JP2008163217A - Lubricating oil composition for metal working - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a lubricating oil composition for metal working, which is free of a chlorine-based extreme-pressure agent, is excellent in extreme pressure property and abrasion property although the composition is a non-chlorine-based metalworking fluid, is excellent in workability to various kinds of irons, non-iron metals or alloys thereof, especially, and has workability which is not inferior to that in the case using chlorine-based metal working oil also in the working of a material which is hard to work, e.g. iron or stainless steel. <P>SOLUTION: The lubricating oil composition for metal working comprises a base oil and a 10-24C α-olefin polymer satisfying conditions of items (1) and (2): (1) the weight average molecular weight is 1,000 to 1,000,000; (2) stereoregular index M2 represented by formula (a): M2(%)=(X/Y)×100 [wherein X is an integrated value of absorption peak strength between 36.2 ppm and 35.3 ppm in<SP>13</SP>C-NMR spectrum; Y is an integrated value of absorption peak strength between 36.2 ppm and 34.5 ppm] is ≥50 mol%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a lubricating oil composition for metal working, more specifically, a so-called non-chlorine metal working lubricating oil, and cold rolling of difficult-to-work materials such as iron, non-ferrous metals or alloys thereof, particularly iron and stainless steel. The present invention relates to a lubricating oil composition for metal working that can be used effectively for metal working such as drawing, punching, forging, coining, bending, stretching, drawing, punching, fine blanking, and the like.

Until now, chlorinated extreme pressure agents such as chlorinated paraffin and pentachlorostearic acid with extremely high extreme pressure have been used for metal processing, especially for difficult-to-process materials such as iron and stainless steel such as chromium and nickel alloys. Containing so-called chlorinated oils have been used.
However, in recent years, it has become complicated and wasteful to dispose of used chlorine-containing lubricating oil due to environmental problems, so it has been forced to switch to non-chlorine metal processing oil that does not contain chlorine. It's getting on. Therefore, development of a new non-chlorine metalworking oil has been attempted.

  For example, it contains a metal processing oil containing a large amount of zinc dithiophosphate (see, for example, Patent Document 1), a sulfur-based extreme pressure agent such as polysulfide, an oxygen-containing compound such as a phosphorus compound and a fatty acid ester, and an organic boron compound. Lubricating oil used for cutting (for example, see Patent Document 2), cutting / grinding oil containing a methacrylate polymer and a sulfur-based extreme pressure agent (for example, see Patent Document 3), and aliphatic primary class An extreme pressure additive containing a basic salt such as an alkaline earth metal of a carboxylic acid and a fatty acid ester, a lubricating oil containing the additive (see, for example, Patent Document 4), and a chemical conversion treatment material such as oxalic acid were applied. There are cutting and grinding oils (for example, see Patent Document 5).

However, any of these non-chlorine metalworking oils does not reach the performance of chlorinated metalworking oils, which are extremely high in extreme pressure. In particular, it is powerless in the processing of difficult-to-process materials such as stainless steel, and it has been put to practical use due to various problems such as deterioration of workability due to poor lubrication, tool wear of molds and the occurrence of scratching on the surface, etc. The current situation is difficult.
Therefore, it is a non-chlorine metalworking oil that does not contain chlorinated extreme pressure agents, has excellent workability, and has a processing performance comparable to that of chlorinated metalworking oil even when processing difficult-to-work materials such as stainless steel. Development of chlorinated metalworking oil is needed.

International Publication WO96 / 33253 JP-A-9-111278 JP 2001-49279 A JP 2003-49185 A JP 2002-88387 A

  Under such circumstances, the present invention is a non-chlorine metal working oil that does not use a chlorine-based extreme pressure agent, has excellent extreme pressure properties and wear resistance, and is suitable for various types of iron and non-ferrous metals or their alloys. An object of the present invention is to provide a lubricating oil composition for metal working which has excellent workability, and in particular has a workability which is not inferior when using a chlorinated metal working oil even in the processing of difficult-to-work materials such as iron and stainless steel. It is what.

As a result of intensive studies to develop a metal processing lubricating oil composition having the above-mentioned preferred properties, the present inventors have found that the object can be achieved by using a specific polymer. The present invention has been completed based on such findings.
That is, the present invention

[1] A lubricating oil composition for metal working, characterized in that the base oil contains an α-olefin polymer having 10 to 24 carbon atoms that satisfies the following conditions (1) and (2):
(1) The weight average molecular weight is 1,000 to 1,000,000,
(2) The stereoregularity index M2 represented by the following formula (a) is 50 mol% or more,
M2 (mol%) = (X / Y) × 100 (a)
[Wherein, X is an integrated value of absorption peak intensity between 36.2 to 35.3 ppm in ¹³ C-NMR spectrum, and Y is an integrated value of absorption peak intensity between 36.2 to 34.5 ppm. Show. ]
[2] The lubricating oil composition for metalworking according to [1] above, wherein the melting point of the polymer of α-olefin measured using a differential scanning calorimeter is 20 to 100 ° C.
[3] The lubricating oil composition for metal working according to [1] or [2], wherein the molecular weight distribution (weight average molecular weight / number average molecular weight) of the α-olefin polymer is 5.0 or less.
[4] The α-olefin polymer is (A) a transition metal compound represented by the following general formula (I), and (B) (B-1) a transition metal compound of the component (A) or a derivative thereof. [1] to [3] which are polymers obtained using a polymerization catalyst containing at least one component selected from (B-2) aluminoxane and a compound capable of reacting with an ionic complex to form an ionic complex ] A lubricating oil composition for metal working according to any one of

[Wherein M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopentadienyl group, respectively. , A substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which form a cross-linked structure via A ¹ and A ² In addition, they may be the same as or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , It may be cross-linked with E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]
[5] The lubricating oil composition for metal working according to any one of [1] to [4], wherein the content of the α-olefin polymer is 0.2 to 30% by mass based on the total amount of the composition. ,
[6] The lubricating oil composition for metalworking according to any one of [1] to [5], further comprising an extreme pressure agent and / or an oily agent,
[7] The extreme pressure agent is one or more extreme pressure agents selected from sulfur extreme pressure agents and phosphorus extreme pressure agents, and the oily agent is selected from fats and oils, fatty acids, alcohols, and fatty acid esters. The metal processing lubricant composition according to [6], and [8] the metal processing lubricant according to any one of [1] to [7], which is used for processing difficult-to-process materials. Composition,
Is to provide.

  According to the present invention, even if it is a non-chlorine metal working oil that does not use a chlorine-based extreme pressure agent, it is excellent in extreme pressure and wear resistance, and excellent in workability with respect to various types of iron and non-ferrous metals or their alloys. In particular, it is possible to provide a lubricating oil composition for metal working having workability comparable to that when using a chlorinated extreme pressure agent in processing difficult-to-work materials such as iron and stainless steel.

The lubricating oil composition for metal working of the present invention (hereinafter sometimes simply referred to as a lubricating oil composition) contains a base oil and a polymer of an α-olefin having 10 to 24 carbon atoms that satisfies specific conditions. It is characterized by doing.
Although there is no restriction | limiting in particular as base oil in the lubricating oil composition of this invention, Kinematic viscosity in 40 degreeC is 10-1000 mm < ² > / s, Preferably it is 30-500 mm < ² > / s mineral oil and synthetic oil, and 100 degreeC A polymer having a kinematic viscosity of 10 to 30000 mm ² / s, preferably 50 to 10000 mm ² / s is suitably used.
Among these, various mineral oils can be exemplified. For example, distillate obtained by subjecting paraffin-based crude oil, intermediate-based crude oil, or naphthenic-based crude oil to atmospheric distillation, or distilling oil obtained by subjecting atmospheric distillation residue oil to vacuum distillation, or purifying it according to a conventional method. For example, solvent refined oil, hydrogenated refined oil, dewaxed oil, and clay-treated oil can be used.

Synthetic oils include polyolefins such as polybutene, polyisobutylene, polypropylene, ethylene-α-olefin copolymers, and hydrogenated products thereof, polyol esters [for example, polyhydric alcohols such as trimethylolpropane, pentaerythritol, sorbitan, etc. An ester compound such as ester of fatty acid], polyalkylene glycol, polyalkylene glycol ether and the like can be used.
Further, examples of the polymer include polymers of the compounds exemplified as the synthetic oil and those having the kinematic viscosity at 100 ° C., such as polybutene, polyisobutylene, polypropylene, and ethylene-α-olefin copolymer. And their hydrogenated products, polyalkylene glycols and the like.
In the lubricating oil composition of the present invention, as the base oil, one kind of the mineral oil may be used, or two or more kinds may be used in combination. Moreover, 1 type of synthetic oil may be used and it may be used in combination of 2 or more types. Further, one type of polymer may be used, or two or more types may be combined. Further, one or more of mineral oil, synthetic oil and polymer may be used in combination with one or more other oils.

