WO2007043190A1 - Procede de production d'un objet moule par injection - Google Patents

Procede de production d'un objet moule par injection Download PDF

Info

Publication number
WO2007043190A1
WO2007043190A1 PCT/JP2005/021610 JP2005021610W WO2007043190A1 WO 2007043190 A1 WO2007043190 A1 WO 2007043190A1 JP 2005021610 W JP2005021610 W JP 2005021610W WO 2007043190 A1 WO2007043190 A1 WO 2007043190A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
carbon atoms
compound
meta
injection
Prior art date
Application number
PCT/JP2005/021610
Other languages
English (en)
Japanese (ja)
Inventor
Hirotaka Uosaki
Kuniaki Kawabe
Motoyasu Yasui
Original Assignee
Mitsui Chemicals, Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Mitsui Chemicals, Inc. filed Critical Mitsui Chemicals, Inc.
Publication of WO2007043190A1 publication Critical patent/WO2007043190A1/fr

Links

Classifications

    • 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
    • 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
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • 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 an injection molded article of thermoplastic resin. More specifically, the present invention relates to a method for producing an injection molded article from a mixture containing a thermoplastic resin and polyolefin wax.
  • Thermoplastic resin is a resin resin that is plasticized by heating and has fluidity, and various molded products are produced by various molding methods. At this time, when thermoplastic resin is injection-molded, it is necessary to impart sufficient fluidity to the thermoplastic resin in order to prevent short shots.
  • a method for imparting sufficient fluidity to a thermoplastic resin a method of injection molding by adding a plasticizer or a lubricant to a thermoplastic resin is known, but this method improves fluidity.
  • other physical properties such as the properties of the molded product, particularly the mechanical strength and heat resistance, are also lowered. For this reason, a thermoplastic resin composition has been proposed that aims to improve mold release and fluidity in injection molding of thermoplastic resin and to prevent deterioration of the properties of the resulting molded product (for example, And Patent Documents 1 to 4).
  • Patent Document 1 JP-A-5-209129
  • Patent Document 2 JP-A-9-111067
  • Patent Document 3 Japanese Patent Laid-Open No. 2000-226478
  • Patent Document 4 Japanese Unexamined Patent Application Publication No. 2004-189864 Disclosure of the invention
  • the present invention is intended to solve the problems associated with the prior art as described above, and in injection molding of a thermoplastic resin, the burning of the resin is prevented, and after injection, It is an object of the present invention to provide a thermoplastic resin injection molding method capable of shortening the cooling time.
  • a mixture containing a thermoplastic resin and a polyolefin wax is obtained at a molding temperature that is 5 ° C. or more lower than the molding temperature in the case where the mixture does not contain the polyolefin wax. It is characterized by injection molding.
  • the polyolefin wax is preferably a polyethylene wax
  • the thermoplastic resin is preferably polypropylene or polyethylene.
  • the fluidity of the thermoplastic resin can be secured even at a low temperature.
  • it is possible to perform injection molding at a low temperature, and to prevent scorching of the resin during the injection molding.
  • it does not include polyolefins! Since it has sufficient fluidity even at the molding temperature, it is possible to sufficiently fill the mold with fine resin and to prevent short shots.
  • the obtained molded product does not show deterioration in characteristics.
  • the molding temperature is low, the mold cooling time can be shortened, the molding cycle can be increased, and the production efficiency of existing equipment can be improved.
  • the method for producing an injection-molded article according to the present invention comprises adding a polyolefin wax to a thermoplastic resin, thereby lowering the temperature by 5 ° C or more compared to the injection molding temperature in the case where the polyolefin wax is not contained.
  • the thermoplastic resin can be injection-molded at a temperature lower by 10 ° C or higher, more preferably at a temperature lower by 15 ° C or higher.
  • the “injection molding temperature when polyolefin resin is not included!” Is an optimum value determined as appropriate depending on the thermoplastic resin used, taking into consideration the molding speed and the physical properties of the resulting molded product. This is the injection molding temperature. For example, in the case of crystalline rosin, the optimum m
  • the injection molding temperature Tpc can be determined.
  • the “injection molding temperature in the case of including polyolefin wax” is an injection molding temperature at which the screw torque is the same as the screw torque of the extruder at the injection molding temperature in the case of not including polyolefin wax.
  • the above “same” includes an error of about 5%.
  • the molding temperature it is possible to prevent scorching during injection molding.
  • the obtained injection-molded product does not show a decrease in physical properties even when polyolefin wax is added.
  • the molding temperature can be lowered, the mold cooling time can be shortened. As a result, the molding cycle can be increased, and productivity can be improved with existing equipment.
  • it can be injection-molded at a low temperature, foaming at a low temperature is also possible.
  • thermoplastic rosin and polyolefin wax used in the production method of the present invention will be described below.
  • thermoplastic resin used in the present invention examples include polyolefins such as low-density polyethylene such as linear linear low-density polyethylene, medium-density polyethylene, high-density polyethylene, polypropylene, and ethylene-propylene copolymer; ethylene acrylic acid copolymer , Ethylene-methacrylic acid copolymers and esterified products thereof, olefin butyl compound copolymers such as ethylene acetate butyl copolymer, ethylene butyl alcohol copolymer; polyester salts such as polyvinyl chloride, polystyrene, polyethylene terephthalate, etc. Fat And acrylic resin such as polymetatalylate, polyamide resin, polycarbonate resin, and polyacetal resin. In addition, these graft copolymers and block copolymers
