CN106661483A

CN106661483A - Lubricant composition and manufacturing method of lubricant composition

Info

Publication number: CN106661483A
Application number: CN201580038573.6A
Authority: CN
Inventors: 儿玉邦彦
Original assignee: Fujifilm Corp
Current assignee: Fujifilm Corp
Priority date: 2014-08-01
Filing date: 2015-07-24
Publication date: 2017-05-10
Also published as: EP3176245A1; JP6348182B2; US20170130160A1; JPWO2016017548A1; WO2016017548A1; EP3176245B1; EP3176245A4

Abstract

The purpose of the present invention is to provide a lubricant composition which reduces both friction and wear at various temperatures and loads, and to provide a production method of the lubricant composition. This lubricant composition contains a composite ester A which includes polyesters formed by condensation of at least: a polyol a1 having a valance of 3 or higher; a mixture b1 which contains at least 75 mass% divalent carboxylic acid of 36-44 carbon atoms and which is a polymer reactant mixture of non-saturated fatty acids of 18-22 carbon atoms, and/or a mixture obtained by hydrogenating the polymer reactant mixture; and a mono-al c1 represented by general expression (1). The ratio of the molar number of hydroxyl groups in a1 / the molar number of carboxylic acid in b1 / the molar number of hydroxyl groups in c1 is 1/1.5-2.0/0.7-1.5, and the content of the complex esters A in the lubricant composition is 0.1-5 wt% with respect to the total mass. General formula (1): R-OH

Description

The manufacture method of lubricant compositions and lubricant compositions

Technical field

The present invention relates to a kind of lubricant compositions.More particularly it relates to a kind of contain specific complex ester Lubricant compositions, which has both low frictional properties and low abrasion.

Background technology

In recent years, from from the viewpoint of reducing energy loss, low friction is required in lubricant (lubricant compositions). Especially in the car, from from the viewpoint of reducing discharge carbon dioxide, it is strongly required to save oiling, that realizes in engine oil low rubs Wipingization is extremely important.It is as Frotteurism, commonly known to have Liquid Lubrication Condition, the friction that there is fluid oil between rubbing surface Boundary lubrication condition and the mixed lubricating state of the centre of these states that face contacts with each other and easily weares and teares.

By taking internal combustion engine lubricant compositions as an example, during engine start, easily cause rupture of oil film, therefore easily become Boundary lubrication condition.As from starting to till oil temperature rises, the viscosity of lubricant compositions is high, therefore viscous drag is big and damage Energy consumption.Also, in idling, produced with the friction under low speed simultaneously as oil temperature rises, therefore easily become boundary lubrication State.In addition to internal combustion engine purposes, also require that lubricant compositions are presented good friction under various temperature, load area Characteristic.

Lubricant compositions typically contain base oil and various additives.Based on oil, have from crude oil the mineral for obtaining Oil, the Esters oil of chemosynthesis, fluorocarbon oil and polyalphaolefin class oil etc..In these oils, due to Esters oil have low flow point, High viscosity index (HVI), high-flash, good lubrication property and biological degradability etc., therefore it is suitable for jet plane, automobile Engine oil and grease etc..

Known Esters oil is used as base oil or additive.Following various esters (patent documentation 1～9) are disclosed for example：It is logical Cross the monoesters of aliphatic monocarboxylic acid and the reaction acquisition of monohydric alcohol；By aliphatic dibasic acid and the two of the reaction acquisition of monohydric alcohol Ester；The polyol ester obtained by the reaction of polyhydric alcohol and aliphatic carboxylic acid；And pass through polyhydric alcohol, polyprotic acid, aliphatic list Complex ester that the reaction of carboxylic acid is obtained etc..

Conventional art document

Patent documentation

Patent documentation 1：Japanese Unexamined Patent Publication 2002-097482 publications

Patent documentation 2：Japanese Unexamined Patent Publication 2005-154726 publications

Patent documentation 3：Japanese Unexamined Patent Publication 2005-232434 publications

Patent documentation 4：Japanese Unexamined Patent Publication 2005-213377 publications

Patent documentation 5：Japanese Unexamined Patent Publication 2005-232470 publications

Patent documentation 6：Japanese Unexamined Patent Application Publication 2001-501989 publication

Patent documentation 7：Japanese Unexamined Patent Application Publication 2001-500549 publication

Patent documentation 8：Japanese Unexamined Patent Application Publication 2001-507334 publication

Patent documentation 9：Japanese Unexamined Patent Application Publication 2002-530476 publication

The summary of invention

Invention technical task to be solved

It is required that lubricant compositions are presented good frictional behavior under various temperature, load area.It is good in order to realize Frictional behavior (low friction), effective method be by reduce lubricant compositions viscous drag, i.e. lowering viscousity reality Low friction under existing Liquid Lubrication Condition, but then, if the lowering viscousity of propulsion lubricant compositions, because of border Abrasion under lubricating status and the deterioration of device that produces just becomes problem.

In order to realize low friction and low abrasion, the ratio addition that investigated in lubricant compositions to specify is each Plant ester composition.But, even if in the lubricant compositions using ester composition as above, also cannot be fully simultaneous Standby low friction and low abrasion, it is difficult to have both these performances under various temperature, load.Therefore, further requirement presents good Good lubrication property, low viscosity and the low frictional properties under Liquid Lubrication Condition and in such as high temperature and high load capacity boundary lubrication The lubricant compositions of the low abrasion under state.

The invention solves the problems that problem be to provide a kind of low frictional properties and low abrasion of having both under various temperature, load Lubricant compositions.

For solving the means of technical task

The present inventor has carried out discovery after various researchs to solve above-mentioned problem, complex ester A containing specified quantitative Lubricant compositions are under the harsh conditions of high temperature and/or high pressure etc, it is also possible to low abrasion and low frictional properties are presented, should Complex ester A contains and add alcohol with carboxylic acid with specific ratio and make the polyester of its condensation.

That is, above-mentioned problem is solved by the present invention of following structure.

[1] a kind of lubricant compositions, which contains complex ester A, complex ester A contain at least by following material condensation form Polyester：More than 3 yuan of polyhydric alcohol a1；The carbon number of 2 yuan of carboxylic acids of the carbon number 36～44 containing at least 75 mass % The polymerization reaction mixture of 18～22 unsaturated fatty acid and by polymerization reaction mixture hydrogenate obtained by mixture At least either mixture b1；And the carboxylic acid mol numbers of the hydroxyl mol numbers/b1 of the monohydric alcohol c1 represented with following formulas (1), a1/ The addition of the hydroxyl mol numbers of c1 is compared for 1/1.5～2.0/0.7～1.5, and the content of complex ester A is relative to lubricant compositions Gross mass is 0.1～5 mass %,

Formula (1)：R-OH

In formula (1), R represents the branched alkyl of the straight chained alkyl of carbon number more than 8 or carbon number more than 8.

[2] lubricant compositions according to [1], wherein, in formula (1), straight chains of the R for carbon number 8～25 The branched alkyl of alkyl or carbon number 8～25.

[3] lubricant compositions according to [1] or [2], wherein,

In formula (1), branched alkyls of the R for the straight chained alkyl or carbon number 16～20 of carbon number 16～20.

[4] lubricant compositions according to any one in [1] to [3], wherein,

In formula (1), R is branched alkyl.

[5] lubricant compositions according to any one in [1] to [4], wherein,

The content of complex ester A is 0.5～2 mass % relative to the gross mass of lubricant compositions.

[6] lubricant compositions according to any one in [1] to [5], wherein,

Hydroxyl mol numbers and c1 by a1 hydroxyl mol numbers amount to hydroxyl mol numbers be set to P, by the carboxylic acid mol of b1 In the case that number is set to Q, the addition of P/Q is compared for 1/0.7～0.95.

[7] lubricant compositions according to any one in [1] to [6], wherein,

The kinematic viscosity at 40 DEG C of complex ester A is 500～2000mm²/s。

[8] lubricant compositions according to any one in [1] to [7], wherein,

Kinematic viscosity at 40 DEG C is 5～100mm²/s。

[9] lubricant compositions according to any one in [1] to [8],

Which also contains medium,

Relative to the gross mass of lubricant compositions, complex ester A containing 0.1～5 mass % and 70～99.9 mass % Medium, relative to the gross mass of lubricant compositions, containing 0～29.9 mass % in addition to complex ester A and medium Other compositions.

[10] lubricant compositions according to [9], wherein,

At least one of the medium in mineral oil, polyolefin oil, ester oil and ether oil.

[11] lubricant compositions according to [9] or [10], wherein,

Other compositions are the compound with least one in zinc, molybdenum, sulfur and phosphorus as constitution element.

[12] lubricant compositions according to any one in [9] to [11], wherein,

Other compositions are organic molybdenum and at least one in organic zinc compound.

[13] lubricant compositions according to any one in [1] to [12], which is used as grease lubricating oil, the demoulding Agent, internal combustion engine oil, intermetallic composite coating (cutting is used) oil, bearing oil, combustion engine fuel, vehicle startup machine oil, gear oil, vapour Automobile-used working oil, ship and airborne vehicle lubricating oil, machinery oil, turbine oil, hydraulic oil, compressor oil, pumping fluid, system Cold oil, Metalworking lubricant, lubricant for magnetic recording medium, micromachine with lubricator, artificial bone with lubricator or ROLLING OIL.

