JP5319992B2 - Lubricating oil composition for gear oil - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lubricating oil composition for use in gear oils which maintains a low viscosity, is still low in the viscosity even at a cryogenic circumstance and also is excellent in the shear stability and oxidation stability. <P>SOLUTION: This lubricating oil composition for use in gear oils includes: a lubricating oil base oil (A) having a viscosity index of 110 or more and a dynamic viscosity at 100&deg;C of 2-7 mm<SP>2</SP>/s; and 5-40 mass% of a 8-20C &alpha;-olefin (co)polymer (B) having a dynamic viscosity at 100&deg;C of 550-2,000 mm<SP>2</SP>/s, a number-average molecular weight (Mn) of 6,000-30,000, a molecular weight distribution (Mw/Mn) of 1.1-1.8, a content of an unsaturated group of 10% or less and a viscosity index within a specified range. <P>COPYRIGHT: (C)2010,JPO&amp;INPIT

Description

  The present invention relates to a lubricating oil composition for gear oils that has low viscosity even at low temperatures, excellent oxidation stability, and little mechanical shear viscosity reduction.

  Gear oil is a lubricating oil for gear devices, and is used to prevent damage and seizure of gear shafts and bearings for automobiles and other high-speed and high-load gears, and load gears for general machines. Such a gear oil is generally required to have a constant viscosity at a high temperature, a low viscosity even at a low temperature, and an excellent shear stability and oxidation stability. In order to improve the temperature characteristics of gear oil, a large amount of a polymer compound having a viscosity index improver and a pour point depressant has been conventionally added. However, a lubricating oil composition containing a large amount of the above-described polymer compound may cause a decrease in viscosity depending on the use conditions under high shear, and a phenomenon such as wear and seizure may be suppressed without obtaining a predetermined viscosity. There is a problem that the performance to be reduced. Further, as a lubricating oil composition having improved temperature characteristics, a refined oil having a high viscosity index and an extreme pressure agent added to an ethylene-α-olefin copolymer have been disclosed (Patent Document 1; No. 63-280796), which has a problem that oxidation stability is not always satisfactory.

In recent years, from the viewpoint of fuel efficiency, automotive gear oil has been studied for low viscosity and high lubrication performance for the purpose of improving fuel efficiency. More recently, emphasis has been placed on reducing friction at start-up and low temperatures, and there is a need for lubricating oils that have low viscosity and low frictional resistance over a wide temperature range from room temperature to low temperatures. On the other hand, from the viewpoint of fuel saving, automotive gear oil tends to have a low viscosity. This low viscosity improves the performance at low temperature, that is, low temperature fluidity, but also decreases the viscosity at high temperature. Therefore, a general commercial gear oil is multi-grade by adding a viscosity index improver. However, if only the viscosity index improver is added, depending on the use conditions under high shear, the viscosity may be lowered and the predetermined viscosity cannot be obtained, and the ability to suppress phenomena such as pitching, wear, and seizure may be reduced. There is sex.
Japanese Unexamined Patent Publication No. 63-280796

  Under these circumstances, the present inventors provide a lubricating oil composition for gear oil that maintains low viscosity, has low viscosity even at extremely low temperatures, and is excellent in shear stability, oxidation stability, and the like. It is for the purpose.

  As a result of intensive studies to develop a lubricating oil composition for gear oil having excellent performance, the present inventors have obtained a specific α-olefin (co) polymer in a predetermined ratio with respect to a specific base oil. It was found that the low-viscosity lubricating oil composition for gear oil blended in (1) could solve the above problems, and the present invention was completed. The present invention has been completed based on such findings.

  That is, the present invention is a lubricating oil composition for gear oil comprising a lubricating base oil (A) and an α-olefin (co) polymer (B) defined by the following (i) to (vi): The present invention provides a gear oil lubricating oil composition comprising 5 to 40% by mass of an α-olefin (co) polymer (B) with respect to the lubricating oil composition.

Lubricating base oil (A);
Viscosity index is 110 or more and kinematic viscosity at 100 ° C. is ² to 7 mm ² / s
α-olefin (co) polymer (B);
(I) (a) a structural unit derived from at least one monomer selected from α-olefins having 8 to 20 carbon atoms in a range of 90 to 100 mol% and (b) a structural unit derived from ethylene. In the range of 0-10 mol%,
(Ii) a kinematic viscosity at 100 ° C. in the range of 550 to 2000 mm ² / s,
(Iii) Number average molecular weight (Mn) is in the range of 6000-30000,
(Iv) a molecular weight distribution (Mw / Mn) in the range of 1.1 to 1.8;
(V) The unsaturated group content at the molecular end is 10% or less, and (vi) the viscosity index satisfies the following formula (1).

Viscosity index ≧ 37.59 ln (kinematic viscosity at 100 ° C.) + 23.08 Formula (1)
(However, ln (kinematic viscosity at 100 ° C.) is the natural logarithm of kinematic viscosity at 100 ° C.)

  The lubricating oil composition for gear oil of the present invention has an excellent balance between low-temperature viscosity characteristics, oxidation stability, and shear stability even when the viscosity is low.

<Lubricant base oil (A)>
The lubricating base oil (A) contained in the gear oil lubricating oil composition of the present invention has a viscosity index of 110 or more, preferably 120 or more, more preferably 130 or more, and a kinematic viscosity of ² to 7 mm ² / s, preferably Is in the range of 3 to 6 mm ² / s. When a lubricating base oil having a kinematic viscosity at 100 ° C. exceeding 7 mm ² / s is used, there is a risk of reducing fuel economy when a lubricating oil composition containing the base oil is used as a gear oil for automobiles. Since a lubricating base oil of less than 2 mm ² / s reduces the viscosity at high temperature and does not provide a sufficient viscosity index, the resulting lubricating oil composition for gear oils may have low temperature fluidity.

As the lubricating base oil (A), various known base oils such as mineral oil, synthetic hydrocarbon oil and ester oil can be used as long as the kinematic viscosity and viscosity index are satisfied.
Mineral oils generally have several grades depending on the method of refining, but generally mineral oils containing 0.5 to 10% wax are used. For example, a highly refined oil having a composition mainly composed of isoparaffin having a low pour point and a high viscosity index produced by a hydrocracking refining method can be used.

  Examples of the synthetic hydrocarbon oil include α-olefin oligomers (PAO), alkylbenzenes, alkylnaphthalenes, and the like, and these can be used alone or in combination of two or more.

  Among these, as the α-olefin oligomer, a low molecular weight oligomer of at least one olefin selected from α-olefins having 8 to 12 carbon atoms can be used. Such an α-olefin oligomer can be produced by cationic polymerization, thermal polymerization, or radical polymerization using a Ziegler catalyst or a Lewis acid as a catalyst.

Alkylbenzenes and alkylnaphthalenes are usually mostly dialkylbenzenes or dialkylnaphthalenes having an alkyl chain length of 6 to 14 carbon atoms. Such alkylbenzenes or alkylnaphthalenes are Friedel of benzene or naphthalene and olefins. Produced by kraft alkylation reaction. The alkylated olefin used in the production of alkylbenzenes or alkylnaphthalenes may be a linear or branched olefin or a combination thereof. These production methods are described, for example, in US Pat. No. 3,909,432.

  As ester oils, monoesters produced from monobasic acids and alcohols; diesters produced from dibasic acids and alcohols, or diols and monobasic acids or acid mixtures; diols, triols (eg trimethylolpropane) And polyol ester produced by reacting tetraol (for example, pentaerythritol), hexaol (for example, dipentaerythritol) and the like with a monobasic acid or an acid mixture. Examples of these esters include tridecyl pelargonate, di-2-ethylhexyl adipate, di-2-ethylhexyl azelate, trimethylolpropane triheptanoate, pentaerythritol tetraheptanoate, and the like.

Of these lubricating base oils (A), mineral oil base oils are particularly preferred from the viewpoint of economy.
<Α-olefin polymer (B)>
The α-olefin (co) polymer (B) contained in the lubricating oil composition for gear oil of the present invention is a polymer that satisfies the requirements defined in the following (i) to (vi).
(I) (a) a structural unit derived from at least one monomer selected from α-olefins having 8 to 20 carbon atoms in a range of 90 to 100 mol% and (b) a structural unit derived from ethylene. In the range of 0-10 mol%,
(Ii) a kinematic viscosity at 100 ° C. in the range of 550 to 2000 mm ² / s,
(Iii) Number average molecular weight (Mn) is in the range of 6000-30000,
(Iv) a molecular weight distribution (Mw / Mn) in the range of 1.1 to 1.8;
(V) The unsaturated group content at the molecular end is 10% or less, and (vi) the viscosity index satisfies the following formula (1).
Viscosity index ≧ 37.59 ln (kinematic viscosity at 100 ° C.) + 23.08 Formula (1)
(However, ln (kinematic viscosity at 100 ° C.) is the natural logarithm of kinematic viscosity at 100 ° C.)

  The (a) monomer having 8 to 20 carbon atoms constituting the α-olefin (co) polymer (B) according to the present invention includes 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene linear α-olefin and 8-methyl-1-nonene , 7-methyl-1-decene, 6-methyl-1-undecene, 6,8-dimethyl-1-decene and the like can be mentioned, and preferably have 8 to 12 carbon atoms. A linear α-olefin, particularly preferably 1-decene.

  An α-olefin polymer having 20 or more carbon atoms has a high viscosity index, but the crystallinity is high, so that the low temperature fluidity may be deteriorated. In addition, an α-olefin polymer having less than 8 carbon atoms has a low viscosity index. In particular, 1-decene (co) polymers are most excellent in the balance of viscosity index and low temperature fluidity.

  The content rate of the structural unit derived from the monomer which consists of (a) C8-C20 alpha olefin which comprises the alpha olefin (co) polymer which concerns on this invention is the range of 90-100 mol%. Preferably, it is 95-100 mol%. An α-olefin copolymer in which the content of a structural unit derived from a monomer comprising an α-olefin is less than 90 mol% may deteriorate the low-temperature viscosity characteristics.

  Moreover, the content rate of the structural unit derived from (b) ethylene which comprises the alpha-olefin (co) polymer which concerns on this invention is the range of 0-10 mol%, Preferably it is the range of 0-5 mol%. is there.

Furthermore, it is preferable that the content rate of the structural unit guide | induced from the (c) C3-C6 alpha-olefin added as needed is the range of 0-30 mol%.
The α-olefin (co) polymer according to the present invention is a polymer of a monomer composed of at least one or more of the above (a) α-olefins having 8 to 20 carbon atoms (α-olefin content 100 mol%). ), Or (b) a copolymer with ethylene. Furthermore, (c) C3-C6 alpha olefin can also be contained as a copolymerization component as needed. Examples of the α-olefin having 3 to 6 carbon atoms include linear α-olefins such as propylene, 1-butene, 1-pentene, and 1-hexene, and branched α-olefins such as 4-methyl-1-pentene. Mention may be made of olefins. These α-olefins can be used alone or in combination of two or more.

According to the present invention α- olefin (co) polymer, a kinematic viscosity at 100 ℃ 550~2000mm ² / s, preferably in the range of 700~1000mm ² / s. Kinematic viscosity is 550mm ²
The α-olefin polymer having a viscosity of less than / s has a low viscosity, and the α-olefin polymer having a viscosity of more than 2,000 mm ² / s has poor shear stability, and the resulting lubricating oil composition for gear oil may have poor performance. is there.

  The α-olefin (co) polymer according to the present invention has a number average molecular weight (Mn) in the range of 6000 to 30000, preferably 12000 to 16000. An α-olefin polymer having a number average molecular weight (Mn) of less than 6000 has low viscosity, an α-olefin polymer having a number average molecular weight of more than 30,000 has poor shear stability, and the resulting lubricating oil composition for gear oil has poor performance. May be inferior.