  • Random copolymers can also be used. In addition, use a blend of two or more of these rosins.
  • the MI (190 ° C) of the high-density polyethylene is preferably in the range of 3.0 to 20 gZlO, more preferably in the range of 4.0 to 15 gZlO.
  • Ml of the high-density polyethylene is in the above range, it is possible to obtain a molded article excellent in texture, rigidity, impact strength, chemical resistance, and the like.
  • the density of the high density polyethylene rather preferably in the range of 942 ⁇ 970kg / m 3, and more preferably in a range of from 950 ⁇ 965kg / m 3.
  • the density of the high-density polyethylene is in the above range, a molded article having excellent texture, rigidity, impact strength, chemical resistance and the like can be obtained.
  • the MI (230 ° C) of the polypropylene a range of 3.0 to 60 gZlO is preferable, and a range of 5.0 to 55 is more preferable.
  • the Ml of polypropylene is in the above range, a molded product excellent in heat resistance, rigidity, etc. can be obtained.
  • the polyolefin wax used in the present invention is an ⁇ -olefin homopolymer or olefin oligomer having a copolymer power, and can be produced using a Ziegler catalyst or a metalocene catalyst.
  • polyethylene waxes such as ethylene homopolymers and copolymers of ethylene and ⁇ -olefins having 3 to 20 carbon atoms are preferred.
  • polyethylene waxes prepared using a metallocene catalyst hereinafter referred to as “ It is preferable to abbreviate it as “meta-orthene-based polyethylene wax”!
  • the at-olefin has 3 to 10 carbon atoms, preferably 3 to 3 propylene and 4 to 1 carbon atoms.
  • the polyolefin wax is measured by gel permeation chromatography.
  • the number average molecular weight (Mn) force in terms of polystyrene is usually 400 to 5,000, preferably 1,000 to 4,000, more preferably 1,500 to 4,000. If the Mn of the positive repffin status is in the above range, the effect of improving the fluidity is large and the effect of reducing the molding temperature is large. Molding at a low molding temperature reduces the cooling time and improves the molding cycle. Further, by lowering the molding temperature, it is possible to suppress thermal deterioration of the resin and to suppress the burning and black spots of the resin that can be achieved simply by suppressing the decrease in the resin strength.
  • the ratio (MwZMn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polystyrene measured by gel permeation chromatography is usually 1.2 to 4.0, It is preferably in the range of 1.5 to 3.5, and more preferably in the range of 1.5 to 3.5.
  • Mw / Mn force Within the above range, mold releasability is excellent and mold contamination can be suppressed.
  • the melting point measured with a differential scanning calorimeter is usually in the range of 65 to 130 ° C, preferably 70 to 130 ° C, more preferably 75 to 130 ° C.
  • DSC differential scanning calorimeter
  • the density measured by the density gradient tube method is usually 850 to 980 kgZm 3 , preferably 870 to 980. More preferably, it is in the range of 890 to 980 kgZm 3 .
  • the density is in the above range, mold releasability is excellent and mold contamination can be suppressed.
  • the polyolefin wax described above has a crystallization temperature (Tc (° C), measured at a temperature drop rate of 2 ° CZ) measured with a differential scanning calorimeter (DSC), and a density (D ( kg / m 3 )) satisfy the following formula (1), preferably the following formula (la), more preferably the following formula (lb).
  • the comonomer composition of the polyolefin wax becomes more uniform, and as a result, the thermoplastic resin, especially the sticky component of the polyolefin, decreases.
  • the tackiness of the mixture or composition containing thermoplastic rosin and polyolefin wax tends to be reduced.
  • the penetration is usually 30 dmm or less, preferably 25 dmm or less, more preferably 20 dmm or less. Below, even more preferably 15 dmm or less is desirable. This is a value measured in accordance with the above-mentioned penetration degree IS K2207. When the penetration is in the above range, a molded article having sufficient strength can be obtained.
  • the amount of acetone extracted is preferably in the range of 0 to 20% by weight, more preferably 0 to 15% by weight.
  • the amount of acetone extracted is in the above range, mold releasability is excellent and mold contamination can be suppressed.
  • the acetone extraction amount is a value measured as follows. Use a filter (made by ADVANCE, No. 84) in a Soxhlet extractor (made of glass), place 200 ml of acetone in the bottom round bottom flask (300 ml), and extract in a 70 ° C hot water bath for 5 hours. Do. Set 10g on the filter for the first box.
  • the polyolefin wax is solid at room temperature and becomes a low-viscosity liquid at 65 to 130 ° C.
  • the polyolefin wax is, for example,
  • (B) (b—1) an organoaluminum oxide compound, (b—2) a compound that reacts with the above-mentioned meta-mouth compound (A) to form an ion pair, and (b-3) Organoaluminum compound power with at least one compound selected
  • the catalyst using an olefin polymerization catalyst that also has strength.
  • a meta-cene catalyst is effective.
  • the meta-octane compound forming the meta-catalyst-based catalyst is a meta-metallic compound of a transition metal selected from Group 4 of the periodic table.
  • a specific example is represented by the following formula (1).
  • 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.
  • 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,
  • the ligand having an enyl skeleton 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, etc.
  • an alkyl or cycloalkyl-substituted cyclopentagel group an indur group, 4, 5, 6, 7-tetrahydroindenyl group, a fluorenyl group, and the like.
  • the hydrogen of the ligand having a cyclopentagel skeleton may be substituted with a halogen atom or a trialkylsilyl group.
  • the ligands having two cyclopentagel skeletons are linked 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 not having a cyclopentagel skeleton) L is a hydrocarbon group having 1 to 12 carbon atoms, 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 valence of the transition metal is 4, it is more specifically represented by the following 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 each independently have a cyclopentadenyl skeleton This is a group (ligand) that has or does not have.