The lubricating oil composition of the present invention contains an α-olefin polymer having 10 to 24 carbon atoms that satisfies specific conditions, specifically, the following conditions (1) and (2).
(1) The weight average molecular weight is 1,000 to 1,000,000,
(2) The stereoregularity index value M2 represented by the following formula (a) is 50 mol% or more,
M2 (mol%) = (X / Y) × 100 (a)
[Wherein, X is an integrated value of absorption peak intensity between 36.2 to 35.3 ppm in ¹³ C-NMR spectrum, and Y is an integrated value of absorption peak intensity between 36.2 to 34.5 ppm. Show. ]
This α-olefin polymer exhibits the effect of increasing the thickness of the lubricating film formed in the lubrication portion, that is, the processed portion, or increasing the strength of the lubricating film, thereby improving extreme pressure properties and wear resistance.

The α-olefin polymer is an α-olefin polymer having 10 to 24 carbon atoms, preferably 16 to 24 carbon atoms. If the α-olefin of the raw material has 10 or more carbon atoms, the α-olefin polymer can exert effects such as increasing the thickness of the lubricating film which is the object of the present invention. If the number of carbon atoms is 24 or less, there is little risk of difficulty in the polymerization reaction when producing an α-olefin polymer.
Specific examples of such α-olefins include 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1 -Nonadecene, 1-eicosene etc. are mentioned, These can be used individually or in combination of 2 or more types.

The α-olefin polymer is required to have a weight average molecular weight of 1,000 to 1,000,000 as in the condition (1). If the weight average molecular weight is 1000 or more, the effect of increasing extreme pressure and wear resistance by increasing the oil film thickness is exhibited. If the weight average molecular weight is 1 million or less, the solubility in the base oil is a problem. There is little fear to become. The weight average molecular weight is more preferably 5000 to 300,000, and further preferably 10,000 to 150,000.
The weight-average molecular weight of the α-olefin polymer was measured by gel permeation chromatography (GPC).

The α-olefin polymer needs to satisfy the condition (2), that is, the stereoregularity index value M2 is 50 mol% or more. If the stereoregularity index value M2 is 50 mol% or more, there are few atactic structures and syndiotactic structures, and the isotactic structure of the polymer is formed well, and the object of the present invention can be achieved. The reason is presumed that the thickness of the lubricating film formed on the lubrication portion, that is, the processed surface, or the strength of the lubricating film is increased by adopting such a structure.
The stereoregularity index value M2 is more preferably 50 to 90 mol%, further preferably 55 to 85 mol%, and particularly preferably 55 to 75 mol%. Thus, by controlling the stereoregularity moderately, it is possible to obtain the effect of maintaining the thickness and strength of the formed lubricating film and at the same time increasing the solubility in the base oil.

The stereoregularity index value M2 is expressed by the following formula (a)
M2 (mol%) = (X / Y) × 100 (a)
[Wherein, X is an integrated value of absorption peak intensity between 36.2 to 35.3 ppm in ¹³ C-NMR spectrum, and Y is an integrated value of absorption peak intensity between 36.2 to 34.5 ppm. Show. ]
Sought by.
The formula (a) Asakura, M .; Demura, Y .; This is in accordance with the method proposed in “Macromolecules, 24, 2334 (1991)” reported by Nishiyama, and the CH ₂ carbon at the side chain α-position in the ¹³ C NMR spectrum is split to reflect the difference in stereoregularity. The isotacticity is obtained by using what is observed. The larger the value of M2, the higher the isotacticity.

In addition, the α-olefin polymer of the present invention has a melting point of 20 to 100 ° C., preferably 20 to 80 ° C., more preferably 20 to 60 ° C. If the melting point of the α-olefin polymer is 20 ° C. or higher, the effect of enhancing extreme pressure properties and wear resistance is good, and if the melting point is 100 ° C. or lower, the handling is easy and the degreasing property is improved. There is no fear of lowering.
In addition, the said melting | fusing point is the value measured using the differential scanning calorimeter (DSC), and is specifically measured with the following method.
[Measuring method of melting point by differential scanning calorimeter]
The sample is held at −10 ° C. for 5 minutes in a nitrogen atmosphere, then heated to 190 ° C. at 10 ° C./min, and held at 190 ° C. for 5 minutes. Next, the temperature is lowered to −10 ° C. at 5 ° C./min, and held at −10 ° C. for 5 minutes. Then, the peak observed from the melting endothermic curve obtained by raising the temperature to 190 ° C. at 10 ° C./min was measured as the melting point (Tm).

The α-olefin polymer of the present invention preferably further has a molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of 5.0 or less. If molecular weight distribution is 5.0 or less, since the density | concentration of the target active ingredient is high, a compounding effect can be improved. The molecular weight distribution is more preferably in the range of 1.5 to 5.0.
The molecular weight distribution (Mw / Mn) is measured by a gel permeation chromatograph (GPC) method.

The production method of the α-olefin polymer of the present invention is not particularly limited, and for example, it can be produced using the metallocene catalyst shown below. That is,
(A) It reacts with the transition metal compound represented by the following general formula (I), and (B) (B-1) the transition metal compound of the component (A) or a derivative thereof to form an ionic complex. This is a method of polymerizing an α-olefin having 10 to 24 carbon atoms using a polymerization catalyst containing at least one kind of component selected from the following compounds and (B-2) aluminoxane.

In the above general formula (I), M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and specific examples include titanium, zirconium, hafnium, yttrium, vanadium, chromium, manganese, nickel, cobalt, palladium. Among them, titanium, zirconium and hafnium are preferable from the viewpoint of olefin polymerization activity.
E ¹ and E ² are respectively substituted cyclopentadienyl group, indenyl group, substituted indenyl group, heterocyclopentadienyl group, substituted heterocyclopentadienyl group, amide group (—N <), phosphine group (—P <), Hydrocarbon group [>CR-,> C <] and silicon-containing group [>SiR-,> Si <] (where R is hydrogen, a hydrocarbon group having 1 to 20 carbon atoms, or a heteroatom-containing group) A ligand selected from among (A), and a crosslinked structure is formed via A ¹ and A ² . E ¹ and E ² may be the same as or different from each other. As E ¹ and E ² , a substituted cyclopentadienyl group, an indenyl group and a substituted indenyl group are preferable.
X represents a σ-bonding ligand, and when there are a plurality of Xs, the plurality of Xs may be the same or different, and may be cross-linked with other X, E ¹ , E ² or Y.
Specific examples of X include a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an aryloxy group having 6 to 20 carbon atoms, an amide group having 1 to 20 carbon atoms, carbon Examples thereof include a silicon-containing group having 1 to 20 carbon atoms, a phosphide group having 1 to 20 carbon atoms, a sulfide group having 1 to 20 carbon atoms, and an acyl group having 1 to 20 carbon atoms.

On the other hand, Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X. Specific examples of the Lewis base of Y include amines, ethers, phosphines, thioethers and the like.
A ¹ and A ² are divalent bridging groups for bonding two ligands, which are a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, germanium containing group, a tin-containing group, -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 — Or —AlR ¹ —, wherein R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which are the same or different from each other. Also good.
Examples of such a crosslinking group include a general formula

（Ｄは炭素、ケイ素又はスズ、Ｒ²及びＲ³はそれぞれ水素原子又は炭素数１〜２０の炭化水素基で、それらは互いに同一でも異なっていてもよく、又互いに結合して環構造を形成していてもよい。ｅは１〜４の整数を示す。）
で表されるものが挙げられ、その具体例としては、メチレン基，エチレン基，エチリデン基，プロピリデン基，イソプロピリデン基，シクロヘキシリデン基，１，２−シクロヘキシレン基，ビニリデン基（ＣＨ₂＝Ｃ＝），ジメチルシリレン基，ジフェニルシリレン基，メチルフェニルシリレン基，ジメチルゲルミレン基，ジメチルスタニレン基，テトラメチルジシリレン基，ジフェニルジシリレン基などを挙げることができる。これらの中で、エチレン基，イソプロピリデン基及びジメチルシリレン基が好適である。
ｑは１〜５の整数で〔（Ｍの原子価）−２〕を示し、ｒは０〜３の整数を示す。
このような一般式（Ｉ）で表される遷移金属化合物の中では、一般式（II）

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

で表される二重架橋型ビスシクロペンタジエニル誘導体を配位子とする遷移金属化合物が好ましい。

The transition metal compound which makes the ligand the double bridge type biscyclopentadienyl derivative represented by these is preferable.