[14] a kind of manufacture method of lubricant compositions, which includes following operation：Obtain the operation of complex ester A；And The concentration for obtaining complex ester A is the operation of the lubricant compositions of 0.1～5 mass %, and the operation for obtaining complex ester A is at least will Following material becomes 1/1.5～2.0/0.7～1.5 with the hydroxyl mol numbers of the carboxylic acid mol numbers/c1 of the hydroxyl mol numbers/b1 of a1 Mode mixes and makes the operation which is condensed：More than 3 yuan of polyhydric alcohol a1；Carbon number 36～44 containing at least 75 mass % The polymerization reaction mixture of the unsaturated fatty acid of the carbon number 18～22 of 2 yuan of carboxylic acids and polymerization reaction mixture is hydrogenated Obtained by least either mixture b1 in mixture；And the monohydric alcohol c1 represented with following formulas (1),

Formula (1)：R-OH

Invention effect

The lubricant compositions of the present invention can play low frictional properties and low abrasion under various temperature, load.This Low frictional properties of the lubricant compositions of invention in low viscosity and under Liquid Lubrication Condition are excellent, such as high temperature, high load capacity Under boundary lubrication condition, it is also possible to play low abrasion.

Specific embodiment

Hereinafter, the present invention is described in detail.Although the constitutive requirements below recorded are sometimes according to representational enforcement Mode and concrete example are illustrated, but the present invention is not limited to this embodiment.In addition, in this manual, use "～" The numerical range of expression refers to the scope that the numerical value being recorded in before and after "～" is included as lower limit and higher limit.

(lubricant compositions)

The lubricant compositions of the present invention are related to a kind of lubricant compositions containing complex ester A, complex ester A contain to Few polyester being condensed by following material：More than 3 yuan of polyhydric alcohol a1；Carbon number 36～44 containing at least 75 mass % 2 yuan of carboxylic acids carbon number 18～22 unsaturated fatty acid polymerization reaction mixture and by polymerization reaction mixture hydrogen At least either mixture b1 in mixture obtained by change；And the monohydric alcohol c1 represented with following formulas (1).Here, a1 The addition of the hydroxyl mol numbers of the carboxylic acid mol numbers/c1 of hydroxyl mol numbers/b1 is compared for 1/1.5～2.0/0.7～1.5, complex ester A Content is 0.1～5 mass % relative to the gross mass of lubricant compositions.

R-OH formulas (1)

Complex ester A used in the lubricant compositions of the present invention can be obtained by the following method：By a1 compositions ～c1 compositions become 1/1.5～2.0/0.7～1.5, excellent with the hydroxyl mol numbers of the carboxylic acid mol numbers/c1 of the hydroxyl mol numbers/b1 of a1 1/1.55～1.9/0.8～1.4, the mode of further preferred 1/1.60～1.8/0.8～1.3 are selected to add and which is condensed instead Should.

And, P is set in the total hydroxyl mol numbers of the hydroxyl mol numbers of hydroxyl mol numbers and c1 by a1, by the carboxylic of b1 In the case that sour mol numbers are set to Q, the addition ratio preferably 1/0.7～1.0 of P/Q, more preferably 1/0.75～0.95, further Preferably 1/0.8～0.9.That is, preferably add in the way of the addition of total hydroxyl mol numbers/total carboxylic acid's mol numbers is than becoming above range Enter each composition to obtain complex ester A.

Thus, by adding each composition with specific ratio and being condensed which, the crosslinking of obtained complex ester A can be made Degree, viscosity, acid number, monohydric alcohol surpluses etc. become optimum.Therefore, only add minimal amount of complex ester A in base oil, just Abrasion can be suppressed, therefore lubricant compositions can maintain the viscosity characteristicses of base oil, and play wear resistance.Also, In the present invention, under any state in Liquid Lubrication Condition, boundary lubrication condition, good friction can be obtained special Property.

The content of complex ester A relative to lubricant compositions gross mass be 0.1～5 mass %, preferably 0.3～ 3 mass %, more preferably 0.5～2 mass %.Thus, only adding a small amount of complex ester A to lubricant compositions, just it is in Now good lubrication property.

(more than 3 yuan of polyhydric alcohol a1)

More than 3 yuan of polyhydric alcohol a1 (being also referred to sometimes a1 compositions, or referred to as a1) is to contain more than 3 in intramolecular The compound of alcohol hydroxyl group and/or phenolic hydroxyl group, the compound preferably containing more than 3 alcohol hydroxyl groups, more preferably with 3 The compound of～6 alcohol hydroxyl groups.

Preferred more than 3 yuan of polyhydric alcohol a1 is the alcohol represented with following formulas (a1-1).

[chemical formula 1]

In formula (a1-1), Z represents m1 units concatenating group, and m1 represents more than 3 integer, preferably 3～6, more preferably 3 Or 4.

Z is preferably aliphatic concatenating group, the alkylidene concatenating group that more preferably can be linked with oxygen atom.Alkylidene links The carbon number of base is preferably 2～20, more preferably 2～15, more preferably 3～10, especially preferably 5～7.Also, From the viewpoint of reducing from friction at high temperature, Z is more preferably with the neopentyl represented with following structural formula (Z-1) The concatenating group of part-structure.

[chemical formula 2]

In structure above (Z-1), * to be represented and be bonded position with hydroxyl or other substituent groups.

As more than 3 yuan of polyhydric alcohol a1, trimethylolethane, trimethylolpropane, glycerol etc. are more preferably enumerated more than 3 yuan More than 5 yuan of 4 yuan of polyhydric alcohol, dipentaerythritols such as first alcohol, tetramethylolmethane, two-trimethylolethane, two-trimethylolpropane etc. Polyhydric alcohol, particularly preferred trimethylolethane, trimethylolpropane.

(the unsaturated lipid of the carbon number 18～22 of 2 yuan of carboxylic acids of the carbon number 36～44 containing at least 75 mass % The polymerization reaction mixture of fat acid and by polymerization reaction mixture hydrogenate obtained by least either mixture b1 in mixture)

The unsaturated fatty acidss of the carbon number 18～22 of 2 yuan of carboxylic acids of the carbon number 36～44 containing at least 75 mass % The polymerization reaction mixture of acid and by polymerization reaction mixture hydrogenate obtained by least either mixture b1 in mixture (have When be also referred to b1 compositions, or referred to as b1) carbon number 36～44 containing at least 75 mass % 2 yuan of carboxylic acids.B1 compositions 2 yuan of carboxylic acids of the carbon number 36～44 of more than at least 80 mass % are preferably comprised, more than further preferably 85 mass %, enters one Step preferably comprises more than 90 mass %, particularly preferably containing more than 94 mass %.That is, b1 compositions are with the 2 of carbon number 36～44 First carboxylic acid is main constituent.The polymerization reaction mixture of the unsaturated fatty acid of the carbon number 18～22 that can be obtained with industrialness In except containing in addition to 2 yuan of carboxylic acids, sometimes with monocarboxylic acid, tricarboxylic acids, but the b1 compositions for using in the present invention relative to The gross mass of polymerization reaction mixture, containing 2 yuan of more than above range carboxylic acids.

As the unsaturated fatty acid of the carbon number 18～22 of the raw material for becoming b1, petroselic acid, Oleic acid, anti-can be enumerated The insatiable hunger of the carbon numbers 18 such as Oleic acid, vaccenic acid, linoleic acid, linolenic acid, alpha-eleostearic acid, β-eleostearic acid, punicic acid, parinaric acid Unsaturated fatty acid, whale oil acid with the carbon number 20 such as fatty acid (preferred Oleic acid, linoleic acid), gadoleic acid, arachidonic acid, The unsaturated fatty acid (preferred erucic acid) of the carbon numbers such as erucic acid 22.By by the one kind or two or more of these unsaturated fatty acids It is polymerized, is obtained in that polymerization reaction mixture.Polymerization reaction mixture is preferably become with 2 yuan of carboxylic acids by methods such as distillations Modes more than 75 mass % is purified.

Especially b1 compositions preferably comprise the dimer of the unsaturated fatty acid of the carbon number 18 of more than 75 mass %, so-called Dimeric dibasic acid or carbon number 22 unsaturated fatty acid dimer, particularly preferably containing dimerization more than 75 mass % Acid.

Here, dimeric dibasic acid refers to that (generally, carbon number is 18) anti-by polymerization or Diels-Alder to unsaturated fatty acid The aliphatic or alicyclic dicarboxylic acid produced in dimerization should be waited.Dimeric dibasic acid contains a large amount of constitutional isomers.As dimeric dibasic acid In contained compound structure, can for example illustrate following structure.

[chemical formula 3]

As the concrete example of dimeric dibasic acid, the TSUNODYME (registered trade mark) of Tsuno Co., Ltd.s manufacture can be enumerated 205th, 216,228,395, Cognis companies, Uniqema companies, the product of Croda companies manufacture can also be used in addition.

