JP5879396B2 - Lubricating oil composition - Google Patents

Description

  The present invention relates to a lubricating oil composition, and more particularly to a lubricating oil composition containing a specific poly-α-olefin produced using a metallocene catalyst.

  In recent years, the viscosity of lubricating oils such as drive system oils has been reduced to improve fuel efficiency. However, there is a problem that the fatigue life of the bearings and gears is reduced when metal contact is likely to occur due to the low viscosity of the lubricating oil. In order to solve this problem, for example, in Patent Documents 1 to 3, by using a base oil having a relatively high viscosity and using it together with a viscosity index improver that is not easily subjected to shearing, fuel economy and fatigue resistance are improved. A method for improving is described.

  However, even the lubricating oil compositions obtained by these methods have problems in terms of durability and shear stability when used in manual transmissions and gear axles with high loads. Therefore, for the purpose of reducing the viscosity at low temperature without changing the viscosity at high temperature and improving the shear stability, poly-α-olefins having high viscosity index and shear stability are usually used. Selected as a base oil. In addition, when further improvement in fuel efficiency at low temperatures is required, it is essential to add a viscosity index improver, and usually a low-viscosity poly-α-olefin and a viscosity index improver are used in combination.

Although there are attempts to obtain a lubricating oil that is excellent in low-temperature characteristics and fatigue resistance and has a small viscosity drop due to shearing, no lubricating oil that is excellent in all these characteristics has been obtained so far. That is, when a commonly used polymethacrylate-based viscosity index improver is used, a decrease in viscosity due to shear and a decrease in fatigue resistance are observed, and the low molecular weight polymethacrylate disclosed in Patent Documents 1 and 2 is observed. When the viscosity index improver of the system is used, the low temperature viscosity characteristic is lowered, and when the olefin copolymer disclosed in Patent Document 3 is used, the fatigue prevention property is improved, but the low temperature viscosity characteristic is lowered.
As described above, even a lubricating oil using poly-α-olefin is not sufficiently satisfactory, and a lubricating oil that is excellent in low-temperature characteristics and anti-fatigue properties and has a small viscosity decrease due to shearing is desired.

JP 2006-117852 A JP 2001-262176 A JP 2008-37963 A

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a lubricating oil composition that is excellent in low-temperature characteristics and fatigue prevention properties and has a small viscosity decrease due to shearing.

As a result of intensive studies, the present inventors have found that conventional poly-α produced with an acid catalyst such as BF ₃ or AlCl ₃ by using a poly-α-olefin having a specific viscosity produced using a metallocene catalyst. Compared to lubricants that use α-olefins, the flash point and evaporability do not decrease, they have excellent low temperature viscosity characteristics without depending on viscosity index improvers, and they also have excellent fatigue resistance. I found it. The present invention has been completed based on such findings.
That is, the present invention
1. Kinematic viscosity at 100 ° C., which is produced using a metallocene catalyst containing a poly -α- olefin 15~300mm ² / s, kinematic viscosity at 100 ° C. of 10 to 20 mm ² / s lubricating oil composition,
2. 2. The lubricating oil composition according to 1 above, further comprising a mineral oil and / or a poly-α-olefin, wherein the mineral oil and the poly-α-olefin have a kinematic viscosity at 100 ° C. of 6 mm ² / s or less. Composition,
3. 3. The lubricating oil composition according to 1 or 2 above, which is for a manual transmission.
In the present specification, poly-α-olefin may be referred to as PAO, and PAO obtained with a metallocene catalyst may be referred to as mPAO. Conventional methods (BF ₃ catalyst, AlCl ₃ catalyst, Ziegler type catalyst) Etc.) may be referred to as conventional PAO.

  According to the present invention, it is possible to obtain a lubricating oil excellent in fatigue resistance as compared with a lubricating oil using conventional PAO. Furthermore, since the viscosity index is increased, the low-temperature viscosity characteristics are improved, and the dependence on the viscosity index improver can be lowered, so that a decrease in viscosity due to shearing is suppressed.

In the lubricating oil composition of the present invention, poly-α-olefin (mPAO) produced using a metallocene catalyst and having a kinematic viscosity at 100 ° C. of 15 to 300 mm ² / s is used. When the kinematic viscosity at 100 ° C. is less than 15 mm ² / s, it becomes difficult for the lubricating oil composition to obtain a high viscosity index, and when it exceeds 300 mm ² / s, the shear stability tends to be poor. From the above viewpoint, 15 to 200 mm ² / s is more preferable. The viscosity index of mPAO is usually 100 to 300, preferably 150 to 250. When the viscosity index is within the above range, the viscosity index of the lubricating oil composition is also increased, and the low-temperature viscosity characteristics are improved.
As described above, the kinematic viscosity at 100 ° C. is used in the present invention to specify the components of the lubricating oil composition. At this time, a mixture prepared by combining a plurality of separately produced oils is used in the present invention. The requirement is not applied as a component of the lubricating oil composition. That is, each component used in the present invention is not a mixture in which kinematic viscosity is adjusted by combining a plurality of non-regulated oils.

  Examples of the monomer for producing mPAO used in the present invention include α-olefins having 3 to 14 carbon atoms. An α-olefin selected from 1-octene, 1-decene and 1-dodecene is preferable because mPAO having the desired kinematic viscosity is easily obtained, and 1-decene is particularly preferable.

Examples of the metallocene catalyst include a catalyst containing a combination of a metallocene compound and a promoter. As the metallocene compound, a compound represented by the general formula (I)
(RC ₅ H ₄ ) ₂ MX ₂ (I)
The metallocene compound represented by these is preferable. In general formula (I), R represents a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, M represents a transition metal element of Group 4 of the periodic table, and X represents a covalent bond or an ionic bond. Represents a ligand.

In general formula (I), R is preferably a hydrogen atom or a hydrocarbon group having 1 to 4 carbon atoms. Specific examples of M include titanium, zirconium, and hafnium. Among these, zirconium is preferable. Specific examples of X include a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, preferably 1 to 10 carbon atoms, an amino group, and 1 to 20 carbon atoms. Preferably 1 to 12 phosphorus-containing hydrocarbon group (for example, diphenylphosphine group), 1 to 20 carbon atoms, preferably 1 to 12 silicon-containing hydrocarbon group (for example, trimethylsilyl group), 1 to 20 carbon atoms are preferable Can include 1 to 12 hydrocarbon groups or halogen-containing boron compounds (for example, B (C ₆ H ₅ ) ₄ , BF _4, etc.). Among these, hydrogen atoms, halogen atoms, hydrocarbons A group selected from a group and an alkoxy group is preferred.

