JP2007146144A - Method for producing thermoplastic resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing a thermoplastic resin composition containing a polyolefin wax excellent in dispersibility in the thermoplastic resin, a molded article excellent in physical properties such as blocking property, dynamic physical properties, etc., by using the thermoplastic resin composition and a method for producing the molded material. <P>SOLUTION: This method for producing the thermoplastic resin composition is produced by melting/kneading a mixture containing (A) particle-formed polyolefin wax consisting of ≥95 wt.% rate of passing through a mesh having 5.66 mmΦ opening of a sieve and also ≥95 wt.% rate of not passing through a mesh having 2.00 mmΦ opening of a sieve and (B) the thermoplastic resin. The molded article obtained from the thermoplastic resin composition and the method for producing the molded article are also provided. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for producing a thermoplastic resin composition, and more specifically, a method for producing a thermoplastic resin composition using a polyolefin wax having a specific shape and a thermoplastic resin, and molding from the thermoplastic resin composition. The present invention relates to a method for producing a body and a molded body obtained from the thermoplastic resin composition.

Conventionally, polyolefin waxes have been used in thermoplastic resin compositions as lubricants, mold release agents, molding aids, and the like (for example, Patent Documents 1 and 2).
The polyolefin wax is usually made into a powder form and made into a mixture with a thermoplastic resin, and this mixture is made into a thermoplastic resin composition with an extruder or the like. However, when manufactured by such a method, composition variation occurs in the mixture, and the polyolefin wax is first dissolved in the molding machine such as an extrusion molding machine as compared with the thermoplastic resin. The dispersion of the polyolefin wax in the plastic resin is not sufficient, and the performance expected as a wax addition effect such as improved mold release is not sufficient compared to the amount of the wax added, and the performance of the resulting thermoplastic resin composition There were also variations and problems.
Japanese Patent Publication No. 5-80492 Special table 2003-528948 gazette

  An object of the present invention is to provide a method for producing a thermoplastic resin composition containing a polyolefin wax excellent in dispersibility with respect to a thermoplastic resin, a method for producing a molded body using the thermoplastic resin composition, and the thermoplastic resin. It is providing the molded object obtained from a composition.

  The present inventors have studied the above-mentioned problems, and by melting and molding a mixture containing a polyolefin wax having a specific shape and a thermoplastic resin, a thermoplastic resin composition having excellent dispersibility of the polyolefin wax can be obtained. In addition, the present inventors have found that the physical properties of a molded article obtained by producing a molded article using this composition are excellent, and have completed the present invention.

That is, the method for producing the thermoplastic resin composition of the present invention comprises:
Particulate polyolefin wax (A) in which the ratio of the amount passing through a mesh with a sieve opening of 5.66 mmΦ is 95% by weight or more and the ratio of the amount passing through a mesh with a sieve opening of 2.00 mmΦ is 95% by weight It is characterized by melt-kneading a mixture containing the resin and the thermoplastic resin (B).

The polyolefin wax (A) is preferably a polyethylene wax, and more preferably a metallocene polyethylene wax.
The molded article of the present invention can be obtained by molding the thermoplastic resin composition thus obtained.

  ADVANTAGE OF THE INVENTION According to this invention, the thermoplastic resin composition excellent in the dispersibility of the polyolefin wax with respect to a thermoplastic resin is obtained. Moreover, the molded object obtained from the thermoresin obtained in this way is excellent also in physical properties, such as blocking property and a mechanical physical property.

Hereinafter, the present invention will be described in detail.
[Polyolefin wax (A)]
The polyolefin wax (A) in the present invention has a crystallization temperature measured by a differential scanning calorimeter (DSC) at a temperature drop rate of 2 ° C./min in the range of 65 to 120 ° C., and gel permeation chromatography ( The number average molecular weight (Mn) in terms of polystyrene measured by GPC) is in the range of 400 to 5,000. In addition, the polystyrene-equivalent number average molecular weight (Mn) being in the range of 400 to 5,000 is synonymous with the polyethylene equivalent number average molecular weight (Mn) being in the range of 200 to 2,500.

The molecular weight in terms of polyethylene is obtained by converting the molecular weight in terms of polystyrene by a general calibration method using a coefficient of the Mark-Houwink viscosity equation.
The coefficients of the Mark-Houwink viscosity equation are as follows.
Coefficient of polystyrene (PS): KPS = 1.38 × 10 ⁻⁴ , aPS = 0.70
Coefficient of polyethylene (PE): KPE = 0.06 × 10 ⁻⁴ , aPE = 0.70
The polyolefin wax (A) of the present invention is characterized by a specific shape.

  The polyolefin wax (A) of the present invention is a pellet-like or tablet-like particle, the ratio of the amount passing through a mesh having a sieve opening of 5.66 mmΦ is 95% by weight or more, and the sieve opening of 2.00 mmΦ. The ratio of the amount not passing through the mesh is 95% by weight.

  When the polyolefin wax (A) having such a particle shape is used, it is excellent in dispersibility when mixed with the thermoplastic resin (B) described later. Moreover, since the polyolefin wax (A) is excellent in dispersibility with respect to the thermoplastic resin (B) when these mixtures are melt-kneaded, the resulting thermoplastic resin composition has excellent properties such as blocking performance and mechanical properties.

The amount of the polyolefin wax (A) that passes through the mesh (hereinafter also referred to as “mesh pass amount”) is 95% by weight or more with a mesh opening of 5.66 mmΦ and a mesh opening of 4.75 mmΦ. It is preferably 70% by weight or more with a mesh and 40% by weight or more with a mesh having a knot opening of 4.00 mmΦ,
More preferably, it is 99% by weight or more with a mesh having a sieve opening of 5.66 mmΦ, 75% by weight or more with a mesh having a mesh opening of 4.75 mmΦ, and 45% by weight or more with a mesh having a mesh opening of 4.00 mmΦ.