  • Examples of meta-orthocene compounds in which M 1 is zirconium and contains at least two ligands having a cyclopentagel skeleton are given below.
  • R 2 At least two of R 4 and R 5 , for example, R 2 and R 3 are groups (ligands) having a cyclopentagel skeleton, and these at least two groups are alkylene groups, substituted alkylene groups, and silylene groups. Alternatively, a bridge-type meta-orthene compound bonded through a substituted silylene group or the like can also be used.
  • R 4 and R 5 are each independently the same as the ligand L other than the ligand having the cyclopentagel skeleton described above.
  • Such bridge type meta-octene compounds include ethylenebis (indul) dimethylzirconium, ethylenebis (indur) zirconium dichloride, isopropylidene (cyclopentagel monofluorenyl) zirconium dichloride, diphenylsilylene biphenyl. Sulfur (Indur) Zirconium Dichloride, Methylphenol Silylene Bis (Indur) Zirconium Dichloride and the like.
  • meta-mouth compound is a meta-mouth compound of the following formula (3) described in JP-A-4-268307.
  • M 1 is a Group 4 transition metal of the periodic table, and specifically includes titanium, zirconium, and hafnium.
  • 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 substituted alkyl group having 1 to 10 carbon atoms; a carbon atom number 6 to 10 -N (R 2 °), —SR 2 °, —OSi (R 2 °), —Si (R 2 °) or —P (R 2 °) groups, 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 14 are particularly preferably hydrogen atoms.
  • R 15 and R 16 are the same as R 13 and R 14 except that they do not include a hydrogen atom, and are preferably the same or different from each other. is there.
  • R 15 and R 16 are preferably halogenated alkyl groups having 1 to 4 carbon atoms, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl and the like. In particular, methyl is preferred.
  • 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; Aryl group having 6 to 10 atoms; a fluoroaryl group having 6 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; a alkenyl group having 2 to 10 carbon atoms; an aryl having 7 to 40 carbon atoms An alkyl group; an arylene alkenyl group having 8 to 40 carbon atoms; or an alkylaryl group having 7 to 40 carbon atoms.
  • R 21 and R 22 or “R 21 and R 23 ” may be combined with the atoms to which they are bonded to form a ring.
  • R 18 and R 19 may be the same as or different from each other, and examples thereof include the same as R 21 .
  • m and n may be the same or different and are each 0, 1 or 2, preferably 0 or 1, and m + n is 0, 1 or 2, preferably 0 or 1.
  • meta-mouth compound represented by the above formula (3) examples include the following compounds. ra c -Ethylene (2-methyl-1-indul) 2-zirconium dichloride, rac-dimethylsilylene (2-methyl 1-indenyl) 2-zirconium dichloride, etc. These meta-mouth compounds can be produced, for example, by the method described in JP-A-4-268307.
  • meta-mouth compound a meta-mouth compound represented by the following formula (4) should be 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, and are 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.
  • R 26 , R 27 , R 28 and R 29 may be the same or different from each other, a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogenated hydrocarbon having 1 to 20 carbon atoms. Indicates a group. 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.
  • R 29 is a substituent other than an aromatic group, it is preferably a hydrogen atom.
  • 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 a thio atom-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 silicon-containing group, a divalent germanium-containing group, a divalent Tin-containing group, 1 O, 1 CO, —S—, —SO—, —SO 1 — —NR 30 —, -P (R 3 °) one, -P (O) (R 3 °) one, -BR 30
  • R 3Q is a hydrogen atom, halogen atom, carbon atom number 1-20 A hydrogenated group, a halogenated hydrocarbon group having 1 to 20 carbon atoms).
  • meta-mouth compound may be a meta-mouth compound represented by the following formula (5).
  • R 26 , R 27 , R 28 and R 29 are the same as the above formula (4).
  • R 26 , R 27 , R 28 and R 29 it is preferred that two groups including R 26 are alkyl groups.
  • R 26 and R 28 , or R 28 and R 29 are alkyl groups. Is preferred.
  • This alkyl group is preferably a secondary or tertiary alkyl group.
  • the alkyl group includes a halogen atom and a halogen-containing group which may be substituted with a silicon-containing group, and examples of the halogen-containing group include the substituents exemplified for R 24 and R 25 .
  • R 26 Of R 28 and R 29 , groups other than alkyl groups are preferably hydrogen atoms. Further, 6 , R 27 , R 28 and R 29 may be such that two groups selected from these forces are bonded 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 described above. A specific example of the meta-mouth compound represented by the above formula (5) is shown below.
  • 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-mouth compound represented by the following formula (6) can be used as a meta-mouth compound.
  • 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 may be substituted with a halogen atom, 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.
  • meta-mouth compound a meta-mouth compound represented by the following 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.
  • ⁇ 4 is titanium, zirconium or hafnium.
  • X 3 is the same as that described in Equation (7) above.
  • Cp is bonded ⁇ to Micromax 4, and a substituted cyclopentadienyl group having a substituent Zeta.
  • ⁇ is oxygen, iow, boron, or an element of group 4 of the periodic table (eg, silicon, germanium, or tin).
  • ⁇ is a ligand containing nitrogen, phosphorus, oxygen or io, and ⁇ and ⁇ may form a condensed ring.
  • a specific example of the meta-mouth compound represented by equation (8) is shown below.
  • meta-mouth compound represented by the following formula (9) is used as the meta-mouth compound.
  • 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 from each other, at least one of which is an aryl group having 11 to 20 carbon atoms, an aryl alkyl group having 12 to 40 carbon atoms, or an aryl hydrocarbon group having 13 to 40 carbon atoms.
  • a force which is an alkylaryl group having 12 to 40 carbon atoms or a group containing a key group, or a group represented by R 31 , and at least two adjacent groups together with the carbon atoms to which they are bonded are singular or A plurality of aromatic rings 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.
