばメチルジクロロシラン、メチルトリクロ ロシラン、ブチルトリクロロシラン、テトラクロロシラン、ジブロモェタン、ビスフエノール Aジグリシジルエーテル、ビスフエノール Fジグリシジルエーテル、エポキシ化大豆油 、ジビュルベンゼン、テトラクロ口錫、ブチルトリクロ口錫、テトラクロ口ゲルマニウム、ビ ス（トリクロロシリル）ェタン、アジピン酸ジェチル、アジピン酸ジメチル、ジメチルテレフ タル酸、ジェチルテレフタル酸、ポリイソシァネートなどが挙げられる。 [0044] A coupling agent can also be used for the above block copolymer, if necessary. As the coupling agent, for example, halogen compound, epoxy compound, carbonyl compound, polyvinyl compound and the like can be mentioned, and specifically, for example, methyldichlorosilane, methyltrichlorosilane, butyltrichlorosilane , Tetrachlorosilane, dibromoethene, bisphenol A diglycidyl ether, bis phenol F diglycidyl ether, epoxidized soybean oil, dibutyl benzene, tetrachloro tin, butyl trichloro tin, tetra black germanium, bis (trichlorosilyl) atane, Examples thereof include jetyl adipate, dimethyl adipate, dimethylterephtalic acid, jetylterephthalic acid, and polyisocyanate.
[0045] 得られた (ィ)変性共役ジェン系重合体は、必要に応じて触媒の残渣を除去し、ま たはフエノール系またはァミン系の老化防止剤を添加し、その後、変性共役ジェン系 重合体溶液力 変性共役ジェン系重合体を単離する。変性共役ジェン系重合体の 単離は、例えば、変性共役ジェン系重合体溶液にアセトンまたはアルコールなどを 加えて沈殿させる方法、変性共役ジェン系重合体溶液を熱湯中に撹拌下投入し溶 媒を蒸留除去する方法、変性共役ジェン系重合体溶液をベント付押し出し機にて溶 媒を蒸留除去する方法などにより行うことができる。本発明に用いられる (ィ)アルコキ シシリル基、アミノ基、酸無水物基、カルボキシル基の少なくとも 1種類の基を有する 変性共役ジェン系重合体の分子量は特に限定されな 、が、 GPC法におけるポリス チレン換算による重量平均分子量で 3万〜 200万、好ましくは 4万〜 100万、さらに 好ましくは 5万〜 50万である。 [0045] The resulting modified (ii) modified conjugated polymer is, if necessary, removed from the catalyst residue, or a phenolic or amine anti-aging agent is added, and then the modified conjugated diene polymer is removed. Polymer solution force The modified conjugated diene polymer is isolated. For example, acetone or alcohol is added to the solution of the modified conjugated diene polymer to precipitate it, and the solution of the modified conjugated diene polymer is poured into hot water under stirring and the solvent is isolated. It can be carried out by a method of distilling and removing, or a method of distilling and removing the solvent of the modified conjugated diene polymer solution using a vented extruder. (I) Alkoki used in the present invention The molecular weight of the modified conjugated diene-based polymer having at least one of a silyl group, an amino group, an acid anhydride group and a carboxyl group is not particularly limited, but it is 30,000 in weight average molecular weight by polystyrene conversion in GPC method. -2,000,000, preferably 40,000 to 1,000,000, more preferably 50,000 to 500,000.
(口）耐衝撃性ゴム変性スチレン系重合体  (Mouth) impact resistance rubber modified styrenic polymer
本発明の熱可塑性榭脂組成物に使用する（口)耐衝撃性ゴム変性スチレン系重合 体は、スチレン系単量体もしくはこれと共重合可能なモノマーとエラストマ一との混合 物を重合することにより得られ、重合方法としては懸濁重合、乳化重合、塊状重合、 塊状 懸濁重合などが一般に行われている。  The impact-modified rubber-modified styrenic polymer used in the thermoplastic resin composition of the present invention comprises polymerizing a styrenic monomer or a mixture of a monomer copolymerizable therewith with the elastomer. As a polymerization method, suspension polymerization, emulsion polymerization, bulk polymerization, bulk suspension polymerization and the like are generally performed.
ここで、スチレン系単量体としては、スチレン、 tert ブチルスチレン、 α—メチルス チレン、 ρ—メチノレスチレン、 ρ ェチルスチレン、 1, 1ージフエニルスチレン、 Ν, Ν ジェチルー ρ—アミノエチルスチレンなどが挙げられる。  Here, as the styrene-based monomer, styrene, tert-butylstyrene, α-methylstyrene, ρ-methinolestyrene, ェ -ethylstyrene, 1,1-diphenylstyrene, Ν, Ν-gethyl-ρ-aminoethylstyrene, etc. It can be mentioned.
また、スチレン系単量体と共重合可能なモノマーとしては、アクリロニトリル、アクリル 酸エステル、メタクリル酸エステル、無水マレイン酸などが挙げられる。また、エラスト マーとしては、天然ゴム、合成イソプレンゴム、ブタジエンゴム、スチレン ブタジエン ゴム、ノ、イスチレンゴム、ポリブタジエン榭脂、クロロプレンゴム、ポリブテンゴム、ゴム 状エチレン プロピレン共重合体、ゴム状ブタジエン—アクリロニトリル共重合体、ブ チルゴム、各種-トリル系ゴム、ゴム状エチレン 酢酸ビュル共重合体、ゴム状ェチ レン アクリル酸エステル共重合体、ゴム状ァタクチックポリプロピレン榭脂、ゴム状ェ チレン アクリル酸アイオノマーなどが使用される。  Further, as a monomer copolymerizable with the styrenic monomer, acrylonitrile, acrylic ester, methacrylic ester, maleic anhydride and the like can be mentioned. In addition, as an elastomer, natural rubber, synthetic isoprene rubber, butadiene rubber, styrene butadiene rubber, 、, ス チ レ ン styrene rubber, polybutadiene resin, chloroprene rubber, polybutene rubber, rubber-like ethylene-propylene copolymer, rubber-like butadiene-acrylonitrile co-weight Combination, butyl rubber, various-tolyl rubber, rubbery ethylene-acetate-acetate copolymer, rubbery ethylene-acrylic acid ester copolymer, rubbery atactic polypropylene resin, rubbery ethylene-acrylic acid ionomer, etc. used.
特に好まし 、耐衝撃性ゴム変性スチレン系重合体としては、耐衝撃性ゴム変性スチ レン重合体、アクリロニトリル—ブタジエン—スチレン共重合体、アクリル酸エステル— ブタジエン スチレン共重合体、メタクリル酸エステル ブタジエン スチレン共重合 体、耐衝撃性ゴム変性スチレン 無水マレイン酸共重合体などが挙げられ、これらは 単独もしくは二種以上の混合物として使用することもできる。  Particularly preferred as the impact-resistant rubber-modified styrene-based polymer, an impact-resistant rubber-modified styrene polymer, an acrylonitrile-butadiene-styrene copolymer, an acrylic ester-butadiene styrene copolymer, a methacrylic ester butadiene styrene Copolymers, impact-resistant rubber-modified styrene-maleic anhydride copolymers, etc. may be mentioned, and they may be used alone or in combination of two or more.
なお、（口)耐衝撃性ゴム変性スチレン系重合体における「耐衝撃性」とは、当該重 合体自体を ICトレーやエンボスキャリアテープに使用した場合、輸送時の衝撃や落 下に耐え得ることをいう。 また、本発明の熱可塑性榭脂組成物において、（口）耐衝撃性ゴム変性スチレン系 重合体を添加しない場合でも、耐衝撃性と剛性のバランスは良好である力 該（口)成 分を加えることで、経済的にさらに耐衝撃性と剛性のバランスを向上させることができ る。 The “impact resistance” of the (mouth) impact resistant rubber-modified styrenic polymer means that when the polymer itself is used as an IC tray or an embossed carrier tape, it can withstand impact or drop during transportation. Say Further, in the thermoplastic resin composition of the present invention, the balance between the impact resistance and the rigidity is good even when the (mouth) impact-resistant rubber-modified styrenic polymer is not added. By adding it, it is possible to further improve the balance between impact resistance and rigidity economically.
[0047] (ハ)非ゴム変性スチレン系重合体  (C) Non-Rubber Modified Styrene Polymer
本発明の熱可塑性榭脂組成物に使用する (ハ)非ゴム変性スチレン系重合体は、 ( 口）耐衝撃性ゴム変性スチレン系重合体およびスチレン系熱可塑性エラストマ一以外 のスチレン系重合体であり、エラストマ一の非存在下、スチレン系単量体もしくはこれ と共重合可能なモノマーを重合することにより得られるものである。スチレン系単量体 と共重合可能なモノマーとしてはアクリロニトリル、アクリル酸エステル、メタクリル酸ェ ステル、無水マレイン酸などが挙げられる。  (C) The non-rubber-modified styrenic polymer used in the thermoplastic resin composition of the present invention is a (mouth) impact resistant rubber-modified styrenic polymer and a styrenic polymer other than styrenic thermoplastic elastomers. They are obtained by polymerizing styrenic monomers or monomers copolymerizable therewith in the absence of an elastomer. Examples of the monomer copolymerizable with the styrenic monomer include acrylonitrile, acrylic ester, methacrylic ester, and maleic anhydride.