  The α-olefin (co) polymer according to the present invention has a molecular weight distribution (Mw / Mn) of 1.1 to 1.8, preferably 1.2 to 1.7. An α-olefin polymer having an Mw / Mn exceeding 1.8 tends to cause a decrease in molecular weight due to shearing in a high molecular weight composition part contained in the α-olefin polymer, and also to wear due to evaporation loss due to heat. There is a fear.

  The α-olefin (co) polymer according to the present invention has an unsaturated group content% at the molecular end of 10% or less, preferably 5% or less, more preferably 1% or less. When the α-olefin polymer having an unsaturated group content of more than 10% is used in a lubricating oil composition for gear oil, thickening due to heat and generation of sludge are likely to occur.

The α-olefin (co) polymer according to the present invention has a viscosity index satisfying the following formula (1).
Viscosity index ≧ 37.59 ln (kinematic viscosity at 100 ° C.) + 23.08 Formula (1)
(However, ln (kinematic viscosity at 100 ° C.) is the natural logarithm of kinematic viscosity at 100 ° C.)
By using an α-olefin (co) polymer satisfying Formula 1, the viscosity is low at low temperatures and it does not contain a high molecular weight polymer such as a viscosity index improver, so it has excellent shear stability and satisfies both. The gear oil composition can be provided, and a fuel saving effect can be expected.

<Method for Producing α-Olefin Polymer (B)>
In order to produce the α-olefin (co) polymer according to the present invention, JP-A-2-41303, JP-A-2-41305, JP-A-2-274703, JP-A-2-274704, JP-A-3-179005, JP-A-3-179006, JP-A-3-19396, JP-A-4-69394, JP-A-5-17589, JP-A-6-122718, JP-A-6-122718 JP-A-8-12127, JP-A-8-239414, JP-A-10-087716, JP-A2000-212194 or WO01 / 27124, WO02 / 074855, WO04 / 029062, EP 088123.
6. A catalyst used in producing an α-olefin (co) polymer as described in EP1416000 can be used.

Specifically, in the production of the α-olefin (co) polymer according to the present invention, for example, the transition metal compound is a group IV transition metal compound (A) in the periodic table,
(B) (B-1) an organometallic compound,
(B-2) an organoaluminum compound,
(B-3) an organoaluminum oxy compound,
(B-4) a compound that reacts with the Group IV transition metal compound (A) to form an ion pair,
In the presence of an olefin polymerization catalyst comprising at least one compound selected from the group consisting of: α-olefin homopolymerization having 8 to 20 carbon atoms, α-olefin having 8 to 20 carbon atoms, ethylene, and further if necessary Thus, a homopolymer or a copolymer can be obtained by copolymerizing an α-olefin having 3 to 6 carbon atoms.
More specifically, (A) and (B) are as follows.

[(A) Transition metal compound]
The transition metal compound (A) used in the present invention can be used without particular limitation as long as it is a transition metal compound of the Periodic Tables IV to VI having a known olefin polymerization ability. Examples thereof include transition metal halides, transition metal alkylates, transition metal alkoxylates, non-crosslinkable or crosslinkable metallocene compounds, and the like. Preferred are group IV transition metal halides, more preferably group IVB transition metal halides, transition metal alkylates, transition metal alkoxylates, non-crosslinkable or crosslinkable metallocene compounds, and the like. Hereinafter, preferred forms of these transition metal compounds (A) will be described.

  Specific examples of transition metal halides, transition metal alkylates, and transition metal alkoxylates include titanium tetrachloride, dimethyltitanium dichloride, tetrabenzyl titanium, tetrabenzyl zirconium, and tetrabutoxy titanium.

Examples of the non-crosslinkable or crosslinkable metallocene compound include compounds represented by the following general formula (2) as a transition metal compound of Group IV of the periodic table having a cyclopentadienyl skeleton.
ML _x (2)
In the formula, M represents one transition metal atom selected from Group IV of the Periodic Table, and is preferably zirconium, titanium, or hafnium, which is a Group IVB transition metal. x is the valence of the transition metal and represents the number of L. L represents a ligand or group coordinated to the transition metal, and at least one L is a ligand having a cyclopentadienyl skeleton, and other than the ligand having the cyclopentadienyl skeleton. L can be coordinated by a halogen and a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene, an anionic ligand or a lone electron pair having 10 or less carbon atoms. It is 1 type of group or atom chosen by the same or different combination from a sex ligand.

  Examples of the ligand having a cyclopentadienyl skeleton include a cyclopentadienyl group, an alkyl-substituted cyclopentadienyl group, an indenyl group, an alkyl-substituted indenyl group, a 4,5,6,7-tetrahydroindenyl group, and a fluorenyl group. Groups, alkyl-substituted fluorenyl groups, and the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

When the compound represented by the general formula (2) includes two or more ligands having a cyclopentadienyl skeleton, among the ligands having two cyclopentadienyl skeletons, an alkylene group, It may be bonded via a substituted alkylene group, a silylene group, a substituted silylene group or the like. (In the following description, such a compound may be referred to as a “crosslinkable metallocene compound”. Other than such a compound may be referred to as a “non-bridged metallocene compound”.)

Among these, preferred are compounds represented by the following general formula (3).
ML _a X _b (3)
Wherein M is a Group IV transition metal, preferably a Group IVB transition metal zirconium, titanium or hafnium, L is a ligand coordinated to the transition metal, a is an integer of 1 or more and represents the number of L, X is a halogen bonded to a transition metal and a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral group having 10 or less carbon atoms, One group or atom selected from a conjugated or non-conjugated diene, an anionic ligand, or a neutral ligand capable of coordinating with a lone electron pair in the same or different combination, and b is an integer of 1 or more. The number of X is indicated.)

In the general formula (3), L is a ligand coordinated to a transition metal, and at least one of them is a ligand having a cyclopentadienyl skeleton. Examples of the ligand having a cyclopentadienyl skeleton include cyclopentadienyl group; methylcyclopentadienyl group, dimethylcyclopentadienyl group, trimethylcyclopentadienyl group, tetramethylcyclopentadienyl group, penta Methylcyclopentadienyl group, ethylcyclopentadienyl group, methylethylcyclopentadienyl group, propylcyclopentadienyl group, methylpropylcyclopentadienyl group, butylcyclopentadienyl group, methylbutylcyclopentadienyl And an alkyl-substituted cyclopentadienyl group such as a hexylcyclopentadienyl group; an indenyl group; a 4,5,6,7-tetrahydroindenyl group; a fluorenyl group, and the like. These groups may be substituted with a halogen atom, a trialkylsilyl group or the like.

In the said General formula (3), a is an integer greater than or equal to 1, and shows the number of L. In the general formula (3), M is zirconium, titanium, or hafnium. X represents a halogen and a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene, an anionic ligand or a lone electron pair having a carbon number of 10 or less, which is bonded to a transition metal. Is a group or atom selected from the same or different combinations from the neutral ligands that can be coordinated with each other. Specific examples of the halogen include fluorine, chlorine, bromine, and iodine. Specific examples of the hydrocarbon group Examples include methyl, ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, , 1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl -1-cyclohexyl. 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- Examples include butadiene. Specific examples of the anionic ligand include alkoxy groups such as methoxy, tert-butoxy and phenoxy, carboxylate groups such as acetate and benzoate, and sulfonate groups such as mesylate and tosylate. Specific examples of neutral ligands that can be coordinated by a lone electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, X may be the same or different combinations. In the said General formula (3), b is an integer greater than or equal to 1, and shows the number of X.

  When the compound represented by the general formula (3) includes two or more ligands having a cyclopentadienyl skeleton, the ligands having two cyclopentadienyl skeletons include ethylene, propylene, and the like A substituted alkylene group such as diphenylmethylene; an alkylidene group such as isopropylidene; a silylene group; a substituted silylene group such as a dimethylsilylene group, a diphenylsilylene group, and a methylphenylsilylene group. Further, the ligands having two or more cyclopentadienyl skeletons may be the same or different.

  When the compound represented by the general formula (3) is a ligand having two cyclopentadienyl skeletons, it is more specifically represented by the following general formula (4) or (5).

（式中、Ｍは、周期律表第ＩＶ族の遷移金属であり、好ましくはＩＶＢ族の遷移金属のジルコニウム、チタン又はハフニウムであり、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸、Ｒ⁹、Ｒ¹⁰は水素、炭化水素基、ケイ素含有炭化水素基から選ばれ、それぞれ同一でも異
なっていてもよく、Ｒ¹からＲ¹⁰までの隣接した置換基は互いに結合して環を形成してい
てもよく、Ｘは、ハロゲン、及び水素原子、炭素数が１〜１０の炭化水素基、あるいは炭素数が１０以下の中性、共役または非共役ジエン、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選ばれた１種の基又は原子であり、ｎは１または２であり、Ｘの個数を示す。）

Wherein M is a Group IV transition metal, preferably a Group IVB transition metal zirconium, titanium or hafnium, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, which may be the same or different, and are adjacent substituents from R ¹ to R ^10. May be bonded to each other to form a ring, and X is a halogen and a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, One group or atom selected from an anionic ligand or a neutral ligand capable of coordinating with a lone electron pair in the same or different combination, n is 1 or 2, and represents the number of X. )

（式中、Ｍは、周期律表第ＩＶ族の遷移金属であり、好ましくはＩＶＢ族の遷移金属のジルコニウム、チタン又はハフニウムであり、Ｒ¹、Ｒ²、Ｒ³、Ｒ⁴、Ｒ⁵、Ｒ⁶、Ｒ⁷、Ｒ⁸は水素、炭化水素基、ケイ素含有炭化水素基から選ばれ、それぞれ同一でも異なっていてもよく、Ｒ¹からＲ⁸までの隣接した置換基は互いに結合して環を形成していてもよく、Ｘは、ハロゲン、及び水素原子、炭素数が１〜１０の炭化水素基、あるいは炭素数が１０以下の中性、共役または非共役ジエン、アニオン配位子または孤立電子対で配位可能な中性配位子から同一または異なる組合せで選ばれた１種の基又は原子であり、ｎは１または２であって、Ｘの個数を示し、Ｑは、炭素、ケイ素またはゲルマニウムから選ばれ、Ｙ¹およ
びＹ²は水素、炭化水素基、ケイ素含有炭化水素基から選ばれ、それぞれ同一でも異なっ
ていてもよく、互いに結合して環を形成していてもよい。）

Wherein M is a Group IV transition metal, preferably a Group IVB transition metal zirconium, titanium or hafnium, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ and R ⁸ are selected from hydrogen, a hydrocarbon group, and a silicon-containing hydrocarbon group, and may be the same or different, and adjacent substituents from R ¹ to R ⁸ are bonded to each other to form a ring. X may be a halogen and a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand or isolated One group or atom selected from neutral ligands that can coordinate with an electron pair in the same or different combinations, n is 1 or 2, and indicates the number of X, Q is carbon, Selected from silicon or germanium, Y ¹ and Y ² are hydrogen, hydrocarbon Selected from a basic group and a silicon-containing hydrocarbon group, which may be the same or different, and may be bonded to each other to form a ring.)

In the general formula (4) or (5), 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 carbon. These are alkylaryl groups of several 7 to 20, 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, and 1-ethyl-1-methylpropyl. 1,1,2,2-tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1- Cyclohexyl, 1-adamantyl, 2-adamantyl, 2-methyl-2-adamantyl, menthyl, norbornyl, benzyl, 2-phenylethyl, 1-tetrahydronaphthyl, 1-methyl-1-tetrahydronaphthyl, phenyl, naphthyl, tolyl, etc. Can be mentioned.

In the general formula (4) or (5), the silicon-containing hydrocarbon group is preferably an alkyl or arylsilyl group having 1 to 4 silicon atoms and 3 to 20 carbon atoms, and specific examples thereof include trimethylsilyl, and tert-butyldimethylsilyl, triphenylsilyl and the like.