The proportion of the polyolefin wax (A) that does not pass through the mesh (hereinafter also referred to as “mesh-on amount”) is 95% by weight or more with a mesh size of 2.00 mmφ and 2.83 mmφ. 80% by weight or more of the mesh and 50% by weight or more of the mesh having a sieve opening of 3.35 mmΦ,
The proportion of the polyolefin wax (A) that does not pass through the mesh is 99% by weight or more with a mesh of 2.00 mmΦ and 85% by weight or more with a mesh of 2.83 mmΦ. More preferably, it is 60% by weight or more with a mesh of 3.35 mmΦ.

When the mesh pass amount and the mesh-on amount are in the above ranges, they can be easily mixed with the thermoplastic resin (B) described later. For example, when the thermoplastic resin (B) is a pellet, a tumbler It can be easily mixed without classification by a mixer such as a mixer.

  The polyolefin wax having such a shape is obtained, for example, by melting a polyolefin wax as a raw material to a melting point or higher, dropping the molten wax onto a cooling steel belt using a tabletizer, and solidifying the wax. be able to.

  The melting temperature of the wax only needs to be equal to or higher than the melting point of the wax and can be appropriately set depending on the wax, but is usually preferably 100 to 160 ° C, more preferably 130 to 150 ° C.

  The temperature of the cooling steel belt may be not higher than the melting point of the wax and can be appropriately set depending on the wax, but is preferably 10 to 40 ° C and more preferably 15 to 30 ° C.

The speed of the cooling steel belt can be appropriately set, but is usually preferably 10 to 25 m / min, and more preferably 10 to 20 m / min.
The polyolefin wax (A) used in the present invention is not particularly limited as long as it is a polyolefin wax. For example, polyethylene wax, polypropylene wax, wax of α-olefin homopolymer, wax of ethylene / α-olefin copolymer, Examples thereof include waxes of ethylene / α-olefin / non-conjugated diene copolymer.

  In the present invention, polyethylene wax, wax of ethylene / α-olefin copolymer, and wax of ethylene / α-olefin / non-conjugated diene copolymer are sometimes collectively referred to as polyethylene wax.

  Among these polyolefin waxes, polyethylene wax and wax of ethylene / α-olefin copolymer are preferable, and polyethylene wax and wax of copolymer of ethylene and α-olefin having 3 to 20 carbon atoms are more preferable. Polyethylene wax, ethylene / propylene copolymer wax, ethylene / 1-butene copolymer wax, ethylene / 1-pentene copolymer wax, ethylene / 1-hexene copolymer wax, ethylene / 4- Methyl-1-pentene copolymer wax, ethylene / 1-octene copolymer wax are more preferable, polyethylene wax, ethylene / propylene copolymer wax, ethylene / 1-butene copolymer wax, ethylene / 1-hexene copolymer wax, A wax of ethylene / 4-methyl-1-pentene copolymer is particularly preferred.

  When the polyolefin wax (A) is the above-mentioned polyolefin wax, the dispersibility with the thermoplastic resin (B) described later, particularly the dispersibility when the thermoplastic resin (B) is a polyolefin resin is essentially excellent.

  The polystyrene-equivalent number average molecular weight (Mn) of the polyolefin wax (A) measured by gel permeation chromatography (GPC) is preferably in the range of 400 to 5,000, more preferably in the range of 700 to 4,500. The range of 800 to 4,000 is even more preferable.

  When Mn of the polyolefin wax (A) is in the above range, the effect of improving the fluidity when producing the thermoplastic resin composition is great, and a homogeneous thermoplastic resin composition can be easily obtained.

  In the present invention, the polyolefin wax (A) may be a polyolefin wax having a polyethylene-equivalent number average molecular weight (Mn) in the range of more than 2,500 and 5,000 or less.

Therefore, in a further aspect of the present invention, the polyethylene wax number average molecular weight (Mn) of the polyolefin wax (A) is preferably in the range of 200 to 5,000.
A range of 00 to 5,000 is more preferable.

  When Mn of the polyolefin wax (A) is in the above range, the effect of improving the fluidity when producing the thermoplastic resin composition is great, and a homogeneous thermoplastic resin composition can be easily obtained.

  The ratio (Mw / Mn) of polystyrene-equivalent weight average molecular weight and number average molecular weight of the polyolefin wax (A) measured by gel permeation chromatography (GPC) is preferably in the range of 1.5 to 4.0. The range of 1.5 to 3.5 is more preferable.

When Mw / Mn of the polyolefin wax (A) is in the above range, the stickiness of the surface of the molded product obtained from the thermoplastic resin of the present invention can be essentially reduced.
The crystallization temperature of the polyolefin wax (A) measured with a differential scanning calorimeter (DSC) at a temperature drop rate of 2 ° C./min is preferably in the range of 65 to 120 ° C., more preferably in the range of 70 to 120 ° C. , Particularly preferably in the range of 70-118 ° C.

When the crystallization temperature of the polyolefin wax (A) is in the above range, the stickiness of the surface of the molded product obtained from the thermoplastic resin of the present invention can be essentially reduced.
The polyolefin wax (A), density measured by the density gradient tube method in compliance with JIS K7112, preferably from 850~980kg / m ^3, more preferably in the range of 870~980kg / m ^3, 890~980kg The range of / m ³ is more preferable.

When the density of the polyolefin wax is in the above range, the molding shrinkage of the molded product obtained from the thermoplastic resin of the present invention can be easily controlled.
Furthermore, the polyolefin wax (A) has the crystallization temperature [Tc (° C.)] measured by a differential scanning calorimeter (DSC) and the density (D (kg / m ³ )) measured by the density gradient method.
Preferably the following formula (I)
0.501 × D-366 ≧ Tc (I)
More preferably, the following formula (Ia)
0.501 × D-366.5 ≧ Tc (Ia)
More preferably, the following formula (Ib)
0.501 × D-367 ≧ Tc (Ib)
Satisfy the relationship.

  When the crystallization temperature (Tc) and the density (D) in the polyolefin wax (A) satisfy the relationship of the above formula, for example, the polyolefin wax (A) is an ethylene / α-olefin copolymer wax. If so, the composition distribution of the copolymer becomes more uniform, and the tack of the molded product obtained from the thermoplastic resin composition containing the polyolefin wax (A) and the thermoplastic resin (B) described later tends to be small.

