JP2007125884A - Manufacturing method of injection molded product - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an injection molding method of a thermoplastic resin capable of preventing the scorching of the thermoplastic resin and shortening a cooling time after injection in the injection molding of the thermoplastic resin. <P>SOLUTION: The manufacturing method of the injection molded product is characterized in that a mixture containing the thermoplastic resin and a polyolefin wax is injection-molded at a molding temperature lower than the molding temperature by 5°C or above in a case that the mixture contains no polyolefin wax. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing an injection molded article of a thermoplastic resin. More specifically, the present invention relates to a method for producing an injection-molded body from a mixture containing a thermoplastic resin and a polyolefin wax.

  The thermoplastic resin is a resin that is plasticized by heating and has fluidity, and various molded products are manufactured by various molding methods. At this time, when injection molding a thermoplastic resin, it is necessary to impart sufficient fluidity to the thermoplastic resin in order to prevent short shots. As a method of imparting sufficient fluidity to the thermoplastic resin, a method of injection molding by adding a plasticizer or a lubricant to the thermoplastic resin is known, but this method improves fluidity, There has also been a problem that physical properties such as properties of molded products, particularly mechanical strength and heat resistance are lowered. For this reason, a thermoplastic resin composition has been proposed for the purpose of improving mold release and fluidity in injection molding of a thermoplastic resin and further preventing deterioration of the properties of the obtained molded product (for example, patent documents). 1-4).

On the other hand, as a method without adding a plasticizer or a lubricant, a method is known in which the molding temperature is raised to sufficiently plasticize the thermoplastic resin and injection molding is performed in this state. However, this method has problems such as burning of the resin and deterioration due to heating in order to increase the molding temperature. Further, in the case of continuous injection molding, it is necessary to cool the mold. However, if the molding temperature is raised, there is a problem that it takes time for cooling and productivity is lowered. For this reason, conventionally, in order to shorten the cooling time, a method such as increasing the capacity of the cooling device has been adopted, but a new capital investment is required, which is not economically preferable.
JP-A-5-209129 JP-A-9-111067 JP 2000-226478 A JP 2004-189864 A

  The present invention is intended to solve the problems associated with the prior art as described above, and in the injection molding of a thermoplastic resin, prevents the resin from being burnt and shortens the cooling time after the injection. It is an object of the present invention to provide a method for injection molding a thermoplastic resin.

  As a result of diligent research to solve the above problems, the present inventor found that injection molding can be performed at a molding temperature lower than conventional by mixing a polyolefin wax with a thermoplastic resin, and the present invention has been completed. .

  That is, in the method for producing an injection-molded article according to the present invention, a mixture containing a thermoplastic resin and a polyolefin wax is injection-molded at a molding temperature that is 5 ° C. or more lower than the molding temperature when the mixture does not contain the polyolefin wax. It is characterized by that.

  In the said manufacturing method, it is preferable to contain 0.1-15 weight part of said polyolefin wax with respect to 100 weight part of said thermoplastic resins. The polyolefin wax is preferably a polyethylene wax, and the thermoplastic resin is preferably polypropylene or polyethylene.

  According to the present invention, the flowability of the thermoplastic resin can be ensured even at a low temperature by adding the polyolefin wax. As a result, it is possible to perform injection molding at a low temperature and prevent scorching of the resin during injection molding. Furthermore, since it has sufficient fluidity even at a molding temperature lower than that in the case where it does not contain polyolefin wax, it is possible to sufficiently fill the resin into the details of the mold and to prevent short shots. In addition, the obtained molded product does not show deterioration in characteristics. Furthermore, since the molding temperature is low, the mold cooling time can be shortened, the molding cycle can be increased, and productivity in existing facilities can be improved.

The method for producing an injection-molded body according to the present invention is a method in which a polyolefin wax is added to a thermoplastic resin, thereby lowering the temperature by 5 ° C. or more, preferably 10 ° C. or more, compared to the injection molding temperature when no polyolefin wax is contained. In this method, the thermoplastic resin can be injection-molded at a temperature, more preferably at a temperature lower by 15 ° C. or more. Here, the “injection molding temperature when no polyolefin wax is included” is an optimum injection molding temperature that is appropriately determined depending on the thermoplastic resin to be used in consideration of the molding speed and the physical properties of the molded article to be obtained. . For example, in the case of a crystalline resin, the optimum injection molding temperature Tpc ₀ can be determined from the crystal melting temperature T _m of the resin by the following formula.

Tpc ₀ = 3/4 × T _m +100
The “injection molding temperature when polyolefin wax is included” 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 when polyolefin wax is not included. Here, the above “same” includes an error of about 5%.

  Thus, by reducing the molding temperature, it is possible to prevent scorching during injection molding. Further, the obtained injection-molded product does not show a decrease in physical properties even when a polyolefin wax is added. In addition, since the molding temperature can be lowered, the mold cooling time can be shortened. As a result, the molding cycle can be increased, and the productivity can be improved with existing equipment. Furthermore, since it can be injection-molded at a low temperature, foaming at a low temperature is also possible.

Hereinafter, the thermoplastic resin and polyolefin wax used in the production method of the present invention will be described.
〔Thermoplastic resin〕
Examples of the thermoplastic resin used in the present invention include low-density polyethylene such as linear linear low-density polyethylene, polyolefin such as medium-density polyethylene, high-density polyethylene, polypropylene, and ethylene-propylene copolymer; ethylene-acrylic acid copolymer , Ethylene-methacrylic acid copolymers and esterified products thereof, ethylene-vinyl acetate copolymers, olefin-vinyl compound copolymers such as ethylene-vinyl alcohol copolymers; polyesters such as polyvinyl chloride, polystyrene, polyethylene terephthalate, etc. Examples thereof include acrylic resins such as resins and polymethacrylates, polyamide resins, polycarbonate resins, and polyacetal resins. Moreover, these graft copolymers, block copolymers, and random copolymers can also be used. Further, two or more of these resins may be blended and used.

As MI (190 degreeC) of the said high density polyethylene, the range of 3.0-20 g / 10min is preferable, and the range of 4.0-15 g / 10min is more preferable. When the MI 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.

As the density of the high density polyethylene is preferably in the range of 942~970kg / m ^3, the range of 950~965kg / m ³ and more preferably. When 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 is preferably in the range of 3.0 to 60 g / 10 minutes, more preferably in the range of 5.0 to 55. When the MI of polypropylene is in the above range, a molded product having excellent heat resistance, rigidity, etc. can be obtained. [Polyolefin Wax]
The polyolefin wax used in the present invention is an olefin oligomer composed of an α-olefin homopolymer or copolymer, and can be produced using a Ziegler catalyst or a metallocene catalyst. Among these, polyethylene waxes such as ethylene homopolymers and copolymers of ethylene and C3-C20 α-olefins are preferred, and polyethylene waxes prepared using a metallocene catalyst (hereinafter referred to as “metallocene polyethylene”). Abbreviated as “wax”).