Mixture b1 can also be comprising mixture obtained by polymerization reaction mixture is hydrogenated.That is, it is mixed as polyreaction Compound, it is also possible to using the mixture that carbon-to-carbon double bond is reduced by methods such as hydrogenations.Mixed by using this polyreaction Thing, improves the oxidative resistance of obtained lubricant compositions.As the dimeric dibasic acid being hydrogenated, Croda company systems can be enumerated The PRIPOL1006 that makes, 1009 etc..Mixture b1 can be hydrogenation obtained by polymerization reaction mixture, or will hydrogenation and The mixture that the polymerization reaction mixture for obtaining is mixed with unhydrided polymerization reaction mixture.

As the concrete example of the polymerization reaction mixture of the unsaturated fatty acid of carbon number 22, the two of erucic acid can be enumerated Polymers.As the concrete example of the dimer of the unsaturated fatty acid of carbon number 22, the manufacture of Croda companies can be enumerated PRIPOL1004。

(monohydric alcohol c1)

Monohydric alcohol c1 (being also referred to sometimes c1 compositions, or referred to as c1) is represented with following formulas (1).

R-OH formulas (1)

In formula (1), R represents the branched alkyl of the straight chained alkyl of carbon number more than 8 or carbon number more than 8.Use R The carbon number of the straight chained alkyl or branched alkyl of expression is respectively more than 8, preferably more than 10, more preferably more than 14.And And, the straight chained alkyl represented with R or the carbon number of branched alkyl are respectively preferably 8～25, more preferably 14～25, further Preferably 16～20.In addition, the straight chained alkyl represented with R or branched alkyl are preferably unsubstituted straight chained alkyl or unsubstituted Branched alkyl.

As the alkyl represented with R, preferred branched alkyl.R is more preferably the branched alkyl of carbon number 8～25, enters one Step is preferably the branched alkyl of carbon number 16～20.By the alkyl represented with R is set to branched structure, can be by complex ester The temperature dependency of viscosity suppress less, and excellent lubrication property can be played in various temperature provinces.

As the concrete example of monohydric alcohol c1, capryl alcohol, decanol, tridecyl alcohol, hexadecanol, octadecanol, 2- can be enumerated Ethyl hexanol, 2- hexyls -1-decanol, the branched alkyl monohydric alcohol of carbon number 14, the branched alkyl monohydric alcohol of carbon number 16, The branched alkyl monohydric alcohol of carbon number 18, branched alkyl monohydric alcohol of carbon number 20 etc..As with preferred side chain The concrete example of alkyl, can enumerate the branched alkyl monohydric alcohol (example of 2-Ethylhexyl Alcohol, 2- hexyls -1-decanol, carbon number 14 Such as, NISSAN CHEMICAL INDUSTRIES.LTD. manufacture, FINE OXOCOL 140N) carbon number 16 branched alkyl Monohydric alcohol (for example, NISSAN CHEMICAL INDUSTRIES.LTD. manufacture, FINE OXOCOL 1600), carbon number 18 Branched alkyl monohydric alcohol (for example, NISSAN CHEMICAL INDUSTRIES.LTD. manufactures, FINE OXOCOL 180 are Row), the branched alkyl monohydric alcohol of carbon number 20 (for example, NISSAN CHEMICAL INDUSTRIES.LTD. manufactures, FINE OXOCOL 2000).Wherein, preferably use 2- hexyls -1-decanol, carbon number 16 branched alkyl monohydric alcohol (for example, NISSAN CHEMICAL INDUSTRIES.LTD. manufacture, FINE OXOCOL 1600), the branched alkyl one of carbon number 18 First alcohol (for example, NISSAN CHEMICAL INDUSTRIES.LTD. manufactures, FINE OXOCOL 180 are serial), carbon number 20 Branched alkyl monohydric alcohol (for example, NISSAN CHEMICAL INDUSTRIES.LTD. manufacture, FINE OXOCOL are 2000).

(other compositions)

In complex ester A, it is also possible to which the composition in addition to a1～c1 is used as further condensation raw material.As entering one The condensation raw material of step, can illustrate 2 yuan of alcohol (2 yuan of alcohol of aliphatic of preferred carbon number 2～40), 1 yuan of carboxylic acid (preferred carbon atom The aliphatic carboxylic acid of number more than 4, the more preferably aliphatic carboxylic acid of carbon number more than 8), (preferred carbon is former for 2 yuan of carboxylic acids beyond b1 The aliphatic dicarboxylic acid of subnumber 4～10).

(complex ester A)

At least mix more than 3 yuan as above of polyhydric alcohol a1, the carbon number 36～44 containing at least 75 mass % 2 yuan of carboxylic acids carbon number 18～22 unsaturated fatty acid polymerization reaction mixture and by polymerization reaction mixture hydrogen At least either mixture b1 in mixture obtained by change and (R is former for the straight chained alkyl or carbon of carbon number more than 8 with R-OH The branched alkyl of subnumber more than 8) the monohydric alcohol c1 that represents, and it is condensed the mixture, it is derived from complex ester A.Complex ester A is extremely Polyester less containing the condensation of above-mentioned a1 compositions, b1 compositions and c1 compositions.

Complex ester A is the mixture of the polyester being at least brokenly condensed containing a1～c1, is for example contained in complex ester A Have only with 1 from the light component of the structure of b1 compositions or with more than 2 oligomer from the structure of b1 compositions Or component of polymer.As light component, 1 in 2 carboxylic acids of the 2 yuan of carboxylic acids that can specifically enumerate main constituent as b1 Or 2 monoesters for reacting and obtaining with the monohydric alcohol of c1 compositions or diester.In complex ester A, contained polyester is derived from due to having The structure of a1 compositions, therefore, it is possible to form cross-linked structure such that it is able to improve lubrication property.And, complex ester A preferably comprises tool There are more than 2 polyester from the structure of a1 compositions.By the structure for deriving from a1 compositions with multiple crosslinking components, energy Three-dimensional crosslinking structure is enough formed, lubrication property is further improved.In terms of the area ratio of GPC, the oligomer in addition to light component Or the content of component of polymer is preferably more than 50%, more preferably 60～85%, more preferably 65～80%.

It is with the weight average molecular weight of the polystyrene standard conversion using gel permeation chromatography (GPC), above-mentioned multiple The molecular weight for closing ester A is preferably 1000～100000, more preferably 2000～20000, further preferred 3000～10000.In addition, The molecular weight of complex ester A is the polyester that a1～c1 is brokenly condensed or above-mentioned light component, oligomer or component of polymer Each molecular weight it is average.By molecular weight is set as proper range, it is possible to obtain low viscosity and good lubrication property.In this theory In bright book, with the weight average molecular weight of polystyrene conversion specifically using the value for determining under the following conditions.

" HLC-8220GPC (Tosoh Corporation manufactures) device ".Use " TSKgel, SuperHZM-H (Tosoh Corporation is manufactured, 4.6mmID × 15cm) ", " TSKgel, SuperHZ4000 (Tosoh Corporation are manufactured, 4.6mmID × 15cm) ", " TSKgel, SuperHZ2000 (Tosoh Corporation manufacture, 4.6mmID × 15cm) " this 3 Root tubing string.

As the condition of GPC, for example, can adopt following conditions.

Eluant THF (tetrahydrofuran)

Flow velocity 0.35ml/min

40 DEG C of temperature of the measurement (tubing string, injection port, RI)

20 minutes analysis times

Test portion concentration 0.1%

10 μ l of sample injection rate

Unreacted c1 compositions can also be contained in complex ester A.Unreacted c1 compositions are relative to complex ester A total amount Content is preferably less than 10%, more preferably less than 6%, especially preferably less than 4%.In aforesaid GPC is determined, energy The content of the area c1 compositions more unreacted than calculating of enough molecular weight peaks using equivalent to c1.

Kinematic viscosity of complex ester A at 40 DEG C is preferably 400～2000mm²/ s, more preferably 500～2000mm²/ s, More preferably 500～1500mm²/ s, is still more preferably 600～1200mm²/ s, especially preferably 700～ 1100mm²/s.Kinematic viscosity at 40 DEG C specifically adopts what is determined in 40.0 DEG C of thermostatic water bath using Ubbelohde viscometer Value.By the viscosity of complex ester A is set to specific region, can press down in the state of the low viscosity for maintaining lubricant compositions System abrasion.

Acid number (the mg numbers of the KOH needed for the neutralization 1g samples) preferably 0～50mgKOH/g of complex ester A, more preferably 0 ～15mgKOH/g, more preferably 2～10mgKOH/g.The acid number (the mg numbers of the KOH needed for neutralization 1g samples) of complex ester A The value for specially determining according to JISK2501 methods.

(manufacture method of complex ester A)

A1 compositions～c1 compositions are become into 1/ with the ratio of the hydroxyl mol numbers of the carboxylic acid mol numbers/c1 of the hydroxyl mol numbers/b1 of a1 1.5～2.0/0.7～1.5, preferably 1/1.55～1.9/0.8～1.4, the side of further preferred 1/1.60～1.8/0.8～1.3 Formula is added, and makes which carry out condensation reaction, is derived from complex ester A.

The mixture being introduced, as previously discussed, to is made to be condensed in the presence of catalyst or condensing agent or under without catalyst Reaction, is derived from complex ester A.