  The penetration of the polyolefin wax (A) measured in accordance with JIS K2207 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.

When the penetration of the polyolefin wax (A) is in the above range, sufficient strength can be imparted to the molded product obtained from the thermoplastic resin composition of the present invention.
The amount of acetone extracted from the polyolefin wax (A) is preferably in the range of 0 to 20% by weight, and more preferably in the range of 0 to 15% by weight.

The amount of acetone extracted is measured as follows.
Using a filter (manufactured 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. hot water bath for 5 hours. The initial wax is set to 10 g on the filter.

The polyolefin wax (A) is solid at normal temperature, and becomes a low-viscosity liquid at 65 to 130 ° C. or higher.
When the amount of acetone extracted from the polyolefin wax (A) is within the above range, the sticky component is reduced, and not only the mold mold is prevented from being stained but also a molded product having no sticky surface can be obtained.

  The method for producing the above-described polyolefin wax (A) is not particularly limited. For example, the polyolefin wax (A) can be obtained by polymerizing monomers such as ethylene and α-olefin using a Ziegler / Natta catalyst or a metallocene catalyst. Among these catalysts, metallocene catalysts are preferable.

Examples of such metallocene catalysts include:
(A) a metallocene compound of a transition metal selected from Group 4 of the periodic table, and (B) (b-1) an organoaluminum oxy compound,
(b-2) a compound that reacts with the bridged metallocene compound (A) to form an ion pair, and
(b-3) An olefin polymerization catalyst comprising at least one compound selected from organoaluminum compounds.
These will be described in detail below.

<Metalocene compounds>
(A) Metallocene compound of transition metal selected from Group 4 of the periodic table The metallocene compound forming the metallocene catalyst is a metallocene compound of transition metal selected from Group 4 of the periodic table. The compound represented by Formula (1) is mentioned.
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, 4,5,6,7-tetrahydroindenyl group, a fluorenyl group, and the like. The hydrogen of the ligand having a cyclopentadienyl skeleton 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 general formula (1) has a transition metal valence of 4, for example, it is more specifically represented by the following general 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, compounds in which the 1,3-position substituted cyclopentadienyl group is replaced with a 1,2-position substituted cyclopentadienyl group can also be used.
Another example of the metallocene compound is R ² , R ³ , R ^{4 in the} general formula (2).
And at least two of R ⁵ , for example, R ² and R ³ are groups having a cyclopentadienyl skeleton (
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>
Moreover, as an example of a metallocene compound, the metallocene compound of Unexamined-Japanese-Patent No. 4-268307 represented by following General formula (3) is mentioned.

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 groups. R ²⁰ 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 contain a hydrogen atom, and may be the same or different from each other, 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 general formula (3), R ¹⁷ is selected from the following group.

= BR ²¹ , = AlR ²¹ , -Ge-, -Sn-, -O-, -S-, = SO, = SO ₂ , =
NR 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 general 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, as a metallocene compound, the metallocene compound represented by following General formula (4) can also be used.

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
Y representing -20 hydrocarbon group, halogenated hydrocarbon group having 1 to 20 carbon atoms, oxygen atom-containing group or sulfur atom-containing group is a divalent hydrocarbon group having 1 to 20 carbon atoms, carbon atom A divalent halogenated hydrocarbon group of 1 to 20, 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 group having 1 to 20 carbon atoms , Halogenated hydrocarbon groups having 1 to 20 carbon atoms).

In the formula (4), at least one pair of R ²⁶ and R ²⁷ , R ²⁷ and R ²⁸ , R ²⁸ and R ²⁹ is bonded to each other, and is coordinated to M ³ Examples of the ligand include those represented by the following formula.

(In the formula, Y is the same as that shown in the previous formula.)
<Example 4 of metallocene compound>
As the metallocene compound, a metallocene compound represented by the following general formula (5) can also be used.

In the formula (5), M ³ , R ²⁴ , R ²⁵ , R ²⁶ , R ²⁷ , R ²⁸ and R ²⁹ are the same as those in the general 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 general formula (5) are shown below. rac-dimethylsilylene-bis (4,7-dimethyl-1-indenyl) zirconium dichloride, r
ac-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.

<Examples of metallocene compounds-5>
As the metallocene compound, a metallocene compound represented by the following general formula (6) can also be used.

In the formula (6), M ³ , R ²⁴ , X ¹ , X ² and Y are the same as those in the general formula (4). R ²⁴ is preferably a hydrocarbon group, particularly preferably an alkyl group having 1 to 4 carbon atoms such as methyl, ethyl, propyl or butyl. R ²⁵ represents an aryl group having 6 to 16 carbon atoms. R ²⁵ is preferably phenyl or naphthyl. The aryl group 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 general 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.

<Examples of metallocene compounds-6>
As the metallocene compound, a metallocene compound represented by the following general 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 imparting 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 general 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-η ⁵ -cyclopentadienyl) silane) titanium dichloride, ((t-butylamide) (tetramethyl-η ⁵ -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.

<Examples of metallocene compounds-7>
Moreover, as a metallocene compound, the metallocene compound represented by following General 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 includes 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 . As the conjugated diene residue formed from X ¹ and X ² , residues of 1,3-butadiene, 2,4-hexadiene, 1-phenyl-1,3-pentadiene and 1,4-diphenylbutadiene are preferable. 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, carbon atom 20 And a halogenated hydrocarbon group having 1 to 20 carbon atoms). Among these divalent groups, those in which the shortest linking 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.

<Examples of metallocene compounds-8>
As the metallocene compound, a metallocene compound represented by the following general 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, carbon atoms from 1 to 20 A halogenated hydrocarbon group). 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.

<Examples of metallocene compounds-9>
Further, as the metallocene compound, a metallocene compound represented by the following general formula (11) can also be used.

