JP2007046017A - Wax composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a wax composition comprising a crystalline higher α-olefin polymer and a hydrocarbon wax and having excellent balance among holding power, hardness and toughness. <P>SOLUTION: The wax composition comprises a combination of (A) 1-99 mass% of the crystalline higher α-olefin polymer obtained by polymerizing (i) one or more kinds of ≥10C higher α-olefins or (ii) one or more kinds of ≥10C higher α-olefins and ≤9C α-olefins and having ≥50 mol% of the higher α-olefin unit content and (B) 99-1 mass% of the hydrocarbon wax. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a wax composition, and more specifically, a wax composition comprising a crystalline higher α-olefin polymer and a hydrocarbon wax, and having a good balance of holding power, hardness, and toughness. It is about.

Conventionally, waxes have been used for corrugated cardboard for water resistance and waterproofing, cosmetics such as lipsticks and pomades, medical treatments such as ointments and suppositories, other glazing of stationery and furniture, polishing agents and paints, fixing lenses, etc. It has been.
And when using for a candle and a lipstick, in order to improve the retention strength (power which maintains the shape after shaping | molding), adding a thickener is performed.
However, the thickening effect on the wax is still not sufficient.
On the other hand, higher α-olefin polymers having 10 or more carbon atoms are known to be used in the same applications as waxes, and have higher hardness and higher holding power than waxes.

Higher α-olefin polymers have higher hardness than waxes, but may crack after molding and have a problem in toughness.
There is also a disclosure of a crystalline higher α-olefin polymer containing 50 mol% or more of α-olefin units having 10 or more carbon atoms (see, for example, Patent Document 1).
In this publication, a crystalline higher α-olefin polymer obtained from a higher α-olefin having 10 or more carbon atoms and having a melting point measured by a differential scanning calorimeter (DSC) in the range of 20 to 100 ° C. Although described as being excellent in compatibility and useful for high-performance waxes, there are no examples to support these.

International Patent Publication No. 03-070790

  An object of the present invention is to provide a wax composition containing a crystalline higher α-olefin polymer and a hydrocarbon wax having an excellent balance of holding power, hardness and toughness.

  As a result of intensive studies on the wax composition in order to solve the above-mentioned problems, the present inventors have blended a specific crystalline higher α-olefin polymer with a hydrocarbon-based wax, thereby improving the holding power, hardness, and toughness. The inventors have found that a wax composition having an excellent balance can be obtained, and have completed the present invention.

That is, the present invention
1. (A) (i) obtained by polymerizing one or more higher α-olefins having 10 or more carbon atoms or (ii) one or more higher α-olefins having 10 or more carbon atoms and one or more α-olefins having 9 or less carbon atoms, A wax composition comprising a combination of 1 to 99% by mass of a crystalline higher α-olefin polymer having a higher α-olefin unit content of 50 mol% or more and (B) 99 to 1% by mass of a hydrocarbon wax,
2. 2. The wax composition according to 1 above, wherein the crystalline higher α-olefin polymer satisfies the following (a) and (b):
(A) Using a suggestion scanning calorimeter (DSC), the polymer was held at 190 ° C. for 5 minutes in a nitrogen atmosphere, then cooled to −10 ° C. at 5 ° C./min, and held at −10 ° C. for 5 minutes. Thereafter, the melting point (Tm) observed from the melting endotherm curve obtained by raising the temperature to 190 ° C. at 10 ° C./min is in the range of 20 to 100 ° C.
(B) A single peak X1 derived from side chain crystallization observed at 15 deg <2θ <30 deg in the wide-angle X-ray scattering intensity distribution is observed.
Is to provide.

  The wax composition of the present invention is excellent in holding power, hardness and toughness balance.

The wax composition of the present invention comprises a combination of (A) a crystalline higher α-olefin polymer of 1 to 99% by mass and (B) a hydrocarbon wax of 99 to 1% by mass. The content ratio of the component (A) is preferably 10 to 99% by mass for the component (A), 90 to 1% by mass for the component (B), more preferably 20 to 99% by mass for the component (A). A component is 80-1 mass%.
When the content of the component (A) is 1% by mass or more, a hardness improving effect and a thickening effect on the wax are sufficient.
Further, when the component (A) is 99% by mass or less, the toughness is sufficient.

The crystalline higher α-olefin polymer used as the component (A) in the present invention (hereinafter sometimes abbreviated as higher α-olefin polymer) is (i) one or more higher α-olefins having 10 or more carbon atoms. Or (ii) obtained by polymerizing a higher α-olefin having 10 or more carbon atoms and one or more α-olefins having 9 or less carbon atoms, and having a higher α-olefin unit content of 50 mol% or more.
As the higher α-olefin, those having 10 to 40 carbon atoms are preferable, and those having 14 to 24 carbon atoms are more preferable.
When the carbon number is 10 or more, the higher α-olefin polymer can be crystallized in the side chain.
Examples of the higher α-olefin having 10 or more carbon atoms include 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene and 1-octadecene.
Examples of the α-olefin having 9 or less carbon atoms include propylene, 1-butene, 1-pentene, 4-methyl-pentene-1, 1-hexene, 1-octene and 1-nonene.

In the higher α-olefin polymer, the content of the higher α-olefin unit having 10 or more carbon atoms is preferably 50 to 100 mol%, more preferably 65 to 100 mol%, still more preferably 80 to 100 mol%, still more preferably. 90 to 100 mol%, very preferably 100 mol%.
When the content of the higher α-olefin unit having 10 or more carbon atoms in the higher α-olefin polymer is 50 mol% or more, the side chain crystallinity becomes good.