In the present invention, R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ^{9 in the} general formula (4) are used.
, R ¹⁰ is 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. In addition, R ¹ , R ² , R ³ , R ⁴ , R ⁵ in the general formula (5),
R ⁶ , R ⁷ and R ⁸ 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 thing similar to the above can be mentioned.

The adjacent substituents from R ¹ to R ¹⁰ on the cyclopentadienyl ring of the general formula (4) may be bonded to each other to form a ring. Such substituted cyclopentadienyl groups include indenyl, 2-methylindenyl, tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,4,4-trimethyltetrahydroindenyl, fluorenyl, benzofluorenyl, dibenzofluro Examples include oleenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like. Moreover, the adjacent substituents from R ¹ to R ⁸ on the cyclopentadienyl ring of the general formula (5) may be bonded to each other to form a ring. Such substituted cyclopentadienyl groups include indenyl, 2-methylindenyl, tetrahydroindenyl, 2-methyltetrahydroindenyl, 2,4,4-trimethyltetrahydroindenyl, fluorenyl, benzofluorenyl, dibenzofluro Examples include oleenyl, octahydrodibenzofluorenyl, octamethyloctahydrodibenzofluorenyl and the like.

In the present invention, M in the general formula (4) or (5) is a group IV transition metal of the periodic table, preferably a group IVB transition metal zirconium, titanium or hafnium.
X is a halogen and a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms, or a neutral, conjugated or nonconjugated diene having 10 or less carbon atoms, an anionic ligand, or a lone electron pair. One group or atom selected from the same or different combinations from the organic ligands. Specific examples of the halogen include fluorine, chlorine, bromine and iodine. Specific examples of the hydrocarbon group include methyl, Ethyl, n-propyl, isopropyl, 2-methylpropyl, 1,1-dimethylpropyl, 2,2-dimethylpropyl, 1,1-diethylpropyl, 1-ethyl-1-methylpropyl, 1,1,2,2 -Tetramethylpropyl, sec-butyl, tert-butyl, 1,1-dimethylbutyl, 1,1,3-trimethylbutyl, neopentyl, cyclohexylmethyl, cyclohexyl, 1-methyl-1-cyclohexyl And the like. 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 -Trance-
eta ^{4-1,4-ditolyl-1,3-butadiene,} s- cis - or s- trans eta ^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 electron pair include organic phosphorus compounds such as trimethylphosphine, triethylphosphine, triphenylphosphine, diphenylmethylphosphine, tetrahydrofuran, diethyl ether, dioxane, 1,2- And ethers such as dimethoxyethane. Among these, X may be the same or different combinations.
n is 1 or 2, and indicates the number of X.

Specific examples of the general formula (4) include cyclopentadienyl trichloride, cyclopentadienyl zirconium trichloride, bis (cyclopentadienyl) titanium dichloride, bis (cyclopentadienyl) zirconium dichloride, bis (penta Methylcyclopentadienyl) zirconium dichloride, (cyclopentadienyl) (pentamethylcyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis ( Bis (butylcyclopentadienyl) zirconium including propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, etc. Bis (dimethylcyclopentadienyl) zirconium dichloride, including bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, bis (1,3-diethylcyclopentadienyl) zirconium dichloride, etc. Bis (methylpropylcyclopentadienyl) containing diethylcyclopentadienyl) zirconium dichloride, bis (methylethylcyclopentadienyl) zirconium dichloride, bis (1-methyl-3-n-propylcyclopentadienyl) zirconium dichloride, etc. ) Bis (methylbutylcyclopentadienyl) zirconium dichloride including zirconium dichloride, bis (1-methyl-3-n-butylcyclopentadienyl) zirconium dichloride, etc. Specific examples of the general formula (5) include ethylene bis (indenyl) zirconium dichloride, ethylene bis (1-indenyl) titanium dichloride, ethylene bis (4,5,6,7-tetrahydroindenyl) zirconium dichloride, Dimethylsilylenebis (methylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (dimethylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (di-tert-butylcyclopentadienyl) zirconium dichloride, dimethylsilylenebis (indenyl) zirconium Dichloride, dimethylsilylene bis (2-methylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4,5-benzindenyl) zirconium dichlori , Dimethylsilylene bis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylsilylene bis (2-methyl-4-naphthylindenyl) zirconium dichloride, dimethylethylenebis (2-methylindenyl) zirconium dichloride, dimethyl Ethylenebis (2-methyl-4,5-benzindenyl) zirconium dichloride, dimethylethylenebis (2-methyl-4-phenylindenyl) zirconium dichloride, dimethylethylenebis (2-methyl-4-naphthylindenyl) zirconium dichloride, Isopropylidene (cyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (cyclopentadienyl) (3,6-di-t-butylfluorenyl) zirconium dichloride, isopropyl Den (methylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, isopropylidene (methyl-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, Isopropylidene (methyl-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, isopropylidene (methyl-tert-butylcyclopentadienyl) (octamethyloctahydridodibenz Fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-di-tert-butylfullyl) Olenyl) zirconium dichloride, diphenylmethylene (methylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, diphenylmethylene (methyl-tert-butylcyclopentadienyl) (Fluorenyl) zirconium dichloride, diphenylmethylene (methyl-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, diphenylmethylene (
Methyl-tert-butylcyclopentadienyl) (octamethyloctahydridodibenzfluorenyl) zirconium dichloride, cyclohexylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylene (cyclopentadienyl) (3, 6 -Di-tert-butylfluorenyl) zirconium dichloride, cyclohexylene (
Methylcyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylene (tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylene (methyl-tert-butylcyclopentadienyl) (fluorenyl) zirconium dichloride, cyclohexylene (Methyl-tert-butylcyclopentadienyl) (3,6-di-tert-butylfluorenyl) zirconium dichloride, cyclohexylene (methyl-tert-butylcyclopentadienyl) (octamethyloctahydridodibenzfluorene) Nyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) ) Zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (3,6-ditert) -Butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride,

Di (p-tert-butylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (2 , 7-dimethylfluorenyl) zirconium dichloride, di (
p-tert-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (pn-butylphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium Dichloride, di (pn-butylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (pn-butylphenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (pn-butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (m-tolyl) ) Methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (m-tolyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (m-tolyl) methylene ( Cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dimethyl, di (p-tolyl) methylene (cyclopenta Dienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride Di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzof Oleenyl) zirconium dimethyl, di (p-tert-butylphenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dimethyl, di (p-isopropylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (p- tert-
Butylphenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, di (4-biphenyl) ) Methylene (cyclopentadienyl) (
2,7-ditert-butylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclopentadienyl) (2,7-dimethylfluorenyl) zirconium dichloride, di (4-biphenyl) methylene (cyclo Pentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride cyclopentylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadiene) Dienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclohexane) Pentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, dimethyl Tylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, di (
p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride , Cyclopentylidene (cyclopentadienyl
) (3,6-ditert-butylfluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, adamantylidene (cyclopentadienyl) ) (3,6-ditert-butylfluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (3,6
-Ditert-butylfluorenyl) zirconium dichloride,

Dimethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diphenylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, di ( p-tolyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, diethylmethylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride , Cyclopentylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, adamantylidene (cyclohexane) Pentadienyl) (octamethylocta (Dolobenzofluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, dimethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, Diethylmethylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Zirconium dichloride, cyclopentylidene (cyclopentadienyl) (octamethylte Lahydrodicyclopentafluorenyl) zirconium dichloride, cyclohexylidene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl)
Zirconium dichloride, adamantylidene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, Dimethylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) Zirconium dichloride, diphenylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl)
Zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) Zirconium dichloride, diethylmethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl)
Zirconium dichloride, cyclopentylidene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, cyclohexylidene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, adamantylidene (cyclopentadienyl) (dibenzo) Fluorenyl) Zirconium dichloride, monophenylmonomethylmethylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, dimethylmethylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, diphenylmethylene (cyclopentadienyl) ) (Dibenzofluorenyl) Zirconium dichloride, di (p-tolyl) methylene (cyclopentadienyl) (dibenzofluorenyl) Zirconium dichloride, diethylmethylene (cyclopentadi) Nyl) (dibenzofluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, ethylene (cyclo Pentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) zirconium dichloride, ethylene (cyclopentadienyl) (octa Methyloctahydrodibenzofluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, propylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, Lopylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) Zirconium dichloride, propylene (cyclopentadienyl) (octamethyltetrahydrodicyclopentafluorenyl) Zirconium dichloride, propylene (cyclopentadienyl) ) (Octamethyloctahydrodibenzofluorenyl) zirconium dichloride,

(Methyl) (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) ) Zirconium dichloride, (methyl) (p-tolyl) methylene (cyclopentadienyl) (2,7-ditert-
Butylfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (methyl) (p-tolyl) methylene (cyclopentadi) Enyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (methyl) (phenyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (methyl) (Benzyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride, (methyl) (benzyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorene) Nyl) zirconium dichloride, (methyl) (benzyl) methylene (
Cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (methyl) (benzyl) methylene (cyclopentadienyl) (2,7-ditert-butylfluorenyl) zirconium dichloride, (Methyl) (benzyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride, (
Examples include methyl) (benzyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride and the like.

  In addition to titanium compounds and hafnium compounds having the same three-dimensional structure, bromide, iodide, etc., for example, JP-A-3-9913, JP-A-2-131488, JP-A-3-21607, Examples thereof include transition metal compounds described in Kaihei 3-106907, JP-A-3-188092, JP-A-4-69394, JP-A-4-300787, WO01 / 27124A1, and the like. .

  The transition metal compound (A) used in the polymerization examples and comparative polymerization examples of the present invention is specifically a compound represented by the following formulas (6), (7), (8), (9). The invention is not limited to this compound.

本発明の重合例および比較重合例では、化合物（６）はビス（１，３−ジメチルシクロペンタジエニル）ジルコニウムジクロライド、化合物（７）はジ（ｐ−トリル）メチレン(シクロペンタジエニル)(オクタメチルオクタヒドロジベンゾフルオレニル) ジルコニウ
ムジクロリド化合物（８）はジフェニルメチレン（シクロペンタジエニル）（フルオレニル）ジルコニウムジクロリド、化合物（９）はジ（ベンジル）メチレン（シクロペンタジエニル）（３,６―ジ−tert―ブチルフルオレニル）ジルコニウムジクロリドと記載して
いる。
得られた遷移金属化合物の構造は、２７０ＭＨｚ １Ｈ-ＮＭＲ（日本電子 ＧＳＨ-２７０）、ＦＤ-質量分析（日本電子ＳＸ-１０２Ａ）により、決定される。

In the polymerization examples and comparative polymerization examples of the present invention, the compound (6) is bis (1,3-dimethylcyclopentadienyl) zirconium dichloride, and the compound (7) is di (p-tolyl) methylene (cyclopentadienyl) ( Octamethyloctahydrodibenzofluorenyl) zirconium dichloride compound (8) is diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride, compound (9) is di (benzyl) methylene (cyclopentadienyl) (3.6) -Di-tert-butylfluorenyl) zirconium dichloride.
The structure of the obtained transition metal compound is determined by 270 MHz 1H-NMR (JEOL GSH-270) and FD-mass spectrometry (JEOL SX-102A).

[(B-1) Organometallic compound]
Specifically, as the (B-1) organometallic compound used in the present invention, an organometallic compound represented by the following formula (10) is used.

R ^a R ^b M ³ (10)
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and M ³ is Mg, Zn or Cd. A dialkyl compound of a Group 2 or Group 12 metal represented by the following periodic table.
These organometallic compounds (B-1) may be used alone or in combination of two or more.

[(B-2) Organoaluminum compound]
Examples of the (B-2) organoaluminum compound used in the present invention include an organoaluminum compound represented by the following general formula (11), a complex of a Group 1 metal represented by the following general formula (12) and aluminum. An alkylated product or an organoaluminum oxy compound can be used.