  Specific examples of the metallocene compound represented by the general formula (I) include bis (cyclopentadienyl) zirconium dichloride, bis (methylcyclopentadienyl) zirconium dichloride, bis (ethylcyclopentadienyl) zirconium dichloride, bis (Iso-propylcyclopentadienyl) zirconium dichloride, bis (n-propylcyclopentadienyl) zirconium dichloride, bis (n-butylcyclopentadienyl) zirconium dichloride, bis (t-butylcyclopentadienyl) zirconium dichloride , Bis (texylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylcyclopentadienyl) zirconium dichloride, bis (trimethylsilylmethylcyclopentadienyl) zirconi Mudichloride, bis (cyclopentadienyl) zirconium chlorohydride, bis (cyclopentadienyl) methylzirconium chloride, bis (cyclopentadienyl) ethylzirconium chloride, bis (cyclopentadienyl) methoxyzirconium chloride, bis (cyclopenta Dienyl) phenylzirconium chloride, bis (cyclopentadienyl) dimethylzirconium, bis (cyclopentadienyl) diphenylzirconium, bis (cyclopentadienyl) dineopentylzirconium, bis (cyclopentadienyl) dihydrozirconium, bis (Cyclopentadienyl) dimethoxyzirconium, and further, in the compounds described above, the chlorine atom of these compounds is substituted with a bromine atom, an iodine atom, a hydrogen atom, a methyl group, Are replaced etc. group, also include those obtained by replacing the zirconium metal centers of the compounds titanium, hafnium.

  As the cocatalyst, methylaluminoxane is preferred. The methylaluminoxane is not particularly limited and conventionally known methylaluminoxane can be used. For example, the general formula (II) or the general formula (III) can be used.

The chain | strand-shaped or cyclic | annular methylaluminoxane represented by these is mentioned. In general formula (II), (III), p represents a polymerization degree and is 3-50 normally, Preferably it is 7-40.

  Examples of the method for producing methylaluminoxane include a method in which methylaluminum is brought into contact with a condensing agent such as water, but the means thereof is not particularly limited and may be reacted according to a known method.

  As for the compounding ratio of the metallocene compound and methylaluminoxane, the methylaluminoxane / metallocene compound (molar ratio) is usually 15 to 150, preferably 20 to 120, and more preferably 25 to 100. If it is 15 or more, the catalytic activity is exhibited, and the yield of the trimer or more suitable as a base oil of the lubricating oil does not decrease due to the formation of the α-olefin dimer. On the other hand, if it is 150 or less, deashing removal of the catalyst will not be incomplete.

  Examples of the metallocene catalyst other than the above include metallocene catalysts using a metallocene compound having a crosslinking group. As the metallocene compound, a metallocene compound having two crosslinking groups is preferable, and a metallocene compound having meso symmetry is particularly preferable. Examples of the metallocene catalyst using the metallocene compound having meso symmetry include, for example, (A) a metallocene compound represented by the following formula (IV), and (B) (B-1) a metallocene compound of the component (A). Alternatively, a metallocene catalyst containing at least one component selected from a compound capable of reacting with a derivative thereof to form an ionic complex and (B-2) aluminoxane may be mentioned.

The compound represented by the formula (IV) is a mesosymmetric compound, and in the formula (IV), M represents a metal element belonging to Groups 3 to 10 of the periodic table. X represents a σ-binding ligand, and when there are a plurality of X, a plurality of X may be the same or different, Y represents a Lewis base, and when there are a plurality of Y, a plurality of Y are the same or different It may be. A represents a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group, -O-, -CO-, -S-,- _{SO 2 -, - Se -,} - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - and -AlR ¹ - shows a bridging group selected from the two a at the same It can be different. R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. E is a group represented by the following formulas (V) and (VI), and the two Es are the same.
The mesosymmetric compound refers to a transition metal compound in which two bridging groups bridge two Es in a bonding mode of (1,1 ′) (2,2 ′).

In formulas (V) and (VI), R ² is a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 4 carbon atoms, a silicon-containing group, or a heteroatom-containing group. Represents a group selected from: When several R < ² > exists, they may mutually be same or different. The bond indicated by the wavy line represents the bond with the bridging group A.

  The crosslinking group A in the formula (IV) is preferably a group represented by the following formula (VII).

B is a skeleton of a bridging group and represents a carbon atom, a silicon atom, a boron atom, a nitrogen atom, a germanium atom, a phosphorus atom, or an aluminum atom. R ³ represents a hydrogen atom, a carbon atom, an oxygen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, an amine-containing group, or a halogen-containing group. n is 1 or 2.

  Specific examples of the metallocene compound represented by the formula (IV) include (1,1′-ethylene) (2,2′-ethylene) -bis (indenyl) zirconium dichloride, (1,1′-methylene) (2 , 2′-methylene) -bis (indenyl) zirconium dichloride, (1,1′-isopropylidene) (2,2′-isopropylidene) -bis (indenyl) zirconium dichloride, (1,1′-ethylene) (2 , 2′-ethylene) -bis (3-methylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (4,5-benzoindenyl) zirconium dichloride, (1 , 1′-ethylene) (2,2′-ethylene) -bis (4-isopropylindenyl) zirconium dichloride, (1,1′-ethylene) (2, '-Ethylene) -bis (5,6-dimethylindenyl) zirconium dichloride, (1,1'-ethylene) (2,2'-ethylene) -bis (4,7-diisopropylindenyl) zirconium dichloride, (1 , 1′-ethylene) (2,2′-ethylene) -bis (4-phenylindenyl) zirconium dichloride, (1,1′-ethylene) (2,2′-ethylene) -bis (3-methyl-4 -Isopropylindenyl) zirconium dichloride, (1,1'-ethylene) (2,2'-ethylene) -bis (5,6-benzoindenyl) zirconium dichloride,

(1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (cyclopentadienyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (indenyl) Zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (3-methylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) Bis (3-n-butylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (3-i-propylindenyl) zirconium dichloride, (1,1′- Dimethylsilylene) (2,2′-dimethylsilylene) bis (3-trimethylsilylmethylindenyl) di Conium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (3-phenylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) ) Bis (4,5-benzoindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (4-isopropylindenyl) zirconium dichloride, (1,1′-dimethyl) Silylene) (2,2′-dimethylsilylene) bis (5,6-dimethylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (4,7-di-) i-propylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilane) Len) bis (4-phenylindenyl) zirconium dichloride, (1,1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (3-methyl-4-i-propylindenyl) zirconium dichloride, (1 , 1′-dimethylsilylene) (2,2′-dimethylsilylene) bis (5,6-benzoindenyl) zirconium dichloride and the like, and those obtained by substituting zirconium in these compounds with titanium or hafnium. Of course, it is not limited to these.