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 from R ⁵ to R ¹² are 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. It may be formed. 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 crosslinked part, and other characteristics that are the chemical structure characteristics of the bridged metallocene compound according to the present invention, a preferable bridged metallocene compound having these characteristics will be described. .

Cyclopentadienyl group The cyclopentadienyl group may or may not be substituted. The cyclopentadienyl group which may or may not be substituted means that R ¹ , R ² , R ³ and R ⁴ possessed by the cyclopentadienyl group moiety in the general formula (11) are all hydrogen atoms. Or any one or more of R ¹ , R ² , R ³ and R ⁴ is a hydrocarbon group (f1), preferably a hydrocarbon group having 1 to 20 carbon atoms (f1 ′), or silicon-containing It means a cyclopentadienyl group substituted by a group (f2), preferably a silicon-containing group (f2 ′) having a total carbon number of 1 to 20. When two or more of R ¹ , 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, alkenyl, alkynyl, 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 in total (f1 ′) includes, in addition to alkyl, alkenyl, alkynyl and aryl groups composed only of carbon and hydrogen, some of the hydrogen atoms directly connected to these carbon atoms are halogen atoms. , An oxygen-containing group, a nitrogen-containing group, a heteroatom-containing hydrocarbon group substituted with a silicon-containing group, or a group in which any two adjacent hydrogen atoms form an alicyclic group. Such a group (f1 ')
As, methyl group, ethyl group, n-propyl group, allyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, linear hydrocarbon group such as 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- Branched hydrocarbon groups such as 2-methylpropyl group; cyclic saturated hydrocarbon groups such as cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, norbornyl group, adamantyl group; phenyl group, naphthyl group, biphenyl group, phenanthryl Groups, cyclic unsaturated hydrocarbon groups such as anthracenyl group and their nuclear alkyl substituents; saturated hydrocarbon groups substituted with aryl groups such as benzyl group and cumyl group; methoxy group, ethoxy group, phenoxy group, N-methylamino group , Hetero atoms such as trifluoromethyl group, tribromomethyl group, pentafluoroethyl group, pentafluorophenyl group It may be mentioned hydrocarbon groups.
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 a total carbon number of 1 to 20 include a trimethylsilyl group and a triphenylsilyl group.

Fluorenyl group The fluorenyl group may or may not be substituted. The fluorenyl group which may or may not be substituted is 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 general formula (11). Are all 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 Means a fluorenyl group substituted with a hydrocarbon group having 1 to 20 carbon atoms (f1 ′) or a silicon-containing group (f2), preferably a silicon-containing group having 1 to 20 carbon atoms (f2 ′) To do. When two or more of R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ , R ¹⁰ , R ¹¹ and R ¹² are substituted, the 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. In view of the ease of production of the catalyst, those in which R ⁶ and R ¹¹ and R ⁷ and R ¹⁰ are the same are preferably used.
A preferred group of the hydrocarbon group (f1) is the above-described hydrocarbon group (f1 ′) having a total carbon number of 1 to 20, and a preferable example of the silicon-containing group (f2) is the above-described total number of carbon atoms of 1 to 20. It is a silicon-containing group (f2 ′).

Covalent bond bridge 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. The important point in the high-temperature solution polymerization of the present invention is that the bridging atom Y of the covalent bond bridging portion has R ¹³ and R ¹⁴ which may be the same or different from each other. A preferred group of the hydrocarbon group (f1) is the above-described hydrocarbon group (f1 ′) having a total carbon number of 1 to 20, and a preferable example of the silicon-containing group (f2) is the above-described total number of carbon atoms of 1 to 20. It is a silicon-containing group (f2 ′).

Other characteristics of the bridged metallocene compound In the general formula (11), Q is halogen, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, They are selected from the same or different combinations from anionic ligands or neutral ligands that can coordinate with a lone pair of electrons. Specific examples of the halogen are fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group are 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, Examples include 1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. Specific examples of neutral, conjugated or non-conjugated dienes having 10 or less carbon atoms include 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 eta 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. 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 neutral ligands that can be coordinated by a lone pair include organophosphorus 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>
Moreover, as a metallocene compound, the metallocene compound represented by the following general 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 represents Ti, Zr
Or Hf, Y is a Group 14 atom, Q can be coordinated by halogen, hydrocarbon group, neutral having 10 or less carbon atoms, conjugated or non-conjugated diene, anionic ligand, and lone pair of electrons Selected from the group consisting of 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 general 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 7 to 20 carbon atoms. And may contain one or more ring structures.

Specific examples thereof include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-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.

In the general formula (12), the silicon-containing hydrocarbon group preferably has 1 silicon.
And an alkyl or arylsilyl group having 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, tert-butyldimethylsilyl, triphenylsilyl and the like.

In the present invention, R ¹ to R ^{14 in} the general 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 general formula (12) may be bonded to 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 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 are fluorine, chlorine, bromine and iodine, and specific examples of the hydrocarbon group are 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, Examples include 1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl and the like. Neutral having 10 or less carbon atoms, and specific examples of the conjugated or non-conjugated 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. 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 the formula (12), there are a plurality of Ys of 2 to 4, but the Ys may be the same as or different from each other. The plurality of R ¹³ and the plurality of R ¹⁴ bonded to Y may be the same as or different from each other. For example, a plurality of R ¹³ bonded to the same Y may be different from each other, or a plurality of R ¹³ bonded to different Y may be the same as each other. 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 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 , and R ¹⁶ are each a hydrogen atom or a hydrocarbon group, n is an integer of 1 to 3, and n = 1 In some cases, R ¹ to R ¹⁶ are not hydrogen atoms and may be the same or different. Adjacent substituents from R ⁵ to R ¹² may combine with each other to form a ring, and R
¹³ and R ¹⁵ 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, 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 which may be the same or different from each other, M is Ti, Zr or Hf, Q is a halogen, a hydrocarbon group, an anionic ligand or a lone pair of electrons You may choose from the neutral ligand which can be coordinated by the same or different combination, and j is an integer of 1-4.
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.
The catalyst component comprises (A) the bridged metallocene compound represented above, and (B) (b-1) an organoaluminum oxy compound, (b-2) reacts with the bridged metallocene compound (A) to form an ion pair. And at least one compound selected from (b-3) organoaluminum compounds.