  • Ariru group, ⁇ reel alkyl group, Ariruaruke - R 31 except R 31 that group, Arukiruari Lumpur group and an aromatic ring to form an aliphatic ring is a hydrogen atom, halogen atom, 1 to carbon atoms 10 alkyl groups or a group containing silicon.
  • R 32 may be the same or different from each other, a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkenyl group having 2 to carbon atoms: LO, 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 2 adjacent groups out of the groups represented by R 32 The groups may form one or more aromatic rings or aliphatic rings together with the carbon atoms to which they are attached.
  • 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, and particularly preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms such as methyl, ethyl, or propyl.
  • a suitable example of such a fluorenyl group having R 32 as a substituent is a 2,7 dialkyl fluoryl group. In this case, the 2,7 dialkyl alkyl group has 1 to 5 carbon atoms.
  • 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 are the same as described above.
  • R 33 and R 34 is preferably an alkyl group having 1 to 3 carbon atoms.
  • X 1 and X 2 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, an oxygen-containing group, Conjugated residue formed from a containing group or a nitrogen-containing group, or X 1 and X 2 .
  • Preferred conjugation residues formed from X 1 and X 2 are residues of 1, 3 butadiene, 2, 4 monohexagen, 1 phenenole 1, 3 pentagen, and 1, 4 diphenyl butadiene. These residues also have 1 to 10 carbon atoms It may be substituted with a hydrocarbon group.
  • 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 silicon-containing group, a divalent germanium-containing group, a divalent Tin-containing group, 1 O, 1 CO—, — S—, — SO—, —SO 1, NR 35 —, — P (R 35 ) —, —P (O) (R 35 ) —, —BR 35 Ma
  • R 35 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.
  • these divalent groups those in which the shortest linking part of Y— is composed of one or two atoms are preferred.
  • R 35 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.
  • Particularly preferred are alkylsilylenes, alkylarylsilylenes or arylylsilylenes, which are preferred.
  • meta-mouth compound the meta-mouth compound represented by the following formula (10) is used.
  • M 3 is a transition metal atom of Group 4 of the periodic table, specifically titanium, zirconium 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 alkyl Ru group, containing Ca Group, oxygen-containing group, xio-containing group, nitrogen-containing group or 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 hydrocarbon group having 1 to 3 carbon atoms, such as methyl, ethyl, n-propyl and i-propyl, a phenol, a An aryl group such as naphthyl or 13 naphthyl or a hydrogen atom is preferred.
  • R 37 may be the same as or different from each other, hydrogen atom, halogen atom, 1 to carbon atom: L0 alkyl group, 6 to 20 carbon atom group, 2 to 10 carbon group.
  • the alkyl group, aryl group, alkyl group, aryl alkyl group, arylalkyl group, and alkylaryl group may be substituted with a halogen.
  • R 37 is preferably a hydrogen atom or an alkyl group, particularly a hydrogen atom or a hydrocarbon having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, and tert-butyl. It is preferably a group.
  • R 36 and R 37 may be the same as or different from each other.
  • 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 number 1 to: an L0 alkyl group, or a carbon atom number 2 to: L0 is an alkenyl group, a silicon-containing group, an oxygen-containing group, a X-containing group, a nitrogen-containing group or a phosphorus-containing group.
  • 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 number 1 to: an L0 alkyl group, or a carbon atom number 2 to: L0 is an alkenyl group, a silicon-containing group, an oxygen-containing group, a X-containing group, a nitrogen-containing group or a phosphorus-containing group.
  • R 39 is preferably an alkyl group having 1 to 3 carbon atoms such as S-methyl, ethyl, or propyl, and the other is a hydrogen atom.
  • X 1 and X 2 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, an oxygen-containing group A X-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 the number of carbon atoms 1
  • divalent hydrocarbon group divalent halogenated hydrocarbon group having 1-20 carbon atoms, divalent silicon-containing group, divalent germanium-containing group, divalent tin-containing group, O, CO-,
  • A1R 4Q — (where R 4Q is a hydrogen atom, halogen atom or carbon atom number 1-20) A hydrogen group, a halogenated hydrocarbon group having 1 to 20 carbon atoms).
  • Y is 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 composite compound represented by the following formula (11) is used.
  • Y is selected from carbon, silicon, germanium and tin nuclear power
  • M is Ti
  • R 10 , R U and R 12 are selected from hydrogen, a hydrocarbon group and a silicon-containing group, and may be the same or different, and adjacent substituents from R 5 to R 12 are bonded to each other to form a ring.
  • R 13 and R ′′ may be selected from hydrocarbon groups and silicon-containing forces, which may be the same or different, and R 13 and R 14 may be bonded to each other to form a ring.
  • Q may be selected from a halogen, a hydrocarbon group, an anion ligand, or a neutral ligand capable of coordinating with a lone pair, in the same or different combination, and j is an integer of 1 to 4.
  • the cyclopentagel group may or may not be substituted.
  • a substituted or unsubstituted cyclopentagenyl group is possessed by the cyclopentagel group in the above formula (11).
  • these substituents may be the same or different from each other.
  • hydrocarbon group having 1 to 20 carbon atoms is an alkyl group, an alkyl group, an alkyl group or an aryl group composed only of carbon and hydrogen. These include those in which any two adjacent hydrogen atoms are replaced at the same time to form an alicyclic or aromatic ring! /.
  • the hydrocarbon group having 1 to 20 carbon atoms in total (f 1 ′) includes an alkyl group, an alkenyl group, an alkynyl group and an aryl group composed only of carbon and hydrogen, and a hydrogen atom directly bonded to these carbon atoms.
  • Such hydrocarbon groups (fl ′) include methyl, ethyl, n-propyl, allyl, n-butyl, n-pentyl, n-xyl, and n-butyl groups.
  • the key group containing group (f 2) is, for example, a group in which the ring carbon of the cyclopentagel group is directly covalently bonded to the key atom, specifically an alkylsilyl group or a arylsilyl group. It is a group.