As the component (B-1) of the component (B), any compound can be used as long as it can react with the metallocene compound of the component (A) to form an ionic complex. Those represented by the following general formulas (VIII) and (IX) can be preferably used.
([L ¹ −R ⁴ ] ^{k +} ) _a ([Z] ⁻ ) _b (VIII)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IX)

In general formulas (VIII) and (IX), L ¹ represents a Lewis base, and L ² represents M ² , R ⁵ R ⁶ M ³ , R ⁷ ₃ C or R ⁸ M ³ . [Z] ⁻ represents a non-coordinating anion [Z ¹ ] ⁻ or [Z ² ] ⁻ . Here, [Z ¹ ] ⁻ is an anion in which a plurality of groups are bonded to the element, that is, [M ¹ G ¹ G ² ... G ^f ] ⁻ (where M ¹ is a group 5-15 element in the periodic table, Preferably, it represents a periodic table group 13 to 15. G ^{1 to} G ^f are each a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a dialkylamino group having 2 to 40 carbon atoms, or 1 to carbon atoms. 20 alkoxy groups, C6-C20 aryl groups, C6-C20 aryloxy groups, C7-C40 alkylaryl groups, C7-C40 arylalkyl groups, C1-C20 A halogen-substituted hydrocarbon group, an acyloxy group having 1 to 20 carbon atoms, an organic metalloid group, or a heteroatom-containing hydrocarbon group having 2 to 20 carbon atoms, wherein two or more of G ^{1 to} G ^f form a ring. which may be .f is [(valence of central metal M ¹⁾ +1] An integer), [Z ^{2] -.} The logarithm of the reciprocal of the acid dissociation constant (pKa) -10 below Bronsted acid alone or Bronsted acid and Lewis acid combination of conjugate base or generally, An acid conjugate salt defined as a super strong acid. A Lewis base may be coordinated. R ⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ⁵ and R ⁶ are a cyclopentadienyl group and a substituted group, respectively. A cyclopentadienyl group, an indenyl group or a fluorenyl group, and R ⁷ represents an alkyl group having 1 to 20 carbon atoms, an aryl group, an alkylaryl group or an arylalkyl group. R ⁸ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an ionic valence of [L ¹ −R ⁴ ], [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents elements 7 to 12 in the periodic table.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.
Specific examples of R ⁴ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ⁵ and R ⁶ include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like. Specific examples of R ⁷ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ⁸ include tetraphenylporphyrin, phthalocyanine, allyl, methallyl, and the like. . Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I ₃ , and specific examples of M ³ include Mn, Fe, Co, Ni, and Zn. And so on. In [Z ¹ ] ⁻ , that is, [M ¹ G ¹ G ² ... G ^f ], specific examples of M ¹ include B, Al, Si, P, As, Sb, etc., preferably B and Al. Can be mentioned. Specific examples of G ¹ and G ^{2 to} G ^f include dialkylamino groups such as dimethylamino group and diethylamino group, alkoxy groups or aryloxy groups such as methoxy group, ethoxy group, n-butoxy group, and phenoxy group. Hydrocarbon groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, n-octyl, n-eicosyl, phenyl, p-tolyl, benzyl, 4-t -Butylphenyl group, 3,5-dimethylphenyl group, etc., fluorine, chlorine, bromine, iodine as halogen atoms, p-fluorophenyl group, 3,5-difluorophenyl group, pentachlorophenyl group as heteroatom-containing hydrocarbon groups, 3,4,5-trifluorophenyl group, pentafluorophenyl group, 3,5-bis (trifluoro Romechiru) phenyl group, such as bis (trimethylsilyl) methyl group, pentamethyl antimony group as organic metalloid group, trimethylsilyl group, trimethylgermyl group, diphenylarsine group, dicyclohexyl antimony group, such as diphenyl boron and the like.

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

Specific examples of the ionic compound that reacts with the transition metal compound of the component (A) to form an ionic complex, that is, the component compound (B-1) include tetrakis (pentafluorophenylboric acid) N, N-dimethylanilinium, triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl (tri-n-butyl) ammonium tetraphenylborate, tetraphenylborate Benzyl (tri-n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methyl tetraphenylborate Lidinium, benzylpyridinium tetraphenylborate, methyl tetraphenylborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) triethylammonium borate, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) boric acid Triphenylammonium, tetrakis (pentafluorophenyl) borate tetra-n-butylammonium, tetrakis (pentafluorophenyl) tetraethylammonium borate, tetrakis (pentafluorophenyl) benzyl borate (tri-n-butyl) ammonium, tetrakis (pentafluorophenyl) ) Methyldiphenylammonium borate, tetrakis (pentafluorophenyl) triphenyl (methyl) ammonium borate Tetrakis (pentafluorophenyl) methylanilinium borate, tetrakis (pentafluorophenyl) dimethylanilinium borate, tetrakis (pentafluorophenyl) trimethylanilinium borate, tetrakis (pentafluorophenyl) methylpyridinium borate, tetrakis (pentafluorophenyl) ) Benzylpyridinium borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), tetrakis (pentafluorophenyl) benzyl benzylborate (2-cyanopyridinium), tetrakis (pentafluorophenyl) methylborate (4-cyanopyridinium), Tetrakis (pentafluorophenyl) borate triphenylphosphonium, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] borate Methylanilinium, ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, ferrocenium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid (1,1′-dimethyl) Ferrocenium), tetrakis (pentafluorophenyl) decamethyl ferrocenium borate, silver tetrakis (pentafluorophenyl) borate, trityl tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) ) Sodium borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, hexafluorophosphorus Examples thereof include silver oxide, silver hexafluoroarsenate, silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.
(B-1) may be used alone or in combination of two or more.

  On the other hand, as the aluminoxane of the component (B-2), the general formula (X)

(Wherein R ⁹ represents a hydrocarbon group such as an alkyl group, alkenyl group, aryl group or arylalkyl group having 1 to 20 carbon atoms, preferably 1 to 12 carbon atoms or a halogen atom, and w represents an average degree of polymerization. Usually, it is an integer of 2 to 50, preferably 2 to 40, wherein each R ⁹ may be the same or different, and a chain aluminoxane represented by the general formula (XI)

(Wherein, R ⁹ and w are the same as those in the general formula (X)).

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

  The use ratio of (A) catalyst component to (B) catalyst component is preferably 10: 1 to 1: 100 in molar ratio when (B-1) compound is used as (B) catalyst component. Preferably, the range of 2: 1 to 1:10 is desirable, and if it deviates from the above range, the catalyst cost per unit mass polymer increases, which is not practical. When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. When deviating from this range, the catalyst cost per unit mass polymer becomes high, which is not practical. Moreover, (B-1) and (B-2) can also be used individually or in combination of 2 or more types as a catalyst component (B).

  As the monomer for producing mPAO, usually an α-olefin having 3 to 14 carbon atoms is used, and specific examples thereof include propylene, 1-butene, 3-methyl-1-butene, 4-methyl- 1-butene, 4-phenyl-1-butene, 1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene, 3,3-dimethyl-1-pentene, 3,4-dimethyl-1- Pentene, 4,4-dimethyl-1-pentene, 1-hexene, 4-methyl-1-hexene, 5-methyl-1-hexene, 6-phenyl-1-hexene, 1-octene, 1-decene, 1- Examples include dodecene and 1-tetradecene. Among these, α-olefins selected from 1-octene, 1-decene, and 1-dodecene are preferable, and 1-decene is particularly preferable.