Hereinafter, the component (B) will be specifically described.
<(B-1) Organoaluminum oxy compound>
As the (b-1) organoaluminum oxy compound used in the present invention, a conventionally known aluminoxane can be used as it is. Specifically, the following general formula (14)

  And / or general formula (15)

(Wherein R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents an integer of 2 or more). In particular, R is a methylaluminoxane in which methyl is a methyl group, and n is 3 More preferably, 10 or more are used. These aluminoxanes may be mixed with some organoaluminum compounds. A characteristic property in the high temperature solution polymerization of the present invention is that a benzene-insoluble organoaluminum oxy compound as 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 types of alkyl groups described in JP-A-2-24701, JP-A-3-103407, and the like It can be suitably used. The “benzene-insoluble” organoaluminum oxy compound used in the high-temperature solution polymerization of the present invention means that the Al component dissolved in benzene at 60 ° C. is usually 10% or less, preferably 5% or less, particularly preferably 5% or less. Is 2% or less, and is insoluble or hardly soluble in benzene.

  Examples of the organoaluminum oxy compound used in the present invention include modified methylaluminoxane as shown in (16) below.

(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 a compound [V] is generally called MMAO. Such MMAO can be prepared by the methods listed in US4960878 and US5041584. In addition, Tosoh Finechem Co., Ltd., etc., which are prepared using trimethylaluminum and triisobutylaluminum and whose R is an isobutyl group, are commercially produced under the names MMAO and TMAO. Such MMAO is an aluminoxane having improved solubility in various solvents and storage stability, and specifically, it is different from those insoluble or hardly soluble in benzene such as the above (14) and (15). It is soluble in aliphatic hydrocarbons and alicyclic hydrocarbons.

Further, the organoaluminum oxy compound used in the present invention includes the following general formula (1
An organoaluminum oxy compound containing boron represented by 7) can also be mentioned.

(In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same or different and each represents a hydrogen atom, a halogen atom or a hydrocarbon having 1 to 10 carbon atoms. Group.)
<(B-2) Compound that reacts with bridged metallocene compound (A) to form an ion pair>
Examples of the compound (b-2) that reacts with the bridged metallocene compound (A) to form an ion pair (hereinafter sometimes abbreviated as “ionic compound”) include JP-A-1-501950, Lewis acids and ionic properties described in 1-502036, JP-A-3-17905, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP5321106, etc. Examples thereof include 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 organic groups, preferably aryl groups.

  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.

Of these, Re ^{e +} is preferably a carbenium cation, an ammonium cation or the like, and particularly preferably a triphenylcarbenium cation, an N, N-dimethylanilinium cation or an N, N-diethylanilinium cation.

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 and tris (3,5-dimethylphenyl) carbenium tetrakis (pentafluorophenyl) borate.

Examples of ammonium salts include trialkyl-substituted ammonium salts, N, N-dialkylanilinium salts, dialkylammonium salts, and the like.
Specific 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) borate, tri (n-butyl) ammonium tetrakis (4-tri Fluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetraphenylborate, di Octadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethyl) Tilphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-dimethylphenyl) borate, dioctadecylmethylammonium tetrakis (4-trifluoromethylphenyl) borate, dioctadecylmethylammonium tetrakis (3,5-ditrifluoromethylphenyl) borate And dioctadecylmethylammonium.

Specific 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- Ditrifluoromethylphenyl) borate, N, N-2,4,6-pentamethylanilinium tetraphenylborate, N, N-2,4,6-pentamethylanilinium tetrakis (pentafluorophenyl) borate, etc. .

  Specific examples of the dialkylammonium salt include di (1-propyl) ammonium tetrakis (pentafluorophenyl) borate and dicyclohexylammonium tetraphenylborate.

In addition, ionic compounds disclosed by the present applicant (Japanese Patent Laid-Open No. 2004-51676) can also be used without limitation.
The ionic compound (b-2) as described above can be used as a mixture of two or more.

<(B-3) Organoaluminum compound>
Examples of the organoaluminum compound that forms the olefin polymerization catalyst (b-3) include, for example, an organoaluminum compound represented by the following general formula [X], a group 1 metal represented by the following general formula (19), and aluminum. Examples thereof include complex 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 a number of 0 ≦ p <3, q is a number of 0 ≦ q <3, and m + n + p + q = 3). Specific examples of such compounds include tri-n-alkylaluminums such as trimethylaluminum, triethylaluminum, tri-n-butylaluminum, trihexylaluminum, trioctylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, Tri-tert-butylaluminum,
Tri-branched alkylaluminums such as tri-2-methylbutylaluminum, tri-3-methylhexylaluminum, tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triphenylaluminum, tritolylaluminum, etc. triaryl aluminum; diisopropyl aluminum hydride, dialkylaluminum hydride such as diisobutylaluminum hydride; formula _{(iC 4 H 9) x Al} y (C 5 H 10) z ( wherein, x, y, z are positive numbers Yes, z ≦ 2x.)
Alkenyl aluminum alkoxide such as isobutylaluminum methoxide and isobutylaluminum ethoxide; Dialkylaluminum alkoxide such as dimethylaluminum methoxide, diethylaluminum ethoxide and dibutylaluminum butoxide; Alkyl aluminum sesquialkoxides such as ethoxide and butylaluminum sesquibutoxide; partially alkoxylated alkylaluminums having an average composition represented by the general formula R ^a _2.5 Al (OR ^b ) _{0.5 and the} like; diethylaluminum phenoxide and diethylaluminum Alkyl aluminum aryloxides such as (2,6-di-t-butyl-4-methylphenoxide); dimethylal Dialkylaluminum halides such as nium chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquichlorides such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; Partially halogenated alkylaluminums such as alkylaluminum dihalides; dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; alkylaluminum dihydrides such as ethylaluminum dihydride and propylaluminum dihydride and other partially Hydrogenated alk Aluminum; ethylaluminum ethoxy chloride, butyl aluminum butoxide cycloalkyl chloride, etc. partially alkoxylated and halogenated alkylaluminum such as ethylaluminum ethoxy bromide and the like.
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.)
A complex alkylated product of a group 1 metal and aluminum in the periodic table represented by: Examples of such a compound include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

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 through a nitrogen atom. Specifically, as such a compound, (C ₂ H ₅ ) ₂ AlN (C ₂ H ₅ ) Al (C ₂ H ₅ ) ₂
And so on.