The higher α-olefin polymer used in the present invention has the following properties.
That is, using a differential scanning calorimeter (DSC), the sample was held at 190 ° C. for 5 minutes, then cooled to −10 ° C. at 5 ° C./minute, held at −10 ° C. for 5 minutes, and then increased to 190 ° C. There is one melting point (Tm) observed from the melting endothermic curve obtained by raising the temperature at a rate of ° C / min, preferably 20-100 ° C, more preferably 20-95 ° C, and even more preferably 25-90. It is a crystalline resin at ° C.
When this melting point (Tm) is 100 ° C. or lower, when mixed with wax, the amount of energy consumption is small and it does not separate during crystallization.
On the other hand, when the melting point (Tm) is 20 ° C. or higher, stickiness does not occur.
Furthermore, the melting peak half width Wm (° C.) defined as the peak width at the midpoint of the height from the base line to the peak top of the entire melting peak at the time of melting point (Tm) measurement is preferably 12 ° C. or less. .
The half width is more preferably 10 ° C. or less, and further preferably 8 ° C. or less.
When the half width is 12 ° C. or less, stickiness does not occur.

In the higher α-olefin polymer used in the present invention, a single peak X1 derived from side chain crystallization observed at 15 deg <2θ <30 deg is usually observed in the wide-angle X-ray scattering intensity distribution measurement.
In the X-ray intensity distribution, when no peak derived from the side chain crystal is observed, or when the peak derived from the side chain crystal is not single, the distribution of crystal components in the higher α-olefin polymer becomes wide and stickiness occurs. It is easy to do and is not preferable.
The wide-angle X-ray scattering intensity distribution can be measured as follows.
That is, using a counter-cathode type rotor flex RU-200 manufactured by Rigaku Denki Co., Ltd., collimating monochromatic light of CuKα ray (wavelength = 1.54 mm) of 30 kV, 100 mA output with a pin hole of φ2 mm, and position sensitive proportional counting Using a tube, a wide angle X-ray scattering (WAXS) intensity distribution is measured with an exposure time of 1 minute.

The higher α-olefin polymer used in the present invention has a polystyrene-equivalent weight average molecular weight (Mw) measured by a gel permeation chromatography (GPC) method, usually about 5,000 to 5,000,000, preferably Is 5,000 to 1,000,000, more preferably 5,000 to 500,000, still more preferably 5,000 to 300,000.
When Mw is 1,000 or more, stickiness does not occur.
On the other hand, when it is 5,000,000 or less, the difference in viscosity from the wax does not increase, and it becomes easy to mix uniformly, which is preferable.
Further, the molecular weight distribution (Mw / Mn) is preferably 5.0 or less, more preferably 4.5 or less.
If the Mw / Mn is 5.0 or less, the composition distribution is not too wide and appropriate,
The possibility of stickiness is reduced.
The higher α-olefin polymers can be used alone or in combination of two or more.

The hydrocarbon wax used as the component (B) in the present invention includes petroleum wax (paraffin wax, microcrystalline wax, petrolatum, etc.), polyolefin wax (polyethylene wax, polypropylene wax, etc.), synthetic wax (Fischer-Tropsch wax, ester wax). Etc.), animal and vegetable waxes (carbana wax, rice cereal wax, beeswax, candelilla wax, rice wax, jojoba oil, lanolin, etc.), animal and vegetable oils and fatty acids (lauric acid, palmitic acid, stearic acid, isostearic acid, behenic acid), oxidation Examples thereof include waxes (oxidized paraffin wax, oxidized microcrystalline wax, oxidized polyethylene wax).
These waxes may be used alone or in combination of two or more.
In the wax composition of the present invention, in addition to the crystalline higher α-olefin polymer of component (A) and (B) hydrocarbon-based wax, various additive components as necessary, for example, colorants such as pigments and dyes, A fragrance | flavor etc. can be contained.

The higher α-olefin polymer used in the present invention can be produced by using the following metallocene-based catalyst, and in particular, contains a C2 symmetric and C1 symmetric transition metal compound capable of synthesizing an isotactic polymer. It is preferred to use a catalyst that does this.
Illustratively, (a) a transition metal compound represented by the general formula (I), and (b) (b-1) an ion reacting with the transition metal compound of the component (a) or a derivative thereof A method for homopolymerizing a higher α-olefin having 10 or more carbon atoms in the presence of a polymerization catalyst containing at least one component selected from a compound capable of forming a functional complex and (b-2) aluminoxane, It is a method of polymerizing two or more higher α-olefins of 10 or more, or a method of polymerizing a higher α-olefin having 10 or more carbon atoms and an α-olefin having 9 or less carbon atoms.

[Wherein, M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopentadienyl group, respectively. , A substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which form a cross-linked structure via A ¹ and A ² In addition, they may be the same as or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , It may be cross-linked with E ² or Y.
Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other. q is an integer of 1 to 5 and represents [(valence of M) -2], and r represents an integer of 0 to 3. ]

In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium. Among them, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity.
E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) A ligand selected from (A) and a cross-linked structure is formed via A ¹ and A ² .
E ¹ and E ² may be the same as or different from each other.
As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group, and a substituted indenyl group are preferable from the viewpoint of higher polymerization activity.

X represents a σ-bonding ligand, and when there are a plurality of X, the plurality of Xs may be the same or different and may be cross-linked with other X, E ¹ , E ² or Y. .
Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, carbon Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.
On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X.
Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.