R ^a _m Al (OR ^b ) _n H _p X ² _q (11)
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X ² represents a halogen atom, and m represents 0 <m ≦ 3,
n is a number 0 ≦ n <3, p is a number 0 ≦ p <3, q is a number 0 ≦ q <3, and m + n + p + q = 3. ) An organoaluminum compound represented by Specific examples of such compounds include trimethylaluminum, triethylaluminum, triisobutylaluminum, and diisobutylaluminum hydride.

M ² AlR ^a ₄ (12)
(Wherein M ² represents Li, Na or K, and R ^a has 1 to 15 carbon atoms, preferably 1
-4 hydrocarbon groups are shown. ) A complex alkylated product of a group 1 metal of the periodic table and aluminum. Examples of such compounds include LiAl (C ₂ H ₅ ) ₄ and LiAl (C ₇ H ₁₅ ) ₄ .

Examples of the organoaluminum compound represented by the general formula (11) include compounds represented by the following general formula (13), (14), (15), or (16).
R ^a _m Al (OR ^b ) _3-m (13)
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 1.5 ≦ m ≦ A number of 3.)
R ^a _m AlX ² _3-m (14)
(In the formula, Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X ² represents a halogen atom, and m is preferably 0 <m <3.)
R ^a _m AlH _3-m (15)
(In the formula, Ra represents ^a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, and m is preferably 2 ≦ m <3.)
R ^a _m Al (OR ^b ) _n X ² _q (16)
(In the formula, R ^a and R ^b may be the same or different from each other, and each represents a hydrocarbon group having 1 to 15 carbon atoms, preferably 1 to 4 carbon atoms, X ² represents a halogen atom, and m represents 0 <m ≦ 3,
n is a number 0 ≦ n <3, q is a number 0 ≦ q <3, and m + n + q = 3. )

More specifically, examples of the aluminum compound represented by the general formula (13), (14), (15), or (16) include trimethylaluminum, triethylaluminum, tri-n-butylaluminum, tripropylaluminum, Tri-n-alkylaluminums such as pentylaluminum, trihexylaluminum, trioctylaluminum, tridecylaluminum; triisopropylaluminum, triisobutylaluminum, trisec-butylaluminum, tritert-butylaluminum, tri-2-methylbutylaluminum, tri 3-methylbutylaluminum, tri-2-methylpentylaluminum, tri-3-methylpentylaluminum, tri-4-methylpentylaluminum, tri-2-methylhexylaluminum, tri-3-me Tri-branched alkylaluminums such as ruhexylaluminum and tri-2-ethylhexylaluminum; tricycloalkylaluminums such as tricyclohexylaluminum and tricyclooctylaluminum; triarylaluminums such as triphenylaluminum and tritolylaluminum; diisopropylaluminum hydride formula _{(i-C 4 H 9)} x Al y (C 5 H 10) z; dialkylaluminum hydrides such as hydride (wherein, x, y, z are each a positive number, and z ≦ 2x.) Alkenyl aluminum such as isoprenylaluminum represented by such as; isobutylaluminum methoxide, isobutylaluminum ethoxide, isobutylaluminum isopropoxide and the like Le aluminum alkoxide; dimethyl aluminum methoxide, diethyl aluminum ethoxide, dibutyl aluminum butoxide dialkylaluminum alkoxides such as Sid; ethylaluminum sesquichloride ethoxide, butyl aluminum sesqui blanking such butoxide alkyl sesquichloride alkoxide; general formula R ^a _2.5 Al (OR ^b) Partially alkoxylated alkylaluminum having an average composition such as _0.5 ; diethylaluminum phenoxide, diethylaluminum (2,6-di-t-butyl-4-methylphenoxide), ethylaluminum bis (2,6 -Di-t-butyl-4-methylphenoxide), diisobutylaluminum (2,6-di-t-butyl-4-methylphenoxide), isobutylaluminum bis (2,
Alkyl aluminum aryloxides such as 6-di-t-butyl-4-methylphenoxide);
Dialkylaluminum halides such as dimethylaluminum chloride, diethylaluminum chloride, dibutylaluminum chloride, diethylaluminum bromide, diisobutylaluminum chloride; alkylaluminum sesquichloride such as ethylaluminum sesquichloride, butylaluminum sesquichloride, ethylaluminum sesquibromide; ethylaluminum dichloride, Partially halogenated alkylaluminums such as alkylaluminum dihalides such as propylaluminum dichloride and butylaluminum dibromide; Dialkylaluminum hydrides such as diethylaluminum hydride and dibutylaluminum hydride; Ethylaluminum dihydride and propylaluminum dihydride Other partially hydrogenated alkylaluminums such as any alkylaluminum dihydride; including partially alkoxylated and halogenated alkylaluminums such as ethylaluminum ethoxychloride, butylaluminum butoxycycloride, ethylaluminum ethoxybromide, etc. Can do.

A compound similar to the compound represented by the general formula (11) can also be used, and examples thereof include an organoaluminum compound in which two or more aluminum compounds are bonded through a nitrogen atom. Specific examples of such a compound include (C ₂ H ₅ ) ₂ AlN (C ₂
H ₅ ) Al (C ₂ H ₅ ) _{2 and the} like.

Examples of the compound represented by the general formula (12) include LiAl (C ₂ H ₅ ) ₄ , Li
Such as Al (C ₇ H _{15) 4} may be cited.
A compound that can form the organoaluminum compound in the polymerization system, for example, a combination of an aluminum halide and an alkyl lithium, or a combination of an aluminum halide and an alkyl magnesium can also be used.

Of these, organoaluminum compounds are preferred.
The organoaluminum compound represented by the general formula (11) or the complex alkylated product of the Group 1 metal and aluminum represented by the general formula (12) is used singly or in combination of two or more. .

[(B-3) Organoaluminum oxy compound]
The (B-3) organoaluminum oxy compound according to the present invention may be a conventionally known aluminoxane or a benzene insoluble organoaluminum oxy compound as exemplified in JP-A-2-78687. Also good.

A conventionally well-known aluminoxane can be manufactured, for example with the following method, and is normally obtained as a solution of a hydrocarbon solvent.
(I) Compounds containing adsorbed water or salts containing water of crystallization, such as magnesium chloride hydrate, copper sulfate hydrate, aluminum sulfate hydrate, nickel sulfate hydrate, first cerium chloride hydrate, etc. A method of reacting adsorbed water or crystal water with an organoaluminum compound by adding an organoaluminum compound such as trialkylaluminum to the suspension of the hydrocarbon.
(II) A method in which water, ice or water vapor is allowed to act directly on an organoaluminum compound such as trialkylaluminum in a medium such as benzene, toluene, ethyl ether or tetrahydrofuran.
(III) A method in which an organotin oxide such as dimethyltin oxide or dibutyltin oxide is reacted with an organoaluminum compound such as trialkylaluminum in a medium such as decane, benzene, or toluene.

  The aluminoxane may contain a small amount of an organometallic component. Further, after removing the solvent or the unreacted organoaluminum compound from the recovered aluminoxane solution by distillation, it may be redissolved in a solvent or suspended in a poor aluminoxane solvent.

Specific examples of the organoaluminum compound used when preparing the aluminoxane include the same organoaluminum compounds as those exemplified as the organoaluminum compound belonging to the above (B-2).

Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum is particularly preferable.
The organoaluminum compounds as described above are used singly or in combination of two or more.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atom, That is, those that are insoluble or hardly soluble in benzene are preferred. These (B-3) organoaluminum oxy compounds are used singly or in combination of two or more.

Aluminoxane prepared from trimethylaluminum is called methylaluminoxane or MAO and is a particularly frequently used compound.
Solvents used for the preparation of aluminoxane include aromatic hydrocarbons such as benzene, toluene, xylene, cumene, and cymene, aliphatic hydrocarbons such as pentane, hexane, heptane, octane, decane, dodecane, hexadecane, and octadecane, and cyclopentane. , Cycloaliphatic hydrocarbons such as cyclohexane, cyclooctane and methylcyclopentane, petroleum fractions such as gasoline, kerosene and light oil, or halides of the above aromatic hydrocarbons, aliphatic hydrocarbons and alicyclic hydrocarbons, especially chlorine And hydrocarbon solvents such as bromide and bromide. Furthermore, ethers such as ethyl ether and tetrahydrofuran can also be used. Of these solvents, aromatic hydrocarbons or aliphatic hydrocarbons are particularly preferable.

  The benzene-insoluble organoaluminum oxy compound used in the present invention has an Al component dissolved in benzene at 60 ° C. of usually 10% or less, preferably 5% or less, particularly preferably 2% or less in terms of Al atoms. It is insoluble or hardly soluble.

  As an organoaluminum oxy compound used in the present invention, an organoaluminum oxy compound containing boron represented by the following general formula (17) can also be exemplified.

（式中、Ｒ^cは炭素原子数が１〜１０の炭化水素基を示す。Ｒ^dは、互いに同一でも異なっていてもよく、水素原子、ハロゲン原子または炭素原子数が１〜１０の炭化水素基を示す。）

(In the formula, R ^c represents a hydrocarbon group having 1 to 10 carbon atoms. R ^d may be the same as or different from each other, and is a hydrogen atom, a halogen atom or a hydrocarbon having 1 to 10 carbon atoms. Group.)

The organoaluminum oxy compound containing boron represented by the general formula (17) contains an alkyl boronic acid represented by the following general formula (18) and an organoaluminum compound in an inert solvent under an inert gas atmosphere. Thus, it can be produced by reacting at -80 ° C to room temperature for 1 minute to 24 hours.
R ^c B (OH) ₂ (18)
(In the formula, R ^c represents the same group as described above.)

Specific examples of the alkyl boronic acid represented by the general formula (18) include methyl boronic acid, ethyl boronic acid, isopropyl boronic acid, n-propyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, n-hexyl boron. Acid, cyclohexyl boronic acid, phenyl boronic acid, 3,5-difluorophenyl boronic acid, pentafluorophenyl boronic acid, 3,
And 5-bis (trifluoromethyl) phenylboronic acid. Among these,
Methyl boronic acid, n-butyl boronic acid, isobutyl boronic acid, 3,5-difluorophenyl boronic acid, and pentafluorophenyl boronic acid are preferred. These may be used alone or in combination of two or more.

  Specific examples of the organoaluminum compound to be reacted with the alkylboronic acid include the same organoaluminum compounds as those exemplified as the organoaluminum compound represented by the general formula (11) or (12). .

  Of these, trialkylaluminum and tricycloalkylaluminum are preferable, and trimethylaluminum, triethylaluminum, and triisobutylaluminum are particularly preferable. These may be used alone or in combination of two or more.

[(B-4) Compound that forms an ion pair by reacting with the Group IV transition metal compound (A)]
Examples of the compound (B-4) that forms an ion pair by reacting with the above Group IV transition metal compound (A) include JP-A-1-501950, JP-A-1-502036, and JP-A-3-1.
Lewis acids, ionic compounds, borane compounds and carborane compounds described in JP-A-79005, JP-A-3-179006, JP-A-3-207703, JP-A-3-207704, USP-5321106, etc. Can be mentioned.

Specifically, as the Lewis acid, a compound represented by BR ₃ (R is a phenyl group which may have a substituent such as fluorine, methyl group, trifluoromethyl group or fluorine) is exemplified. For example, trifluoroboron, triphenylboron, tris (4-fluorophenyl) boron, tris (3,5-difluorophenyl) boron, tris (4-fluoromethylphenyl) boron, tris (pentafluorophenyl) boron, tris (p-Tolyl) boron, tris (o-tolyl) boron, tris (3,5-dimethylphenyl) boron, trimethylboron, triisobutylboron and the like can be mentioned.

  Examples of the ionic compound include a compound represented by the following general formula (19).

