WO2007043189A1 - Process for producing blow-molded object - Google Patents

Process for producing blow-molded object Download PDF

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Publication number
WO2007043189A1
WO2007043189A1 PCT/JP2005/021609 JP2005021609W WO2007043189A1 WO 2007043189 A1 WO2007043189 A1 WO 2007043189A1 JP 2005021609 W JP2005021609 W JP 2005021609W WO 2007043189 A1 WO2007043189 A1 WO 2007043189A1
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group
carbon atoms
compound
atom
hydrocarbon group
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PCT/JP2005/021609
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French (fr)
Japanese (ja)
Inventor
Hirotaka Uosaki
Kuniaki Kawabe
Motoyasu Yasui
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Mitsui Chemicals, Inc.
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Publication of WO2007043189A1 publication Critical patent/WO2007043189A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
    • B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/06—Waxes

Definitions

  • the present invention relates to a method for producing a molded body, and more particularly to a method for producing a molded body by melting a mixture containing a thermoplastic resin and a polyolefin wax, and performing blow molding.
  • Blow molding is one of the methods for producing a molded body of a resin material. It is a building material such as an outer wall that is made only of containers such as bottles and tanks, automobile parts such as automobile exterior parts, and industrial machine parts. It has also been used in the manufacture of electrical and electronic parts.
  • Patent Document 1 JP-A-11-254512
  • Patent Document 2 Pamphlet of International Publication No. 97Z45246
  • An object of the present invention is to provide a method for improving the moldability in blow molding without impairing the physical properties of the molded body and efficiently producing the molded body.
  • the inventors of the present invention have studied the above-described problems, and when a mixture containing a thermoplastic resin and a specific polyolefin wax is melted to produce a molded article by blow molding, the moldability of blow molding is improved. Moreover, it should be possible to manufacture molded products efficiently without damaging the physical properties of the molded products. As a result, the present invention has been completed.
  • the method for producing the molded article of the present invention includes:
  • the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is in the range of 400 to 5,000, and the melting point measured by differential scanning calorimeter (DSC) is 65 to 120 ° C. It is characterized by melting and blow-molding a mixture containing polyolefin wax (B) in the above range.
  • polyolefin wax (B) a meta-orthene-based polyethylene wax is preferred, and a polyethylene wax is more preferred.
  • a molded body can be produced efficiently by blow forming without impairing the physical properties of the molded body, and this production method is also excellent in moldability.
  • thermoplastic resin (A) is a thermoplastic polymer having a polystyrene-reduced number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 8,000 or more, or a blend thereof. Say things.
  • thermoplastic rosin (A) used in the present invention is not particularly limited.
  • Polyolefins such as low density polyethylene, medium density polyethylene, high density polyethylene, linear linear low density polyethylene, polypropylene, cyclic olefin polymers, ethylene propylene copolymers, cyclic olefin copolymers;
  • Styrene polymers such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, etc .;
  • Ethylene-methacrylic acid copolymer ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, ethylene vinyl alcohol copolymer;
  • Polycarbonate polymetatalylate
  • Polyesters such as polyethylene terephthalate and polybutylene terephthalate
  • Polyamides such as nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon MXD6, wholly aromatic polyamide, semi-aromatic polyamide;
  • Examples include polyacetals and blends of these rosins.
  • thermoplastic resins low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear linear low-density polyethylene, polypropylene, and ethylene-propylene copolymer are more preferable than polyolefin. More preferred are polyethylene and polypropylene.
  • thermoplastic rosin (A) is the above rosin, a good molded article having excellent dispersibility with the polyolefin wax (B) described later and having no stickiness on the surface can be obtained.
  • MI JIS K7210; 190 ° C test load 2.16kgf
  • MI JIS K7210; 190 ° C test load 2.16kgf
  • L Og / 10 minutes in range force S preferably 0.01 to 0.80 g / 10 minutes
  • Range power of S is preferred.
  • a range of 942 ⁇ 970kg / m 3 is rather preferable, preferably from the range force 944 ⁇ 965kg / m 3! / ⁇ .
  • MI JIS K7210; 230 ° C test load 2.16 kgf
  • a range of 0.1 to 3.5 gZlO is preferable, and a range of 0.4 to 1.5 is more preferable.
  • thermoplastic wax (A) is mixed with polyolefin wax.
  • Polyolefin wax in the present invention is in the range of 65 to 120 ° C. of crystallization temperature measured with a differential scanning calorimeter (DSC) under the condition of a temperature drop rate of 2 ° C.Z, and gel permeation chromatography (The number average molecular weight (Mn) in terms of polystyrene measured by (GPC) is 40. Those in the range of 0 to 5,000.
  • thermoplastic resin (A) When a mixture of such a polyolefin wax added to thermoplastic resin (A) is melted and blow molded, the melt viscosity of the resin decreases, so the flow rate of the motor is reduced as well as the motor load during extrusion is reduced. Improves the molding speed. Further, the surface of the molded body is modified, and a molded body having a smooth surface can be obtained. Furthermore, since molding can be performed at a low molding temperature, the cooling time is shortened, the thermal degradation of the resin, the burning of the resin, and the black spots can be suppressed just by improving the molding site, and the mechanical strength of the molded product is excellent. It will be.
  • the polyolefin wax (B) used in the present invention is not particularly limited.
  • polyethylene wax, polypropylene wax, a -olefin homopolymer wax, ethylene Z a-olefin copolymer wax, ethylene Z examples include waxes of a-olefin Z non-conjugated diene copolymer.
  • polyethylene waxes polyethylene waxes, polyethylene waxes that are preferred for ethylene- ⁇ -olefin copolymer waxes, and waxes that are copolymerized with ethylene and ⁇ -olefins having 3 to 20 carbon atoms are more preferred.
  • Meguta polyethylene, ethylene ⁇ propylene copolymer wax, ethylene Z1-butene copolymer wax, ethylene Zl pentene copolymer wax, ethylene Zl-hexene copolymer wax, ethylene Z4-methyl-1 Pentene copolymer wax, polyethylene Zl Otaten copolymer wax is more preferred polyethylene wax, ethylene Z propylene copolymer wax, ethylene Zi-butene copolymer wax, ethylene Zi hexene copolymer Wax, ethylene Z4 methyl 1 pentene Wa Ttasu polymers are particularly preferred.
  • the polyolefin wax (B) is the above-described polyolefin wax, it is excellent in dispersibility with the thermoplastic resin (A), in particular, the polyolefin resin, for example, there is no stickiness on the surface, and a good molded product is obtained. can get.
  • the polystyrene equivalent number average molecular weight (Mn) of the above polyolefin wax (B) measured by gel permeation chromatography (GPC) is preferably in the range of 400 to 5,000, and in the range of 700 to 4,500. More preferred than force, 800-4,000 range power ⁇ even more preferred! / ,.
  • the ratio (MwZMn) of polystyrene-equivalent weight average molecular weight and number average molecular weight of the above polyolefin wax (B) measured by gel permeation chromatography (GPC) is
  • a range power of 1.5 to 4.0 is preferred, and a range power of 1.5 to 3.5 is preferred! / ⁇ .
  • the crystallization temperature measured by SC is particularly preferably in the range of 70 to 120 ° C, more preferably in the range of 70 to 120 ° C, in the range of 65 to 120 ° C.
  • the polio Lev in wax (B), the density ⁇ was measured by a density gradient tube method in conformity with JIS K7112 or the range force S preferably of 850 ⁇ 980kg / m 3, Mashi range force RiYoshimi of 870 ⁇ 980kg / m 3 Ku, still more preferably range force of 890 ⁇ 980kg / m 3! / ⁇ .
  • the polyolefin wax (B) has the crystallization temperature [Tc (° C)] measured by a differential scanning calorimeter (DSC) and the density (D (kg / m 3 )) measured by the density gradient method.
  • Tc crystallization temperature
  • DSC differential scanning calorimeter
  • D density
  • the polyolefin wax (B) when the crystallization temperature (Tc) and the density (D) satisfy the relationship of the above formula, for example, the polyolefin wax (B) is ethylene ⁇ -o. If the wax is a olefin copolymer, the composition distribution of the copolymer becomes more uniform and the thermoplasticity There is a tendency that a molded product obtained by blow molding has a smaller tack from a mixture containing the resin (A) and the polyolefin wax (B).
  • Odmm or less preferably 25 dmm or less, more preferably 20 dmm or less, and even more preferably 15 dmm or less.
  • Polio reflex in wax (B) acetone extraction quantity is preferably in the range of 0-20 0/0 device 0
  • a range of ⁇ 15% by weight is more preferred.
  • the amount of acetone extracted is measured as follows.
  • the polyolefin wax (B) is solid at room temperature and becomes a low-viscosity liquid at 65 to 130 ° C or higher.
  • the method for producing the polyolefin wax (B) described above is not particularly limited.
  • it is obtained by polymerizing monomers such as ethylene and (X-olefin) with a Ziegler Z-Natta catalyst and a metalocene catalyst.
  • a metalocene catalyst is preferable.
  • meta-catacene catalysts examples include:
  • an olefin polymerization catalyst comprising at least one compound selected from the group consisting of:
  • the meta-octane compound that forms the meta-catalyst catalyst is a meta-metal compound of a transition metal selected from Group 4 of the periodic table.
  • a specific example is represented by the following general formula (1). Compounds that can be used.
  • M 1 is a transition metal selected from Group 4 force of the periodic table
  • X is a valence of transition metal M 1
  • L is a ligand.
  • the transition metal represented by M 1 include zirconium, titanium, and hafnium.
  • L is a ligand coordinated to the transition metal M 1, and at least one of the ligands L is a ligand having a cyclopentagel skeleton, and the coordination having this cyclopentaphenyl skeleton The child may have a substituent.
  • Examples of the ligand L having a cyclopentagenyl skeleton include a cyclopentagel group, a methylcyclopentaenyl group, an ethylcyclopentagel group, n- or i-propyl cyclopentagel. Group, ni sec— or t-butylcyclopentagel group, dimethylcyclopentagel group, methylpropyl cyclopentagel group, methylbutylcyclopentaenyl group, methylbenzylcyclopentagel group And alkyl- or cycloalkyl-substituted cyclopentagel groups such as indur, 4,5,6,7-tetrahydroindul, and fluorenyl.
  • the ligand hydrogen having a cyclopentagel skeleton may be substituted with a halogen atom or a trialkylsilyl group.
  • the ligands having two cyclopentagel skeletons are connected to each other. Is bonded via an alkylene group such as ethylene or propylene; a substituted alkylene group such as isopropylidene or diphenylmethylene; a substituted silylene group such as a silylene group, a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group. It may be done.
  • an alkylene group such as ethylene or propylene
  • a substituted alkylene group such as isopropylidene or diphenylmethylene
  • a substituted silylene group such as a silylene group, a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group. It may be done.
  • a ligand other than a ligand having a cyclopentagel skeleton (a ligand having no cyclopentagel skeleton) L is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group , Aryloxy group, sulfonic acid-containing group (one SO R 1 ), halogen atom or hydrogen atom (here
  • R 1 is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom, or an aryl group substituted with an alkyl group. ).
  • the meta-mouth compound represented by the general formula (1) is more specifically represented by the following general formula (2).
  • M 1 is a transition metal selected from Group 4 force of the periodic table
  • R 2 is a group (ligand) having a cyclopentagel skeleton
  • R 4 and R 5 are each independently a force having a cyclopentadenyl skeleton or a group (ligand) having no cyclopentagenyl skeleton.
  • M 1 is zirconium and contains at least two ligands having a cyclopentagel skeleton.
  • R 2 At least two of R 4 and R 5 , for example, R 2 and R 3 are groups (coordinators) having a cyclopentadenyl skeleton, and these at least two groups are an alkylene group, a substituted alkylene group, or a silylene group.
  • R 4 and R 5 are each independently the same as the ligand L other than the ligand having a cyclopenta Jeniru skeleton described above.
  • bridge-type meta-octene compounds include ethylene bis (indul) dimethylzirconium, ethylenebis (indul) zirconium dichloride, isopropylidene. (Cyclopentagel-fluoroenyl) zirconium dichloride, diphenylsilylene bis (indul) zirconium dichloride, methyl ferrosilylene bis (indul) zirconium dichloride.
  • meta-mouth compound is a meta-mouth compound described in JP-A-4-268307 represented by the following general formula (3).
  • M 1 is a transition metal of Group 4 of the periodic table, specifically titanium, zirconium or c Funiumu.
  • R 11 and R 12 may be the same or different from each other; a hydrogen atom that may be the same or different; an alkyl group having 1 to carbon atoms; an alkyl group having 1 to LO; an alkoxy group having 1 to carbon atoms; an alkoxy group having 6 carbon atoms; ; Aryloxy group having 6 to 10 carbon atoms; carbon atom number 2 to: alkenyl group having L0; aryl hydrocarbon group having 7 to 40 carbon atoms; alkyl aryl group having 7 to 40 carbon atoms; An arylalkyl group having 8 to 40 carbon atoms; or a halogen atom, and R 11 and R 12 are preferably chlorine atoms.
  • R 13 and R may be the same or different from each other; a hydrogen atom; a halogen atom; an optionally halogenated alkyl group having 1 to 10 carbon atoms; and a carbon atom number 6 to 10 of Ari Le group;. N (R 2 °) , - SR 2 °, - OSi (R 2 °), - Si (R 2 °) , or - P (R 2 °) group, where
  • R 2Q is a halogen atom, preferably a chlorine atom; an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms; or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms.
  • R 13 and R 1 4 are each particularly preferably a hydrogen atom.
  • R 15 and R 16 are the same as R 13 and R 14 except that a hydrogen atom is not contained, and may be the same as or different from each other.
  • R 15 and R 16 are preferably alkyl groups having 1 to 4 carbon atoms which may be halogenated, specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl and the like. In particular, methyl is preferred.
  • R 17 is selected from the following group forces.
  • M 2 is silicon, germanium or tin, preferably silicon or germanium.
  • R 21 , R 22 and R 23 may be the same or different from each other; a hydrogen atom; a halogen atom; an alkyl group having 1 to 10 carbon atoms; a fluoroalkyl group having 1 to 10 carbon atoms; 6-10 carbon aryl group; 6-6 carbon atom fluoroaryl group; 1-10 carbon atom alkoxy group; 2-10 carbon atom group; 7-40 carbon atom alkyl group Group: an arylalkyl group having 8 to 40 carbon atoms; or an alkylaryl group having 7 to 40 carbon atoms.
  • R 21 and R 22" or “R 2 1 and R 23" may form a connexion ring such together with the atom to which they are bonded.
  • R 18 and R 19 are the same thing, and the like and Yogu R 21 be also different! / ⁇ the same to each other ⁇ .
  • m and n may be the same or different from each other and are each 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1.
  • Examples of the meta-mouth compound represented by the general formula (3) include the following compounds. rac ethylene (2-methyl 1-indul) monozirconium monodichloride, rac
  • meta-mouth compounds can be produced, for example, by the method described in JP-A-4-268307.
  • meta-mouth compound represented by the following general formula (4) is used.
  • M 3 represents a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium, hafnium, or the like.
  • R 24 and R 25 may be the same or different from each other.
  • R 24 is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl or propyl.
  • R 25 is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl.
  • R 28 and R 29 represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other.
  • a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group is preferable.
  • At least one pair of R 26 and R 27 , R 2 7 and R 28 , R 28 and R 29 together with the carbon atom to which they are bonded forms a monocyclic aromatic ring. Also good.
  • R 29 is a substituent other than an aromatic group, hydrogen An atom is preferred.
  • X 1 and X 2 may be the same or different from each other, hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen atom-containing group
  • Y representing a thio atom-containing group is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, or a divalent group.
  • R 3Q is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms).
  • M 3 contains a monocyclic aromatic ring formed by combining at least one of R 26 and R 27 , R 27 and R 28 , R 28 and R 29 , and M 3
  • Examples of the ligand to be coordinated include those represented by the following formula.
  • meta-octene compound As the meta-octene compound, it is possible to use a meta-octene compound represented by the following general formula (5).
  • R 26 , R 28 and R 29 are the same as in the general formula (4).
  • R 26 , R 28 and R 29 it is preferable that two groups including R 26 are alkyl groups.
  • R 26 and R 2 8 , or R 28 and R 29 are preferably alkyl groups. .
  • This alkyl group is secondary or A tertiary alkyl group is preferred.
  • the alkyl group is a halogen atom which may be substituted with a halogen atom or a silicon-containing group. Examples of the halogen-containing group include the substituents exemplified for R 24 and R 25 .
  • the group other than the alkyl group is preferably a hydrogen atom.
  • 6 , R 27 , R 28 and R 29 may be formed by bonding two groups selected from these forces to each other to form a monocyclic or polycyclic ring other than an aromatic ring.
  • the halogen atom include those similar to the above R 24 and R 25 .
  • Examples of X 1 , X 2 and Y are the same as those described above.
  • meta-mouth compound represented by the general formula (5) Specific examples of the meta-mouth compound represented by the general formula (5) are shown below. rac Dimethylsilylene monobis (4,7 dimethyl mono 1-indul) zirconium dichloride, rac—Dimethylsilylene mono bis (2,4,7 Trimethyl mono 1-indul) zirconium dichloride, r ac Dimethylsilylene monobis (2,4, 6 Trimethyl 1-indul) Zirconium dichloride, etc.
  • transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.
  • a force R type or S type generally used as a racemate can also be used.
  • meta-octacene compound a meta-caffeine compound represented by the following general formula (6) is used.
  • R 24 is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl.
  • R 25 represents an aryl group having 6 to 16 carbon atoms.
  • R 25 is preferably phenyl or naphthyl.
  • the aryl group is a halogen atom, charcoal It may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
  • X 1 and X 2 are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
  • transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.
  • meta-mouth compound a meta-mouth compound represented by the following general formula (7) is used.
  • M 4 is a group 4 of the periodic table or a lanthanide series metal.
  • La is a derivative of a delocalized ⁇ bond group, and is a group that imparts a constrained geometry to the metal ⁇ 4 active site.
  • X 3 is a hydrogen atom, a halogen atom, a hydrocarbon group having 20 or less carbon atoms, a silyl group containing 20 or less silicon, or a germanyl group containing 20 or less germanium, which may be the same or different from each other. is there.
  • Micromax 4 is titanium, zirconium or hafnium.
  • X 3 is the same as that described in the general formula (7).
  • Cp is ⁇ -bonded to ⁇ 4 and has a substituent ⁇ It is a substituted cyclopentadenyl group.
  • Z is oxygen, iow, boron, or an element of group 4 of the periodic table (eg, keye, germanium, or tin).
  • Y is a ligand containing nitrogen, phosphorus, oxygen or io, and Z and Y may form a condensed ring.
  • a specific example of a meta-mouth compound represented by the formula (8) is shown below. (Dimethyl (t butylamide) (tetramethyl-7?
  • meta-mouth compound a meta-mouth compound represented by the following general formula (9) is used.
  • M 3 is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium.
  • R 31 may be the same or different, and at least one of them is an aryl group having 11 to 20 carbon atoms, an aryl alkyl group having 12 to 40 carbon atoms, an aryl hydrocarbon having 13 to 40 carbon atoms. At least two groups adjacent to each other, together with the carbon atom to which they are bonded, or a group of 12 to 40 carbon atoms or a C-containing group, or a group represented by R 31 , One or more aromatic or aliphatic rings are formed.
  • the ring formed by R 31 as a whole number of carbon atoms including carbon atoms to which R 31 is bonded is from 4 to 20.
  • Aryl group, aryl group, aryl group, alkyl group Lumpur group and an aromatic ring, R 31 other than R 31 that forms an aliphatic ring is a hydrogen atom, a halogen atom, an alkyl group or Kei-containing group having 1 to 10 carbon atoms.
  • R 32 is Yogu hydrogen atom be different even same each other, a halogen atom, an alkyl group having 1 to 10 carbon atoms, Ariru group having 6 to 20 carbon atoms, 2 carbon atoms: L0 alkenyl group, 7 to 40 carbon atom alkyl group, 8 to 40 carbon atom alkyl group, 7 to 40 carbon atom alkyl group, key group, oxygen group, nitrogen group, nitrogen group An element-containing group or a phosphorus-containing group. Further, at least two adjacent groups out of the groups represented by R 32 may form one or more aromatic rings or aliphatic rings together with the carbon atoms to which they are bonded.
  • the ring formed by R 32 as a whole number of carbon atoms including carbon atoms to which R 32 is bonded is from 4 to 20, except R 32 that forms form an aromatic ring, an aliphatic ring R 32 in the formula is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a key group containing silicon.
  • the group in which the two groups represented by R 32 form one or more aromatic rings or aliphatic rings includes an embodiment in which the fluorenyl group has a structure as shown in the following formula.
  • R is preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl.
  • a fluorenyl group having R 32 as a substituent a 2,7 dialkyl fluorenyl group can be cited as a suitable example.
  • the 2,7 dialkyl alkyl group has 1 to 5 carbon atoms.
  • An alkyl group is mentioned.
  • R 31 and R 32 may be the same as or different from each other.
  • R 33 and R 34 may be the same or different from each other, and may be the same hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon Alkyl group having 2 to 10 atoms, arylalkyl group having 7 to 40 carbon atoms, arylalkyl group having 8 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, and containing carbon Group, oxygen-containing group, xio-containing group, nitrogen-containing group or phosphorus-containing group is there.
  • X 1 and X 2 may be the same or different from each other, hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing group A X-containing group or a nitrogen-containing group, or a conjugation residue formed from X 1 and X 2 .
  • the conjugated gen residue formed from X 1 and X 2 is preferably a 1,3 butadiene, 2,4 hexagene, 1 phenylene 1,3 pentene, or 1,4 diphenol butadiene residue, These residues may be further substituted with a hydrocarbon group having 1 to 10 carbon atoms.
  • X 1 and X 2 are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a X-containing group.
  • Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent carbon-containing group, a divalent germanium-containing group, a divalent Tin-containing group, O, 1 CO, 1 S—, 1 SO—, —SO 1, NR 35 , 1 P (R 35 ), 1 P (0) (R 35 ), 1 BR 35 or 1 Al
  • R 35 (wherein R 35 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms).
  • these divalent groups those in which the shortest linking part of Y— is composed of one or two atoms are preferable.
  • R 3 5 is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms.
  • Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group, or a divalent germanium-containing group, and more preferably a divalent silicon-containing group.
  • Particularly preferred are alkylsilylene, alkylarylsilylene or arylylsilylene.
  • meta-mouth compound a meta-mouth compound represented by the following general formula (10) is used.
  • M 3 is a transition metal atom of Group 4 of the periodic table, specifically titanium, Jill co - a ⁇ beam or hafnium, preferably zirconium.
  • R 36 may be the same or different from each other, hydrogen atom, halogen atom, carbon atom number 1 to: L0 alkyl group, carbon atom number 6 to: L0 aryl group, carbon atom number 2 to: L0 alkenyl A group, a silicon-containing group, an oxygen-containing group, a X-containing group, a nitrogen-containing group or a phosphorus-containing group.
  • the above alkyl group and alkenyl group may be substituted with a halogen atom.
  • R 36 is preferably an alkyl group, an aryl group or a hydrogen atom, particularly a methyl, ethyl, n-propyl or i-propyl hydrocarbon group having 1 to 3 carbon atoms, phenyl, a An aryl group such as naphthyl or ⁇ -naphthyl or a hydrogen atom is preferable.
  • R 37 may be the same or different from each other, hydrogen atom, halogen atom, carbon atom number 1 to: L0 alkyl group, carbon atom number 6 to 20 aryl group, carbon atom number 2 to 10 alkyl group , 7 to 40 carbon atom alkyl group, 8 to 40 carbon atom aryl group, 7 to 40 carbon atom alkyl group, silicon-containing group, oxygen-containing group, X-containing group A nitrogen-containing group or a phosphorus-containing group.
  • the alkyl group, aryl group, alkyl group, aryl alkyl group, aryl hydrocarbon group and alkyl aryl group may be substituted with halogen.
  • R 37 is preferably a hydrogen atom or an alkyl group, particularly a hydrogen atom or a carbon atom number of 1 to 4 of methyl, ethyl, ⁇ -propyl, i-propyl, n-butyl, and tert butyl.
  • the hydrocarbon group is preferably.
  • R 36 and R 37 may be the same as or different from each other.
  • One of R 38 and R 39 is an alkyl group having 1 to 5 carbon atoms, and the other is a hydrogen atom, a halogen atom, or a carbon atom having 1 to: an alkyl group having L0, or 2 to carbon atoms having an L0.
  • Alkellyl group, silicon-containing group, oxygen-containing It is a group, a thio group, a nitrogen group or a phosphorus group.
  • one of R 38 and R 39 is an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, and propyl, and the other is a hydrogen atom.
  • X 1 and X 2 may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, A containing group or a nitrogen-containing group, or a conjugation residue formed from X 1 and X 2 .
  • a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable.
  • Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, O CO S -, - SO- , -SO -, - NR 4 ° -, - P (R 4 °) -, - P (0) (R 4 °) -, - BR 4 ° - Or
  • R 4Q is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms).
  • Y is preferably a divalent hydrocarbon-containing group having 1 to 5 carbon atoms, preferably a divalent hydrocarbon-containing group or a divalent germanium-containing group.
  • alkylsilylene, alkylarylsilylene or arylylsilylene which are more preferred! /.
  • meta-mouth compound a meta-mouth compound represented by the following general formula (11) is used.
  • Y is selected from carbon, silicon, germanium and tin atoms
  • M is Ti, Zr or Hf R 1Q
  • R U and R 12 are hydrogen, a hydrocarbon group, selected from Kei-containing group, adjacent substituents of up Yogu R 5 or et R 12 be different or identical or not bonded to each other to form a ring
  • R 13 and R 14 may be selected from a hydrocarbon group and a silicon-containing group, and may be the same or different, and R 13 and R 14 may be bonded to each other to form a ring. May be.
  • Q may be selected from the same or different combinations from a halogen, a hydrocarbon group, a lone ligand, or a neutral ligand capable of coordinating with a lone pair
  • j is an integer of 1 to 4.
  • the cyclopentagel group may or may not be substituted.
  • the cyclopentagel group which may or may not be substituted, is a group in which R 2 , R 3 and R 4 are all hydrogenated by the cyclopentagel group moiety in the general formula (11).
  • a force that is an atom, or one or more of the scales 1 , R 2 , R 3 and R 4 is a hydrocarbon group (fl), preferably a hydrocarbon group having 1 to 20 carbon atoms in total (fl ')
  • a cyclopentagel group (12) preferably a cyclopentagel group substituted with a C 1 -C 20 group ( ⁇ ').
  • the hydrocarbon group having 1 to 20 carbon atoms in total is an alkyl, alkenyl, alkynyl, or aryl group composed only of carbon and hydrogen. This includes those in which any two adjacent hydrogen atoms are simultaneously substituted to form an alicyclic or aromatic ring.