Next, A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, and a silicon-containing group. Group, germanium-containing group, tin-containing group, —O—, —CO—, —S—, —SO ₂ —, —Se—, —NR ¹ —, —PR ¹ —, —P (O) R ¹ —, —BR ¹ — or —AlR ¹ —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, May be different.
Examples of such a bridging group include a general formula

(D is carbon, silicon, germanium or tin, R ² and R ³ are each a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, which may be the same or different from each other, and are bonded to each other to form a ring structure. (E represents an integer of 1 to 4)
Specific examples thereof include methylene group, ethylene group, ethylidene group, propylidene group, isopropylidene group, cyclohexylidene group, 1,2-cyclohexylene group, vinylidene group (CH ₂ = C =), a dimethylsilylene group, a diphenylsilylene group, a methylphenylsilylene group, a dimethylgermylene group, a dimethylstannylene group, a tetramethyldisylylene group, and a diphenyldisilylene group.
Among these, an ethylene group, an isopropylidene group, and a dimethylsilylene group are preferable from the viewpoint of higher polymerization activity. q is an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3.
Among the transition metal compounds represented by the general formula (I), the general formula (II)

The transition metal compound which makes the ligand the double bridge type biscyclopentadienyl derivative represented by these is preferable.
In the above general formula (II), M, A ¹ , A ² , q and r are the same as those in the general formula (I).
X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1.
Specific examples of X ¹ include the same examples as those exemplified in the description of X in formula (I).
Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different, may be crosslinked with other Y ¹ or X ^1.
Specific examples of Y ¹ are the same as those exemplified in the description of Y in the general formula (I).
R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. One must not be a hydrogen atom.
R ^{4 to} R ⁹ may be the same as or different from each other, and adjacent groups may be bonded to each other to form a ring.
Among these, it is preferable that R ⁶ and R ⁷ form a ring and R ⁸ and R ⁹ form a ring.
As R ⁴ and R ⁵ , a group containing a hetero atom such as oxygen, halogen, or silicon is preferable because of high polymerization activity.

The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably contains silicon in the bridging group between the ligands.
Specific examples of the transition metal compound represented by the general formula (I) include (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene). (2,1′-methylene) -bis (indenyl) zirconium dichloride, (1,2′-isopropylidene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene)- (5,6-dimethylindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1,2'-ethylene ) (2,1′-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,2′-ethylene) (2,1′-ethylene) -bis (3-methyl-4-isopropylindenyl) Zirconium dichloride, (1,2'-ethylene) (2,1'-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-ethylene) (2,1'-isopropylidene) -Bis (indenyl) zirconium dichloride,

(1,2′-methylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride, (1,2′-methylene) (2,1′-isopropylidene) -bis (indenyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (3-methylindenyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-n-butylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethyl Silylene) bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2 1'-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1, 2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4,5-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (4- Isopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (4,7-diisopropylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) ) Bis (4-phenylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) bis (3-methyl-4-isopropylindenyl) zirconium dichloride, (1,2 ' -Dimethylsilylene) (2,1'-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (indenyl) zirconium Dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-methyl Indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-isopropylidene) -bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'- Isopropylidene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-trimethylsilylindenyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-isopropylidene) -bis (3-phenylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-methylene) -bis ( Indenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene ) -Bis (3-isopropylindenyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride, (1,2'- Dimethylsilylene) (2,1′-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1 2'-dimethylsilylene) (2,1'-methylene) -bis (3-trimethylsilylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (indenyl) zirconium dichloride , (1,2'-Diphenylsilylene) (2,1'-methylene) -bis (3-methylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis ( 3-isopropylindenyl) zirconium dichloride, (1,2'-diphenylsilylene) (2,1'-methylene) -bis (3-n-butylindenyl) zirconium dichloride,

(1,2′-Diphenylsilylene) (2,1′-methylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, (1,2′-diphenylsilylene) (2,1′-methylene) -bis ( 3-trimethylsilylindenyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, 1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2 , 1′-ethylene) (3-methylcyclopentadienyl) (3′-methylcyclopentadiene) ) Zirconium dichloride, (1,2'-ethylene) (2,1'-methylene) (3-methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-ethylene) ) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3 -Methylcyclopentadienyl) (3'-methylcyclopentadienyl) zirconium dichloride, (1,2'-methylene) (2,1'-isopropylidene) (3-methylcyclopentadienyl) (3'- Methylcyclopentadienyl) zirconium dichloride,

(1,2′-isopropylidene) (2,1′-isopropylidene) (3-methylcyclopentadienyl) (3′-methylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) ( 2,1′-dimethylsilylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′- Isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3 4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-eth ) (2,1′-methylene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1 ′ -Isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-methylene) (2,1′-methylene) (3 4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride,

(1,2′-methylene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′- Isopropylidene) (2,1′-isopropylidene) (3,4-dimethylcyclopentadienyl) (3 ′, 4′-dimethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2 , 1′-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2, 1'-dimethylsilylene) (3-methyl-5-ethylcyclopentadienyl) (3'-methyl-5'-ethylcyclopentadienyl) di Conium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcyclopentadienyl) Zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) (3-methyl-5-n-butylcyclopentadienyl) (3'-methyl-5'-n-butylcyclopenta) Dienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) ) Zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, ( 1,2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-isopropylidene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylcyclopentadienyl) zirconium dichloride , (1,2'-dimethylsilylene) (2,1'-isopropylidene) (3-methyl-5-phenylcyclopentadienyl) (3′-Methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-ethylcyclopentadienyl) (3 ′ -Methyl-5'-ethylcyclopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-ethylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl -5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl -5'-n-butylcyclopentadienyl) zirconium dichloride,