  • Examples of the C-containing group (f2 ′) having 1 to 20 carbon atoms include trimethylsilyl group and triphenylsilyl group.
  • the fluorenyl group may or may not be substituted.
  • the substituted or unsubstituted fluorine group means R 5 held by the fluorine group moiety in the above formula (11), A force in which R 9, R 1Q , R 11 and R 12 are all hydrogen atoms, or R 5 , At least one of R 9 , R 1Q , R 11 and R 12 is a hydrocarbon group (f 1), preferably a hydrocarbon group having 1 to 20 total carbon atoms (fl ′), or It means a fluorenyl group substituted with a silicon-containing group (f 2), preferably a C-containing group (f 2,) having a total carbon number of 1 to 20.
  • R 5 , R 6 When two or more of R 9 , R 1Q , R 11 and R 12 are substituted, these substituents may be the same or different from each other.
  • R 5 , R 6 , R 9, R 1Q, R 11 and R 1 2 may be bonded to form a ring adjacent groups together. In view of ease of catalyst production, those in which R 6 and R u , and R 7 and R 1Q are the same are preferably used.
  • a preferred hydrocarbon group (fl) is a hydrocarbon group (fl ') having a total carbon number of 1 to 20, and examples of a preferable silicon-containing group (f 2) include those having a total carbon number of It is a group containing 1 to 20 (f 2 ').
  • the main chain part of the bond connecting the cyclopentadenyl group and the fluorenyl group is a divalent covalent bond containing one carbon, silicon, germanium and tin atom.
  • An important point in the case of high temperature solution polymerization 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.
  • the preferred hydrocarbon group (fl) is the hydrocarbon group (f 1 ′) having the total carbon number of 1 to 20, and preferably the example of the silicon-containing group (f 2) has the total carbon number of 1 to 20 C-containing groups (f2 ').
  • Q is halogen, a hydrocarbon group having 1 to: L0, or carbon.
  • the number is selected from neutral, conjugated or non-conjugated gen, ionic ligands or neutral ligands capable of coordinating with lone pairs in the same or different combinations.
  • Specific examples of halogen are fluorine, chlorine, bromine, and iodine.
  • hydrocarbon groups are 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, conjugated or non-conjugated genes with 10 or less carbon atoms include: s cis—or s trans—r? 4 — 1, 3 butadiene, s—cis or s—trans 7? '—1, 4 Di-Fuenolei 1,3 Butagen, s cis or s Trans 1 4 — 3—Methylolene 1,3 Pentagen, s—cis or s Trans ⁇ 1,4-Dipentenoyl 1,3 Butadiene, s cis or s Trans 7? 2, 4—Hexagen, s cis or s trans 7? 1, 3 Pentagen, s cis 1 or s trans 1 7?
  • cation ligand examples 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.
  • meta-mouth compound a meta-mouth compound represented by the following formula (12) is used.
  • R 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , R U , R 12 , R 13 , R 14 are hydrogen, hydrocarbon group, and silicon-containing group
  • R 1 to R 14 may be the same or different and may be bonded to each other to form a ring.
  • M is Ti, Zr or Hf, and Y is Group 14 atom, Q is halogen, hydrocarbon group, neutral with 10 or less carbon atoms, conjugated or non-conjugated gen, anion ligand, and neutral ligand force capable of coordination with lone pair Are selected from the group consisting of the same or different combinations, n is an integer of 2 to 4, and j is an integer of 1 to 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 a carbon number.
  • 7-20 alkylaryl groups which may contain one or more ring structures. Specific examples include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-jetylpropyl, 1-ethyl-1 methylpropyl.
  • the hydrocarbon-containing hydrocarbon group is preferably an alkyl or aryl silyl group having 1 to 4 carbon atoms and 3 to 20 carbon atoms.
  • Examples include silylsilyl, tertbutyldimethylsilyl, triphenylsilyl and the like.
  • R 1 to R ′′ in the above formula (12) are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different from each other.
  • 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 selected from the group consisting of a halogen, a hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or non-conjugated gen, a-on ligand, and a neutral ligand capable of coordination with a lone pair. 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-ethynole 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 can be mentioned.
  • neutral, conjugated or non-conjugated genes with less than 10 carbon atoms include s-cis or s-trans 4-1, 3 butadiene, s-cis or s-trans 7? 4 —1, 4 ? Jifue two Lou 1, 3-butadiene, s-cis one or s trans one 4-3-methyl-1, 3 pen Tin, s-cis or s trans 4 1, 4 Jipenjinore 1, 3-butadiene, s-cis or s trans 7 4 - 2, 4 Hexagen, s cis or s trans 1 4—1, 3—Pentagen, s cis 1 or s trans 1 4 —1, 4—ditrinole —1, 3—butadiene, s—cis or s—trans 7 4 —1, 4 Bis (trimethylenosilyl) -1,3-butadiene and the like.
  • a specific example of a lion ligand is methoxy And alkoxy groups such as 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, and diphenylmethylphosphine, or tetrahydrofuran and jetyl ether. And ethers such as dixanthone and 1,2-dimethoxyethane. When j is an integer of 2 or more, multiple Qs may be the same or different.
  • 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 with each other!
  • Group 4 transition metal compound represented by the formula (12) include a compound represented by the following formula (13).
  • R 5 , R 6 , R 7 , R 8 , R 9 , R 1Q , R U , R 12 are selected from a hydrogen atom, a hydrocarbon group, and a silicon-containing group, and may be the same or different.
  • the adjacent substituents from R 5 to R 12 may be bonded to each other to form a ring, and R 13 and R 15 may be bonded to each other to form a ring.
  • R 13 and R 15 may be bonded to each other to form a ring, and 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 M may be Ti, Zr, or Hf, and Q may be a halogen, a hydrocarbon group, a lone ligand, or a neutral ligand that can coordinate with a lone pair of electrons. You may choose the same or different combinations, and j is an integer from 1 to 4.
  • meta-cene compounds such as 9 and 10 are listed in JP-A-2004-175707, WO200lZ027124, WO2004 / 029062, WO2004Z083265, and the like.
  • meta-mouth compounds described above can 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.
  • a conventionally known aluminoxane can be used as it is as the organoaluminum compound (b-1).