In the above general formula (II), M, A ¹ , A ² , q and r are the same as those in the general formula (I).
X ¹ represents a σ-bonding ligand, and when plural X ^1, a plurality of X ¹ may be the same or different, may be crosslinked with other X ¹ or Y ^1. Specific examples of X ¹ include the same examples as those exemplified in the description of X in formula (I).
Y ¹ represents a Lewis base, if Y ¹ is plural, Y ¹ may be the same or different, may be crosslinked with other Y ¹ or X ^1. Specific examples of Y ¹ are the same as those exemplified in the description of Y in the general formula (I).
R ^{4 to} R ⁹ each represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, or a heteroatom-containing group. One must not be a hydrogen atom. R ^{4 to} R ⁹ may be the same as or different from each other, and adjacent groups may be bonded to each other to form a ring. Among these, it is preferable that R ⁶ and R ⁷ form a ring and R ⁸ and R ⁹ form a ring.
As R ⁴ and R ⁵ , a group containing a heteroatom such as oxygen, halogen, or silicon is preferable because of high polymerization activity.
The transition metal compound having the double-bridged biscyclopentadienyl derivative as a ligand preferably contains silicon in the bridging group between the ligands.
Representative examples of the transition metal compound represented by the general formula (I) include (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium chloride. , (1,2′-ethylene) (2,1′-ethylene) -bis (indenyl) zirconium dichloride and the like.

Next, as the component (B-1) in the component (B), any component can be used as long as it can form an ionic complex by reacting with the transition metal compound of the component (A). The following general formulas (III) and (IV) can be used.
([L ¹ −R ¹⁰ ] ^{k +} ) _a ([Z] ⁻ ) _b (III)
([L ² ] ^{k +} ) _a ([Z] ⁻ ) _b (IV)
(However, L ² is M ² , R ¹¹ R ¹² M ³ , R ¹³ ₃ C or R ¹⁴ M ^3. ) [In the formulas (III) and (IV), L ¹ is a Lewis base, [Z] ⁻ Is a non-coordinating anion [Z ¹ ] ⁻ and [Z ² ] ⁻ , where [Z ¹ ] ⁻ is an anion having a plurality of groups bonded to the element, ie, [M ¹ G ¹ G ² ... G ^f ] ^- (wherein, M ¹ is the periodic table 5-15 group element, preferably a periodic table 13-15 group element .G ¹ ~G ^f each represent a hydrogen atom, a halogen atom, 1 to carbon atoms 20 alkyl groups, C2-C40 dialkylamino groups, C1-C20 alkoxy groups, C6-C20 aryl groups, C6-C20 aryloxy groups, C7-C40 alkyls Aryl group, arylalkyl group having 7 to 40 carbon atoms, halogen-substituted hydrocarbon group having 1 to 20 carbon atoms, acyloxy having 1 to 20 carbon atoms , Organometalloid radicals, or two or more may form a ring .f of .G ¹ ~G ^f indicating a hetero atom-containing hydrocarbon group having 2 to 20 carbon atoms [(the central metal M ¹ an integer valence) +1]), [Z ^{2] -.} is the reciprocal of the acid dissociation constant logarithm (pKa) is -10 or less Bronsted acid alone or Bronsted acid and Lewis acid combined conjugate base Or a conjugate base of an acid generally defined as a super strong acid. A Lewis base may be coordinated. R ¹⁰ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group or an arylalkyl group, and R ¹¹ and R ¹² are a cyclopentadienyl group and a substituted group, respectively. cyclopentadienyl group, an indenyl group or a fluorenyl group, R ¹³ represents an alkyl group, an aryl group, alkylaryl group or arylalkyl group having 1 to 20 carbon atoms. R ¹⁴ represents a macrocyclic ligand such as tetraphenylporphyrin or phthalocyanine. k is an ionic valence of [L ¹ −R ¹⁰ ], [L ² ], an integer of 1 to 3, a is an integer of 1 or more, and b = (k × a). M ² includes elements in groups 1 to ³ , 11 to 13, and 17 of the periodic table, and M ³ represents elements 7 to 12 in the periodic table. ]
What is represented by these can be used conveniently.

Here, specific examples of L ¹ include ammonia, methylamine, aniline, dimethylamine, diethylamine, N-methylaniline, diphenylamine, N, N-dimethylaniline, trimethylamine, triethylamine, tri-n-butylamine, methyldiphenylamine, Amines such as pyridine, p-bromo-N, N-dimethylaniline, p-nitro-N, N-dimethylaniline, phosphines such as triethylphosphine, triphenylphosphine, diphenylphosphine, thioethers such as tetrahydrothiophene, benzoic acid Examples thereof include esters such as ethyl acid, and nitriles such as acetonitrile and benzonitrile.
Specific examples of R ¹⁰ include hydrogen, methyl group, ethyl group, benzyl group, and trityl group. Specific examples of R ¹¹ and R ¹² include cyclopentadienyl group and methylcyclopentadienyl group. , Ethylcyclopentadienyl group, pentamethylcyclopentadienyl group, and the like.
Specific examples of R ¹³ include a phenyl group, a p-tolyl group, and a p-methoxyphenyl group. Specific examples of R ¹⁴ include tetraphenylporphyrin, phthalocyanine, allyl, methallyl, and the like. .
Specific examples of M ² include Li, Na, K, Ag, Cu, Br, I, and I _3. Specific examples of M ³ include Mn, Fe, Co, Ni, Zn, and the like. Can be mentioned.

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

Specific examples of non-coordinating anions, that is, Bronsted acids having a pKa of −10 or less or a conjugate base [Z ² ] ^{− in} combination of Bronsted acids and Lewis acids include trifluoromethanesulfonic acid anions (CF ₃ SO ₃ ) ^- , bis (trifluoromethanesulfonyl) methyl anion, bis (trifluoromethanesulfonyl) benzyl anion, bis (trifluoromethanesulfonyl) amide, perchlorate anion (ClO ₄ ) ^- , trifluoroacetate anion (CF ₃ CO ₂ ) ^- , Hexafluoroantimony anion (SbF ₆ ) ^- , fluorosulfonate anion (FSO ₃ ) ^- , chlorosulfonate anion (ClSO ₃ ) ^- , fluorosulfonate anion / 5-antimony fluoride (FSO ₃ / SbF ₅ ) ^- , Fluorosulfonic acid anion / 5-fluoride Arsenic _{(FSO 3 / AsF 5) -} , trifluoromethanesulfonic acid / antimony pentafluoride _{(CF 3 SO 3 / SbF 5} ) - and the like.
Representative examples of such ionic compounds that react with the transition metal compound of the component (A) to form an ionic complex, that is, (B-1) component compounds include: trimethylammonium tetraphenylborate, tetraphenyl Examples thereof include tetraethylammonium borate, methyl (tri-n-butyl) ammonium tetraphenylborate, benzyl (tri-n-butyl) ammonium tetraphenylborate, and dimethyldiphenylammonium tetraphenylborate.
Such (B-1) component may be used individually by 1 type, and may be used in combination of 2 or more type.
On the other hand, as the aluminoxane of the component (B-2), the general formula (V)

（式中、Ｒ¹⁵は炭素数１〜２０、好ましくは１〜１２のアルキル基，アルケニル基，アリール基，アリールアルキル基などの炭化水素基あるいはハロゲン原子を示し、ｗは平均重合度を示し、通常２〜５０、好ましくは２〜４０の整数である。尚、各Ｒ¹⁵は同じでも異なっていてもよい。）
で示される鎖状アルミノキサン、及び一般式（ＶＩ）

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

（式中、Ｒ¹⁵及びｗは前記一般式（Ｖ）におけるものと同じである。）
で示される環状アルミノキサンを挙げることができる。
前記アルミノキサンの製造法としては、アルキルアルミニウムと水などの縮合剤とを接触させる方法が挙げられるが、その手段については特に限定はなく、公知の方法に準じて反応させればよい。
このような（Ｂ−２）成分の代表例としては、メチルアルミノキサン、エチルアルミノキサン、ブチルアルミノキサンなどが挙げられる。
これらのアルミノキサンは１種を単独で用いてもよく、２種以上を組み合わせて用いてもよい。

(In the formula, R ¹⁵ and w are the same as those in the general formula (V).)
The cyclic aluminoxane shown by these can be mentioned.
Examples of the method for producing the aluminoxane include a method in which an alkylaluminum is brought into contact with a condensing agent such as water, but the means is not particularly limited and may be reacted according to a known method.
Typical examples of such component (B-2) include methylaluminoxane, ethylaluminoxane, butylaluminoxane and the like.
These aluminoxanes may be used individually by 1 type, and may be used in combination of 2 or more type.