特に好ましい非ゴム変性スチレン系重合体としては、ポリスチレン、スチレン OL メチルスチレン共重合体、アクリロニトリル—スチレン共重合体、アクリロニトリル—メタ クリル酸エステルースチレン共重合体などが挙げられ、これらは単独もしくは二種以 上の混合物として使用することができる。  Particularly preferable non-rubber-modified styrene polymers include polystyrene, styrene OL methyl styrene copolymer, acrylonitrile-styrene copolymer, acrylonitrile-methacrylic acid ester-styrene copolymer, etc. It can be used as a mixture of species and more.
[0048] (二）導電性カーボン  (2) Conductive Carbon
(二）導電性カーボンとして、ファーネスブラック、チャンネルブラック、ガスブラック、 アセチレンブラック、アークブラック、ケッチェンブラックなどの導電性カーボンブラック を用いることで導電性が向上する。中でも、比表面積が大きぐ導電性に優れたファ 一ネスブラック、ケッチェンブラック、特にケッチェンブラックが好ましい。さらに、これら の導電性カーボンブラックを組み合わせた導電性複合カーボンブラックでもよヽ。導 電性カーボンブラックの比表面積としては、 100〜l,500m2Zg、特に 500〜1,500 m2Zg程度が好ましい。導電性カーボンブラックの巿販時の平均粒径は、（ィ)成分 の割合と密接な関係を有し、一概には規定できないが、通常、 1ηπι〜10 /ζ πι、好ま しくは 5nm〜l μ m、さらに好ましくは 10〜100nm程度である。 (2) The conductivity is improved by using conductive carbon black such as furnace black, channel black, gas black, acetylene black, arc black, ketjen black as the conductive carbon. Among them, fineness black, ketjen black, and particularly ketjen black, which are excellent in conductivity and have a large specific surface area, are preferable. Furthermore, conductive composite carbon blacks combining these conductive carbon blacks may also be used. The specific surface area of conductive carbon black, 100~l, 500m 2 Zg, especially 500 to 1,500 m 2 about Zg are preferred. The average particle size of conductive carbon black at the time of sale has a close relationship with the ratio of (i) component, and can not be generally specified, but usually 1 ηπ ι 10/10 ζ π ι, preferably 5 nm to 1 More preferably, it is about 10 to 100 nm.
[0049] 熱可塑性榭脂組成物の (ィ）、（口）、（ハ）、（二)の配合割合は、（ィ）が 2. 5〜35重 量部、（口）が 0〜50重量部、（ハ）力 0〜90重量部、（二）が 1〜15重量部であり、好 ましくは (ィ）が 2. 5〜25重量部、（口）が 0〜45重量部、（ハ）が 50〜90重量部、（二 )が 2〜13重量部、さら好ましくは (ィ）が 2. 5〜20重量部、（口）が 0〜40重量部、（ ハ）が 50〜90重量部、（二）が 3〜13重量部 [ただし、（ィ） + (口） + (ハ） + (二） = 10 0重量部]である。 The blending proportions of (i), (mouth), (ha) and (2) of the thermoplastic resin composition are as follows: (i) is 2.5 to 35 parts by weight, and (o) is 0 to 50 Parts by weight, (ha) force 0 to 90 parts by weight, (2) 1 to 15 parts by weight, preferably (i) 2.5 to 25 parts by weight, (mouth) 0 to 45 parts by weight , (Ha) 50-90 parts by weight, (two 2) to 13 parts by weight, more preferably (i) 2.5 to 20 parts by weight, (mouth) 0 to 40 parts by weight, (c) 50 to 90 parts by weight, (2) 3 to 13 Parts by weight [However, (i) + (mouth) + (ha) + (2) = 100 parts by weight].
(ィ）が 2. 5重量部未満では耐衝撃性、低温特性、導電性に劣り、一方、 35重量部 を超えると流動性、剛性に劣る。（口）が 50重量部を超えるとコストパフォーマンス、剛 性に劣り、（ハ）が 40重量部未満ではコストパフォーマンス、剛性に劣り、一方、 90重 量部を超えると耐衝撃性に劣り、（二）が 1重量部未満では導電性に劣り、一方、 15 重量咅を超えるとコストノ フォーマンスに劣る。  If (b) is less than 2.5 parts by weight, impact resistance, low temperature properties and conductivity are poor, while if it exceeds 35 parts by weight, fluidity and rigidity are poor. If the (mouth) exceeds 50 parts by weight, cost performance and rigidity are poor, and if (ha) is less than 40 parts by weight, cost performance and rigidity are poor, while if it exceeds 90 parts by weight, impact resistance is poor If the amount is less than 1 part by weight, the conductivity is inferior, while if it exceeds 15 parts by weight, the cost performance is inferior.
[0050] <熱可塑性榭脂組成物の製造方法 >  <Method of Producing Thermoplastic Resin Composition>
本発明の熱可塑性榭脂組成物は、従来公知のあらゆる配合方法によって製造する ことができる。例えば、オープンロール、インテンシブミキサー、インターナルミキサー 、コニーダー、 2軸ローター付きの連続混練機、 1軸押出機、 2軸押出機などの一般 的な混和機を用いた溶融混練方法、各成分を溶剤に溶解または分散混合後溶剤を 加熱除去する方法が用いられる。  The thermoplastic resin composition of the present invention can be produced by any conventionally known compounding method. For example, melt-kneading method using a general mixing machine such as open roll, intensive mixer, internal mixer, co-kneader, continuous kneader with twin-screw rotor, single-screw extruder, twin-screw extruder, etc. After dissolution or dispersal mixing, the method of heating and removing the solvent is used.
[0051] 本発明の熱可塑性榭脂組成物は、従来公知の方法、例えば、押出成形、射出成 形、二色射出成形、サンドイッチ成形、中空成形、圧縮成形、真空成形、回転成形、 パウダースラッシュ成形、蒸気発泡成形、積層成形、カレンダー成形、ブロー成形な どによって、実用上有用な成形品に加工することができる。また、必要に応じて、発泡 、粉末、延伸、接着、印刷、塗装、メツキなどの加工を施してもよい。  [0051] The thermoplastic resin composition of the present invention can be obtained by any known method, for example, extrusion molding, injection molding, two-color injection molding, sandwich molding, hollow molding, compression molding, vacuum molding, rotational molding, powder slush. It can be processed into a practically useful molded article by molding, steam foam molding, lamination molding, calendar molding, blow molding and the like. If necessary, processing such as foaming, drawing, drawing, bonding, printing, painting, and plating may be performed.
[0052] なお、本発明の熱可塑性榭脂組成物には、他のスチレン ブタジエン スチレン ブロック共重合体、スチレン イソプレン スチレンブロック共重合体を少量併用する ことができる。また、他の熱可塑性エラストマ一や熱可塑性榭脂、例えばエチレン— 酢酸ビュル共重合体、エチレン アクリル酸ェチル共重合体、ァタクチックポリプロピ レン、 1, 2—ポリブタジエン、あるいはエチレン プロピレンゴムなどの他の重合体を 併用することが可能である。この場合、あらかじめ本発明の熱可塑性榭脂組成物と上 記他の重合体とを、任意の割合で混練りしたのち、ペレツトイ匕およびまたは粉体ィ匕し て使用することもできる。  In the thermoplastic resin composition of the present invention, other styrene butadiene styrene block copolymer and styrene isoprene styrene block copolymer can be used together in a small amount. In addition, other thermoplastic elastomers and thermoplastic resins such as ethylene-butyl acetate copolymer, ethylene-acrylic acid ethyl acetate copolymer, atactic polypropylene, 1,2-polybutadiene, ethylene propylene rubber and the like It is possible to use the polymer of In this case, the thermoplastic resin composition of the present invention and the above-mentioned other polymer may be kneaded at an arbitrary ratio and then used as a pellet and / or powder.
さらに、本発明の熱可塑性榭脂組成物には、必要に応じて各種添加剤、例えば、 老化防止剤、熱安定剤、耐候剤、金属不活性剤、紫外線吸収剤、光安定剤、銅害 防止剤などの安定剤；防菌 ·防かび剤；分散剤；軟化剤；可塑剤；発泡剤；発泡助剤； 着色剤；フェライトなどの金属粉末；ガラス繊維；金属繊維などの無機繊維；炭素繊維 、ァラミド繊維などの有機繊維;複合繊維、チタン酸カリウムゥイスカーなどの無機ウイ スカー；ガラスビーズ、ガラスバルーン、ガラスフレーク、ハイド口タルサイト、カオリン、 けい藻土、グラフアイト、軽石、ェボ粉、コットンフロック、コルク粉、硫酸バリウム、フッ 素榭脂、ポリマービーズなどの充填剤またはこれらの混合物；ポリオレフインワックス、 セルロースパウダー、ゴム粉などの充填剤;低分子量ポリマーなどを廃合してもよ 、。 その他にもシリカ、タルク、炭酸カルシウム、導電性カーボン以外のカーボンブラック などの充填剤、架橋剤、水酸ィ匕マグネシウムなどの難燃剤などの添加剤を配合する こともできる。また、本発明の目的の達成を損なわない程度にゴム質重合体、熱可塑 性榭脂などを適宜配合してもよ ヽ。 Furthermore, various additives such as, for example, Stabilizers such as anti-aging agents, heat stabilizers, weathering agents, metal deactivators, ultraviolet light absorbers, light stabilizers, copper inhibitors, anti-fungal / anti-mold agents, dispersants, softeners, plasticizers, foams Coloring agent; metal powder such as ferrite; glass fiber; inorganic fiber such as metal fiber; carbon fiber, organic fiber such as aramid fiber; composite fiber, inorganic whisker such as potassium titanate whisker; Fillers such as glass beads, glass balloons, glass flakes, hyacinthtalcite, kaolin, diatomaceous earth, graphite, pumice, rubble powder, cotton flock, cork powder, barium sulfate, fluorine resin, polymer beads or Mixtures of these; fillers such as polyolefin wax, cellulose powder and rubber powder; low molecular weight polymers etc. may be scrapped. In addition, additives such as fillers such as silica, talc, calcium carbonate and carbon black other than conductive carbon, crosslinking agents, and flame retardants such as magnesium hydroxide can also be blended. In addition, a rubbery polymer, a thermoplastic resin and the like may be appropriately blended to such an extent that the achievement of the object of the present invention is not impaired.