  • Specific examples of such a known aluminoxane include compounds represented by the following formula (14) or the following formula (15).
  • R is a hydrocarbon group having 1 to C carbon atoms: n is an integer of 2 or more.
  • n 3 or more, preferably 10 or more, particularly methylaluminoxane, which is an R-catayl group, are preferred.
  • aluminoxanes may be mixed with some organic aluminum compounds.
  • a benzene-insoluble organoaluminum compound as exemplified in JP-A-2-78687 can also be applied.
  • An aluminoxane having an alkyl group can also be suitably used.
  • the term “benzene insoluble” in an organoaluminum oxide compound means that the A1 component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of A1 atoms.
  • organoaluminum compound (b-1) used in the present invention the following (1)
  • Examples thereof include modified methylaluminoxane having the structure 6).
  • R represents a hydrocarbon group having 1 to 10 carbon atoms, and m and n represent an integer of 2 or more.
  • This modified methylaluminoxane is prepared using trimethylaluminum and an alkylaluminum other than trimethylaluminum.
  • Such modified methylaluminoxane is commonly called MMAO.
  • Such MMAO can be prepared by the methods listed in U.S. Pat. No. 4,960,878 and U.S. Pat. No. 5041584.
  • 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 the above formulas (14) and (15). However, it is soluble in aliphatic hydrocarbons and alicyclic hydrocarbons.
  • organoaluminum oxide compound (b-1) used in the present invention include an organoaluminum oxide compound containing boron represented by the following formula (17). You can also.
  • R e represents a hydrocarbon group having 1 to L carbon atoms.
  • R d may be the same or different from each other, hydrogen atoms, halogen atoms, or carbon atom number power ⁇ ⁇ Represents 10 hydrocarbon groups.
  • JP-A-1-501950 discloses a compound (b-2) that reacts with the meta-orthene compound (A) to form an ion pair (hereinafter sometimes abbreviated as “ionic compound”).
  • ionic compound Japanese Laid-open Patent Publication No. 1-502036, No. 3-179005, No. 3-179006, No. 3-207703, No. 3-207704, US Pat. No. 5,321,106, etc.
  • 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 + includes H +, a carbanium cation, an oxoumuum cation, an ammonium cation, a phosphonium cation, a cycloheptyl aryl cation, and a pharmium cation having a transition metal.
  • ⁇ 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, 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, and tri (n-butyl) ammonium cation.
  • Trialkylammonium cations such as isobutylammonium cation, N, N dimethylalyurium N, N Dialkylaluminum Cations, Diisopropylammonium Cations, Dicyclohexylammonium Cations Etc.
  • phosphonium cation examples include triarylphosphonium cations, such as triphenylphosphonium cation, tris (methylphenol) phosphonium cation, and tris (dimethylphenol) phosphonium cation. It is done.
  • R 0 ′′ is preferably a carbium cation, an ammonium cation, etc., particularly a triphenylcarbium cation, an N, N dimethylarium cation, or an N, N jetylarium cation.
  • carbaum salt examples include triphenyl carbe tetraphenol ruporate, triphenyl carbe tetrakis (pentafluorophenol) borate, triphenyl carbe tetrakis (3, 5 —Ditrifluoromethylphenol) borate, tris (4-methylphenyl) carbtetrakis (pentafluorophenol) borate, tris (3,5-dimethyldimethyl) carbtetrakis (Pentafluorophenol) borate and the like.
  • ammonium salts include trialkyl-substituted ammonium salts, N, N dialkyl ammonium salts, dialkyl ammonium salts, and the like.
  • trialkyl-substituted ammonium salt examples include triethyl ammonium tetraphenol ruborate, tripropyl ammonium tetraphenol porate, tri (n-butyl) ammonium tetraphenol porate, trimethyl ammonium tetrakis (p-tolyl) borate, Trimethylammonium tetrakis (o-tolyl) borate, tri (n-butyl) ammonium tetrakis (pentafluorophenol) borate, triethylammonium tetrakis (pentafluorophenol) borate, tripropylammonium tetrakis (penta Fluorophenol) borate, tripropylammonium tetrakis (2,4 dimethylphenol) borate, tri (n-butyl) ammoniumtetrakis (3,5-dimethylphenol) borate, tri (n-butyl) ammonium Umutet
  • N, N dialkylayuyurumu salt examples include, for example, N, N dimethylayumuterutrafolate, N, N dimethylayuyumutetrakis (pentafluorophenol) borate, N, N dimethylayuyumu tetrakis (3,5-ditrifluoromethylphenyl) borate, N, N jetylureum tetraphenolate, N, N jetylurium tetrakis (pentafluorophenyl) borate, N, N jetylureum tetrakis (3,5 ditrifluoromethylphenol) borate, N, N— 2, 4, 6 pentamethylaureum tetraphenolate, N, N- 2, 4, 6 pentamethylaurium tetrakis (pentafluoro) Lophe) borate and the like.
  • dialkyl ammonium salt examples include di (1 propyl) ammonium tetrakis (pentafluorophenol) borate, dicyclohexyl ammonium tetraphenol, and the like.
  • Japanese Patent Laid-Open No. 2004-516766 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 compound that forms the olefin polymerization catalyst (b-3) examples include, for example, an organoaluminum compound represented by the following formula (19), a complex of a Group 1 metal represented by the following formula (20) and aluminum. Examples thereof include alkylated products.
  • M 2 represents Li, Na or K
  • R a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.
  • tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum
  • Tri-branched alkyl aluminums such as isopropyl aluminum, triisobutyl aluminum, tri sec butyl aluminum, tri tert butyl aluminum, tri 2-methylbutyl aluminum, tri 3 methyl hexyl aluminum, tri 2 hexyl aluminum aluminum
  • tricyclohexyl aluminum Tricycloalkylaluminum such as tricyclooctylaluminum
  • Triarylaluminum such as triphenylaluminum and tritolylaluminum
  • Diisopropylaluminum-humide Id diisobutylaluminum dialkyl aluminum such as hydride - ⁇ beam hydride
  • Alkenyl aluminum such as isoprenylaluminum, etc .
  • alkylaluminum alkoxides such as isobutylaluminum methoxide and isobutylaluminum ethoxide; dimethylaluminum methoxide, jetylaluminum ethoxide, dibutylaluminum butoxide, etc.
  • Dialkylaluminum alkoxides; alkylalkylene sesquialkoxides such as ethylaluminum sesquibutoxide and butylaluminum sesquibutoxide; having an average composition represented by the general formula R a Al (OR b )
  • alkylaluminum bite oxides such as jetylaluminum phenoxide and jetylaluminum (2, 6-di-tert-butyl-4-methylphenoxide); dimethylaluminum chloride and jetylaluminum -Dialkylaluminum halides such as umuchloride, dibutylaluminum chloride, jetylaluminum bromide, diisobutylaluminum chloride; ethers such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide, etc.