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. The range of 2: 1 to 1:10 is desirable.
When the compound (B-2) is used, the molar ratio is preferably 1: 1 to 1: 1000000, more preferably 1:10 to 1: 10000. Moreover, (B-1) and (B-2) can also be used individually or in combination of 2 or more types as a catalyst component (B).
In addition to the components (A) and (B), the polymerization catalyst for producing the α-olefin polymer of the present invention can use an organoaluminum compound as the component (C).

Here, as the organoaluminum compound of component (C), the general formula (VII)
R ¹⁶ _v AlJ _3-v (VII)
[Wherein, R ¹⁶ represents an alkyl group having 1 to 10 carbon atoms, J represents a hydrogen atom, an alkoxy group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or a halogen atom, and v represents 1 to 3 carbon atoms. (It is an integer)
The compound shown by these is used.
Representative examples of the compound represented by the general formula (VII) include triisopropylaluminum, triisobutylaluminum, diethylaluminum chloride and the like.
These organoaluminum compounds may be used alone or in combination of two or more.

  The use ratio of the catalyst component (A) to the catalyst component (C) is preferably 1: 1 to 1: 10000, more preferably 1: 5 to 1: 2000, still more preferably 1:10 to 1 in terms of molar ratio. : The range of 1000 is desirable. By using the catalyst component (C), the polymerization activity per transition metal can be improved.

In the production of the α-olefin polymer of the present invention, at least one catalyst component can be supported on a suitable carrier and used.
The type of the carrier is not particularly limited, and any of inorganic oxide carriers, other inorganic carriers, and organic carriers can be used. In particular, inorganic oxide carriers or other inorganic carriers are preferable.
Specific examples of the inorganic oxide carrier include SiO ₂ , Al ₂ O ₃ , MgO, ZrO ₂ , TiO ₂ , Fe ₂ O ₃ , B ₂ O ₃ , CaO, ZnO, BaO, ThO ₂ and mixtures thereof. Examples thereof include silica alumina, zeolite, ferrite, and glass fiber. Of these, SiO ₂ and Al ₂ O ₃ are particularly preferable.

In the α-olefin polymer used in the present invention, the polymerization method is not particularly limited, and any method such as a slurry polymerization method, a gas phase polymerization method, a bulk polymerization method, a solution polymerization method, and a suspension polymerization method may be used. However, a slurry polymerization method and a gas phase polymerization method are particularly preferable.
Regarding the polymerization conditions, the polymerization temperature is usually −100 to 250 ° C., preferably −50 to 200 ° C., more preferably 0 to 130 ° C., and the use ratio of the catalyst to the reaction raw material is: raw material monomer / component (A) Ratio) is preferably 1 to 10 ⁸ , particularly 100 to 10 ⁵ , polymerization time is usually 5 minutes to 10 hours, reaction pressure is preferably normal pressure to 20 MPa (gauge), more preferably normal pressure to 10 MPa (gauge). is there.
In the method for producing an α-olefin polymer used in the present invention, it is preferable to add hydrogen because polymerization activity is improved. When hydrogen is used, it is usually from normal pressure to 5 MPa (gauge), preferably from normal pressure to 3 MPa (gauge), more preferably from normal pressure to 2 MPa (gauge).

  In the present invention, the α-olefin polymer having 10 to 24 carbon atoms is preferably contained in the range of 0.5 to 30% by mass based on the total amount of the composition. If the content of the α-olefin polymer is 0.5% by mass or more, the effect of enhancing extreme pressure properties and wear resistance is recognized, and if the content of the α-olefin polymer is 30% by mass or less, , There is no risk of solubility. The content of the α-olefin polymer is more preferably in the range of 1 to 20% by mass.

In the lubricating oil composition for metal working of the present invention, it is preferable to contain an extreme pressure agent and / or an oily agent in addition to the α-olefin polymer having 10 to 24 carbon atoms.
By containing these extreme pressure agents and oily agents, the effect of further enhancing extreme pressure properties and wear resistance is recognized. This is because the α-olefin polymer having 10 to 24 carbon atoms itself has a spacer effect of increasing the thickness of the lubricating film in the lubricating portion and a function of increasing the strength of the lubricating film, This is presumed to further enhance the strength of the lubricating film formed by the oily agent.

In the present invention, it is particularly preferable to use one or more extreme pressure agents selected from sulfur-based extreme pressure agents and phosphorus-based extreme pressure agents as the extreme pressure agent.
Examples of the sulfur-based extreme pressure agent include sulfur powder, polysulfide, sulfurized fat and oil, and sulfurized mineral oil. Among these, polysulfide is preferable from the viewpoint of effect, and active polysulfide is particularly preferable.
Examples of the polysulfide include, for example, the general formula (VIII)
R ¹⁷ -Sx-R ¹⁸ (VIII)
(In the formula, each of R ¹⁷ and R ¹⁸ represents an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkylaryl group having 7 to 20 carbon atoms, or an arylalkyl group having 7 to 20 carbon atoms. And they may be the same or different from each other, and x is a compound represented by an integer of 2 to 10.)
The dialkyl polysulfide represented by these is mentioned.
Specific examples of R ¹⁷ and R ¹⁸ include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, various pentyl groups, various hexyl groups. And various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, various dodecyl groups, cyclohexyl group, cyclooctyl group, phenyl group, naphthyl group, tolyl group, xylyl group, benzyl group, phenethyl group and the like.
Among the polysulfides, an active type mixture in which 5% by mass of mineral oil (ISOVG 100) is added exhibits “3” or “4” in a copper plate corrosion test (JISK-2513; 100 ° C., 1 hour), that is, Active polysulfide is more preferred.
Accordingly, x in the general formula (VIII) is preferably 3 to 6, and R ¹⁷ and R ¹⁸ are each an alkyl group having 12 to 20 carbon atoms.

Examples of the sulfurized fats and oils include animal and vegetable oils and fats such as beef tallow, pork fat and fish fats, rapeseed oil and soybean oil; unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid and fatty acids extracted from these animal and vegetable oils and fats; Examples thereof include unsaturated fatty acid esters obtained by reacting unsaturated fatty acids with various alcohols and acid chlorides; and those obtained by sulfurizing a mixture of these by any method.
Moreover, as a sulfide mineral oil, what dissolved elemental sulfur in mineral oil and what contains about 0.1-1 mass% normally as a sulfur content are used.
Among these sulfur-based extreme pressure agents, active polysulfide is preferable in terms of performance.

These sulfur type extreme pressure agents may be used individually by 1 type, and 2 or more types may be mixed and used for them. Moreover, it is preferable that the compounding quantity of a sulfur type extreme pressure agent is 1-20 mass% in conversion of sulfur on the basis of the composition whole quantity, and it is more preferable that it is 2-15 mass%. If the compounding amount of the sulfur-based extreme pressure agent is 1% by mass or more in terms of sulfur, the effect of further enhancing the extreme pressure property is recognized, and if it is 20% by mass or less, there is no fear of adverse effects such as corrosion.
Moreover, when a sulfur type extreme pressure agent is polysulfide, it is preferable that the compounding quantity of polysulfide is 3-40 mass%, and it is more preferable that it is 5-30 mass%.

On the other hand, examples of the phosphorus extreme pressure agent include phosphate esters and amine salts thereof, zinc dithiophosphate (ZnDTP), sulfurized oxydithiophosphate molybdenum dithiophosphate (MoDTP), and the like.
Examples of the phosphoric acid esters include phosphoric acid esters, acidic phosphoric acid esters, phosphorous acid esters, and acidic phosphorous acid esters. These are all alkyl groups or alkenyl groups having 4 to 30 carbon atoms, preferably 4 to 18 carbon atoms, aryl groups, alkylaryl groups, or arylalkyl groups having 6 to 30 carbon atoms, preferably 6 to 18 carbon atoms. Those having a group selected from are preferred. However, the alkyl group or alkenyl group having 4 to 30 carbon atoms may be linear, branched or cyclic.