[0053] 本発明の熱可塑性榭脂組成物は、薄膜状に成形することにより、導電性が付与さ れたフィルムおよびシートが得られる。  The thermoplastic resin composition of the present invention can be formed into a thin film to obtain films and sheets to which conductivity has been imparted.
ここで、フィルムおよびシートの成形条件としては、 T ダイ法等を用いた公知の成 型法を用いて、榭脂温度 180°C以上にて行う。また基材との多層成型を用いても成 形できる。  Here, as a forming condition of the film and the sheet, the resin temperature is set to 180 ° C. or more using a known forming method using a T-die method or the like. It can also be molded using multilayer molding with a substrate.
ここで、このようにして得られるフィルムおよびシートの厚さは、通常、 10〜1,000 m、好ましくは 50〜800 μ mである。  Here, the thickness of the film and sheet thus obtained is usually 10 to 1,000 m, preferably 50 to 800 μm.
得られる導電性フィルムおよびシートは、特に ICトレー、キャリアテープ (エンボスキ ャリアテープ）、 ICコンテナー、トップカバーテープ、電磁波シールドシートなどの用 途に有用である。  The conductive film and sheet thus obtained are particularly useful in applications such as IC trays, carrier tapes (embossed carrier tapes), IC containers, top cover tapes, electromagnetic wave shielding sheets and the like.
実施例  Example
[0054] 以下、実施例によって本発明をさらに具体的に説明するが、本発明はこれらの実施 例によって何ら制限を受けるものではない。なお、実施例、比較例中の部および％は 、特に断らない限り重量基準である。  Hereinafter, the present invention will be more specifically described by way of examples, but the present invention is not limited at all by these examples. In the examples and comparative examples, parts and% are by weight unless otherwise specified.
[0055] <変性共役ジェン系重合体の製造 >  <Production of Modified Conjugated Gen-Based Polymer>
以下に記載の 1)〜12)の方法により、変性共役ジェン系重合体を製造した。 なお、各種の測定は下記の方法に拠った。 A modified conjugated gen-based polymer was produced by the methods 1) to 12) described below. In addition, various measurement depended on the following method.
[0056] (i)ビュル結合（1, 2結合および 3, 4結合)含量  (I) Bull bond (1, 2 bond and 3, 4 bond) content
赤外吸収スペクトル法 (モレロ法）によって求めた。  It was determined by infrared absorption spectroscopy (Morero method).
(ii)結合スチレン含量  (ii) bound styrene content
赤外吸収スペクトル法により、検量線を作成し求めた。  A calibration curve was prepared and determined by infrared absorption spectroscopy.
(iii)重量平均分子量  (iii) Weight average molecular weight
ゲルパーミエーシヨンクロマトグラフィー（GPC) (東ソ一社製、 HLC— 8120)を用い てポリスチレン換算で求めた。  It was determined in terms of polystyrene using gel permeation chromatography (GPC) (manufactured by Tosoh Co., Ltd., HLC-8120).
(iv)カルボキシル基および酸無水物基含量（mmolZg)  (iv) Carboxyl group and acid anhydride group content (mmol Zg)
Macromol. synth. , 4, 9 (1972)記載の滴定法により求めた。  They were determined by the titration method described in Macromol. Synth., 4, 9 (1972).
すなわち、変性重合体を精製後、有機溶剤に溶解し、指示薬としてフエノールフタ レインを用い、溶液の色が無色から淡紅色に変化するまで、水酸化カリウム溶液で滴 定することにより求めた。  That is, after the modified polymer was purified, it was dissolved in an organic solvent, and phenolphthalein was used as an indicator, and it was determined by titration with a potassium hydroxide solution until the color of the solution changed from colorless to pink.
(V)ァノレコキシシリノレ基含量 (mmol/g)  (V) Ganolechixiliole group content (mmol / g)
赤外吸収スペクトルにより、変性化合物に存在する Si— OC H  According to the infrared absorption spectrum, Si-OC H present in the modified compound
6 5結合に起因する 1, 6 5 due to bonding 1,
250cm_1付近の吸収量により作成した検量線力も定量した。また、変性剤に存在す るアルコキシシリル基が Si— OCH、 Si— OC H、 Si— OC (CH ) (C H )結合の The calibration curve force created by the amount of absorption around 250 cm 1 was also quantified. In addition, the alkoxysilyl group present in the modifier is Si—OCH, Si—OC 2 H, Si—OC 2 (CH 2) 2 (CH 2) bond
3 2 5 3 2 2 5 場合は、 1, 100cm—1付近の吸収量により作成した検量線から定量した。ただし、定 量された値を GPC法で得られたポリスチレン換算数平均分子量 Mnと、アルコキシシ リル基の分子量で除して、アルコキシシリル基のモル数とした。 In the case of 3 2 5 3 2 2 5 5, it was quantified from a calibration curve prepared by the amount of absorption near 1,100 cm− 1 . However, the number of moles of alkoxysilyl group was defined by dividing the quantified value by the polystyrene equivalent number average molecular weight Mn obtained by the GPC method and the molecular weight of the alkoxysilyl group.
(vi)アミノ基含量 (mmolZg)  (vi) Amino group content (mmol Zg)
Analy. Chem. 564頁（1952)記載のアミン滴定法による定量により求めた。すな わち、変性重合体を精製後、有機溶剤に溶解し、指示薬としてメチルバイオレットを 用い、溶液の色が紫から水色に変化するまで、過塩素酸の酢酸溶液 (HCIO ZCH  It calculated | required by the quantification by the amine titration method of Analy. Chem. Page 564 (1952). That is, after the modified polymer is purified, it is dissolved in an organic solvent, methyl violet is used as an indicator, and the acetic acid solution of perchloric acid is used until the color of the solution changes from purple to light blue (HCIO ZCH
4 3 4 3
COOH)で滴定することにより求めた。 It was determined by titration with COOH).
[0057] 1)変性共役ジェン系重合体 (ィー 1)の製造 1) Production of Modified Conjugated Gen-Based Polymer (i)
窒素置換された内容積 100リットルの反応容器に、シクロへキサン 50kg、スチレン 2 . Okgおよび sec—ブチルリチウム 9. 5gをカ卩え、重合開始温度 50°Cにて 1段目重合 し、反応完結後、温度を 70°Cとして 1, 3 ブタジエン 5. 9kgを添カ卩して断熱にて 2 段目重合した。 30分後、スチレン 2. Okgを添加し 3段目重合し、反応完結後、 1, 3 —ブタジエン 0. 1kgを添カ卩してさらに 4段目重合を行った。この系内にメチルトリフエ ノキシシラン 43. Ogを加え、 30分反応させた。反応後、反応液を常温、常圧に戻して 反応容器より抜き出し、老化防止剤としてィルガノックス 1010を 100g添加後、水中 に撹拌投入して溶媒を水蒸気蒸留除去することによって、表 1に記す重合体 (ィー 1) を得た。得られた重合体 (ィ— 1)のアルコキシシリル基含量は 0. 0187mmol/gで めつに。 50 kg of cyclohexane, 2.O kg of styrene and 9.5 g of sec-butyllithium were charged in a nitrogen-substituted 100-liter reaction vessel, and the first polymerization was performed at a polymerization initiation temperature of 50 ° C. After completion of the reaction, the temperature was adjusted to 70.degree. C., and 5. 9 kg of 1,3-butadiene was added, and the second stage polymerization was conducted by heat insulation. Thirty minutes later, 2.O kg of styrene was added to carry out the third stage polymerization, and after completion of the reaction, 0.1 kg of 1,3-butadiene was added to carry out the fourth stage polymerization. Into this system, 43.Og of methyltriphenoxysilane was added and reacted for 30 minutes. After the reaction, the reaction solution is returned to normal temperature and normal pressure, taken out from the reaction vessel, 100 g of Irganox 1010 is added as an anti-aging agent, and stirred into water to remove the solvent by steam distillation. I got (Y 1). The content of alkoxysilyl group in the obtained polymer (i-1) was 0.187 mmol / g and was m.
また、重合体 (ヒ— 1)は、メチルトリフエノキシシランを使用しない以外は、重合体 (ィ 1)に準じて重合して得た未変性共役ジェン系重合体である。  Further, the polymer (Hy-1) is a non-modified conjugated diene-based polymer obtained by polymerizing according to the polymer (I) except that methyltriphenoxysilane is not used.