  The number of carbon atoms of the α-olefin in the copolymer of ethylene and the α-olefin having 3 to 20 carbon atoms is preferably 3 to 10, including propylene having 3 carbon atoms, 1-butene having 4 carbon atoms, and the number of carbon atoms. 5 1-pentene, 6-carbon 1-hexene and 4-methyl-1-pentene, 8-carbon 1-octene and the like are more preferable. Propylene, 1-butene, 1-hexene, 4-methyl-1 -Pentene is particularly preferred.

  The polyolefin wax has a polyethylene-equivalent number average molecular weight (Mn) measured by gel permeation chromatography of usually 400 to 5,000, preferably 1,000 to 4,000, more preferably 1,500 to 5,000. It is in the range of 4,000. When the Mn of the polyolefin wax is in the above range, the effect of improving the fluidity is great and the effect of reducing the molding temperature is great. Molding at a low molding temperature shortens the cooling time and improves the molding cycle. Furthermore, by lowering the molding temperature, it is possible not only to suppress the thermal deterioration of the resin and the resin strength, but also to suppress the scorching and black spots of the resin.

  Moreover, the ratio (Mw / Mn) of the weight average molecular weight (Mw) and the number average molecular weight (Mn) in terms of polyethylene measured by gel permeation chromatography is usually 1.2 to 4.0, preferably 1. .5 to 3.5, more preferably 1.5 to 3.0. When Mw / Mn is in the above range, the mold releasability is excellent and mold contamination can be suppressed.

  The melting point measured with a differential scanning calorimeter (DSC) is usually in the range of 65 to 130 ° C, preferably 70 to 130 ° C, more preferably 75 to 130 ° C. When the melting point is in the above range, the mold releasability is excellent, and mold contamination can be suppressed.

The density measured by the density gradient tube method is usually 850 to 980 kg / m ³ , preferably 870 to 870.
980 kg / m ^3, more preferably in the range of 890~980kg / m ^3. When the density is in the above range, the mold releasability is excellent, and mold contamination can be suppressed.

The polyolefin wax has a crystallization temperature (Tc (° C.) measured by a differential scanning calorimeter (DSC), measured at a temperature drop rate of 2 ° C./min) and a density (D (kg / kg) measured by a density gradient tube method). m ³ )) and the following formula (Ib), preferably the following formula (Ia), more preferably the following formula (Ib)
) Is preferably satisfied.

0.501 × D-366 ≧ Tc (I)
0.501 × D-366.5 ≧ Tc (Ia)
0.501 × D-367 ≧ Tc (Ib)
If the crystallization temperature (Tc) and density (D) of the polyolefin wax satisfy the relationship of the above formula, the comonomer composition of the polyolefin wax becomes more uniform, and as a result, the sticky component of the thermoplastic resin, particularly polyolefin, decreases. The tackiness of a mixture or composition containing a thermoplastic resin and a 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, and even more preferably 15 dmm or less. The penetration is a value measured according to JIS 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. When the acetone extraction amount is within the above range, the mold releasability is excellent and mold contamination can be suppressed.

  In addition, the acetone extraction amount is a value measured as follows. Using a filter (made by ADVANCE, No. 84) in a Soxhlet extractor (made of glass), 200 ml of acetone is placed in a lower round bottom flask (300 ml), and extraction is performed in a 70 ° C. water bath for 5 hours. . The initial wax is set to 10 g on the filter.

The polyolefin wax is solid at room temperature and becomes a low-viscosity liquid at 65 to 130 ° C.
The polyolefin wax includes, for example, (A) a metallocene compound of a transition metal selected from Group 4 of the periodic table,
(B) (b-1) an organoaluminum oxy compound, (b-2) at least one selected from a compound that reacts with the metallocene compound (A) to form an ion pair, and (b-3) an organoaluminum compound. It is preferable to manufacture using the olefin polymerization catalyst which consists of these compounds. In particular, when producing a polyolefin wax having a small Mw / Mn, a metallocene catalyst is effective.

(A) Metallocene compounds of transition metals selected from Group 4 of the periodic table:
The metallocene compound that forms the metallocene catalyst is a metallocene compound of a transition metal selected from Group 4 of the periodic table, and specific examples include compounds represented by the following formula (1).

M ¹ Lx (1)
Here, M ¹ is a transition metal selected from Group 4 of the periodic table, x is a valence of the transition metal M ¹ , and L is a ligand. Examples of the transition metal represented by M ¹ include zirconium, titanium, hafnium and the like. L is a ligand coordinated to the transition metal M ^1, and at least one of the ligands L is a ligand having a cyclopentadienyl skeleton, and the ligand having this cyclopentadienyl skeleton. The ligand may have a substituent. Examples of the ligand L having a cyclopentadienyl skeleton include a cyclopentadienyl group, a methylcyclopentadienyl group, an ethylcyclopentadienyl group, an n- or i-propylcyclopentadienyl group, n-, alkyl such as i-, sec- or t-butylcyclopentadienyl group, dimethylcyclopentadienyl group, methylpropylcyclopentadienyl group, methylbutylcyclopentadienyl group, methylbenzylcyclopentadienyl group, An alkyl-substituted cyclopentadienyl group; and an indenyl group, a 4,5,6,7-tetrahydroindenyl group, a fluorenyl group, and the like. The hydrogen of the ligand having a cyclopentadienyl skeleton is
It may be substituted with a halogen atom or a trialkylsilyl group.

  When the metallocene compound has two or more ligands having a cyclopentadienyl skeleton as the ligand L, the ligands having two cyclopentadienyl skeletons are ethylene, propylene. Or a substituted alkylene group such as isopropylidene or diphenylmethylene; a substituted silylene group such as a silylene group or a dimethylsilylene group, a diphenylsilylene group, or a methylphenylsilylene group.

Examples of ligands other than ligands having a cyclopentadienyl skeleton (ligands having no cyclopentadienyl skeleton) L include hydrocarbon groups having 1 to 12 carbon atoms, alkoxy groups, aryloxy groups, sulfones. Acid-containing group (—SO ₃ R ¹ ), halogen atom or hydrogen atom (where 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 alkyl group) A substituted aryl group).

(Example 1 of metallocene compound)
When the metallocene compound represented by the above formula (1) has a transition metal valence of 4, for example, it is more specifically represented by the following formula (2).