It is preferred that being heated in condensation, or make to exist with the solvent of water or low mass molecule alcohol azeotropic in right amount.Thus, it is combined Ester A will not be coloured, and reaction is also swimmingly carried out.The varsol of 100～200 DEG C of the preferred boiling point of the solvent, further preferred 100 ～170 DEG C of varsol, most preferably 110～160 DEG C of varsol.As these solvents, can for example enumerate toluene, two Toluene, trimethylbenzene etc..If the amount added is excessive, temperature of liquid is close to the solvent, is difficult to be condensed.On the other hand, if It is very few, then will not swimmingly carry out azeotropic.From from the viewpoint of productivity, solvent is not preferably used to carry out condensation reaction.

Although can accelerate reaction by using catalyst, the post processing for removing catalyst is numerous and diverse, becomes complex ester A The reason for coloring, therefore preferably do not use catalyst.But, in a situation of use where, with common catalyst using common Condition and operation.Japanese Unexamined Patent Application Publication 2001-501989 publication, Japanese Unexamined Patent Application Publication 2001-500549 can be referred to regard to this content List of references in publication, Japanese Unexamined Patent Application Publication 2001-507334 publication and Japanese Unexamined Patent Application Publication 2002-509563 publication.

Terminate add after, with 120～250 DEG C of temperature of liquid, preferably 130～240 DEG C, further preferred 150～230 DEG C, it is particularly preferred 170～230 DEG C reaction.Thus, the solvent azeotropic containing water or low mass molecule alcohol, cools down in cooling position, becomes Liquid and separate.Remove the water.After can also reacting at low temperature, further react at high temperature.

With regard to the response time, due to calculating theoretical water yield according to the molal quantity for adding, thus preferably by reaction carry out to The time point of the water yield is obtained, but is difficult to be fully completed reaction.Even if resonable Theory water yield is 60～99% time point knot Shu Fanying, the lubrication property of the lubricant compositions containing complex ester A for having obtained are also good.Response time is 1～24 hour, Preferably 3～20 hours, more preferably 5～18 hours, most preferably 6～15 hours.

As preferred reaction condition, preferably it is solvent-free, without catalyst under reacted 1～10 hour with 170～200 DEG C After (preferably 2～8 hours), 1～10 hour (preferably 2～8 hours) are further reacted with 201 DEG C～240 DEG C.

(compositions in addition to complex ester A of lubricant compositions)

The present invention relates to a kind of at least lubricant compositions containing complex ester A.For example, can in lubricant compositions Addition complex ester A and various additives and/or medium.

It is preferred that the lubricant compositions of the present invention also contain medium, relative to the gross mass of lubricant compositions, contain 0.1 The medium of complex ester A of～5 mass % and 70～99.9 mass %, relative to the gross mass of lubricant compositions, containing 0～ The other compositions in addition to complex ester A and medium of 29.9 mass %.

Can be calculated with relationship below by adding the climbing (%) of the kinematic viscosity that complex ester A causes.Following In relational expression, NA is represented and is not added complex ester A, the only kinematic viscosity of medium and other compositions at 40 DEG C, NB represent plus Enter the kinematic viscosity at 40 DEG C during complex ester A.

Kinematic viscosity climbing (%)=[{ (NB)-(NA) }/(NA)] × 100

The climbing (%) preferably less than 15% of kinematic viscosity, more preferably less than 10%, further preferred less than 5%, especially Its preferably less than 2%, most preferably less than 1.5%.It is preferred that adding multiple in the way of kinematic viscosity climbing becomes above range Close ester A to prepare the lubricant compositions of the present invention.

(medium)

As medium (also referred to base oil), can enumerate selected from mineral oil, lipidic compounds, polyolefin oil (such as poly- α Alkene), silicone oil, ether oil (such as perfluoro polyether oil, diphenyl ether derivative), ester oil (such as aromatic ester oils, mono fatty acid Ester, bis-fatty acid diester, polyol Ester Lubricating Oil) it is one kind or two or more.Wherein, preferred medium is selected from mineral oil, polyene At least one of hydrocarbon ils, ester oil.

In the present invention, " medium " refers to the All Media of commonly referred to as " mobility liquid ".But, in room temperature or made With at a temperature of, need not be liquid, in addition to liquid, it is also possible to using the material of the either types such as solid and gel.Close It is not particularly limited in the medium that can be used in the present invention, can be selected from various liquid according to purposes.With regard to can The medium for using in the present invention, can refer to 0067～0096 section of Japanese Unexamined Patent Publication 2011-89106 publications of record.It is situated between The matter preferably 1～500mm of the kinematic viscosity at 40 DEG C²/ s, more preferably 1.5～200mm²/ s, further preferred 2～50mm²/s。

The viscosity index (VI) of medium is preferably more than 90, more preferably more than 105, more preferably more than 110.Also, The viscosity index (VI) of medium is preferably less than 160.By by viscosity index (VI) set within the above range, optimization viscosity-temperature profile with And thermo oxidative stability, preventing property of volatilization, abrasion preventing property improve.

In addition, viscosity index (VI) described in the present invention refers to the viscosity index (VI) determined according to JIS K 2283-1993.

(other compositions in addition to complex ester A and medium)

The preferred compound of the other compositions in addition to complex ester A and medium, the lubrication added to the present invention The preferred additive of agent compositionss is the compound with least one in zinc, molybdenum, sulfur and phosphorus as constitutive requirements.This Plant the function that compound has friction improver, antiwear additive, antioxidant etc..With at least one in zinc, molybdenum, sulfur and phosphorus The compound that zinc, molybdenum, sulfur and phosphorus can be contained with any state in compound is referred to as the compound of constitution element.Tool For body, can enumerate as compounds containing zinc, molybdenum, sulfur and phosphorus such as monomer (oxidation number 0), ion, complex.As This compound, can enumerate organic molybdenum, inorganic molybdenum compounds, organic zinc compound, (Asia) phosphoric acid derivatives, organic Sulphur compound etc..Wherein, preferred organic molybdenum and organic zinc compound.

1 kind can only be added extremely with regard to at least one in zinc, molybdenum, sulfur and phosphorus as the compound of constitution element The lubricant compositions of the present invention, it is also possible to combine two or more and add to the lubricant compositions of the present invention.Will with zinc, At least one in molybdenum, sulfur and phosphorus combines two or more as the compound of constitution element to be added to the lubricant combination of the present invention In the case of thing, the organic molybdenum compound of preferred compositions, inorganic molybdenum compounds, organic zinc compound, (Asia) phosphoric acid derivatives and Two or more in organosulfur compound, more preferably combines organic molybdenum and organic zinc compound.

Hereinafter, to organic molybdenum, inorganic molybdenum compounds, organic zinc compound, (Asia) phosphoric acid derivatives and organic The respective preferred mode of sulphur compound is illustrated.

Used as the organic molybdenum for being used as additive in lubricant compositions, can enumerate molybdenum dithiophosphate (has When be also referred to MoDTP) etc. the organic molybdenum containing phosphorus.

As other organic molybdenums, can enumerate and (be also referred to sometimes with the molybdenum dithiocarbamate that following formula is represented The organic molybdenum containing sulfur such as MoDTC).As the organic molybdenum containing sulfur, such as preferably N, bis--octyl groups of N-, two sulfur Vulcanize oxygen molybdenum (C for carbamic acid₈- Mo (DTC)), N, bis--tridecyls of N- aminodithioformic acid sulfuration oxygen molybdenum (C₁₆-Mo (DTC)) etc..

[chemical formula 4]

In above-mentioned formula, R¹～R⁴Can be with identical, it is also possible to different, separately represent alkyl.R¹～R⁴It is preferred that distinguishing It independently is alkyl or aryl.

Contain the organic molybdenum of sulfur as other, the network of inorganic molybdenum compounds and organic compounds containing sulfur can be enumerated Compound.The inorganic molybdenum used in complex, i.e. organic molybdenum as inorganic molybdenum compounds and organic compounds containing sulfur Compound, for example, can enumerate the molybdenums such as the molybdenum oxides such as molybdenum dioxide, molybdenum trioxide, ortho-molybdic acid, para-molybdic acid, (many) molybdenum sulfides The molybdenum sulfides such as molybdate, molybdenum bisuphide, molybdenum trisulfide, molybdenum pentasulfide, many molybdenum sulfides such as acid, the slaine of these molybdic acids, ammonium salt, Halogenation molybdenum such as molybdenum sulfide, the slaine of molybdenum sulfide or amine salt, molybdenum chloride etc..Also, as inorganic molybdenum compounds and sulfur-bearing Organic compounds containing sulfur used in the complex of organic compound, i.e. organic molybdenum, for example, can enumerate alkyl (sulfur Generation) xanthate, thiadiazoles, dimercaptothiodiazole, sulfocarbonate, curing tetraalkyl thiram, double (two (thio) alkyl two Thiophosphate) disulphide, organic (gathering) thioether, sulfurised ester etc..

Contain the organic molybdenum of sulfur as other, the molybdenum chemical combination containing sulfur such as molybdenum sulfide, molybdenum sulfide can be enumerated Complex of thing and alkenyl succinimide etc..