式中、Ｒ^e+としては、Ｈ⁺、カルベニウムカチオン、オキソニウムカチオン、アンモニ
ウムカチオン、ホスホニウムカチオン、シクロヘプチルトリエニルカチオン、遷移金属を有するフェロセニウムカチオンなどが挙げられる。Ｒ^f〜Ｒⁱは、互いに同一でも異なっていてもよく、有機基、好ましくはアリール基または置換アリール基である。

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

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

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

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

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

Specific examples of the carbenium salt include triphenylcarbenium tetraphenylborate, triphenylcarbeniumtetrakis (pentafluorophenyl) borate, triphenylcarbeniumtetrakis (3,5-ditrifluoromethylphenyl) borate, tris (4-methyl). (Phenyl) carbenium tetrakis (pentafluorophenyl) borate, tris (
And 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-trifluoromethylphenyl) borate, Tri (n-butyl) ammonium tetrakis (3,5-ditrifluoromethylphenyl) borate, tri (n-butyl) ammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrapheny Ruborate, dioctadecylmethylammonium tetrakis (p-tolyl) borate, dioctadecylmethylammonium tetrakis (o-tolyl) borate, dioctadecylmethylammonium tetrakis (pentafluorophenyl) borate, dioctadecylmethylammonium tetrakis (2,4-dimethylphenyl) ) 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 and the like. .

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

  Further, ferrocenium tetrakis (pentafluorophenyl) borate, triphenylcarbenium pentaphenylcyclopentadienyl complex, N, N-diethylanilinium pentaphenylcyclopentadienyl complex, or the following formula (20) or (21) And a borate compound containing an active hydrogen represented by the following formula (22), a borate compound containing a silyl group represented by the following formula (23), and the like.

（式中、Ｅｔはエチル基を示す。）

(In the formula, Et represents an ethyl group.)

［Ｂ− Ｑｎ（Ｇｑ（Ｔ−Ｈ）ｒ）ｚ］^-Ａ⁺ （２２）
式（２２）中、Ｂはホウ素を表す。Ｇは多結合性ヒドロカーボンラジカルを表し、好ましい多結合性ヒドロカーボンとしては炭素数１〜２０を含むアルキレン、アリレン、エチレン、アルカリレンラジカルであり、Ｇの好ましい例としては、フェニレン、ビスフェニレン、ナフタレン、メチレン、エチレン、プロピレン、１，４-ブタジエン、ｐ-フェニレンメチレンがあげられる。多結合性ラジカルＧはｒ＋１の結合、すなわち一つの結合はボレートアニオンと結合し、Ｇのその他の結合ｒは（Ｔ−Ｈ）基と結合する。Ａ⁺はカチオ
ンである。

[B- Qn (Gq (T- H) r) z] - A + (22)
In formula (22), B represents boron. G represents a multi-bonded hydrocarbon radical. Preferred multi-bonded hydrocarbons are alkylene, arylene, ethylene, and alkalin radicals having 1 to 20 carbon atoms. Preferred examples of G include phenylene, bisphenylene, Examples include naphthalene, methylene, ethylene, propylene, 1,4-butadiene, and p-phenylenemethylene. The multi-bond radical G is an r + 1 bond, that is, one bond is bonded to a borate anion, and the other bond r of G is bonded to a (TH) group. A ⁺ is a cation.

T in the above formula (22) represents O, S, NR ^j , or PR ^j , and R ^j represents a hydrocarbanyl radical, a trihydrocarbanylsilyl radical, a trihydrocarbanylgermanium radical, or a hydride. q is an integer of 1 or more, preferably 1. The TH group includes —OH, —SH, —NRH, or —PR ^j H, where R ^j is a hydrocarbyl radical or hydrogen having 1 to 18 carbon atoms, preferably 1 to 10 carbon atoms. is there. Preferred R ^j groups are alkyl, cycloalkyl, allyl, allylalkyl or alkylallyl having 1 to 18 carbon atoms. -OH, -SH, -NR ^j H or -PR ^j H may be, for example, -C (O) -OH, -C (S) -SH-C (O) -NR j H, and C (O
) -PR ^j H is also acceptable. The most preferred group having active hydrogen is the -OH group. Q is hydride, dihydrocarbylamide, preferably dialkylamide, halide, hydrocarbyl oxide, alkoxide, allyl oxide, hydrocarbyl, substituted hydrocarbyl radical and the like. Here, n + z is 4.

As [B-Qn (Gq (TH) r) z] in the above formula (22), for example, triphenyl (hydroxyphenyl) borate, diphenyl-di (hydroxyphenyl) borate, triphenyl (2,4-dihydroxyphenyl) Borate, tri (p-tolyl) (hydroxyphenyl) borate, tris (pentafluorophenyl) (hydroxyphenyl) borate, tris (2,4-dimethylphenyl) (hydroxyphenyl) borate, tris (3,5-dimethylphenyl) (Hydroxyphenyl) borate, tris [3,5-di (trifluoromethyl) phenyl] (hydroxyphenyl) borate, tris (pentafluorophenyl) (2-hydroxyethyl) borate, tris (pentafluorophenyl) (4-hydroxy Butyl) borate, tris (pentafluorophenyl) (4-hydroxycyclohex Le) borate, tris (pentafluorophenyl) [4- (4-hydroxyphenyl) phenyl] borate, tris (pentafluorophenyl) (6-hydroxy-2-naphthyl) borate, and the like, most preferably tris (
Pentafluorophenyl) (4-hydroxyphenyl) borate. Furthermore, it is preferable to substitute the —OH group of the borate compound with —NHR ^j (where R ^j is methyl, ethyl, t-butyl).

Examples of A ⁺ that is a counter cation of the borate compound include a carbonium cation, a tropylium cation, an ammonium cation, an oxonium cation, a sulfonium cation, and a phosphonium cation. Also included are metal cations and organometallic cations whose confidence is easily reduced. Specific examples of these cations include triphenylcarbonium ion, diphenylcarbonium ion, cycloheptatrinium, indenium, triethylammonium, tripropylammonium, tributylammonium, dimethylammonium, dipropylammonium, dicyclohexylammonium, trioctylammonium, N, N-dimethylammonium, diethylammonium, 2,4,6-pentamethylammonium, N, N-dimethylphenylammonium, di- (i-propyl) ammonium, dicyclohexylammonium, triphenylphosphonium, triphosphonium, tridimethylphenyl Phosphonium, tri (methylphenyl) phosphonium, triphenylphosphonium ion, triphenyloxonium ion , Triethyloxonium ion, pyrinium, silver ion, gold ion, platinum ion, copper ion, palladium ion, mercury ion, ferrocenium ion and the like. Of these, ammonium ions are particularly preferred.
[B-Qn (Gq (SiR k R l R m) r) z] - A + (23)

In formula (23), B represents boron. G represents a multi-bonded hydrocarbon radical. Preferred multi-bonded hydrocarbons are alkylene, arylene, ethylene, and alkalin radicals having 1 to 20 carbon atoms. Preferred examples of G include phenylene, bisphenylene, Examples include naphthalene, methylene, ethylene, propylene, 1,4-butadiene, and p-phenylenemethylene. The multi-bond radical G is bonded to r + 1, that is, one bond is bonded to the borate anion, and the other bond r of G is bonded to the (SiR ^k R ^l R ^m ) group. A ⁺ is a cation.

R ^k , R ¹ and R ^m in the above general formula represent a hydrocarbanyl radical, a trihydrocarbanylsilyl radical, a trihydrocarbanylgermanium radical, a hydrogen radical, an alkoxy radical, a hydroxy radical or a halogen compound radical. R ^k , R ^l , R ^m
May be the same or independent. Q is hydride, dihydrocarbylamide, preferably dialkylamide, halide, hydrocarbyl oxide, alkoxide, allyl oxide, hydrocarbyl, substituted hydrocarbyl radical, and more preferably a pentafluorobenzyl radical. Here, n + z is 4.

The formula (23) in the [B-Qn (Gq (SiR k R l R m) r) z] - as, for example, triphenyl (4-dimethylchlorosilyl phenyl) borate, diphenyl chromatography di (4-dimethylchlorosilyl phenyl ) Borate, triphenyl (4-dimethylmethoxysilylphenyl) borate, tri (p-tolyl) (4-triethoxysilylphenyl) borate, tris (pentafluorophenyl) (4-dimethylchlorosilylphenyl) borate, tris (penta Fluorophenyl) (4-dimethylmethoxysilylphenyl) borate, tris (pentafluorophenyl) (4-trimethoxysilylphenyl) borate, tris (pentafluorophenyl) (6-dimethylchlorosilyl-2-naphthyl) borate, etc. .

A ⁺ which is the counter cation of the borate compound is The same thing as A ^<+> in the said Formula (22) is mentioned.
Specific examples of the borane compound include decaborane, bis [tri (n-butyl) ammonium] nonaborate, bis [tri (n-butyl) ammonium] decaborate, bis [tri (n-butyl) ammonium] undecaborate, bis Anion salts such as [tri (n-butyl) ammonium] dodecaborate, bis [tri (n-butyl) ammonium] decachlorodecaborate, bis [tri (n-butyl) ammonium] dodecachlorododecaborate, tri (n -Butyl) ammonium bis (dodecahydridododecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (dodecahydridododecaborate) nickelate (III) and other metal borane anion salts Can be mentioned.

Specific examples of the carborane compound include 4-carbanonaborane, 1,3-dicarbanonaborane, 6,9-dicarbadecarborane, dodecahydride-1-phenyl-1,3-
Dicarbanonaborane, dodecahydride-1-methyl-1,3-dicarbanonaborane, undecahydride-1,3-dimethyl-1,3-dicarbanonaborane, 7,8-dicarbaundecaborane, 2 , 7-Dicarbaoundecaborane, Undecahydride-7,8-dimethyl-7
, 8-dicarbaound decaborane, dodecahydride-11-methyl-2,7-dicarbaound decaborane, tri (n-butyl) ammonium 1-carbadecaborate, tri (n-butyl) ammonium 1-carbaound decaborate , Tri (n-butyl) ammonium 1-carbadodecaborate, tri (n-butyl) ammonium 1-trimethylsilyl-1-carbadecaborate, tri (n-butyl) ammonium bromo-1-carbadodecaborate, tri (n- Butyl) ammonium 6-carbadecaborate, tri (n-butyl) ammonium 6-carbadecaborate,
Tri (n-butyl) ammonium 7-carbaundecaborate, tri (n-butyl) ammonium 7,8-dicarboundeborate, tri (n-butyl) ammonium 2,9-dicarboundeborate, tri (n- Butyl) ammonium dodecahydride-8-methyl-7,9-
Dicarbaound decaborate, tri (n-butyl) ammonium undecahydride-8-ethyl-7,9-dicarbaundecaborate, tri (n-butyl) ammonium undecahydride-8-butyl-7,9-dicarbaun Decaborate, tri (n-butyl) ammonium undecahydride-8-allyl-7,9-dicarbaound decaborate, tri (n-butyl) ammonium undecahydride-9-trimethylsilyl-7,8-dicarbaound decaborate , Salts of anions such as tri (n-butyl) ammonium undecahydride-4,6-dibromo-7-carbaundecaborate; tri (n-butyl) ammonium bis (nonahydride-
1,3-dicarbanonaborate) cobaltate (III), tri (n-butyl) ammonium bis (
Undecahydride-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbundecaborate) cobaltate (III), tri (n-Butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) nickelate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) Cuprate (III), tri (n-butyl) ammonium bis (undecahydride-7,8-dicarbaundecaborate) aurate (III), tri (n-butyl) ammonium bis (nonahydride-7, 8-Dimethyl-7,8-dicarbaundecaborate) ferrate (III), tri (n-butyl) ammonium bis (nonahydride-7,8-dimethyl-7,8-dicarbaundecaborate) chromate (III), Li (n- butyl) ammonium bis (tribromo octa-7,8-dicarbaundecaborate deca borate) cobaltate (III), tris [tri (n- butyl) ammonium] bis (undecapeptide hydride 7-
Carbundecaborate) chromate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) manganate (IV), bis [tri (n-
(Butyl) ammonium] bis (undecahydride-7-carbaundecaborate) cobaltate (III), bis [tri (n-butyl) ammonium] bis (undecahydride-7-carbaundecaborate) nickelate And salts of metal carborane anions such as (IV).