R ² _k R ³ _l R ⁴ _m R ⁵ _n M ¹ (2)
Here, M ¹ is a transition metal selected from Group 4 of the periodic table, R ² is a group (ligand) having a cyclopentadienyl skeleton, and R ³ , R ⁴ and R ⁵ are each independently cyclopentadienyl. A group (ligand) having or not having a skeleton. k is an integer of 1 or more, and k + l + m + n = 4.

Examples of metallocene compounds in which M ¹ is zirconium and contains at least two ligands having a cyclopentadienyl skeleton are given below. Bis (cyclopentadienyl) zirconium monochloride monohydride, bis (cyclopentadienyl) zirconium dichloride, bis (1-methyl-3-butylcyclopentadienyl) zirconium bis (trifluoromethanesulfonate), bis (1, 3-dimethylcyclopentadienyl) zirconium dichloride and the like.

Among the above compounds, a compound in which the 1,3-position substituted cyclopentadienyl group is replaced with a 1,2-position substituted cyclopentadienyl group can also be used.
As another example of the metallocene compound, in the above formula (2), at least two of R ² , R ³ , R ⁴ and R ⁵ , for example, R ² and R ³ are groups having a cyclopentadienyl skeleton (coordination A bridge-type metallocene compound in which at least two groups are bonded via an alkylene group, a substituted alkylene group, a silylene group, a substituted silylene group, or the like. At this time, R ⁴ and R ⁵ are each independently the same as the ligand L other than the ligand having the cyclopentadienyl skeleton described above.

  Examples of such bridge-type metallocene compounds include ethylenebis (indenyl) dimethylzirconium, ethylenebis (indenyl) zirconium dichloride, isopropylidene (cyclopentadienyl-fluorenyl) zirconium dichloride, diphenylsilylenebis (indenyl) zirconium dichloride, methyl Examples include phenylsilylene bis (indenyl) zirconium dichloride.

(Example 2 of metallocene compound)
Another example of the metallocene compound is a metallocene compound represented by the following formula (3) described in JP-A-4-268307.

Here, M ¹ is a periodic table Group 4 transition metal, specifically, titanium, zirconium,
Hafnium is mentioned.
R ¹¹ and R ¹² may be the same or different from each other, and are a hydrogen atom; an alkyl group having 1 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; Aryloxy group having 6 to 10 carbon atoms; alkenyl group having 2 to 10 carbon atoms; arylalkyl group having 7 to 40 carbon atoms; alkylaryl group having 7 to 40 carbon atoms; arylalkenyl 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 ¹⁴ may be the same or different from each other, and are a hydrogen atom; a halogen atom; an optionally halogenated alkyl group having 1 to 10 carbon atoms; an aryl group having 6 to 10 carbon atoms; (R ²⁰ ) ₂ , —SR ²⁰ , —OSi (R ²⁰ ) ₃ , —Si (R ²⁰ ) ₃ or —P (R ²⁰
₂ ) Here, R ²⁰ is a halogen atom, preferably a chlorine atom;
, Preferably an alkyl group having 1 to 3; 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 a hydrogen atom is not contained, and may be the same or different from each other, and are preferably the same. R ¹⁵ and R ¹⁶ are preferably an optionally halogenated alkyl group having 1 to 4 carbon atoms, specifically, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, trifluoromethyl and the like. Particularly preferred is methyl.

In the above formula (3), R ¹⁷ is selected from the following group.

= BR ²¹ , = AlR ²¹ , -Ge-, -Sn-, -O-, -S-, = SO, = SO ₂ , = N
R ²¹ , = CO, = PR ²¹ , = P (O) R ^{21 and the} like.
M ² is silicon, germanium or tin, preferably silicon or germanium.
Here, R ²¹ , R ²² and R ²³ may be the same or different from each other, and are hydrogen atom; halogen atom; alkyl group having 1 to 10 carbon atoms; fluoroalkyl group having 1 to 10 carbon atoms; carbon atom An aryl group having 6 to 10 carbon atoms; a fluoroaryl group having 6 to 10 carbon atoms; an alkoxy group having 1 to 10 carbon atoms; an alkenyl group having 2 to 10 carbon atoms; an arylalkyl group having 7 to 40 carbon atoms; An arylalkenyl 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 form a ring together with the atoms to which they are bonded. R ¹⁷ may be = CR ²¹ R ²² , = SiR ²¹ R ²² , = GeR ²¹ R ²² , -O-, -S-, = SO, = PR ²¹ or = P (O) R ^21. preferable. 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.

  Examples of the metallocene compound represented by the above formula (3) include the following compounds. rac-ethylene (2-methyl-1-indenyl) 2-zirconium dichloride, rac-dimethylsilylene (2-methyl-1-indenyl) 2-zirconium dichloride, and the like. These metallocene compounds can be produced, for example, by the method described in JP-A-4-268307.

(Example 3 of metallocene compound)
Moreover, the metallocene compound represented by the following formula (4) can also be used as the metallocene compound.

In Formula (4), M ³ represents a transition metal atom of Group 4 of the periodic table, and specifically, titanium, zirconium, hafnium, and the like. R ²⁴ and R ²⁵ may be the same or different and are each 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 A containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group; R ²⁴ is preferably a hydrocarbon group, and 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, and are 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 of R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , and R ²⁸ and R ²⁹ may form a monocyclic aromatic ring together with the carbon atoms to which they are bonded. Good. 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, it is preferably a hydrogen atom. X ¹
And X ² may be the same or different from each other, and are a hydrogen atom, a halogen atom, or a carbon atom of 1
-20 hydrocarbon group, a C1-C20 halogenated hydrocarbon group, an oxygen atom containing group, or a sulfur atom containing group is shown. 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 ₂ —, —NR ³⁰ —
^{, -P (R 30) -,} - P (O) (R 30) -, - BR 30 - or -AlR ³⁰ - (provided that, R ³⁰ is a hydrogen atom, a halogen atom, a hydrocarbon having 1 to 20 carbon atoms Group, a halogenated hydrocarbon group having 1 to 20 carbon atoms).

In formula (4), it contains a monocyclic aromatic ring formed by bonding at least one of R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ to each other, and coordinates to M ³ Examples of the ligand to be used include those represented by the following formula.

In the formula, Y is the same as that shown in formula (4).
(Example 4 of metallocene compound)
Moreover, the metallocene compound represented by the following formula (5) can also be used as the metallocene compound.