  • the hydrocarbon group having 1 to 20 carbon atoms (fl ') includes, in addition to alkyl, alkyl, alkyl, and aryl groups composed of only carbon and hydrogen, one of the hydrogen atoms directly connected to these carbons.
  • Examples of such a group (fl ′) include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n_Otachil group, n-nonyl group, n-decanyl group and other linear hydrocarbon groups; Propyl group, t-butyl group, amyl group, 3-methylpentyl group, 1,1-jetylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl Branched hydrocarbon group such as 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl Cyclic hydrocarbon groups such
  • the silicon-containing group ( ⁇ ) is, for example, a group in which a ring carbon of a cyclopentagenyl group is directly covalently bonded to a silicon atom, specifically an alkylsilyl group or a arylsilyl group.
  • Examples of the C 1 to C 20 -containing group ( ⁇ ′) include a trimethylsilyl group and a triphenylsilyl group.
  • the fluorenyl group may or may not be substituted. It may or may not be substituted! ⁇
  • the fluorenyl group means R 5 held by the fluorenyl group moiety in the general formula (11), R 9,
  • R 1Q , R 11 and R 12 is a hydrocarbon group (fl), preferably a hydrocarbon group having 1 to 20 carbon atoms in total (fl ′), or a silicon-containing group (12), Preferably, it means a fluorine group substituted with a carbon-containing group 02 ′) having 1 to 20 carbon atoms in total.
  • R 5 When two or more of RR 1Q , R 11 and R 12 are substituted, those substituents may be the same or different from each other. Also, R 5, R 6, R 7, R 8, R 9, R 10, R 11 and R 12 are adjacent contact groups are bonded to each other to form a ring! /, I be! /,. In view of the ease of production of the catalyst, those in which R 6 and R u and R 7 and R 1Q are the same are preferably used.
  • a preferred group of the hydrocarbon group (fl) is the above-described hydrocarbon group (fl ′) having 1 to 20 carbon atoms, and a preferable example of the silicon-containing group (12) is the above-mentioned total carbon number of 1 to 20 This is a C-containing group ( ⁇ ').
  • the main chain part of the bond connecting the cyclopentagenyl group and the fluorenyl group is a divalent covalent bond containing one carbon, silicon, germanium and tin atom.
  • the important point in the high-temperature solution polymerization of the present invention is that the bridging atom Y of the covalent bond bridging portion has R 13 and R 14 which may be the same or different from each other.
  • a preferred group of the hydrocarbon group (fl) is the hydrocarbon group (fl ′) having a total carbon number of 1 to 20 described above, and a preferable example of the silicon-containing group (12) is the above-mentioned total number of carbon atoms of 1 to 20.
  • Q is a halogen, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated gen, carbon ion ligand or lone electron pair having 10 or less carbon atoms.
  • the neutral ligands that can be coordinated are selected in the same or different combinations.
  • Specific examples of the halogen include fluorine, chlorine, bromine and iodine.
  • hydrocarbon group examples include methyl, ethyl, ⁇ -propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2 , 2-dimethylpropyl, 1,1-jetylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like.
  • neutral, conjugated or non-conjugated genes with 10 or fewer carbon atoms include s-cis- or s-trans-7 ⁇ 4 -1,3-butadiene, s-cis- or s-trans-7? '-1,4-diphenyl-1,3-butadiene, S-cis- or S-trans-7?' -3-methyl-1,3-pentagen, s-cis- or s-trans-4-1 , 4-dibenzyl-1,3-butadiene, s-cis- or s-trans-7?
  • organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, or tetrahydrofuran, jetyl.
  • Ether, dioxane, 1,2-dimeth And ethers such as ki carten.
  • j is an integer from 1 to 4, and when j is 2 or more, Q's are the same or different from each other! /.
  • meta-mouth compound a meta-mouth compound represented by the following general formula (12) is used.
  • R 2 , R 3 , R 4 , R 5 , R. , R 7 , R 8 , R 9 , R 10 , R U , R 12 , R 13 , R 14 are selected from hydrogen, a hydrocarbon group, and a silicon-containing group, and may be the same or different. Adjacent substituents from 1 to R 14 may be bonded to each other to form a ring.
  • M is Ti, Zr or Hf
  • Y is a Group 14 atom
  • Q is a halogen, hydrocarbon group.
  • n 2
  • An integer of ⁇ 4 j is an integer of 1 ⁇ 4.
  • the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an aryl alkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or It is an alkylaryl group having 7 to 20 carbon atoms, and may contain one or more ring structures.
  • the C-containing hydrocarbon group is preferably an alkyl or aryl silyl group having 1 to 4 carbon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert -Butyldimethylsilyl, triphenylsilyl and the like.
  • R "from R 1 in the general formula (12) hydrogen, a hydrocarbon group, selected from Kei-containing hydrocarbon group, each of which may be the same or different.
  • Preferred hydrocarbon groups, containing Kei containing Specific examples of the hydrocarbon group include those similar to the above.
  • M in the general formula (12) is a group 4 element of the periodic table, that is, zirconium, titanium, or hafnium, preferably zirconium.
  • Y is a Group 14 atom, preferably a carbon atom or a silicon atom.
  • n is an integer of 2 to 4, preferably 2 or 3, particularly preferably 2.
  • Q is a group consisting of a halogen, a hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or non-conjugated gen, a lone ligand, and a neutral ligand capable of coordination with a lone pair of electrons. Selected in the same or different combinations.
  • Q is a hydrocarbon group, it is more preferably a hydrocarbon group having 1 to: L0 carbon atoms.
  • halogen include fluorine, chlorine, bromine and iodine.
  • hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-jetylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like.
  • Y is a force in which a plurality of 2 to 4 exist.
  • a plurality of Y may be the same as or different from each other.
  • the plurality of R 13 and the plurality of R 14 bonded to Y may be the same as or different from each other.
  • a plurality of R 13 bonded to the same Y may be different from each other, or a plurality of R 13 bonded to different Y may be the same as each other.
  • R 13 or R 14 may form a ring.
  • Group 4 transition metal compound represented by the formula (12) include a compound represented by the following formula (13).
  • Adjacent substituents up to R 5 force R 12 may be bonded together to form a ring
  • R 13 and R 15 may be bonded to each other V ⁇ to form a ring
  • R 13 and R When 15 is bonded to each other to form a ring, at the same time, R 14 and R 16 may be bonded to each other to form a ring.
  • Y 1 and Y 2 are group 14 atoms and are the same or different from each other M is Ti, Zr or Hf
  • Q is a neutral ligand force that can be coordinated by a halogen, a hydrocarbon group, a lone ligand, or a lone pair of electrons, in the same or different combinations. You can choose j is an integer from 1 to 4.
  • meta-octacene compounds such as 9 and 10 are listed in JP-A-2004-175707 publications WO200lZ027124, WO2004 / 029062, WO2004Z083265 and the like.
  • the meta-senic compound described above may be used alone or in combination of two or more. Further, the meta mouth mixture may be diluted with a hydrocarbon or a halogenated hydrocarbon.
  • the catalyst component includes (A) the above-mentioned cross-linked meta-molecular compound, and (B) (b-1) an organic aluminum compound, (b-2) the above-mentioned cross-linked meta-molecular compound ( It is composed of a compound that reacts with A) to form an ion pair, and (b-3) an organoaluminum compound force that is selected from at least one compound.
  • Component (B) will be specifically described below.
  • (b-1) organoaluminum compound used in the present invention a conventionally known aluminoxane can be used as it is. Specifically, the following general formula (14)
  • R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more
  • n represents an integer of 2 or more
  • Aluminoxanes having n of 3 or more, preferably 10 or more are used. These aluminoxanes may be mixed with some organic aluminum compounds.
  • a characteristic characteristic of the high-temperature solution polymerization of the present invention is that it is also possible to apply a benzene-insoluble organic alcoholic compound as exemplified in JP-A-2-78687.
  • organoaluminum compounds described in JP-A-2-167305, two or more types of alkyl groups described in JP-A-2-24701, JP-A-3-03407 An aluminoxane having bismuth can also be suitably used.
  • the “benzene-insoluble” organoaluminum compound used in the high-temperature solution polymerization of the present invention means that the A1 component dissolved in benzene at 60 ° C. is usually 10% or less in terms of A1 atom, preferably 5 % Or less, particularly preferably 2% or less, and is insoluble or hardly soluble in benzene.
  • organoaluminum compound used in the present invention examples include modified methylaluminoxane as shown in (16) below.
  • R is a hydrocarbon group having 1 to 10 carbon atoms, and m and n are integers of 2 or more.
  • This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum.
  • a compound [V] is generally called MMAO!
  • Such MMAO can be prepared by the methods listed in US4960878 and US5041584.
  • Tosoh 'Finechem Co., Ltd. also used trimethylaluminum and triisobutylaluminum.
  • R is an isobutyl group.
  • MMAO and TMAO t are commercially produced under the name!
  • Such MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, it is insoluble or hardly soluble in benzene as in (14) and (15) above. The difference is that it dissolves in aliphatic and alicyclic hydrocarbons.
  • organoaluminum compound used in the present invention examples include an organoaluminum compound containing boron represented by the following general formula (17).
  • R d represents a hydrocarbon group having from 10 to 10 carbon atoms.
  • R d may be the same or different from each other, a hydrogen atom, a halogen atom, or a carbon atom having a number of carbon atoms of up to 10 carbon atoms. Indicates a hydrogen group.
  • ⁇ (b-2) Compound that forms an ion pair by reacting with the bridged meta-octacene compound (A)> Compound that reacts with the bridged meta-mouth compound (A) to form an ion pair (b-2) May be abbreviated as “ionic compound”) as disclosed in JP-A-1-501950, JP-A-1-502030, JP-A-3-179005, JP-A-3-179006, Examples include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-207703, JP-A-3-207704, USP5321106 and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.
  • the ionic compound preferably employed is a compound represented by the following general formula (18).
  • R e + is, carbenium - Umukachion, Okiso - Umukachion, ammonium - ⁇ beam cation, phospho - Umukachion, Puchirutorie cyclohexane - Rukachion, have a transition metal Hue mouth thermium cations.
  • ⁇ May be the same as or different from each other, and are an organic group, preferably an aryl group.
  • carb cation examples include triphenyl carb cation, tris (methyl phen) carb cation and tri-substituted carb cation such as tris (dimethyl phen) carb cation. Can be mentioned.
  • ammonium cation examples include trimethyl ammonium cation, triethyl ammonium cation, tri (n-propyl) ammonium cation, triisopropyl ammonium cation, tri (n-butyl) ammonium cation, tri Trialkylammonium cations such as isobutylammonium cation, ⁇ , ⁇ -dimethyl-rium cation, ⁇ , ⁇ -jetylarium cation, ⁇ , ⁇ - 2,4,6-pentamethylarium cation, etc. And dialkyl ammonium cations such as -dialkyl ammonium cation, diisopropyl ammonium cation and dicyclohexyl ammonium cation.
  • phosphonium cation examples include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenol) phosphonium cation, and tris (dimethylphenol) phosphomucation. It is done.
  • Re e + is preferably a carbium cation, an ammonium cation, etc., particularly a triphenylcarbium cation, ⁇ , ⁇ -dimethylarium cation, ⁇ , ⁇ -jetylarium cation. ,.
  • carbaum salt examples include triphenyl carbamate tetraphenol, triphenyl carbaum tetrakis (pentafluorophenol) borate, triphenyl carbaum tetrakis (3,5- Ditrifluoromethylphenol) borate, tris (4-methylphenol) carbtetrakis (pentafluorophenol) borate, tris (3,5-dimethylphenol) carbtetrakis ( (Pentafluorophenol) borate and the like.
  • ammonium salt examples include trialkyl-substituted ammonium salts, ⁇ , ⁇ -dialkylauryum salts, dialkylammonium salts, and the like.
  • trialkyl-substituted ammonium salt examples include, for example, triethylammonium salt. Tetraphenolate, tripropylammonium tetraphenolate, tri (n-butyl) ammoniumtetraphenolate, trimethylammoniumtetrakis (p-tolyl) borate, trimethylammoniumtetrakis (0-tolyl) borate, tri (n-Butyl) ammumute trakis (pentafluorophenol) borate, triethylammonium tetrakis (pentafluorophenol) borate, tripropylammonium tetrakis (pentafluorophenol) borate, tripropylammonium -Umtetrakis (2,4-dimethylphenol) borate, tri (n-butyl) ammotetrakis (3,5-dimethylphenol) borate, tri (n-butyl) ammo-tetra
  • ⁇ , ⁇ -dialkyl dimethylureum salts include, for example, ⁇ , ⁇ -dimethyl dimethyl-tetrafluorophosphate, ⁇ , ⁇ -dimethyldimethyl-tetrakis (pentafluorophenol) borate, ⁇ , ⁇ -Dimethylaureum tetrakis (3,5-ditrifluoromethylphenol) borate, ⁇ , ⁇ -demethylaureum tetrakisole, ⁇ , ⁇ -deethylaureum tetrakis (pentafluorophenol) Borate, ⁇ , ⁇ -jetylalyumum tetrakis (3,5-ditrifluoromethylphenol) borate, ⁇ , ⁇ -2,4,6-pentamethyla-ryumteto laurate, ⁇ , ⁇ -2,4, Examples include 6-pentamethylauryum tetrakis (pentafluorophenol) borate
  • dialkyl ammonium salt examples include di (1-propyl) ammonium tetrakis (pentafluorophenol) borate and dicyclohexyl ammonium tetraphenol borate.
  • ionic compounds disclosed by the present applicant Japanese Patent Laid-Open No. 2004-516766 can be used without limitation.
  • the ionic compound (b-2) as described above can be used in combination of two or more.
  • organoaluminum compounds that form an olefin polymerization catalyst examples include organoaluminum compounds represented by the following general formula [X], group 1 metals represented by the following general formula (19), and aluminum. And a complex alkylated product thereof.
  • Such compounds include trimethyl aluminum, Application Benefits ethyl aluminum, tri n- butylaluminum, hexyl aluminum to tri, tri n such Toriokuchi Le aluminum - alkylaluminium; triisopropyl aluminum, triiso butylaluminum, tri sec- Tri-branched alkylaluminums such as butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; tricyclohexylaluminum, tricyclooctylaluminum Tricycloalkylaluminum such as triphenylaluminum, triarylaluminum such as tritolyl aluminum, diisopropylaluminum hydride, di In the general formula G- CH) Al (CH) (wherein, x, y, z are each a positive number, and z ⁇ 2
  • Alkenyl aluminum such as isoprenyl aluminum represented by: Alkyl aluminum alkoxide such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide; Dialkyl aluminum such as dimethyl aluminum methoxide, jetyl aluminum ethoxide, dibutyl aluminum butoxide Alkoxides; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; partially having an average composition represented by the general formula R a Al (OR b )
  • M 2 represents a Li, Na or K
  • R a is Ca carbon atoms ⁇ to 15, preferably a 1-4 hydrocarbon group.
  • a complex alkyl compound of a group 1 metal and aluminum examples include LiAl (C H) and LiAl (C H).
  • a compound similar to the compound represented by the general formula (20) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. it can. Specific examples of such compounds include (C H) A1N (C H) A1 (
  • trimethylaluminum and triisobutylaluminum are preferably used as the (b-3) organoaluminum compound.
  • the polyolefin wax used in the present invention can be obtained by the ability to homopolymerize ethylene in a normal liquid phase in the presence of the above-mentioned meta-locene catalyst, or by copolymerizing ethylene and ⁇ -olefin.
  • the usage of each component and the order of addition are arbitrarily selected. However, the following method is exemplified.
  • At least two or more of the catalyst components may be in contact with each other in advance.
  • a hydrocarbon solvent is generally used, but a 1-year-old refin may be used as a solvent.
  • the monomers used here are as described above.
  • Polymerization methods include suspension polymerization in which polyolefin wax is present as particles in a solvent such as hexane, gas phase polymerization in which a solvent is not used, and a polymerization temperature of 140 ° C or higher. It is possible to perform solution polymerization in which polyolefin wax is polymerized in the state of coexistence with a solvent or when melted alone. Among them, solution polymerization is preferred in terms of both economy and quality. You may go on. When the polymerization is carried out by a batch method, the catalyst component is used in the concentration described below.
  • Ingredient (A) is, per liter of the reaction volume, typically 10 9 to 10-1 mol, preferably 10- 8 used in such an amount that the ⁇ 10 2 mol.
  • Component (b-1) is a molar ratio of component (b-1) to all transition metal atoms (M) in component (A) [(b-1) / M] force usually from 0.01 to 5, 000, preferably in an amount such as 0.05 to 2,000! /.
  • Component (b-2) is a molar ratio of the ionic compound in component (b-2) to the total transition metal (M) in component (A) [(b-2) ZM] force. It is used in an amount of 01 to 5,000, preferably 1 to 2,000.
  • Component (b-3) is a molar ratio of component (b-3) to transition metal atom (M) in component (A) [(b 3) ZM] 1S usually 1 to: L0000, preferably 1 Used in an amount of ⁇ 5000.
  • the temperature of the polymerization reaction is usually 20 to +200 when 10 g of wax is set on the filter. C, preferably 50 to 180 ° C, more preferably 70 to 180 ° C, and the pressure is usually more than 0 to 7.8 MPa (80 kgfZcm 2 , gauge pressure) or less, preferably more than 0 to 4.9 MPa ( 50kgf / cm 2 , gauge pressure)
  • ethylene and a-olefin used as necessary are as described above. It is fed to the polymerization system in such an amount that a polyolefin wax having a specific composition is obtained.
  • a molecular weight regulator such as hydrogen can be added.
  • the produced polymer is usually obtained as a polymerization solution containing the polymer, so that polyolefin wax can be obtained by processing in a conventional manner.
  • polyolefin wax (B) having the above-mentioned Mn, Mw / Mn, melting point range, other preferred V, and physical properties can be easily obtained, and also obtained using such a catalyst.
  • Polyolefin wax (B) has a great effect of improving the fluidity, and by simply increasing the molding speed significantly, the sticky component is reduced and a molded product having no stickiness on the surface can be obtained.
  • thermoplastic resin (A) polyolefin, preferably low density polyethylene, medium density polyethylene, high density polyethylene, linear linear low density polyethylene, polypropylene, ethylene propylene copolymer, more preferably high density.
  • polyethylene and polypropylene are used, the dispersibility of the thermoplastic resin (A) and the polyolefin wax (B) will be good, and the flow rate improvement effect will be greater and the molding speed will be further increased. A molded product with less stickiness on the surface can be obtained.
  • the amount of the polyolefin wax (B) thus obtained is usually in the range of 0.01 to 20 parts by weight, preferably 0.1 to 100 parts by weight of the thermoplastic resin (A). It is in the range of ⁇ 10 parts by weight, more preferably in the range of 0.3 to 5 parts by weight.
  • the polyolefin wax (B) When the polyolefin wax (B) is blended within the above range, the effect of improving the fluidity is great, and the molding speed is greatly improved. In addition, since molding is possible at a low molding temperature, the cooling time is shortened and the molding cycle is improved. Further, by lowering the molding temperature, it is possible to suppress the thermal deterioration of the resin and to suppress the burning and black spots of the resin just by suppressing the decrease of the resin strength.
  • the mixture before blow molding may further include an antioxidant, an ultraviolet absorber, a light stabilizer and the like as necessary. You may add additives, such as a fixed agent, a metal sarcophagus, a filler, a flame retardant.
  • antioxidants such as findered phenolic compounds, phosphite compounds, and thioether compounds
  • UV absorbers such as benzotriazole compounds and benzophenone compounds
  • light stabilizers such as hindered amine compounds
  • Examples of the metal sarcophagus include stearates such as magnesium stearate, calcium stearate, barium stearate and zinc stearate.
  • filler examples include calcium carbonate, titanium oxide, barium sulfate, talc, clay, and carbon black.
  • the flame retardant examples include halogen compounds such as halogenated diphenyl ethers such as degabrom diphenyl ether, octabrom diphenyl ether, halogenated polycarbonate, etc .; Inorganic compounds such as hydroxyaluminum hydroxide; phosphorus compounds and the like.
  • halogen compounds such as halogenated diphenyl ethers such as degabrom diphenyl ether, octabrom diphenyl ether, halogenated polycarbonate, etc .
  • Inorganic compounds such as hydroxyaluminum hydroxide; phosphorus compounds and the like.
  • antibacterial and antifungal agents examples include organic compounds such as imidazole compounds, thiazole compounds, -tolyl compounds, haloalkyl compounds, and pyridine compounds; silver, silver compounds, zinc compounds, copper compounds, Examples include inorganic substances such as titanium compounds and inorganic compounds.
  • thermally stable silver and silver-based compounds are preferable.
  • Examples of the silver compound include silver salts such as silver complexes, fatty acids, and phosphoric acids.
  • these materials are porous such as zeolite, silica gel, zirconium phosphate, calcium phosphate, hydrated talcite, hydroxyapatite, calcium silicate, etc. In some cases, it is supported on a structure.
  • additives examples include colorants, plasticizers, anti-aging agents, colorants, plasticizers, and oils.
  • the molded article of the present invention can be obtained by melting a mixture containing the thermoplastic resin (A) and the polyolefin wax (B) and blow-molding the mixture.
  • blow molding methods include extrusion blow molding and injection blow molding.
  • the molded article of the present invention is obtained by extrusion blow molding
  • the mixture containing the thermoplastic resin (A) and the polyolefin wax (B) is usually melted, and the resin temperature is usually 170 to 240 ° C.
  • stretch to an appropriate magnification when extrusion blow molding, stretch to an appropriate magnification.
  • the resin temperature is usually in the range of 170 to 220 ° C, preferably in the range of 180 to 210 ° C.
  • the molded body is obtained by extruding and wearing the mold in a range of the resin temperature usually in the range of 160 to 210 ° C, preferably in the range of 170 to 200 ° C. Further, it may be stretched during extrusion blow molding.
  • the resin is usually extruded from a die in the range of 190 to 230 ° C, preferably 200 to 220 ° C.
  • the molded body can be obtained by attaching the resin to the mold at a resin temperature of usually 180 to 220 ° C, preferably 190 to 210 ° C.
  • the extrusion blow molding may be stretched.
  • the force capable of obtaining a molded article by blow molding under the above-described conditions the thermoplastic resin (A) containing no polyolefin wax (B) is obtained.
  • the physical properties of the resulting molded product are not impaired even when molded under conditions of usually 0 to 30 ° C or less, preferably 10 to 20 ° C or less.
  • a molded body can be produced.
  • bottles such as cosmetic bottles, detergent bottles and bath detergent bottles, industrial chemical cans, drum cans, tanks, building materials such as tanks and outer walls, automobile parts such as automobile exterior parts, Molded bodies that can be used for industrial machine parts, electrical / electronic parts, etc. are obtained.
  • the measuring method of a physical property is as follows.
  • Example 1 Blow molding was performed in the same manner as in Example 1 except that the molding temperature used in Example 1 was changed from 180 ° C to 200 ° C without adding the PEPE wax, and a bottle with an internal volume of 1500 mL was molded. And evaluated. Table 1 shows the evaluation results.
  • Example 1 Blow molding was carried out in the same manner as in Example 1 except that the power used in Example 1 was the same except that no power was added to the PE metal wax. The evaluation results are shown in Table 1.
  • the molding temperature is lowered from 200 ° C to 180 ° C.
  • the molding cycle is improved.
  • the molding temperature is lowered from 200 ° C to 180 ° C without adding polyolefin wax, the appearance and drop strength deteriorate, the mold and molding cycle become longer, and the productivity deteriorates. Can be divided.
  • the measuring method of a physical property is as follows.
  • Table 2 shows the evaluation results.
  • Example 2 Blow molding was performed in the same manner as in Example 1 except that the molding temperature used in Example 3 was changed from 180 ° C to 200 ° C without adding the PE metal wax, and a bottle with an inner volume of 1500 mL was molded. And evaluated. Table 1 shows the evaluation results.
  • Example 1 Blow molding was carried out in the same manner as in Example 1 except that the power used in Example 1 was the same except that no power was added to the PE metal wax. The evaluation results are shown in Table 1.
  • the molding temperature is lowered from 170 ° C to 150 ° C. It can be seen that the molding cycle is improved as well as the appearance and drop strength are not impaired. In addition, if the molding temperature is lowered from 170 ° C to 150 ° C without adding polyolefin wax, the appearance and drop strength will deteriorate, and the mold and molding cycle will become longer, resulting in poor productivity. I understand.

Abstract

A process in which molded objects are efficiently produced by improving moldability in blow molding without impairing material properties of the molded articles. The process comprises: melting a mixture comprising a thermoplastic resin and a polyolefin wax having a number-average molecular weight (Mn), as determined through measurement by gel permeation chromatography (GPC) and calculation for polystyrene, of 400-5,000 and a crystallization temperature as determined with a differential scanning calorimeter (DSC) of 65-120°C; and blow-molding the melt.

Description

明 細 書  Specification
ブロー成形体の製造方法  Method for producing blow molded article
技術分野  Technical field
[0001] 本発明は成形体を製造する方法に関し、より詳細には、熱可塑性榭脂とポリオレフ インワックスとを含む混合物を溶融して、ブロー成形により成形体を製造する方法に 関する。  TECHNICAL FIELD [0001] The present invention relates to a method for producing a molded body, and more particularly to a method for producing a molded body by melting a mixture containing a thermoplastic resin and a polyolefin wax, and performing blow molding.
背景技術  Background art
[0002] ブロー成形は、榭脂素材力 成形体を製造する方法の 1つであり、ボトル、タンクな どの容器類だけでなぐ外壁などの建築資材、自動車外装部品などの自動車部品、 工業機械部品、電気 ·電子部品等の製造にも用いられてきている。  [0002] Blow molding is one of the methods for producing a molded body of a resin material. It is a building material such as an outer wall that is made only of containers such as bottles and tanks, automobile parts such as automobile exterior parts, and industrial machine parts. It has also been used in the manufacture of electrical and electronic parts.
特に近年では、成形品の諸物性を損なうことなぐブロー成形自体の生産性を向上 する方法が求められて 、る。  Particularly in recent years, there is a demand for a method for improving the productivity of blow molding without damaging the physical properties of the molded product.
[0003] 例えば、ブロー成形を行う成形機、成形条件を改良することにより生産性を向上す る方法が検討されている（例えば、特許文献 1および 2参照。 )0 [0003] For example, the molding machine to perform blow molding, how to improve the productivity by improving the molding conditions have been studied (for example, see Patent Documents 1 and 2.) 0
しかし、このように特殊な成形機、成形条件を用いなくても、成形体自体の物性を損 なうことなく生産性向上する方法が求められており、また従来のこれら方法によっても 生産 ¾向上のためには、 V、まだ改善の余地があった。  However, there is a need for a method for improving productivity without impairing the physical properties of the molded body itself without using a special molding machine and molding conditions as described above. For V, there was still room for improvement.