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 is obtained by homopolymerizing ethylene in a normal liquid phase or copolymerizing ethylene and an 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 in the concentrations 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 mol per liter of reaction volume. It is used in such an amount that it becomes a mole.

Component (b-1) has a molar ratio [(b-1) / M] of component (b-1) to all transition metal atoms (M) in component (A) of 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. 0.01 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 1-1.
The amount used is 0000, preferably 1 to 5000.

In the polymerization reaction, the temperature is usually 10 g of wax set on a filter, -20 to + 200 ° C., preferably 50 to 180 ° C., more preferably 70 to 180 ° C., and the pressure usually exceeds 0. It is performed under conditions of 8 MPa (80 kgf / cm ² , gauge pressure) or less, preferably more than 0 and 4.9 MPa (50 kgf / cm ² , gauge pressure) or less.

  In the polymerization, ethylene and the α-olefin used as necessary are supplied to the polymerization system in such an amount ratio that a polyolefin wax having the specific composition described above can be obtained. In the polymerization, a molecular weight regulator such as hydrogen can 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.
In the present invention, it is particularly preferable to use a catalyst containing the metallocene compound shown in <Example 6 of metallocene compound>.

When such a catalyst is used, a polyolefin wax (A) having the above-described Mn, Mw / Mn, melting point range, and other preferable physical properties can be easily obtained, and a polyolefin wax ( The thermoplastic resin composition of the present invention containing A) has a large effect of improving fluidity, and not only greatly increases the molding speed of such a thermoplastic resin composition, but also reduces stickiness components and causes stickiness on the surface. A molded body can be obtained.

[Thermoplastic resin (B)]
In the present invention, the polyolefin wax (A) is mixed with the thermoplastic resin (B). In the present invention, the thermoplastic resin (B) is a gel permeation chromatography (
A thermoplastic polymer having a polystyrene-reduced number average molecular weight (Mn) measured by GPC) of 8,000 or more, preferably a thermoplastic polymer exceeding 10,000, or a blend thereof.

There is no restriction | limiting in particular in the thermoplastic resin (B) used by this invention, For example, a low density polyethylene, a medium density polyethylene, a high density polyethylene, a linear linear low density polyethylene, a polypropylene, a cyclic olefin polymer, an ethylene propylene copolymer , Polyolefins such as cyclic olefin copolymers;
Styrene polymers such as polystyrene, acrylonitrile-styrene copolymer, acrylonitrile-butadiene-styrene copolymer;
Polyvinyl chloride, polyvinylidene chloride;
Ethylene-methacrylic acid copolymer, ethylene-methacrylic acid ester copolymer, ethylene-vinyl acetate copolymer, ethylene-vinyl alcohol copolymer;
Polycarbonate, polymethacrylate;
Polyesters such as polyethylene terephthalate and polybutylene terephthalate;
Polyamides such as nylon 6, nylon 11, nylon 12, nylon 46, nylon 66, nylon MXD6, wholly aromatic polyamide, semi-aromatic polyamide;
Examples include polyacetals and blends of these resins.

  Among these thermoplastic resins, polyolefin is preferable, and low density polyethylene, medium density polyethylene, high density polyethylene, linear linear low density polyethylene, polypropylene, and ethylene-propylene copolymer are more preferable.

When the thermoplastic resin (B) is the above resin, a polyolefin wax (A
Therefore, the thermoplastic resin composition containing the thermoplastic resin (B) has a great effect of improving fluidity and further tends to improve the molding speed. Moreover, from the said resin composition, it is easy to obtain the favorable molded object which does not have stickiness on the surface, for example. Furthermore, since the polyolefin wax is well dispersed in the molded product, it is possible to suppress the performance degradation of the molded product such as a decrease in the strength of the molded product and bleed out of low molecular weight components due to the addition of the conventional wax.

Further, the shape of the thermoplastic resin (B) is preferably pellet-shaped or tablet-shaped particles.
〔Additive〕
In the present invention, in addition to the polyolefin wax (A) and the thermoplastic resin (B), the mixture for producing the thermoplastic resin composition is further optionally added with an antioxidant, an ultraviolet absorber, and a light stabilizer. You may add additives, such as stabilizers, such as an agent, metal soap, a filler, and a flame retardant.

Examples of the stabilizer include antioxidants such as hindered phenol compounds, phosphite compounds, and thioether compounds;
UV absorbers such as benzotriazole compounds and benzophenone compounds;
Examples thereof include light stabilizers such as hindered amine compounds.

Examples of the metal soap include stearates such as magnesium stearate, calcium stearate, barium stearate, and zinc stearate.
Examples of the filler include calcium carbonate, titanium oxide, barium sulfate, talc, clay, and carbon black.

  Examples of the flame retardant include halogenated diphenyl ethers such as degabromo diphenyl ether and octabromo diphenyl ether, halogen compounds such as halogenated polycarbonates; antimony trioxide, antimony tetraoxide, antimony pentoxide, sodium pyroantimonate, aluminum hydroxide, etc. Inorganic compounds; phosphorus compounds and the like.

Moreover, a compound such as tetrafluoroethylene can be added as a flame retardant aid for preventing drip.
Examples of the antibacterial and antifungal agents include organic compounds such as imidazole compounds, thiazole compounds, nitrile compounds, haloalkyl compounds, and pyridine compounds;
Examples include inorganic substances such as silver, silver compounds, zinc compounds, copper compounds, and titanium compounds, and inorganic compounds.
Among these compounds, thermally stable silver and silver-based compounds are preferable.