In the formula (5), M ³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are the same as in the above formula (4). Of R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ , two groups including R ²⁶ are preferably alkyl groups, and R ²⁶ and R ²⁸ , or R ²⁸ and R ²⁹ are alkyl groups. preferable. This alkyl group is preferably a secondary or tertiary alkyl group. The alkyl group may be substituted with a halogen atom or a silicon-containing group. Examples of the halogen atom and silicon-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. R ²⁶ , R ²⁷ , R ^28, and R ²⁹ may form a monocyclic ring or a polycyclic ring other than an aromatic ring by combining two groups selected from these groups. Examples of the halogen atom are the same as those described above for R ²⁴ and R ²⁵ . Examples of X ¹ , X ² and Y are the same as those described above.

  Specific examples of the metallocene compound represented by the above formula (5) are shown below. rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2,4,7-trimethyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2 , 4,6-trimethyl-1-indenyl) 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. The transition metal compound is usually used as a racemate, but can also be used in the R-type or S-type.

(Example of metallocene compound-5)
Moreover, the metallocene compound represented by following formula (6) can also be used as a metallocene compound.

In the formula (6), M ³ , R ²⁴ , X ¹ , X ² and Y are the same as in the above 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 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.

Specific examples of the metallocene compound represented by the above formula (6) are shown below. rac-dimethylsilylene-bis (4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4-phenyl-1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl) -4- (α-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2-methyl-4- (β-naphthyl) -1-indenyl) zirconium dichloride, rac-dimethylsilylene-bis (2 -Methyl-4- (1-anthryl) -1-indenyl) 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.

(Example of metallocene compound-6)
Further, as the metallocene compound, a metallocene compound represented by the following formula (7) can also be used.

LaM ⁴ X ³ ₂ (7)
Here, M ⁴ is a periodic table group 4 or lanthanide series metal. La is a derivative of a delocalized π bond group, and is a group that imparts a constraining geometry to the metal M ⁴ active site. X ³ may be the same or different from each other, and 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.

  Among these compounds, a compound represented by the following formula (8) is preferable.

In the formula (8), M ⁴ is titanium, zirconium or hafnium. X ³ is the same as that described in the above formula (7). Cp is a substituted cyclopentadienyl group having a π bond to M ⁴ and having a substituent Z. Z is oxygen, sulfur, boron or an element belonging to Group 4 of the periodic table (for example, silicon, germanium or tin). Y is a ligand containing nitrogen, phosphorus, oxygen or sulfur, and Z and Y may form a condensed ring. Specific examples of the metallocene compound represented by the formula (8) are shown below. (Dimethyl (t-butylamide) (tetramethyl-η5-cyclopentadienyl) silane) titanium dichloride, ((t-butylamide) (tetramethyl-η5-cyclopentadienyl) -1,2-ethanediyl) titanium dichloride, etc. . In the metallocene compound, a compound in which titanium is replaced with zirconium or hafnium can be exemplified.

(Example 7 of metallocene compound)
Further, as the metallocene compound, a metallocene compound represented by the following formula (9) can also be used.

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 as or different from each other, and at least one of them is an aryl group having 11 to 20 carbon atoms, an arylalkyl group having 12 to 40 carbon atoms, an arylalkenyl group having 13 to 40 carbon atoms, carbon An alkylaryl group having 12 to 40 atoms or a silicon-containing group, or at least two adjacent groups among the groups represented by R ³¹ , together with the carbon atoms to which they are bonded, one or more aromatic rings Or an aliphatic ring is formed. In this case, the ring formed by R ^31, it is 4 to 20 carbon atoms in all including carbon atoms to which R ³¹ is bonded. Aryl group, arylalkyl group, arylalkenyl group, an alkylaryl 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 having 1 to 10 carbon atoms Or a silicon-containing group. R ³² may be the same as or different from each other, and may be 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 10 carbon atoms, or a carbon atom. An arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group It is. Further, at least two adjacent groups among 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 has 4 to 20 carbon atoms in all including carbon atoms to which R ³² is bonded, an aromatic ring, other than R ³² that forms an aliphatic ring R ³² is a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, or a silicon-containing group. 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 represented by the following formula.

R ³² 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-fluorenyl group. In this case, the 2,7-dialkyl alkyl group has 1 to 1 carbon atoms. 5 alkyl groups. R ³¹ and R ³² may be the same as or different from each other. R ³³ and R ³⁴ may be the same as or different from each other, and are the same hydrogen atom, halogen atom, alkyl group having 1 to 10 carbon atoms, aryl group having 6 to 20 carbon atoms, and 2 to 2 carbon atoms. 10 alkenyl groups, arylalkyl groups having 7 to 40 carbon atoms, arylalkenyl groups having 8 to 40 carbon atoms, alkylaryl groups having 7 to 40 carbon atoms, silicon-containing groups, oxygen-containing groups, sulfur-containing groups, A nitrogen-containing group or a phosphorus-containing group. Of these, at least one of 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 and are each 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, sulfur A conjugated diene residue formed from a containing group or a nitrogen-containing group, or X ¹ and X ² . The conjugated diene residue formed from X ¹ and X ² is preferably a residue of 1,3-butadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene, or 1,4-diphenylbutadiene. 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 sulfur-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, —O—, —CO—, —S—, —SO—, —SO ₂ —
^{, -NR 35 -, - P (} R 35) -, - P (O) (R 35) -, - BR 35 - or -AlR ³⁵ - (provided that, R ³⁵ is a hydrogen atom, a halogen atom, C 1 -C -20 hydrocarbon groups and halogenated hydrocarbon groups having 1 to 20 carbon atoms). Among these divalent groups, those in which the shortest connecting portion of -Y- is composed of one or two atoms are preferable. 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, more preferably a divalent silicon-containing group. Particularly preferred is silylene, alkylarylsilylene or arylsilylene.

(Example of metallocene compound-8)
Further, as the metallocene compound, a metallocene compound represented by the following formula (10) can also be used.

In formula (10), 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 as or different from each other, and includes a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and silicon-containing Group, oxygen-containing group, sulfur-containing group, nitrogen-containing group or phosphorus-containing group. The alkyl group and alkenyl group may be substituted with a halogen atom. Of these, 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, phenyl, α-naphthyl. And an aryl group such as β-naphthyl or a hydrogen atom. R ³⁷ may be the same or different from each other, and may be 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 10 carbon atoms, or a carbon atom. An arylalkyl group having 7 to 40 carbon atoms, an arylalkenyl group having 8 to 40 carbon atoms, an alkylaryl group having 7 to 40 carbon atoms, a silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group It is. Note that the alkyl group, aryl group, alkenyl group, arylalkyl group, arylalkenyl group, and alkylaryl group may be substituted with halogen. Of these, R ³⁷ is preferably a hydrogen atom or an alkyl group, and particularly a hydrogen atom or a carbon atom having 1 to 4 carbon atoms such as methyl, ethyl, n-propyl, i-propyl, n-butyl, or tert-butyl. A hydrogen group is preferred. 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, an alkyl group having 1 to 10 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. A silicon-containing group, an oxygen-containing group, a sulfur-containing group, a nitrogen-containing group or a phosphorus-containing group. Among these, it is preferable that any 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 and are each 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, sulfur A conjugated diene residue formed from a containing group or a nitrogen-containing group, or X ¹ and X ² . Among 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 ₂ —, —NR ⁴⁰ —, —P (R ⁴⁰ )
-, - P (O) ( R 40) -, - BR 40 - or -AlR ⁴⁰ - (provided that, R ⁴⁰ is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, 1 to carbon atoms 20 halogenated hydrocarbon groups). Among these, 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. An alkylsilylene, an alkylarylsilylene or an arylsilylene is particularly preferable.