特許文献 1 :特開平 11— 254512号公報  Patent Document 1: JP-A-11-254512
特許文献 2：国際公開第 97Z45246号パンフレット  Patent Document 2: Pamphlet of International Publication No. 97Z45246
発明の開示  Disclosure of the invention
発明が解決しょうとする課題  Problems to be solved by the invention
[0004] 本発明の目的は、成形体の物性を損なうことなぐブロー成形における成形性を向 上し、効率よく成形体を製造する方法を提供することにある。 [0004] An object of the present invention is to provide a method for improving the moldability in blow molding without impairing the physical properties of the molded body and efficiently producing the molded body.
課題を解決するための手段  Means for solving the problem
[0005] 本発明者らは上記課題を検討し、熱可塑性榭脂と特定のポリオレフインワックスとを 含む混合物を溶融して、ブロー成形により成形体を製造すると、ブロー成形の成形 性が向上し、しかも成形品の物性を損なうことなく効率よく成形品を製造できることを 見い出し本発明を完成するに至った。 [0005] The inventors of the present invention have studied the above-described problems, and when a mixture containing a thermoplastic resin and a specific polyolefin wax is melted to produce a molded article by blow molding, the moldability of blow molding is improved. Moreover, it should be possible to manufacture molded products efficiently without damaging the physical properties of the molded products. As a result, the present invention has been completed.
すなわち本発明の成形体を製造する方法は、  That is, the method for producing the molded article of the present invention includes:
熱可塑性榭脂 (A)と、  Thermoplastic rosin (A),
ゲルパーミエーシヨンクロマトグラフィー（GPC)で測定したポリスチレン換算の数平均 分子量 (Mn)が 400〜5, 000の範囲にあり、示差走査熱量計 (DSC)で測定した融 点が 65〜120°Cの範囲であるポリオレフインワックス（B)とを含む混合物を溶融しブ ロー成形することに特徴がある。  The number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography (GPC) is in the range of 400 to 5,000, and the melting point measured by differential scanning calorimeter (DSC) is 65 to 120 ° C. It is characterized by melting and blow-molding a mixture containing polyolefin wax (B) in the above range.
[0006] 上記ポリオレフインワックス（B)としてはポリエチレンワックスが好ましぐメタ口セン系 ポリエチレンワックスがより好まし 、。 発明の効果 [0006] As the polyolefin wax (B), a meta-orthene-based polyethylene wax is preferred, and a polyethylene wax is more preferred. The invention's effect
[0007] 本発明によれば、成形体の物性を損なうことなく効率よくブロー形成により成形体を 製造することができ、またこの製造方法は成形性にも優れる。  [0007] According to the present invention, a molded body can be produced efficiently by blow forming without impairing the physical properties of the molded body, and this production method is also excellent in moldability.
発明を実施するための最良の形態  BEST MODE FOR CARRYING OUT THE INVENTION
[0008] 以下、本発明を詳細に説明する。 [0008] Hereinafter, the present invention will be described in detail.
〔熱可塑性榭脂 (A)〕  [Thermoplastic resin (A)]
本発明では熱可塑性榭脂 (A)とは、ゲルパーミエーシヨンクロマトグラフィー（GPC) で測定したポリスチレン換算の数平均分子量 (Mn)が 8, 000以上の熱可塑性の重 合体、またはそれらのブレンド物をいう。  In the present invention, the thermoplastic resin (A) is a thermoplastic polymer having a polystyrene-reduced number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 8,000 or more, or a blend thereof. Say things.
[0009] 本発明で用いる熱可塑性榭脂 (A)には特に制限はなぐ例えば [0009] The thermoplastic rosin (A) used in the present invention is not particularly limited.
低密度ポリエチレン、中密度ポリエチレン、高密度ポリエチレン、直鎖線状低密度ポリ エチレン、ポリプロピレン、環状ォレフィン重合体、エチレン プロピレン共重合体、 環状ォレフィン共重合体などのポリオレフイン；  Polyolefins such as low density polyethylene, medium density polyethylene, high density polyethylene, linear linear low density polyethylene, polypropylene, cyclic olefin polymers, ethylene propylene copolymers, cyclic olefin copolymers;
ポリスチレン、アクリロニトリル一スチレン共重合体、アクリロニトリル一ブタジエン一ス チレン共重合体、などのスチレン系重合体；  Styrene polymers such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer, etc .;
ポリ塩ィ匕ビニル、ポリ塩ィ匕ビユリデン；  Poly salt vinyl, poly salt vinylidene;
エチレンーメタクリル酸共重合体、エチレンーメタクリル酸エステル共重合体、ェチレ ンー酢酸ビニル共重合体、エチレン ビニルアルコール共重合体、；  Ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, ethylene vinyl alcohol copolymer;
ポリカーボネート、ポリメタタリレート； ポリエチレンテレフタレート、ポリブチレンテレフタレートなどのポリエステル； ナイロン 6、ナイロン 11、ナイロン 12、ナイロン 46、ナイロン 66、ナイロン MXD6、全 芳香族ポリアミド、半芳香族ポリアミドなどのポリアミド； Polycarbonate, polymetatalylate; Polyesters such as polyethylene terephthalate and polybutylene terephthalate; Polyamides such as nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon MXD6, wholly aromatic polyamide, semi-aromatic polyamide;
ポリアセタール、およびこれら榭脂のブレンド物などが挙げられる。  Examples include polyacetals and blends of these rosins.
[0010] これら熱可塑性榭脂の中でも、ポリオレフインが好ましぐ低密度ポリエチレン、中密 度ポリエチレン、高密度ポリエチレン、直鎖線状低密度ポリエチレン、ポリプロピレン、 エチレン プロピレン共重合体がより好ましぐ高密度ポリエチレン、ポリプロピレンが さらに好ましい。 [0010] Among these thermoplastic resins, low-density polyethylene, medium-density polyethylene, high-density polyethylene, linear linear low-density polyethylene, polypropylene, and ethylene-propylene copolymer are more preferable than polyolefin. More preferred are polyethylene and polypropylene.
熱可塑性榭脂 (A)が上記榭脂である場合には、後述するポリオレフインワックス (B) との分散性に優れ、例えば表面にベたつきがない、良好な成形体が得られる。  When the thermoplastic rosin (A) is the above rosin, a good molded article having excellent dispersibility with the polyolefin wax (B) described later and having no stickiness on the surface can be obtained.
[0011] 上記高密度ポリエチレンの MI (JIS K7210 ; 190°C 試験荷重 2. 16kgf)としては 0. 01〜： L Og/10分の範囲力 S好ましく、 0. 01〜0. 80g/10分の範囲力 Sより好まし い。 [0011] MI (JIS K7210; 190 ° C test load 2.16kgf) of the above-mentioned high-density polyethylene is 0.01 to: L Og / 10 minutes in range force S, preferably 0.01 to 0.80 g / 10 minutes Range power of S is preferred.
高密度ポリエチレンの Mlが上記範囲にある場合には、風合い、剛性、衝撃強度、 耐薬品性などに優れた成形体を得ることができる。  When the Ml of the high-density polyethylene is in the above range, a molded article excellent in texture, rigidity, impact strength, chemical resistance, etc. can be obtained.
[0012] また、上記高密度ポリエチレンの密度としては、 942〜970kg/m3の範囲が好まし く、 944〜965kg/m3の範囲力より好まし!/ヽ。 [0012] Further, as the density of the high density polyethylene, a range of 942~970kg / m 3 is rather preferable, preferably from the range force 944~965kg / m 3! /ヽ.
高密度ポリエチレンの密度が上記範囲にある場合には、風合い、剛性、衝撃強度、 耐薬品性などに優れた成形体を得ることができる。  When the density of the high-density polyethylene is in the above range, a molded article excellent in texture, rigidity, impact strength, chemical resistance, etc. can be obtained.
上記ポリプロピレンの MI (JIS K7210 ; 230°C 試験荷重 2. 16kgf)としては 0. 1〜3. 5gZlO分の範囲が好ましぐ 0. 4〜1. 5の範囲がより好ましい。  As the MI (JIS K7210; 230 ° C test load 2.16 kgf) of the above polypropylene, a range of 0.1 to 3.5 gZlO is preferable, and a range of 0.4 to 1.5 is more preferable.
[0013] ポリプロピレンの Mlが上記範囲にある場合には、耐熱性、耐薬品性などに優れた 成形体を得ることができる。 [0013] When the Ml of polypropylene is in the above range, a molded article having excellent heat resistance and chemical resistance can be obtained.
〔ポリオレフインワックス（B)〕  [Polyolefin wax (B)]
本発明では、上記熱可塑性榭脂 (A)にポリオレフインワックスを混合して使用する。 なお本発明でポリオレフインワックスとは、降温速度 2°CZ分の条件で示差走査熱量 計 (DSC)で測定した結晶化温度力 65〜120°Cの範囲にあり、ゲルパーミエーショ ンクロマトグラフィー（GPC)で測定したポリスチレン換算の数平均分子量 (Mn)が 40 0〜5, 000の範囲にあるものをいう。このようなポリオレフインワックスを熱可塑性榭脂 (A)に添加した混合物を溶融してブロー成形すると、榭脂の溶融粘度が低下するた め、押出時のモーター負荷が低減されるだけでなぐ流動性が改良され、成形速度 が向上する。また、成形体の表面が改質され、なめらかな表面を持つ成形体を得るこ とができる。さらに、低い成形温度で成形できるので、冷却時間が短縮され、成形サ イタルが向上するだけでなぐ榭脂の熱劣化、榭脂の焼け焦げ、および黒点を抑制で き、成形体の力学強度も優れたものとなる。 In the present invention, the thermoplastic wax (A) is mixed with polyolefin wax. Polyolefin wax in the present invention is in the range of 65 to 120 ° C. of crystallization temperature measured with a differential scanning calorimeter (DSC) under the condition of a temperature drop rate of 2 ° C.Z, and gel permeation chromatography ( The number average molecular weight (Mn) in terms of polystyrene measured by (GPC) is 40. Those in the range of 0 to 5,000. When a mixture of such a polyolefin wax added to thermoplastic resin (A) is melted and blow molded, the melt viscosity of the resin decreases, so the flow rate of the motor is reduced as well as the motor load during extrusion is reduced. Improves the molding speed. Further, the surface of the molded body is modified, and a molded body having a smooth surface can be obtained. Furthermore, since molding can be performed at a low molding temperature, the cooling time is shortened, the thermal degradation of the resin, the burning of the resin, and the black spots can be suppressed just by improving the molding site, and the mechanical strength of the molded product is excellent. It will be.
[0014] 本発明で用いられるポリオレフインワックス (B)としては特に制限はなぐ例えば、ポ リエチレンワックス、ポリプロピレンワックス、 a—ォレフイン単独重合体のワックス、ェ チレン Z aーォレフイン共重合体のワックス、エチレン Z aーォレフイン Z非共役ジ ェン共重合体のワックスなどを挙げることができる。 [0014] The polyolefin wax (B) used in the present invention is not particularly limited. For example, polyethylene wax, polypropylene wax, a -olefin homopolymer wax, ethylene Z a-olefin copolymer wax, ethylene Z Examples include waxes of a-olefin Z non-conjugated diene copolymer.
これらポリオレフインワックスの中でも、ポリエチレンワックス、エチレン Ζ α ォレフ イン共重合体のワックスが好ましぐポリエチレンワックス、エチレンと炭素原子数が 3 〜20の範囲の α ォレフインとの共重合体のワックスがより好ましぐポリエチレンヮッ タス、エチレン Ζプロピレン共重合体のワックス、エチレン Z1—ブテン共重合体のヮ ッタス、エチレン Zl ペンテン共重合体のワックス、エチレン Zl—へキセン共重合 体のワックス、エチレン Z4—メチルー 1 ペンテン共重合体のワックス、エチレン Zl オタテン共重合体のワックスがさらに好ましぐポリエチレンワックス、エチレン Zプ ロピレン共重合体のワックス、エチレン Zi—ブテン共重合体のワックス、エチレン Zi へキセン共重合体のワックス、エチレン Z4 メチル 1 ペンテン共重合体のヮ ッタスが特に好ましい。  Among these polyolefin waxes, polyethylene waxes, polyethylene waxes that are preferred for ethylene-α-olefin copolymer waxes, and waxes that are copolymerized with ethylene and α-olefins having 3 to 20 carbon atoms are more preferred. Meguta polyethylene, ethylene Ζ propylene copolymer wax, ethylene Z1-butene copolymer wax, ethylene Zl pentene copolymer wax, ethylene Zl-hexene copolymer wax, ethylene Z4-methyl-1 Pentene copolymer wax, polyethylene Zl Otaten copolymer wax is more preferred polyethylene wax, ethylene Z propylene copolymer wax, ethylene Zi-butene copolymer wax, ethylene Zi hexene copolymer Wax, ethylene Z4 methyl 1 pentene Wa Ttasu polymers are particularly preferred.
[0015] ポリオレフインワックス（B)が上記ポリオレフインワックスである場合には、熱可塑性 榭脂 (A)、特にポリオレフイン樹脂との分散性に優れ、例えば表面にベたつきがない 、良好な成形体が得られる。  [0015] When the polyolefin wax (B) is the above-described polyolefin wax, it is excellent in dispersibility with the thermoplastic resin (A), in particular, the polyolefin resin, for example, there is no stickiness on the surface, and a good molded product is obtained. can get.
上記ポリオレフインワックス（B)の、ゲルパーミエーシヨンクロマトグラフィー（GPC)で 測定したポリスチレン換算の数平均分子量（Mn)は、 400〜5, 000の範囲が好まし く、 700〜4, 500の範囲力より好ましく、 800〜4, 000の範囲力 ^さらにより好まし!/、。  The polystyrene equivalent number average molecular weight (Mn) of the above polyolefin wax (B) measured by gel permeation chromatography (GPC) is preferably in the range of 400 to 5,000, and in the range of 700 to 4,500. More preferred than force, 800-4,000 range power ^ even more preferred! / ,.
[0016] ポリオレフインワックス（B)の Mnが上記範囲にある場合には、流動性の改良効果が 大きぐ成形速度が大きく向上する。 [0016] When the Mn of the polyolefin wax (B) is in the above range, the effect of improving fluidity is obtained. Large molding speed is greatly improved.
上記ポリオレフインワックス（B)の、ゲルパーミエーシヨンクロマトグラフィー（GPC)で 測定したポリスチレン換算の重量平均分子量と数平均分子量との比（MwZMn)は The ratio (MwZMn) of polystyrene-equivalent weight average molecular weight and number average molecular weight of the above polyolefin wax (B) measured by gel permeation chromatography (GPC) is
、 1. 5〜4. 0の範囲力好ましく、 1. 5〜3. 5の範囲力より好まし!/ヽ。 A range power of 1.5 to 4.0 is preferred, and a range power of 1.5 to 3.5 is preferred! / ヽ.
[0017] ポリオレフインワックス（B)の MwZMnが上記範囲にある場合には、表面にベたつ きがな ヽ成形体が得られる。 [0017] When the MwZMn of the polyolefin wax (B) is in the above range, a molded product without stickiness on the surface is obtained.
上記ポリオレフインワックス (B)の、降温速度 2°CZ分の条件で示差走査熱量計 (D Differential scanning calorimeter (D) of the above-mentioned polyolefin wax (B) under the condition of a temperature drop rate of 2 ° CZ
SC)で測定した結晶化温度は、 65〜120°Cの範囲が好ましぐ 70〜120°Cの範囲 力 り好ましぐ 70〜118°Cの範囲にあることが特に好ましい。 The crystallization temperature measured by SC) is particularly preferably in the range of 70 to 120 ° C, more preferably in the range of 70 to 120 ° C, in the range of 65 to 120 ° C.
[0018] ポリオレフインワックス（B)の結晶化温度が上記範囲にある場合には、表面にベた つきがな 、成形体を得ることができる。 [0018] When the crystallization temperature of the polyolefin wax (B) is in the above range, a molded product can be obtained without sticking to the surface.
上記ポリオレフインワックス（B)の、 JIS K7112に準拠して密度勾配管法で測定し た密度 ίま、 850〜980kg/m3の範囲力 S好ましく、 870〜980kg/m3の範囲力 り好 ましく、 890〜980kg/m3の範囲力さらに好まし!/ヽ。 The polio Lev in wax (B), the density ί was measured by a density gradient tube method in conformity with JIS K7112 or the range force S preferably of 850~980kg / m 3, Mashi range force RiYoshimi of 870~980kg / m 3 Ku, still more preferably range force of 890~980kg / m 3! /ヽ.
[0019] ポリオレフインワックスの密度が上記範囲にある場合には、成形体の成形収縮率を 容易に制御できる。 [0019] When the density of the polyolefin wax is in the above range, the molding shrinkage of the molded article can be easily controlled.
さらにポリオレフインワックス (B)は、示差走査熱量計 (DSC)で測定した上記結晶 化温度〔Tc (°C)〕と、上記密度勾配法で測定した密度 (D (kg/m3) )とが、好ましくは 下記式 (I) Further, the polyolefin wax (B) has the crystallization temperature [Tc (° C)] measured by a differential scanning calorimeter (DSC) and the density (D (kg / m 3 )) measured by the density gradient method. Preferably the following formula (I)
0. 501 X D- 366 ≥ Tc · '· (Ι)  0. 501 X D- 366 ≥ Tc '' (Ι)
より好ましくは、下記式 (la)  More preferably, the following formula (la)
0. 501 X D— 366. 5 ≥ Tc "- (la)  0. 501 X D—366. 5 ≥ Tc "-(la)
さらに好ましくは、下記式 (lb)  More preferably, the following formula (lb)
0. 501 X D- 367 ≥ Tc "- (lb)  0. 501 X D- 367 ≥ Tc "-(lb)
の関係を満たす。  Satisfy the relationship.
[0020] ポリオレフインワックス (B)にお 、て結晶化温度 (Tc)と密度（D)とが上記式の関係 を満たしている場合には、例えば、ポリオレフインワックス（B)がエチレン Ζ α—ォレ フィン共重合体のワックスであると、共重合体の組成分布がより均一となり、熱可塑性 榭脂 (A)とポリオレフインワックス (B)を含む混合物から、ブロー成形により得られる成 形体のタックが小さくなる傾向にある。 [0020] In the polyolefin wax (B), when the crystallization temperature (Tc) and the density (D) satisfy the relationship of the above formula, for example, the polyolefin wax (B) is ethyleneΖα-o. If the wax is a olefin copolymer, the composition distribution of the copolymer becomes more uniform and the thermoplasticity There is a tendency that a molded product obtained by blow molding has a smaller tack from a mixture containing the resin (A) and the polyolefin wax (B).
[0021] またポリオレフインワックス（B)の JIS K2207に準拠して測定した針入度は、通常 3[0021] The penetration of the polyolefin wax (B) measured in accordance with JIS K2207 is usually 3
Odmm以下であり、好ましくは 25dmm以下、より好ましくは 20dmm以下、さらに好ま しくは 15dmm以下である。 Odmm or less, preferably 25 dmm or less, more preferably 20 dmm or less, and even more preferably 15 dmm or less.
ポリオレフインワックス (B)の針入度が上記範囲にある場合には、十分な強度を有 する成形体を得ることができる。  When the penetration of the polyolefin wax (B) is in the above range, a molded product having sufficient strength can be obtained.
[0022] ポリオレフインワックス（B)のアセトン抽出分量は 0〜20重量0 /0の範囲が好ましぐ 0[0022] Polio reflex in wax (B) acetone extraction quantity is preferably in the range of 0-20 0/0 device 0
〜15重量％の範囲がより好ましい。 A range of ˜15% by weight is more preferred.
なお、アセトン抽出分量は以下のようにして測定される。  The amount of acetone extracted is measured as follows.
ソックスレー抽出器 (ガラス製）に、フィルター (ADVANCE社製、 No. 84)を使用 し、下段の丸底フラスコ（300ml)にアセトン 200mlを装入に 70°Cの湯浴で 5時間抽 出を行う。初めのワックスは 10gをフィルター上にセットする。  Using a filter (made by ADVANCE, No. 84) for a Soxhlet extractor (made of glass), 200 ml of acetone was charged into the lower round bottom flask (300 ml), and extracted in a 70 ° C water bath for 5 hours. Do. Set 10g of the first wax on the filter.
[0023] ポリオレフインワックス（B)は、常温で固体であり、 65〜130°C以上で、低粘度の液 体となる。 [0023] The polyolefin wax (B) is solid at room temperature and becomes a low-viscosity liquid at 65 to 130 ° C or higher.
ポリオレフインワックス (B)のアセトン抽出分が上記範囲にある場合には、ベたつき 成分が減少し、金型の汚れが抑制されるだけでなぐ表面にベたつきがない成形体 を得ることができる。  When the acetone extract of the polyolefin wax (B) is in the above range, the sticky component is reduced, and a molded product with no stickiness on the surface can be obtained by only suppressing mold contamination. it can.
[0024] 上述したポリオレフインワックス (B)の製造方法については特に限定はなぐ例えば エチレン、 (Xーォレフインなどの単量体を、チーグラー Zナッタ触媒、メタ口セン系触 媒により重合して得られる。これら触媒の中でも、メタ口セン系触媒が好ましい。  [0024] The method for producing the polyolefin wax (B) described above is not particularly limited. For example, it is obtained by polymerizing monomers such as ethylene and (X-olefin) with a Ziegler Z-Natta catalyst and a metalocene catalyst. Among these catalysts, a metalocene catalyst is preferable.
このようなメタ口セン系触媒としては、例えば、  Examples of such meta-catacene catalysts include:
(A) 周期表第 4族力も選ばれる遷移金属のメタ口センィ匕合物、並びに  (A) a meta-metallic compound of a transition metal from which periodic group 4 forces are also selected, and
(B) (b-1)有機アルミニウムォキシィ匕合物、  (B) (b-1) an organoaluminum oxide compound,
(b-2)前記架橋メタ口セン化合物 (A)と反応してイオン対を形成する化合物および (b-2) a compound that forms an ion pair by reacting with the bridged meta-incene compound (A) and
(b- 3)有機アルミニウム化合物 (b-3) Organoaluminum compound
とから選ばれる少なくとも 1種以上の化合物とからなるォレフィン重合用触媒を 挙げることができる。 以下にこれらについて詳細に説明する。 And an olefin polymerization catalyst comprising at least one compound selected from the group consisting of: These will be described in detail below.
[0025] <メタ口セン化合物 >  [0025] <Metaguchicene compound>
(A) 周期表第 4族力も選ばれる遷移金属のメタ口センィ匕合物  (A) Transition metal metaguchisen compound with group 4 forces selected from the periodic table
メタ口セン系触媒を形成するメタ口センィ匕合物は、周期表第 4族から選ばれる遷移 金属のメタ口センィ匕合物であり、具体的な例としては下記一般式（1)で表される化合 物が挙げられる。  The meta-octane compound that forms the meta-catalyst catalyst is a meta-metal compound of a transition metal selected from Group 4 of the periodic table. A specific example is represented by the following general formula (1). Compounds that can be used.
MJLx M J Lx
ここで、 M1は周期表第 4族力 選ばれる遷移金属、 Xは遷移金属 M1の原子価、 Lは 配位子である。 M1で示される遷移金属の例としては、ジルコニウム、チタン、ハフユウ ムなどがある。 Lは遷移金属 M1に配位する配位子であって、そのうち少なくとも 1個の 配位子 Lはシクロペンタジェ-ル骨格を有する配位子であって、このシクロペンタジ ェニル骨格を有する配位子は置換基を有して 、てもよ 、。シクロペンタジェニル骨格 を有する配位子 Lとしては、例えばシクロペンタジェ-ル基、メチルシクロペンタジェ ニル基、ェチルシクロペンタジェ-ル基、 n—または i—プロビルシクロペンタジェ-ル 基、 n i sec—または tーブチルシクロペンタジェ-ル基、ジメチルシクロペンタ ジェ-ル基、メチルプロビルシクロペンタジェ-ル基、メチルブチルシクロペンタジェ ニル基、メチルベンジルシクロペンタジェ -ル基等のアルキルまたはシクロアルキル 置換シクロペンタジェ-ル基；さらにインデュル基、 4,5, 6,7—テトラヒドロインデュル 基、フルォレニル基などが挙げられる。このシクロペンタジェ-ル骨格を有する配位 子の水素は、ハロゲン原子またはトリアルキルシリル基などで置換されて 、てもよ 、。 Here, M 1 is a transition metal selected from Group 4 force of the periodic table, X is a valence of transition metal M 1 , and L is a ligand. Examples of the transition metal represented by M 1 include zirconium, titanium, and hafnium. L is a ligand coordinated to the transition metal M 1, and at least one of the ligands L is a ligand having a cyclopentagel skeleton, and the coordination having this cyclopentaphenyl skeleton The child may have a substituent. Examples of the ligand L having a cyclopentagenyl skeleton include a cyclopentagel group, a methylcyclopentaenyl group, an ethylcyclopentagel group, n- or i-propyl cyclopentagel. Group, ni sec— or t-butylcyclopentagel group, dimethylcyclopentagel group, methylpropyl cyclopentagel group, methylbutylcyclopentaenyl group, methylbenzylcyclopentagel group And alkyl- or cycloalkyl-substituted cyclopentagel groups such as indur, 4,5,6,7-tetrahydroindul, and fluorenyl. The ligand hydrogen having a cyclopentagel skeleton may be substituted with a halogen atom or a trialkylsilyl group.
[0026] 上記のメタ口セン化合物力 配位子 Lとしてシクロペンタジェ-ル骨格を有する配位 子を 2個以上有する場合には、そのうち 2個のシクロペンタジェ-ル骨格を有する配 位子同士が、エチレン、プロピレン等のアルキレン基;イソプロピリデン、ジフエ-ルメ チレン等の置換アルキレン基;シリレン基またはジメチルシリレン基、ジフエ-ルシリレ ン基、メチルフエ-ルシリレン基等の置換シリレン基などを介して結合されて 、てもよ い。 [0026] When there are two or more ligands having a cyclopentagel skeleton as the ligand L, the ligands having two cyclopentagel skeletons are connected to each other. Is bonded via an alkylene group such as ethylene or propylene; a substituted alkylene group such as isopropylidene or diphenylmethylene; a substituted silylene group such as a silylene group, a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group. It may be done.