  Examples of the phosphate ester include triaryl phosphate, trialkyl phosphate, trialkylaryl phosphate, triarylalkyl phosphate, trialkenyl phosphate, and the like. Specifically, for example, triphenyl phosphate, tricresyl phosphate, benzyl diphenyl phosphate, and the like. , Ethyl diphenyl phosphate, tributyl phosphate, ethyl dibutyl phosphate, cresyl diphenyl phosphate, dicresyl phenyl phosphate, ethyl phenyl diphenyl phosphate, diethyl phenyl phenyl phosphate, propyl phenyl diphenyl phosphate, dipropyl phenyl phenyl phosphate, triethyl phenyl phosphate, tripropyl phenyl Phosphate, butyl pheny Diphenyl phosphate, dibutylphenyl phenyl phosphate, tributylphenyl phosphate, trihexyl phosphate, tri (2-ethylhexyl) phosphate, tridecyl phosphate, trilauryl phosphate, trimyristyl phosphate, tripalmityl phosphate, tristearyl phosphate, 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 And isostearyl acid phosphate.
Examples of phosphites include triethyl phosphite, tributyl phosphite, triphenyl phosphite, tricresyl phosphite, tri (nonylphenyl) phosphite, tri (2-ethylhexyl) phosphite, tridecyl phosphite , Trilauryl phosphite, triisooctyl phosphite, diphenylisodecyl phosphite, tristearyl phosphite, trioleyl phosphite and the like.
Examples of the acidic phosphite include dibutyl hydrogen phosphite, dilauryl hydrogen phosphite, dioleyl hydrogen phosphite, distearyl hydrogen phosphite, and diphenyl hydrogen phosphite.
The phosphoric acid esters also include thiophosphoric acid esters in which part or all of the oxygen atoms of the phosphoric acid esters are substituted with sulfur atoms.

  Furthermore, as amines that form amine salts with these, for example, an alkyl or alkenyl group having 3 to 30 carbon atoms, preferably 4 to 18 carbon atoms, 6 to 30 carbon atoms, preferably 6 to 15 carbon atoms. Examples thereof include mono-substituted amines, di-substituted amines, and tri-substituted amines having an aryl group or arylalkyl group or a hydroxyalkyl group having 2 to 30 carbon atoms, preferably 2 to 18 carbon atoms. However, the alkyl group or alkenyl group having 3 to 30 carbon atoms may be linear, branched or cyclic.

  Examples of the mono-substituted amine include butylamine, pentylamine, hexylamine, cyclohexylamine, octylamine, laurylamine, stearylamine, oleylamine, and benzylamine. Disubstituted amines include dibutylamine, dipentylamine, dihexylamine, dicyclohexylamine, dioctylamine, dilaurylamine, distearylamine, dioleylamine, dibenzylamine, stearyl monoethanolamine, decyl monoethanolamine, hexyl Examples include monopropanolamine, benzyl monoethanolamine, phenyl monoethanolamine, and tolyl monopropanol. Examples of tri-substituted amines include tributylamine, tripentylamine, trihexylamine, tricyclohexylamine, trioctylamine, trilaurylamine, tristearylamine, trioleylamine, tribenzylamine, dioleyl monoethanolamine, dilauryl monopropanolamine. , Dioctyl monoethanolamine, dihexyl monopropanolamine, dibutyl monopropanolamine, oleyl diethanolamine, stearyl dipropanolamine, lauryl diethanolamine, octyl dipropanolamine, butyl diethanolamine, benzyl diethanolamine, phenyl diethanolamine , Tolyl dipropanolamine, xylyl diethanolamine, trieta Ruamin, tri propanolamine.

As zinc dithiophosphate (ZnDTP) and sulfurized oxydithiophosphate molybdenum dithiophosphate (MoDTP), an alkyl group having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, an aryl group having 6 to 20 carbon atoms, and 7 to 7 carbon atoms. Examples thereof include those having 20 alkylaryl groups or arylalkyl groups having 7 to 20 carbon atoms, and the alkyl group may be a primary alkyl group or a secondary alkyl group.
Among these phosphorus-based extreme pressure agents, phosphites or amine salts thereof, zinc dithiophosphate (ZnDTP) and the like are preferable from the viewpoint of performance.

  The said phosphorus type extreme pressure agent may be used individually by 1 type, and 2 or more types may be mixed and used for it. The compounding amount of the phosphorus extreme pressure agent is preferably 0.1 to 2.0% by mass and 0.15 to 1.5% by mass in terms of phosphorus based on the total amount of the composition. More preferred. If the compounding amount of the phosphorus extreme pressure agent is 0.1% by mass or more in terms of phosphorus, the effect of further enhancing the extreme pressure property is recognized, and if it is 2.0% by mass or less, there is no risk of adverse effects such as corrosion. .

The oily agent is preferably at least one selected from, for example, fats and oils, fatty acids, alcohols, and fatty acid esters.
Examples of the oils and fats include vegetable oils such as soybean oil, linseed oil, rapeseed oil, olive oil and palm oil, and animal oils such as beef tallow and lard.
Examples of fatty acids include oleic acid, linoleic acid, linolenic acid and the like obtained from the oils and fats, and have a linear or branched chain, saturated or unsaturated carbon atoms of 12 to 24, more preferably carbon The fatty acid of several 12-18 is mentioned.
In addition, dibasic acids are included in the fatty acids. Examples of the dibasic acids include saturated or unsaturated carbon atoms having 8 to 40 carbon atoms, and further 10 to 30 carbon atoms, which have a linear or branched chain. Of the dibasic acid.
Moreover, as alcohols, a C8-C18 monovalent | monohydric aliphatic saturated or unsaturated alcohol can be mentioned preferably, for example. This alcohol may be linear or branched.
Furthermore, examples of the fatty acid esters include esters of the above fatty acids or dibasic acids and alcohols.
Among these oily agents, oils and fats (especially vegetable oils) and saturated or unsaturated dibasic acids having 8 to 40 carbon atoms are preferable in terms of performance.

  These oily agents may be used alone or in combination of two or more. The blending amount of the oily agent is preferably 5 to 80% by mass, more preferably 15 to 70% by mass based on the total amount of the composition. If the blending amount of the oily agent is 5% by mass or more, an effect of further improving the wear resistance is recognized, and if it is 80% by mass or less, an effect commensurate with the blending amount is obtained.

In the lubricating oil composition for metal working of the present invention, various additives such as a dispersant, an antioxidant, a rust inhibitor, a corrosion inhibitor, and an antifoaming agent are optionally added within a range that does not impair the object of the present invention. Further, a viscosity index improver and the like can be appropriately contained.
Examples of the dispersant include polybutenyl succinic acid (mono, bis) imide, fatty acid amide, and boronated compounds thereof, and benzylamine.
Examples of the antioxidant include amines such as alkylated diphenylamine, phenyl-α-naphthylamine and alkylated α-naphthylamine, phenols such as 2,6-di-t-butyl-p-cresol, and 2,6 -Sulfur-based compounds such as di-t-butyl-4- [4,6-bis (octylthio) -1,3,5-triazin-2-ylamino] phenol and dilaurylthiodipropionate.
Examples of rust inhibitors and corrosion inhibitors include sorbitan esters, neutral alkali metal or alkaline earth metal sulfonate, alkali metal or alkaline earth metal phenate, alkali metal or alkaline earth metal salicylate, thiadiazole, benzotriazole, Examples of the antifoaming agent include dimethylpolysiloxane and fluoroether.
Examples of the viscosity index improver include polymethacrylate, dispersed polymethacrylate, olefin copolymer (for example, ethylene-propylene copolymer) and the like.
The blending amount of these additives may be appropriately selected according to the purpose, but is usually blended so as to be 30% by mass or less based on the total amount of the composition.

The method for producing the lubricating oil composition for metal working of the present invention can be usually produced by the following method.
First, the base oil is heated to about 60 to 100 ° C., and the α-olefin polymer is added little by little and stirred until uniform. Next, keeping the stirring mixture at a temperature at which fluidity can be secured (usually about 30 to 100 ° C.), the remaining extreme pressure agent and oil agent are added, and then desired additives such as antioxidants and antifoaming agents. Mix. After mixing all the substrates, the mixture is vigorously stirred at approximately 60 to 80 ° C. for 15 minutes to 1 hour to obtain the desired composition.