As organic molybdenum, the organic molybdenum without constitution element phosphorus or sulfur can be used.As without structure Into element phosphor or the organic molybdenum of sulfur, molybdenum-amine complex, molybdenum-butanimide complex, organic acid can be specifically enumerated Molybdenum salt, the molybdenum salt of alcohol etc., wherein, the molybdenum salt of preferred molybdenum-amine complex, the molybdenum salt of organic acid and alcohol.

As the inorganic molybdenum compounds for being used as additive in lubricant compositions, and have with inorganic molybdenum compounds and sulfur-bearing The inorganic molybdenum compounds phase that the example of the inorganic molybdenum compounds used in the complex of machine compound, i.e. organic molybdenum is enumerated Together.

As the organic zinc compound for being used as additive in lubricant compositions, the dithio for preferably being represented with following formula Zinc phosphate (ZDTP), diphosphonic acid zinc (ZDP).

[chemical formula 5]

In above-mentioned formula, Q¹、Q²、Q³、Q⁴Can be each identical, it is also possible to different, separately represent isopropyl, fourth Base, isobutyl group, amyl group, isopentyl, neopentyl, hexyl, heptyl, octyl group, 2- ethylhexyls, nonyl, decyl, undecyl, ten The alkyl of the carbon numbers such as dialkyl group, tridecyl, isotridecyl, myristyl, palmityl, stearyl 8～20.

As the zinc dithiophosphate (ZDTP) represented with above-mentioned formula, normal-butyl-n-pentyl dithio phosphorus is particularly preferred as Sour zinc (C₄/C₅ZnDTP), two -2- ethylhexyl zinc dithiophosphate (C₈) or isopropyl -1- ethyl-butyl dithio phosphorus ZnDTP Sour zinc (C₃/C₆ZnDTP)。

In the lubricant compositions of the present invention, in the case of using organic molybdenum, relative to lubricant combination Thing gross mass, in terms of molybdenum content, preferably comprises 10～2000ppm, further preferably 10～1000ppm, further preferably 50～800ppm, particularly preferably containing 100～600ppm.

Also, in the case of using organic zinc compound, its content is contained with zinc relative to lubricant compositions gross mass Gauge, preferably comprise 100～50000ppm, further preferably 100～30000ppm, further preferably 100～ 10000ppm, particularly preferably containing 200～2000ppm, most preferably 300～1200ppm.

By containing organo-metallic compounds such as the organic molybdenums or organic zinc compound in lubricant compositions Amount sets within the above range, it is possible to increase the stability of lubricant compositions, can improve in the harshness bar such as high temperature and/or high pressure Lubrication property under part, can play more excellent greasy property and abrasion rejection ability.

As (Asia) phosphoric acid derivatives, can with aforesaid zinc dithiophosphate (ZDTP), diphosphonic acid zinc (ZDP) other The aliphatic phosphate esters such as the aromatic phosphoric esters such as phosphorous acid esters, phosphoric acid ester, tricresyl phosphate, trialkylphosphate are excellent The example of choosing is illustrated.Wherein, the more preferably aliphatic phosphate ester such as the aromatic phosphoric ester such as tricresyl phosphate, trialkylphosphate Deng.

As organosulfur compound, preferred polysulfide ether, more preferably dialkyl polysulfide.

As the other compositions in addition to complex ester A and medium, in addition to above-claimed cpd, can enumerate and be selected from Such as viscosity index improver (preferably poly- (methyl) alkyl acrylate, (methyl) alkyl acrylate-there is polar group The polymer and copolymer of (methyl) acrylate copolymer, butadiene, alkene or alkylated styrenes), antioxidant it is (excellent Select hindered phenol compound, alkyl monosulfide phenolic compounds, aromatic amines compound, low sulfur peroxide decomposers, oil-soluble copper Compound), abluent (alkali metal salt or alkali earth metal salt of sulfate, phenolate, carboxylate, phosphate and salicylate, (boric acid modified) bromosuccinimide, succinate), dispersant (preferred phenolate, sulfonate, sulfuration phenolate, salicylic acid Salt, naphthenate, stearate, carbamate, thiocarbamate, phosphorus derivant, succinic acid derivative (such as long-chain Substituted alkenyl succinic acid derivative, bromosuccinimide derivant, hydrocarbon replace succinic acid compound, succinate, succinate Amide), Mannich base), pour point depressant (preferred polymethyl acrylate, polyacrylate, Nomex base, halogenated paraffins The condensation product of (Haloparaffin wax) and aromatic compound, vinyl carboxylic acid ester polymer and dialkyl group fumaric acid The terpolymer of ester, fatty acid vinyl ester and allyl vinyl ether), corrosion inhibitor (preferred thiadiazoles), sealing phase Hold agent (preferred organic phosphate, aromatic ester, aromatic hydrocarbon, ester (for example, butyl benzyl phthalic ester) and polybutene Succinic anhydrides), defoamer (preferred polydimethylsiloxane), antirust agent, friction improver, abrasion preventing agent and thickening agent 1 Plant or two or more.

By adding this additive, the preferred function as lubricant compositions such as abrasion suppression can be given.Close In the additive that can be used in the present invention, can be with reference to 0098～0165 section of Japanese Unexamined Patent Publication 2011-89106 publications Record.

(properties of lubricant compositions)

Kinematic viscosity of the lubricant compositions of the present invention at 40 DEG C is preferably 500mm²/ below s, more preferably 200mm²/ below s, more preferably 100mm²/ below s, especially preferably 50mm²/ below s, most preferably 5～50mm²/ s.With regard to viscosity, due to requiring to be more suitable for the viscosity of use environment, it is therefore desirable to be consistent with its use environment.In this specification In, kinematic viscosity of the lubricant compositions at 40 DEG C is specifically adopted and is surveyed in 40.0 DEG C of thermostatic water bath using Ubbelohde viscometer Fixed value.

(manufacture methods of lubricant compositions)

The present invention relates to a kind of concentration of the operation and complex ester A for obtaining complex ester A is the lubricant of 0.1～5 mass % The manufacture method of compositionss, and it is related to a kind of lubricant compositions manufactured by this manufacture method.Obtain the work of complex ester A Sequence is following operation：At least by more than 3 yuan of polyhydric alcohol a1,2 yuan of carboxylics of the carbon number 36～44 containing at least 75 mass % Acid carbon number 18～22 unsaturated fatty acid polymerization reaction mixture and by polymerization reaction mixture hydrogenate and obtain Mixture at least either mixture b1 and the monohydric alcohol c1 that represented with following formulas (1) with the hydroxyl mol numbers/b1 of a1 The hydroxyl mol numbers of carboxylic acid mol numbers/c1 become the mode of 1/1.5～2.0/0.7～1.5 and mix, and be condensed which.

Formula (1)：R-OH

With regard to the blending ratio of a1 compositions～c1 compositions, the hydroxyl mol of the carboxylic acid mol numbers/c1 of the hydroxyl mol numbers/b1 of a1 Number for 1/1.5～2.0/0.7～1.5, preferably 1/1.55～1.9/0.8～1.4, more preferably 1/1.60～ 1.8/0.8～1.3.

Complex ester A is added in oil medium or aqueous medium in the way of concentration becomes 0.1～5 mass %, is made Its dissolving and/or dispersion, the lubricant compositions thus, it is possible to prepare the present invention.Dissolving and/or dispersion can also be under heatings Carry out.

Can also prepare the lubricant compositions of the present invention as lubricant composition.In this approach, in order to ensure Suitable for grease purposes when Practical Performance, further can not damage in the range of the purpose of the present invention as needed Suitably add thickening agent etc..One mode of lubricant composition is the compositionss of the thickening agent also containing 10～50 mass %. The additive that can add when hereinafter, to preparing as lubricant composition is illustrated.

In the example of the thickening agent that can add, can be using soaps thickening agent, swellings such as metallic soap, composition metal soaps Soil, silica gel, ureas thickening agent (carbamide compound, urea ammonia carbamate compound, carbamate compounds etc.) on-soap thickening All thickening agents such as agent.In the middle of these, from the damage to the part by resin manufacture it is little from the viewpoint of, preferably use soaps Thickening agent, ureas thickening agent.

As soaps thickening agent, for example, can enumerate soda soap, calcium soap, aluminium soap, lithium soap etc., in the middle of these, from resistance to water and From the viewpoint of heat stability, preferred lithium soap.As lithium soap, for example, can enumerate lithium stearate or lithium -12- hydroxy stearic acid esters Deng.

Also, as ureas thickening agent, for example, can enumerate carbamide compound, urea ammonia carbamate compound, carbamic acid Ester compounds or their mixture etc..

As carbamide compound, urea ammonia carbamate compound and carbamate compounds, for example, can enumerate allophanamide Compound, three carbamide compounds, four carbamide compounds, polyurea compound be not (including double urea compound, three carbamide compounds and four ureas Compound), urea ammonia carbamate compound, diurethane compound or their mixture etc..It is preferred that enumerating allophanamide chemical combination Thing, urea ammonia carbamate compound, diurethane compound or their mixture.

As kollag, can for example enumerate politef, boron nitride, fullerene, graphite, fluorographite, three Poly cyanamid cyanurate, molybdenum bisuphide, molybdenum dithiocarbamate, antimony trisulfide, alkali (alkaline earth) metal borate etc..