[0027] シクロペンタジェ-ル骨格を有する配位子以外の配位子（シクロペンタジェ -ル骨 格を有しない配位子) Lとしては、炭素原子数 1 12の炭化水素基、アルコキシ基、 ァリーロキシ基、スルフォン酸含有基（一 SO R1)、ハロゲン原子または水素原子 (ここ [0027] A ligand other than a ligand having a cyclopentagel skeleton (a ligand having no cyclopentagel skeleton) L is a hydrocarbon group having 1 to 12 carbon atoms, an alkoxy group , Aryloxy group, sulfonic acid-containing group (one SO R 1 ), halogen atom or hydrogen atom (here
3  Three
で、 R1はアルキル基、ハロゲン原子で置換されたアルキル基、ァリール基、ハロゲン 原子で置換されたァリール基またはアルキル基で置換されたァリール基である。 )な どが挙げられる。 R 1 is an alkyl group, an alkyl group substituted with a halogen atom, an aryl group, an aryl group substituted with a halogen atom, or an aryl group substituted with an alkyl group. ).
[0028] <メタ口セン化合物の例 1 >  [0028] <Example 1 of metaguchicene compound>
上記一般式（1)で表されるメタ口センィ匕合物が、例えば遷移金属の原子価が 4であ る場合、より具体的には下記一般式 (2)で表される。  For example, when the valence of the transition metal is 4, the meta-mouth compound represented by the general formula (1) is more specifically represented by the following general formula (2).
R2 R3R4 R5 M1 - -- (2) R 2 R 3 R 4 R 5 M 1 --(2)
k 1 m n  k 1 m n
ここで、 M1は周期表第 4族力 選ばれる遷移金属、 R2はシクロペンタジェ-ル骨格を 有する基 (配位子）、
Figure imgf000009_0001
R4及び R5はそれぞれ独立にシクロペンタジェニル骨格を有 する力または有しない基 (配位子）である。 kは 1以上の整数であり、 k+l+m+n=4 である。 Here, M 1 is a transition metal selected from Group 4 force of the periodic table, R 2 is a group (ligand) having a cyclopentagel skeleton,
Figure imgf000009_0001
R 4 and R 5 are each independently a force having a cyclopentadenyl skeleton or a group (ligand) having no cyclopentagenyl skeleton. k is an integer of 1 or more, and k + l + m + n = 4.
[0029] M1がジルコニウムであり、かつシクロペンタジェ-ル骨格を有する配位子を少なくと も 2個含むメタ口セン化合物の例を次に挙げる。ビス（シクロペンタジェ -ル）ジルコ- ゥムモノクロリドモノハイドライド、ビス（シクロペンタジェ -ル）ジルコニウムジクロリド、 ビス（1ーメチルー 3 ブチルシクロペンタジェ -ル）ジルコニウムビス（トリフルォロメタ ンスルホナト）、ビス（1,3 ジメチルシクロペンタジェ -ル）ジルコニウムジクロリドなど [0029] The following are examples of meta-octene compounds in which M 1 is zirconium and contains at least two ligands having a cyclopentagel skeleton. Bis (cyclopentagel) zirconium monochloride monohydride, bis (cyclopentagel) zirconium dichloride, bis (1-methyl-3-butylcyclopentagel) zirconium bis (trifluoromethanesulfonate), bis (1, 3 Dimethylcyclopentagel) Zirconium dichloride, etc.
[0030] 上記の化合物の中で、 1,3—位置換シクロペンタジェ -ル基を 1,2—位置換シクロ ペンタジェ-ル基に置き換えたィ匕合物も用いることができる。 [0030] Among the above compounds, compounds obtained by replacing the 1,3-position substituted cyclopentagel group with the 1,2-position substituted cyclopentagel group can also be used.
またメタ口センィ匕合物の別の例としては、上記一般式（2)において、 R2、
Figure imgf000009_0002
R4及び R5の少なくとも 2個、例えば R2及び R3がシクロペンタジェニル骨格を有する基 (配位 子)であり、この少なくとも 2個の基がアルキレン基、置換アルキレン基、シリレン基ま たは置換シリレン基などを介して結合されているブリッジタイプのメタ口センィ匕合物を 使用することもできる。このとき R4及び R5は、それぞれ独立に、前述したシクロペンタ ジェニル骨格を有する配位子以外の配位子 Lと同様である。 Further, as another example of the meta mouth compound, in the above general formula (2), R 2 ,
Figure imgf000009_0002
At least two of R 4 and R 5 , for example, R 2 and R 3 are groups (coordinators) having a cyclopentadenyl skeleton, and these at least two groups are an alkylene group, a substituted alkylene group, or a silylene group. Alternatively, a bridge-type metamouth compound bonded via a substituted silylene group or the like can also be used. In this case R 4 and R 5 are each independently the same as the ligand L other than the ligand having a cyclopenta Jeniru skeleton described above.
[0031] このようなブリッジタイプのメタ口セン化合物としては、エチレンビス（インデュル）ジメ チルジルコニウム、エチレンビス（インデュル）ジルコニウムジクロリド、イソプロピリデン (シクロペンタジェ -ル一フルォレニル）ジルコニウムジクロリド、ジフエ-ルシリレンビ ス（インデュル）ジルコニウムジクロリド、メチルフエ-ルシリレンビス（インデュル）ジル コ-ゥムジクロリドなどが挙げられる。 [0031] Examples of such bridge-type meta-octene compounds include ethylene bis (indul) dimethylzirconium, ethylenebis (indul) zirconium dichloride, isopropylidene. (Cyclopentagel-fluoroenyl) zirconium dichloride, diphenylsilylene bis (indul) zirconium dichloride, methyl ferrosilylene bis (indul) zirconium dichloride.
[0032] <メタ口セン化合物の例 2>  <Example 2 of metaguchicene compound>
またメタ口センィ匕合物の例としては、下記一般式（3)で表される特開平 4— 268307 号公報記載のメタ口センィ匕合物が挙げられる。  An example of a meta-mouth compound is a meta-mouth compound described in JP-A-4-268307 represented by the following general formula (3).
[0033] [化 1] [0033] [Chemical 1]
Figure imgf000010_0001
Figure imgf000010_0001
[0034] ここで、 M1は周期表第 4族遷移金属であり、具体的にはチタニウム、ジルコニウム、ハ フニゥムが挙げられる。 [0034] wherein, M 1 is a transition metal of Group 4 of the periodic table, specifically titanium, zirconium or c Funiumu.
R11及び R12は互いに同一でも異なっていてもよぐ水素原子;炭素原子数 1〜： LOの アルキル基；炭素原子数 1〜： L0のアルコキシ基；炭素原子数 6〜： L0のァリール基；炭 素原子数 6〜 10のァリー口キシ基；炭素原子数 2〜： L0のァルケ-ル基；炭素原子数 7 〜40のァリールアルキル基；炭素原子数 7〜40のアルキルァリール基；炭素原子数 8〜40のァリールァルケ-ル基；またはハロゲン原子であり、 R11及び R12は、塩素原 子であることが好ましい。 R 11 and R 12 may be the same or different from each other; a hydrogen atom that may be the same or different; an alkyl group having 1 to carbon atoms; an alkyl group having 1 to LO; an alkoxy group having 1 to carbon atoms; an alkoxy group having 6 carbon atoms; ; Aryloxy group having 6 to 10 carbon atoms; carbon atom number 2 to: alkenyl group having L0; aryl hydrocarbon group having 7 to 40 carbon atoms; alkyl aryl group having 7 to 40 carbon atoms; An arylalkyl group having 8 to 40 carbon atoms; or a halogen atom, and R 11 and R 12 are preferably chlorine atoms.
[0035] R13及び R"は互いに同一でも異なっていてもよぐ水素原子；ノヽロゲン原子；ノヽロゲ ン化されていてもよい炭素原子数 1〜10のアルキル基;炭素原子数 6〜10のァリー ル基； N(R2°) 、— SR2°、— OSi(R2°) 、— Si(R2°)または— P(R2°)基である。ここで、 [0035] R 13 and R "may be the same or different from each other; a hydrogen atom; a halogen atom; an optionally halogenated alkyl group having 1 to 10 carbon atoms; and a carbon atom number 6 to 10 of Ari Le group;. N (R 2 °) , - SR 2 °, - OSi (R 2 °), - Si (R 2 °) , or - P (R 2 °) group, where
2 3 3 2  2 3 3 2
R2Qはハロゲン原子、好ましくは塩素原子;炭素原子数 1〜10、好ましくは 1〜3のァ ルキル基；または炭素原子数 6〜 10、好ましくは 6〜8のァリール基である。 R13及び R 14は、特に水素原子であることが好ましい。 [0036] R15及び R16は、水素原子が含まれないことを除き R13及び R14と同じであって、互いに 同じでも異なっていてもよぐ好ましくは同じである。 R15及び R16は、好ましくはハロゲ ン化されていてもよい炭素原子数 1〜4のアルキル基、具体的にはメチル、ェチル、 プロピル、イソプロピル、ブチル、イソブチル、トリフルォロメチル等が挙げられ、特にメ チルが好ましい。 R 2Q is a halogen atom, preferably a chlorine atom; an alkyl group having 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms; or an aryl group having 6 to 10 carbon atoms, preferably 6 to 8 carbon atoms. R 13 and R 1 4 are each particularly preferably a hydrogen atom. [0036] R 15 and R 16 are the same as R 13 and R 14 except that a hydrogen atom is not contained, and may be the same as or different from each other. R 15 and R 16 are preferably alkyl groups having 1 to 4 carbon atoms which may be halogenated, specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl and the like. In particular, methyl is preferred.
[0037] 上記一般式（3)にお 、て、 R17は次の群力 選ばれる。 [0037] In the general formula (3), R 17 is selected from the following group forces.
[0038] [化 2]  [0038] [Chemical 2]
Figure imgf000011_0001
Figure imgf000011_0001
Figure imgf000011_0002
Figure imgf000011_0002
、21 . m21 21 , 21. M 21 21
[0039] =BR \ =A1R \—Ge—、 一Sn—、 一O—、 一S—、 =SO、 =SO ゝ =NR \ =C  [0039] = BR \ = A1R \ —Ge—, 1 Sn—, 1 O—, 1 S—, = SO, = SO ゝ = NR \ = C
2  2
0、 =PR21、 =P (0)R21など。 M2はケィ素、ゲルマニウムまたは錫、好ましくはケィ素 またはゲルマニウムである。ここで、 R21、 R22及び R23は互いに同一でも異なっていても よぐ水素原子;ハロゲン原子;炭素原子数 1〜10のアルキル基;炭素原子数 1〜10 のフルォロアルキル基；炭素原子数 6〜 10のァリール基；炭素原子数 6〜 10のフル ォロアリール基；炭素原子数 1〜10のアルコキシ基；炭素原子数 2〜10のァルケ-ル 基；炭素原子数 7〜40のァリールアルキル基；炭素原子数 8〜40のァリールァルケ -ル基；または炭素原子数 7〜40のアルキルァリール基である。「R21と R22」または「R2 1と R23」とは、それぞれそれらが結合する原子と一緒になつて環を形成してもよい。ま た、 R17は、 =CR21R22、 =SiR21R22、 =GeR21R22、— O—、— S—、 =SO、 =PR21ま たは = P (O) R21であることが好ま U 、。 R18及び R19は互 ヽに同一でも異なって!/ヽても よぐ R21と同じものが挙げられる。 m及び nは互いに同一でも異なっていてもよぐそ れぞれ 0、 1または 2、好ましくは 0または 1であり、 m+nは 0、 1または 2、好ましくは 0 または 1である。 [0040] 上記一般式（3)で表されるメタ口センィ匕合物の例としては、次の化合物が挙げられ る。 rac エチレン（2—メチル 1—インデュル） 一ジルコニウム一ジクロライド、 rac 0, = PR 21 , = P (0) R 21 etc. M 2 is silicon, germanium or tin, preferably silicon or germanium. R 21 , R 22 and R 23 may be the same or different from each other; a hydrogen atom; a halogen atom; an alkyl group having 1 to 10 carbon atoms; a fluoroalkyl group having 1 to 10 carbon atoms; 6-10 carbon aryl group; 6-6 carbon atom fluoroaryl group; 1-10 carbon atom alkoxy group; 2-10 carbon atom group; 7-40 carbon atom alkyl group Group: an arylalkyl group having 8 to 40 carbon atoms; or an alkylaryl group having 7 to 40 carbon atoms. The "R 21 and R 22" or "R 2 1 and R 23" may form a connexion ring such together with the atom to which they are bonded. Also, R 17 is = CR 21 R 22 , = SiR 21 R 22 , = GeR 21 R 22 , — O—, — S—, = SO, = PR 21 or = P (O) R 21 U, prefer to be. R 18 and R 19 are the same thing, and the like and Yogu R 21 be also different! /ヽthe same to each otherヽ. m and n may be the same or different from each other and are each 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1. [0040] Examples of the meta-mouth compound represented by the general formula (3) include the following compounds. rac ethylene (2-methyl 1-indul) monozirconium monodichloride, rac
2  2
-ジメチルシリレン（2—メチル一 1—インデュル） -ジルコニウム ジクロライドなど n -Dimethylsilylene (2-methyl-1,1-indul) -zirconium dichloride, etc. n
2  2
これらのメタ口センィ匕合物は、例えば、特開平 4— 268307号公報に記載の方法で製 造することができる。  These meta-mouth compounds can be produced, for example, by the method described in JP-A-4-268307.
[0041] <メタ口セン化合物の例 3 > [0041] <Example 3 of metaguchicene compound>
また、メタ口センィ匕合物としては、下記一般式 (4)で表されるメタ口センィ匕合物を用 いることちでさる。  Moreover, as a meta-mouth compound, the meta-mouth compound represented by the following general formula (4) is used.
[0042] [化 3] [0042] [Chemical 3]
Figure imgf000012_0001
Figure imgf000012_0001
[0043] 式 (4)中、 M3は、周期表第 4族の遷移金属原子を示し、具体的にはチタニウム、ジル コニゥム、ハフニウムなどである。 R24及び R25は互いに同一でも異なっていてもよぐ 水素原子、ハロゲン原子、炭素原子数 1〜20の炭化水素基、炭素原子数 1〜20の ハロゲン化炭化水素基、ケィ素含有基、酸素含有基、ィォゥ含有基、窒素含有基ま たはリン含有基を示す。 R24は炭化水素基であることが好ましぐ特にメチル、ェチル またはプロピルの炭素原子数 1〜3のアルキル基であることが好まし 、。 R25は水素原 子または炭化水素基が好ましぐ特に水素原子、またはメチル、ェチルもしくはプロピ ルの炭素原子数 1〜3のアルキル基であることが好ましい。
Figure imgf000012_0002
R28及び R29は、 互いに同一でも異なっていてもよぐ水素原子、ハロゲン原子、炭素原子数 1〜20の 炭化水素基、炭素原子数 1〜20のハロゲンィ匕炭化水素基を示す。これらの中では水 素原子、炭化水素基またはハロゲン化炭化水素基であることが好ましい。 R26と R27、 R 27と R28、 R28と R29のうち少なくとも 1組は、それらが結合している炭素原子と一緒になつ て、単環の芳香族環を形成していてもよい。また芳香族環を形成する基以外に、炭 化水素基またはハロゲンィ匕炭化水素基が 2個以上ある場合には、これらが互いに結 合して環状になっていてもよい。なお R29が芳香族基以外の置換基である場合、水素 原子であることが好ましい。 X1及び X2は互いに同一でも異なっていてもよぐ水素原 子、ハロゲン原子、炭素原子数 1〜20の炭化水素基、炭素原子数 1〜20のハロゲン 化炭化水素基、酸素原子含有基またはィォゥ原子含有基を示す Yは、炭素原子数 1 〜20の 2価の炭化水素基、炭素原子数 1〜20の 2価のハロゲン化炭化水素基、 2価 のケィ素含有基、 2価のゲルマニウム含有基、 2価のスズ含有基、 O 、 一 CO—、 — S―、— SO—、 -SO―、— NR3。—、— P(R3。)—、— P(0)(R3。)—、—BR3。—また [0043] In the formula (4), M 3 represents a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium, hafnium, or the like. R 24 and R 25 may be the same or different from each other. A hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, Oxygen-containing group, xio-containing group, nitrogen-containing group or phosphorus-containing group. R 24 is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 3 carbon atoms, such as methyl, ethyl or propyl. R 25 is preferably a hydrogen atom or a hydrocarbon group, particularly preferably a hydrogen atom, or an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl or propyl.
Figure imgf000012_0002
R 28 and R 29 represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other. Among these, a hydrogen atom, a hydrocarbon group, or a halogenated hydrocarbon group is preferable. At least one pair of R 26 and R 27 , R 2 7 and R 28 , R 28 and R 29 together with the carbon atom to which they are bonded forms a monocyclic aromatic ring. Also good. In addition, when there are two or more hydrocarbon groups or halogenated hydrocarbon groups other than the group forming the aromatic ring, they may be bonded to each other to form a ring. When R 29 is a substituent other than an aromatic group, hydrogen An atom is preferred. X 1 and X 2 may be the same or different from each other, hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen atom-containing group Or Y representing a thio atom-containing group is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, or a divalent group. germanium-containing group, a divalent tin-containing group, O, one CO-, - S -, - SO- , -SO -, - NR 3. —, — P (R 3. ) —, — P (0) (R 3. ) —, —BR 3 . -Also
2  2
は—A1R3Q—（ただし、 R3Qは水素原子、ハロゲン原子、炭素原子数 1〜20の炭化水 素基、炭素原子数 1〜20のハロゲン化炭化水素基)を示す。 Is —A1R 3Q — (wherein R 3Q is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms).
[0044] 式 (4)において、 R26と R27、 R27と R28、 R28と R29のうち少なくとも 1組が互いに結合して 形成する単環の芳香族環を含み、 M3に配位する配位子としては、次式で表されるも のなどが挙げられる。 [0044] In the formula (4), M 3 contains a monocyclic aromatic ring formed by combining at least one of R 26 and R 27 , R 27 and R 28 , R 28 and R 29 , and M 3 Examples of the ligand to be coordinated include those represented by the following formula.
[0045] [化 4] [0045] [Chemical 4]
Figure imgf000013_0001
Figure imgf000013_0001
[0046] (式中、 Yは前式に示したものと同じである。 )  [0046] (In the formula, Y is the same as that shown in the previous formula.)
<メタ口セン化合物の例 4 >  <Example 4 of metaguchisen compound>
メタ口セン化合物としては、また下記一般式（5)で表されるメタ口セン化合物を用い ることちでさる。  As the meta-octene compound, it is possible to use a meta-octene compound represented by the following general formula (5).
[0047] [化 5] [0047] [Chemical 5]
… （5 )… (Five )
Figure imgf000013_0002
Figure imgf000013_0002
式 (5)中、 M3、 R24、 R25、 R2°、 R28及び R29は、上記一般式 (4)と同じである。 R26、 R28及び R29のうち、 R26を含む 2個の基がアルキル基であることが好ましぐ R26と R 28 ,または R28と R29がアルキル基であることが好ましい。このアルキル基は、 2級または 3級アルキル基であることが好ましい。またこのアルキル基は、ハロゲン原子、ケィ素 含有基で置換されていてもよぐハロゲン原子、ケィ素含有基としては、 R24、 R25で例 示した置換基が挙げられる。 R26、 R27、 R28及び R29のうち、アルキル基以外の基は、水 素原子であることが好ましい。また 6、 R27、 R28及び R29は、これら力 選ばれる 2種の 基が互!、に結合して芳香族環以外の単環あるいは多環を形成して 、てもよ 、。ハロ ゲン原子としては、上記 R24及び R25と同様のものが挙げられる。 X1、 X2及び Yとしては 、上記と同様のものが挙げられる。 In the formula (5), M 3 , R 24 , R 25 , R 2 °, R 28 and R 29 are the same as in the general formula (4). Of R 26 , R 28 and R 29 , it is preferable that two groups including R 26 are alkyl groups. R 26 and R 2 8 , or R 28 and R 29 are preferably alkyl groups. . This alkyl group is secondary or A tertiary alkyl group is preferred. The alkyl group is a halogen atom which may be substituted with a halogen atom or a silicon-containing group. Examples of the halogen-containing group include the substituents exemplified for R 24 and R 25 . Of R 26 , R 27 , R 28 and R 29 , the group other than the alkyl group is preferably a hydrogen atom. Further, 6 , R 27 , R 28 and R 29 may be formed by bonding two groups selected from these forces to each other to form a monocyclic or polycyclic ring other than an aromatic ring. Examples of the halogen atom include those similar to the above R 24 and R 25 . Examples of X 1 , X 2 and Y are the same as those described above.
[0049] 上記一般式（5)で表されるメタ口センィ匕合物の具体的な例を次に示す。 rac ジメ チルシリレン一ビス（4,7 ジメチル一 1—インデュル）ジルコニウムジクロリド、 rac— ジメチルシリレン一ビス（2,4,7 トリメチル一 1—インデュル）ジルコニウムジクロリド、 r ac ジメチルシリレン一ビス（2,4,6 トリメチル一 1—インデュル）ジルコニウムジクロ リドなど。 [0049] Specific examples of the meta-mouth compound represented by the general formula (5) are shown below. rac Dimethylsilylene monobis (4,7 dimethyl mono 1-indul) zirconium dichloride, rac—Dimethylsilylene mono bis (2,4,7 Trimethyl mono 1-indul) zirconium dichloride, r ac Dimethylsilylene monobis (2,4, 6 Trimethyl 1-indul) Zirconium dichloride, etc.
[0050] これらの化合物において、ジルコニウム金属を、チタニウム金属、ハフニウム金属に 置換えた遷移金属化合物を用いることもできる。遷移金属化合物は、通常ラセミ体と して用いられる力 R型または S型を用いることもできる。  In these compounds, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used. As the transition metal compound, a force R type or S type generally used as a racemate can also be used.
<メタ口セン化合物の例 5 >  <Example 5 of metaguchisen compound>
メタ口セン化合物として、下記一般式 (6)で表されるメタ口セン化合物を使用するこ とちでさる。  As the meta-octacene compound, a meta-caffeine compound represented by the following general formula (6) is used.
[0051] [化 6] [0051] [Chemical 6]
Figure imgf000014_0001
Figure imgf000014_0001
式 (6)中、 M3、 R24、 X1、 ^及び Yは、上記一般式 (4)と同じである。 R24は炭化水素 基であることが好ましぐ特にメチル、ェチル、プロピルまたはブチルの炭素原子数 1 〜4のアルキル基であることが好ましい。 R25は、炭素原子数 6〜16のァリール基を示 す。 R25はフエ-ル、ナフチルであることが好ましい。ァリール基は、ハロゲン原子、炭 素原子数 1〜20の炭化水素基または炭素原子数 1〜20のハロゲン化炭化水素基で 置換されていてもよい。 X1及び X2としては、ハロゲン原子、炭素原子数 1〜20の炭化 水素基であることが好まし 、。 In the formula (6), M 3 , R 24 , X 1 , ^ and Y are the same as in the general formula (4). R 24 is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl. R 25 represents an aryl group having 6 to 16 carbon atoms. R 25 is preferably phenyl or naphthyl. The aryl group is a halogen atom, charcoal It may be substituted with a hydrocarbon group having 1 to 20 carbon atoms or a halogenated hydrocarbon group having 1 to 20 carbon atoms. X 1 and X 2 are preferably a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms.
[0053] 上記一般式 (6)で表されるメタ口センィ匕合物の具体的な例を次に示す。 rac ジメ チルシリレン一ビス（4 フエ-ル一 1—インデュル）ジルコニウムジクロリド、 rac ジメ チノレシリレン一ビス（2—メチノレ一 4 フエ-ノレ一 1—インデニノレ）ジノレコ-ゥムジクロリ ド、 rac ジメチルシリレン一ビス（2—メチル 4— ( a—ナフチル） 1 インデュル )ジルコニウムジクロリド、 rac ジメチルシリレン ビス（2—メチルー 4一 ( β ナフチ ル） 1—インデュル）ジルコニウムジクロリド、 rac ジメチルシリレン—ビス（2—メチ ル一 4— ( 1—アントリル）一 1—インデュル）ジルコニウムジクロリドなど。またこれらィ匕 合物において、ジルコニウム金属をチタニウム金属またはハフニウム金属に置き換え た遷移金属化合物を用いることもできる。  A specific example of the meta-mouth compound represented by the general formula (6) is shown below. rac Dimethylylylene bis (4-phenol 1-indul) zirconium dichloride, rac dimethyl styrene silylene bis (2-methinore 4-phenol 1-indenole) dinolecum-dichloride, rac dimethylsilylene bis (2— Methyl 4— (a—Naphtyl) 1 Indul) Zirconium Dichloride, rac Dimethylsilylene Bis (2—Methyl-4 (β-Naphthyl) 1—Indul) Zirconium Dichloride, rac Dimethylsilylene—Bis (2—Methyl 4) ( 1-anthryl) 1-indul) zirconium dichloride and the like. In these compounds, transition metal compounds in which zirconium metal is replaced with titanium metal or hafnium metal can also be used.
[0054] <メタ口セン化合物の例 6 >  [0054] <Example 6 of metaguchicene compound>
またメタ口センィ匕合物として、下記一般式（7)で表されるメタ口センィ匕合物を用いるこ とちでさる。  In addition, as a meta-mouth compound, a meta-mouth compound represented by the following general formula (7) is used.
LaM4X3 - " (7) LaM 4 X 3 -"(7)
2  2
ここで、 M4は周期表第 4族またはランタ-ド系列の金属である。 Laは非局在化 π結 合基の誘導体であり、金属 Μ4活性サイトに拘束幾何形状を付与している基である。 X 3は互いに同一でも異なっていてもよぐ水素原子、ハロゲン原子、炭素原子数 20以 下の炭化水素基、 20以下のケィ素を含有するシリル基または 20以下のゲルマニウム を含有するゲルミル基である。 Here, M 4 is a group 4 of the periodic table or a lanthanide series metal. La is a derivative of a delocalized π bond group, and is a group that imparts a constrained geometry to the metal Μ 4 active site. X 3 is a hydrogen atom, a halogen atom, a hydrocarbon group having 20 or less carbon atoms, a silyl group containing 20 or less silicon, or a germanyl group containing 20 or less germanium, which may be the same or different from each other. is there.
[0055] この化合物の中では、次式（8)で示される化合物が好まし！/、。  [0055] Among these compounds, the compound represented by the following formula (8) is preferred! /.