(1,2′-dimethylsilylene) (2,1′-ethylene) (3-methyl-5-phenylcyclopentadienyl) (3′-methyl-5′-phenylcyclopentadienyl) zirconium dichloride, (1 , 2′-dimethylsilylene) (2,1′-methylene) (3-methyl-5-ethylcyclopentadienyl) (3′-methyl-5′-ethylcyclopentadienyl) zirconium dichloride, (1,2 ′ -Dimethylsilylene) (2,1'-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,2'-dimethyl Silylene) (2,1′-methylene) (3-methyl-5-n-butylcyclopentadienyl) (3′-methyl-5′-n-butylsilane) Lopentadienyl) zirconium dichloride, (1,2'-dimethylsilylene) (2,1'-methylene) (3-methyl-5-phenylcyclopentadienyl) (3'-methyl-5'-phenylcyclopentadienyl) Zirconium dichloride, (1,2′-ethylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1,2′-ethylene) (2,1′-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride,

(1,2′-methylene) (2,1′-methylene) (3-methyl-5-isopropylcyclopentadienyl) (3′-methyl-5′-isopropylcyclopentadienyl) zirconium dichloride, (1, 2'-methylene) (2,1'-isopropylidene) (3-methyl-5-isopropylcyclopentadienyl) (3'-methyl-5'-isopropylcyclopentadienyl) zirconium dichloride, (1,1 ' -Dimethylsilylene) (2,2'-dimethylsilylene) bisindenylzirconium dichloride, (1,1'-diphenylsilylene) (2,2'-dimethylsilylene) bisindenylzirconium dichloride, (1,1'-dimethyl Silylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1 ′ Diisopropylsilylene) (2,2′-dimethylsilylene) bisindenylzirconium dichloride, (1,1′-dimethylsilylene) (2,2′-diisopropylsilylene) bisindenylzirconium dichloride, (1,1′-dimethylsilylene) Indenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilyleneindenyl) (2,2′-diphenylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diphenylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylindenyl) zirconium dichloride,

(1,1′-dimethylsilyleneindenyl) (2,2′-diphenylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′-diisopropylsilyleneindenyl) (2,2′-dimethylsilylene-3 -Trimethylsilylindenyl) zirconium dichloride, (1,1'-dimethylsilyleneindenyl) (2,2'-diisopropylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1'-diisopropylsilyleneindenyl) (2 , 2′-Diisopropylsilylene-3-trimethylsilylindenyl) zirconium dichloride, (1,1′-dimethylsilyleneindenyl) (2,2′-dimethylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride, (1 1'-diphenylsilyleneindenyl) (2,2'-diphenylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1'-diphenylsilyleneindenyl) (2,2'-dimethylsilylene-3-trimethylsilyl) Methylindenyl) zirconium dichloride, (1,1′-dimethylsilyleneindenyl) (2,2′-diphenylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride,

(1,1'-diisopropylsilyleneindenyl) (2,2'-dimethylsilylene-3-trimethylsilylmethylindenyl) zirconium dichloride, (1,1'-dimethylsilyleneindenyl) (2,2'-diisopropylsilylene- 3-trimethylmethylsilylindenyl) zirconium dichloride, (1,1′-diisopropylsilyleneindenyl) (2,2′-diisopropylsilylene-3-trimethylmethylsilylindenyl) zirconium dichloride, and the like, and zirconium in these compounds is titanium. Or the thing substituted by hafnium can be mentioned. Of course, it is not limited to these.
Further, it may be an analogous compound of another group or a lanthanoid series metal element.
In the above compound, (1,1 ′ −) (2,2′−) may be (1,2 ′ −) (2,1′−), or (1,2 ′ −) (2 , 1'-) may be (1, 1'-) (2, 2'-).

Next, as the component (b-1) of the component (b), any component can be used as long as it can react with the transition metal compound of the component (a) to form an ionic complex. The following general formulas (III) and (IV) can be used.
([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
(However, L ² is ^{M 2, R 11 R 12 M} 3, R 13 3 C or R ¹⁴ M ^3.)
[In the formulas (III) and (IV), L ¹ is a Lewis base, [Z] ⁻ is a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is a plurality of An anion in which the group is bonded to the element, that is, [M ¹ G ¹ G ² ... G ^f ] ⁻ (where M ¹ is a group 5-15 element of the periodic table, preferably a group 13-15 element of the periodic table) G ^{1 to} G ^f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, or an alkyl group having 6 to 20 carbon atoms. Aryl group, aryloxy group having 6 to 20 carbon atoms, alkylaryl group having 7 to 40 carbon atoms, arylalkyl group having 7 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, 1 to 20 carbon atoms An acyloxy group, an organic metalloid group, or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms Two or more of G ^{1 to} G ^f may form a ring, f is an integer of [(valence of central metal M ¹ ) +1]), [Z ² ] ⁻ is It represents a conjugate base of a Bronsted acid alone or a combination of Bronsted acid and Lewis acid having a logarithm (pKa) of the reciprocal of the acid dissociation constant of -10 or less, or a conjugate base of an acid generally defined as a super strong acid. In addition, a Lewis base may be coordinated. R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹¹ and R ¹² are each a cyclopentadienyl group or a substituted group. cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹³ represents an alkyl group, an aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an ionic valence of [L ¹ −R ¹⁰ ], [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents elements 7 to 12 in the periodic table. ]
What is represented by these can be used conveniently.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.

Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like.
Specific examples of R ¹³ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹⁴ include tetraphenylporphyrin, phthalocyanine, allyl, methallyl, and the like. .
Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ³ include Mn, Fe, Co, Ni, and Zn. And so on.

In [Z ¹ ] ⁻ , that is, [M ¹ G ¹ G ² ... G ^f ], specific examples of M ¹ include B, Al, Si, P, As, Sb, etc., preferably B and Al. Can be mentioned.
Specific examples of G ¹ and G ^{2 to} G ^f include hydrocarbons such as dimethylamino group and diethylamino group as dialkylamino groups, methoxy group, ethoxy group, n-butoxy group and phenoxy group as alkoxy groups or aryloxy groups. Methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-octyl group, n-eicosyl group, phenyl group, p-tolyl group, benzyl group, 4-t-butyl group Phenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon groups, 3, 4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Chill) phenyl group, such as bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexyl antimony group, such as diphenyl boron and the like.

Specific examples of non-coordinating anions, that is, Bronsted acids having a pKa of −10 or less or a conjugate base [Z ² ] ⁻ of a combination of Bronsted acids and Lewis acids include trifluoromethanesulfonate anions (CF ₃ SO ₃ ) ⁻ , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ⁻ , trifluoroacetate anion (CF ₃ CO ₂₎ ^-, hexafluoroantimony anion (SbF ₆₎ ^-, fluorosulfonic acid anion (FSO ₃₎ ^-, chlorosulfonic acid anion (ClSO ₃₎ ^-, fluorosulfonic acid anion / antimony pentafluoride (FSO ₃ / SbF ₅ ) ^-, fluorosulfonic acid anion 5- fluoride arsenic ^{_{(FSO 3 / AsF 5) -}} , trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.

  Specific examples of such an ionic compound that reacts with the transition metal compound of component (a) to form an ionic complex, that is, (b-1) component compound, include triethylammonium tetraphenylborate, tetraphenylboric acid. Tri-n-butylammonium, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, dimethyldiphenyl tetraphenylborate Ammonium, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, benzylpyridinium tetraphenylborate, tetrapheny Methyl borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) Tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) tetraethylammonium borate, benzyl (tri-n-butyl) ammonium borate, tetrakis (pentafluorophenyl) methyldiphenylammonium borate, tetrakis (pentafluoro) Phenyl) triphenyl (methyl) ammonium borate, tetrakis (pentafluorophenyl) methylanilinium borate, Tetrakis (pentafluorophenyl) borate dimethylanilinium tetrakis (pentafluorophenyl) borate trimethyl anilinium tetrakis (pentafluorophenyl) borate methylpyridinium,

Benzylpyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyltetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4 -Cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylanilinium borate, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, Tetraphenylborate tetraphenylporphyrin manganese, tetrakis (pentafluorophenyl) ferrocenium borate, tetrakis (pentafluorophenyl) Acid (1,1'-dimethylferrocenium), tetrakis (pentafluorophenyl) borate decamethylferrocenium, tetrakis (pentafluorophenyl) silver borate, tetrakis (pentafluorophenyl) trityl borate, tetrakis (pentafluorophenyl) Lithium borate, tetrakis (pentafluorophenyl) sodium borate, tetrakis (pentafluorophenyl) tetraphenylporphyrin manganese borate, silver tetrafluoroborate, silver hexafluorophosphate, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, Examples thereof include silver trifluoromethanesulfonate. One type of (b-1) may be used, or two or more types may be used in combination.
On the other hand, as the aluminoxane of the component (b-2), the general formula (V)

(Wherein R ¹⁵ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization. Usually, it is an integer of 2 to 50, preferably 2 to 40. Note that each R ¹⁵ may be the same or different.
A chain aluminoxane represented by the general formula (VI)

（式中、Ｒ¹⁵及びｗは上記一般式（Ｖ）におけるものと同じである。)

(In the formula, R ¹⁵ and w are the same as those in the general formula (V)).

The cyclic aluminoxane represented by these can be mentioned.
Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method.
For example, (1) a method in which an organoaluminum compound is dissolved in an organic solvent and contacting it with water, (2) a method in which an organoaluminum compound is initially added during polymerization, and water is added later, (3) metal There are a method for reacting water adsorbed on salt and the like, water adsorbed on inorganic and organic substances with an organoaluminum compound, and (4) a method for reacting tetraalkyldialuminoxane with trialkylaluminum and further reacting with water. .
The aluminoxane may be insoluble in toluene. These aluminoxanes may be used alone or in combination of two or more.

The use ratio of (a) catalyst component to (b) catalyst component is preferably 10: 1 to 1: 100 in terms of molar ratio when (b-1) compound is used as (b) catalyst component. The range of 2: 1 to 1:10 is desirable, and if it is within the above range, the catalyst cost per unit mass polymer does not become so high and is practical.
When the (b-2) compound is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000.
If it exists in this range, the catalyst cost per unit mass polymer will not become so high, and it is practical.
Moreover, (b-1) and (b-2) can also be used individually or in combination of 2 or more types as a catalyst component (b).

In addition to the above components (a) and (b), the polymerization catalyst for producing the higher α-olefin polymer used in the present invention can use an organoaluminum compound as the component (c).
Here, as the organoaluminum compound of component (c), the general formula (VII)
R ¹⁶ _v AlJ _3-v (VII)
[Wherein R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 It is an integer. ]
The compound represented by these is used.
Specific examples of the compound represented by the general formula (VII) include trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride. , Diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride and the like.
These organoaluminum compounds may be used alone or in combination of two or more.