As wax, for example, the various waxes of native paraffin, mineral oilses or synthesis class can be illustrated, brown coal can be specifically enumerated Wax, Brazil wax, the amide compound of higher fatty acids, paraffin, microwax, Tissuemat E, polyolefin-wax, ester type waxes etc..

Additionally, as having benzotriazole, benzimidazole, thiadiazoles etc. known to matal deactivator, these metals can be added Passivator.

Thickening agent can be added in lubricant composition.As thickening agent, for example, can enumerate polymethyl acrylate, gather Isobutene., polystyrene etc..It is known that poly- (methyl) acrylate with the abnormal sound prevented under cold district low temperature Effect.

(purposes of lubricant compositions)

The lubricant compositions of the present invention are for example supplied to can be used in reducing friction between 2 sliding surfaces.The present invention Lubricant compositions can sliding surface formed epithelium.As the material of sliding surface, machinery can be specifically enumerated in iron and steel The frame for movement alloys such as structure carbon steel, nickel chromium triangle steel nickel chromium molybdenum steel material chrome steel chrome molybdenum steel Al-Cr-Mo steel Steel, rustless steel, Maraging steel etc..

As the material of sliding surface, the various metals being also used extensively by addition to iron and steel or in addition to metal inorganic Or organic material.As inorganic or organic material in addition to metal, various plastics, ceramics, carbon etc. can be enumerated and its mixed Zoarium etc..More specifically, as the metal material in addition to iron and steel, cast iron, copper copper-lead aluminium alloy, its casting can be enumerated Part and bidery metal.

In addition, with regard to the material of sliding surface, 0168～0175 section of Japanese Unexamined Patent Publication 2011-89106 publications can be referred to Record.

The lubricant compositions of the present invention can be used in various uses.For example, can act as grease lubricating oil, take off Mould agent, internal combustion engine oil, internal combustion engine engine oil, intermetallic composite coating (cutting is used) oil, bearing oil, combustion engine fuel, car Engine oil, gear oil, automobile working oil, ship and airborne vehicle lubricating oil, machinery oil, turbine oil, hydraulic oil, Compressor oil, pumping fluid, refrigerating machine oil, Metalworking lubricant, lubricant for magnetic recording medium, micromachine lubrication Agent, artificial bone with lubricator, shock absorber fluid or ROLLING OIL.Also, also it is used in reciprocating motion type or revolving closed The air-conditioning or refrigerator of type compressor, air conditioner for automobile or dehumidifier, freezer, freezing and refrigeration warehouse, automatic vending machine, display Chillers such as cabinet, chemical industry equipment etc..

As the Metalworking lubricant of not chloride based compound, such as to metal materials such as ferrum Steel material or aluminium alloys Material carries out hot rolling or carries out cutting etc. useful during processing, and the cold-rolled lubricating oil as aluminum, cutting oil, grinding oil, drawing processing The plastic working oil of the Metalworking fluids such as oil, punch process oil or metal is useful, especially as mill when high speed, high load capacity processing Damage, the inhibitor of damaged, surface roughness it is useful, and as being applicable to low speed, the heavy cuts such as wire pulling method, drill gun processing In Metalworking fluid composition be also useful.

Further, it is possible to be used in various grease lubricating oil, lubricant for magnetic recording medium, micromachine with lubricator Or artificial bone is with lubricator etc..Also, due to can be by the elementary composition as carbohydrate of compositionss, therefore by by example Such as it is widely used in cake mix (cakemix), salad dressing, shortening, chocolate etc. as emulsifying, decentralized, solvable agent , using based on the sorbitan fatty acid esters containing polyoxyethylene ether and edible oil oil compositionss as lubricating oil, The completely harmless high perofmrnace lubricating oils of human body can will be used for the manufacturing equipment or medical device part of food manufacturing production line Lubrication.

Also, disperseed by the lubricant compositions of the present invention are emulsified into water system, or in polar solvent Or disperseed in resin medium, can act as cutting oil or ROLLING OIL.

Also, the lubricant compositions of the present invention can also be used in various uses as releasing agent.For example, can serve as Polycarbonate resin, flame-retardant copolycarbonate resin, as the figure used in electronic photo device or electrostatic recording apparatus etc. Crystalline polyester resin, various molding thermoplastic resin composition and semiconductor package as the main constituent of formation toner The releasing agent of dress composition epoxy resin etc..

Also, anti-fouling agent can also be used as, the anti-fouling agent passes through to be rubbed in the fiber products such as dress material in advance or be coated, Promotion is attached to the disengaging of the dirt of fiber product, so as to prevent fiber product of making dirty.

[embodiment]

Hereinafter, enumerate embodiment and comparative example is further specifically described to the feature of the present invention.In following examples The loyal purport without departing from the present invention such as the material that illustrates, usage amount, ratio, process content, processing sequence, just can be suitably Change.Therefore, the scope of the present invention should not be limited to concrete example described below to explain.

The synthesis ＞ of ＜ complex ester A-1

It is (Tsuno Co., the Ltd. manufacture of 9.38g trimethylolpropanes, b1 compositions i.e. 100.0g dimeric dibasic acids by a1 compositions TSUNODYME395, C36 dicarboxylic acids contain rate 95%) and c1 compositions are 50.6g2- hexyls -1-decanol (NISSAN CHEMICAL INDUSTRIES.LTD. the FINE OXOCOL for manufacturing 1600) (hydroxyls of the carboxylic acid mol numbers/monohydric alcohol of the hydroxyl mol numbers/b1 of a1 During the ratio of base mol numbers=1/1.7/1) adds the reaction vessel with Dean-Rodney Stark (Dean-Stark) dehydration device.Make a1 The mixture of～c1 compositions is reacted 5 hours with 190 DEG C under the nitrogen stream of 0.3L/min, is further reacted 4 hours with 220 DEG C. The water that removal is produced in the reaction.Reactant is let cool to room temperature, complex ester A-1 is obtained as the fraction of yellow transparent.

The synthesis ＞ of ＜ complex ester A-2

By the use of the trimethylolpropane as a1 compositions, as b1 compositions dimeric dibasic acid (Tsuno Co., Ltd. manufacture TSUNODYME228, C36 dicarboxylic acids are containing rate 81%) and as 2- hexyls -1-decanol (the NISSAN CHEMICAL of c1 compositions INDUSTRIES.LTD. the FINE OXOCOL for manufacturing 1600), with the carboxylic acid mol numbers/monohydric alcohol of the hydroxyl mol numbers/b1 of a1 The ratio of hydroxyl mol numbers becomes 1/1.7/1 mode and adds.The mixture is condensed using the synthesis identical method with A-1, is obtained Complex ester A-2.

The synthesis ＞ of ＜ complex ester A-3

By the use of the trimethylolpropane as a1 compositions, as b1 compositions dimeric dibasic acid (Tsuno Co., Ltd. manufacture TSUNODYME216, C36 dicarboxylic acids are containing rate 79%) and as 2- hexyls -1-decanol (the NISSAN CHEMICAL of c1 compositions INDUSTRIES.LTD. the FINE OXOCOL for manufacturing 1600), with the carboxylic acid mol numbers/monohydric alcohol of the hydroxyl mol numbers/b1 of a1 The ratio of hydroxyl mol numbers becomes 1/1.7/1 mode and adds.The mixture is condensed using the synthesis identical method with A-1, is obtained Complex ester A-3.

The synthesis ＞ of ＜ complex ester A-4

By the use of the trimethylolpropane as a1 compositions, as dimeric dibasic acid (the Croda companies manufacture being hydrogenated of b1 compositions PRIPOL1009, C36 dicarboxylic acids containing rate 98%) and as 2- hexyls -1-decanol (the NISSAN CHEMICAL of c1 compositions INDUSTRIES.LTD. the FINE OXOCOL for manufacturing 1600), with the carboxylic acid mol numbers/monohydric alcohol of the hydroxyl mol numbers/b1 of a1 The ratio of hydroxyl mol numbers becomes 1/1.7/1 mode and adds.The mixture is condensed using the synthesis identical method with A-1, is obtained Complex ester A-4.

The synthesis ＞ of ＜ complex ester A-5

By the use of the trimethylolpropane as a1 compositions, as the polymerization with the dicarboxylic acids of C44 as main constituent of b1 compositions Thing (PRIPOL1004, C44 dicarboxylic acids of Croda companies manufacture contain rate 95%) is and as the 2- hexyls -1-decanol of c1 compositions (the FINE OXOCOL 1600 of NISSAN CHEMICAL INDUSTRIES.LTD. manufactures), with the hydroxyl mol numbers/b1's of a1 The ratio of the hydroxyl mol numbers of carboxylic acid mol numbers/monohydric alcohol becomes 1/1.7/1 mode and adds.Using the synthesis identical side with A-1 Method is condensed the mixture, obtains complex ester A-5.

The synthesis ＞ of ＜ complex ester A-6

By the use of the trimethylolpropane as a1 compositions, as b1 compositions dimeric dibasic acid (Tsuno Co., Ltd. manufacture TSUNODYME395, C36 dicarboxylic acids contain rate 95%) and as the 2-Ethylhexyl Alcohol of c1 compositions, with the hydroxyl mol numbers/b1 of a1 The ratio of hydroxyl mol numbers of carboxylic acid mol numbers/monohydric alcohol become 1/1.7/1 mode and add.Using the synthesis identical with A-1 Method is condensed the mixture, obtains complex ester A-6.