As said silver type compound, silver salts, such as a silver complex, a fatty acid, and phosphoric acid, can be mentioned.
When silver and silver-based compounds are used as antibacterial and antifungal agents, these substances can be used in porous structures such as zeolite, silica gel, zirconium phosphate, calcium phosphate, hydrotalcite, hydroxyapatite, and calcium silicate. In some cases, it is used while being supported.

Examples of other additives include pigments, colorants, plasticizers, anti-aging agents, and oils.
[Method for producing thermoplastic resin composition]
In the method for producing a thermoplastic resin composition of the present invention, a mixture containing a polyolefin wax (A), a thermoplastic resin (B), and, if necessary, an additive is first prepared. There are no particular limitations on the method for preparing the mixture. For example, these compounds may be simply placed in a container and shaken or mixed using a mixing device such as a tumbler or Henschel mixer.

  The thermoplastic resin composition of the present invention can be obtained by melt-kneading the mixture thus prepared. The melt kneading can be performed, for example, with an extruder, a plast mill, a Brabender, a kneader, a roll mixer, a Banbury mixer, or the like.

  The temperature at the time of melt kneading is not particularly limited as long as the polyolefin wax (A), the thermoplastic resin (B) and the like are melted. For example, when the thermoplastic resin is polypropylene, the temperature is usually 190. It is the range of -300 degreeC, Preferably it is the range of 200-250 degreeC.

  The blending amount of the polyolefin wax (A) in the thermoplastic resin composition obtained in the present invention is not particularly limited, but is usually 0.01 to 20 parts by weight with respect to 100 parts by weight of the thermoplastic resin (B). The range is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight.

When the polyolefin wax (A) is blended within the above range, the effect of improving the fluidity at the time of molding of the thermoplastic resin composition obtained is great, and the molding speed tends to be further improved. In addition, molding can be performed at a lower molding temperature than when the polyolefin wax (A) is not added, the cooling time is shortened, and the molding cycle tends to be improved. Furthermore, by lowering the molding temperature, not only the thermal deterioration of the resin is suppressed and the decrease in the resin strength is suppressed, but there is a tendency that the scorching and black spots of the resin can be suppressed.

[Molded body]
The molded article of the present invention is obtained by molding the thermoplastic resin composition.
Examples of the molding method include injection molding, extrusion molding, blow molding, and other known molding methods.

For example, when the molded article of the present invention is obtained by extrusion blow molding, a thermoplastic resin composition containing a polyolefin wax (A) and a thermoplastic resin (B) is usually used in a resin temperature range of 170 to 240 ° C. After extruding as a tubular parison from a die and holding the parison in a mold having a shape to be imparted, air is blown into the mold, and the molded article is obtained by wearing the mold at a normal resin temperature of 160 to 230 ° C. Further, when extrusion blow molding, it may be stretched to an appropriate magnification. When extrusion blow molding is performed using high-density polyethylene as the thermoplastic resin (A), the resin temperature is usually in the range of 170 to 220 ° C., preferably Is extruded from a die in a range of 180 to 210 ° C., and a molded body is obtained by attaching the resin temperature to a mold in a range of usually 160 to 210 ° C., preferably 170 to 200 ° C. Further, it may be stretched during extrusion blow molding.

  When extrusion blow molding is performed using polypropylene as the thermoplastic resin (A), the resin temperature is usually in the range of 190 to 230 ° C, preferably in the range of 200 to 220 ° C, and the resin temperature is usually 180 to 220. A molded body is obtained by wearing the mold in the range of ° C, preferably in the range of 190 to 210 ° C. Further, it may be stretched during extrusion blow molding.

These blow moldings can be performed by an appropriate molding machine corresponding to each blow molding method.
When injection molding is performed using polypropylene as the thermoplastic resin (A), the cylinder temperature during injection molding is usually in the range of 180 to 400 ° C, preferably 200 to 300 ° C, more preferably 200 to 250 ° C. The injection pressure is usually in the range of 10 to 200 MPa, preferably 20 to 150 MPa, and the mold temperature is usually in the range of 20 to 200 ° C., preferably 20 to 80 ° C., more preferably 20 to 60 ° C.

  When extrusion sheet molding or film molding is performed using a T-die extruder or the like using polypropylene as the thermoplastic resin (A), it is usually 200 to 300 ° C, preferably 200 to 270 ° C, more preferably 200 to 250 ° C. A molded body can be obtained by extrusion molding within a range. A stretched film can be obtained by stretching a film extruded from an extruder by, for example, a tenter method (longitudinal and transverse stretching, transverse and longitudinal stretching), a simultaneous biaxial stretching method, a uniaxial stretching method, or the like.

  Moreover, foaming extrusion molding can be performed by mixing a foaming agent with the thermoplastic resin composition of the present invention at the time of molding. In the case of foam extrusion, the die and sizing die designs must be created taking into account the foaming ratio and the like. An organic or inorganic chemical foaming agent is preferred as the foaming agent for producing the foamed molded article in the present invention. Generally used as chemical blowing agents are azodicarbonamide (ADCA), azobisisobutyronitrile (AIBN), N, N'-dinitrosopentamethylenetetramine (DPT), 4,4'-oxybis (benzene). Sulfonyl hydrazide) (OBSH), sodium hydrogen carbonate (bicarbonate), ammonium carbonate and the like. Alternatively, two or more of the above foaming agents may be mixed and used as the foaming agent. Moreover, you may use foaming adjuvants, such as a zinc compound, a urea compound, an acidic substance, and amines. Furthermore, you may use the masterbatch of the foaming agent which improved the handleability.

When a mixture in which such a polyolefin wax is added to the thermoplastic resin (B) described later is melted and molded, the melt viscosity of the resin is lowered, so the load during molding, for example, the motor load during extrusion molding is reduced. In addition, the fluidity tends to be improved and the molding speed tends to increase. Moreover, the surface of the molded body is modified, and a molded body having a smooth surface can be obtained. Furthermore, since molding can be performed at a low molding temperature, not only the cooling time is shortened and the molding cycle is improved, but also thermal degradation of the resin, scorching of the resin, and black spots can be suppressed, and the mechanical strength of the molded body is excellent. Become.