(Example 9 of metallocene compound)
A metallocene compound represented by the following formula (11) can also be used as the metallocene compound.

In the formula (11), Y is selected from carbon, silicon, germanium and tin atoms, M is Ti, Zr or Hf, and R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰
R ¹¹ 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 R ⁵ to R ¹² are 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 from each other, 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 anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair in the same or different combination, and j is an integer of 1 to 4. )
Hereinafter, after describing sequentially the cyclopentadienyl group, the fluorenyl group, the bridge | crosslinking part, and other characteristics which are the characteristics on the chemical structure of the metallocene compound used for this invention, the preferable metallocene compound which has these characteristics is demonstrated.

(Cyclopentadienyl group)
The cyclopentadienyl group may or may not be substituted. The substituted or unsubstituted cyclopentadienyl group means that R ¹ , R ² , R ³ and R ⁴ possessed by the cyclopentadienyl group moiety in the formula (11) are all hydrogen atoms, or R ¹ , R ² , R ³ and R ⁴ are each a hydrocarbon group (f1), preferably a hydrocarbon group having 1 to 20 carbon atoms (f1 ′), or a silicon-containing group (f2) , Preferably a cyclopentadienyl group substituted with a silicon-containing group (f2 ′) having a total carbon number of 1 to 20. R ¹ ,
When two or more of R ² , R ³ and R ⁴ are substituted, these substituents may be the same as or different from each other. Further, the hydrocarbon group having 1 to 20 carbon atoms in total is an alkyl group, alkenyl group, alkynyl group, or aryl group composed of only carbon and hydrogen. These include 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 (f1 ′) includes, in addition to an alkyl group, an alkenyl group, an alkynyl group, and an aryl group composed of only carbon and hydrogen, a part of hydrogen atoms directly connected to these carbon atoms. Includes a heteroatom-containing hydrocarbon group substituted with a halogen atom, an oxygen-containing group, a nitrogen-containing group or a silicon-containing group, or a group in which any two adjacent hydrogen atoms form an alicyclic group. As such a hydrocarbon group (f1 ′), a methyl group, an ethyl group, an n-propyl group, an allyl group, an n-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, linear hydrocarbon group such as n-octyl group, n-nonyl group, n-decanyl group; isopropyl group, t-butyl group, amyl group, 3-methylpentyl group, 1,1-diethylpropyl group, 1, 1-dimethylbutyl group, 1-methyl-1-propylbutyl group, 1,1-propylbutyl group, 1,1-dimethyl-2-methylpropyl group, 1-methyl-1-isopropyl-2-methylpropyl group, etc. A branched hydrocarbon group of: cyclic saturated hydrocarbon group such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, naphthy Group, biphenyl group, phenanthryl group, cyclic unsaturated hydrocarbon group such as anthracenyl group and their nuclear alkyl substituents; saturated hydrocarbon group substituted with aryl group such as benzyl group, cumyl group; methoxy group, ethoxy group, phenoxy Mention may be made of heteroatom-containing hydrocarbon groups such as the group N-methylamino group, trifluoromethyl group, tribromomethyl group, pentafluoroethyl group, pentafluorophenyl group.

  The silicon-containing group (f2) is, for example, a group in which a ring carbon of a cyclopentadienyl group is directly covalently bonded to a silicon atom, and specifically an alkylsilyl group or an arylsilyl group. Examples of the silicon-containing group (f2 ′) having 1 to 20 carbon atoms include a trimethylsilyl group and a triphenylsilyl group.

(Fluorenyl group)
The fluorenyl group may or may not be substituted. The substituted or unsubstituted fluorenyl group means that all of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² possessed by the fluorenyl group moiety in the above formula (11) are hydrogen atoms. Or at least one of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² is a hydrocarbon group (f1), preferably having a total carbon number of 1 Means a fluorenyl group substituted with a hydrocarbon group (f1 ′) from 1 to 20 or a silicon-containing group (f2), preferably a silicon-containing group (f2 ′) having a total carbon number of 1 to 20. When two or more of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are substituted, these substituents may be the same or different from each other. Good. Further, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² may be bonded to each other to form a ring. R ⁶ and R ¹¹ , and those in which R ⁷ and R ¹⁰ are identical to each other are preferably used because of ease of catalyst production.

  The preferred hydrocarbon group (f1) is the hydrocarbon group (f1 ′) having 1 to 20 carbon atoms, and the preferred silicon-containing group (f2) is silicon having 1 to 20 carbon atoms. It is a containing group (f2 ′).

(Covalent bond)
The main chain part of the bond connecting the cyclopentadienyl group and the fluorenyl group is a divalent covalent bond containing one carbon, silicon, germanium and tin atom. An important point in 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 (f1) is the hydrocarbon group (f1 ′) having 1 to 20 carbon atoms, and the preferred silicon-containing group (f2) is silicon having 1 to 20 carbon atoms. It is a containing group (f2 ′).

(Other features of metallocene compounds)
In the formula (11), Q can be coordinated by halogen, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene, anionic ligand or lone electron pair having 10 or less carbon atoms. The neutral ligands 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, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-diethylpropyl, 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 can be mentioned. Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated dienes, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ⁴ - 1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3-methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4- Dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene, s-cis- or s
-Trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -1, 4-bis (trimethylsilyl) -1,3-butadiene and the like can be mentioned. Specific examples of the anionic 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 the neutral ligand that can coordinate with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. j is an integer of 1 to 4, and when j is 2 or more, Qs may be the same or different from each other.

(Example of metallocene compound-10)
Further, as the metallocene compound, a metallocene compound represented by the following formula (12) can also be used.