The synthesis ＞ of ＜ complex ester A-7

By the use of the trimethylolpropane as a1 compositions, as the polymerization with the dicarboxylic acids of C44 as main constituent of b1 compositions Thing (PRIPOL1004, C44 dicarboxylic acids of Croda companies manufacture contain rate 95%) and as the 2-Ethylhexyl Alcohol of c1 compositions, with The ratio of the hydroxyl mol numbers of the carboxylic acid mol numbers/monohydric alcohol of the hydroxyl mol numbers/b1 of a1 becomes 1/1.7/1 mode and adds.Using with The synthesis identical method of A-1 is condensed the mixture, obtains complex ester A-7.

The synthesis ＞ of ＜ complex ester A-8

By the use of the trimethylolpropane as a1 compositions, as b1 compositions dimeric dibasic acid (Tsuno Co., Ltd. manufacture TSUNODYME395, C36 dicarboxylic acids contain rate 95%) and as the 2-Ethylhexyl Alcohol of c1 compositions, with the hydroxyl mol numbers/b1 of a1 The ratio of hydroxyl mol numbers of carboxylic acid mol numbers/monohydric alcohol become the mode of 1/1.5/0.75 and add.Using identical with the synthesis of A-1 Method be condensed the mixture, obtain complex ester A-8.

The synthesis ＞ of ＜ complex ester A-9

By the use of the trimethylolpropane as a1 compositions, as b1 compositions dimeric dibasic acid (Tsuno Co., Ltd. manufacture TSUNODYME395, C36 dicarboxylic acids contain rate 95%) and as the 2-Ethylhexyl Alcohol of c1 compositions, with the hydroxyl mol numbers/b1 of a1 The ratio of hydroxyl mol numbers of carboxylic acid mol numbers/monohydric alcohol become the mode of 1/2.0/1.33 and add.Using identical with the synthesis of A-1 Method be condensed the mixture, obtain complex ester A-9.

The synthesis ＞ of ＜ complex ester A-10

By the use of the trimethylolpropane as a1 compositions, as b1 compositions dimeric dibasic acid (Tsuno Co., Ltd. manufacture TSUNODYME395, C36 dicarboxylic acids are containing rate 95%) and as 2- hexyls -1-decanol (the NISSAN CHEMICAL of c1 compositions INDUSTRIES.LTD. the FINE OXOCOL for manufacturing 1600), with the carboxylic acid mol numbers/monohydric alcohol of the hydroxyl mol numbers/b1 of a1 The ratio of hydroxyl mol numbers becomes 1/1.57/1 mode and adds.The mixture is condensed using the synthesis identical method with A-1, is obtained Obtained complex ester A-10.

The synthesis ＞ of ＜ complex ester A-11

By the use of the trimethylolpropane as a1 compositions, as b1 compositions dimeric dibasic acid (Tsuno Co., Ltd. manufacture TSUNODYME395, C36 dicarboxylic acids are containing rate 95%) and as 2- hexyls -1-decanol (the NISSAN CHEMICAL of c1 compositions INDUSTRIES.LTD. the FINE OXOCOL for manufacturing 1600), with the carboxylic acid mol numbers/monohydric alcohol of the hydroxyl mol numbers/b1 of a1 The ratio of hydroxyl mol numbers becomes 1/2.0/1 mode and adds.The mixture is condensed using the synthesis identical method with A-1, is obtained Complex ester A-11.

The synthesis ＞ of ＜ complex ester A-12

By the use of the trimethylolpropane as a1 compositions, as b1 compositions dimeric dibasic acid (Tsuno Co., Ltd. manufacture TSUNODYME395, C36 dicarboxylic acids are containing rate 95%) and as 2- hexyls -1-decanol (the NISSAN CHEMICAL of c1 compositions INDUSTRIES.LTD. the FINE OXOCOL for manufacturing 1600), with the carboxylic acid mol numbers/monohydric alcohol of the hydroxyl mol numbers/b1 of a1 The ratio of hydroxyl mol numbers becomes 1/1.85/1 mode and adds.The mixture is condensed using the synthesis identical method with A-1, is obtained Obtained complex ester A-12.

The synthesis ＞ of ＜ complex ester A-13

By the use of the trimethylolpropane as a1 compositions, as b1 compositions dimeric dibasic acid (Tsuno Co., Ltd. manufacture Unitary of TSUNODYME395, C36 dicarboxylic acids containing branched alkyl with carbon number 18 of the rate 95%) and as c1 compositions Alcohol (the FINE OXOCOL 180N of NISSAN CHEMICAL INDUSTRIES.LTD. manufactures), with the hydroxyl mol numbers/b1 of a1 The ratio of hydroxyl mol numbers of carboxylic acid mol numbers/monohydric alcohol become 1/1.7/1 mode and add.Using the synthesis identical with A-1 Method is condensed the mixture, obtains complex ester A-13.

The synthesis ＞ of ＜ complex ester A-14

By the use of the trimethylolpropane as a1 compositions, as b1 compositions dimeric dibasic acid (Tsuno Co., Ltd. manufacture TSUNODYME395, C36 dicarboxylic acids contain rate 95%) and as the n-octadecane alcohol of c1 compositions, with the hydroxyl mol numbers/b1 of a1 The ratio of hydroxyl mol numbers of carboxylic acid mol numbers/monohydric alcohol become 1/1.7/1 mode and add.Using the synthesis identical with A-1 Method is condensed the mixture, obtains complex ester A-14.

The composition of complex ester A-1～A-14 such as table 1.Also, each composition is as follows.

＜ a1 composition ＞

TMP：Trimethylolpropane

PE：Tetramethylolmethane

＜ b1 composition ＞

C36-1：Tsuno Co., Ltd.s manufacture, and TSUNODYME395, C36 dicarboxylic acids contain rate 95%

C36-2：Tsuno Co., Ltd.s manufacture, and TSUNODYME228, C36 dicarboxylic acids contain rate 81%

C36-3：Tsuno Co., Ltd.s manufacture, and TSUNODYME216, C36 dicarboxylic acids contain rate 79%

C36-4：(Croda companies manufacture the dimeric dibasic acid being hydrogenated, and 98%) PRIPOL1009, C36 dicarboxylic acids contain rate

C44-1：(Croda companies manufacture polymer with the dicarboxylic acids of C44 as main constituent, PRIPOL1004, C44 dicarboxyl 95%) acid contain rate

＜ c1 composition ＞

EH8B：2-Ethylhexyl Alcohol

HD16B：(NISSAN CHEMICAL INDUSTRIES.LTD. are manufactured 2- hexyls -1-decanol, FINE OXOCOL 1600)

OD18B：Monohydric alcohol (the NISSAN CHEMICAL of the branched alkyl with carbon number 18 INDUSTRIES.LTD. manufacture, FINE OXOCOL 180N)

OD18N：N-octadecane alcohol

DD20B：Monohydric alcohol (the NISSAN CHEMICAL of the branched alkyl with carbon number 20 INDUSTRIES.LTD. manufacture, FINE OXOCOL are 2000)

[table 1]

＜ compares the synthesis ＞ with complex ester X-1

When complex ester A-1 is synthesized, the 20mol% of dimeric dibasic acid is substituted by into adipic acid, with the hydroxyl mol numbers/b1's of a1 The ratio of the hydroxyl mol numbers of carboxylic acid mol numbers/monohydric alcohol becomes 1/1.4/1 mode and adds.Using the synthesis phase with complex ester A-1 Same method is condensed the mixture, obtains to compare and uses complex ester X-1.

＜ compares the synthesis ＞ with complex ester X-2

By the use of the trimethylolpropane as a1 compositions, as b1 compositions dimeric dibasic acid (Tsuno Co., Ltd. manufacture TSUNODYME395, C36 dicarboxylic acids containing rate 95%) and as the 2- hexyls -1-decanol of c1 compositions, with the hydroxyl mol numbers of a1/ The ratio of the hydroxyl mol numbers of the carboxylic acid mol numbers/monohydric alcohol of b1 becomes the mode of 1/2.11/1.45 and adds.Using the synthesis with A-1 Identical method is condensed the mixture, obtains to compare and uses complex ester X-2.

＜ compares the synthesis ＞ with complex ester X-3

By the use of the trimethylolpropane as a1 compositions, as b1 compositions dimeric dibasic acid (Tsuno Co., Ltd. manufacture TSUNODYME395, C36 dicarboxylic acids containing rate 95%) and as the 2- hexyls -1-decanol of c1 compositions, with the hydroxyl mol numbers of a1/ The ratio of the hydroxyl mol numbers of the carboxylic acid mol numbers/monohydric alcohol of b1 becomes the mode of 1/1.48/0.73 and adds.Using the synthesis with A-1 Identical method is condensed the mixture, obtains to compare and uses complex ester X-3.

＜ compares the synthesis ＞ with complex ester X-4

When complex ester A-1 is synthesized, the 50mol% of dimeric dibasic acid is substituted by into adipic acid, with the hydroxyl mol numbers/b1's of a1 The ratio of the hydroxyl mol numbers of carboxylic acid mol numbers/monohydric alcohol becomes the mode of 1/0.92/1.01 and adds.Using the conjunction with complex ester A-1 The mixture is condensed into identical method, is obtained to compare and is used complex ester X-4.