  • Alkyl aluminum sesquihalides Alkyl aluminums such as ethyl aluminum dichloride; Partially halogenated alkyl aluminums such as ureum dihalide; Dialkylaluminum hydrides such as jetyl aluminum hydride and dibutyl aluminum hydride; Ethyl aluminum dihydride and propyl aluminum dihydride
  • Other partially hydrogenated alkylaluminums such as alkylaluminum-mudihydrides; partially alkoxylated and halogenated alkylaluminums such as ethylminumium ethoxy chloride, butylaluminum butoxycyclide, ethylaluminum ethoxybromide -You can mention um.
  • Specific examples of the compound represented by the above formula (20) include LiAl (C H), LiAl (C H), and the like.
  • 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. Specific examples of such a compound include (C H) A1N (C H) A1 (C H).
  • trimethylaluminum and triisobutylaluminum are preferably used as the (b-3) organoaluminum compound.
  • the polyolefin wax used in the present invention can be obtained by copolymerizing ethylene or a-year-old olefin with the ability to homopolymerize ethylene or ⁇ -olefin in a normal liquid phase in the presence of the above-mentioned meta-orthocene catalyst.
  • the usage method of each component and the order of addition are arbitrarily selected. The following methods are exemplified.
  • component (A) and component (B) are added to the polymerization vessel in any order.
  • 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-olefin 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. , Polymerization with polyolefin wax coexisting with solvent or melted alone In particular, solution polymerization is preferred in terms of both economy and quality.
  • the polymerization reaction may be carried out by either a batch method or a continuous method. When the polymerization is carried out by a batch method, the above catalyst components are used under the concentration conditions described below.
  • Ingredient (A) is, per liter of the reaction volume, typically 10 9-10 - 1 mol, preferably from 10 8 to : LO—Used in an amount of 2 moles.
  • 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) has a molar ratio [(b-2) ZM] between the ionic compound in component (b-2) and the total transition metal (M) in component (A). In general, it is used in an amount of 0.5 to 5,000, preferably 1 to 2,000.
  • Component (b-3) has a molar ratio [(b 3) ZM] of component (b-3) to transition metal atom (M) in component (A) usually from 1 to: L0000, preferably Used in an amount of 1 to 5000.
  • the polymerization reaction is carried out at a temperature of usually 20 to + 200 ° C, preferably 50 to 180 ° C, more preferably 70 to 180 ° C, and a pressure of usually more than 0 7.8 MPa ( 80kgfZcm 2 , gauge pressure) or less, preferably more than 0 4.9MPa (Gauge pressure) Performed under the following conditions.
  • Ethylene and Z or ⁇ -olefin are supplied to polymerize them in the presence of the above-mentioned meta-locene catalyst.
  • a molecular weight regulator such as hydrogen may 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.
  • a catalyst containing a meta-caffeine compound shown in (Example 6 of meta-caffeine compound) is particularly preferable.
  • thermoplastic resin and the polyolefin wax may be mixed in advance (preliminary mixing) before being supplied to the injection molding machine, or the polyolefin wax is supplied to the resin supplied to the injection molding machine (for example, side feed). And may be mixed. In any of the above cases, A mixture of thermoplastic rosin and polyolefin wax is formed.
  • the premixing method is not particularly limited, and may be melt mixing or dry blending.
  • Various additives can be mixed depending on the application.
  • the production method of the present invention can use a low-temperature foaming agent because low-temperature foaming is possible.
  • the mixture is used for 100 parts by weight of the thermoplastic resin with respect to 100 parts by weight of the thermoplastic resin wax. It is desirable to contain 0.5 to 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 7 parts by weight.
  • thermoplastic resin and polyolefin wax thus obtained by premixing or side feed is injection molded into a desired shape.
  • the injection molding can be performed under conventionally known conditions.
  • the molding temperature (resin temperature) is usually 180 to 400 ° C, preferably 200 to 300 ° C, more preferably 200 to 250.
  • injection pressure force S is usually 10 to 200 MPa, preferably 20 to 150 MPa
  • the mold temperature is usually 20 to 200 ° C, preferably 20 to 80 ° C, more preferably 20 to 60 ° C. .
  • a propylene block copolymer (trade name: Prime Polypro J704WA, manufactured by Prime Polymer Co., Ltd., crystal melting temperature: 160 ° C.) was injection-molded under the following conditions to produce molded products, and various physical properties were evaluated. The results are shown in Table 1.
  • Injection molding machine Toshiba Machine Co., Ltd., 55ton injection molding machine (IS55EPM1.5B) Molding temperature: 220 ° C
  • Mold temperature 40 ° C Mold cooling time: 20 seconds
  • a flat plate (100mm x 100mm x 3mm thickness) is injection molded under the above conditions with the above injection molding machine, and after cooling the mold for a predetermined time, the molded product in the mold is pushed out with an ejector pin.
  • a flat plate (100 mm x 100 mm x 3 mm thick) was injection molded under the above conditions using the above injection molding machine, and the flow mark was observed.
  • test piece was prepared under the above conditions, and the tensile yield stress was measured in accordance with JIS K7161.
  • test specimens were prepared under the above conditions, and the flexural modulus and flexural strength were measured according to JIS K7171.
  • Test pieces were prepared using the above injection molding machine under the above conditions, and Vicat soft saddle points were measured in accordance with JIS K7206.
  • test pieces were prepared under the above conditions, and Izod impact values were measured according to JIS K7110.
  • a comparison between Examples 1 and 2 and Comparative Example 1 shows that when a polyolefin wax (polyolefin wax) is added to a thermoplastic resin, no molding temperature is added. It can be seen that even when o ° c is lowered, injection molding can be performed without deteriorating the physical properties of the molded product. Further, it can be seen that the mold cooling time can be shortened.