[0058] 2)変性共役ジェン系重合体 (ィ 2)の製造 2) Production of Modified Conjugated Polymer (2)
窒素置換された内容積 100リットルの反応容器に、シクロへキサン 50kg、スチレン 2 . 0kgおよび 3 リチォ 1 N, N ビス（トリメチルシリル）ァミノプロパン 31. lgを 加え、重合開始温度 50°Cにて 1段目重合し、反応完結後、温度を 70°Cとして 1, 3- ブタジエン 6. 0kgを添カ卩して断熱にて 2段目重合した。 30分後、スチレン 2. 0kgを 添加し 3段目重合を行った。反応後、反応溶液を常温、常圧に戻して反応容器より抜 き出し、次いで、（ィ— 1)と同様に、老化防止剤を添加後、反応溶液を水中に撹拌投 入して溶媒を水蒸気蒸留除去することによって、表 1に記す重合体 (ィ— 2)を得た。 得られた重合体 (ィ 2)のァミノ基含量は 0. 0092mmol/gであった。  50 kg of cyclohexane, 2.0 kg of styrene and 31. 1 g of 3 lithium 1N, N bis (trimethylsilyl) aminopropane are added to a reaction vessel with an internal volume of 100 liters purged with nitrogen, and one stage is established at a polymerization initiation temperature of 50 ° C. After completion of the reaction, the temperature was adjusted to 70 ° C., 6.0 kg of 1,3-butadiene was added, and the second stage polymerization was conducted by heat insulation. Thirty minutes later, 2.0 kg of styrene was added to carry out the third stage polymerization. After the reaction, the reaction solution is returned to normal temperature and normal pressure and removed from the reaction vessel, then, as in (I-1), after addition of an antioxidant, the reaction solution is stirred into water and the solvent is removed. Removal by steam distillation gave a polymer (II-2) described in Table 1. The amino group content of the obtained polymer (2) was 0. 0092 mmol / g.
[0059] 3)変性共役ジェン系重合体 (ィ 3)の製造 3) Production of Modified Conjugated Genic Polymer (3)
窒素置換された内容積 100リットルの反応容器に、シクロへキサン 50kg、スチレン 2 . 0kg、および 2, 2, 5, 5—テ卜ラメチル— 1— (3—リチォプロピル）— 1—ァザ— 2, 5 —ジシラシクロペンタンを 30. 8g加え、重合開始温度 50°Cにて 1段目重合し、反応 完結後、温度を 70°Cとして 1, 3 ブタジエン 6. 0kgを添加して断熱にて 2段目重合 した。 30分後、スチレン 2. 0kgを添加し 3段目重合を行った。反応後、反応溶液を常 温、常圧に戻して反応容器より抜き出し、次いで、（ィ—1)と同様に、老化防止剤を 添加後、反応溶液を水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、 表 1に記す重合体 (ィ— 3)を得た。得られた重合体 (ィ— 3)のァミノ基含量は 0. 009 5mmolZ gであった 0 In a 100-liter reaction vessel purged with nitrogen, 50 kg of cyclohexane, 2.0 kg of styrene, and 2, 2, 5, 5-tetramethyl-1-(3-lithiumpropyl)-1- 3,5 g of disilacyclopentane was added and the first stage polymerization was carried out at a polymerization initiation temperature of 50 ° C, and after completion of the reaction, the temperature was set to 70 ° C and 6.0 kg of 1,3-butadiene was added for heat insulation. The second stage polymerization took place. Thirty minutes later, 2.0 kg of styrene was added to carry out the third stage polymerization. After the reaction, the reaction solution is returned to normal temperature and pressure and withdrawn from the reaction vessel, and then, as in (I-1), after addition of an anti-aging agent, the reaction solution is stirred into water and steam distilled. By removing, a polymer (I-3) described in Table 1 was obtained. The amino group content of the obtained polymer (i-3) is 0. 009. 0 which was 5 mmol Z g
[0060] 4)変性共役ジェン系重合体 (ィー 4)の製造  4) Production of Modified Conjugated Polymer (4)
窒素置換された内容積 100リットルの反応容器に、シクロへキサン 50kg、スチレン 2 . Okgおよび sec ブチルリチウム 9. 5gをカ卩え、重合開始温度 50°Cにて 1段目重合 し、反応完結後、温度を 70°Cとして 1, 3 ブタジエン 6. Okgを添カ卩して断熱にて 2 段目重合した。 30分後、スチレン 2. Okgを添加し 3段目重合を行った。その後、該重 合体の活性点に P— {2— [N, N ビス（トリメチルシリル）ァミノ]ェチル }スチレン 86. 9gを加え、 30分反応させた。反応後、反応溶液を常温、常圧に戻して反応容器より 抜き出し、次いで、（ィ— 1)と同様に、老化防止剤を添加後、反応溶液を水中に撹拌 投入して溶媒を水蒸気蒸留除去することによって、表 1に記す重合体 (ィ— 4)を得た 。得られた重合体 (ィ— 4)のァミノ基含量は 0. 0254mmolZgであった。  50 kg of cyclohexane, 2.O kg of styrene and 9.5 g of sec-butyl lithium were charged in a nitrogen-substituted 100-liter reaction vessel, and the first step polymerization was carried out at a polymerization initiation temperature of 50 ° C to complete the reaction. After that, the temperature was adjusted to 70 ° C., and 6. O kg of 1,3-butadiene was added, and the second stage polymerization was performed by heat insulation. Thirty minutes later, 2.O kg of styrene was added to carry out the third stage polymerization. Thereafter, 86.9 g of P- {2- [N, N bis (trimethylsilyl) amino] ethyl} styrene was added to the active site of the polymer, and reacted for 30 minutes. After the reaction, the reaction solution is returned to normal temperature and normal pressure and taken out from the reaction vessel, then, as in (I-1), after addition of an antioxidant, the reaction solution is stirred into water and the solvent is removed by steam distillation By doing this, the polymer (I-4) described in Table 1 was obtained. The amino group content of the obtained polymer (i-4) was 0.0254 mmol Zg.
[0061] 5)変性共役ジェン系重合体 (ィ 5)の製造  5) Production of Modified Conjugated Genic Polymer (5)
重合開始剤に sec ブチルリチウムを用いて、表 2の (ィ— 5)に示す共重合体構造 になるように重合開始剤の量、単量体種類、単量体量、重合温度、重合時間などを 変化させて、上記 1)の製法に準じ重合体を得た。次いで、該重合体の活性点に N— ベンジリデンェチルァミン 15. 9gをカ卩え、 30分反応させた。反応後、反応溶液を常 温、常圧に戻して反応容器より抜き出し、次いで、（ィ—1)と同様に、老化防止剤を 添加後、反応溶液を水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、 表 2に記す重合体 (ィ— 5)を得た。得られた重合体 (ィ— 5)のァミノ基含量は 0. 009 5mmol, gで teつた 0 Using sec-butyl lithium as the polymerization initiator, the amount of the polymerization initiator, the kind of monomer, the amount of the monomer, the polymerization temperature, the polymerization time, and the copolymer structure as shown in Table 2 (5). The polymer was obtained according to the production method of the above 1) by changing etc. Next, 15.9 g of N-benzylidene ethyl amine was added to the active site of the polymer and reacted for 30 minutes. After the reaction, the reaction solution is returned to normal temperature and pressure and withdrawn from the reaction vessel, and then, as in (I-1), after addition of an anti-aging agent, the reaction solution is stirred into water and steam distilled. By removing, a polymer (I-5) described in Table 2 was obtained. The amino group content of the obtained polymer (i-5) is 0.0.05 mmol, g of 0.
[0062] 6)変性共役ジェン系重合体 (ィ 6)の製造  6) Production of Modified Conjugated Genic Polymer (6)
窒素置換された内容積 100リットルの反応容器に、シクロへキサン 50kg、スチレン 2 . Okgおよび sec ブチルリチウム 9. 5gをカ卩え、重合開始温度 50°Cにて重合した。 反応完結後、温度を 80°Cとしてブタジエン 6. Okgをゆっくり添加して等温にて 2段目 重合した。 30分後、スチレン 2. 0kgを添加し 3段目重合した。反応完結後、ケトンィ匕 合物および Zまたはエステルイ匕合物および Zまたはアルデヒド化合物としてべンズァ ルデヒドをリビングリチウムの橙色が無色になるまで添加したところ、 14. lg必要であ つた。その後、無水フタル酸 19. 7g添加した。反応後、反応溶液を常温、常圧に戻し て反応容器より抜き出し、次いで、（ィー 1)と同様に、老化防止剤を添加後、反応溶 液を水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、表 2に記す重合 体 (ィ - 6)を得た。得られた重合体 (ィ - 6)の酸無水物基とカルボキシル基含量は 0 . 0085mmolZgであった。 Into a reaction vessel with an inner volume of 100 liters and substituted with nitrogen, 50 kg of cyclohexane, 2.O kg of styrene and 9.5 g of sec-butyl lithium were added, and polymerization was carried out at a polymerization initiation temperature of 50 ° C. After completion of the reaction, 6.O kg of butadiene was slowly added at a temperature of 80 ° C. to conduct isothermal second-stage polymerization. After 30 minutes, 2.0 kg of styrene was added and polymerization was performed in the third stage. After completion of the reaction, a ketone compound and Z or an ester complex and Z or benzene as an aldehyde compound were added until the color of the living lithium became colorless, and 14.lg was necessary. Thereafter, 19.7 g of phthalic anhydride was added. After the reaction, the reaction solution is returned to normal temperature and pressure. The reaction solution is added to water after stirring and the solvent is removed by steam distillation to obtain the polymers described in Table 2. I got 6). The content of the acid anhydride group and the carboxyl group of the resulting polymer (i-6) was 0. 0085 mmol Zg.