[0056] [化 7]  [0056] [Chemical 7]
… （8 )... (8)
Figure imgf000015_0001
Figure imgf000015_0001
式（8)中、 Μ4は、チタン、ジルコニウムまたはハフニウムである。 X3は上記一般式（7) で説明したものと同様である。 Cpは Μ4に π結合しており、かつ置換基 Ζを有する置 換シクロペンタジェニル基である。 Zは酸素、ィォゥ、ホウ素または周期表第 4族の元 素（例えばケィ素、ゲルマニウムまたは錫)である。 Yは窒素、リン、酸素またはィォゥ を含む配位子であり、 Zと Yとで縮合環を形成していてもよい。このような式 (8)で表さ れるメタ口センィ匕合物の具体的な例を次に示す。（ジメチル (t ブチルアミド) (テトラメ チル— 7? 5—シクロペンタジェ -ル)シラン)チタンジクロリド、（(t ブチルアミド) (テトラ メチルー 5 シクロペンタジェ-ル ) 1,2—エタンジィル）チタンジクロリドなど。また このメタ口セン化合物にお 、て、チタンをジルコニウムまたはハフニウムに置き換えた ィ匕合物を挙げることちでさる。 Wherein (8), Micromax 4 is titanium, zirconium or hafnium. X 3 is the same as that described in the general formula (7). Cp is π-bonded to Μ 4 and has a substituent Ζ It is a substituted cyclopentadenyl group. Z is oxygen, iow, boron, or an element of group 4 of the periodic table (eg, keye, germanium, or tin). Y is a ligand containing nitrogen, phosphorus, oxygen or io, and Z and Y may form a condensed ring. A specific example of a meta-mouth compound represented by the formula (8) is shown below. (Dimethyl (t butylamide) (tetramethyl-7? 5 -cyclopentagel) silane) titanium dichloride, ((t butylamide) (tetramethyl- 5 cyclopentagel) 1,2-ethanediyl) titanium dichloride, and the like. In addition, in this metamouth compound, mention may be made of compounds in which titanium is replaced by zirconium or hafnium.
[0058] <メタ口セン化合物の例 7 >  [0058] <Example 7 of metaguchicene compound>
またメタ口センィ匕合物としては、下記一般式（9)で表されるメタ口セン化合物を使用 することちでさる。  Further, as the meta-mouth compound, a meta-mouth compound represented by the following general formula (9) is used.
[0059] [化 8]  [0059] [Chemical 8]
Figure imgf000016_0001
Figure imgf000016_0001
[0060] 式（9)中、 M3は周期表第 4族の遷移金属原子であり、具体的には、チタニウム、ジル コ -ゥムまたはハフニウムであり、好ましくはジルコニウムである。 R31は互いに同一で も異なっていてもよぐそのうち少なくとも 1個が炭素原子数 11〜20のァリール基、炭 素原子数 12〜40のァリールアルキル基、炭素原子数 13〜40のァリールァルケ-ル 基、炭素原子数 12〜40のアルキルァリール基またはケィ素含有基である力、または R31で示される基のうち隣接する少なくとも 2個の基が、それらの結合する炭素原子と ともに、単数または複数の芳香族環または脂肪族環を形成している。この場合、 R31 により形成される環は、 R31が結合する炭素原子を含んで全体として炭素原子数が 4 〜20である。ァリール基、ァリールアルキル基、ァリールァルケ-ル基、アルキルァリ ール基及び芳香族環、脂肪族環を形成している R31以外の R31は、水素原子、ハロゲ ン原子、炭素原子数 1〜10のアルキル基またはケィ素含有基である。 R32は互いに同 一でも異なっていてもよぐ水素原子、ハロゲン原子、炭素原子数 1〜10のアルキル 基、炭素原子数 6〜20のァリール基、炭素原子数 2〜： L0のアルケニル基、炭素原子 数 7〜40のァリールアルキル基、炭素原子数 8〜40のァリールァルケ-ル基、炭素 原子数 7〜40のアルキルァリール基、ケィ素含有基、酸素含有基、ィォゥ含有基、窒 素含有基またはリン含有基である。また、 R32で示される基のうち隣接する少なくとも 2 個の基が、それらの結合する炭素原子とともに、単数または複数の芳香族環または 脂肪族環を形成していてもよい。この場合、 R32により形成される環は、 R32が結合する 炭素原子を含んで全体として炭素原子数が 4〜20であり、芳香族環、脂肪族環を形 成している R32以外の R32は、水素原子、ハロゲン原子、炭素原子数 1〜10のアルキ ル基またはケィ素含有基である。なお、 R32で示される 2個の基が、単数または複数の 芳香族環または脂肪族環を形成して構成される基にはフルォレニル基が次式のよう な構造になる態様も含まれる。 In Formula (9), M 3 is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium or hafnium, preferably zirconium. R 31 may be the same or different, and at least one of them is an aryl group having 11 to 20 carbon atoms, an aryl alkyl group having 12 to 40 carbon atoms, an aryl hydrocarbon having 13 to 40 carbon atoms. At least two groups adjacent to each other, together with the carbon atom to which they are bonded, or a group of 12 to 40 carbon atoms or a C-containing group, or a group represented by R 31 , One or more aromatic or aliphatic rings are formed. In this case, the ring formed by R 31 as a whole number of carbon atoms including carbon atoms to which R 31 is bonded is from 4 to 20. Aryl group, aryl group, aryl group, alkyl group Lumpur group and an aromatic ring, R 31 other than R 31 that forms an aliphatic ring is a hydrogen atom, a halogen atom, an alkyl group or Kei-containing group having 1 to 10 carbon atoms. R 32 is Yogu hydrogen atom be different even same each other, a halogen atom, an alkyl group having 1 to 10 carbon atoms, Ariru group having 6 to 20 carbon atoms, 2 carbon atoms: L0 alkenyl group, 7 to 40 carbon atom alkyl group, 8 to 40 carbon atom alkyl group, 7 to 40 carbon atom alkyl group, key group, oxygen group, nitrogen group, nitrogen group An element-containing group or a phosphorus-containing group. Further, at least two adjacent groups out of the groups represented by R 32 may form one or more aromatic rings or aliphatic rings together with the carbon atoms to which they are bonded. In this case, the ring formed by R 32 as a whole number of carbon atoms including carbon atoms to which R 32 is bonded is from 4 to 20, except R 32 that forms form an aromatic ring, an aliphatic ring R 32 in the formula is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a key group containing silicon. The group in which the two groups represented by R 32 form one or more aromatic rings or aliphatic rings includes an embodiment in which the fluorenyl group has a structure as shown in the following formula.
[0061] [ィ匕 9]
Figure imgf000017_0001
[0061] [9]
Figure imgf000017_0001
[0062] R ま、水素原子またはアルキル基であることが好ましぐ特に水素原子またはメチル 、ェチル、プロピルの炭素原子数 1〜3の炭化水素基であることが好ましい。このよう な置換基として R32を有するフルォレニル基としては、 2,7 ジアルキル フルォレニ ル基が好適な例として挙げられ、この場合の 2,7 ジアルキルのアルキル基としては 、炭素原子数 1〜5のアルキル基が挙げられる。また、 R31と R32は、互いに同一でも異 なっていてもよい。 R33及び R34は互いに同一でも異なっていてもよぐ上記と同様の水 素原子、ハロゲン原子、炭素原子数 1〜10のアルキル基、炭素原子数 6〜20のァリ ール基、炭素原子数 2〜 10のァルケ-ル基、炭素原子数 7〜40のァリールアルキル 基、炭素原子数 8〜40のァリールァルケ-ル基、炭素原子数 7〜40のアルキルァリ ール基、ケィ素含有基、酸素含有基、ィォゥ含有基、窒素含有基またはリン含有基で ある。これらのうち、 R33及び R34は、少なくとも一方が炭素原子数 1〜3のアルキル基 であることが好ましい。 X1及び X2は互いに同一でも異なっていてもよぐ水素原子、ハ ロゲン原子、炭素原子数 1〜20の炭化水素基、炭素原子数 1〜20のハロゲン化炭 化水素基、酸素含有基、ィォゥ含有基もしくは窒素含有基、または X1と X2とから形成 された共役ジェン残基である。 X1と X2とから形成された共役ジェン残基としては、 1,3 ブタジエン、 2,4 へキサジェン、 1 フエ二ルー 1,3 ペンタジェン、 1,4ージフエ -ルブタジエンの残基が好ましく、これらの残基はさらに炭素原子数 1〜 10の炭化水 素基で置換されていてもよい。 X1及び X2としては、ハロゲン原子、炭素原子数 1〜20 の炭化水素基またはィォゥ含有基であることが好ましい。 Yは、炭素原子数 1〜20の 2価の炭化水素基、炭素原子数 1〜20の 2価のハロゲン化炭化水素基、 2価のケィ 素含有基、 2価のゲルマニウム含有基、 2価のスズ含有基、 O 、 一 CO 、 一 S— 、 一 SO—、 -SO 一、 NR35 、 一 P(R35) 、 一 P(0)(R35) 、 一 BR35 または一 Al R is preferably a hydrogen atom or an alkyl group, particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl or propyl. As such a fluorenyl group having R 32 as a substituent, a 2,7 dialkyl fluorenyl group can be cited as a suitable example. In this case, the 2,7 dialkyl alkyl group has 1 to 5 carbon atoms. An alkyl group is mentioned. R 31 and R 32 may be the same as or different from each other. R 33 and R 34 may be the same or different from each other, and may be the same hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, carbon Alkyl group having 2 to 10 atoms, arylalkyl group having 7 to 40 carbon atoms, arylalkyl group having 8 to 40 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, and containing carbon Group, oxygen-containing group, xio-containing group, nitrogen-containing group or phosphorus-containing group is there. Among these, it is preferable that at least one of R 33 and R 34 is an alkyl group having 1 to 3 carbon atoms. X 1 and X 2 may be the same or different from each other, hydrogen atom, halogen atom, hydrocarbon group having 1 to 20 carbon atoms, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen-containing group A X-containing group or a nitrogen-containing group, or a conjugation residue formed from X 1 and X 2 . The conjugated gen residue formed from X 1 and X 2 is preferably a 1,3 butadiene, 2,4 hexagene, 1 phenylene 1,3 pentene, or 1,4 diphenol butadiene residue, These residues may be further substituted with a hydrocarbon group having 1 to 10 carbon atoms. X 1 and X 2 are preferably a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a X-containing group. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent carbon-containing group, a divalent germanium-containing group, a divalent Tin-containing group, O, 1 CO, 1 S—, 1 SO—, —SO 1, NR 35 , 1 P (R 35 ), 1 P (0) (R 35 ), 1 BR 35 or 1 Al
2  2
R35 （ただし、 R35は水素原子、ハロゲン原子、炭素原子数 1〜20の炭化水素基、炭 素原子数 1〜20のハロゲンィ匕炭化水素基)を示す。これらの 2価の基のうちでも、 Y—の最短連結部が 1個または 2個の原子で構成されているものが好ましい。また、 R 35は、ハロゲン原子、炭素原子数 1〜20の炭化水素基、炭素原子数 1〜20のハロゲ ン化炭化水素基である。 Yは、炭素原子数 1〜5の 2価の炭化水素基、 2価のケィ素 含有基または 2価のゲルマニウム含有基であることが好ましぐ 2価のケィ素含有基で あることがより好ましぐアルキルシリレン、アルキルァリールシリレンまたはァリールシ リレンであることが特に好ましい。 R 35 (wherein R 35 represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms). Among these divalent groups, those in which the shortest linking part of Y— is composed of one or two atoms are preferable. R 3 5 is a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms. Y is preferably a divalent hydrocarbon group having 1 to 5 carbon atoms, a divalent silicon-containing group, or a divalent germanium-containing group, and more preferably a divalent silicon-containing group. Particularly preferred are alkylsilylene, alkylarylsilylene or arylylsilylene.
[0063] <メタ口セン化合物の例 8 >  [0063] <Example 8 of metaguchicene compound>
またメタ口センィ匕合物としては、下記一般式（10)で表されるメタ口セン化合物を用 いることちでさる。  Further, as a meta-mouth compound, a meta-mouth compound represented by the following general formula (10) is used.
[0064] [化 10] [0064] [Chemical 10]
Figure imgf000019_0001
Figure imgf000019_0001
式（10)中、 M3は周期表第 4族の遷移金属原子であり、具体的にはチタニウム、ジル コ -ゥムまたはハフニウムであり、好ましくはジルコニウムである。 R36は互いに同一で も異なっていてもよぐ水素原子、ハロゲン原子、炭素原子数 1〜： L0のアルキル基、 炭素原子数 6〜： L0のァリール基、炭素原子数 2〜： L0のアルケニル基、ケィ素含有基 、酸素含有基、ィォゥ含有基、窒素含有基またはリン含有基である。なお、上記アル キル基及びァルケ-ル基は、ハロゲン原子で置換されていてもよい。 R36はこれらのう ち、アルキル基、ァリール基または水素原子であることが好ましぐ特にメチル、ェチ ル、 n プロピル、 i プロピルの炭素原子数 1〜3の炭化水素基、フエニル、 aーナ フチル、 β ナフチルなどのァリール基または水素原子であることが好ましい。 R37は 互いに同一でも異なっていてもよぐ水素原子、ハロゲン原子、炭素原子数 1〜： L0の アルキル基、炭素原子数 6〜20のァリール基、炭素原子数 2〜 10のァルケ-ル基、 炭素原子数 7〜40のァリールアルキル基、炭素原子数 8〜40のァリールァルケ-ル 基、炭素原子数 7〜40のアルキルァリール基、ケィ素含有基、酸素含有基、ィォゥ含 有基、窒素含有基またはリン含有基である。なお、上記アルキル基、ァリール基、ァ ルケ-ル基、ァリールアルキル基、ァリールァルケ-ル基、アルキルァリール基は、ハ ロゲンが置換していてもよい。 R37はこれらのうち、水素原子またはアルキル基であるこ と力 子ましく、特に水素原子またはメチル、ェチル、 η—プロピル、 i—プロピル、 n—ブ チル、 tert ブチルの炭素原子数 1〜4の炭化水素基であることが好ましい。また、 上記 R36と R37は、互いに同一でも異なっていてもよい。 R38及び R39は、いずれか一方 が炭素原子数 1〜5のアルキル基であり、他方は水素原子、ハロゲン原子、炭素原子 数 1〜： L0のアルキル基、炭素原子数 2〜： L0のァルケ-ル基、ケィ素含有基、酸素含 有基、ィォゥ含有基、窒素含有基またはリン含有基である。これらのうち、 R38及び R39 は、いずれか一方がメチル、ェチル、プロピルなどの炭素原子数 1〜3のアルキル基 であり、他方は水素原子であることが好ましい。 X1及び X2は互いに同一でも異なって いてもよぐ水素原子、ハロゲン原子、炭素原子数 1〜20の炭化水素基、炭素原子 数 1〜20のハロゲン化炭化水素基、酸素含有基、ィォゥ含有基もしくは窒素含有基 、または X1と X2とから形成された共役ジェン残基である。これらのうち、ハロゲン原子 または炭素原子数 1〜20の炭化水素基であることが好ましい。 Yは、炭素原子数 1〜 20の 2価の炭化水素基、炭素原子数 1〜20の 2価のハロゲン化炭化水素基、 2価の ケィ素含有基、 2価のゲルマニウム含有基、 2価のスズ含有基、 O CO S―、— SO—、 -SO―、— NR4°—、— P(R4°)—、— P(0)(R4°)—、— BR4°—または Wherein (10), M 3 is a transition metal atom of Group 4 of the periodic table, specifically titanium, Jill co - a © beam or hafnium, preferably zirconium. R 36 may be the same or different from each other, hydrogen atom, halogen atom, carbon atom number 1 to: L0 alkyl group, carbon atom number 6 to: L0 aryl group, carbon atom number 2 to: L0 alkenyl A group, a silicon-containing group, an oxygen-containing group, a X-containing group, a nitrogen-containing group or a phosphorus-containing group. The above alkyl group and alkenyl group may be substituted with a halogen atom. R 36 is preferably an alkyl group, an aryl group or a hydrogen atom, particularly a methyl, ethyl, n-propyl or i-propyl hydrocarbon group having 1 to 3 carbon atoms, phenyl, a An aryl group such as naphthyl or β-naphthyl or a hydrogen atom is preferable. R 37 may be the same or different from each other, hydrogen atom, halogen atom, carbon atom number 1 to: L0 alkyl group, carbon atom number 6 to 20 aryl group, carbon atom number 2 to 10 alkyl group , 7 to 40 carbon atom alkyl group, 8 to 40 carbon atom aryl group, 7 to 40 carbon atom alkyl group, silicon-containing group, oxygen-containing group, X-containing group A nitrogen-containing group or a phosphorus-containing group. The alkyl group, aryl group, alkyl group, aryl alkyl group, aryl hydrocarbon group and alkyl aryl group may be substituted with halogen. Among these, R 37 is preferably a hydrogen atom or an alkyl group, particularly a hydrogen atom or a carbon atom number of 1 to 4 of methyl, ethyl, η-propyl, i-propyl, n-butyl, and tert butyl. The hydrocarbon group is preferably. R 36 and R 37 may be the same as or different from each other. One of R 38 and R 39 is an alkyl group having 1 to 5 carbon atoms, and the other is a hydrogen atom, a halogen atom, or a carbon atom having 1 to: an alkyl group having L0, or 2 to carbon atoms having an L0. Alkellyl group, silicon-containing group, oxygen-containing It is a group, a thio group, a nitrogen group or a phosphorus group. Among these, it is preferable that one of R 38 and R 39 is an alkyl group having 1 to 3 carbon atoms such as methyl, ethyl, and propyl, and the other is a hydrogen atom. X 1 and X 2 may be the same or different from each other, and may be a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogenated hydrocarbon group having 1 to 20 carbon atoms, an oxygen-containing group, A containing group or a nitrogen-containing group, or a conjugation residue formed from X 1 and X 2 . Of these, a halogen atom or a hydrocarbon group having 1 to 20 carbon atoms is preferable. Y is a divalent hydrocarbon group having 1 to 20 carbon atoms, a divalent halogenated hydrocarbon group having 1 to 20 carbon atoms, a divalent silicon-containing group, a divalent germanium-containing group, a divalent tin-containing group, O CO S -, - SO- , -SO -, - NR 4 ° -, - P (R 4 °) -, - P (0) (R 4 °) -, - BR 4 ° - Or
2  2
-AIR40- (ただし、 R4Qは水素原子、ハロゲン原子、炭素原子数 1〜20の炭化水素 基、炭素原子数 1〜20のハロゲンィ匕炭化水素基)を示す。これらのうち Yは、炭素原 子数 1〜5の 2価の炭化水素基、 2価のケィ素含有基または 2価のゲルマニウム含有 基であることが好ましぐ 2価のケィ素含有基であることがより好ましぐアルキルシリレ ン、アルキルァリールシリレンまたはァリールシリレンであることが特に好まし！/、。 -AIR 40- (wherein R 4Q is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon group having 1 to 20 carbon atoms). Of these, Y is preferably a divalent hydrocarbon-containing group having 1 to 5 carbon atoms, preferably a divalent hydrocarbon-containing group or a divalent germanium-containing group. Especially preferred are alkylsilylene, alkylarylsilylene or arylylsilylene, which are more preferred! /.
[0066] <メタ口セン化合物の例 9 >  [0066] <Example 9 of metaguchicene compound>
またメタ口センィ匕合物としては、下記一般式（11)で表されるメタ口セン化合物を用 いることちでさる。  Further, as a meta-mouth compound, a meta-mouth compound represented by the following general formula (11) is used.
[0067] [化 11]  [0067] [Chemical 11]
Figure imgf000020_0001
Figure imgf000020_0001
[0068] 式（11)において、 Yは炭素、ケィ素、ゲルマニウムおよびスズ原子から選ばれ、 Mは Ti、 Zrまたは Hfであり、
Figure imgf000021_0001
R1Q、 RUおよび R12は水素、 炭化水素基、ケィ素含有基から選ばれ、それぞれ同一でも異なっていてもよぐ R5か ら R12までの隣接した置換基は互いに結合して環を形成してもよぐ R13、 R14は炭化水 素基およびケィ素含有基から選ばれ、それぞれ同一でも異なっていてもよぐ R13およ び R14が互いに結合して環を形成してもよい。 Qはハロゲン、炭化水素基、ァ-オン配 位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選 んでもよく、 jは 1〜4の整数である。 ) [0068] In the formula (11), Y is selected from carbon, silicon, germanium and tin atoms, and M is Ti, Zr or Hf
Figure imgf000021_0001
R 1Q, R U and R 12 are hydrogen, a hydrocarbon group, selected from Kei-containing group, adjacent substituents of up Yogu R 5 or et R 12 be different or identical or not bonded to each other to form a ring R 13 and R 14 may be selected from a hydrocarbon group and a silicon-containing group, and may be the same or different, and R 13 and R 14 may be bonded to each other to form a ring. May be. Q may be selected from the same or different combinations from a halogen, a hydrocarbon group, a lone ligand, or a neutral ligand capable of coordinating with a lone pair, and j is an integer of 1 to 4. )
以下、本発明に関わる架橋メタ口センィ匕合物の化学構造上の特徴であるシクロペン タジェニル基、フルォレニル基、架橋部、およびその他特徴について順次説明した 後に、これらの特徴を併せ持つ好ましい架橋メタ口センィ匕合物を説明する。 Hereinafter, the cyclopentagenyl group, the fluorenyl group, the cross-linked part, and other characteristics, which are the chemical structural characteristics of the cross-linked meta-molecular complex related to the present invention, will be described in order, and then a preferred cross-linked meta-molecular complex having these characteristics together. Explain the compound.
シクロペンタジェ -ル某 Cyclopentagel
シクロペンタジェ -ル基は置換されて ヽても 、なくてもょ 、。置換されて ヽても 、なく てもよぃシクロペンタジェ-ル基とは、上記一般式（11)におけるシクロペンタジェ- ル基部分が保有する 、 R2、 R3および R4が全て水素原子である力、または尺1、 R2、 R3 および R4の内の 、ずれか一つ以上が炭化水素基 (fl)、好ましくは総炭素数 1から 20の 炭化水素基 (fl')、またはケィ素含有基 (12)、好ましくは総炭素数 1から 20のケィ素含有 基 (β')で置換されたシクロペンタジェ-ル基であることを意味する。
Figure imgf000021_0002
R3および R 4の内の二つ以上が置換されている場合は、それらの置換基は相互に同一でも異な つていてもよい。また、総炭素数 1から 20の炭化水素基とは、炭素および水素のみか ら構成されるアルキル、ァルケ-ル、アルキニル、ァリール基である。この中には、隣 接する任意の二つの水素原子が同時に置換されて脂環族あるいは芳香族環を形成 しているものも含む。総炭素数 1から 20の炭化水素基 (fl')としては、炭素および水素 のみから構成されるアルキル、ァルケ-ル、アルキ -ル、ァリール基以外に、これらの 炭素に直結した水素原子の一部がハロゲン原子、酸素含有基、窒素含有基、ケィ素 含有基で置換されたへテロ原子含有炭化水素基や、隣接する任意の二つの水素原 子が脂環族を形成しているものも含む。このような基 (fl')としては、メチル基、ェチル 基、 n-プロピル基、ァリル (allyl)基、 n-ブチル基、 n-ペンチル基、 n-へキシル基、 n-へ プチル基、 n_オタチル基、 n-ノニル基、 n-デカニル基などの直鎖状炭化水素基;イソ プロピル基、 t-ブチル基、アミル基、 3-メチルペンチル基、 1,1-ジェチルプロピル基、 1,1-ジメチルブチル基、 1-メチル -1-プロピルブチル基、 1,1-プロピルブチル基、 1,1- ジメチル -2-メチルプロピル基、 1-メチル -1-イソプロピル- 2-メチルプロピル基などの 分岐状炭化水素基；シクロペンチル基、シクロへキシル基、シクロへプチル基、シクロ ォクチル基、ノルボル-ル基、ァダマンチル基などの環状飽和炭化水素基;フエ-ル 基、ナフチル基、ビフヱニル基、フヱナントリル基、アントラセ-ル基などの環状不飽 和炭化水素基およびこれらの核アルキル置換体；ベンジル基、タミル基などのァリー ル基の置換した飽和炭化水素基；メトキシ基、エトキシ基、フエノキシ基 N-メチルアミ ノ基、トリフルォロメチル基、トリブロモメチル基、ペンタフルォロェチル基、ペンタフル オロフェ-ル基などのへテロ原子含有炭化水素基を挙げることができる。 The cyclopentagel group may or may not be substituted. The cyclopentagel group, which may or may not be substituted, is a group in which R 2 , R 3 and R 4 are all hydrogenated by the cyclopentagel group moiety in the general formula (11). A force that is an atom, or one or more of the scales 1 , R 2 , R 3 and R 4 is a hydrocarbon group (fl), preferably a hydrocarbon group having 1 to 20 carbon atoms in total (fl ') Or a cyclopentagel group (12), preferably a cyclopentagel group substituted with a C 1 -C 20 group (β ').
Figure imgf000021_0002
When two or more of R 3 and R 4 are substituted, these substituents may be the same or different from each other. The hydrocarbon group having 1 to 20 carbon atoms in total is an alkyl, alkenyl, alkynyl, or aryl group composed only of carbon and hydrogen. This includes those in which any two adjacent hydrogen atoms are simultaneously substituted to form an alicyclic or aromatic ring. The hydrocarbon group having 1 to 20 carbon atoms (fl ') includes, in addition to alkyl, alkyl, alkyl, and aryl groups composed of only carbon and hydrogen, one of the hydrogen atoms directly connected to these carbons. A hetero atom-containing hydrocarbon group in which a part is substituted with a halogen atom, an oxygen-containing group, a nitrogen-containing group, or a silicon-containing group, or in which any two adjacent hydrogen atoms form an alicyclic group Including. Examples of such a group (fl ′) include methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n_Otachil group, n-nonyl group, n-decanyl group and other linear hydrocarbon groups; Propyl group, t-butyl group, amyl group, 3-methylpentyl group, 1,1-jetylpropyl group, 1,1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl Branched hydrocarbon group such as 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group; cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl Cyclic hydrocarbon groups such as benzene, norbornyl and adamantyl groups; cyclic unsaturated hydrocarbon groups such as phenol, naphthyl, biphenyl, phenanthryl and anthracyl groups and their nuclear alkyl substitution Body: saturated hydrocarbon group substituted with aryl group such as benzyl group, Tamyl group; methoxy group, ethoxy group, phenoxy group, N-methylamino group, trifluoromethyl group, tribromomethyl group, pen Furuoroechiru group, Pentafuru Orofe - can be exemplified hetero atom-containing hydrocarbon group such as Le group.
ケィ素含有基 (β)とは、例えば、シクロペンタジェニル基の環炭素がケィ素原子と直 接共有結合して 、る基であり、具体的にはアルキルシリル基ゃァリールシリル基であ る。総炭素数 1から 20のケィ素含有基 (β')としては、トリメチルシリル基、トリフエニルシ リル基等を例示することができる。 The silicon-containing group (β) is, for example, a group in which a ring carbon of a cyclopentagenyl group is directly covalently bonded to a silicon atom, specifically an alkylsilyl group or a arylsilyl group. . Examples of the C 1 to C 20 -containing group (β ′) include a trimethylsilyl group and a triphenylsilyl group.