Abstract

L'invention concerne un procédé de production d'un objet moulé par injection, caractérisé par le moulage par injection d'un mélange comprenant une résine thermoplastique et une cire polyoléfine à une température de moulage inférieure d'au moins 5 °C à la température de moulage pour le mélange ne contenant pas la cire polyoléfine. Dans le moulage par injection d'une résine thermoplastique au moyen de ce procédé destiné à produire un objet moulé par injection, le grillage de la résine est évité et le temps de refroidissement après l'injection peut être diminué.
PCT/JP2005/021610 2005-10-07 2005-11-24 Procede de production d'un objet moule par injection WO2007043190A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005295665 2005-10-07
JP2005-295665 2005-10-07

Publications (1)

Publication Number Publication Date
WO2007043190A1 true WO2007043190A1 (fr) 2007-04-19

Family

ID=37942458

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/021610 WO2007043190A1 (fr) 2005-10-07 2005-11-24 Procede de production d'un objet moule par injection

Country Status (2)

Country Link
TW (1) TW200726620A (fr)
WO (1) WO2007043190A1 (fr)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007114009A1 (fr) * 2006-03-30 2007-10-11 Mitsui Chemicals, Inc. Procédé de production d'un objet moulé par moulage par injection
JP2007268777A (ja) * 2006-03-30 2007-10-18 Mitsui Chemicals Inc 射出成形による成形体の製造方法
JP2007268779A (ja) * 2006-03-30 2007-10-18 Mitsui Chemicals Inc 射出成形による成形体の製造方法
JP2007268778A (ja) * 2006-03-30 2007-10-18 Mitsui Chemicals Inc 射出成形による成形体の製造方法
JP2007268920A (ja) * 2006-03-31 2007-10-18 Mitsui Chemicals Inc 射出成形による成形体の製造方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH083381A (ja) * 1994-06-15 1996-01-09 Solvay & Cie ポリオレフィン系組成物及びその成形品の製造方法
JP2001150474A (ja) * 1999-11-30 2001-06-05 Daihatsu Motor Co Ltd 射出成形方法、射出成形品およびマスターバッチ
JP2004051769A (ja) * 2002-07-19 2004-02-19 Nissan Motor Co Ltd 自動車内装成形品

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH083381A (ja) * 1994-06-15 1996-01-09 Solvay & Cie ポリオレフィン系組成物及びその成形品の製造方法
JP2001150474A (ja) * 1999-11-30 2001-06-05 Daihatsu Motor Co Ltd 射出成形方法、射出成形品およびマスターバッチ
JP2004051769A (ja) * 2002-07-19 2004-02-19 Nissan Motor Co Ltd 自動車内装成形品

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
"'96 Plastics Tenkazai", 25 August 1996, KABUSHIKI KAISHA CMC, ISBN: 4-88231-151-8, pages: 188 - 191, XP003010990, Y *
MOTOYAMA T.: "Biran Gomu Purasuchikku Haigo Yakuhin (revised edition)", 15 October 1974, RUBBER DIGEST CO., pages: 303 - 307, XP003010989 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2007114009A1 (fr) * 2006-03-30 2007-10-11 Mitsui Chemicals, Inc. Procédé de production d'un objet moulé par moulage par injection
JP2007268777A (ja) * 2006-03-30 2007-10-18 Mitsui Chemicals Inc 射出成形による成形体の製造方法
JP2007268779A (ja) * 2006-03-30 2007-10-18 Mitsui Chemicals Inc 射出成形による成形体の製造方法
JP2007268778A (ja) * 2006-03-30 2007-10-18 Mitsui Chemicals Inc 射出成形による成形体の製造方法
JP2007268920A (ja) * 2006-03-31 2007-10-18 Mitsui Chemicals Inc 射出成形による成形体の製造方法

Also Published As

Publication number Publication date
TW200726620A (en) 2007-07-16

Similar Documents

Publication Publication Date Title
EP0818472B2 (fr) Copolymères de cyclooléfines, compositions et moulages à partir de ces polymères
JP5166678B2 (ja) オレフィン重合体の製造方法
US20050159566A1 (en) Process for producing highly flowable propylene polymer and highly flowable propylene polymer
US20080064805A1 (en) Process for producing injection molded product
JP2003516451A (ja) 非晶質ポリマーと結晶質ポリマーとの架橋型ブレンド物及びその利用方法
JP2003516452A (ja) 非晶質ポリマーと結晶質ポリマーとの架橋型ブレンド物の調製方法
JP4868853B2 (ja) 超高分子量エチレン系重合体
WO2007043188A1 (fr) Procede de production d'un objet moule par injection
WO2007043190A1 (fr) Procede de production d'un objet moule par injection
JPH10180964A (ja) 二軸延伸複層フィルム
WO2007052368A1 (fr) Procede de preparation d'une composition de resine thermoplastique
WO2004081063A1 (fr) Film d'emballage fait en resine ethylenique
US20070082998A1 (en) Process for producing injection molded product
JP2012149188A (ja) オレフィン重合体の製造方法
JP3749590B2 (ja) エチレン・α−オレフィン共重合体組成物およびその用途
US20070080483A1 (en) Process for producing injection molded product
JP2007268778A (ja) 射出成形による成形体の製造方法
JP3610377B2 (ja) ブロー成形用樹脂組成物からなる医療用容器
JP4828223B2 (ja) 熱可塑性樹脂成形体
JP2007125884A (ja) 射出成形体の製造方法
JP2007125883A (ja) 射出成形体の製造方法
JP4846503B2 (ja) ブロー成形体の製造方法
WO2007114009A1 (fr) Procédé de production d'un objet moulé par moulage par injection
JP3746348B2 (ja) プロピレン系共重合体フィルム
JP6666089B2 (ja) プロピレン系樹脂組成物および成形体

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 05809763

Country of ref document: EP

Kind code of ref document: A1