[0063] 7)変性共役ジェン系重合体 (ィ 7)の製造  7) Production of Modified Conjugated Polymer (7)
窒素置換された内容積 100リットルの反応容器に、シクロへキサン 50kg、スチレン 2 . Okg、および sec ブチルリゥム 9. 5gをカ卩え、重合開始温度 50°Cにて重合した。反 応完結後、温度を 80°Cとしてブタジエン 6. Okgをゆっくり添加して等温にて 2段目重 合した。 30分後、スチレン 2. Okgを添加し 3段目重合した。反応完結後、ケトン化合 物および Zまたはエステルイ匕合物および Zまたはアルデヒド化合物としてアセトンをリ ビングリチウムの橙色が無色になるまで添加したところ、 7. 7g必要であった。その後 、無水トリメリト酸クロリド 28. lg添加した。反応後、反応溶液を常温、常圧に戻して反 応容器より抜き出し、次いで、（ィ—1)と同様に、老化防止剤を添加後、反応溶液を 水中に撹拌投入して溶媒を水蒸気蒸留除去することによって、表 2に記す重合体 (ィ 7)を得た。得られた重合体 (ィー 7)の酸無水物基とカルボキシル基の合計が 0. 0 16mmolZ gであった。  Into a reaction vessel with an internal volume of 100 liters and substituted with nitrogen, 50 kg of cyclohexane, 2.O kg of styrene and 9.5 g of sec butyllithium were added, and polymerization was carried out at a polymerization initiation temperature of 50 ° C. After completion of the reaction, 6.O kg of butadiene was slowly added at a temperature of 80 ° C. to perform isothermal second stage polymerization. Thirty minutes later, 2.O kg of styrene was added and polymerization was performed in the third stage. After completion of the reaction, the ketone compound and Z or an ester complex and Z or acetone as an aldehyde compound were added until the orange color of ribing lithium became colorless, and 7.7 g was required. After that, 28. lg of trimellitic anhydride chloride was added. After the reaction, the reaction solution is returned to normal temperature and pressure and removed from the reaction vessel, and then, as in (I-1), after addition of an anti-aging agent, the reaction solution is stirred into water and steam distilled. By removing, a polymer (7) described in Table 2 was obtained. The total of the acid anhydride group and the carboxyl group of the obtained polymer (7) was 0.10 mmol Z g.
[0064] 8)変性共役ジェン系重合体 (ィ 8)の製造  8) Production of modified conjugated diene-based polymer (I 8)
重合体 (ィ一 3)に準じて重合後、この系内にメチルトリフエノキシシラン 31. 7gを加 え、 30分反応させた。反応後、反応液を常温、常圧に戻して反応容器より抜き出し、 (ィー 1)と同様に、老化防止剤を添加後、水中に撹拌投入して溶媒を水蒸気蒸留除 去することによって、表 2に記す重合体 (ィ— 8)を得た。得られた重合体 (ィ— 8)のァ ルコキシシリル基含量は 0. 0190mmolZg、アミノ基含量は 0. 0085mmol/gであ つた o  After polymerization according to the polymer (3), 31.7 g of methyltriphenoxysilane was added to this system and reacted for 30 minutes. After the reaction, the reaction solution is returned to normal temperature and normal pressure and taken out from the reaction vessel, and an anti-aging agent is added as in (i), and then stirred into water and the solvent is removed by steam distillation. The polymer (I-8) described in Table 2 was obtained. The alkoxysilyl group content of the obtained polymer (i-8) was 0.290 mmol Zg, and the amino group content was 0. 0085 mmol / g o
[0065] 9)変性共役ジェン系重合体 (ィー 9)〜(ィ 12)の製造  9) Production of Modified Conjugated Gen-Based Polymer (i 9) to (i 12)
重合体 (ィ— 1)に準じて、表 2, 3に示すようなアルコキシシリル基を有する変性共 役ジェン系重合体になるように変性ィ匕合物の種類と量およびスチレン、ブタジエン、 s ec プチルリゥムの量を変化させて、表 2または 3に記す重合体 (ィー 9)〜(ィ 12) を得た。 なお、重合体（ヒー 2)は、 N, N—ビス（トリメチルシリル）ァミノプロピルメチルジェト キシシランを使用しない以外は重合体 (ィー 12)に準じて重合して得た未変性共役ジ ェン系重合体である。 According to the polymer (II), the kind and amount of the modified compound, styrene, butadiene, s, and so on, as shown in Tables 2 and 3, so as to be a modified copolymer having an alkoxysilyl group. By changing the amount of ectobutyl lum, the polymers (i 9) to (i 12) described in Table 2 or 3 were obtained. The polymer (He 2) is a non-modified conjugated diene obtained by polymerizing according to the polymer (i 12) except that N, N-bis (trimethylsilyl) aminopropylmethyl jetoxysilane is not used. It is a base polymer.
[0066] 10)変性共役ジェン系重合体 (ィ 13) [0066] 10) Modified Conjugated Gen-Based Polymer (-13)
共役ジェンとしてブタジエンの代わりにイソプレンを使用し、その他は重合体 (ィ一 1 Instead of butadiene as a conjugated gene, isoprene is used, and the other is a polymer.
)に準じて行い、表 3に記す重合体 (ィ— 13)を得た。 The polymer (I-13) described in Table 3 was obtained in the same manner as in the above.
[0067] 11)変性共役ジェン系重合体 (ィ 14)〜(ィ 15) 11) Modified Conjugated Gen-Based Polymer (−14) to (−15)
窒素置換された内容積 100リットルの反応容器に、シクロへキサン 50kg、スチレン 2 . Okg、エチレングリコールジェチルエーテル 16. 3gおよび sec ブチルリチウム 9. 5gを加え、重合開始温度 50°Cにて 1段目重合し、反応完結後、温度を 70°Cとしてブ タジェン 5. 9kgをゆっくり添加して断熱にて 2段目重合した。 30分後、スチレン 2. Ok gを添加し 3段目重合し、反応完結後、 1, 3 ブタジエン 0. 1kgを添加してさらに 4段 目重合を行った。この系内にメチルジェトキシ (t—アミ口キシ）シラン 29. 5gを加え、 3 0分反応させた。反応後、反応液を常温、常圧に戻して反応容器より抜き出し、（ィー 1)と同様に、老化防止剤を添加後、水中に撹拌投入して溶媒を水蒸気蒸留除去す ることによって、表 4に記す重合体 (ィ— 14)を得た。得られた重合体 (ィ— 14)のアル コキシシリル基含量は 0. 0180mmolZgであった。  50 kg of cyclohexane, 2.O kg of styrene, 16.3 g of ethylene glycol jetyl ether and 9. 5 g of sec-butyl lithium were added to a nitrogen-substituted 100-liter reaction vessel, and the polymerization initiation temperature was 50 ° C. 1 Stage polymerization was carried out, and after completion of the reaction, the temperature was adjusted to 70 ° C., and 5.59 kg of butadiene was slowly added to carry out the second stage polymerization with heat insulation. Thirty minutes later, 2.Ok g of styrene was added to carry out the third stage polymerization, and after completion of the reaction, 0.1 kg of 1,3 butadiene was added to carry out the fourth stage polymerization. Into this system, 29.5 g of methyl jetoxy (t-amino xyoxy) silane was added and allowed to react for 30 minutes. After the reaction, the reaction solution is returned to normal temperature and normal pressure, and is withdrawn from the reaction vessel, and an antiaging agent is added as in (i), and then stirred into water to remove the solvent by steam distillation. The polymer (I-14) described in Table 4 was obtained. The alkoxysilyl group content of the obtained polymer (i-14) was 0.10180 mmol Zg.
(ィ 15)は、（ィ 14)に準じて、表 4に示すようなアルコキシシリル基を有する変 性共役ジェン系重合体になるようにエチレングリコールジェチルエーテル量、変性化 合物の種類と量を変化させて重合体 (ィ— 15)を得た。  The amount of ethylene glycol jetyl ether, the type of modified compound, and the kind of the modified compound are as shown in Table 4 in accordance with (I), so as to obtain a variable conjugated diene-based polymer having an alkoxysilyl group. The amount was changed to obtain a polymer (i-15).
なお、重合体 (ヒー 3)は、メチルジェトキシ (t—アミ口キシ)シランを使用しない以外 は重合体 (ィー 14)に準じて重合して得た未変性共役ジェン系重合体である。  The polymer (He-3) is a non-modified conjugated diene-based polymer obtained by polymerizing according to the polymer (i) except that the methyl jetoxy (t-amino acid) silane is not used. .