フルォレニル某 Fluorenyl
フルォレニル基は置換されて ヽても 、なくてもょ 、。置換されて!ヽても 、なくてもよ!ヽ フルォレニル基とは、上記一般式（11)におけるフルォレニル基部分が保有する R5、
Figure imgf000022_0001
R9、The fluorenyl group may or may not be substituted. It may or may not be substituted! ヽ The fluorenyl group means R 5 held by the fluorenyl group moiety in the general formula (11),
Figure imgf000022_0001
R 9,
R1Q、 R11および R12の内のいずれか一つ以上が炭化水素基 (fl)、好ましくは総炭素数 1 から 20の炭化水素基 (fl')、またはケィ素含有基 (12)、好ましくは総炭素数 1から 20のケ ィ素含有基 02')で置換されたフルォレ -ル基であることを意味する。 R5、
Figure imgf000022_0002
R R1Q、 R11および R12の内の二つ以上が置換されている場合は、それらの置換基は相 互に同一でも異なっていてもよい。また、 R5、 R6、 R7、 R8、 R9、 R10、 R11および R12は、隣 接する基が互いに結合して環を形成して!/、てもよ!/、。触媒のその製造上の容易性か ら R6と Ru、および R7と R1Qが相互に同一であるものが好んで使用される。 Any one or more of R 1Q , R 11 and R 12 is a hydrocarbon group (fl), preferably a hydrocarbon group having 1 to 20 carbon atoms in total (fl ′), or a silicon-containing group (12), Preferably, it means a fluorine group substituted with a carbon-containing group 02 ′) having 1 to 20 carbon atoms in total. R 5 ,
Figure imgf000022_0002
When two or more of RR 1Q , R 11 and R 12 are substituted, those substituents may be the same or different from each other. Also, R 5, R 6, R 7, R 8, R 9, R 10, R 11 and R 12 are adjacent contact groups are bonded to each other to form a ring! /, I be! /,. In view of the ease of production of the catalyst, those in which R 6 and R u and R 7 and R 1Q are the same are preferably used.
炭化水素基 (fl)の好ましい基は、前記した総炭素数 1から 20の炭化水素基 (fl')であり 、ケィ素含有基 (12)の好ましい例は、前記した総炭素数 1から 20のケィ素含有基 (β')で ある。 共有結合架橋 A preferred group of the hydrocarbon group (fl) is the above-described hydrocarbon group (fl ′) having 1 to 20 carbon atoms, and a preferable example of the silicon-containing group (12) is the above-mentioned total carbon number of 1 to 20 This is a C-containing group (β '). Covalent bond
シクロペンタジェニル基とフルォレニル基を結ぶ結合の主鎖部は、炭素、ケィ素、ゲ ルマニウムおよびスズ原子を一つ含有する 2価の共有結合架橋である。本発明の高 温溶液重合において重要な点は、共有結合架橋部の架橋原子 Yが、相互に同一で も異なっていてもよい R13と R14を有することである。炭化水素基 (fl)の好ましい基は、前 記した総炭素数 1から 20の炭化水素基 (fl')であり、ケィ素含有基 (12)の好ましい例は、 前記した総炭素数 1から 20のケィ素含有基 (β')である。 The main chain part of the bond connecting the cyclopentagenyl group and the fluorenyl group is a divalent covalent bond containing one carbon, silicon, germanium and tin atom. The important point in the high-temperature solution polymerization of the present invention is that the bridging atom Y of the covalent bond bridging portion has R 13 and R 14 which may be the same or different from each other. A preferred group of the hydrocarbon group (fl) is the hydrocarbon group (fl ′) having a total carbon number of 1 to 20 described above, and a preferable example of the silicon-containing group (12) is the above-mentioned total number of carbon atoms of 1 to 20. There are 20 key groups (β ').
架橋メタ口セン化合物のその他の特徴 Other features of cross-linked metaguchicene compounds
前記一般式（11)において、 Qはハロゲン、炭素数が 1〜10の炭化水素基、または炭 素数が 10以下の中性、共役または非共役ジェン、ァ-オン配位子または孤立電子対 で配位可能な中性配位子から同一または異なる組み合わせで選ばれる。ハロゲンの 具体例としては、フッ素、塩素、臭素、ヨウ素であり、炭化水素基の具体例としては、メ チル、ェチル、 η-プロピル、イソプロピル、 2-メチルプロピル、 1,1-ジメチルプロピル、 2, 2-ジメチルプロピル、 1,1-ジェチルプロピル、 1-ェチル -1-メチルプロピル、 1,1,2,2 -テトラメチルプロピル、 sec-ブチル、 tert-ブチル、 1,1-ジメチルブチル、 1,1,3-トリメチ ルブチル、ネオペンチル、シクロへキシルメチル、シクロへキシル、 1-メチル -1-シクロ へキシル等が挙げられる。炭素数が 10以下の中性、共役または非共役ジェンの具体 例としては、 s-シス-または s-トランス- 7} 4-1,3-ブタジエン、 s-シス-または s-トランス- 7? '-1,4-ジフエニル- 1,3-ブタジエン、 S-シス-または S-トランス- 7? '-3-メチル -1,3-ぺ ンタジェン、 s-シス-または s-トランス- 4-1, 4-ジベンジル- 1,3-ブタジエン、 s-シス-ま たは s-トランス- 7? 4-2,4-へキサジェン、 s-シス-または s-トランス- 7} -1, 3-ペンタジェ ン、 S-シス-または S-トランス- 7? 4- 1,4-ジトリル- 1,3-ブタジエン、 S-シス-または S-トラン ス- 7? 4-1, 4-ビス (トリメチルシリル) -1,3-ブタジエン等が挙げられる。ァ-オン配位子の 具体例としては、メトキシ、 tert-ブトキシ、フエノキシ等のアルコキシ基、アセテート、ベ ンゾエート等のカルボキシレート基、メシレート、トシレート等のスルホネート基等が挙 げられる。孤立電子対で配位可能な中性配位子の具体例としては、トリメチルホスフ イン、トリェチルホスフィン、トリフエ-ルホスフィン、ジフエ-ルメチルホスフィンなどの 有機リンィ匕合物、またはテトラヒドロフラン、ジェチルエーテル、ジォキサン、 1,2-ジメト キシェタン等のエーテル類が挙げられる。 jは 1〜4の整数であり、 jが 2以上の時は、 Q は互いに同一でも異なって!/、てもよ!/、。 In the general formula (11), Q is a halogen, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated gen, carbon ion ligand or lone electron pair having 10 or less carbon atoms. The neutral ligands that can be coordinated are selected in the same or different combinations. Specific examples of the halogen include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, η-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2 , 2-dimethylpropyl, 1,1-jetylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. Specific examples of neutral, conjugated or non-conjugated gens with 10 or fewer carbon atoms include s-cis- or s-trans-7} 4 -1,3-butadiene, s-cis- or s-trans-7? '-1,4-diphenyl-1,3-butadiene, S-cis- or S-trans-7?' -3-methyl-1,3-pentagen, s-cis- or s-trans-4-1 , 4-dibenzyl-1,3-butadiene, s-cis- or s-trans-7? 4 -2,4-hexagen, s-cis- or s-trans-7} -1,3-pentadiene emissions, S- cis - or S- trans -? 7 4 - 1,4-ditolyl - 1,3, S- cis - or S- trans -? 7 4 -1, 4-bis (trimethylsilyl) - Examples include 1,3-butadiene. Specific examples of the cation ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organophosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, or tetrahydrofuran, jetyl. Ether, dioxane, 1,2-dimeth And ethers such as kichetan. j is an integer from 1 to 4, and when j is 2 or more, Q's are the same or different from each other! /.
[0069] <メタ口セン化合物の例 10 > [0069] <Example 10 of metaguchicene compound>
またメタ口センィ匕合物としては、下記一般式（12)で表されるメタ口セン化合物を用 いることちでさる。  Further, as a meta-mouth compound, a meta-mouth compound represented by the following general formula (12) is used.
[0070] [化 12] [0070] [Chemical 12]
Figure imgf000024_0001
Figure imgf000024_0001
[0071] 式中、
Figure imgf000024_0002
R2、 R3、 R 4、 R 5、 R。、 R 7、 R 8、 R 9、 R 10、 R U、 R 12、 R 13、 R 14は水素、炭化水 素基、ケィ素含有基から選ばれ、それぞれ同一でも異なっていてもよぐ R 1から R 14ま での隣接した置換基は互いに結合して環を形成してもよぐ Mは Ti、 Zrまたは Hfで あり、 Yは第 14族原子であり、 Qはハロゲン、炭化水素基、炭素数が 10以下の中性、 共役または非共役ジェン、ァニオン配位子、および孤立電子対で配位可能な中性 配位子力もなる群から同一または異なる組合せで選ばれ、 nは 2〜4の整数、 jは 1〜 4の整数である。 [0071] where
Figure imgf000024_0002
R 2 , R 3 , R 4 , R 5 , R. , R 7 , R 8 , R 9 , R 10 , R U , R 12 , R 13 , R 14 are selected from hydrogen, a hydrocarbon group, and a silicon-containing group, and may be the same or different. Adjacent substituents from 1 to R 14 may be bonded to each other to form a ring. M is Ti, Zr or Hf, Y is a Group 14 atom, Q is a halogen, hydrocarbon group. Selected from the group consisting of neutral, conjugated or non-conjugated gen, anion ligand, and neutral ligand capable of coordinating with a lone electron pair, in the same or different combination, and n is 2 An integer of ~ 4, j is an integer of 1 ~ 4.
[0072] 上記一般式（12)において、炭化水素基としては、好ましくは炭素数 1〜20のアル キル基、炭素数 7〜20のァリールアルキル基、炭素数 6〜20のァリール基、または炭 素数 7〜20のアルキルァリール基であり、 1つ以上の環構造を含んでいてもよい。 その具体例としては、メチル、ェチル、 n-プロピル、イソプロピル、 2-メチルプロピル 、 1,1-ジメチルプロピル、 2,2-ジメチルプロピル、 1, 1-ジェチルプロピル、 1-ェチル -1- メチルプロピル、 1, 1, 2,2-テトラメチルプロピル、 sec-ブチル、 tert-ブチル、 1,1-ジメチ ルブチル、 1,1, 3-トリメチルブチル、ネオペンチル、シクロへキシルメチル、シクロへキ シル、 1-メチル -1-シクロへキシル、 1-ァダマンチル、 2-ァダマンチル、 2-メチル -2-ァ ダマンチル、メンチル、ノルボルニル、ベンジル、 2-フエ-ルェチル、 1-テトラヒドロナ フチル、 1-メチル -1-テトラヒドロナフチル、フエ-ル、ナフチル、トリル等が挙げられる [0072] In the general formula (12), the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an aryl alkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or It is an alkylaryl group having 7 to 20 carbon atoms, and may contain one or more ring structures. Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-jetylpropyl, 1-ethyl-1-methyl Propyl, 1, 1, 2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohex Sil, 1-methyl-1-cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl -1-tetrahydronaphthyl, phenol, naphthyl, tolyl, etc.
[0073] 上記一般式（12)において、ケィ素含有炭化水素基としては、好ましくはケィ素数 1 〜4、炭素数 3〜20のアルキルまたはァリールシリル基であり、その具体例としては、 トリメチルシリル、 tert-ブチルジメチルシリル、トリフエ-ルシリル等が挙げられる。 本発明において、上記一般式（12)の R1から R"は水素、炭化水素基、ケィ素含有 炭化水素基から選ばれ、それぞれ同一でも異なっていてもよい。好ましい炭化水素 基、ケィ素含有炭化水素基の具体例としては、上記と同様のものを挙げることができ る。 [0073] In the above general formula (12), the C-containing hydrocarbon group is preferably an alkyl or aryl silyl group having 1 to 4 carbon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert -Butyldimethylsilyl, triphenylsilyl and the like. In the present invention, R "from R 1 in the general formula (12) hydrogen, a hydrocarbon group, selected from Kei-containing hydrocarbon group, each of which may be the same or different. Preferred hydrocarbon groups, containing Kei containing Specific examples of the hydrocarbon group include those similar to the above.
[0074] 上記一般式（12)のシクロペンタジェ -ル環上の R 1から R "までの隣接した置換基 は、互いに結合して環を形成してもよい。 [0074] The adjacent substituents from R 1 to R "on the cyclopentagel ring of the general formula (12) may be bonded to each other to form a ring.
一般式（12)の Mは、周期律表第 4族元素、すなわちジルコニウム、チタンまたはハ フニゥムであり、好ましくはジルコニウムである。  M in the general formula (12) is a group 4 element of the periodic table, that is, zirconium, titanium, or hafnium, preferably zirconium.
Yは第 14族原子であり、好ましくは炭素原子または珪素原子である。 nは 2〜4の整 数であり、好ましくは 2または 3、特に好ましくは 2である。  Y is a Group 14 atom, preferably a carbon atom or a silicon atom. n is an integer of 2 to 4, preferably 2 or 3, particularly preferably 2.
[0075] Qはハロゲン、炭化水素基、炭素数が 10以下の中性、共役または非共役ジェン、 ァ-オン配位子および孤立電子対で配位可能な中性配位子力 なる群から同一ま たは異なる組み合わせで選ばれる。 Qが炭化水素基であるとき、より好ましくは炭素 数が 1〜： L0の炭化水素基である。 [0075] Q is a group consisting of a halogen, a hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or non-conjugated gen, a lone ligand, and a neutral ligand capable of coordination with a lone pair of electrons. Selected in the same or different combinations. When Q is a hydrocarbon group, it is more preferably a hydrocarbon group having 1 to: L0 carbon atoms.
ハロゲンの具体例としては、フッ素、塩素、臭素、ヨウ素であり、炭化水素基の具体 例としては、メチル、ェチル、 n-プロピル、イソプロピル、 2-メチルプロピル、 1,1-ジメ チルプロピル、 2,2-ジメチルプロピル、 1,1-ジェチルプロピル、 1-ェチル -1-メチルプ 口ピル、 1,1, 2,2-テトラメチルプロピル、 sec-ブチル、 tert-ブチル、 1,1-ジメチルブチ ル、 1,1, 3-トリメチルブチル、ネオペンチル、シクロへキシルメチル、シクロへキシル、 1 -メチル -1-シクロへキシル等が挙げられる。炭素数が 10以下の中性、共役または非 共役ジェンの具体例としては、 s-シス-または s-トランス- 4-1,3-ブタジエン、 S-シス- または s-トランス- η -1,4-ジフエニル- 1,3-ブタジエン、 S-シス-または S-トランス- -Specific examples of halogen include fluorine, chlorine, bromine and iodine. Specific examples of hydrocarbon groups include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-jetylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated diene, s- cis - or s- trans - 4-1,3-butadiene, S- cis - Or s-trans-η-1,4-diphenyl-1,3-butadiene, S-cis- or S-trans--
3-メチル -1,3-ペンタジェン、 S-シス-または S-トランス- 7? 4- 1,4-ジベンジル- 1,3-ブタ ジェン、 s-シス-または s-トランス- 7? 4-2,4-へキサジェン、 s-シス-または s-トランス- 7}3-methyl-1,3-Pentajen, S- cis - or S- trans -? 7 4 - 1,4-dibenzyl - 1,3-butadiene, s- cis - or s- trans -? 7 4 -2 , 4-hexagen, s-cis- or s-trans-7}
4- 1,3-ペンタジェン、 S-シス-または S-トランス- 7? 4- 1,4-ジトリル- 1,3-ブタジエン、 S-シ ス-または s-トランス- η 4-1, 4-ビス（トリメチルシリル) -1,3-ブタジエン等が挙げられる。 ァ-オン配位子の具体例としては、メトキシ、 tert-ブトキシ、フエノキシ等のアルコキシ 基、アセテート、ベンゾエート等のカルボキシレート基、メシレート、トシレート等のスル ホネート基等が挙げられる。孤立電子対で配位可能な中性配位子の具体例としては 、トリメチルホスフィン、トリェチルホスフィン、トリフエニルホスフィン、ジフエニルメチル ホスフィンなどの有機リンィ匕合物、またはテトラヒドロフラン、ジェチルエーテル、ジォ キサン、 1、 2—ジメトキシェタン等のエーテル類が挙げられる。 jが 2以上の整数であ る場合は、複数の Qは同一でも異なっていてもよい。 4 - 1,3 Pentajen, S- cis - or S- trans -? 7 4 - 1,4-ditolyl - 1,3, S- sheet scan - or s- trans - eta 4 -1, 4- Examples thereof include bis (trimethylsilyl) -1,3-butadiene. Specific examples of the cation ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, or tetrahydrofuran, jetyl ether, dioxane. And ethers such as 1,2-dimethoxyethane. When j is an integer of 2 or more, multiple Qs may be the same or different.
[0076] 式（12)において、 Yは 2〜4の複数個存在する力 複数の Yは相互に同一であって も異なっていてもよい。 Yに結合する複数の R13及び複数の R14は、それぞれ相互に同 一であっても異なっていてもよい。例えば同一の Yに結合する複数の R13が相互に異 なっていてもよいし、異なる Yに結合する複数の R13が相互に同一であってもよい。ま た、 R13もしくは R14同士が環を形成して 、てもよ 、。 [0076] In the formula (12), Y is a force in which a plurality of 2 to 4 exist. A plurality of Y may be the same as or different from each other. The plurality of R 13 and the plurality of R 14 bonded to Y may be the same as or different from each other. For example, a plurality of R 13 bonded to the same Y may be different from each other, or a plurality of R 13 bonded to different Y may be the same as each other. Also, R 13 or R 14 may form a ring.
[0077] 式（12)で表される第 4族遷移金属化合物の好ましい例として、下記式（13)で表さ れる化合物を挙げることができる。  [0077] Preferable examples of the Group 4 transition metal compound represented by the formula (12) include a compound represented by the following formula (13).
[0078] [化 13]  [0078] [Chemical 13]
Figure imgf000026_0001
Figure imgf000026_0001
[0079] 式（13)中、 R R2、 R3、 R4、 R5、 R。、 R R
Figure imgf000026_0002
R 10、 R U、 R 12は水素原子、炭化 水素基、ケィ素含有基から選ばれ、それぞれ同一でも異なっていてもよぐ R 13、 R "、 R 15、 R 16は水素原子または炭化水素基であり、 nは 1〜3の整数であり、 n= lのときは 前記 R 1から R 16は同時に水素原子ではなぐそれぞれ同一でも異なっていてもよい。 R5力 R 12までの隣接した置換基は互いに結合して環を形成してもよぐ R 13と R 15は互 Vヽに結合して環を形成してもよく、また R 13と R 15は互!、に結合して環を形成すると同 時に R 14と R 16は互いに結合して環を形成してもよぐ Y1および Y2は第 14族原子であり 相互に同一でも異なっていてもよぐ Mは Ti、 Zrまたは Hfであり、 Qはハロゲン、炭化 水素基、ァ-オン配位子または孤立電子対で配位可能な中性配位子力 同一また は異なる組合せで選んでもよぐ jは 1〜4の整数である。 During [0079] Formula (13), RR 2, R 3, R 4, R 5, R. , RR
Figure imgf000026_0002
R 10 , R U , and R 12 are selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and may be the same or different from each other R 13 , R ", R 15 and R 16 are a hydrogen atom or a hydrocarbon group, n is an integer of 1 to 3, and when n = l, R 1 to R 16 may be the same or different at the same time, not a hydrogen atom. Good. Adjacent substituents up to R 5 force R 12 may be bonded together to form a ring R 13 and R 15 may be bonded to each other V ヽ to form a ring, and R 13 and R When 15 is bonded to each other to form a ring, at the same time, R 14 and R 16 may be bonded to each other to form a ring. Y 1 and Y 2 are group 14 atoms and are the same or different from each other M is Ti, Zr or Hf, and Q is a neutral ligand force that can be coordinated by a halogen, a hydrocarbon group, a lone ligand, or a lone pair of electrons, in the same or different combinations. You can choose j is an integer from 1 to 4.
このようなメタ口セン化合物の例一 9、 10のようなィ匕合物は特開 2004— 175707号公 報 WO200lZ027124、 WO2004/029062, WO2004Z083265等に挙げら れている。  Examples of such meta-octacene compounds such as 9 and 10 are listed in JP-A-2004-175707 publications WO200lZ027124, WO2004 / 029062, WO2004Z083265 and the like.
[0080] 以上に説明したメタ口センィ匕合物は、単独であるいは 2種以上組み合せて用いられ る。またメタ口センィ匕合物は、炭化水素またはハロゲンィ匕炭化水素などに希釈して用 いてもよい。  [0080] The meta-senic compound described above may be used alone or in combination of two or more. Further, the meta mouth mixture may be diluted with a hydrocarbon or a halogenated hydrocarbon.
触媒成分は、（A)前記で表される架橋メタ口センィ匕合物、並びに (B) (b- 1)有機アル ミニゥムォキシィ匕合物、（b-2)前記架橋メタ口センィ匕合物 (A)と反応してイオン対を形 成する化合物、および (b- 3)有機アルミニウム化合物力 選ばれる少なくても 1種の化 合物から構成される。  The catalyst component includes (A) the above-mentioned cross-linked meta-molecular compound, and (B) (b-1) an organic aluminum compound, (b-2) the above-mentioned cross-linked meta-molecular compound ( It is composed of a compound that reacts with A) to form an ion pair, and (b-3) an organoaluminum compound force that is selected from at least one compound.
[0081] 以下、（B)成分について具体的に説明する。 [0081] Component (B) will be specifically described below.
< (b-l)有機アルミニウムォキシ化合物 >  <(b-l) Organoaluminoxy compound>
本発明で用いられる (b-1)有機アルミニウムォキシィ匕合物は、従来公知のアルミノキ サンをそのまま使用できる。具体的には、下記一般式（14)  As the (b-1) organoaluminum compound used in the present invention, a conventionally known aluminoxane can be used as it is. Specifically, the following general formula (14)
[0082] [化 14] [0082] [Chemical 14]
Figure imgf000027_0001
Figure imgf000027_0001
[0083] および Zまたは一般式（15)  [0083] and Z or the general formula (15)
[0084] [化 15]
Figure imgf000028_0001
[0084] [Chemical 15]
Figure imgf000028_0001
[0085] (ここで、 Rは炭素数 1〜10の炭化水素基、 nは 2以上の整数を示す。 )で代表される化 合物を挙げることができ、特に Rがメチル基であるメチルアルミノキサンで nが 3以上、 好ましくは 10以上のものが利用される。これらアルミノキサン類に若干の有機アルミ二 ゥム化合物が混入して 、ても差し支えな 、。本発明の高温溶液重合にぉ 、て特徴的 な性質は、特開平 2-78687号公報に例示されて 、るようなベンゼン不溶性の有機ァ ルミ-ゥムォキシィ匕合物をも適用できることである。また、特開平 2-167305号公報に 記載されている有機アルミニウムォキシィ匕合物、特開平 2-24701号公報、特開平 3-1 03407号公報に記載されている二種類以上のアルキル基を有するアルミノキサンなど も好適に利用できる。なお、本発明の高温溶液重合で用いられる「ベンゼン不溶性 の」有機アルミニウムォキシィ匕合物とは、 60°Cのベンゼンに溶解する A1成分が A1原子 換算で通常 10%以下、好ましくは 5%以下、特に好ましくは 2%以下であり、ベンゼンに対 して不溶性または難溶性であることを 、う。  [0085] (wherein R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more), particularly a methyl group in which R is a methyl group. Aluminoxanes having n of 3 or more, preferably 10 or more are used. These aluminoxanes may be mixed with some organic aluminum compounds. A characteristic characteristic of the high-temperature solution polymerization of the present invention is that it is also possible to apply a benzene-insoluble organic alcoholic compound as exemplified in JP-A-2-78687. Also, organoaluminum compounds described in JP-A-2-167305, two or more types of alkyl groups described in JP-A-2-24701, JP-A-3-03407 An aluminoxane having bismuth can also be suitably used. The “benzene-insoluble” organoaluminum compound used in the high-temperature solution polymerization of the present invention means that the A1 component dissolved in benzene at 60 ° C. is usually 10% or less in terms of A1 atom, preferably 5 % Or less, particularly preferably 2% or less, and is insoluble or hardly soluble in benzene.
[0086] また、本発明で用いられる有機アルミニウムォキシィ匕合物としては下記（16)のよう な修飾メチルアルミノキサン等も挙げられる。  [0086] Further, examples of the organoaluminum compound used in the present invention include modified methylaluminoxane as shown in (16) below.
[0087] [化 16]
Figure imgf000028_0002
[0087] [Chemical 16]
Figure imgf000028_0002
[0088] (ここで、 Rは炭素数 1〜10の炭化水素基、 m,nは 2以上の整数を示す。 )  (Here, R is a hydrocarbon group having 1 to 10 carbon atoms, and m and n are integers of 2 or more.)
この修飾メチルアルミノキサンはトリメチルアルミニウムとトリメチルアルミニウム以外の アルキルアルミニウムを用いて調製されるものである。このような化合物 [V]は一般に MMAOと呼ばれて!/、る。このような MMAOは US4960878および US5041584で挙げられ ている方法で調製することが出来る。また、東ソー 'ファインケム社等力ももトリメチル アルミニウムとトリイソブチルアルミニウムを用いて調製した Rがイソブチル基であるも のが MMAOや TMAO t 、つた名称で商業生産されて!、る。このような MMAOは各種 溶媒への溶解性および保存安定性を改良したアルミノキサンであり、具体的には上 記（14)、 （15)のようなベンゼンに対して不溶性または難溶性のものとは違い、脂肪 族炭化水素や脂環族炭化水素に溶解するものである。 This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum. Such a compound [V] is generally called MMAO! Such MMAO can be prepared by the methods listed in US4960878 and US5041584. In addition, Tosoh 'Finechem Co., Ltd. also used trimethylaluminum and triisobutylaluminum. R is an isobutyl group. MMAO and TMAO t are commercially produced under the name! Such MMAO is an aluminoxane with improved solubility in various solvents and storage stability. Specifically, it is insoluble or hardly soluble in benzene as in (14) and (15) above. The difference is that it dissolves in aliphatic and alicyclic hydrocarbons.
[0089] さらに、本発明で用いられる有機アルミニウムォキシィ匕合物としては、下記一般式 (1 7)で表されるボロンを含んだ有機アルミニウムォキシィ匕合物を挙げることもできる。  [0089] Further, examples of the organoaluminum compound used in the present invention include an organoaluminum compound containing boron represented by the following general formula (17).