In the formula, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² , R ¹³ , R ¹⁴ are hydrogen or a hydrocarbon group. Selected from silicon-containing groups, which may be the same or different, and adjacent substituents from R ¹ to R ¹⁴ may be bonded to each other to form a ring, and M is Ti,
Zr or Hf, Y is a Group 14 atom, Q is a halogen, a hydrocarbon group, neutral with 10 or less carbon atoms, conjugated or nonconjugated diene, anionic ligand, and coordination with a lone pair They are selected from the group consisting of possible neutral ligands in the same or different combinations, n is an integer of 2 to 4, and j is an integer of 1 to 4.

  In the above formula (12), the hydrocarbon group is preferably an alkyl group having 1 to 20 carbon atoms, an arylalkyl group having 7 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an alkyl group having 7 to 20 carbon atoms. An alkylaryl group that 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-diethylpropyl, 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, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, naphthyl, tolyl, etc. Can be mentioned.

  In the above formula (12), the silicon-containing hydrocarbon group is preferably an alkyl or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms. Specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl. , Triphenylsilyl and the like.

In the present invention, R ¹ to R ^{14 in} the formula (12) are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different. Specific examples of preferred hydrocarbon groups and silicon-containing hydrocarbon groups include the same as those described above.

The adjacent substituents from R ¹ to R ¹⁴ on the cyclopentadienyl ring of the above formula (12) are
They may combine with each other to form a ring.
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 the same or different combination from the group consisting of halogen, hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or non-conjugated diene, anionic ligand and neutral ligand capable of coordinating with a lone electron pair. To be elected. When Q is a hydrocarbon group, it is more preferably a hydrocarbon group having 1 to 10 carbon atoms.

Specific examples of the halogen include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2, 2-dimethylpropyl, 1,1-diethylpropyl, 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 can be mentioned. Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated dienes, s- cis - or s- trans eta ^{4-1,3-butadiene,} s- cis - or s- trans eta ⁴ - 1,4-diphenyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -3
-Methyl-1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-dibenzyl-1,3-butadiene, s-cis- or s-trans-η ⁴ -2,4-hexadiene , S-cis- or s-trans-η ⁴ -1,3-pentadiene, s-cis- or s-trans-η ⁴ -1,4-ditolyl-1,3-butadiene, s-cis- or s- Examples include trans-η ⁴ -1,4-bis (trimethylsilyl) -1,3-butadiene. Specific examples of the anionic 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 the neutral ligand that can coordinate with a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, and diphenylmethylphosphine, or tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. When j is an integer greater than or equal to 2, several Q may be the same or different.

In Formula (12), there are a plurality of Ys of 2 to 4, but the Ys may be the same 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. R ¹³ or R ¹⁴ may form a ring.

  Preferable examples of the Group 4 transition metal compound represented by the formula (12) include a compound represented by the following formula (13).

In the formula (13), R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ , R ¹² are hydrogen atoms, hydrocarbon groups, silicon R ¹³ , R ¹⁴ , R ¹⁵ , R ¹⁶ are hydrogen atoms or hydrocarbon groups, n is an integer of 1 to 3, and n = 1. In some cases, R ¹ to R ¹⁶ are not simultaneously hydrogen atoms but 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, R ¹³ and R ¹⁵ may be bonded to each other to form a ring, and R ¹³ and R ¹⁵ are R ¹⁴ and R ¹⁶ may combine with each other to form a ring by bonding to each other to form a ring, and Y ¹ and Y ² are group 14 atoms which may be the same or different from each other. Is Ti, Zr or Hf, Q may be selected from halogen, hydrocarbon group, anionic ligand or neutral ligand capable of coordinating with a lone electron pair in the same or different combination, and j is 1-4 Is an integer.

  Examples of such metallocene compounds such as Examples-9 and 10 are listed in JP-A No. 2004-175707, WO2001 / 027124, WO2004 / 029062, WO2004 / 083265, and the like.

  The metallocene compounds described above are used alone or in combination of two or more. The metallocene compound may be diluted with a hydrocarbon or a halogenated hydrocarbon.

(B-1) Organoaluminum oxy compound:
In the present invention, a conventionally known aluminoxane can be used as it is as the organoaluminum oxy compound (b-1). Specific examples of such a known aluminoxane include compounds represented by the following formula (14) or the following formula (15).

(In the formula, R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more.)
Among these compounds, those in which R is a methylaluminoxane where R is a methyl group and n is 3 or more, preferably 10 or more are preferred. These aluminoxanes may be mixed with some organoaluminum compounds.

  In the case of performing high temperature solution polymerization, a benzene-insoluble organoaluminum oxy compound exemplified in JP-A-2-78687 can also be applied. Further, organoaluminum oxy compounds described in JP-A-2-167305, aluminoxanes having two or more kinds of alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like are also included. It can be suitably used. The “benzene insoluble” in the organoaluminum oxy compound means that the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms. It is insoluble or hardly soluble.

  In addition, examples of the organoaluminum oxy compound (b-1) used in the present invention include modified methylaluminoxane having the following structure (16).

(Here, 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 generally called MMAO. Such MMAO can be prepared by the methods listed in US Pat. No. 4,960,878 and US Pat. No. 5,041,584.

  In addition, modified methylaluminoxane prepared by using trimethylaluminum and triisobutylaluminum from Tosoh Finechem Co., Ltd. and having R as an isobutyl group is commercially produced under the names MMAO and TMAO.

  Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability. Specifically, the MMAO is insoluble or hardly soluble in benzene as in the above formulas (14) and (15). Unlike, it dissolves in aliphatic hydrocarbons and alicyclic hydrocarbons.

  Furthermore, examples of the organoaluminum oxy compound (b-1) used in the present invention include an organoaluminum oxy compound containing boron represented by the following formula (17).

(In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same as or different from each other, and is a hydrogen atom, a halogen atom or a hydrocarbon having 1 to 10 carbon atoms. Group.)
(B-2) A compound that reacts with the metallocene compound (A) to form an ion pair:
Examples of the compound (b-2) (hereinafter sometimes abbreviated as “ionic compound”) that forms an ion pair by reacting with the metallocene compound (A) include JP-A-1-501950 and JP-A-1. Lewis described in JP-502036, JP-A-3-179005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, US Pat. No. 5,321,106, and the like. Examples thereof include acids, ionic compounds, borane compounds and carborane compounds. Furthermore, heteropoly compounds and isopoly compounds can also be mentioned.

  In the present invention, the ionic compound preferably employed is a compound represented by the following general formula (18).

In the formula, R ^{e +} includes H ⁺ , carbenium cation, oxonium cation, ammonium cation, phosphonium cation, cycloheptyltrienyl cation, ferrocenium cation having a transition metal, and the like. R ^{f to} R ⁱ may be the same as or different from each other, and are an organic group, preferably an aryl group.

  Specific examples of the carbenium cation include trisubstituted carbenium cations such as triphenylcarbenium cation, tris (methylphenyl) carbenium cation, and tris (dimethylphenyl) carbenium cation.