  The mixing ratio of the metallocene compound represented by the general formula (I) or (IV) and the α-olefin having 3 to 14 carbon atoms [metallocene compound (mmol) / α-olefin (L)] is usually 0.01 to 0. .4, preferably 0.05 to 0.3, and more preferably 0.1 to 0.2. When 0.01 or more, sufficient catalytic activity is obtained, and when 0.4 or less, the yield of the trimer or more oligomer suitable as the base oil of the lubricating oil is improved, and the catalyst is deashed. Removal will not be incomplete.

  The polymerization of the α-olefin having 3 to 14 carbon atoms is preferably performed in the presence of hydrogen. The amount of hydrogen added is usually 0.1 to 50 kPa, preferably 0.5 to 30 kPa, and more preferably 1 to 10 kPa. Sufficient catalytic activity is obtained when the amount of hydrogen added is 0.1 kPa or more. On the other hand, when it is 50 kPa or less, the production of raw material α-olefin saturates can be reduced, and the desired yield of mPAO is obtained. Will improve.

  The polymerization of the α-olefin having 3 to 14 carbon atoms is not limited in the reaction method, and may be performed in the absence of a solvent or in a solvent, and any method may be used. When using a reaction solvent, for example, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, alicyclic hydrocarbons such as cyclopentane, cyclohexane, and methylcyclohexane, and aliphatic hydrocarbons such as pentane, hexane, heptane, and octane Halogenated hydrocarbons such as chloroform and dichloromethane. The temperature of the polymerization reaction is usually 0 to 100 ° C, preferably 20 to 80 ° C, more preferably 30 to 70 ° C. By being in the above range, sufficient catalytic activity can be obtained, and the yield of trimer or higher oligomer suitable as a base oil for lubricating oil can be improved. Polymerization by the above method can produce mPAO having a selectivity of trimer or higher of 50% or higher.

  Depending on the purpose, the mPAO obtained by the above method may be further treated. For example, in order to improve thermal stability or oxidation stability, hydrogenation may be performed. Moreover, what is necessary is just to distill, when obtaining the lubricating base oil which has a desired characteristic. The temperature of the hydrogenation treatment is usually 50 to 300 ° C, preferably 60 to 250 ° C, more preferably 70 to 200 ° C, and the hydrogen pressure is usually 0.1 to 10 MPa, preferably 0.5 to 2 MPa, more preferably. Is 0.7 to 1.5 MPa. In the hydrogenation treatment, a general hydrogenation catalyst containing Pd, Ni, or the like can be used. The temperature in the distillation is usually 200 ° C. to 300 ° C., preferably 220 to 280 ° C., more preferably 230 to 270 ° C., and the pressure is usually 0.1 to 15 Pa, preferably 0.4 to 7 Pa, more preferably 0.00. 6-4 Pa.

  The mPAO obtained by the above method, mPAO after hydrogenation treatment or distillation has about 1 short chain branch per molecule (usually 0.6 to 1.2, preferably 0.7 to 1.1). More preferably 0.8 to 1.0) (in this specification, a methyl group, an ethyl group, and a propyl group are referred to as short-chain branches). Further, the short chain branch is mainly a methyl group, and the proportion of the methyl group is usually 80 mol% or more, preferably 85 mol% or more, more preferably 90 mol% or more.

  Thus, mPAO is different from conventional PAO in terms of molecular structure and high homogeneity, and exhibits high oxidation stability and high viscosity index, and is excellent as a lubricating base oil. For this reason, the lubricating oil composition of the present invention has improved fatigue resistance unlike a lubricating oil composition using conventional PAO. In addition, by increasing the viscosity index, the low-temperature viscosity characteristics are improved, and the dependence on the viscosity index improver is reduced, thereby suppressing a decrease in viscosity due to shearing.

The lubricating oil composition of the present invention may contain other base oil together with the MPAO, kinematic viscosity at 100 ° C. of the lubricating oil composition 10 to 20 mm ² / s, preferably is 12 to 18 mm ² / s . If it is less than 10 mm ² / s, the wear resistance is insufficient, and if it exceeds 20 mm ² / s, the fuel efficiency tends to be inferior. The content of mPAO and other base oils can be appropriately determined according to the purpose, but based on the total amount of the lubricating oil composition, the content of mPAO is usually 30 to 95% by mass, preferably 50 to 95% by mass, Other base oil is 0-65 mass% normally, Preferably it is 0-45 mass%.

As the base oil, it is preferably 6 mm ² / s or less base oil kinematic viscosity at 100 ° C., base oil 1.5~5.5mm ² / s is more preferable. Examples of the base oil include mineral oil and PAO. When the kinematic viscosity at 100 ° C. is 6 mm ² / s or less, excellent viscosity characteristics can be obtained.

  As mineral oils, for example, a lubricating oil fraction obtained by distillation under reduced pressure of atmospheric residual oil obtained by atmospheric distillation of crude oil is solvent desorbed, solvent extraction, hydrocracking, solvent dewaxing, hydrorefining And a base oil produced by isomerizing a wax produced by a mineral oil wax, a Fischer-Tropsch process, or the like (gas-liquid wax).

These mineral oils preferably have a viscosity index of 90 or more, more preferably 100 or more, and even more preferably 110 or more. If the viscosity index is 90 or more, the viscosity index of the lubricating oil composition can be kept high. Further, the aromatic content (% C _A ) of the mineral oil is preferably 3 or less, preferably 2 or less, more preferably 1 or less, and the sulfur content is preferably 100 mass ppm or less, and 50 mass ppm. The following is more preferable. % C _A is less than or equal to 3, if the sulfur content of less than 100 mass ppm, it is possible to maintain the oxidation stability of a lubricating oil composition favorably.

The PAO may be a PAO obtained with a metallocene catalyst or a conventional PAO. These hydrogenated products may also be used.
In the present invention, the mineral oil may be used singly or in combination of two or more, the PAO may be used singly or in combination of two or more, and the mineral oil one or more and the PAO in combination of one or more. It may be used.

  As will be described later, the lubricating oil composition of the present invention may contain an additive, and a solubilizing agent may be added to the base oil in order to improve the solubility. In particular, in the case of a lubricating oil composition containing no mineral oil, it is preferable to add a solubilizing agent. Examples of the dissolution aid include ester compounds such as fatty acid esters and aromatic-containing compounds.

  The lubricating oil composition of the present invention is a known additive as long as the object of the present invention is not impaired, such as an extreme pressure agent, an oily agent, an antioxidant, a rust inhibitor, a metal deactivator, a cleaning dispersant, A viscosity index improver, a pour point depressant, an antifoaming agent and the like can be blended.

  Examples of the extreme pressure agent include phosphate esters such as phosphate esters, acid phosphate esters, phosphite esters, and acid phosphite esters, amine salts of these phosphate esters, and sulfur-based extreme pressure agents. Preferably mentioned.