EXAMPLES Next, although an Example demonstrates this invention further in detail, this invention is not limited at all by these examples.
Various characteristics were determined according to the following methods.
(1) Weight average molecular weight, molecular weight distribution By GPC method, the polystyrene equivalent mass average molecular weight Mw and number average molecular weight Mn were measured, and molecular weight distribution (Mw / Mn) was calculated using them.
<GPC measuring device>
Column: TOSO GMHHR-H (S) HT
Detector: RI detector for liquid chromatogram WATERS 150C
<Measurement conditions>
Solvent: 1,2,4-trichlorobenzene Measurement temperature: 145 ° C
Flow rate: 1.0 ml / min Sample concentration: 2.2 mg / ml Injection volume: 160 microliter Calibration curve: Universal Calibration
Analysis program: HT-GPC (Ver, 1.0)

(2) Measurement of stereoregularity index value M2 (mol%)
<Measurement equipment and measurement conditions>
¹³ C-NMR measuring apparatus: EX-400 manufactured by JEOL Ltd.
Measurement temperature: 130 ° C
Pulse width: 45 °
Integration count: 1000 times Solvent: 90:10 (volume ratio) mixed solvent of 1,2,4-trichlorobenzene and heavy benzene
<Calculation of stereoregularity index value M2>
In the spectrum obtained by the above measurement, six large absorption peaks based on the mixed solvent are observed at 127 to 135 ppm. Among these peaks, the fourth peak value from the low magnetic field side is set to 131.1 ppm, which is used as a reference for chemical shift. At this time, an absorption peak based on CH ₂ carbon at the α-position of the side chain is observed in the vicinity of 34 to 37 ppm. From these, M2 (mol%) was calculated | required using Formula (a).
(3) Melting point (Tm)
Using a differential scanning calorimeter (DSC), the melting point (Tm) was measured by the method described in the specification.

[Production Example 1: Production of 1-octadecene polymer]
(I) Preparation of 2-chlorodimethylsilylindene Under a nitrogen stream, 50 mL of THF (tetrahydrofuran) and 2.5 g (41 mmol) of magnesium were added to a 1 liter three-necked flask, and 1,2-dibromoethane was added thereto. .1 ml was added and stirred for 30 minutes to activate the magnesium. After stirring, the solvent was extracted and 50 ml of THF was newly added.
A solution of 5.0 g (25.6 mmol) of 2-bromoindene in THF (200 ml) was added dropwise thereto over 2 hours. After completion of the dropwise addition, the mixture was stirred at room temperature for 2 hours, cooled to −78 ° C., and a solution of 3.1 mL (25.6 mmol) of dichlorodimethylsilane in THF (100 mL) was added dropwise over 1 hour and stirred for 15 hours. Then, the solvent was distilled off.
The residue was extracted with 200 ml of hexane, and then the solvent was distilled off to obtain 6.6 g (24.2 ml) of 2-chlorodimethylsilylindene (yield 94%).
(Ii) [Production of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene)]
Under a nitrogen stream, 400 ml of THF and 8 g of 2-chlorodimethylsilylindene obtained in the above (i) were added to a 1 liter three-necked flask and cooled to -78 ° C. To this solution, 38.5 ml (38.5 mmol) of a THF solution (1.0 mol / liter) of LiN (SiMe ₃ ) ₂ was added dropwise.
After stirring at room temperature for 15 hours, the solvent was distilled off and extracted with 300 ml of hexane. The solvent was distilled off to obtain 2.0 g (6.4 mmol) of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) -bis (indene) (yield 33.4%). ).

(Iii) Preparation of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium chloride.
Under a nitrogen stream, 50 ml of ether in a 200 ml Schlenk bottle and 3.5 g of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) bis (indene) obtained in (ii) above (10. 2 mmol) was added. A hexane solution (1.60 M, 12.8 ml) of n-butyllithium (n-BuLi) was added dropwise thereto at -78 ° C.
After contacting at room temperature for 8 hours, the solvent was distilled off, and the obtained solid was dried under reduced pressure to obtain 5.0 g of a white solid.
This solid was dissolved in 50 ml of THF, and 1.4 ml of iodomethyltrimethylsilane was added dropwise thereto at room temperature.
10 ml of water was added and the organic phase was extracted with 50 ml of ether. The organic phase was dried and the solvent was distilled off. 50 ml of ether was added thereto, and a hexane solution of n-BuLi (1.60 M, 12.4 ml) was added dropwise at -78 ° C. After raising to room temperature and stirring for 3 hours, ether was distilled off. The obtained solid was washed with 30 ml of hexane and then dried under reduced pressure.
5.11 g of this white solid was made turbid in 50 ml of toluene, and 2.0 g (8.6 mmol) of zirconium tetrachloride suspended in 10 ml of toluene in another Schlenk was added.
After stirring at room temperature for 12 hours, the solvent was distilled off and the residue was washed with 50 ml of hexane.
By recrystallizing the residue from 30 ml of dichloromethane, 1.2 g of yellow fine crystals of (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (indenyl) (3-trimethylsilylmethylindenyl) zirconium chloride (Yield 25%).
(Iv) Production of 1-octadecene polymer To a heat-dried 1 liter autoclave, 200 ml of heptane, 200 ml of 1-octadecene, 0.5 mmol of triisobutylaluminum and 1 mmol of methylaluminoxane were added, and 0.03 MPa of hydrogen was further introduced. .
The temperature was raised to 60 ° C. with stirring, and (1,2′-dimethylsilylene) (2,1′-dimethylsilylene) (3-trimethylsilylmethylindenyl) (indenyl) zirconium dichloride prepared in (iii) above was added. 1 micromole was added and polymerized for 30 minutes.
After completion of the polymerization reaction, the reaction product was heated and dried under reduced pressure to obtain 25 g of 1-octadecene polymer.
As described above, an α-olefin polymer 1 having 18 carbon atoms was obtained. The polymer 1 had a weight average molecular weight of 30000, a stereoregularity index value M2 of 68.2 mol%, a melting point of 42 ° C., and a molecular weight distribution (Mw / Mn) of 1.80.

[Production Example 2]
An α-olefin polymer 2 having 20 to 24 carbon atoms is obtained in the same manner as in Production Example 1, except that an α-olefin mixture having 20 to 24 carbon atoms is used instead of 1-octadecene as a polymerization raw material. It was. This polymer 2 had a weight average molecular weight of 98000, a stereoregularity index value M2 of 62.4 mol%, a melting point of 52 ° C., and a molecular weight distribution (Mw / Mn) of 4.1. .

[Comparative Example-1]
A cylindrical squeezing experiment was carried out under the following conditions using a commercially available chlorinated squeezed oil (“Daphne Master Draw 612L” manufactured by Idemitsu Kosan Co., Ltd.) having a kinematic viscosity at 40 ° C. of 37 mm ² / s.
<Experimental conditions for cylindrical diaphragm experiment>
Testing machine: T-Toshi deep drawing testing machine Plate material: US304 (φ70mm, thickness 0.8mm)
Punch: KD11 (φ32.0mm, shoulder R5mm)
Dice: KD11 (φ34.8mm, shoulder R5mm)
Wrinkle presser force: 0.4t
Drawing depth: 20 mm
Aperture speed: 10 mm / s
Number of processing: 20 Evaluation item: Punch load <Experimental result>
Although 20 plates were processed, the punch load was stable at 2.6 tf, and the test piece and tool were free from wear and scratches, and showed excellent workability.
[Comparative Example-2]
A cylindrical squeezing experiment was conducted under the same conditions as in Comparative Example 1 using a commercially available sulfur-based metalworking oil (non-chlorine, sulfur content 2.6 mass%) having a kinematic viscosity at 40 ° C. of 78 mm ² / s.
<Experimental result>
Twenty plates were processed, but the punch load gradually increased from 2.5 tf and finally reached 2.84 tf. In addition, vertical scratches occurred on the test piece immediately after the start, and innumerable large and small vertical scratches were finally observed. Insufficient processability and galling was observed on the die.
[Comparative Example-3]
40% by mass of naphthenic mineral oil having a kinematic viscosity at 40 ° C. of 101 mm ² / s, 20% by mass of active sulfur-based polysulfide (“Dairub S940” manufactured by Dainippon Ink), 28% by mass of rapeseed oil, phosphorus-based compound (Georail Hydrogen) Phosfite, “VANLUBE 672” manufactured by Vanderbilt, 10% by mass and 2% by mass of paraffin wax (“paraffin wax” manufactured by Nippon Seiki) were mixed to prepare an oil agent having a kinematic viscosity at 40 ° C. of 78 mm ² / s. A cylindrical squeezing experiment was performed on this adjusted oil under the same conditions as in Comparative Example 1.
<Experimental result>
Although the punch load was stable at 2.55 tf, fine vertical scratches were observed on the specimen immediately after the start. In addition, galling marks were observed on the dice although they were slight.