In the production of the higher α-olefin polymer according to the present invention, preliminary contact may be carried out using the components (a), (b) and (c) described above.
The preliminary contact can be performed by bringing the component (a) into contact with, for example, the component (b). However, the method is not particularly limited, and a known method can be used.
These preliminary contacts are effective in reducing the catalyst cost, such as improving the catalyst activity and reducing the proportion of the (b) component that is the promoter.
Further, by bringing the component (a) and the component (b-2) into contact with each other, an effect of improving the molecular weight can be seen together with the above effect.
The preliminary contact temperature is usually -20 ° C to 200 ° C, preferably -10 ° C to 150 ° C, more preferably 0 ° C to 80 ° C.
In the preliminary contact, an aliphatic hydrocarbon, an aromatic hydrocarbon, or the like can be used as the inert hydrocarbon of the solvent. Particularly preferred among these are aliphatic hydrocarbons.

The use ratio of the catalyst component (a) to the catalyst component (c) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, still more preferably 1:10 to 1 in terms of molar ratio. : The range of 1000 is desirable.
By using the catalyst component (c), the polymerization activity per transition metal can be improved. By making the use ratio in the above range, the organoaluminum compound is not wasted, and the α-olefin polymer. It does not remain in large quantities.

The higher α-olefin polymer used in the present invention is obtained by homopolymerizing a higher α-olefin having 10 or more carbon atoms, polymerizing two or more higher α-olefins having 10 or more carbon atoms, using the polymerization catalyst described above, or It is produced by polymerizing a higher α-olefin having 10 or more carbon atoms and an α-olefin having 9 or less carbon atoms.
In this case, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. Legal is particularly preferred.

About polymerization conditions, superposition | polymerization temperature is -100-250 degreeC normally, Preferably it is -50-200 degreeC, More preferably, it is 0-130 degreeC.
Further, the ratio of the catalyst to the reaction raw material is preferably 1 to 10 ⁸ , particularly preferably 100 to 10 ^{5 in} terms of raw material monomer / component (a) (molar ratio).
Furthermore, the polymerization time is usually about 5 minutes to 10 hours, and the reaction pressure is preferably normal pressure to 20 MPa (gauge), more preferably normal pressure to 10 MPa (gauge).
In the production of the higher α-olefin polymer used in the present invention, it is preferable to add hydrogen since the polymerization activity is improved.
When hydrogen is used, the pressure is usually normal pressure to 5 MPa (gauge), preferably normal pressure to 3 MPa (gauge), and more preferably normal pressure to 2 MPa (gauge).

Examples of the method for adjusting the molecular weight of the higher α-olefin polymer include selection of the type of each catalyst component, the amount used, the polymerization temperature, and polymerization in the presence of hydrogen.
An inert gas such as nitrogen may be present.
When using a polymerization solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane , Halogenated hydrocarbons such as chloroform and dichloromethane can be used.
These solvents may be used alone or in combination of two or more.
Moreover, you may use monomers, such as an alpha olefin, as a solvent.
Depending on the polymerization method, it can be carried out without solvent.

The higher α-olefin polymer used in the present invention can also be produced using a Ziegler-based catalyst containing (d) a solid catalyst component and (e) an organoaluminum compound, in addition to the catalyst described above.
(D) The solid catalyst component contains magnesium, titanium and, if necessary, an electron donating compound. (D-1) Magnesium compounds such as dimethylmagnesium, diethylmagnesium, diethoxymagnesium and magnesium chloride, d-2) Titanium compounds such as tetramethoxytitanium and titanium tetrachloride, and (d-3) alcohols, phenols, ketones, aldehydes, carboxylic acids, malonic acids, organic acids or inorganic acids as necessary. Oxygen-containing electron donors such as esters, monoethers, diethers, and ethers such as polyethers are included.
Of these, diesters of polyvalent carboxylic acids such as dibutyl phthalate are preferred. In the production of the solid catalyst component, a chlorinating agent such as silicon tetrachloride may be added.

Examples of the organoaluminum compound (e) include triethylaluminum and triisobutylaluminum.
One kind of organoaluminum compound may be used, or two or more kinds may be used in combination.
(F) An electron donating compound may be added to the Ziegler-based catalyst as a third component, if necessary.
Examples of the component (f) include organic silicon compounds such as dicyclopentyldimethoxysilane, cyclohexylmethyldimethoxysilane, and cyclohexylisobutyldimethoxysilane.

Although there is no restriction | limiting in particular about the usage-amount of each catalyst component in the said Ziegler type | system | group catalyst, (d) A solid catalyst component will be the range of 0.00005-1 mmol normally per 1L of reaction volumes in conversion of a titanium atom. Such an amount is used, and (e) the organoaluminum compound is used in such an amount that the aluminum / titanium (atomic ratio) is usually in the range of 1 to 1000, preferably 10 to 500.
When this atomic ratio is in the above range, sufficient catalytic activity can be obtained.
When (f) an electron donating compound such as an organosilicon compound is used as the third component, (f) electron donating compound / (e) organoaluminum compound (molar ratio) is usually 0.001 to 5. The amount used is about 0, preferably 0.01 to 2.0, more preferably 0.05 to 1.0.
When this molar ratio is in the above range, sufficient catalytic activity can be obtained.