  Examples of phosphate esters include triaryl phosphate, trialkyl phosphate, trialkylaryl phosphate, triarylalkyl phosphate fluoride, trialkenyl phosphate, and the like, for example, triphenyl phosphate, tricresyl phosphate, benzyldiphenyl phosphate, ethyl Diphenyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethyl phenyl diphenyl phosphate, di (ethylphenyl) phenyl phosphate, propylphenyl diphenyl phosphate, di (propylphenyl) phenyl phosphate, triethylphenyl phosphate, Tripropylphenyl phosphate Butylphenyl diphenyl phosphate, di (butylphenyl) phenyl phosphate, tributylphenyl phosphate, trihexyl phosphate, tri (2-ethylhexyl) phosphate, tridecyl phosphate, trilauryl phosphate, trimyristyl phosphate, tripalmityl phosphate, tristearyl phosphate, A trioleyl phosphate etc. can be mentioned.

Examples of the acidic phosphate ester include 2-ethylhexyl acid phosphate, ethyl acid phosphate, butyl acid phosphate, oleyl acid phosphate, tetracosyl acid phosphate, isodecyl acid phosphate, lauryl acid phosphate, tridecyl acid phosphate, stearyl acid phosphate , Isostearyl acid phosphate and the like.
Examples of phosphites include triethyl phosphite, tributyl phosphite, triphenyl phosphite, tricresyl phosphite, tri (nonylphenyl) phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite, Examples include trilauryl phosphite, triisooctyl phosphite, diphenylisodecyl phosphite, tristearyl phosphite, and trioleyl phosphite.
Examples of the acidic phosphite include dibutyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, distearyl hydrogen phosphite, and diphenyl hydrogen phosphite. Of the above phosphoric acid esters, tricresyl phosphate and triphenyl phosphate are preferred.

  Examples of amines that form amine salts with these phosphate esters include mono-substituted amines such as butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine, and benzylamine. Examples of disubstituted amines include dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl monoethanolamine, decyl Examples include monoethanolamine, hexyl monopropanolamine, benzyl monoethanolamine, phenyl monoethanolamine, and tolyl monopropanolamine. Examples of trisubstituted amines include tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenzylamine, dioleyl monoethanolamine, dilauryl monopropanol Amine, dioctyl monoethanolamine, dihexyl monopropanolamine, dibutyl monopropanolamine, oleyl diethanolamine, stearyl dipropanolamine, lauryl diethanolamine, octyl dipropanolamine, butyl diethanolamine, benzyl diethanolamine, phenyl Diethanolamine, tolyl dipropanolamine, xylyl diethanolamine, tri Ethanolamine, and the like tripropanolamine.

Any sulfur-based extreme pressure agent may be used as long as it has a sulfur atom in the molecule and can be dissolved or uniformly dispersed in the lubricant base oil to exhibit the extreme pressure agent and excellent friction characteristics. Examples of such compounds include sulfurized fats and oils, sulfurized fatty acids, sulfurized esters, sulfurized olefins, dihydrocarbyl polysulfides, thiadiazole compounds, thiophosphates (thiophosphites, thiophosphates), alkylthiocarbamoyl compounds, thiocarbamate compounds, thioterpene compounds. And dialkylthiodipropionate compounds. Here, sulfurized fats and oils are obtained by reacting sulfur and sulfur-containing compounds with fats and oils (lard oil, whale oil, vegetable oil, fish oil, etc.), and the sulfur content is not particularly limited, but generally 5 to 30 mass. % Is preferred. Specific examples thereof include sulfurized lard, sulfurized rapeseed oil, sulfurized castor oil, sulfurized soybean oil, and sulfurized rice bran oil. Examples of the sulfurized fatty acid include sulfurized oleic acid, and examples of the sulfurized ester include sulfurized methyl oleate and sulfurized rice bran fatty acid octyl.
Preferred examples of the dihydrocarbyl polysulfide include dibenzyl polysulfide, various dinonyl polysulfides, various didodecyl polysulfides, various dibutyl polysulfides, various dioctyl polysulfides, diphenyl polysulfide, dicyclohexyl polysulfide, and the like.

Examples of thiadiazole compounds include 2,5-bis (n-hexyldithio) -1,3,4-thiadiazole, 2,5-bis (n-octyldithio) -1,3,4-thiadiazole, 2,5 -Bis (n-nonyldithio) -1,3,4-thiadiazole, 2,5-bis (1,1,3,3-tetramethylbutyldithio) -1,3,4-thiadiazole, 3,5-bis ( n-hexyldithio) -1,2,4-thiadiazole, 3,6-bis (n-octyldithio) -1,2,4-thiadiazole, 3,5-bis (n-nonyldithio) -1,2,4 -Thiadiazole, 3,5-bis (1,1,3,3-tetramethylbutyldithio) -1,2,4-thiadiazole, 4,5-bis (n-octyldithio) -1,2,3-thiadiazole 4,5-bis n- nonyldithio) -1,2,3-thiadiazole, 4,5-bis (1,1,3,3-tetramethylbutyl dithio) -1,2,3-thiadiazoles such as can be a preferably exemplified.
Examples of the thiophosphate include alkyl trithiophosphite, aryl or alkylaryl thiophosphate, zinc dialkyldithiophosphate and the like. Particularly preferred are lauryl trithiophosphite, triphenylthiophosphate, and zinc dilauryl dithiophosphate.

Examples of the alkylthiocarbamoyl compound include bis (dimethylthiocarbamoyl) monosulfide, bis (dibutylthiocarbamoyl) monosulfide, bis (dimethylthiocarbamoyl) disulfide, bis (dibutylthiocarbamoyl) disulfide, and bis (diamilthiocarbamoyl) disulfide. Bis (dioctylthiocarbamoyl) disulfide and the like can be preferably mentioned.
Further, as the thiocarbamate compound, for example, zinc dialkyldithiocarbamate, as the thioterpene compound, for example, a reaction product of phosphorus pentasulfide and pinene, and as the dialkylthiodipropionate compound, for example, dilaurylthiodipropionate. And distearyl thiodipropionate. Of these, thiadiazole compounds and benzyl sulfide are preferable from the viewpoints of extreme pressure, friction characteristics, thermal oxidation stability, and the like.
These extreme pressure agents may be used individually by 1 type, and may be used in combination of 2 or more type. The blending amount is usually selected in the range of 0.01 to 10% by mass, preferably 0.05 to 5% by mass, based on the total amount of the lubricating oil composition, from the viewpoint of balance between effects and economy.

Examples of oil-based agents include aliphatic saturated and unsaturated monocarboxylic acids such as stearic acid and oleic acid, polymerized fatty acids such as dimer acid and hydrogenated dimer acid, hydroxy fatty acids such as ricinoleic acid and 12-hydroxystearic acid, lauryl Aliphatic saturated and unsaturated monoalcohols such as alcohol and oleyl alcohol, aliphatic saturated and unsaturated monoamines such as stearylamine and oleylamine, aliphatic saturated and unsaturated monocarboxylic amides such as lauric acid amide and oleic acid amide, etc. Can be mentioned.
These may be used individually by 1 type and may be used in combination of 2 or more type. Moreover, the compounding quantity is 0.01-10 mass% normally on the basis of lubricating oil composition whole quantity basis, Preferably it selects in the range of 0.1-5 mass%.