[Example-1]
40% by mass of naphthenic mineral oil having a kinematic viscosity at 40 ° C. of 101 mm ² / s, 20% by mass of active sulfur-based polysulfide (“Dairub S940” manufactured by Dainippon Ink), 28% by mass of rapeseed oil, phosphorus-based compound (Georail Hydrogen) Phosphite, “VANLUBE 672” manufactured by Vanderbilt, 10% by mass and 2% by mass of the polymer 1 obtained in Production Example 1 were mixed to prepare an oil having a kinematic viscosity at 40 ° C. of 74 mm ² / s. The prepared oil agent was subjected to a cylindrical drawing experiment under the same conditions as in Comparative Example 1.
<Experimental result>
The punch load was initially 2.52 tf, but gradually decreased to the fifth sheet and became constant at 2.48 tf. The test piece and tool were free from wear and scratches and showed excellent workability equivalent to that of chlorine.
[Comparative Example-4]
Using a commercially available chlorine-based oil agent (chlorine content: 27% by mass) having a kinematic viscosity at 40 ° C. of 56 mm ² / s, intermittent cutting was carried out as a pseudo evaluation method for broaching oil shown below. This evaluation method has a high correlation with die wear in punching such as fine blanking, and the performance of the oil can be predicted by comparing the change in feed force (increase due to tool wear) as the cutting resistance.
<Intermittent cutting test conditions>
Workpiece: S45C, φ81mm, 8 slits Tool: SKH51
Cutting speed v: 50 m / min (200 rpm)
Cutting depth t: 1 mm, feed f = 1 μm / rev
Cutting length L: Repeated 5 mm × 5 times Total number of passes: 5 mm × 5 times × 8 slits ÷ 0.001 mm = equivalent to 200,000 shots <Experimental result>
The initial cutting force (feed force) increased from 60N to 240N as the cutting distance increased. Moreover, the cutting surface showed remarkable roughness in the latter half after the equivalent of 100,000 shots.

Example-2
30% by mass of naphthenic mineral oil with a kinematic viscosity at 40 ° C. of 101 mm ² / s, 10% by mass of naphthenic mineral oil with a kinematic viscosity at 40 ° C. of 399 mm ² / s, active sulfur-based polysulfide (“Dairub S940” manufactured by Dainippon Ink and Materials) 15% by mass, rapeseed oil 38% by mass, palm oil 2% by mass, polymer 1 obtained in Production Example 1 2% by mass, zinc dithiophosphate (OLONITE, “OLOA 260”) 3% by mass Then, an oil agent having a kinematic viscosity at 40 ° C. of 96 mm ² / s was prepared. An intermittent cutting test was performed on this prepared oil in the same manner as in Comparative Example-4.
<Experimental result>
Although the feed force increases from 80N to 160N, the change in cutting resistance (feed force) is sufficiently small compared to the commercially available chlorinated oil of Comparative Example 4, and the cutting surface is glossy and rough. It was small.
[Comparative Example-5]
Using a commercially available chlorine oil (40 ° C. kinematic viscosity 16000 mm ² / s), a flat plate pull-out test was performed under the following conditions.
<Plate drawing test conditions>
Testing machine: Instron testing machine Area reduction rate: 20.4%
Sliding speed: 200 mm / s
Test temperature: 24 ° C
Pull-out distance: 150mm
Test piece (plate): SUS304 (10 mm × 300 mm × 4 mm)
Punch: WC (2.0R)
Evaluation item: Comparison of average drawing resistance <Experimental results>
There was no occurrence of galling or scratches, and stable drawing with a drawing resistance of 1400 kgf was possible.

[Comparative Example-6]
Polybutene having a kinematic viscosity at 100 ° C. of 4300 mm ² / s 45% by mass (2000H made by Idemitsu Kosan Co., Ltd.), 20% by mass of active sulfur polysulfide (Dairubu S940 made by Dainippon Ink), 24% by mass of rapeseed oil, 5% by mass of palm oil, C22 dibasic acid (8,13-dimethyl-8,12-eicosadienic acid, IPU-22 manufactured by Okamura Oil Co., Ltd.) 3% by mass, viscosity index improver (polymethacrylate, manufactured by Sanyo Chemical Industries, "Aclude 915") 3% by mass was mixed to prepare a drawing-only oil having a kinematic viscosity at 40 ° C. of 7400 mm ² / s. The prepared oil agent was subjected to a flat plate drawing experiment in the same manner as Comparative Example-5.
<Experimental result>
Although the initial pulling resistance was 1180 kgf, which was lower than that of the commercial chlorinated oil of Comparative Example-5, the pulling resistance increased with processing, eventually exceeded 2670 kgf, and fractured. Significant plate excavation type galling was seen on the drawing surface.
Example-3
45% by mass of polybutene having a kinematic viscosity at 100 ° C. of 4300 mm ² / s (“2000H” manufactured by Idemitsu Kosan Co., Ltd.), 20% by mass of active sulfur-based polysulfide (Dairubu S940 manufactured by Dainippon Ink), 22% by mass of rapeseed oil, 5% by mass of palm oil %, 2% by weight of the polymer 2 obtained in Production Example 2, 3% by weight of dibasic acid having 22 carbon atoms (8,13-dimethyl-8,12-eicosadienic acid, IPU-22 manufactured by Okamura Oil Co., Ltd.), viscosity 3% by mass of an index improver (polymethacrylate, manufactured by Sanyo Kasei Kogyo Co., Ltd., “Aclude 915”) was mixed to prepare a drawing-only oil agent having a kinematic viscosity at 40 ° C. of 7400 mm ² / s. The prepared oil agent was subjected to a flat plate drawing test in the same manner as in Comparative Example-5.
<Experimental result>
Compared with the commercially available chlorinated oil of Comparative Example-5, there was no occurrence of galling or scratches, and the drawing resistance was 1150 kgf.

Example-4
Polybutene having a kinematic viscosity at 100 ° C. of 4300 mm ² / s 42% by mass (2000H made by Idemitsu Kosan), 20% by mass of active sulfur polysulfide (Dairubu S940 made by Dainippon Ink), 22% by mass of rapeseed oil, 5% by mass of palm oil, 5% by mass of the polymer 2 obtained in Production Example 2), 3% by mass of dibasic acid having 22 carbon atoms (8,13-dimethyl-8,12-eicosadienic acid, IPU-22 manufactured by Okamura Oil Co., Ltd.), viscosity index 3% by mass of an improver (polymethacrylate, manufactured by Sanyo Kasei Kogyo Co., Ltd., “Accru 915”) was mixed to prepare a drawing-only oil agent having a kinematic viscosity at 40 ° C. of 13200 mm ² / s. The prepared oil agent was subjected to a flat plate drawing experiment in the same manner as Comparative Example-5.
<Experimental result>
Compared with the commercially available chlorinated oil of Comparative Example-5, there was no occurrence of galling or scratches, and the drawing resistance was 1210 kgf.
[Example-5]
40% by mass of polybutene having a kinematic viscosity of 100 ° C. of 4300 mm ² / s (2000H made by Idemitsu Kosan), 17% by mass of active sulfur-based polysulfide (Dairubu S940 made by Dainippon Ink), 22% by mass of rapeseed oil, 5% by mass of palm oil, 10% by mass of the polymer 2 obtained in Production Example 2, 3% by mass of a dibasic acid having 22 carbon atoms (IPU-22, manufactured by Okamura Oil Co., Ltd.), a viscosity index improver (polymethacrylate, manufactured by Sanyo Chemical Industries, Ltd. 915 ") 3% by mass was mixed to prepare an exclusive oil for drawing with a kinematic viscosity at 40 ° C of 26400 mm ² / s. The prepared oil agent was subjected to a flat plate drawing experiment in the same manner as Comparative Example-5.
<Experimental result>
Compared with the commercially available chlorinated oil of Comparative Example-5, there was no occurrence of galling or scratches, and the drawing resistance was 1290 kgf.
[Example-6]
40% by mass of polyolefin having a kinematic viscosity at 40 ° C. of 37500 mm ² / s (Lucanto HC-2000 manufactured by Mitsui Chemicals), 17% by mass of active sulfur-based polysulfide (Dailube S940 manufactured by Dainippon Ink), 22% by mass of rapeseed oil, 5% of palm oil 10% by mass of the polymer 2 obtained in Production Example 2, 3% by mass of dibasic acid having 22 carbon atoms (8,13-dimethyl-8,12-eicosadienic acid, IPU-22 manufactured by Okamura Oil Co., Ltd.), 3% by mass of a viscosity index improver (polymethacrylate, manufactured by Sanyo Kasei Kogyo Co., Ltd., “Aclude 915”) was mixed to prepare a drawing-only oil agent having a kinematic viscosity at 40 ° C. of 12100 mm ² / s. The prepared oil agent was subjected to a flat plate drawing test in the same manner as in Comparative Example-5.
<Experimental result>
Compared with the commercially available chlorinated oil of Comparative Example-5, there was no occurrence of galling or scratches, and the drawing resistance was 1140 kgf.