[0068] 12)変性共役ジェン系重合体 (ィ 16) 12) Modified Conjugated Gen-Based Polymer (-16)
窒素置換された内容積 100リットルの反応容器に、シクロへキサン 50kg、スチレン 2 . Okgおよび sec ブチルリチウム 9. Ogをカ卩え、重合開始温度 50°Cにて 1段目重合 し、反応完結後、温度を 80°Cとしてブタジエン 4. 9kgおよびスチレン lkgをゆっくり 添加して等温にて 2段目重合した。 30分後、スチレン 2. Okgを添加し 3段目重合し、 反応完結後、 1, 3 ブタジエン 0. lkgを添加してさらに 4段目重合を行った。一部取 り出したこのブロック重合体の 2段目のビニル結合は 12%含有し、 GPCで測定した 重量平均分子量は 10万であった。そして、この系内にメチルトリフエノキシシラン 40. 7gを加え、 30分反応させた。反応後、常温、常圧に戻して反応容器より抜き出し、 ( ィー 1)と同様に、老化防止剤を添加後、水中に撹拌投入して溶媒を水蒸気蒸留除 去することによって、表 4に記す重合体 (ィ— 16)を得た。得られた重合体 (ィ— 16) のアルコキシシリル基含量は 0. 0185mmol/gであつた。 50 kg of cyclohexane, 2.O kg of styrene and sec-butyl lithium 9. Og in a 100 l reaction vessel filled with nitrogen and carrying out polymerization in the first stage at a polymerization initiation temperature of 50 ° C to complete the reaction After that, the temperature was changed to 80 ° C., and 4.9 kg of butadiene and 1 kg of styrene were slowly added to perform isothermal second-stage polymerization. Thirty minutes later, 2.O kg of styrene was added to carry out the third stage polymerization, and after completion of the reaction, 0.1 kg of 1,3-butadiene was added to carry out the fourth stage polymerization. Partially The second stage vinyl bond of this block polymer contained 12%, and the weight average molecular weight measured by GPC was 100,000. Then, 40.7 g of methyltriphenoxysilane was added to this system and reacted for 30 minutes. After the reaction, the temperature is returned to normal temperature and normal pressure, and the reaction vessel is taken out from the reaction vessel. After adding the antiaging agent as described in (A), stirring into water is carried out and the solvent is removed by steam distillation. The title polymer (i-16) was obtained. The alkoxysilyl group content of the obtained polymer (i-16) was 0.1085 mmol / g.
なお、重合体 (ヒ— 4)は、メチルトリフエノキシシランを使用しない以外は、重合体（ ィ 16)に準じて重合して得た未変性共役ジェン系重合体である。  Here, the polymer (4) is a non-modified conjugated diene-based polymer obtained by polymerizing according to the polymer (1) except that methyltriphenoxysilane is not used.
[表 1] [table 1]
Figure imgf000028_0001
Figure imgf000028_0001
(a)メチルトリフエノキシシラン (a) Methyltriphenoxysilane
(b) 3—リチォ一 1— N, N ビス（トリメチルシリル）ァミノプロパン  (b) 3-Lithio 1-N, N Bis (trimethylsilyl) aminopropane
(c) 2, 2, 5, 5—テトラメチルー 1一（3 リチォプロピル） 1ーァザ  (c) 2, 2, 5, 5-tetramethyl-1 (3 lithium) 1-
シクロペンタン Cyclopentane
(d) p- {2- [N, N ビス（トリメチルシリル）ァミノ]ェチル }スチレン (d) p- {2- [N, N bis (trimethylsilyl) amino] ethyl} styrene
[0071] [表 2] [Table 2]
Figure imgf000029_0002
Figure imgf000029_0002
(a)メチルトリフエノキシシラン (a) Methyltriphenoxysilane
(c) 2, 2, 5, 5—テ卜ラメチル (3—リチォプロピノレ) アザ 2, 5 ジシラ  (c) 2, 2, 5, 5—Tetrauramethyl (3-lithiopropinore) aza 2, 5 Disila
(e) N—ベンジリデンェチルァミン (e) N-benzylidene ethyl amine
(f)無水フタル酸  (f) Phthalic anhydride
(g)無水トリメリト酸クロリド  (g) trimellitic anhydride chloride
(h)メチルジェトキシ (t アミ口キシ）シラン  (h) Methyl jetoxy (t-amino-xy) silane
[0073] [表 3]  [0073] [Table 3]
Figure imgf000029_0003
Figure imgf000029_0003
[0074] (a)メチルトリフエノキシシラン (A) Methyltriphenoxysilane
(i) N,
Figure imgf000029_0001
ァミノプロピルトリエトキシシラン (i) N,
Figure imgf000029_0001
Aminopropyltriethoxysilane
(j) N, N— ス m  (j) N, N—S m
(k) N, N— ス m [0075] [表 4] (k) N, N—S m [Table 4]
Figure imgf000030_0001
Figure imgf000030_0001
[0076] (a)メチルトリフエノキシシラン (A) Methyltriphenoxysilane
(h)メチルジェトキシ (t アミ口キシ）シラン  (h) Methyl jetoxy (t-amino-xy) silane
(k) N, N ビス（トリメチルシリル）ァミノプロピルメチルジェトキシシラン  (k) N, N Bis (trimethylsilyl) aminopropylmethyl jetoxysilane
[0077] (2)各種成分 (2) Various components
実施例および比較例において用いた各種の成分は、以下のとおりである。  The various components used in the Examples and Comparative Examples are as follows.
(ィ)変性共役ジェン系重合体  (I) Modified conjugated gen polymer
表 1〜表 4に示す構造を有する水添共役ジェン系重合体 (ィー 1)〜 (ィー 16)、 （ヒ 1)〜（ヒー 4)  Hydrogenated conjugated diene-based polymers having the structures shown in Tables 1 to 4 (D1) to (D16), (D1) to (D4)
(口）耐衝撃性ゴム変性スチレン系重合体  (Mouth) impact resistance rubber modified styrenic polymer
日本ポリスチレン社製 HIPS M220  Japan polystyrene company HIPS M220
(ハ)非ゴム変性スチレン系重合体  (C) Non-rubber-modified styrenic polymer
日本ポリスチレン社製 GPPS G440K  Japan polystyrene company GPPS G440K
(二)導電性カーボン  (2) Conductive carbon
花王社製 ケッチェンブラック EC  Kao Corporation Ketjen Black EC
[0078] 熱可朔性榭脂組成物の特性 [0078] Properties of the heat fusible resin composition
(1)表面固有抵抗性 (導電性）  (1) Surface resistivity (conductive)
JIS K7194に準じて、低抵抗率計を用いて、表面抵抗値を測定した。 The surface resistance value was measured using a low resistivity meter according to JIS K7194.
(2)耐衝撃性 (2) Impact resistance
(2)— 1 DuPont衝撃強さ  (2)-1 DuPont impact strength
DuPont衝撃試験器 (東洋精機社製）にて JIS K7211の落錘衝撃試験方法に沿 つて 50%破壊エネルギーを求めた。 0. 5mmのシートを用いて、荷重は 300g、撃心 突端の半径は 7. 9mm、撃心受台の半径は 8. 1mmで行った。 According to the drop weight impact test method of JIS K7211 with DuPont impact tester (made by Toyo Seiki Co., Ltd.) I asked for 50% destruction energy. Using a 0.5 mm sheet, the load was 300 g, the radius of the tip was 7. 9 mm, and the radius of the pedestal was 8. 1 mm.
(2) -2 フィルム衝撃強さ  (2) -2 film impact strength
フィルムインパクトテスター（東洋精機社製）にて、 0. 25mmのシートを用いて、衝 撃球面直径 12. 7mm,振り子重量 15kg 'cmの条件で測定した。  It was measured with a film impact tester (made by Toyo Seiki Co., Ltd.) using a sheet of 0.25 mm under the conditions of an impact spherical diameter of 12.7 mm and a pendulum weight of 15 kg'cm.
[0079] (3)導電性カーボンの脱落性 (3) Dropout of conductive carbon
縦 15cm X横 15cmのシートを固定し、その上にコピー用紙を 20mmスパンで 10回 往復運動させて、摩擦によるコピー用紙の色の変化を目視で観察し、以下の基準で 評価した。  A sheet of 15 cm long and 15 cm wide was fixed, and the copy paper was reciprocated 10 times with a 20 mm span thereon, and the change in color of the copy paper due to friction was visually observed and evaluated according to the following criteria.
〇：カーボンの付着がない。  ○: There is no adhesion of carbon.
X：カーボンが付着する。  X: Carbon adheres.
[0080] (4)低温特性 (4) Low temperature characteristics
0°Cにおける DuPont衝撃強さにて評価した。  It evaluated by DuPont impact strength in 0 degreeC.
(5)剛性  (5) Rigidity
JIS K7127に準拠し、引張試験を行い弾性率で評価した。  According to JIS K7127, a tensile test was performed to evaluate by the elastic modulus.
[0081] 実施例 1 Example 1
変性共役ジェン系重合体 (ィー 1) Z耐衝撃性ゴム変性スチレン系重合体 Z非ゴム 変性スチレン系重合体 Z導電性カーボン (重量比） = 10Z20Z60Z10の割合でド ライブレンドし、ナカタ-機械社 NVC— 50の押出機を使用しシリンダー温度 200°C にてコンパウンドしストランドカットし、ペレット化した。その後、このコンパウンドペレット 品を 15cm巾の T ダイ金型、押出機およびフィルム 'シート引取装置 F1— T3付属 のラボプラストミル 100C100 (東洋精機社製）にて厚み 0. 25mmおよび 0. 5mmの シートを作製した。このシートを用い、各特性の評価結果を表 5に示す。  Denatured Conjugated Gen-Based Polymer (i) Z Impact Resistant Rubber-Modified Styrenic Polymer Z Non-Rubbed Modified Styrenic Polymer Z Conductive carbon (Weight ratio) = 10Z20 Z60 The resultant was compounded, strand cut and pelletized at a cylinder temperature of 200 ° C. using an NVC-50 extruder. After that, the compound pellet product was measured using a 15 cm wide T die mold, an extruder, and a Labo Plastomill 100C100 (made by Toyo Seiki Co., Ltd.) attached to a film 'sheet take-up device F1-T3 sheet having a thickness of 0.25 mm and 0.5 mm. Was produced. Evaluation results of each property are shown in Table 5 using this sheet.