Examples of the antioxidant include amine-based antioxidants, phenol-based antioxidants, and sulfur-based antioxidants.
Examples of amine-based antioxidants include monoalkyl diphenylamines such as monooctyldiphenylamine and monononyldiphenylamine, 4,4′-dibutyldiphenylamine, 4,4′-dipentyldiphenylamine, 4,4′-dihexyldiphenylamine, 4, Polyalkyldiphenylamines such as 4'-diheptyldiphenylamine, 4,4'-dioctyldiphenylamine, dialkyldiphenylamines such as 4,4'-dinonyldiphenylamine, tetrabutyldiphenylamine, tetrahexyldiphenylamine, tetraoctyldiphenylamine, tetranonyldiphenylamine , Α-naphthylamine, phenyl-α-naphthylamine, butylphenyl-α-naphthylamine, pentylphenyl-α-naphthylamine, hexyl Butylphenyl -α- naphthylamine, heptylphenyl -α- naphthylamine, octylphenyl -α- naphthylamine, there may be mentioned naphthylamine such as nonylphenyl -α- naphthylamine, among others things dialkyl diphenylamine is preferred.

Examples of the phenolic antioxidant include monophenols such as 2,6-di-tert-butyl-4-methylphenol and 2,6-di-tert-butyl-4-ethylphenol, 4,4′- Examples include diphenols such as methylene bis (2,6-di-tert-butylphenol) and 2,2′-methylene bis (4-ethyl-6-tert-butylphenol).
Examples of the sulfur-based antioxidant include phenothiazine, pentaerythritol-tetrakis- (3-laurylthiopropionate), bis (3,5-tert-butyl-4-hydroxybenzyl) sulfide, thiodiethylenebis (3- ( 3,5-di-tert-butyl-4-hydroxyphenyl)) propionate, 2,6-di-tert-butyl-4- (4,6-bis (octylthio) -1,3,5-triazine-2- And methylamino) phenol.
These antioxidants may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, the compounding quantity is 0.01-10 mass% normally on the basis of lubricating oil composition whole quantity, Preferably it selects in the range of 0.03-5 mass%.

Examples of the rust preventive include alkyl or alkenyl succinic acid derivatives such as dodecenyl succinic acid half ester, octadecenyl succinic anhydride, dodecenyl succinic acid amide, sorbitan monooleate, glycerin monooleate, pentaerythritol monooleate, etc. Polyhydric alcohol partial esters, rosin amines, amines such as N-oleyl sarcosine, dialkyl phosphite amine salts, and the like can be used. These may be used individually by 1 type and may be used in combination of 2 or more type.
A preferable blending amount of these rust preventives is in a range of 0.01 to 5% by mass, particularly preferably in a range of 0.05 to 2% by mass based on the total amount of the lubricating oil composition.
As the metal deactivator, for example, benzotriazole-based, thiadiazole-based, gallic acid ester-based compounds, and the like can be used.
A preferable blending amount of these metal deactivators is 0.01 to 0.4% by mass based on the total amount of the lubricating oil composition, and a range of 0.01 to 0.2% by mass is particularly preferable.

Examples of cleaning dispersants include metal detergents such as alkaline earth metal sulfonates, alkaline earth metal phenates, alkaline earth metal salicylates, alkaline earth metal phosphonates, alkenyl succinimides, benzyl amines, alkyl polyamines, alkenyl succinates. Examples include ashless dispersants such as acid esters. These washing dispersants may be used alone or in combination of two or more.
For example, a combination of an overbased calcium sulfonate having a total base number of 300 to 700 mg KOH / g and an alkyl group or alkenyl group-substituted succinimide having an average molecular weight of 1000 to 3500 and / or a boron-containing hydrocarbon-substituted succinimide is preferable. . The blending amount of these detergent dispersants is usually about 0.1 to 30% by mass, preferably 0.5 to 10% by mass, based on the total amount of the lubricating oil composition.

  As the viscosity index improver, for example, polymethacrylate, dispersed polymethacrylate, olefin copolymer (for example, ethylene-propylene copolymer), dispersed olefin copolymer, styrene copolymer (for example, Styrene-diene hydrogenated copolymer, etc.). The blending amount of the viscosity index improver is usually 5% by mass or less, preferably 3% by mass or less, based on the total amount of the lubricating oil composition. In the present invention, since mPAO having a high viscosity index is used, sufficient performance can be obtained without using a viscosity index improver or in a small amount. For this reason, the characteristic that the viscosity fall by shearing is small is acquired.

Examples of the pour point depressant include polymethacrylate.
As the antifoaming agent, liquid silicone is suitable, and methylsilicone, fluorosilicone, and polyacrylate can be used.
A preferable blending amount of these antifoaming agents is 0.0005 to 0.01% by mass based on the total amount of the lubricating oil composition.

  The lubricating oil composition of the present invention can be used without particular limitation in applications where fuel economy is required. Specific examples include drive system oils such as transmission oils. In particular, the lubricating oil composition of the present invention is preferably used as a manual transmission oil composition.

  EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.

In addition, the property and performance of the base oil and the lubricating oil composition obtained in each example were determined according to the following method.
(1) Kinematic viscosity at 100 ° C. The kinematic viscosity at 100 ° C. was measured according to JIS K2283.
(2) Viscosity index Measured according to JIS K2283.
(3) Low temperature viscosity (BF viscosity)
Based on JPI-5S-26-85, the viscosity at −26 ° C. was measured.
(4) Flash point Measured according to JIS K2265.
(5) NOACK test The amount of evaporation was measured at 200 ° C. for 1 hour in accordance with JPI-5S-41-93.
(6) Shear stability test (Sonic test)
In accordance with JASO M347, the viscosity reduction rate relative to the new oil having a kinematic viscosity at 100 ° C. after 1 hour was calculated.
(7) Fatigue life test A rolling four-ball test was used to measure the time at which pitching occurred. The measurement conditions were a SUJ-2 3/4 inch ball, 6.9 GPa, 2200 rpm, oil temperature 90 ° C.

Production Example 1 (Production of PAO with metallocene catalyst 1)
After adding 2.5 L of degassed and dehydrated 1-decene with nitrogen bubbling and 2.5 L of degassed and dehydrated toluene to a stainless steel autoclave with an internal volume of 5 L purged with nitrogen, the temperature was raised to 65 ° C. 40 ml of a toluene solution of methylaluminoxane adjusted to 1.0 mol / L was added.
Next, 10 mL of a toluene solution of bis (cyclopentadienyl) zirconium dichloride adjusted to 40 mmol / L was added, and the reaction was carried out at 65 ° C. for 3 hours while continuously supplying 5 kPa of hydrogen and stirring.
The compounding ratio of the metallocene compound and 1-decene in the above reaction was 0.16 mmol / (1-decene) L, and the methylaroxane / metallocene compound (molar ratio) = 100. The reaction was stopped with 500 mL of 1% dilute hydrochloric acid, washed twice with 100 mL of deionized water, and the solution obtained by decomposing and removing the catalyst component was analyzed by gas chromatography. The yield of the oligomer was 86%, The selectivity over the isomer was 49% dimer, 17% trimer, 10% tetramer, 6% pentamer, and 18% hexamer. Further, when elemental analysis of this solution was performed, it was found that Cl, Al, and Zr were all <2 ppm by mass and substantially no catalyst residue was contained.