[Example-7]
40% by mass of polybutene having a kinematic viscosity of 100 ° C. of 4300 mm ² / s (2000H made by Idemitsu Kosan), 17% by mass of active sulfur-based polysulfide (Dairubu S940 made by Dainippon Ink), 22% by mass of rapeseed oil, 5% by mass of palm oil, 10% by mass of the polymer 2 obtained in Production Example 2, 3% by mass of a dibasic acid having 22 carbon atoms (8,13-dimethyl-8,12-eicosadienic acid, “IPU-22” manufactured by Okamura Oil Co., Ltd.), viscosity 3% by mass of an index improver (polymethacrylate, manufactured by Sanyo Kasei Kogyo Co., Ltd., “Aclude 915”) was mixed to prepare a drawing-only oil agent having a kinematic viscosity at 40 ° C. of 26400 mm ² / s. The plate material was changed to aluminum material A3003 under the same conditions as in Comparative Example-5 for this prepared oil agent, and a flat plate drawing experiment was performed.
<Experimental result>
Compared with the commercially available chlorinated oil of Comparative Example-5, there was no occurrence of galling or scratches, and the drawing resistance was 570 kgf, so that it was possible to process almost a mirror surface.
[Example-8]
25% by mass of polybutene having a kinematic viscosity at 100 ° C. of 4300 mm ² / s (“2000H” manufactured by Idemitsu Kosan), 20% by mass of active sulfur-based polysulfide (“Dairub S940” manufactured by Dainippon Ink), 37% by mass of olive oil, 10% of palm oil 2% by mass of the polymer 2 obtained in Production Example 2 and 3% by mass of dibasic acid having 22 carbon atoms (8,13-dimethyl-8,12-eicosadienic acid, “IPU-22” manufactured by Okamura Oil Co., Ltd.) %, 3% by mass of a viscosity index improver (polymethacrylate, manufactured by Sanyo Chemical Industries, Ltd., “Accru 915”) was mixed to prepare a drawing-only oil agent having a kinematic viscosity at 40 ° C. of 840 mm ² / s. The prepared oil was changed to Inconel 600 under the same conditions as in Comparative Example-5, and a flat plate drawing test was performed.
<Experimental result>
There was no occurrence of galling or scratches, and the drawing resistance was 960 kgf (comparative example-5 commercial chlorine oil: 1180 kgf).

[Example-9]
Polybutene having a kinematic viscosity at 100 ° C. of 4300 mm ² / s 57% by mass (2000H made by Idemitsu Kosan Co., Ltd.), 8% by mass of a phosphorus extreme pressure agent (“VANLUBE 627” made by Vanderbilt), 25% by mass of rapeseed oil, 5% by mass of palm oil 2% by mass of the polymer 2 obtained in Production Example 2 and 3% by mass of a viscosity index improver (polymethacrylate, manufactured by Sanyo Chemical Industries, Ltd., “Aclude 915”) were mixed, and the kinematic viscosity at 40 ° C. was 9600 mm ^2. The oil for exclusive use of drawing / s was adjusted. The prepared oil agent was subjected to a flat plate drawing experiment in the same manner as Comparative Example-5.
<Experimental result>
Compared with the commercially available chlorinated oil of Comparative Example-5, there was no occurrence of galling or scratches, and the drawing resistance was 1230 kgf.
[Comparative Example-7]
Using the commercially available sulfur-based metalworking oil used in Comparative Example-2, cold forging experiments were performed under the following conditions.
<Cold forging experiment conditions>
Testing machine: SAKAMUURA NP-450H
Number of steps: 4-step punching Processing speed: 150 pieces / minute Test piece: S-45C for manufacturing hexagon flange nuts (φ19 mm × 9.5 × 10 mm)
Punch and die material: SKH, SKD
<Experimental result>
Tool wear was remarkably observed with 30,000 commercially available sulfur-based metalworking oils of Comparative Example-2, and the mold had to be replaced.
[Example-10]
Using the oil used in Example-2, a cold forging test was performed under the same conditions as in Comparative Example-6.
<Experimental result>
Tool wear was remarkably observed with 30,000 commercially available sulfur-based metal working oils of Comparative Example-2, and the mold had to be replaced. On the other hand, with this oil, 105,000 pieces could be processed.

  The lubricating oil composition for metal working of the present invention is excellent in extreme pressure and wear resistance, even in a non-chlorine metal working oil, excellent in workability for various iron, and non-ferrous metals or their alloys, It is possible to provide a metal working lubricating oil composition having workability that is not inferior to that when a chlorine-based extreme pressure agent is used in processing difficult-to-process materials such as iron and stainless steel.

Claims (8)

A lubricating oil composition for metal working, comprising a base oil containing a polymer of an α-olefin having 10 to 24 carbon atoms that satisfies the following conditions (1) and (2).
(1) The weight average molecular weight is 1,000 to 1,000,000,
(2) The stereoregularity index M2 represented by the following formula (a) is 50 mol% or more,
M2 (mol%) = (X / Y) × 100 (a)
[Wherein, X is an integrated value of absorption peak intensity between 36.2 to 35.3 ppm in ¹³ C-NMR spectrum, and Y is an integrated value of absorption peak intensity between 36.2 to 34.5 ppm. Show. ]   The lubricating oil composition for metal working according to claim 1, wherein the melting point of the α-olefin polymer measured by a differential scanning calorimeter is 20 to 100 ° C.   3. The lubricating oil composition for metal working according to claim 1, wherein the α-olefin polymer has a molecular weight distribution (weight average molecular weight / number average molecular weight) of 5.0 or less. The α-olefin polymer reacts with (A) the transition metal compound represented by the following general formula (I), and (B) (B-1) the transition metal compound of component (A) or a derivative thereof. A polymer obtained by using a polymerization catalyst containing at least one component selected from a compound capable of forming an ionic complex and (B-2) aluminoxane. Lubricating oil composition for metal working.

[Wherein M represents a metal element of Groups 3 to 10 of the periodic table or a lanthanoid series, and E ¹ and E ² represent a substituted cyclopentadienyl group, an indenyl group, a substituted indenyl group, and a heterocyclopentadienyl group, respectively. , A substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group and a silicon-containing group, which form a cross-linked structure via A ¹ and A ² In addition, they may be the same as or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , It may be cross-linked with E ² or Y. Y represents a Lewis base, and when there are a plurality of Y, the plurality of Y may be the same or different, and may be cross-linked with other Y, E ¹ , E ² or X, and A ¹ and A ² are A divalent bridging group that binds two ligands, a hydrocarbon group having 1 to 20 carbon atoms, a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, a silicon-containing group, a germanium-containing group, a tin-containing group , -O -, - CO -, - S -, - SO 2 -, - Se -, - NR 1 -, - PR 1 -, - P (O) R 1 -, - BR 1 - or -AlR ¹ - R ¹ represents a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms or a halogen-containing hydrocarbon group having 1 to 20 carbon atoms, which may be the same as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]   The lubricating oil composition for metal working according to any one of claims 1 to 4, wherein the content of the α-olefin polymer is 0.5 to 30% by mass based on the total amount of the composition.   Furthermore, the lubricating oil composition for metalworking in any one of Claims 1-5 containing an extreme pressure agent and / or an oiliness agent.   The extreme pressure agent is one or more compounds selected from sulfur extreme pressure agents and phosphorus extreme pressure agents, and the oily agent is one or more compounds selected from fats and oils, fatty acids, alcohols, and fatty acid esters. The lubricating oil composition for metal working according to claim 6.   The lubricating oil composition for metal working according to any one of claims 1 to 7, which is used for processing difficult-to-process materials.