[0090] [化 17]
Figure imgf000029_0001
[0090] [Chemical 17]
Figure imgf000029_0001
[0091] (式中、 は炭素原子数カ^〜 10の炭化水素基を示す。 Rdは、互いに同一でも異なつ ていてもよぐ水素原子、ハロゲン原子または炭素原子数力 〜 10の炭化水素基を示 す。） [0091] (In the formula, represents a hydrocarbon group having from 10 to 10 carbon atoms. R d may be the same or different from each other, a hydrogen atom, a halogen atom, or a carbon atom having a number of carbon atoms of up to 10 carbon atoms. Indicates a hydrogen group.)
< (b-2)架橋メタ口セン化合物 (A)と反応してイオン対を形成する化合物 > 架橋メタ口セン化合物 (A)と反応してイオン対を形成する化合物 (b-2) (以下、「イオン 性化合物」と略称する場合がある。）としては、特開平 1-501950号公報、特開平 1-502 036号公報、特開平 3-179005号公報、特開平 3-179006号公報、特開平 3-207703号 公報、特開平 3-207704号公報、 USP5321106号などに記載されたルイス酸、イオン性 化合物、ボランィ匕合物およびカルボランィ匕合物などを挙げることができる。さらに、へ テロポリ化合物およびイソポリ化合物も挙げることができる。  <(b-2) Compound that forms an ion pair by reacting with the bridged meta-octacene compound (A)> Compound that reacts with the bridged meta-mouth compound (A) to form an ion pair (b-2) May be abbreviated as “ionic compound”) as disclosed in JP-A-1-501950, JP-A-1-502030, JP-A-3-179005, JP-A-3-179006, Examples include Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-3-207703, JP-A-3-207704, USP5321106 and the like. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.
[0092] 本発明において、好ましく採用されるイオン性ィ匕合物は下記一般式（18)で表され る化合物である。  In the present invention, the ionic compound preferably employed is a compound represented by the following general formula (18).
[0093] [化 18]  [0093] [Chemical 18]
Figure imgf000029_0002
Figure imgf000029_0002
式中、 Re+としては、 、カルべ-ゥムカチオン、ォキソ-ゥムカチオン、アンモ-ゥム カチオン、ホスホ-ゥムカチオン、シクロへプチルトリエ-ルカチオン、遷移金属を有 するフエ口セ-ゥムカチオンなどが挙げられる。 〜 は、互いに同一でも異なってい てもよく、有機基、好ましくはァリール基である。 In the formula, R e + is, carbenium - Umukachion, Okiso - Umukachion, ammonium - © beam cation, phospho - Umukachion, Puchirutorie cyclohexane - Rukachion, have a transition metal Hue mouth thermium cations. ~ May be the same as or different from each other, and are an organic group, preferably an aryl group.
前記カルべ-ゥムカチオンとして具体的には、トリフエ-ルカルベ-ゥムカチオン、ト リス (メチルフエ-ル)カルべ-ゥムカチオン、トリス (ジメチルフエ-ル)カルべ-ゥムカチ オンなどの三置換カルべ-ゥムカチオンなどが挙げられる。  Specific examples of the carb cation include triphenyl carb cation, tris (methyl phen) carb cation and tri-substituted carb cation such as tris (dimethyl phen) carb cation. Can be mentioned.
[0095] 前記アンモ-ゥムカチオンとして具体的には、トリメチルアンモ-ゥムカチオン、トリ ェチルアンモ-ゥムカチオン、トリ (n-プロピル)アンモ-ゥムカチオン、トリイソプロピル アンモ-ゥムカチオン、トリ (n-ブチル)アンモ-ゥムカチオン、トリイソブチルアンモ-ゥ ムカチオンなどのトリアルキルアンモ-ゥムカチオン、 Ν,Ν-ジメチルァ-リュウムカチ オン、 Ν,Ν-ジェチルァ-リュウムカチオン、 Ν,Ν- 2,4,6-ペンタメチルァ-リュウムカチ オンなどの Ν,Ν-ジアルキルァ-リュウムカチオン、ジイソプロピルアンモ-ゥムカチォ ン、ジシクロへキシルアンモ-ゥムカチオンなどのジアルキルアンモ-ゥムカチオンな どが挙げられる。 [0095] Specific examples of the ammonium cation include trimethyl ammonium cation, triethyl ammonium cation, tri (n-propyl) ammonium cation, triisopropyl ammonium cation, tri (n-butyl) ammonium cation, tri Trialkylammonium cations such as isobutylammonium cation, Ν, Ν-dimethyl-rium cation, Ν, Ν-jetylarium cation, Ν, Ν- 2,4,6-pentamethylarium cation, etc. And dialkyl ammonium cations such as -dialkyl ammonium cation, diisopropyl ammonium cation and dicyclohexyl ammonium cation.
[0096] 前記ホスホ-ゥムカチオンとして具体的には、トリフエ-ルホスホ-ゥムカチオン、トリ ス (メチルフエ-ル)ホスホ-ゥムカチオン、トリス (ジメチルフエ-ル)ホスホ-ゥムカチォ ンなどのトリアリールホスホ-ゥムカチオンなどが挙げられる。  [0096] Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenol) phosphonium cation, and tris (dimethylphenol) phosphomucation. It is done.
上記のうち、 Re+としては、カルべ-ゥムカチオン、アンモ-ゥムカチオンなどが好まし く、特にトリフエ-ルカルベ-ゥムカチオン、 Ν,Ν-ジメチルァ-リュウムカチオン、 Ν,Ν- ジェチルァ-リュウムカチオンが好まし 、。 Of the above, Re e + is preferably a carbium cation, an ammonium cation, etc., particularly a triphenylcarbium cation, Ν, Ν-dimethylarium cation, Ν, Ν-jetylarium cation. ,.
[0097] カルべ-ゥム塩として具体的には、トリフエ-ルカルベ-ゥムテトラフエ-ルポレート 、トリフエ-ルカルベ-ゥムテトラキス (ペンタフルォロフエ-ル)ボレート、トリフエ-ルカ ルベ-ゥムテトラキス (3,5-ジトリフルォロメチルフエ-ル)ボレート、トリス (4-メチルフエ -ル)カルべ-ゥムテトラキス (ペンタフルォロフエ-ル)ボレート、トリス (3,5-ジメチルフ ェ -ル)カルべ-ゥムテトラキス (ペンタフルォロフエ-ル)ボレートなどを挙げることがで きる。  [0097] Specific examples of the carbaum salt include triphenyl carbamate tetraphenol, triphenyl carbaum tetrakis (pentafluorophenol) borate, triphenyl carbaum tetrakis (3,5- Ditrifluoromethylphenol) borate, tris (4-methylphenol) carbtetrakis (pentafluorophenol) borate, tris (3,5-dimethylphenol) carbtetrakis ( (Pentafluorophenol) borate and the like.
[0098] アンモ-ゥム塩としては、トリアルキル置換アンモ-ゥム塩、 Ν,Ν-ジアルキルァユリ- ゥム塩、ジアルキルアンモ-ゥム塩などを挙げることができる。  [0098] Examples of the ammonium salt include trialkyl-substituted ammonium salts, Ν, Ν-dialkylauryum salts, dialkylammonium salts, and the like.
トリアルキル置換アンモ-ゥム塩として具体的には、たとえばトリェチルアンモ -ゥム テトラフエ-ルポレート、トリプロピルアンモ-ゥムテトラフエ-ルポレート、トリ (n-ブチ ル)アンモ-ゥムテトラフエ-ルポレート、トリメチルアンモ-ゥムテトラキス (p-トリル)ボレ ート、トリメチルアンモ-ゥムテトラキス (0-トリル)ボレート、トリ (n-ブチル)アンモ-ゥムテ トラキス (ペンタフルォロフエ-ル)ボレート、トリェチルアンモ-ゥムテトラキス (ペンタフ ルォロフエ-ル)ボレート、トリプロピルアンモ-ゥムテトラキス (ペンタフルォロフエ-ル) ボレート、トリプロピルアンモ-ゥムテトラキス (2,4-ジメチルフエ-ル)ボレート、トリ (n-ブ チル)アンモ-ゥムテトラキス (3,5-ジメチルフエ-ル)ボレート、トリ (n-ブチル)アンモ- ゥムテトラキス (4-トリフルォロメチルフエ-ル)ボレート、トリ (n-ブチル)アンモ-ゥムテト ラキス (3,5-ジトリフルォロメチルフエ-ル)ボレート、トリ (n-ブチル)アンモ-ゥムテトラキ ス (0-トリル)ボレート、ジォクタデシルメチルアンモ-ゥムテトラフヱ-ルポレート、ジォ クタデシルメチルアンモ-ゥムテトラキス (p-トリル)ボレート、ジォクタデシルメチルアン モ-ゥムテトラキス (◦-トリル)ボレート、ジォクタデシルメチルアンモ-ゥムテトラキス (ぺ ンタフルオロフェ -ル)ボレート、ジォクタデシルメチルアンモ-ゥムテトラキス (2, 4-ジメ チルフエ-ル)ボレート、ジォクタデシルメチルアンモ-ゥムテトラキス (3,5-ジメチルフ ェニル)ボレート、ジォクタデシルメチルアンモ-ゥムテトラキス (4-トリフルォロメチルフ ェ -ル)ボレート、ジォクタデシルメチルアンモ-ゥムテトラキス (3,5-ジトリフルォロメチ ルフエニル)ボレート、ジォクタデシルメチルアンモ -ゥムなどが挙げられる。 Specific examples of the trialkyl-substituted ammonium salt include, for example, triethylammonium salt. Tetraphenolate, tripropylammonium tetraphenolate, tri (n-butyl) ammoniumtetraphenolate, trimethylammoniumtetrakis (p-tolyl) borate, trimethylammoniumtetrakis (0-tolyl) borate, tri (n-Butyl) ammumute trakis (pentafluorophenol) borate, triethylammonium tetrakis (pentafluorophenol) borate, tripropylammonium tetrakis (pentafluorophenol) borate, tripropylammonium -Umtetrakis (2,4-dimethylphenol) borate, tri (n-butyl) ammotetrakis (3,5-dimethylphenol) borate, tri (n-butyl) ammo-tetrakis (4-trifluoromethyl) (Fuel) Borate, Tri (n-Butyl) Ammumute Lataki (3,5-Ditrifluoromethyl) Tylfyl) borate, tri (n-butyl) ammonium tetrakis (0-tolyl) borate, dioctadecylmethylammonium tetraporate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, di Octadecylmethyl ammonium tetrakis (◦-tolyl) borate, Dioctadecyl methyl ammonium tetrakis (pentafluorophenol) borate, Dioctadecyl methyl ammonium tetrakis (2,4-dimethylphenyl) ) Borate, dioctadecyl methyl ammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecyl methyl ammonium tetrakis (4-trifluoromethyl phenol) borate, dioctadecyl methyl ammonium Umtetrakis (3,5-ditrifluoromethyl) borate, dioctadecylmethylammonium And so on.
[0099] Ν,Ν-ジアルキルァユリ-ゥム塩として具体的には、たとえば Ν,Ν-ジメチルァ-リュウ ムテトラフエ-ルポレート、 Ν,Ν-ジメチルァユリ-ゥムテトラキス (ペンタフルォロフエ- ル)ボレート、 Ν,Ν-ジメチルァユリ-ゥムテトラキス (3,5-ジトリフルォロメチルフエ-ル） ボレート、 Ν,Ν-ジェチルァユリ-ゥムテトラフエ-ルポレート、 Ν,Ν-ジェチルァ-リュウ ムテトラキス (ペンタフルォロフエ-ル)ボレート、 Ν,Ν-ジェチルァユリ-ゥムテトラキス（ 3,5-ジトリフルォロメチルフエ-ル)ボレート、 Ν,Ν- 2,4,6-ペンタメチルァ-リュウムテト ラフエ-ルポレート、 Ν,Ν-2,4,6-ペンタメチルァユリ-ゥムテトラキス (ペンタフルオロフ ェ -ル)ボレートなどが挙げられる。  [0099] Specific examples of Ν, Ν-dialkyl dimethylureum salts include, for example, Ν, Ν-dimethyl dimethyl-tetrafluorophosphate, Ν, Ν-dimethyldimethyl-tetrakis (pentafluorophenol) borate, Ν, Ν-Dimethylaureum tetrakis (3,5-ditrifluoromethylphenol) borate, Ν, Ν-demethylaureum tetrakisole, Ν, Ν-deethylaureum tetrakis (pentafluorophenol) Borate, Ν, Ν-jetylalyumum tetrakis (3,5-ditrifluoromethylphenol) borate, Ν, Ν-2,4,6-pentamethyla-ryumteto laurate, Ν, Ν-2,4, Examples include 6-pentamethylauryum tetrakis (pentafluorophenol) borate.
[0100] ジアルキルアンモ-ゥム塩として具体的には、たとえばジ (1-プロピル)アンモ-ゥム テトラキス (ペンタフルォロフエ-ル)ボレート、ジシクロへキシルアンモ-ゥムテトラフエ -ルボレートなどが挙げられる。 その他、本出願人によって開示 (特開 2004-51676号公報）されているイオン性ィ匕合 物も制限無く使用が可能である。 [0100] Specific examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenol) borate and dicyclohexyl ammonium tetraphenol borate. In addition, ionic compounds disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can be used without limitation.
尚、上記のようなイオン性ィ匕合物 (b- 2)は、 2種以上混合して用いることができる。 < (b-3)有機アルミニウム化合物 >  The ionic compound (b-2) as described above can be used in combination of two or more. <(b-3) Organoaluminum compound>
ォレフィン重合触媒を形成する (b-3)有機アルミニウム化合物としては、例えば下記 一般式 [X]で表される有機アルミニウム化合物、下記一般式（19)で表される第 1族金 属とアルミニウムとの錯アルキル化物などを挙げることができる。  (B-3) Examples of organoaluminum compounds that form an olefin polymerization catalyst include organoaluminum compounds represented by the following general formula [X], group 1 metals represented by the following general formula (19), and aluminum. And a complex alkylated product thereof.
Ra Al(ORb) H X (19) R a Al (OR b ) HX (19)
m n p q  m n p q
(式中、 Raおよび Rbは、互いに同一でも異なっていてもよぐ炭素原子数が 1〜15、 好ましくは 1〜4の炭化水素基を示し、 Xはハロゲン原子を示し、 mは 0<m≤3、 nは 0≤ n< 3、 pは 0≤p< 3、 qは 0≤q< 3の数であり、かつ m + n + p + q=3である。）で表される 有機アルミニウム化合物。このような化合物の具体例として、トリメチルアルミニウム、ト リエチルアルミニウム、トリ n-ブチルアルミニウム、トリへキシルアルミニウム、トリオクチ ルアルミニウムなどのトリ n-アルキルアルミニウム；トリイソプロピルアルミニウム、トリイソ ブチルアルミニウム、トリ sec-ブチルアルミニウム、トリ tert-ブチルアルミニウム、トリ 2- メチルブチルアルミニウム、トリ 3-メチルへキシルアルミニウム、トリ 2-ェチルへキシル アルミニウムなどのトリ分岐鎖アルキルアルミニウム；トリシクロへキシルアルミニウム、ト リシクロォクチルアルミニウムなどのトリシクロアルキルアルミニウム；トリフエニルアルミ ユウム、トリトリルアルミニウムなどのトリアリールアルミニウム；ジイソプロピルアルミ-ゥ ムハイドライド、ジイソブチルアルミニウムハイドライドなどのジアルキルアルミニウムハ イドライド；一般式 G- C H ) Al (C H ) (式中、 x、 y、 zは正の数であり、 z≤2xである。 ) (In the formula, R a and R b each represent a hydrocarbon group having 1 to 15, preferably 1 to 4 carbon atoms, which may be the same or different from each other, X represents a halogen atom, and m represents 0. <m≤3, n is 0≤ n <3, p is 0≤p <3, q is a number 0≤q <3, and m + n + p + q = 3.) Organoaluminum compound. Specific examples of such compounds include trimethyl aluminum, Application Benefits ethyl aluminum, tri n- butylaluminum, hexyl aluminum to tri, tri n such Toriokuchi Le aluminum - alkylaluminium; triisopropyl aluminum, triiso butylaluminum, tri sec- Tri-branched alkylaluminums such as butylaluminum, tri-tert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; tricyclohexylaluminum, tricyclooctylaluminum Tricycloalkylaluminum such as triphenylaluminum, triarylaluminum such as tritolyl aluminum, diisopropylaluminum hydride, di In the general formula G- CH) Al (CH) (wherein, x, y, z are each a positive number, and z≤2x); dialkylaluminum Ha Idoraido such Seo-butyl aluminum hydride.
4 9 X y 5 10 z  4 9 X y 5 10 z
などで表されるイソプレニルアルミニウムなどのァルケ-ルアルミニウム；イソブチルァ ルミ-ゥムメトキシド、イソブチルアルミニウムエトキシドなどのアルキルアルミニウムァ ルコキシド；ジメチルアルミニウムメトキシド、ジェチルアルミニウムエトキシド、ジブチ ルアルミニウムブトキシドなどのジアルキルアルミニウムアルコキシド；ェチルアルミ- ゥムセスキエトキシド、ブチルアルミニウムセスキブトキシドなどのアルキルアルミ-ゥ ムセスキアルコキシド;一般式 Ra Al(ORb) などで表される平均組成を有する部分的 Alkenyl aluminum such as isoprenyl aluminum represented by: Alkyl aluminum alkoxide such as isobutyl aluminum methoxide, isobutyl aluminum ethoxide; Dialkyl aluminum such as dimethyl aluminum methoxide, jetyl aluminum ethoxide, dibutyl aluminum butoxide Alkoxides; alkylaluminum sesquialkoxides such as ethylaluminum sesquiethoxide and butylaluminum sesquibutoxide; partially having an average composition represented by the general formula R a Al (OR b )
2.5 0.5  2.5 0.5
にアルコキシ化されたアルキルアルミニウム；ジェチルアルミニウムフエノキシド、ジェ チルアルミニウム (2,6-ジ -t-ブチル -4-メチルフエノキシド)などのアルキルアルミ-ゥ ムァリー口キシド；ジメチルアルミニウムクロリド、ジェチルアルミニウムクロリド、ジブチ ルアルミニウムクロリド、ジェチルアルミニウムブロミド、ジイソブチルアルミニウムクロリ ドなどのジアルキルアルミニウムハライド；ェチルアルミニウムセスキク口リド、ブチルァ ルミ-ゥムセスキク口リド、ェチルアルミニウムセスキブロミドなどのアルキルアルミ-ゥ ムセスキノ、ライド；ェチルアルミニウムジクロリドなどのアルキルアルミニウムジハライド などの部分的にハロゲン化されたアルキルアルミニウム；ジェチルアルミニウムヒドリド 、ジブチルアルミニウムヒドリドなどのジアルキルアルミニウムヒドリド；ェチルアルミ-ゥ ムジヒドリド、プロピルアルミニウムジヒドリドなどのアルキルアルミニウムジヒドリドなど その他の部分的に水素化されたアルキルアルミニウム；ェチルアルミニウムエトキシク 口リド、ブチルアルミニウムブトキシクロリド、ェチルアルミニウムエトキシブロミドなどの 部分的にアルコキシ化およびハロゲン化されたアルキルアルミニウムなどを挙げるこ とがでさる。 Alkoxylated to aluminum; jetyl aluminum phenoxide, Alkyl-aluminum-mouth oxides such as tilaluminum (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, jetylaluminum chloride, dibutylaluminum chloride, jetylaluminum bromide, diisobutyl Dialkylaluminum halides such as aluminum chlorides; alkylaluminum sesquiquinolides such as ethylaluminum sesquiquinolide, butylaluminum sesquiquinolide, ethylaluminum sesquibromide, rides; Partially halogenated alkylaluminums; dialkylaluminum hydrides such as jetylaluminum hydride and dibutylaluminum hydride; Other partially hydrogenated alkylaluminums such as propylaluminum dihydride, such as propylaluminum dihydride; partially alkoxylated such as ethylaluminum ethoxy chloride, butylaluminum butoxycyclide, ethylaluminum ethoxybromide and the like Mention may be made of halogenated alkylaluminum.
M2AlRa (20) M 2 AlR a (20)
4  Four
(式中、 M2は Li、 Naまたは Kを示し、 Raは炭素原子数カ^〜 15、好ましくは 1〜4の炭化 水素基を示す。 ) (Wherein, M 2 represents a Li, Na or K, R a is Ca carbon atoms ^ to 15, preferably a 1-4 hydrocarbon group.)
で表される周期律表第 1族金属とアルミニウムとの錯アルキルィ匕物。このような化合物 としては、 LiAl(C H )、 LiAl(C H )などを例示することができる。  A complex alkyl compound of a group 1 metal and aluminum. Examples of such compounds include LiAl (C H) and LiAl (C H).
2 5 4 7 15 4  2 5 4 7 15 4
[0102] また、上記一般式 (20)で表される化合物に類似する化合物も使用することができ、 例えば窒素原子を介して 2以上のアルミニウム化合物が結合した有機アルミニウム化 合物を挙げることができる。このような化合物として具体的には、（C H ) A1N(C H )A1(  [0102] A compound similar to the compound represented by the general formula (20) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded via a nitrogen atom. it can. Specific examples of such compounds include (C H) A1N (C H) A1 (
2 5 2 2 5 2 5 2 2 5
C H )などを挙げることができる。 C H).
2 5 2  2 5 2
入手容易性の点から、（b— 3)有機アルミニウム化合物としては、トリメチルアルミ- ゥム、トリイソブチルアルミニウムが好んで用いられる。  From the viewpoint of availability, trimethylaluminum and triisobutylaluminum are preferably used as the (b-3) organoaluminum compound.
[0103] <重合> [0103] <Polymerization>
本発明で用いられるポリオレフインワックスは、上記メタ口セン系触媒の存在下に、 エチレンを通常液相で単独重合する力、またはエチレンおよび α—ォレフィンを共重 合させることにより得られる。重合の際には、各成分の使用法、添加順序は任意に選 ばれるが、以下のような方法が例示される。 The polyolefin wax used in the present invention can be obtained by the ability to homopolymerize ethylene in a normal liquid phase in the presence of the above-mentioned meta-locene catalyst, or by copolymerizing ethylene and α-olefin. During polymerization, the usage of each component and the order of addition are arbitrarily selected. However, the following method is exemplified.
[0104] [ql]成分 (A)を単独で重合器に添加する方法。  [0104] A method wherein [ql] component (A) is added alone to the polymerization vessel.
[q2]成分 (A)および成分 (B)を任意の順序で重合器に添加する方法。  [q2] A method in which component (A) and component (B) are added to the polymerization vessel in any order.
上記 [q2]の方法においては、各触媒成分の少なくとも 2つ以上は予め接触されてい てもよい。この際、一般に炭化水素溶媒が用いられるが、 a一才レフインを溶媒として 用いてもよい。なお、ここで用いる各モノマーは、前述した通りである。  In the method [q2], at least two or more of the catalyst components may be in contact with each other in advance. In this case, a hydrocarbon solvent is generally used, but a 1-year-old refin may be used as a solvent. The monomers used here are as described above.
[0105] 重合方法は、ポリオレフインワックスがへキサン等の溶媒中に粒子として存在する状 態で重合する懸濁重合、溶媒を用いないで重合する気相重合、そして 140°C以上の 重合温度で、ポリオレフインワックスが溶剤と共存または単独で溶融した状態で重合 する溶液重合が可能であり、その中でも溶液重合が経済性と品質の両面で好まし ヽ 重合反応は、バッチ法あるいは連続法いずれの方法で行ってもよい。重合をバッチ 法で実施するに際しては、前記の触媒成分は次に説明する濃度下で用いられる。  [0105] Polymerization methods include suspension polymerization in which polyolefin wax is present as particles in a solvent such as hexane, gas phase polymerization in which a solvent is not used, and a polymerization temperature of 140 ° C or higher. It is possible to perform solution polymerization in which polyolefin wax is polymerized in the state of coexistence with a solvent or when melted alone. Among them, solution polymerization is preferred in terms of both economy and quality. You may go on. When the polymerization is carried out by a batch method, the catalyst component is used in the concentration described below.
[0106] 上記のようなォレフィン重合用触媒を用いて、ォレフィンの重合を行うに際して、成 分 (A)は，反応容積 1リットル当り、通常 10— 9〜10— 1モル、好ましくは 10— 8〜 10— 2モルに なるような量で用いられる。 [0106] using Orefin polymerization catalyst as described above, when performing polymerization of Orefin, Ingredient (A) is, per liter of the reaction volume, typically 10 9 to 10-1 mol, preferably 10- 8 used in such an amount that the ~ 10 2 mol.
成分 (b— 1)は、成分 (b— 1)と、成分 (A)中の全遷移金属原子 (M)とのモル比〔 (b — 1) /M〕力通常 0. 01〜5, 000、好ましくは 0. 05〜2, 000となるような量で用!/、 られる。成分 (b— 2)は、成分 (b— 2)中のイオン性化合物と、成分 (A)中の全遷移金 属 (M)とのモル比〔（b— 2) ZM〕力 通常 0. 01〜5, 000、好ましくは 1〜2, 000とな るような量で用いられる。成分 (b— 3)は、成分 (b— 3)と、成分 (A)中の遷移金属原 子 (M)とのモル比〔（b 3) ZM〕 1S 通常 1〜： L0000、好ましくは 1〜5000となるよう な量で用いられる。  Component (b-1) is a molar ratio of component (b-1) to all transition metal atoms (M) in component (A) [(b-1) / M] force usually from 0.01 to 5, 000, preferably in an amount such as 0.05 to 2,000! /. Component (b-2) is a molar ratio of the ionic compound in component (b-2) to the total transition metal (M) in component (A) [(b-2) ZM] force. It is used in an amount of 01 to 5,000, preferably 1 to 2,000. Component (b-3) is a molar ratio of component (b-3) to transition metal atom (M) in component (A) [(b 3) ZM] 1S usually 1 to: L0000, preferably 1 Used in an amount of ~ 5000.
[0107] 重合反応は、温度が通常、ワックス 10gをフィルター上にセットして、 20〜+ 200 。C、好ましくは 50〜180°C、さらに好ましくは 70〜180°Cで、圧力が通常、 0を超えて 7. 8MPa (80kgfZcm2、ゲージ圧）以下、好ましくは 0を超えて 4. 9MPa (50kgf/ cm2,ゲージ圧）以下の条件下に行われる。 [0107] The temperature of the polymerization reaction is usually 20 to +200 when 10 g of wax is set on the filter. C, preferably 50 to 180 ° C, more preferably 70 to 180 ° C, and the pressure is usually more than 0 to 7.8 MPa (80 kgfZcm 2 , gauge pressure) or less, preferably more than 0 to 4.9 MPa ( 50kgf / cm 2 , gauge pressure)
重合に際して、エチレンおよび必要に応じて用いられる aーォレフインは、前記した 特定組成のポリオレフインワックスが得られるような量割合で重合系に供給される。ま た重合に際しては、水素などの分子量調節剤を添加することもできる。 In the polymerization, ethylene and a-olefin used as necessary are as described above. It is fed to the polymerization system in such an amount that a polyolefin wax having a specific composition is obtained. In the polymerization, a molecular weight regulator such as hydrogen can be added.