In the production of the higher α-olefin polymer used in the present invention, from the viewpoint of polymerization activity, the α-olefin may be preliminarily polymerized first and then the main polymerization may be performed as desired.
There is no particular limitation on the polymerization type in this main polymerization, and it can be applied to any of solution polymerization, slurry polymerization, bulk polymerization, etc., and further applicable to both batch polymerization and continuous polymerization, under different conditions. It is also applicable to the two-stage polymerization and multistage polymerization.
Regarding the reaction conditions, the polymerization pressure is not particularly limited, and is usually from atmospheric pressure to about 8 MPa, preferably from 0.2 to 5 MPa, and the polymerization temperature is usually from about 0 to 200 ° C., preferably from the viewpoint of polymerization activity. Is appropriately selected within the range of 30 to 100 ° C.
The polymerization time depends on the type of raw material α-olefin and the polymerization temperature, and cannot be determined generally, but is usually about 5 minutes to 20 hours, preferably 10 minutes to 10 hours.
The molecular weight can be adjusted by adding a chain transfer agent, preferably by adding hydrogen. Further, an inert gas such as nitrogen may be present.

There is no restriction | limiting in particular in the manufacturing method of the wax composition of this invention, It can manufacture by a conventionally well-known method.
That is, it can manufacture by mixing (A) and (B) component and the additive component used as needed, and melt-stirring.
In this case, the component (A) may be heated and dissolved to lower the viscosity, and then the component (B) and the additive component may be mixed. After the component (B) is heated and dissolved to lower the viscosity, (A ) Component and additive component may be mixed.
This stirring is usually performed in a temperature range of 40 to 200 ° C, preferably 40 to 150 ° C, more preferably 40 to 100 ° C.
Further, the components (A) and (B) and the additive component may be mixed and melt-kneaded.
Specifically, the wax of the present invention is prepared by blending each component and kneading using a normal kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a roll mixer, a Brabender plastograph, and a kneader. A composition is obtained.
In particular, since the component (B) is solid at room temperature and becomes a powder, it is easy to handle and at the same time has a low melting point of usually 100 ° C. or lower, which is advantageous for the production of the wax composition of the present invention. .

The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to these examples.
The physical properties of the higher α-olefin polymer were measured by the following methods.
(1) Melting point (Tm) and melting peak half width (Wm)
Differential scanning calorimeter (manufactured by Perkin Elmer, DSC-7), 10 mg of a sample was held at 190 ° C. for 5 minutes in a nitrogen atmosphere, then cooled to −10 ° C. at 5 ° C./min, and at −10 ° C. for 5 minutes. After the holding, the peak top of the maximum peak from the melting endothermic curve obtained by raising the temperature to 190 ° C. at 10 ° C./min was defined as the melting point (Tm).
Furthermore, the peak width at the midpoint of the height from the base line to the peak top of the entire melting peak at the time of Tm measurement was defined as the melting peak half-width Wm.

(2) Peak (X1) and number of peaks The peak (X1) derived from side chain crystallization observed at 15 deg <2θ <30 deg in the wide-angle X-ray scattering intensity distribution measurement was measured.
The wide-angle X-ray scattering intensity distribution is obtained by collimating monochromatic light of 30 kV, 100 mA output CuKα ray (wavelength = 1.54 mm) with a pinhole of φ2 mm using Rigaku Denki Co., Ltd. Rotorflex RU-200. Using a position-sensitive proportional counter, wide-angle X-ray scattering (WAXS) intensity distribution was measured with an exposure time of 1 minute.
The number of peaks is the number of peaks (X1).

(3) Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn)
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method under the following apparatus and conditions.
GPC measuring device: Waters Alliance GPC2000 manufactured by Waters
Column: TOSO GMHHR-H (S) HT
Detector: RI detector measurement conditions for liquid chromatography Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml
Injection volume: 160 μl
Calibration curve: Universal Calibration

Production Example 1 (Production of higher α-olefin polymer)
(1) Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride (1,2′-dimethylsilylene) (2, 3.0 g (6.97 mmol) of a lithium salt of 1′-dimethylsilylene) -bis (indene) was dissolved in 50 mL of THF (tetrahydrofuran) and cooled to −78 ° C.
2.1 mL (14.2 mmol) of iodomethyltrimethylsilane was slowly added dropwise and stirred at room temperature for 12 hours.
The solvent was distilled off, 50 mL of ether was added, and the mixture was washed with a saturated ammonium chloride solution.
After liquid separation, the organic phase was dried to remove the solvent, and 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) was obtained. (Yield 84%).
Next, 3.04 g (5.88 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindene) obtained above in a Schlenk bottle under a nitrogen stream. ) And 50 mL of ether.
The mixture was cooled to −78 ° C., and a hexane solution of n-BuLi (1.54 M, 7.6 mL (1.7 mmol)) was added dropwise.
After raising to room temperature and stirring for 12 hours, ether was distilled off. The obtained solid was washed with 40 mL of hexane to obtain 3.06 g (5.07 mmol) of lithium salt as an ether adduct (yield 73%).
The results of measurement by ¹ H-NMR (90 MHz, THF-d ₈ ) are as follows.
δ: 0.04 (s, 18H, trimethylsilyl); 0.48 (s, 12H, dimethylsilylene); 1.10 (t, 6H, methyl); 2.59 (s, 4H, methylene); 3.38 (Q, 4H, methylene); 6.2-7.7 (m, 8H, Ar-H)