After removing the monomer and dimer from the solution obtained by decomposing and removing the catalyst component under reduced pressure, 1 mass% of palladium / alumina catalyst (5% Pd supported product) was added to a 5 L stainless steel autoclave purged with nitrogen. In addition, hydrogen 0.8 MPa was continuously supplied and reacted at 85 ° C. for 5 hours while stirring. Then, the said catalyst was removed by filtration, and the obtained hydrogenated liquid was fractionally distilled at 1.33 Pa and 200-270 degreeC using the simple distillation apparatus. When the residue after fractional distillation was examined by gas chromatography, it was 5.0% by mass of a tetramer, 12.8% by mass of a pentamer, and 82.2% by mass or more of a hexamer. The average degree of polymerization is 7.5, the number of short chain branches is 12/1000 carbons, and the average number of short chain branches per molecule of the oligomer is 0.90. It was also revealed that the short-chain branching group species were substantially composed of methyl group branching, with 93.0 mol% methyl group branching, 2.5 mol% ethyl group branching, and 4.5 mol% propyl group branching.
This residue has a kinematic viscosity of 40 ° C. of 11.91 mm ² / s, a kinematic viscosity of 100 ° C. of 16.94 mm ² / s, a viscosity index of 155, a pour point <−50 ° C., a flash point of 278 ° C., and an evaporation amount (Noack) of 1.8%. Met. This residue was used as mPAO-1 for the production of a lubricating oil composition.
The average degree of polymerization was determined by GPC (gel permeation chromatography) measurement [average degree of polymerization: number average molecular weight / PS (polystyrene) equivalent monomer molecular weight (each molecular weight corresponding to 3, 4, pentamer, respectively) The average value divided by 3, 4 and 5)]. Further, the number of short chain branches (number / 1000 carbons), the average number of short chain branches per molecule of the oligomer (average degree of polymerization × monomer carbon number × short chain branch number / 1000), and the branching group ratio are ¹³ C-NMR ( Determined by CDCl ₃ ) measurement. The 40 ° C. kinematic viscosity was measured according to JISK2283. The pour point was measured according to JISK2269.

Production Example 2 (Production of PAO with metallocene catalyst 2)
After adding 2.5 L of degassed and dehydrated 1-decene by nitrogen bubbling to a 5 L stainless steel autoclave purged with nitrogen, the temperature was raised to 50 ° C. and adjusted to 1.0 mol / L of methylaluminoxane. 12 ml of toluene solution was added.
Next, 10 mL of a toluene solution of bis (cyclopentadienyl) zirconium dichloride adjusted to 40 mmol / L was added, and the reaction was carried out at 50 ° C. for 7 hours while continuously supplying and stirring 5 kPa of hydrogen.
The compounding ratio of the metallocene compound and 1-decene in the above reaction was 0.16 mmol / (1-decene) L, and the methylaroxane / metallocene compound (molar ratio) = 30. The reaction was stopped with 500 mL of 1% dilute hydrochloric acid, washed twice with 100 mL of deionized water, and the solution obtained by decomposing and removing the catalyst component was analyzed by gas chromatography. The yield of the oligomer was 94%, The selectivity over the body was 42% dimer, 11% trimer, 7% tetramer, 5% pentamer, and 35% hexamer over 35%. Further, when elemental analysis of this solution was performed, it was found that Cl, Al, and Zr were all <2 ppm by mass and substantially no catalyst residue was contained.

After removing the monomer and dimer from the solution obtained by decomposing and removing the catalyst component under reduced pressure, 1 mass% of palladium / alumina catalyst (5% Pd supported product) was added to a 5 L stainless steel autoclave purged with nitrogen. In addition, hydrogen 0.8 MPa was continuously supplied and reacted at 85 ° C. for 5 hours while stirring. Then, the said catalyst was removed by filtration, and the obtained hydrogenated liquid was fractionally distilled at 1.33 Pa and 200-270 degreeC using the simple distillation apparatus. When the residue after fractional distillation was examined, it was 9.9% by mass of tetramer, 10.1% by mass of pentamer, and 80.0% by mass of hexamer or more. The average degree of polymerization is 9.2, the number of short chain branches is 9.6 / 1000 carbon, and the average number of short chain branches per molecule of the oligomer is 0.88. It was also revealed that the short-chain branching group species were substantially composed of methyl group branching, with 93.0 mol% methyl group branching, 2.5 mol% ethyl group branching, and 4.5 mol% propyl group branching.
This residue has a kinematic viscosity at 40 ° C. of 208.1 mm ² / s, a kinematic viscosity at 100 ° C. of 27.34 mm ² / s, a viscosity index of 168, a pour point of −50 ° C., a flash point of 276 ° C., and an evaporation amount (Noack) of 1.7%. there were. This residue was used as mPAO-2 for the production of a lubricating oil composition.

Production Example 3 (Production of PAO with metallocene catalyst 3)
A stainless steel autoclave with an internal volume of 5 L was sufficiently dried and after nitrogen substitution, 1770 mL of 1-dodecene, 1230 mL of 1-octene, and then 2.25 mmol of triisobutylaluminum were added, and the temperature was raised to 86 ° C. Separately prepared catalyst mixture (1.5 mL of triisobutylaluminum in a 100 mL glass Schlenk bottle under a nitrogen atmosphere (0.5 mmol / mL toluene solution; 3.0 mL), (1,1′-dimethylsilylene) (2 , 2′-dimethylsilylene) -bis (cyclopentadienyl) zirconium dichloride 30 μmol (5 μmol / mL in toluene; 6.0 mL) and powdered N, N-dimethylanilinium tetrakis (pentafluorophenyl) borate After adding 06 mmol (48 mg) and stirring at room temperature for about 1 minute, 12 mL of 1-dodecene (15 mL) and further stirring at room temperature for 1 hour) were added, 20 kPa of hydrogen was introduced, and polymerization was started. After polymerization at 86 ° C. for 120 minutes, the remaining 12 mL of the catalyst mixed solution was added, and further reacted at 86 ° C. for 120 minutes, and then 100 mL of methanol was added to stop the polymerization. The contents were taken out and added to 1000 mL of 1% by mass NaOH aqueous solution and stirred. This solution was transferred to a separatory funnel, the organic layer was separated, the organic layer was washed with water, and the organic layer was removed with Toyo Filter Paper 2C filter paper. Toluene, raw materials, methanol and the like were distilled off from the resulting solution with a rotary evaporator (oil bath 100 ° C. under reduced pressure of about 1.0 × 10 ⁻⁴ MPa) to obtain 2143 g of a colorless transparent liquid. Furthermore, distillation was performed at 180 ° C. under a reduced pressure of 5 × 10 ⁻⁶ Pa using a thin film distillation apparatus (molecular distillation apparatus MS-300 special model manufactured by Shibata Kagaku, high vacuum evacuation apparatus DS-212Z). 2036 g of polymer was obtained by removing. The polymer obtained was put into a stainless steel autoclave having an internal volume of 5 L, a stabilized nickel catalyst (SN750, manufactured by Sakai Chemical Industry Co., Ltd.) was added so as to be 1% by mass, and then at 130 ° C. under 2 MPa of hydrogen. Reacted for hours. After completion of the reaction, the temperature was cooled to around 80 ° C., the contents were taken out, and the catalyst component was separated by filtration at 70 ° C. using a 1 μm filter to obtain 2010 g of hydrogenated product.
The hydrogenated product is, 40 ° C. kinematic viscosity 1883mm ² / s, 100 ℃ kinematic viscosity 190 mm ² / s, viscosity index 231, was pour point -40 ° C.. This hydrogenated product was used as mPAO-3 for the production of a lubricating oil composition.