In addition, the compound (B) which reacts with the above group IV transition metal compound (A) to form an ion pair can be used in combination of two or more.
As the component (B) used in the polymerization example of the present invention, the organoaluminum oxy compound (B-3) shown above was used. Specifically, it is a commercially available MAO / toluene solution manufactured by Nippon Alkyl Aluminum Co., Ltd.

  In addition, in the preparation of the olefin polymerization catalyst used in the present invention, a carrier can be used as necessary. The carrier is usually an inorganic or organic compound and is a granular or particulate solid. Among these, examples of the inorganic compound include porous oxides, inorganic chlorides, clays, clay minerals, and ion exchange layered compounds.

Specific examples of the porous oxide include SiO ₂ , Al ₂ O ₃ , MgO, ZrO, TiO ₂ and B _2.
O ₃ , CaO, ZnO, BaO, ThO ₂ etc., or composites or mixtures containing these are used, for example natural or synthetic zeolite, SiO ₂ —MgO, SiO ₂ —Al ₂ O ₃ , SiO ₂ —TiO ₂ , SiO _{2 -V 2 O 5, SiO 2} -Cr 2 O 3, etc. can be used SiO ₂ -TiO ₂ -MgO.

In the present invention, an α-olefin is (co) polymerized in the presence of the olefin polymerization catalyst as described above to produce an olefin low molecular weight polymer.
Specific embodiments for producing the α-olefin (co) polymer according to the present invention will be described in detail below.

  In the present invention, the α-olefin polymerization reaction is carried out in a hydrocarbon medium. Specific examples of such hydrocarbon media include aliphatic hydrocarbons such as propane, butane, pentane, hexane, heptane, octane, decane, dodecane, and kerosene, and alicyclic carbons such as cyclopentane, cyclohexane, and methylcyclopentane. Examples thereof include aromatic hydrocarbons such as hydrogen, benzene, toluene and xylene, halogenated hydrocarbons such as ethylene chloride, chlorobenzene and dichloromethane, and petroleum fractions such as gasoline, kerosene and light oil. Furthermore, the olefin used for superposition | polymerization can also be used.

In the present invention, the polymerization is carried out in the presence of the α-olefin polymerization catalyst as described above. In this case, the Group IV transition metal compound (A) is a concentration of the transition metal atom in the polymerization reaction system. As usual in an amount ranging from 10 ⁻⁸ to 1 gram atom / liter, preferably from 10 ⁻⁷ to 10 ⁻¹ gram atom / liter.

Component (B-1) is a molar ratio of (B-1) component to all transition metal atoms (M) in component (A) [(
B-1) / M] is usually used in an amount of 0.01 to 5000, preferably 0.05 to 2000. Component (B-2) has a molar ratio [(B-2) / M] of (B-2) component to all transition metal atoms (M) in component (A) of usually 100 to 25000, preferably The amount used is 500 to 10,000. Component (B-3) has a molar ratio [(B-3) / M] of the aluminum atoms in component (B-3) and all transition metals (M) in component (A) usually 10 to 10. The amount used is 5000, preferably 20-2000. In the component (B-4), the molar ratio [(B-4) / M] of the component (B-4) and the transition metal atom (M) in the component (A) is usually 1 to 50, preferably 1. It is used in such an amount that it becomes ~ 20.

  Moreover, the polymerization temperature of the α-olefin using such an α-olefin polymerization catalyst is usually in the range of −50 to + 200 ° C., preferably 0 to 180 ° C. The polymerization pressure is usually from normal pressure to 10 MPa gauge pressure, preferably from normal pressure to 5 MPa gauge pressure, and the polymerization reaction can be carried out in any of batch, semi-continuous and continuous methods. Furthermore, the polymerization can be performed in two or more stages having different reaction conditions. The molecular weight of the α-olefin (co) polymer obtained can be adjusted by allowing hydrogen to be present in the polymerization system or changing the polymerization temperature.

<Lubricating oil composition for gear oil>
The lubricating oil composition for gear oil of the present invention is a lubricating oil composition for gear oil comprising the lubricating base oil (A) and the α-olefin (co) polymer (B), and the lubricating oil composition 5-40 mass% of (alpha) -olefin (co) polymer (B) is included with respect to a thing.

The lubricating oil composition for gear oil of the present invention preferably has a kinematic viscosity at 40 ° C. of 80 mm ² /
The kinematic viscosity at 40 ° C. is more preferably 70 to 80 mm ² / s, and particularly preferably 70 to 76 mm ² / s. The kinematic viscosity at 100 ° C. is controlled in the range of 13.5 to 14.5 mm ² / s, more preferably the kinematic viscosity at 100 ° C. is controlled in the range of 13.8 to 14.2 mm ² / s. It has been done. Kinematic viscosity at 40 ° C. is 80 mm ² / s or less, a kinematic viscosity at 100 ° C. is the in the range of 13.5~14.5mm ² / s, contribute to fuel efficiency because it maintained a low viscosity at cold start.

  The lubricating oil composition for gear oil according to the present invention comprises a compatibilizer, a detergent-dispersant, an antioxidant, a corrosion inhibitor, an anti-resistance, in addition to the lubricating base oil (A) and the α-olefin (co) polymer. You may contain the at least 1 sort (s) of additive chosen from the group which consists of an abrasion agent, a friction modifier, a pour point depressant, a rust preventive agent, an antifoamer, and an extreme pressure agent.

<Compatibilizer>
As a compatibilizing agent contained in the lubricating oil composition for gear oil of the present invention, an ester can be blended. Examples of the esters include dibasic acids (eg, phthalic acid, succinic acid, alkyl succinic acid, alkenyl succinic acid, maleic acid, azelaic acid, peric acid, sebacic acid, fumaric acid, adipic acid, linoleic acid dimer, etc.). Esters with alcohols (for example, butyl alcohol, hexyl alcohol, 2-ethylhexyl alcohol, dodecyl alcohol, ethylene glycol, diethylene glycol monoether, propylene glycol, etc.); C5-C18 monocarboxylic acids and polyols (for example, neopentyl) Glycol, trimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, etc.); other polyoxyalkylene glycols, polyoxyalkylene glycol esters Polyoxyalkylene glycol ether, phosphoric acid ester, etc. can also be mentioned. The content of these compatibilizers is 10 to 25% by mass, preferably 14 to 22% by mass, based on the total weight of the lubricating oil composition for gear oil.

<Cleaning dispersant>
Various known detergent dispersants can be used as the detergent dispersant contained in the gear oil lubricating oil composition of the present invention. Specifically, for example, metal sulfonate, metal phenate, metal phosphonate, succinimide and the like can be exemplified, and usually used in a range of 0 to 15% by mass.

<Antioxidant>
As the antioxidant contained in the gear oil lubricating oil composition of the present invention, various known antioxidants can be used. Specific examples include phenolic and amine compounds such as 2,6-di-tert-butyl-4-methylphenol. An antioxidant is used in 0-3 mass% as needed.

<Rust preventive>
Examples of the rust inhibitor contained in the lubricating oil composition for gear oil of the present invention include, for example, fatty acid, alkenyl succinic acid half ester, fatty acid soap, alkyl sulfonate, polyhydric alcohol fatty acid ester, fatty acid amine, paraffin oxide, alkyl A polyoxyethylene ether etc. are mentioned, These are normally used in the ratio of 0-3 mass%.

<Antiwear agent>
As the antiwear agent contained in the lubricating oil composition for gear oil of the present invention, various known antiwear agents can be used. Specifically, for example, inorganic or organic molybdenum compounds such as molybdenum disulfide, organic boron compounds such as alkyl mercaptyl borate; graphite, antimony sulfide, boron compounds, polytetrafluoroethylene and the like can be exemplified. The antiwear agent is used in the range of 0 to 3% by mass as necessary.

<Friction modifier>
Various known friction modifiers can be used as the friction modifier contained in the gear oil lubricating oil composition of the present invention. Specifically, for example, an amine compound, a fatty acid amide, having at least one alkyl group or alkenyl group having 6 to 30 carbon atoms, particularly a linear alkyl group or linear alkenyl group having 8 to 24 carbon atoms in the molecule, Examples thereof include fatty acid metal salts. Examples of the amine compound include aliphatic (poly) amines having a linear or branched alkyl group or alkenyl group, or alkylene oxide adducts thereof. The friction modifier is used in the range of 0 to 3% by mass as necessary.

<Pour point depressant>
Various known pour point depressants can be used as the pour point depressant contained in the gear oil lubricating oil composition of the present invention. Specifically, for example, polymethacrylate, alkylnaphthalene and the like can be exemplified, and they are usually used in the range of 0 to 3% by mass.

<Rust preventive>
As a rust preventive agent contained in the lubricating oil composition for gear oil of the present invention, various known rust preventive agents can be used. Specific examples include various amine compounds, carboxylic acid metal salts, polyhydric alcohol esters, phosphorus compounds, sulfonates, and the like. A rust preventive is used in the range of 0 to 3% by mass as necessary.

<Antifoaming agent>
Various known antifoaming agents can be used as the antifoaming agent contained in the lubricating oil composition for gear oil of the present invention. Specific examples include silicone compounds such as dimethylsiloxane and silica gel dispersion, alcohol compounds and ester compounds. An antifoamer is used in the range of 0-0.2 mass% as needed.

<Extreme pressure agent>
Various known extreme pressure agents can be used as the extreme pressure agent contained in the gear oil lubricating oil composition of the present invention. Specifically, for example, sulfur extreme pressure agents such as sulfides, sulfoxides, sulfones, thiophosphinates, thiocarbonates, sulfurized fats and oils, sulfurized olefins; phosphoric acid esters, phosphorous acid esters, phosphoric acid esters Illustrative are phosphoric acids such as amine salts and phosphite amines; and halogen compounds such as chlorinated hydrocarbons. An extreme pressure agent is used in the range of 0 to 15% by mass as necessary.

EXAMPLES Hereinafter, although this invention is demonstrated further more concretely based on an Example, this invention is not limited by these Examples.
The physical properties of the lubricating base oil (A) and the α-olefin (co) polymer (A) according to the present invention were measured by the following methods.

(1) Kinematic viscosity (mm ² / s) and viscosity index Based on JIS K2283, the kinematic viscosity at 40 ° C. (KV 40 ° C.) and the kinematic viscosity at 100 ° C. (KV 100 ° C.) were measured, and the viscosity index was calculated.

(2) Number average molecular weight (Mn) and molecular weight distribution (Mw / Mn)
The number average molecular weight (Mn) and molecular weight distribution (Mw / Mn) were measured as follows using GPC (Chromatopack C-R4A) manufactured by Shimadzu Corporation. The separation column is TSKG6000H XL, G4000H XL, G3000H XL, G2000H XL, the column temperature is 40 ° C., the mobile phase is tetrahydrofuran (Wako Pure Chemical Industries), the development rate is 0.8 ml / min, the sample concentration Was 0.2 mass%, the sample injection amount was 20 microliters, and a differential refractometer was used as a detector. As the standard polystyrene, those manufactured by Tosoh Corporation were used.

(3) Unsaturated group content at molecular fragment end The unsaturated group content at the molecular fragment end was measured as follows using an EX400 nuclear magnetic resonance apparatus manufactured by JEOL. ¹ H-NMR was measured at room temperature on a sample prepared by adjusting the polymer to 2% by mass in deuterated chloroform (Aldrich, 99.8 atom% D) as a lock solvent in a sample tube. As for the peak of each hydrogen of the polymer, the peak (A) based on the terminal saturated methyl group is 0.65 to 0.85 ppm, and the peak (B) based on the vinylidene group is 4.
70 ppm to 4.80 ppm, peaks (C) and (D) based on vinyl groups of 4.8 each.
5 to 5.0 ppm and 5.7 to 5.9 ppm, peaks (E) based on internal olefins are observed at 5.10 to 5.30 ppm, and peaks (F) based on methylene groups are observed at 0.90 to 2.0 ppm. The If the peak areas of each peak (A), (B), (C), (D), (E), (F) are SA, SB, SC, SD, SE, SF, respectively, The number N of unsaturated bonds is calculated by the following formula (24) from the peak intensities of (A), (B), (C), (D), (E), and (F).