[0082] 実施例 2〜28、比較例 1〜4 Examples 2 to 28 and Comparative Examples 1 to 4
表 5〜表 10に示す配合処方を用い実施例 1と同様に試験片を作製し、物性評価を 行った。結果を以下の表 5〜表 10に示す。 [0083] [表 5] Test pieces were produced in the same manner as in Example 1 using the formulation shown in Tables 5 to 10, and the physical properties were evaluated. The results are shown in Tables 5 to 10 below. [Table 5]
X X
Figure imgf000032_0001
Figure imgf000032_0001
[0084] [表 6] 実施例番号 7 8 9 10 11 12 配合処方  [Table 6] Example No. 7 8 9 10 11 12 Formulation
(ィ） 成分：製造番号 ィ— 7 ィー 8 ィ一 8 ィー 8 ィ一 8 ィー 9 部 1 0 1 0 1 0 2 0 7 2 5 (I) Component: Serial number B 8 B 8 B 8 B 9 Part 1 0 1 0 1 0 2 0 7 2 5
(口） 成分：部 2 0 2 0 2 3 0 2 3 0 (Mouth) Component: Part 2 0 2 0 2 3 0 2 3 0
X  X
(八） 成分：部 6 0 6 0 6 0 6 5 6 0 6 5 (8) Component: Part 6 0 6 0 6 0 6 5 6 0 6 5
(二） 成分：部 1 0 1 0 7 1 5 1 0 1 0 導電性 （Ω · c m) 5X105 9X106 1 X103 (2) Component: Part 1 0 1 0 7 1 5 1 0 1 0 Conductivity (Ω · cm) 5X10 5 9X10 6 1 X10 3
耐衝撃性  Impact resistance
X  X
DuPont衝撃強さ （ J ) 1.5 1.4 1.6 1.6 1.7 1.3 フィルム衝撃強さ 21 19 23 26 22 23 DuPont Impact Strength (J) 1.5 1.4 1.6 1.6 1.7 1.3 Film Impact Strength 21 19 23 26 22 23
( k g f · c m/ c m) (k g f · c m / c m)
導電性カーボン脱落性 O 〇 〇 O 〇 〇 Conductive carbon detack O OO O OO
0°Cでの DuPont衝撃（ J ) 0.8 0.7 0.8 0.7 0.7 0.8 剛性 （MP a) 1200 1150 1300 1350 1400 1050 DuPont Impact (J) at 0 ° C (J) 0.8 0.7 0.8 0.7 0.7 0.8 Stiffness (MP a) 1200 1150 1300 1350 1400 1050
[0085] [表 7] [Table 7]
Figure imgf000033_0001
Figure imgf000033_0001
[0086] [表 8] [Table 8]
X  X
実施例番号 19 20 21 22 23 24 配合処方  Example No. 19 20 21 22 23 24 Formulation
(ィ） 成分：製造番号 ィ— 16 ィー 8 ィー 1 2 ィ— 12 ィ— 1 2 ィー 12 部 1 0 1 0 1 0 X 2 3 1 0 2 0 (B) Component: Serial number B 1 8 2 1 12 1 12 12 1 0 1 0 1 0 X 2 3 1 0 2 0
(口） 成分：部 2 0 2 5 2 5 0 1 5 0(Mouth) Component: Part 2 0 2 5 2 5 0 1 5 0
(八） 成分：部 6 0 6 0 6 0 7 0 6 3 6 5(8) Component: Part 6 0 6 0 6 0 7 0 6 3 6 5
(二） 成分：部 1 0 5 5 7 1 2 1 5 導電性 （Ω · c m) 3X 10s 4X107 9X104 8X 103 耐衝撃性 (2) Component: Part 1 0 5 5 7 1 2 1 5 Conductivity (Ω · cm) 3X 10 s 4X 10 7 9X 10 4 8X 10 3 Impact resistance
DuPont衝撃強さ （ J ) 1.5 1.8 2.0 1.9 1.5 1.4 フィルム衝撃強さ 19 25 29 24 20 19 DuPont Impact Strength (J) 1.5 1.8 2.0 1.9 1.5 1.4 Film Impact Strength 19 25 29 24 20 19
( k g f - c m/ c m) (k g f-c m / c m)
導電性カーボン脱落性 〇 o 〇 〇 o o Conductive carbon detackiness o o o o o o
0°Cでの DuPont衝撃（ J ) 0.7 0.9 0.9 0.8 0.7 0.8 剛性 （MP a ) 1100 1200 1100 1150 1300 1400 DuPont impact (J) at 0 ° C (J) 0.7 0.9 0.9 0.8 0.7 0.8 Stiffness (MP a) 1100 1200 1100 1150 1300 1400
[0087] [表 9] [Table 9]
Figure imgf000034_0001
Figure imgf000034_0001
[0089] 表 5〜表 9より、本発明の組成物である実施例 1〜28では、物性のバランスの取れ た熱可塑性榭脂組成物であることが分力ゝる。 From Tables 5 to 9, in Examples 1 to 28, which are the composition of the present invention, it is necessary to be a thermoplastic resin composition having well-balanced physical properties.
これに対し、表 10から、本発明の変性共役ジェン系重合体ではない未変性重合体 を用いた比較例は導電性に劣り、導電カーボンの脱落があり、実施例に比べて劣つ ていた。  On the other hand, it is apparent from Table 10 that the comparative example using the non-modified polymer which is not the modified conjugated gen-based polymer of the present invention is inferior in conductivity and has falling of conductive carbon, which is inferior to the examples. .
産業上の利用可能性 本発明の熱可塑性榭脂組成物は、自動車内装材用、電気，電子部品用、建築材 用などの用途に有用であり、特に半導体や電子部品用包装材料などとして用いられ る。特に、本発明により得られる導電性が付与されたフィルム 'シートは、 ICトレー、キ ャリアテープなどの用途に有用である。 Industrial applicability The thermoplastic resin composition of the present invention is useful in applications such as automotive interior materials, electricity, electronic components, construction materials, etc., and is particularly used as a packaging material for semiconductors and electronic components. In particular, the conductive film 'sheets obtained by the present invention are useful for applications such as IC trays and carrier tapes.

Claims

請求の範囲 The scope of the claims
[1] (ィ)アルコキシシリル基、アミノ基、酸無水物基、およびカルボキシル基の群力も選 ばれた少なくとも 1種の基を有する変性共役ジェン系重合体 2. 5〜35重量部、 (口）耐衝撃性ゴム変性スチレン系重合体 0〜50重量部、  [1] (5) modified conjugated diene-based polymer having at least one group selected from alkoxysilyl group, amino group, acid anhydride group, and carboxyl group; ) Impact-resistant rubber-modified styrenic polymer 0 to 50 parts by weight,
(ハ)非ゴム変性スチレン系重合体 40〜90重量部、ならびに  (C) 40 to 90 parts by weight of a non-rubber-modified styrene polymer,
(二)導電性カーボン 1〜15重量部 [ただし、（ィ） + (口） + (ハ） + (二） = 100重量 部]  (2) 1 to 15 parts by weight of conductive carbon [where (i) + (mouth) + (ha) + (2) = 100 parts by weight]
を主成分とする熱可塑性榭脂組成物。  Thermoplastic resin composition containing as a main component.
[2] (ィ)変性共役ジェン系重合体が、次に示す方法 (a)〜 (e)の群力も選ばれた少なく とも 1種で製造された重合体のいずれかである請求項 1に記載の熱可塑性榭脂組成 物。 [2] (i) The modified conjugated diene polymer is any one of the polymers produced by at least one type selected from the group powers of the methods (a) to (e) shown below. Thermoplastic resin composition as described.
(a)共役ジェンと芳香族ビニル化合物を有機アルカリ金属化合物の存在下で重合 し、得られた共役ジェン系重合体にアルコキシシランィ匕合物を反応させることにより 製造された重合体。  (a) A polymer produced by polymerizing a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound, and reacting the resulting conjugated diene polymer with an alkoxysilane compound.
(b)共役ジェンと芳香族ビ-ルイ匕合物を、アミノ基を有する有機アルカリ金属化合 物の存在下で重合することにより製造された重合体。  (b) A polymer produced by polymerizing a conjugated diene and an aromatic bi-Lewi complex in the presence of an organic alkali metal compound having an amino group.
(c)共役ジェンとアミノ基を有する不飽和単量体と芳香族ビニル化合物とを有機ァ ルカリ金属化合物の存在下で重合することにより製造された重合体。  (c) A polymer produced by polymerizing an unsaturated monomer having a conjugated gene and an amino group and an aromatic vinyl compound in the presence of an organic metal compound.
(d)共役ジェンと芳香族ビニル化合物を有機アルカリ金属化合物の存在下で重合 し、得られた共役ジェン系重合体に下記一般式（1)で表される化合物を反応させる ことにより製造された重合体。  (d) manufactured by polymerizing a conjugated diene and an aromatic vinyl compound in the presence of an organic alkali metal compound, and reacting the resulting conjugated diene polymer with a compound represented by the following general formula (1) Polymer.