  Specific examples of the ammonium cation include trialkylammonium cations such as trimethylammonium cation, triethylammonium cation, tri (n-propyl) ammonium cation, triisopropylammonium cation, tri (n-butyl) ammonium cation, and triisobutylammonium cation. N, N-dimethylanilinium cation, N, N-diethylanilinium cation, N, N-2,4,6-pentamethylanilinium cation, etc., N, N-dialkylanilinium cation, diisopropylammonium cation, dicyclohexyl And dialkyl ammonium cations such as ammonium cations.

  Specific examples of the phosphonium cation include triarylphosphonium cations such as triphenylphosphonium cation, tris (methylphenyl) phosphonium cation, and tris (dimethylphenyl) phosphonium cation.

Among the above, as R ^{e +} , a carbenium cation, an ammonium cation, and the like are preferable, and a triphenylcarbenium cation, an N, N-dimethylanilinium cation, and an N, N-diethylanilinium cation are particularly preferable.

  Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methyl). And phenyl) carbenium tetrakis (pentafluorophenyl) borate, tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate, and the like.

Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and the like.
Examples of the trialkyl-substituted ammonium salt include triethylammonium tetraphenylborate, tripropylammonium tetraphenylborate, tri (n-butyl) ammonium tetraphenylborate, trimethylammonium tetrakis (p-tolyl) borate, trimethylammonium tetrakis (o-tolyl). ) Borate, tri (n-butyl) ammonium tetrakis (pentafluorophenyl) borate, triethylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (pentafluorophenyl) borate, tripropylammonium tetrakis (2,4-dimethylphenyl) ) Borate, tri (n-butyl) ammonium tetrakis (3,5-dimethylphenyl) bore Tri (n-butyl) ammonium tetrakis (4-trifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o -Tolyl) borate, dioctadecylmethylammonium tetraphenylborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, di Octadecylmethylammonium tetrakis (2,4-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate , Dioctadecyl methyl ammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecyl methyl ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, such as dioctadecyl methyl ammonium.

  Examples of N, N-dialkylanilinium salts include N, N-dimethylanilinium tetraphenylborate, N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate, N, N-dimethylanilinium tetrakis (3,5 -Ditrifluoromethylphenyl) borate, N, N-diethylanilinium tetraphenylborate, N, N-diethylanilinium tetrakis (pentafluorophenyl) borate, N, N-diethylanilinium tetrakis (3,5-ditrifluoromethyl) Phenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate and the like.

  Examples of the dialkyl ammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

Furthermore, an ionic compound disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can also be used without limitation.
Two or more ionic compounds (b-2) as described above can be used in combination.

(B-3) Organoaluminum compound:
Examples of the (a-3) organoaluminum compound forming the olefin polymerization catalyst include 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.

R ^a _m Al (OR ^b ) _n H _p X _q (19)
(In the formula, R ^a and R ^b may be the same or different from each other, each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, 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 of 0 ≦ q <3, and m + n + p + q = 3.)
M ² AlR ^a ₄ (20)
(In the formula, M ² represents Li, Na or K, and R ^a represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms.)
Specific examples of the compound represented by the above formula (19) include tri-n-alkylaluminum such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum; triisopropylaluminum, triisobutylaluminum, Tri-branched alkylaluminums such as tri-sec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; tricyclohexylaluminum, tricyclooctylaluminum and the like Cycloalkylaluminum; Triarylaluminum such as triphenylaluminum and tolylaluminum; diisopropyl Aluminum hydride, diisobutyl aluminum dialkyl hydride such as hydride; formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z ( wherein, x, y, z are each a positive number, z ≦ 2x.) Alkenyl aluminum such as isoprenyl aluminum, etc .; alkyl aluminum alkoxide such as isobutyl aluminum methoxide and isobutyl aluminum ethoxide; dialkyl aluminum such as dimethyl aluminum methoxide, diethyl aluminum ethoxide and dibutyl aluminum butoxide alkoxide; Table etc. general formula _{^{R a 2.5 Al (OR b)}} 0.5; ethylaluminum sesquichloride ethoxide, butyl aluminum sesqui butoxide alkyl sesquichloride alkoxides such as A partially alkoxylated alkylaluminum having an average composition of: aluminium alkyloxide such as diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide); dimethylaluminum chloride, diethyl Dialkylaluminum halides such as aluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquihalides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; alkylaluminum dihalides such as ethylaluminum dichloride Partially halogenated alkylaluminum such as die Dialkyl aluminum hydrides such as til aluminum hydride and dibutyl aluminum hydride; Other partially hydrogenated alkyl aluminums such as alkyl aluminum dihydride such as ethyl aluminum dihydride and propyl aluminum dihydride; Ethyl aluminum ethoxy chloride and butyl aluminum butoxy chloride And partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxybromide.

Specific examples of the compound represented by the above formula (20) include LiAl (C ₂ H ₅ ) ₄ , LiAl (
C ₇ H ₁₅ ) _{4 and the} like can be exemplified. Moreover, the compound similar to the compound represented by the said General formula (20) can also be used, For example, the organoaluminum compound which two or more aluminum compounds couple | bonded through the nitrogen atom can be mentioned. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂ .

From the viewpoint of availability, trimethylaluminum and triisobutylaluminum are preferably used as the (b-3) organoaluminum compound.
(polymerization)
The polyolefin wax used in the present invention can be obtained by homopolymerizing ethylene or α-olefin in a normal liquid phase or copolymerizing ethylene and α-olefin in the presence of the metallocene catalyst. In the polymerization, the method of using each component and the order of addition are arbitrarily selected, and the following methods are exemplified.

[Q1] A method of adding the component (A) alone to the polymerization vessel.
[Q2] A method of adding the component (A) and the component (B) to the polymerization vessel in an arbitrary order.
In the method [q2], at least two or more of the catalyst components may be in contact with each other in advance. At this time, a hydrocarbon solvent is generally used, but an α-olefin may be used as a solvent. The monomers used here are as described above.

The polymerization method includes suspension polymerization in which polyolefin wax is polymerized in the presence of particles in a solvent such as hexane, gas phase polymerization in which a solvent is not used, and polymerization temperature of 140 ° C. or higher. Solution polymerization that polymerizes in the coexistence or melted state is possible, and among these, solution polymerization is preferable in terms of both economy and quality.

The polymerization reaction may be performed 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.
When the olefin polymerization is carried out using the olefin polymerization catalyst as described above, the component (A) is usually 10 ⁻⁹ to 10 ⁻¹ mol, preferably 10 ⁻⁸ to 10 ⁻² , per liter of the reaction volume. It is used in such an amount that it becomes a mole.