Ａ：メチル；０．６５〜０．８５ｐｐｍ
Ｂ：ビニリデン；４．７０〜４．８０ｐｐｍ
Ｃ：ビニル；４．８５〜５．００ｐｐｍ
Ｄ：ビニル；５．７０〜５．９０ｐｐｍ
Ｅ：内部オレフィン（３置換体）；５．１〜５．３ｐｐｍ
Ｆ：メチレン；０．９〜２．０ｐｐｍ
分子片末端における不飽和基の含有率は、上記式（２４）より求めたＮとＶＰＯにより測定した絶対平均分子量Ｍを用いて、下記式（２５）にて算出される。

A: Methyl; 0.65-0.85 ppm
B: Vinylidene; 4.70 to 4.80 ppm
C: Vinyl; 4.85 to 5.00 ppm
D: Vinyl; 5.70-5.90 ppm
E: Internal olefin (trisubstituted product); 5.1 to 5.3 ppm
F: Methylene; 0.9 to 2.0 ppm
The unsaturated group content at the end of the molecular piece is calculated by the following formula (25) using the absolute average molecular weight M measured by N and VPO determined from the above formula (24).

Unsaturated group content [%] at molecular terminal end = N × M × (2/14) (25)
N: Number of unsaturated groups [units / total protons]
M: Absolute molecular weight

(5) Pour point (° C)
The pour point was measured according to JIS-K-2269. The physical properties of the lubricating oil composition for gear oil containing the lubricating base oil (A) and the α-olefin (co) polymer (B) according to the present invention are as follows: It measured by the following method.

(1) Viscosity characteristics (mm ² / s)
In accordance with JIS K2283, the kinematic viscosity at 40 ° C. (KV 40 ° C.) and the kinematic viscosity at 100 ° C. (KV 100 ° C.) were measured, and the viscosity index was calculated.

(2) Low temperature viscosity (mPa · s)
Low temperature viscosity measured Brookfield viscosity in -40 degreeC (based on JPI 5S-26-85). Evaluation set 150,000 mPa * s or less as the pass.

(3) Shear stability Shear stability was evaluated using a KRL shear stability tester in accordance with the method described in DIN 52350-6. The blended oil was placed under shearing conditions (1450 rpm) at 60 ° C. for 20 hours, and the rate of decrease in kinematic viscosity at 100 ° C. before and after the test was evaluated.

(4) Oxidation stability In the oxidation performance test, a test method based on the lubricating oil oxidation stability test (ISOT) for internal combustion engines specified in JIS K2514 was used. The test method is as shown below, and the performance evaluation is as follows. The kinematic viscosity after the 96 hr test is determined by JIS K2283 (the kinematic viscosity test method for crude oil and petroleum products and the petroleum product viscosity index calculation method). Determined by potentiometric titration method defined in K2501 (Petroleum product neutralization number test method). The rate of change is calculated from these values, and it is evaluated that the smaller the rate of change, the more the oxidative degradation can be suppressed. Moreover, it performed by the presence or absence of sludge generation.

ISOT test conditions Sample oil 250 ml Catalyst Cu: Thickness 0.5 mm, 26 mm × 60.4 mm Fe: Thickness 0.5 mm, 26 mm × 121.4 mm Coiled and wound in a cylindrical shape Stirring speed 1300 rpm Temperature 165.5 ℃
The α-olefin (co) polymer used in Examples and Comparative Examples was produced by the following method.

Note that bis (1,3-dimethylcyclopentadienyl) zirconium dichloride used in Examples and Comparative Examples was synthesized with reference to the method described in JP-A No. 2000-136195. Di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) Zirconium dichloride was synthesized with reference to the method described in JP-A No. 2004-182715. Diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride was synthesized with reference to the method described in JP-A-2-274703. Di (benzyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride was synthesized with reference to the method described in JP-A No. 2004-189666.

[Polymerization Example 1]
A 1000 ml autoclave thoroughly purged with nitrogen was charged with 400 ml of heptane and 100 ml of 1-decene, followed by addition of 0.2 mmol of a heptane solution of triisobutylaluminum, and di (p-tolyl) methylene (cyclopentadienyl) ( Octamethyloctahydrodibenzofluorenyl) Toluene solution of zirconium dichloride 0.001 mmol [0.001 mmol in terms of zirconium atom], N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate heptane slurry 0.004 mmol In addition, after the temperature was raised to 50 ° C., the pressure was increased to 0.8 MPa · G with hydrogen gas, the temperature was set to 55 ° C., and polymerization was performed while stirring for 60 minutes. After the polymerization, cooling and depressurization were performed, and a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1 mol / L hydrochloric acid aqueous solution and stirred. This solution was transferred to a separatory funnel, and the organic layer was separated. Then, the organic layer was washed with 500 ml of water, and the organic layer was separated, and 175 ° C. under reduced pressure (1 mmHg) and 1 unreacted with the solvent. -Decene was distilled off.

  The yield of the obtained transparent liquid 1-decene polymer was 30.8 g, and the polymerization activity was 30.8 kg-polymer / mmol-Zr · hr. Table 1 shows the physical properties of the resulting 1-decene polymer (Polymer 1).

[Polymerization Example 2]
A 1000 ml autoclave thoroughly purged with nitrogen was charged with 425 ml of heptane and 75 ml of 1-decene, followed by addition of 0.2 mmol of a heptane solution of triisobutylaluminum, and di (p-tolyl) methylene (cyclopentadienyl) ( Octamethyloctahydrodibenzofluorenyl) Toluene solution of zirconium dichloride 0.002 mmol [0.002 mmol in terms of zirconium atom], N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate heptane slurry 0.008 mmol In addition, after raising the temperature to 55 ° C, the pressure was increased to 0.8 MPa · G with hydrogen gas, and the temperature was increased to 60 ° C.
Polymerization was conducted with stirring for 0 minute. After the polymerization, cooling and depressurization were performed, and a small amount of isopropanol was added to terminate the polymerization. The polymer solution was added to 300 ml of 1 mol / L hydrochloric acid aqueous solution and stirred. This solution was transferred to a separatory funnel, and the organic layer was separated. Then, the organic layer was washed with 500 ml of water, and the organic layer was separated, and 175 ° C. under reduced pressure (1 mmHg) and 1 unreacted with the solvent. -Decene was distilled off.

  The yield of the obtained transparent liquid 1-decene polymer was 15.5 g, and the polymerization activity was 7.8 kg-polymer / mmol-Zr · hr. Table 1 shows the physical properties of the resulting 1-decene polymer (Polymer 2).

[Polymerization Example 3]
In Polymerization Example 2, a 1-decene polymer was obtained in the same manner as Polymerization Example 2 except that the polymerization temperature was changed from 60 ° C to 40 ° C.

  The yield of the obtained transparent liquid 1-decene polymer was 19.3 g, and the polymerization activity was 9.7 kg-polymer / mmol-Zr · hr. Table 1 shows the physical properties of the resulting 1-decene polymer (Polymer 3).

[Polymerization Example 4]
A 1000 ml glass polymerization vessel sufficiently purged with nitrogen was charged with 250 ml of n-decane and 250 ml of 1-decene and heated to 75 ° C. Subsequently, 0.002 mmol [0.002 mmol in terms of zirconium atom] of a toluene solution of diphenylmethylene (cyclopentadienyl) (fluorenyl) zirconium dichloride was added, and methylaluminoxane [M
AO] [10% toluene solution made by Japanese alkylaluminum] in terms of aluminum atom is 2 m
mol, and then hydrogen gas 35 L / hr is added to the glass container to bring the temperature to 80 ° C.
Polymerization was conducted with stirring for 0 minute. During the polymerization, hydrogen gas was continuously supplied while maintaining 80 ° C. After the polymerization, the gas supply was stopped, and a small amount of isopropanol was added to stop the polymerization. The polymer solution was added to 300 ml of 1 mol / L hydrochloric acid aqueous solution and stirred. This solution was transferred to a separatory funnel, and the organic layer was separated. Then, the organic layer was washed with 500 ml of water, and the organic layer was separated, and 175 ° C. under reduced pressure (1 mmHg) and 1 unreacted with the solvent. -Decene was distilled off.

  The yield of the obtained transparent liquid 1-decene polymer was 29.4 g, and the polymerization activity was 14.7 kg-polymer / mmol-Zr · hr. Table 1 shows the physical properties of the obtained 1-decene polymer (polymer 4).

[Polymerization Example 5]
A 1000 ml glass polymerization vessel sufficiently purged with nitrogen was charged with 250 ml of n-decane and 250 ml of 1-decene, and the temperature was raised to 95 ° C. Subsequently, 0.002 mmol of toluene solution of di (benzyl) methylene (cyclopentadienyl) (3,6-ditert-butylfluorenyl) zirconium dichloride [0.002 mmol in terms of zirconium atom] was added, and methylaluminoxane was added. [MAO] [10% toluene solution made by Japanese alkylaluminum] was converted to aluminum atom and 2 mmol was added, and then hydrogen gas 20 L / hr in a glass container,
Ethylene gas 5 L / hr was added, the temperature was set to 100 ° C., and polymerization was performed with stirring for 60 minutes.
During the polymerization, hydrogen gas and ethylene gas were continuously supplied while maintaining 100 ° C. After the polymerization, the gas supply was stopped, and a small amount of isopropanol was added to stop the polymerization. The polymer solution was added to 300 ml of 1 mol / L hydrochloric acid aqueous solution and stirred. This solution was transferred to a separatory funnel, and the organic layer was separated. Then, the organic layer was washed with 500 ml of water, and the organic layer was separated, and 175 ° C. under reduced pressure (1 mmHg) and 1 unreacted with the solvent. -Decene was distilled off.

  The yield of the obtained transparent liquid 1-decene · ethylene copolymer was 11.8 g, and the polymerization activity was 5.9 kg-polymer / mmol-Zr · hr. Table 1 shows the physical properties of the resulting 1-decene / ethylene copolymer (Copolymer 5).

[Comparative Polymerization Example 1]
Using a continuous polymerization reactor, purified toluene is 1 L / hr, purified 1-decene is 1 L / hr methylaluminoxane [MAO] (Japan alkylaluminum 10% toluene solution) in terms of aluminum atoms, 11 mmol / L, bis (1,3-Dimethylcyclopentadienyl) zirconium dichloride is continuously supplied at a rate of 0.02 mmol / L in terms of zirconium atoms, and at the same time in the polymerization vessel, nitrogen is 250 L / hr and hydrogen is 50 L / hr. The polymerization was carried out under the conditions of a polymerization temperature of 20 ° C., a normal pressure, and a residence time of 1.0 hour. The polymer solution was continuously withdrawn from the polymerization vessel, and the polymerization was stopped by adding a small amount of methanol. Add 1 L of water and a little hydrochloric acid (about 20 mL) to the polymer solution.
After stirring for a minute, leave to stand and separate the aqueous layer. Next, 2 L of water is added and stirred for 10 minutes, and then allowed to stand to separate the aqueous layer. This was repeated twice. Then, colorless and transparent liquid polymer was obtained by removing toluene from a polymer solution. Furthermore, this liquid polymer was dried under reduced pressure (15 mmHg) at 180 ° C. for 1 hour.
The polymerization activity was 710 g-polymer / mmol-Zr · hr. Table 1 shows the physical properties of the obtained 1-decene polymer (Comparative Polymer 1).