R1R2C = N-Y- - - - (1) R 1 R 2 C = NY----(1)
[上記一般式（1)中、 R1および R2はそれぞれ独立に水素原子、炭素数 1〜20のアル キル基、炭素数 6〜20のァリール基、炭素数 7〜20のァラルキル基または炭素数 1 〜 100のオルガノシロキシ基である。また、 Yは水素原子、炭素数 3〜18のトリアルキ ルシリル基、炭素数 1〜20のアルキル基、炭素数 6〜20のァリール基、炭素数 7〜2 0のァラルキル基または炭素数 1〜： L00のオルガノシロキシ基である。 ] [In the above general formula (1), R 1 and R 2 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms, or carbon It is an organosiloxy group of several 1 to 100. Y is a hydrogen atom, a trialkylsilyl group having 3 to 18 carbon atoms, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 20 carbon atoms or 1 to 6 carbon atoms: It is an organosiloxy group of L00. ]
(e)共役ジェンと芳香族ビニルイ匕合物を有機アルカリ金属化合物の存在下で重合 し、得られた共役ジェン系重合体に、ケトンィ匕合物、エステルイ匕合物およびアルデヒ ド化合物の群力 選ばれた少なくとも 1種を反応させた後、酸無水物および Zまたは 酸ハライドと反応させることにより製造された重合体。 (e) Polymerization of conjugated diene and aromatic vinyl compound in the presence of an organic alkali metal compound And react with the acid anhydride and Z or the acid halide after reacting at least one selected from the group consisting of ketone compound, ester compound and aldehyde compound with the conjugated diene polymer obtained. Polymers produced by
(ィ)変性共役ジェン系重合体が、アルコキシシリル基とアミノ基を有する変性共役 ジェン系重合体であり、かつ下記 (f)〜 (h)の群力 選ばれた少なくとも 1種の方法に より製造された変性共役ジェン系重合体である、請求項 1に記載の熱可塑性重合体 組成物。  (I) The modified conjugated diene polymer is a modified conjugated polymer having an alkoxysilyl group and an amino group, and the group power of the following (f) to (h) is selected by at least one selected method. The thermoplastic polymer composition according to claim 1, which is a modified conjugated diene-based polymer produced.
(f)共役ジェンと芳香族ビ-ルイ匕合物を、アミノ基を有する有機アルカリ金属化合物 の存在下で重合し、得られた共役ジェン系重合体に下記一般式（2)で表される化合 物を反応させた変性重合体。  (f) A conjugated diene-based polymer obtained by polymerizing conjugated diene and an aromatic bi-Louisinated compound in the presence of an organic alkali metal compound having an amino group is represented by the following general formula (2) Modified polymer in which compound is reacted.
R3 Si (OR4) X …… (2) R 3 Si (OR 4 ) X ...... (2)
(.4— m— n) m n  (.4-m-n) m n
[式中、 R3は炭素数 1〜20のアルキル基、炭素数 6〜20のァリール基、炭素数 7〜2 0のァラルキル基または炭素数 1〜： L00のオルガノシロキシ基であり、 R3が複数ある 場合は、各 R3は同じ基でも異なる基でもよい。 R4は炭素数 1〜20のアルキル基、炭 素数 6〜20のァリール基、炭素数 7〜20のァラルキル基であり、 R4が複数ある場合 は、各 R4は同じ基でも異なる基でもよい。 Xは少なくとも Ο原子、 Si原子のいずれか 1 つ以上含む極性基を有する置換基であり、 Xが複数ある場合は、各 Xは同じ基でも異 なる基でもよく、また、各 Xは独立の置換基でも環状構造を形成していてもよい。 mは 1、 2または 3であり、 nは 0、 1、 2または 3の整数を示す。 mと nの和は 1〜4である。 ]Wherein, R 3 is an alkyl group, Ariru group having 6 to 20 carbon atoms, 1 to several 7-2 Ararukiru group or a carbon number of 0 carbon atoms of 1 to 20 carbon atoms: a L00 organosiloxy group, R 3 When there are a plurality of, each R 3 may be the same or different. R 4 is an alkyl group having 1 to 20 carbon atoms, Ariru group having a carbon number of 6-20, a Ararukiru group having 7 to 20 carbon atoms, if R 4 have more than one purpose, each R 4 is different even in the same group group Good. X is a substituent having a polar group containing at least one or more of Ο atom and Si atom, and when there are a plurality of X, each X may be the same or different group, and each X is independent It may have a substituent or a cyclic structure. m is 1, 2 or 3 and n is an integer of 0, 1, 2 or 3. The sum of m and n is 1 to 4. ]
(g)共役ジェンとアミノ基を有する不飽和単量体と芳香族ビニル化合物とを有機ァ ルカリ金属化合物の存在下で重合し、得られた共役ジェン系重合体に上記一般式（ 2)で表される化合物を反応させた変性重合体。 (g) A conjugated diene polymer obtained by polymerizing an unsaturated monomer having an conjugated group and an amino group and an aromatic vinyl compound in the presence of an organic alkali metal compound is shown by the above general formula (2) The modified polymer which made the compound represented react.
(h)共役ジェンと芳香族ビ-ルイ匕合物を有機アルカリ金属化合物の存在下で重合 し、得られた共役ジェン系重合体に下記一般式 (7)で表される化合物を反応させた 変性重合体。  (h) A conjugated diene polymer obtained by polymerizing a conjugated diene and an aromatic bi-loyl compound in the presence of an organic alkali metal compound, and reacting the compound represented by the following general formula (7) with the obtained conjugated polymer Modified polymer.
R12 Si (OR13) Z …… (7) R 12 Si (OR 13 ) Z ...... (7)
(4-p-q) p q  (4-p-q) p q
[式中、 R12は炭素数 1〜20のアルキル基、炭素数 6〜20のァリール基、炭素数 7〜 20のァラルキル基または炭素数 1〜： L00のオルガノシロキシ基であり、 R12が複数あ る場合は、各 R12は同じ基でも異なる基でもよい。 R13は炭素数 1〜20のアルキル基、 炭素数 6〜20のァリール基、炭素数 7〜20のァラルキル基であり、 R13が複数ある場 合は、各 R13は同じ基でも異なる基でもよい。 Zは N原子を含む極性基を有する置換 基であり、 Zが複数ある場合は、各 Zは同じ基でも異なる基でもよぐまた、各 Zは独立 の置換基でも環状構造を形成していてもよい。 Pは 1、 2または 3であり、 qは 1、 2また は 3の整数を示す。 pと qの和は 1〜4である。 ] Wherein, R 12 is an alkyl group, Ariru group having 6 to 20 carbon atoms, 1 to Ararukiru group or the number of carbon atoms in the carbon number 7-20 having 1 to 20 carbon atoms: a L00 organosiloxy group, R 12 is More than one In the latter case, each R 12 may be the same or different. R 13 is an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 20 carbon atoms, and when there are a plurality of R 13 groups, each R 13 may be the same or different groups May be. Z is a substituent having a polar group containing an N atom, and when there are a plurality of Z, each Z may be the same group or a different group, and each Z may form a cyclic structure even with an independent substituent. It is also good. P is 1, 2 or 3 and q is an integer of 1, 2 or 3. The sum of p and q is 1 to 4. ]
[4] (口）耐衝撃性ゴム変性スチレン系重合体力 耐衝撃性ゴム変性スチレン重合体、 アクリロニトリル—ブタジエン―スチレン共重合体、アクリル酸エステル―ブタジエン スチレン共重合体、メタクリル酸エステル ブタジエン スチレン共重合体、および 耐衝撃性ゴム変性スチレン—無水マレイン酸共重合体の群力 選ばれた少なくとも 1 種である請求項 1〜3いずれかに記載の熱可塑性榭脂組成物。  (4) Impact resistant rubber modified styrenic polymer Impact resistant rubber modified styrenic polymer, acrylonitrile-butadiene-styrene copolymer, acrylate ester-butadiene styrene copolymer, methacrylate ester butadiene styrene copolymer The thermoplastic resin composition according to any one of claims 1 to 3, which is at least one selected from the group consisting of a combination and a rubber-modified styrene-maleic anhydride copolymer.
[5] (ハ）非ゴム変性スチレン系重合体力 ポリスチレン、スチレン一 a—メチルスチレン 共重合体、アクリロニトリル スチレン共重合体、およびアクリロニトリルーメタクリル酸 エステルースチレン共重合体の群力 選ばれた少なくとも 1種である請求項 1〜4い ずれかに記載の熱可塑性榭脂組成物。  [5] (C) Power of non-rubber-modified styrenic polymer Grouping power of polystyrene, styrene-a-methylstyrene copolymer, acrylonitrile-styrene copolymer, and acrylonitrile-methacrylic acid ester-styrene copolymer At least one selected The thermoplastic resin composition according to any one of claims 1 to 4, which is a seed.
[6] (二)導電性カーボン力 ケッチェンブラックである請求項 1〜5いずれかに記載の熱 可塑性榭脂組成物。  The thermoplastic resin composition according to any one of claims 1 to 5, which is ketjen black.
[7] 請求項 1〜6 ヽずれかに記載の熱可塑性榭脂組成物を成形してなる導電性フィル ムおよび導電性シート。  [7] A conductive film and a conductive sheet formed by molding the thermoplastic resin composition according to any one of claims 1 to 6.
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