  In the component (b-1), the molar ratio [(b-1) / M] of the component (b-1) and all transition metal atoms (M) in the component (A) is usually 0.01 to 5, 000, preferably 0.05 to 2,000. In the component (b-2), the molar ratio [(b-2) / M] of the ionic compound in the component (b-2) and the total transition metal (M) in the component (A) is usually 0. .5 to 5,000, preferably 1 to 2,000. The component (b-3) has a molar ratio [(b-3) / M] of the component (b-3) and the transition metal atom (M) in the component (A) of usually 1 to 10,000, preferably It is used in an amount of 1 to 5000.

In the polymerization reaction, the temperature is usually −20 to + 200 ° C., preferably 50 to 180 ° C., more preferably 70 to 180 ° C., and the pressure usually exceeds 0 to 7.8 MPa (80 kgf / cm ²
, Gauge pressure) or less, preferably 0 to 4.9 MPa (50 kgf / cm ² , gauge pressure) or less.

  In the presence of the metallocene catalyst, ethylene and / or α-olefin is supplied to polymerize them. At this time, a molecular weight regulator such as hydrogen may be added. When polymerized in this manner, the produced polymer is usually obtained as a polymerization solution containing the polymer, so that a polyolefin wax can be obtained by treatment by a conventional method.

As the metallocene catalyst, a catalyst containing a metallocene compound shown in (Example 6 of metallocene compound) is particularly preferable.
<Mixture of thermoplastic resin and polyolefin wax>
The thermoplastic resin and the polyolefin wax may be mixed (preliminarily mixed) in advance 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 mixed. May be. In any of the above cases, a mixture of a thermoplastic resin and a polyolefin wax is formed at the time of injection. The premixing method is not particularly limited, and may be melt mixing or dry blending. In addition, the above mixture includes antioxidants, ultraviolet absorbers, light stabilizers, colorants, metal soaps, plasticizers, foaming agents, fillers, anti-aging agents, flame retardants, antibacterial and antifungal agents, etc. Various additives can be mixed accordingly. In particular, the production method of the present invention can use a low-temperature foaming agent because low-temperature foaming is possible.

  As described above, in order to injection-mold a thermoplastic resin at a low temperature as compared with the case where no polyolefin wax is contained, the mixture is usually 0.5 to 100 parts by weight of the polyolefin wax with respect to 100 parts by weight of the thermoplastic resin. It is desirable to contain 15 parts by weight, preferably 1 to 10 parts by weight, more preferably 2 to 7 parts by weight.

The mixture of the thermoplastic resin and the polyolefin wax thus obtained by premixing or side feed is injection molded into a desired shape.
The said injection molding can be implemented on conventionally well-known conditions. Specifically, the molding temperature (resin temperature) is usually 180 to 400 ° C, preferably 200 to 300 ° C, more preferably 200 to 250 ° C, and the injection pressure 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
~ 60 ° C.

[Example]
EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by this Example.

[Comparative Example 1]
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 conditions]
Injection molding machine: 55ton injection molding machine (IS55EPNi1.5B) manufactured by Toshiba Machine Co., Ltd.
Molding temperature: 220 ° C
Injection pressure: 105MPa
Mold temperature: 40 ℃
Mold cooling time: 20 seconds [physical property evaluation]
(Releasability)
A flat plate (100 mm × 100 mm × 3 mm thickness) was 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 was extruded with an ejector pin. The determination was made according to the following criteria.
○: The molded product is released without resistance and does not deform.
X: The molded product is deformed due to large release resistance due to sticking to the mold.

(Flow mark)
A flat plate (100 mm × 100 mm × 3 mm thickness) was injection molded under the above conditions using the injection molding machine, and the flow mark was observed.
○: No flow mark ×: With flow mark (Tensile yield stress)
Test pieces were prepared under the above conditions using the above injection molding machine, and the tensile yield stress was measured in accordance with JIS K7161.

(Bending elastic modulus, bending strength)
Test pieces were prepared under the above conditions using the above injection molding machine, and the flexural modulus and flexural strength were measured according to JIS K7171.

(Heat-resistant)
A test piece was prepared under the above conditions using the injection molding machine, and the Vicat softening point was measured in accordance with JIS K7206.

(Impact resistance)
Test pieces were prepared under the above conditions using the above injection molding machine, and Izod impact values were measured according to JIS K7110.

[Comparative Example 2]
Except that the molding temperature was changed to 190 ° C., an injection molding of the propylene block copolymer was attempted in the same manner as in Comparative Example 1, but a short shot was obtained and a good molded product could not be obtained.

[Examples 1 and 2]
Metallocene polyethylene wax (Excellex (registered trademark) 30200BT) prepared using a metallocene catalyst in 100 parts by weight of a propylene block copolymer (trade name: Prime Polypro J704WA, manufactured by Prime Polymer Co., Ltd., crystal melting temperature: 160 ° C.) Made by Mitsui Chemicals, Inc., ethylene content 95 mol%, density: 913 kg / m ³ , average molecular weight (Mn) = 2000, molecular weight distribution (Mw / Mn) = 2.5, crystallization temperature (Tc) = 86 ° C.) 1 part by weight or 3 parts by weight was added and thoroughly mixed in a tumbler mixer to prepare a mixture of polypropylene and polyethylene wax.

  This mixture was used in place of the propylene block copolymer, the molding temperature was changed to 190 ° C., and the mold cooling time was changed to 15 seconds. The injection molding was performed in the same manner as in Comparative Example 1, and various physical properties were evaluated. . The results are shown in Table 1.

  When Examples 1 and 2 are compared with Comparative Example 1, when a polyolefin wax (metallocene wax) is added to a thermoplastic resin (polyolefin), the physical properties of the molded product are reduced even when the molding temperature is not increased by 20 ° C. It can be seen that injection molding can be performed without lowering. Further, it can be seen that the mold cooling time can be shortened.

Claims (5)

  A method for producing an injection-molded article, characterized in that a mixture containing a thermoplastic resin and a polyolefin wax is injection-molded at a molding temperature lower by 5 ° C. or more than a molding temperature when the mixture does not contain the polyolefin wax.   The method for producing an injection-molded article according to claim 1, wherein 0.1 to 15 parts by weight of the polyolefin wax is contained with respect to 100 parts by weight of the thermoplastic resin.   The method for producing an injection-molded article according to claim 1 or 2, wherein the polyolefin wax is polyethylene wax.   The method for producing an injection-molded article according to any one of claims 1 to 3, wherein the thermoplastic resin is polypropylene or polyethylene.   An injection-molded product obtained by the production method according to claim 1.