EXAMPLES Hereinafter, although an Example demonstrates this invention, this invention is not limited at all by these Examples.
[material]
Thermoplastic resin: Polypropylene (Prime Polypro F113G, manufactured by Prime Polymer Co., Ltd.) (mesh-on ratio of sieve opening 2.00 mmΦ 100% by weight; mesh pass ratio of sieve opening 5.66 mmΦ 100% by weight ]
Wax (1): EXELEX 30200BT (manufactured by Mitsui Chemicals, Inc.) [ethylene content: 95 mol%, density: 913 kg / m ³ , average molecular weight (Mn) = 2000, particle size: mesh opening 5.66 mmΦ Pass, mesh opening with sieve opening 2.00mmΦ)
Wax (2): Excellex 30200B (manufactured by Mitsui Chemicals, Inc.) [ethylene content: 95 mol%, density: 913 kg / m ³ , average molecular weight (Mn) = 2000, particle size: sieve opening 2.00 mmΦ mesh Pass, average particle size 350 μm)
[Evaluation]
The following items were evaluated.

[Mixability of wax]
The presence or absence of wax adhesion on the inner wall of the tumbler mixer was evaluated visually.
○ No deposit △ Some deposits × There are deposits [Classification in the hopper]
The classification in the hopper during extrusion was visually observed with a 20 mmφ single screw extruder.

○ No classification △ Slightly classified × Immediately classified [Molding processability]
A 20 mmφ single-screw extruder and a T-die having a lip width of 240 mm were used to prepare and evaluate a film by setting the rotation speed to 70 rpm, the cylinder temperature, and the die temperature to 210 ° C.

○ No unevenness in thickness △ Unevenness in thickness is slightly noticeable × Unevenness in thickness is quite noticeable [Example 1]
(1) Preparation of wax pellets Metallocene polyethylene wax prepared using a metallocene catalyst (Excellex (registered trademark) 30200B (Mitsui Chemicals, Inc., ethylene content: 95 mol%, density: 913 kg / m ³⁾ The average molecular weight (Mn): 2000) was dissolved in a tank kept at 140 ° C., and the cooling steel belt was pelletized by a tabletizer set at a speed of 20 m / min and a temperature of 20 ° C. Through a sieve of 3.5 mesh (aperture: 5.66 mm) and 9 mesh (aperture: 2.00 mm), pellets having a particle size in the range of 2.00 to 5.66 mm were prepared. The pellets are 100% by weight on a mesh with a sieve opening of 2.00 mmΦ and 85% by weight on a mesh with a sieve opening of 2.83 mmΦ. Emissions, mesh 70 wt% on the sieve opening 3.35Mmfai, mesh 80% by weight pass sieve opening 4.00Mmfai, it was mesh 90% by weight pass the sieve mesh opening 4.75Mmfai.

(2) Manufacture of thermoplastic resin composition 100 parts by weight of polypropylene (Prime Polypro F113G, manufactured by Prime Polymer Co., Ltd.), which is a thermoplastic resin, was added to pellets of metallocene polyethylene wax prepared in (1) above. 5 parts by weight was added and mixed with a tumbler mixer for 10 minutes to prepare a mixture of polypropylene and polyethylene wax.
Table 1 shows the evaluation results of the mixing property of the wax and the classification in the hopper during the extrusion.

(3) Manufacture of a molded object About the mixture of the polypropylene manufactured in said (2), and a polyethylene-type wax, rotation speed 70rpm, cylinder temperature, and die temperature are 210 by a 20 mm diameter single screw extruder, T die with a lip width of 240 mm. A film was prepared at a temperature of ° C., and the molding processability was evaluated.

[Examples 2-3]
A thermoplastic resin composition and a molded body were produced in the same manner as in Example 1 except that the amount of pelletized wax added was changed so that the composition shown in Table 1 was obtained. The evaluation results are shown in Table 1.

[Comparative Example 1]
(1) Production of thermoplastic resin composition (example of using wax without pelletizing (tablet))
100 parts by weight of polypropylene (Prime Polypro F113G, manufactured by Prime Polymer Co., Ltd.) which is a thermoplastic resin, powder of metallocene polyethylene wax (particle size: mesh pass with sieve opening 2.00 mmΦ, average particle size 350 μm) 0.5 part by weight was added and mixed for 10 minutes in a tumbler mixer to make a mixture of polypropylene and polyethylene wax.
Table 1 shows the evaluation results of the mixing property of the wax and the classification in the hopper during the extrusion.

(2) Manufacture of a molded object About the powder mixture of the polypropylene and polyethylene-type wax manufactured by said (1), rotation speed 70rpm, cylinder temperature, and die temperature with a 20mmphi single screw extruder and T die with a lip width of 240mm. Was set to 210 ° C., a film was produced, and molding processability was evaluated.

[Comparative Examples 2-3]
As shown in Table 1, a thermoplastic resin composition and a molded body were produced in the same manner as in Comparative Example 1 except that the amount of wax added was changed. The evaluation results are shown in Table 1.

Claims (5)

Particulate polyolefin wax (A) in which the ratio of the amount passing through a mesh with a sieve opening of 5.66 mmΦ is 95% by weight or more and the ratio of the amount passing through a mesh with a sieve opening of 2.00 mmΦ is 95% by weight When,
A method for producing a thermoplastic resin composition by melt-kneading a mixture containing a thermoplastic resin (B).   The method for producing a thermoplastic resin composition according to claim 1, wherein the polyolefin wax (A) is a polyethylene wax.   The method for producing a thermoplastic resin composition according to claim 1, wherein the polyolefin wax (A) is a polyethylene wax obtained using a metallocene catalyst.   The method to manufacture a molded object from the thermoplastic resin composition of any one of Claims 1-3.   The molded object obtained from the thermoplastic resin composition of any one of Claims 1-3.