[0108] このようにして重合させると、生成した重合体は通常これを含む重合液として得られ るので、常法により処理するとポリオレフインワックスが得られる。  [0108] When polymerized in this manner, the produced polymer is usually obtained as a polymerization solution containing the polymer, so that polyolefin wax can be obtained by processing in a conventional manner.
本発明にお 、ては、特にくメタ口センィ匕合物の例 6 >で示したメタ口セン化合物 を含む触媒の使用が好まし 、。  In the present invention, it is particularly preferable to use a catalyst containing the meta-orcene compound shown in Example 6> of the meta-orcene compound.
このような触媒を用いると上述した Mn、 Mw/Mn,融点の範囲、その他の好まし V、物性を有するポリオレフインワックス (B)が容易に得られ、またこのような触媒を用い て得られたポリオレフインワックス (B)は、流動性の改良効果が大きぐ成形速度を大 きく向上させるだけでなぐベたつき成分が減少し、表面にベたつきがない成形体を 得ることができる。  When such a catalyst is used, polyolefin wax (B) having the above-mentioned Mn, Mw / Mn, melting point range, other preferred V, and physical properties can be easily obtained, and also obtained using such a catalyst. Polyolefin wax (B) has a great effect of improving the fluidity, and by simply increasing the molding speed significantly, the sticky component is reduced and a molded product having no stickiness on the surface can be obtained.
[0109] 熱可塑性榭脂 (A)として、ポリオレフイン、好ましくは、低密度ポリエチレン、中密度 ポリエチレン、高密度ポリエチレン、直鎖線状低密度ポリエチレン、ポリプロピレン、ェ チレン プロピレン共重合体、より好ましくは高密度ポリエチレン、ポリプロピレン、を 用いた場合には、熱可塑性榭脂 (A)とポリオレフインワックス (B)との分散性が良好に なり、流動性の改良効果がより大きぐ成形速度をさらに大きく向上させることができ、 表面にベたつきが少ない成形体を得ることができる。  [0109] As the thermoplastic resin (A), polyolefin, preferably low density polyethylene, medium density polyethylene, high density polyethylene, linear linear low density polyethylene, polypropylene, ethylene propylene copolymer, more preferably high density. When polyethylene and polypropylene are used, the dispersibility of the thermoplastic resin (A) and the polyolefin wax (B) will be good, and the flow rate improvement effect will be greater and the molding speed will be further increased. A molded product with less stickiness on the surface can be obtained.
[0110] このようにして得られるポリオレフインワックス (B)の配合量は、熱可塑性榭脂 (A) 1 00重量部に対して、通常 0. 01〜20重量部の範囲、好ましくは 0. 1〜10重量部の 範囲、より好ましくは 0. 3〜5重量部の範囲である。  [0110] The amount of the polyolefin wax (B) thus obtained is usually in the range of 0.01 to 20 parts by weight, preferably 0.1 to 100 parts by weight of the thermoplastic resin (A). It is in the range of ˜10 parts by weight, more preferably in the range of 0.3 to 5 parts by weight.
上記範囲でポリオレフインワックス (B)を配合すると、流動性の改良効果が大きぐ 成形速度が大きく向上する。また、低い成形温度で成形可能となるため、冷却時間 が短縮され、成形サイクルが向上する。さら〖こ、成形温度を低くすることにより、榭脂 の熱劣化を抑制し、榭脂強度の低下を抑制するだけでなぐ榭脂の焼け焦げや黒点 を抑制することができる。  When the polyolefin wax (B) is blended within the above range, the effect of improving the fluidity is great, and the molding speed is greatly improved. In addition, since molding is possible at a low molding temperature, the cooling time is shortened and the molding cycle is improved. Further, by lowering the molding temperature, it is possible to suppress the thermal deterioration of the resin and to suppress the burning and black spots of the resin just by suppressing the decrease of the resin strength.
[0111] 〔添加剤〕  [0111] [Additive]
本発明では、ブロー成形前の混合物に、熱可塑性榭脂 (A)とポリオレフインワックス (B)とに加えて、さらに必要に応じて、酸化防止剤、紫外線吸収剤、光安定剤等の安 定剤、金属石鹼、充填剤、難燃剤等の添加剤を加えててもよい。 In the present invention, in addition to the thermoplastic resin (A) and the polyolefin wax (B), the mixture before blow molding may further include an antioxidant, an ultraviolet absorber, a light stabilizer and the like as necessary. You may add additives, such as a fixed agent, a metal sarcophagus, a filler, a flame retardant.
上記安定剤としては、フィンダードフエノール系化合物、フォスファイト系化合物、チ ォエーテル系化合物などの酸化防止剤；  Examples of the stabilizer include antioxidants such as findered phenolic compounds, phosphite compounds, and thioether compounds;
ベンゾトリアゾール系化合物、ベンゾフエノン系化合物などの紫外線吸収剤； ヒンダードアミン系化合物などの光安定剤が挙げられる。  UV absorbers such as benzotriazole compounds and benzophenone compounds; and light stabilizers such as hindered amine compounds.
[0112] 上記金属石鹼としては、ステアリン酸マグネシウム、ステアリン酸カルシウム、ステア リン酸バリウム、ステアリン酸亜鉛などのステアリン酸塩等が挙げられる。  [0112] Examples of the metal sarcophagus include stearates such as magnesium stearate, calcium stearate, barium stearate and zinc stearate.
上記充填剤としては、炭酸カルシウム、酸化チタン、硫酸バリウム、タルク、クレー、 カーボンブラックなどが挙げられる。  Examples of the filler include calcium carbonate, titanium oxide, barium sulfate, talc, clay, and carbon black.
上記難燃剤としては、デガブロムジフエ-ルエーテル、ォクタブロムジフエ-ルエー テル等のハロゲン化ジフエ-ルエーテル、ハロゲン化ポリカーボネイトなどのハロゲン 化合物；三酸化アンチモン、四酸化アンチモン、五酸化アンチモン、ピロアンチモン 酸ソーダ、水酸ィ匕アルミニウムなどの無機化合物；リン系化合物などが挙げられる。  Examples of the flame retardant include halogen compounds such as halogenated diphenyl ethers such as degabrom diphenyl ether, octabrom diphenyl ether, halogenated polycarbonate, etc .; Inorganic compounds such as hydroxyaluminum hydroxide; phosphorus compounds and the like.
[0113] また、ドリップ防止のため難燃助剤としてはテトラフルォロエチレン等の化合物を添 カロすることがでさる。  [0113] Further, in order to prevent drip, it is possible to add a compound such as tetrafluoroethylene as a flame retardant aid.
上記抗菌剤、防カビ剤としては、イミダゾール系化合物、チアゾール系化合物、 -ト リル系化合物、ハロアルキル系化合物、ピリジン系化合物などの有機化合物； 銀、銀系化合物、亜鉛系化合物、銅系化合物、チタン系化合物などの無機物質、無 機化合物などが挙げられる。  Examples of the antibacterial and antifungal agents include organic compounds such as imidazole compounds, thiazole compounds, -tolyl compounds, haloalkyl compounds, and pyridine compounds; silver, silver compounds, zinc compounds, copper compounds, Examples include inorganic substances such as titanium compounds and inorganic compounds.
これら化合物のなかでも、熱的に安定で性能の高い銀、銀系化合物が好ましい。  Among these compounds, thermally stable silver and silver-based compounds are preferable.
[0114] 上記銀系化合物としては、銀錯体、脂肪酸、リン酸等銀塩を挙げることができる。 [0114] Examples of the silver compound include silver salts such as silver complexes, fatty acids, and phosphoric acids.
銀および銀系化合物を抗菌剤、防カビ剤として用いる場合には、これら物質はゼオラ イト、シリカゲル、リン酸ジルコニウム、リン酸カルシュゥム、ハイド口タルサイト、ヒドロキ シアパタイト、ケィ酸カルシウムなどの多孔性構造体に担持させて使用する場合もあ る。  When silver and silver compounds are used as antibacterial and antifungal agents, these materials are porous such as zeolite, silica gel, zirconium phosphate, calcium phosphate, hydrated talcite, hydroxyapatite, calcium silicate, etc. In some cases, it is supported on a structure.
[0115] その他添加剤としては、着色剤、可塑剤、老化防止剤、着色剤、可塑剤、オイルな どが挙げられる。  [0115] Examples of other additives include colorants, plasticizers, anti-aging agents, colorants, plasticizers, and oils.
〔ブロー成形〕 本発明の成形体は、上記熱可塑性榭脂 (A)とポリオレフインワックス (B)とを含む混 合物を溶融し、ブロー成形をして得られる。 [Blow molding] The molded article of the present invention can be obtained by melting a mixture containing the thermoplastic resin (A) and the polyolefin wax (B) and blow-molding the mixture.
[0116] ブロー成形の方法としては、押出ブロー成形、射出ブロー成形などが挙げられる。 [0116] Examples of blow molding methods include extrusion blow molding and injection blow molding.
例えば押出ブロー成形で本発明の成形体を得る場合には、通常、上記熱可塑性 榭脂 (A)とポリオレフインワックス (B)とを含む混合物を溶融し、通常榭脂温度 170〜 240°Cの範囲でダイよりチューブ状パリソンとして押出し、次いで付与すべき形状の 金型中にパリソンを保持した後、空気を吹き込み通常榭脂温度 160〜230°Cの範囲 で金型に着装し成形体が得られる。また押出ブロー成形する際には適切な倍率に延 伸してちょい。  For example, when the molded article of the present invention is obtained by extrusion blow molding, the mixture containing the thermoplastic resin (A) and the polyolefin wax (B) is usually melted, and the resin temperature is usually 170 to 240 ° C. Extruded as a tubular parison from the die in the range, and then held the parison in the mold of the shape to be imparted, and then blown in air, and then mounted on the mold in the normal temperature range of 160-230 ° C to obtain a molded product It is done. Also, when extrusion blow molding, stretch to an appropriate magnification.
[0117] 熱可塑性榭脂 (A)として高密度ポリエチレンを用いて押出ブロー成形する場合に は、榭脂温度が通常 170〜220°Cの範囲、好ましくは 180〜210°Cの範囲でダイより 押出し、榭脂温度が通常 160〜210°Cの範囲、好ましくは 170〜200°Cの範囲で金 型に着装することで成形体が得られる。また押出ブロー成形する際には延伸をしても よい。  [0117] When extrusion blow molding is performed using high-density polyethylene as the thermoplastic resin (A), the resin temperature is usually in the range of 170 to 220 ° C, preferably in the range of 180 to 210 ° C. The molded body is obtained by extruding and wearing the mold in a range of the resin temperature usually in the range of 160 to 210 ° C, preferably in the range of 170 to 200 ° C. Further, it may be stretched during extrusion blow molding.
[0118] 熱可塑性榭脂 (A)としてポリプロピレンを用いて押出ブロー成形する場合には、榭 脂温度が通常 190〜230°Cの範囲、好ましくは 200〜220°Cの範囲でダイより押出 し、榭脂温度が通常 180〜220°Cの範囲、好ましくは 190〜210°Cの範囲で金型に 着装することで成形体が得られる。また押出ブロー成形する際には延伸をしてもよい これらブロー成形は、それぞれのブロー成形法に対応をした適切な成形機で行うこ とがでさる。  [0118] When extrusion blow molding is performed using polypropylene as the thermoplastic resin (A), the resin is usually extruded from a die in the range of 190 to 230 ° C, preferably 200 to 220 ° C. The molded body can be obtained by attaching the resin to the mold at a resin temperature of usually 180 to 220 ° C, preferably 190 to 210 ° C. In addition, the extrusion blow molding may be stretched. These blow moldings can be carried out with an appropriate molding machine corresponding to each blow molding method.
[0119] 本発明によれば上述の条件でブロー成形することにより成形体が得られる力 本発 明の製造方法によれば、ポリオレフインワックス (B)を含まな ヽ熱可塑性榭脂 (A)の 混合物からブロー成形する場合と比較して、通常 0〜30°C以下、好ましくは 10〜20 °C以下の条件で成形しても、得られる成形体の物性は損なわれず、し力も生産性よく 成形体を製造できる。  [0119] According to the present invention, the force capable of obtaining a molded article by blow molding under the above-described conditions. According to the production method of the present invention, the thermoplastic resin (A) containing no polyolefin wax (B) is obtained. Compared to the case of blow molding from a mixture, the physical properties of the resulting molded product are not impaired even when molded under conditions of usually 0 to 30 ° C or less, preferably 10 to 20 ° C or less. A molded body can be produced.
[0120] このようにして、たとえばィ匕粧瓶、洗剤瓶、入浴用洗剤瓶などのボトル、工業用薬品 缶、ドラム缶、タンク、外壁などの建築資材、自動車外装部品などの自動車部品、ェ 業機械部品、電気 ·電子部品等に用いることができる成形体が得られる。 [0120] In this way, for example, bottles such as cosmetic bottles, detergent bottles and bath detergent bottles, industrial chemical cans, drum cans, tanks, building materials such as tanks and outer walls, automobile parts such as automobile exterior parts, Molded bodies that can be used for industrial machine parts, electrical / electronic parts, etc. are obtained.
実施例  Example
[0121] 以下、本発明を実施例により説明するが、本発明は、これら実施例により何ら限定 されるものではない。  [0121] Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to these examples.
〔実施例 1〜2〕  (Examples 1 and 2)
ポリプロピレン榭脂であるプライムポリプロ B221WA(MI = 0. 5gZlO分； 230°C Prime Polypropylene B221WA (MI = 0.5gZlO min; 230 ° C)
2. 16kgf 、密度： 910kgZm3) ( (株）プライムポリマー社製）に、メタ口セン PEヮッ タス (エタセレックス (登録商標） 30200BT 三井化学 (株)社製、エチレン含量 95m ol%、密度： 913kgZm3、平均分子量 Mn= 2000)を表 1の割合で添加し、タンブラ 一ミキサー中で十分混合してポリオレフイン樹脂の混合物を作成した。これらのポリオ レフイン樹脂の混合物について成形温度 180°Cでブロー成形を行い、内容量 1500 mLのボトルを成形して評価した。 2. 16kgf, density: 910kgZm 3 ) (manufactured by Prime Polymer Co., Ltd.) and Metaguchisen PE vita (Etacelex (registered trademark) 30200BT, Mitsui Chemicals, Inc., ethylene content 95 mol%, density: 913kgZm) 3 , average molecular weight Mn = 2000) was added at a ratio shown in Table 1, and thoroughly mixed in a tumbler mixer to prepare a polyolefin resin mixture. The mixture of these polyolefin resins was blow-molded at a molding temperature of 180 ° C, and a bottle with an internal volume of 1500 mL was molded and evaluated.
[0122] 成形条件 [0122] Molding conditions
成形機 （株）日本製鋼所社製 JEB— 15ブロー成形機  Molding machine JEB-15 blow molding machine manufactured by Nippon Steel Works, Ltd.
1パリソン 2モールド方式  1 Parison 2 Mold method
金型温度 25°C  Mold temperature 25 ° C
吹き込みエアー圧力 0. 5MPa  Blowing air pressure 0.5 MPa
製品重量 80 ± 2. 5g  Product weight 80 ± 2.5 g
なお、物性の測定方法は次の通りである。  In addition, the measuring method of a physical property is as follows.
C外観]  C appearance]
ボトルの外観を目視で観察し、評価した。  The appearance of the bottle was visually observed and evaluated.
〇 厚みむらがない  〇 No uneven thickness
△ 厚みむらが若干目立つ  △ Uneven thickness is noticeable
X 厚みむらがかなり目立つ  X Unevenness of thickness is quite noticeable
[満注容量]  [Full capacity]
成形したボトルの口にまで水を注ぎその重量を測定した。  Water was poured into the mouth of the molded bottle and its weight was measured.
[落下強度]  [Drop strength]
ボトルに水を 800mL入れ、 1. 2mの高さ力 容器を落下させてボトルが白化するか または割れた個数で評価した。 Put 800mL of water in the bottle, 1. 2m height force Can the bottle fall down by dropping the container? Or it evaluated by the number of cracks.
[ショット数]  [number of shots]
1時間あたりに製品ボトルを作製した個数として算出した。  It was calculated as the number of product bottles produced per hour.
[成形サイクル]  [Molding cycle]
ボトル 1個製造するために必要な時間として算出した。  Calculated as the time required to produce one bottle.
[0123] 評価結果を表 1に示す。 [0123] The evaluation results are shown in Table 1.
〔比較例 1〕  (Comparative Example 1)
実施例 1で用いたメタ口セン PEワックスを添加せずに、成形温度を 180°Cから 200 °Cに変更した以外は実施例 1と同様にブロー成形を行い、内容量 1500mLのボトル を成形して評価した。評価結果を表 1に示す。  Blow molding was performed in the same manner as in Example 1 except that the molding temperature used in Example 1 was changed from 180 ° C to 200 ° C without adding the PEPE wax, and a bottle with an internal volume of 1500 mL was molded. And evaluated. Table 1 shows the evaluation results.
[0124] 〔比較例 2〕 [Comparative Example 2]
実施例 1で用 、たメタ口セン PEワックスを添加しな力 た以外は実施例 1と同様に ブロー成形を行い、内容量 1500mLのボトルを成形して評価した。評価結果を表 1 に示す。  Blow molding was carried out in the same manner as in Example 1 except that the power used in Example 1 was the same except that no power was added to the PE metal wax. The evaluation results are shown in Table 1.
[0125] [表 1] 実施例 1 実施例 2 比較例 1 t K例 2 [0125] [Table 1] Example 1 Example 2 Comparative Example 1 tK Example 2
B221 WA (部） 100 100 100 100  B221 WA (part) 100 100 100 100
ェクセレックス（部） 2 3 0 0 成形温度 180 180 200 180  Exelex (part) 2 3 0 0 Molding temperature 180 180 200 180
80.7 81.3 79.6 78.2  80.7 81.3 79.6 78.2
外観 〇 〇 O X  Appearance ○ ○ O X
¾注容里 1674 1674 1673 1669  ¾Note Yuri 1674 1674 1673 1669
落下強度 (個 /10個） 0 0 0 7  Drop strength (pieces / 10 pieces) 0 0 0 7
ショット数（個/ h) 259 264 202 174  Number of shots (pieces / h) 259 264 202 174
成形サイクル（S) 28 27 36 41  Molding cycle (S) 28 27 36 41
[0126] 上記表 1からも明らかな様に、本発明によれば、成形温度を 200°Cから 180°Cに下げ ても、外観、落下強度は損なわれないだけでなぐ成形サイクルも向上していることが 分かる。また、ポリオレフインワックスを添加せずに成形温度を 200°Cから 180°Cに下 げると、外観、落下強度が悪化し、しカゝも成形サイクルも長くなり、生産性が悪化して 、ることが分力る。 [0126] As is apparent from Table 1 above, according to the present invention, the molding temperature is lowered from 200 ° C to 180 ° C. However, it can be seen that not only the appearance and drop strength are not impaired, but also the molding cycle is improved. In addition, when the molding temperature is lowered from 200 ° C to 180 ° C without adding polyolefin wax, the appearance and drop strength deteriorate, the mold and molding cycle become longer, and the productivity deteriorates. Can be divided.
〔実施例 3〜4〕 (Examples 3 to 4)
ポリエチレン榭脂であるハイゼックス 5100B (Ml = 0. 27gZlO分； 190°C 2. 16k gf、密度： 944kgZm3) ( (株）プライムポリマー社製）に、メタ口セン PEワックス（エタセ レックス (登録商標) 40800T 三井化学 (株)社製、エチレン含量 95mol%、密度： 9 80kgZm3、平均分子量 Mn= 2200)を表 2の割合で添加し、タンブラ一ミキサー中 で十分混合してポリオレフイン樹脂の混合物を作成した。これらのポリオレフイン榭脂 の混合物にっ 、てブロー成形を行 、、内容量 lOOOmLのボトルを成形して評価した 成形条件 Polyethylene榭脂HI-ZEX 5100B (Ml = 0. 27gZlO min; 190 ° C 2. 16k gf, Density: 944kgZm 3) to (Ltd. Prime manufactured Polymer Co.), meta port Sen PE wax (Etase Rex (registered trademark ) 40800T Mitsui Chemicals, Inc., ethylene content 95 mol%, density: 980 kgZm 3 , average molecular weight Mn = 2200) was added in the proportions shown in Table 2, and mixed thoroughly in a tumbler mixer to prepare a mixture of polyolefin resin. Created. Molding conditions evaluated by blow molding with a mixture of these polyolefin resin and molding bottles with an inner volume of lOOOOmL
成形機 （株)プラコ一社製 3B50中空成形機  Molding machine 3B50 hollow molding machine manufactured by Placo Co., Ltd.
1パリソン 1モールド方式  1 parison 1 mold method
金型温度 25°C  Mold temperature 25 ° C
吹き込みエアー圧力 0. 5MPa  Blowing air pressure 0.5 MPa
製品重量 67± 2g  Product weight 67 ± 2g
なお、物性の測定方法は次の通りである。 In addition, the measuring method of a physical property is as follows.
C外観] C appearance]
ボトルの外観を目視で観察し、評価した。 The appearance of the bottle was visually observed and evaluated.
〇 厚みむらがない  〇 No uneven thickness
△ 厚みむらが若干目立つ  △ Uneven thickness is noticeable
X 厚みむらがかなり目立つ  X Unevenness of thickness is quite noticeable
[満注容量]  [Full capacity]
成形したボトルの口にまで水を注ぎその重量を測定した。 Water was poured into the mouth of the molded bottle and its weight was measured.
[落下強度] [Drop strength]
ボトルに水を 600mL入れ、 1. 2mの高さ力 容器を落下させてボトルが割れた個数 で評価した。 Put 600mL of water in the bottle, 1.2m height force Number of broken bottles by dropping the container It was evaluated with.
[ショット数]  [number of shots]
1時間あたりに製品ボトルを作製した個数として算出した。  It was calculated as the number of product bottles produced per hour.
[成形サイクル]  [Molding cycle]
ボトル 1個製造するために必要な時間として算出した。  Calculated as the time required to produce one bottle.
評価結果を表 2に示す。  Table 2 shows the evaluation results.
[0127] 〔比較例 3〕 [Comparative Example 3]
実施例 3で用いたメタ口セン PEワックスを添加せずに、成形温度を 180°Cから 200 °Cに変更した以外は実施例 1と同様にブロー成形を行い、内容量 1500mLのボトル を成形して評価した。評価結果を表 1に示す。  Blow molding was performed in the same manner as in Example 1 except that the molding temperature used in Example 3 was changed from 180 ° C to 200 ° C without adding the PE metal wax, and a bottle with an inner volume of 1500 mL was molded. And evaluated. Table 1 shows the evaluation results.
〔比較例 4〕  (Comparative Example 4)
実施例 1で用 、たメタ口セン PEワックスを添加しな力 た以外は実施例 1と同様に ブロー成形を行い、内容量 1500mLのボトルを成形して評価した。評価結果を表 1 に示す。  Blow molding was carried out in the same manner as in Example 1 except that the power used in Example 1 was the same except that no power was added to the PE metal wax. The evaluation results are shown in Table 1.
[0128] [表 2] [0128] [Table 2]
Figure imgf000041_0001
Figure imgf000041_0001
[0129] 上記表 2からもあきらかな様に、本発明によれば、成形温度を 170°Cから 150°Cに下 げても、外観、落下強度は損なわれないだけでなぐ成形サイクルも向上していること が分かる。また、ポリオレフインワックスを添加せずに成形温度を 170°Cから 150°Cに 下げると、外観、落下強度が悪化し、しカゝも成形サイクルも長くなり、生産性が悪化し ていることが分かる。 [0129] As is clear from Table 2 above, according to the present invention, the molding temperature is lowered from 170 ° C to 150 ° C. It can be seen that the molding cycle is improved as well as the appearance and drop strength are not impaired. In addition, if the molding temperature is lowered from 170 ° C to 150 ° C without adding polyolefin wax, the appearance and drop strength will deteriorate, and the mold and molding cycle will become longer, resulting in poor productivity. I understand.

Claims

請求の範囲 The scope of the claims
[1] 熱可塑性榭脂 (A)と、  [1] Thermoplastic rosin (A),
ゲルパーミエーシヨンクロマトグラフィー（GPC)で測定したポリスチレン換算の数平 均分子量 (Mn)が 400〜5, 000の範囲にあり、降温速度 2°CZ分の条件で示差走 查熱量計 (DSC)で測定した結晶化温度が 65〜120°Cの範囲であるポリオレフイン ワックス (B)とを含む混合物を溶融し、  Differential scanning calorimeter (DSC) with a polystyrene equivalent number average molecular weight (Mn) measured by gel permeation chromatography (GPC) in the range of 400 to 5,000 and a temperature drop rate of 2 ° CZ Melting a mixture comprising polyolefin wax (B) having a crystallization temperature measured in the range of 65 to 120 ° C,
ブロー成形により成形体を製造する方法。  A method for producing a molded body by blow molding.
[2] 上記ポリオレフインワックス (B)がポリエチレンワックスである請求項 1に記載の成形 体を製造する方法。 [2] The method for producing a molded article according to claim 1, wherein the polyolefin wax (B) is a polyethylene wax.
[3] 上記ポリオレフインワックス (B)カ^タ口セン系触媒を用いて得られるポリエチレンヮ ックスである請求項 1に記載の成形体を製造する方法。  [3] The method for producing a molded article according to claim 1, which is a polyethylene wax obtained using the polyolefin wax (B) catalyst-based catalyst.
PCT/JP2005/021609 2005-10-07 2005-11-24 Process for producing blow-molded object WO2007043189A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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JP2003528948A (en) * 2000-03-29 2003-09-30 クラリアント・ゲゼルシヤフト・ミト・ベシユレンクテル・ハフツング Applications of polyolefin wax in synthetic resin processing
JP2004059868A (en) * 2002-07-31 2004-02-26 Mitsui Chemicals Inc Lubricant for chlorine-containing resin and chlorine-containing resin composition
JP2004059867A (en) * 2002-07-31 2004-02-26 Mitsui Chemicals Inc Thermoplastic resin composition

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JP2000063649A (en) * 1998-08-13 2000-02-29 Idemitsu Petrochem Co Ltd Thermoplastic resin composition and injection-molded product
JP2003528948A (en) * 2000-03-29 2003-09-30 クラリアント・ゲゼルシヤフト・ミト・ベシユレンクテル・ハフツング Applications of polyolefin wax in synthetic resin processing
JP2004059868A (en) * 2002-07-31 2004-02-26 Mitsui Chemicals Inc Lubricant for chlorine-containing resin and chlorine-containing resin composition
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