Production Example 4 (Production of PAO with metallocene catalyst 4)
In Production Example 1, fractions mainly composed of trimer were collected from fractions obtained by fractional distillation under conditions of 1.33 Pa and 200 to 270 ° C. (trimer 90.1% by mass, Tetramer 9.3 wt%, pentamer 0.5 wt%). This fraction has an average degree of polymerization of 3.0, a short chain branch number of 30.1 / 1000 carbon, and an average short chain branch number of 0.90 per oligomer molecule. It was also revealed that the short-chain branching group species consisted of methyl group branching, with 98.6 mol% methyl group branching and 1.4 mol% ethyl group branching.
This fraction has a kinematic viscosity of 40 ° C. of 14.45 mm ² / s, a kinematic viscosity of 100 ° C. of 3.55 mm ² / s, a viscosity index of 129, a pour point <−50 ° C., a flash point of 240 ° C., and an evaporation amount (Noack) of 10.7. It was mass%. This fraction was used as mPAO-4 for the production of a lubricating oil composition.

Examples 1-5 and Comparative Examples 1-6
Lubricating oil compositions were prepared using the base oils and additives shown in Table 1 and blended in the proportions shown in Table 1. The properties are shown in Table 1.

mPAO-1: PAO by metallocene catalyst (kinematic viscosity at 100 ° C. 17 mm ² / s, viscosity index 155)
mPAO-2: PAO by metallocene catalyst (kinematic viscosity at 100 ° C. 27 mm ² / s, viscosity index 168)
mPAO-3: PAO by metallocene catalyst (kinematic viscosity at 100 ° C. 190 mm ² / s, viscosity index 247)
mPAO-4: PAO by metallocene catalyst (kinematic viscosity at 100 ° C. 3.5 mm ² / s, viscosity index 127)
Mineral oil: Group III mineral oil (kinematic viscosity at 100 ° C. 4.4 mm ² / s, viscosity index 127)
PAO-1: Conventional PAO (kinematic viscosity at 100 ° C. 4 mm ² / s, viscosity index 125)
PAO-2: Conventional PAO (kinematic viscosity at 100 ° C. 10 mm ² / s, viscosity index 139)
PAO-3: Conventional PAO (kinematic viscosity at 100 ° C. 40 mm ² / s, viscosity index 149)
PAO-4: Conventional PAO (kinematic viscosity at 100 ° C. 100 mm ² / s, viscosity index 176)
Esters: Nippon Oil & Fats Co., Ltd. Unistar H334R
VII-1: Viscosity index improver [polymethacrylate (Mw: 45000)]
VII-2: Viscosity index improver [ethylene-propylene copolymer (Mw: 5000)]
Additive: ANGRAMOL9001N manufactured by Nihon Lubrizol

In Examples 1 to 5 using mPAO, it has excellent low-temperature characteristics, and excellent results are also obtained in the shear stability test and fatigue life test. These excellent properties are not at the expense of other properties, and there is no significant reduction in flash point or deterioration in evaporation.
On the other hand, in Comparative Examples 1 to 6 that do not use mPAO, some evaluation items have performance equivalent to that of the lubricating oil composition using mPAO, but the compatibility with other characteristics cannot be achieved.
Specifically, since Comparative Example 1 is highly dependent on the viscosity index improver, its performance is greatly inferior in the shear stability test and fatigue life test. In Comparative Example 2, although the disadvantage of Comparative Example 1 is eliminated by using an olefin copolymer-based viscosity index improver, the low temperature characteristics are inferior. In Comparative Examples 3-6, it is a lubricating oil composition which does not use a viscosity index improver, and the balance of various performances is improved, but it is generally inferior to the lubricating oil compositions of the examples.

  According to the present invention, it is possible to obtain a lubricating oil excellent in fatigue resistance as compared with a lubricating oil using conventional PAO. Furthermore, since the viscosity index is increased, the low-temperature viscosity characteristics are improved, the dependence on the viscosity index improver is reduced, and viscosity reduction due to shearing is suppressed. The lubricating oil composition of the present invention having such characteristics is preferably used in applications where fuel economy is required.

Claims (6)

A drive system lubricating oil composition having a kinematic viscosity at 100 ° C. of 10 to 20 mm ² / s, comprising the following (1) to (3):
(1) Poly-α-olefin having a kinematic viscosity at 100 ° C. of 15 to 300 mm ² / s produced using a metallocene catalyst (2) Fatty acid ester (3) The kinematic viscosity at 100 ° C. is 6 mm ² / s or less. that was prepared using the main Tarosen catalyst poly -α- olefin Furthermore, the drive system lubricating oil composition of Claim 1 containing the mineral oil whose kinematic viscosity in 100 degreeC is 6 mm < ² > / s or less . The drive system lubricating oil composition according to claim 1 or 2 , wherein the content of the poly-α-olefin according to (1) is 50 to 95% by mass based on the total amount of the lubricating oil composition. ^2. The drive system lubricating oil composition according to claim 1, wherein the poly-α-olefin according to (3) has a kinematic viscosity at 100 ° C. of 1.5 to 5.5 mm ² / s. It is a manufacturing method of the drive system lubricating oil composition given in any 1 paragraph of Claims 1-4 ,
Poly-α-olefin produced using a metallocene catalyst and having a kinematic viscosity at 100 ° C. of 15 to 300 mm ² / s, and poly-α produced using a metallocene catalyst and having a kinematic viscosity at 100 ° C. of 6 mm ² / s or less -Preparing a base oil containing olefins ;
Adding a fatty acid ester to the base oil;
Further, a step of adding one or more selected from an extreme pressure agent, an oily agent, an antioxidant, a rust inhibitor, a metal deactivator, a cleaning dispersant, a viscosity index improver, a pour point depressant and an antifoaming agent. And a method for producing a drive system lubricating oil composition. The use method for the transmission of the drive system lubricating oil composition according to any one of claims 1 to 4 .