The lithium salt obtained under a nitrogen stream was dissolved in 50 mL of toluene.
After cooling to -78 ° C, a suspension of 1.2 g (5.1 mmol) of zirconium tetrachloride, which had been cooled to -78 ° C in advance, in toluene (20 mL) was added dropwise.
After dropping, the mixture was stirred at room temperature for 6 hours. The solvent of the reaction solution was distilled off.
The obtained residue was recrystallized from dichloromethane to obtain 0.9 g (1 of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride. .33 mmol) was obtained (yield 26%).
The results of measurement by ¹ H-NMR (90 MHz, CDCl ₃ ) are as follows.
δ: 0.0 (s, 18H, trimethylsilyl); 1.02, 1.12 (s, 12H, dimethylsilylene); 2.51 (dd, 4H, methylene); 7.1-7.6 (m, 8H, Ar-H)

(2) Polymerization of higher α-olefin After charging 400 mL of 1-octadecene (Idemitsu Kosan Co., Ltd., Linearlen 18) into a heat-dried autoclave with an internal volume of 1 L under a nitrogen stream, heptane of triisobutylaluminum 0.25 mL (2.0 mmol / mL) of solution was added.
Then, the temperature was raised to 60 ° C. while stirring at 400 rpm, and methylaluminoxane (manufactured by Albemarle, converted to aluminum: 3.0 mmol), (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) under a nitrogen stream. ) 3.0 μmol (10 μmol / mL toluene solution, 0.3 mL) of bis (3-trimethylsilylmethylindenyl) zirconium dichloride was added.
Then, 0.09 MPa of hydrogen was introduced, and polymerization was performed for 2 hours.
After completion of the polymerization, 3 mL of methanol was added to stop the polymerization reaction.
After depressurization, the reaction mixture was poured into 400 mL of acetone to precipitate a polymer, and then the supernatant was removed by decantation and dried under reduced pressure at 150 ° C. for 8 hours to obtain 89 g of a higher α-olefin polymer. .
The physical properties of the obtained polymer were measured as follows: melting point (Tm): 41.2 ° C., melting peak half width (Wm); 2.2, Mw; 121,000, Mw / Mn; 1.8, X1; It was 0.0 ° (the number of peaks was 1).

Examples 1-3 and Comparative Examples 1-2
100 g of a mixture of the higher α-olefin polymer obtained in Production Example 1 and a wax (150 ° F .; 65.6 ° C.) manufactured by Nippon Seiki Co., Ltd. (mixing mass ratio: 100/0, 75/25, 50/50) , 25/75, 0/100) was charged into a 500 mL sample bottle, placed in an oil bath at 120 ° C., and stirred for 1 minute using a metal spatula to obtain a sample.
About the obtained sample, the viscosity in 100 degreeC was measured using the B-type viscometer.
Moreover, about the obtained sample, the penetration and the crack at the time of penetration measurement and a linear expansion coefficient were measured by the following method.
These measurement results are shown in Table 1.
(1) Penetration and cracks during penetration measurement Measured according to JIS K2235-5.4.
Measuring device: RPM-101 (automatic penetration tester)
Needle: For wax (JIS K2235-1991)
Weight: 50g made of brass
Measurement temperature: 25 ° C
(2) Linear expansion coefficient It measured based on JISK7197.
Measuring instrument: SEIKO TMA / SS6100
Weight: 49mN
Temperature rising rate 5 ° C / min Measuring temperature: 25-30 ° C
From Table 1, it can be seen that the wax composition of the present invention has an excellent balance of holding power (penetration), toughness (cracking at the time of penetration measurement) and hardness (viscosity).
Moreover, the wax composition of this invention has the linear expansion coefficient reduced by blending a higher alpha-olefin polymer. This means that the volume change of the wax composition with respect to the temperature change is reduced, which is convenient for applications that require precision such as insulation of electronic parts and lens fixation.

  Since the wax composition of the present invention has the above-mentioned properties, for example, cosmetics (lipstick, pomade, cream, eyebrow, eye shadow, tic, pack, shampoo, rinse), medical (ointment, suppository, emulsion, surgical) Bandages, compresses, stationery (crayons, crepes, pencils, carbon paper), glazing (wood, furniture, leather, automobiles, paper, confectionery, textiles), candles, skin creams, textile oils, confectionery Materials, model materials, sculpture materials, leather finishing materials, insulation materials wax paper, musical instruments, grafting wax printing, mold article manufacturing Fruit wax coating, various greases, ski wax, wax dyeing, polish, car wax, Metal processing oil, rubber anti-aging agent, tire, adhesive, processed paper, heat storage agent, agricultural chemical, fertilizer, abrasive (metal, stainless steel), oil lubricant (grease, mold release agent, paint), dental Dental wax, stationary applications (lenses, embedded) etc., are preferably used.

Claims (2)

  (A) (i) obtained by polymerizing one or more higher α-olefins having 10 or more carbon atoms or (ii) one or more higher α-olefins having 10 or more carbon atoms and one or more α-olefins having 9 or less carbon atoms, A wax composition comprising a combination of 1 to 99% by mass of a crystalline higher α-olefin polymer having a higher α-olefin unit content of 50 mol% or more and (B) 99 to 1% by mass of a hydrocarbon wax. The wax composition according to claim 1, wherein the crystalline higher α-olefin polymer satisfies the following (a) and (b).
(A) Using a suggestion scanning calorimeter (DSC), the polymer was held at 190 ° C. for 5 minutes in a nitrogen atmosphere, then cooled to −10 ° C. at 5 ° C./min, and held at −10 ° C. for 5 minutes. Thereafter, the melting point (Tm) observed from the melting endotherm curve obtained by raising the temperature to 190 ° C. at 10 ° C./min is in the range of 20 to 100 ° C.
(B) A single peak X1 derived from side chain crystallization observed at 15 deg <2θ <30 deg in the wide-angle X-ray scattering intensity distribution is observed.