[Comparative polymerization example 2]
In Comparative Polymerization Example 1, the place where nitrogen 250 L / hr and hydrogen 50 L / hr are used is changed to ethylene 250 L / hr, nitrogen 50 L / hr and the temperature 20 ° C. is changed to 32 ° C. Polymerization was carried out by the method.
The polymerization activity was 320 g-polymer / mmol-Zr · hr. Table 1 shows the physical properties of the resulting 1-decene / ethylene copolymer (Comparative Copolymer 2).

[Comparative Polymerization Example 3]
In Comparative Polymerization Example 1, bis (1,3-dimethylcyclopentadienyl) zirconium dichloride is used in place of di (p-tolyl) methylene (cyclopentadienyl) (octamethyloctahydrodibenzofluorenyl) zirconium dichloride. This was carried out in the same manner as Comparative Polymerization Example 1 using 0.04 mmol of toluene solution [0.04 mmol in terms of zirconium atoms] and changing the temperature at 20 ° C. to 15 ° C.

  The polymerization activity was 78 g-polymer / mmol-Zr · hr. Table 1 shows the physical properties of the obtained 1-decene polymer (Comparative Polymer 3).

比較例で用いた他の重合体は以下の通りである。
（１）ポリ−１−デセン（ＰＡＯ−１０００）
ポリ１−デセン；エクソンモービル社製、商品名；ＳｐｅｃｔｒａＳｙｎ Ｕｌｔｒａ１０００
（２）エチレン−プロピレン共重合体（ＨＣ２０００）
１００℃での動粘度：２０００ｍｍ²／ｓ、粘度指数：３００、Ｍｎ：８２８０、三井
化学社製、商品名；ルーカントＨＣ２０００
（３）ポリメタクリレート系重合体
三洋化成社製、商品名ＡＣ−８０７
物性を表２に示す。

Other polymers used in the comparative examples are as follows.
(1) Poly-1-decene (PAO-1000)
Poly 1-decene; manufactured by ExxonMobil Co., Ltd., trade name; SpectraSyn Ultra1000
(2) Ethylene-propylene copolymer (HC2000)
Kinematic viscosity at 100 ° C .: 2000 mm ² / s, viscosity index: 300, Mn: 8280, manufactured by Mitsui Chemicals, trade name: Lucant HC2000
(3) Polymethacrylate polymer manufactured by Sanyo Kasei Co., Ltd., trade name AC-807
The physical properties are shown in Table 2.

実施例及び比較例で用いた潤滑油基油（Ａ）、およびその他添加剤は以下のものを用いた。

The lubricating base oil (A) and other additives used in the examples and comparative examples were as follows.

<Lubricant base oil (A)>
(1) Mineral oil (Nexbase 3050)
Hydro-refined base oil classified as Group 3 defined by APPENDIX E of API 1509 established by the American Petroleum Institute. .0mm ² / s
(2) Synthetic oil (PAO-4)
Product name; Shinflud 401 manufactured by Nippon Steel Chemical Co., Ltd.
Viscosity index: 122, kinematic viscosity at 100 ° C .: 3.9 mm ² / s
(3) Synthetic oil (PAO-6)
Product name; Shinflud 601 manufactured by Nippon Steel Chemical Co., Ltd.
Viscosity index: 136, kinematic viscosity at 100 ° C .: 5.8 mm ² / s

<Compatibilizer>
Diisodecyl adipate (DIDA), manufactured by Daihachi Chemical Industry Co., Ltd.
<Extreme pressure agent>
LUBRIZOL, trade name: Anglamol 98-A
<Pour point depressant>
Polymethacrylate compound Sanyo Kasei Co., Ltd., trade name: ACLUBE AC136

[Example 1]
Highly refined mineral oil (Nexbase 3050) having a kinematic viscosity of 5.0 mm ² / s at 100 ° C .: 7
A lubricating oil composition for gear oil was obtained by blending 5.3%, polymer 1: 18.2% obtained in Polymerization Example 1, and extreme pressure agent 6.5%. Table 3 shows the evaluation results of temperature-viscosity characteristics, low-temperature viscosity, shear stability, and oxidation stability of the obtained gear oil lubricating oil composition.

[Example 2]
Poly-α-olefin (PAO-4) 64.8 having a kinematic viscosity at 100 ° C. of 3.9 mm ² / s
%, Polymer 2 obtained in Polymerization Example 2: 13.7%, Extreme Pressure Agent: 6.5%, Diisodecyldiadipate (DIDA): 15% were blended to obtain a lubricating oil composition for gear oil. Table 3 shows the evaluation results of temperature-viscosity characteristics, low-temperature viscosity, shear stability, and oxidation stability of the obtained gear oil lubricating oil composition.

Example 3
Highly refined mineral oil (Nexbase 3050) having a kinematic viscosity at 100 ° C. of 5.0 mm ² / s: 79.
A lubricating oil composition for gear oil was obtained by blending 0%, polymer 3: 14.5% obtained in Polymerization Example 3, and 6.5% extreme pressure agent. Table 3 shows the evaluation results of temperature-viscosity characteristics, low-temperature viscosity, shear stability, and oxidation stability of the obtained gear oil lubricating oil composition.

Example 4
Poly-α-olefin (PAO-6) having a kinematic viscosity at 100 ° C. of 5.8 mm ² / s: 72.
9%, Polymer 4: obtained in Polymerization Example 4: 5.6%, extreme pressure agent 6.5%, diisodecyldiadipate (DIDA) 15% were blended to obtain a lubricating oil composition for gear oil. Table 3 shows the evaluation results of temperature-viscosity characteristics, low-temperature viscosity, shear stability, and oxidation stability of the obtained gear oil lubricating oil composition.

Example 5
Poly-α-olefin (PAO-6) having a kinematic viscosity of 5.8 mm ² / s at 100 ° C .: 64.
8%, Copolymer 5 obtained in Polymerization Example 5: 13.7%, Extreme pressure agent: 6.5%, Diisodecyldiadipate (DIDA): 15% were blended to obtain a lubricating oil composition for gear oil. It was. Table 3 shows the evaluation results of temperature-viscosity characteristics, low-temperature viscosity, shear stability, and oxidation stability of the obtained gear oil lubricating oil composition.

〔比較例１〕
１００℃動粘度５．０ｍｍ²／ｓの高度精製鉱油（Ｎｅｘｂａｓｅ３０５０）：８９．
２％、比較重合例１で得られた比較重合体１：４．３％、極圧剤：６．５％を配合しギヤ油用潤滑油組成物を得た。得られたギヤ油用潤滑油組成物の温度―粘度特性、低温粘度、剪断安定性、酸化安定性の評価結果を表４に示す。

[Comparative Example 1]
Highly refined mineral oil (Nexbase 3050) having a kinematic viscosity of 100 ° C. of 5.0 mm ² / s: 89.
A lubricating oil composition for gear oil was obtained by blending 2%, Comparative Polymer 1: 4.3% obtained in Comparative Polymerization Example 1, and Extreme Pressure Agent: 6.5%. Table 4 shows the evaluation results of temperature-viscosity characteristics, low temperature viscosity, shear stability, and oxidation stability of the obtained lubricating oil composition for gear oil.

[Comparative Example 2]
Synthetic oil (PAO-4) having a kinematic viscosity of 100 ° C. of 3.9 mm ² / s: 66.7%, Comparative polymerization example 2
A comparative copolymer 2: 11.8%, an extreme pressure agent: 6.5%, and DIDA: 15.0% obtained in the above were blended to obtain a lubricating oil composition for gear oil. Table 4 shows the evaluation results of temperature-viscosity characteristics, low temperature viscosity, shear stability, and oxidation stability of the obtained lubricating oil composition for gear oil.

[Comparative Example 3]
Highly refined mineral oil (Nexbase 3050) having a kinematic viscosity of 100 ° C. of 5.0 mm ² / s: 83.
8%, Comparative Polymer 3 obtained in Comparative Polymerization 3: 9.2%, Extreme Pressure Agent: 6.5%, Pour Point Depressant: 0.5% were blended to obtain a lubricating oil composition for gear oil. It was. Table 4 shows the evaluation results of temperature-viscosity characteristics, low temperature viscosity, shear stability, and oxidation stability of the obtained lubricating oil composition for gear oil.

[Comparative Example 4]
Highly refined mineral oil (Nexbase 3050) having a kinematic viscosity of 100 ° C. of 5.0 mm ² / s: 78.
9%, PAO-1000 (SpectraSyn Ultra1000): 14.6%
An extreme pressure agent: 6.5% was blended to obtain a lubricating oil composition for gear oil. Table 4 shows the evaluation results of temperature-viscosity characteristics, low temperature viscosity, shear stability, and oxidation stability of the obtained lubricating oil composition for gear oil.

[Comparative Example 5]
Highly refined mineral oil (Nexbase 3050) having a kinematic viscosity of 100 ° C. of 5.0 mm ² / s: 89.
A lubricating oil composition for gear oil was obtained by blending 5%, Lucant HC-2000: 3.5%, extreme pressure agent: 6.5%, and pour point depressant: 0.5%. Table 4 shows the evaluation results of temperature-viscosity characteristics, low temperature viscosity, shear stability, and oxidation stability of the obtained lubricating oil composition for gear oil.

[Comparative Example 6]
Synthetic oil (PAO-4) having a kinematic viscosity of 100 ° C. of 3.9 mm ² / s: 57.5%, polymethacrylate polymer (AC-807): 21.6%, extreme pressure agent: 6.5%, DIDA : 14.4% was blended to obtain a lubricating oil composition for gear oil. Table 4 shows the evaluation results of temperature-viscosity characteristics, low temperature viscosity, shear stability, and oxidation stability of the obtained lubricating oil composition for gear oil.

  The lubricating oil composition for gear oil of the present invention has an excellent balance between low-temperature viscosity characteristics, oxidation stability, and shear stability even when the viscosity is low. Therefore, it can be suitably used as a lubricating oil composition for various gear oils for automobiles, industrial use, agriculture use and the like. In particular, it can be suitably used as a lubricating oil composition for automobile gear oil.

Claims (4)

A lubricating oil composition for gear oil comprising a lubricating base oil (A) and an α-olefin (co) polymer (B) defined by the following (i) to (vi), the lubricating oil composition: In contrast, a lubricating oil composition for gear oil, comprising 5 to 40% by mass of an α-olefin (co) polymer (B).
Lubricating base oil (A);
Viscosity index is 110 or more and kinematic viscosity at 100 ° C. is ² to 7 mm ² / s
α-olefin (co) polymer (B);
(I) (a) a structural unit derived from at least one monomer selected from α-olefins having 8 to 20 carbon atoms in a range of 90 to 100 mol% and (b) a structural unit derived from ethylene. In the range of 0-10 mol%,
(Ii) a kinematic viscosity at 100 ° C. in the range of 550 to 2000 mm ² / s,
(Iii) Number average molecular weight (Mn) is in the range of 6000-30000,
(Iv) a molecular weight distribution (Mw / Mn) in the range of 1.1 to 1.8;
(V) The unsaturated group content at the molecular end is 10% or less, and (vi) the viscosity index satisfies the following formula (1).
Viscosity index ≧ 37.59 ln (kinematic viscosity at 100 ° C.) + 23.08 Formula (1)
(However, ln (kinematic viscosity at 100 ° C.) is the natural logarithm of kinematic viscosity at 100 ° C.)   The lubricating oil composition for gear oil according to claim 1, wherein the α-olefin having 8 to 20 carbon atoms is 1-decene.   The lubricating oil composition for gear oil further comprises a compatibilizer, detergent dispersant, antioxidant, corrosion inhibitor, antiwear agent, friction modifier, pour point depressant, rust inhibitor, antifoaming agent and extreme pressure. The gear oil lubricating oil composition according to claim 1 or 2, comprising at least one additive selected from the group consisting of agents. Kinematic viscosity at 40 ° C. is not more than 80 mm ² / s, and a gear oil according to claim 1 in the range kinematic viscosity of 13.5~14.5mm ² / s at 100 ° C. Lubricating oil composition.