Relatively with the composition such as table 2 of complex ester X-1～X-4.

[table 2]

(embodiment 1～28)

Complex ester A shown in table 1 is mixed with base oil, lubricant compositions are prepared for.In addition, having used following basis Oil.

B1：Fortune of the mineral oil (JX Nippon Oil＆Energy Corporation are manufactured, super oily N46) at 40 DEG C Kinetic viscosity 46.1mm²/s

B2：(ANDEROL companies manufacture poly-a-olefin oil, ANDEROL FGC kinematic viscositys 32) at 40 DEG C 32.6mm²/s

B3：(ANDEROL companies manufacture ester oil, ANDEROL kinematic viscosity 28.0mm 495) at 40 DEG C²/s

B4：Add 500ppm in B1 as the molybdenum dithiocarbamate of Mo contents, 1000ppm as the two of Zn contents The base oil of D2EHDTPA zinc, the kinematic viscosity 46.2mm at 40 DEG C²/s

(comparative example 1～8)

Comparison complex ester shown in complex ester A shown in table 1 or table 2 is mixed with base oil, lubricant group is prepared for Compound.

(evaluation)

＜ coefficient of frictions evaluate ＞

With regard to each embodiment and the lubricant compositions of comparative example, using oscillating mode friction wear testing machine (Optimol Instruments Prueftechnik GmbH companies manufacture, trade name：SRV 3), in vibration number 50Hz, load 10N, amplitude Under conditions of 1mm, 1 hour friction-wear test is carried out at temperature 40 DEG C (conditions 1) and 80 DEG C (condition 2) respectively, determine 30 The coefficient of friction of minute.Top test film has used 10mmSUJ-2 balls, bottom test film to use 24mmSUJ-2 disks.Utilize Top test film after microscopic test, but almost do not find abrasion, it is believed that can see from fluid lubrication region Measure the frictional behaviour in mixed lubrication region.The coefficient of friction for observing is evaluated according to following benchmark.By the result It is shown in table 4 below.

It is with the coefficient of friction of the condition 1 of comparative example 1 as 100% by other evaluation result standardization, following to evaluate.Value is got over Little, coefficient of friction is less, is expressed as good lubrication property.The coefficient of friction of a, b declines to a great extent, and is judged as that improvement is big. Although the coefficient of friction of c, d declines, effect is little.E compared with comparative example 1, on an equal basis or below which, is judged as not finding to improve.Separately Outward, in the test of condition 1 and 2, the evaluation of more than b is set to into qualified evaluation.

a：Less than 60%

b：60% less than 70%

c：70% less than 80%

d：80% less than 95%

e：More than 95%

＜ wear evaluation ＞

Using above-mentioned testing machine, in addition to load, temperature are set to following conditions, carry out and Test of Friction phase Same test.

[table 3]

	Wear test 1 (condition 3)	Wear test 2 (condition 4)
			Load	300N	400N
Temperature	80℃	120℃

The wear trace of the top test film after test is observed using microscope.To obtain in the wear test 1 of comparative example 1 The wear scar diameter for obtaining carrys out standardization for 100%, is evaluated according to following benchmark.The results are shown in table 4 below.

Value is less, represents that abrasion is fewer.The wear trace of a～c is substantially little, is judged as that improvement is big.The wear trace of d Though little, effect is little.E is equal with the wear test 1 of comparative example 1, is judged as not finding to improve.Be judged as the abrasion of f more than than Compared with the abrasion of the wear test 1 of example 1.In addition, in the test of condition 3 and 4, the evaluation of more than c is set to qualified evaluation.

a：Less than 50%

b：50% less than 70%

c：70% less than 85%

d：85% less than 95%

e：95% less than 105%

f：More than 105%

The composition and evaluation result of embodiment and the lubricant compositions of comparative example are shown in into table 4.

[table 4]

As shown in Table 4, in embodiment, under wide temperature range and loading condiction, excellent lubrication property is presented And wear resistance.On the other hand, it is known that, in a comparative example, fail to have both lubrication property and wear resistance.

Then, equably mix the grease (SHC Grease 460WT) and complex ester A of the manufacture of Mobil companies, obtain Obtained lubricant composition.Using with above-mentioned wear evaluation identical method, the lubricant composition is tested, is carried out It is following to evaluate.In addition, in evaluation, being set to 100% with the wear scar diameter obtained in the wear test 1 of comparative example G1 Standardization, is evaluated according to following benchmark.The results are shown in following tables.

Value is less, represents that abrasion is fewer.The wear trace of a～c is substantially little, is judged as that improvement is big.The wear trace of d Though little, effect is little.The wear test 1 of e and comparative example G1 is equal, is judged as not finding to improve.Be judged as the abrasion of f frequently compared with The abrasion of the wear test 1 of example G1 is big.In addition, in the test of condition 3 and 4, the evaluation of more than c is set to qualified evaluation.

a：Less than 50%

b：50% less than 70%

c：70% less than 85%

d：85% less than 95%

e：95% less than 105%

f：More than 105%

[table 5]

As shown in Table 5, in embodiment, show under wide temperature range and loading condiction excellent wear-resistant Property.Thus, the lubricant compositions of the present invention also have good lubrication property in lubricant composition.

Claims

1. a kind of lubricant compositions, which contains complex ester A, and complex ester A contains and is at least condensed by following material a1, b1 and c1 Polyester：

More than 3 yuan of polyhydric alcohol a1；

2 yuan of carboxylic acids, carbon number 18～22 the unsaturated fatty acids of the carbon number 36～44 containing at least 75 mass % Polymerization reaction mixture and by the polymerization reaction mixture hydrogenate obtained by least either mixture b1 in mixture；

The monohydric alcohol c1 represented with following formulas (1),

The addition of the hydroxyl mol numbers of the carboxylic acid mol numbers/c1 of the hydroxyl mol numbers/b1 of the a1 compares for 1/1.5～ 2.0/0.7～1.5,

The content of complex ester A is 0.1～5 mass % relative to the gross mass of the lubricant compositions,

Formula (1)：R-OH

2. lubricant compositions according to claim 1, wherein,

In the formula (1), branched alkyls of the R for the straight chained alkyl or carbon number 8～25 of carbon number 8～25.

3. lubricant compositions according to claim 1 and 2, wherein,

In the formula (1), branched alkyls of the R for the straight chained alkyl or carbon number 16～20 of carbon number 16～20.

4. lubricant compositions according to any one of claim 1 to 3, wherein,

In the formula (1), R is branched alkyl.

5. lubricant compositions according to any one of claim 1 to 4, wherein,

The content of complex ester A is 0.5～2 mass % relative to the gross mass of the lubricant compositions.

6. lubricant compositions according to any one of claim 1 to 5, wherein,

Hydroxyl mol numbers and the c1 by the a1 hydroxyl mol numbers amount to hydroxyl mol numbers be set to P, by the b1's In the case that carboxylic acid mol numbers are set to Q, the addition of P/Q is compared for 1/0.7～0.95.

7. lubricant compositions according to claim 1 to any one of, wherein,

The kinematic viscosity at 40 DEG C of complex ester A is 500～2000mm²/s。

8. lubricant compositions according to any one of claim 1 to 7, wherein,

Kinematic viscosity at 40 DEG C is 5～100mm²/s。

9. lubricant compositions according to any one of claim 1 to 8,

Which also contains medium,

Relative to the gross mass of the lubricant compositions, complex ester A containing 0.1～5 mass % and 70～99.9 matter The medium of amount %,

Relative to the gross mass of the lubricant compositions, containing 0～29.9 mass % except complex ester A and described Other compositions beyond medium.

10. lubricant compositions according to claim 9, wherein,

11. lubricant compositions according to claim 9 or 10, wherein,

The other compositions are the compound with least one in zinc, molybdenum, sulfur and phosphorus as constitution element.

12. lubricant compositions according to any one of claim 9 to 11, wherein,

The other compositions are organic molybdenum and at least one in organic zinc compound.

13. lubricant compositions according to any one of claim 1 to 12, which is used as grease lubricating oil, the demoulding Agent, internal combustion engine oil, intermetallic composite coating (cutting is used) oil, bearing oil, combustion engine fuel, vehicle startup machine oil, gear oil, vapour It is automobile-used working oil, ship and airborne vehicle lubricating oil, machinery oil, turbine oil, bearing oil, hydraulic oil, compressor oil, true Empty pump oil, refrigerating machine oil, Metalworking lubricant, lubricant for magnetic recording medium, micromachine with lubricator, artificial bone use Lubricant or ROLLING OIL.

14. a kind of manufacture method of lubricant compositions, which includes following operation：

Obtain the operation of complex ester A；And

The concentration for obtaining complex ester A is the operation of the lubricant compositions of 0.1～5 mass %,

The operation for obtaining complex ester A is with the hydroxyl mol numbers/b1 of the a1 at least by following material a1, b1, c1 The hydroxyl mol numbers of carboxylic acid mol numbers/c1 become the mode of 1/1.5～2.0/0.7～1.5 and mix and make its operation being condensed：

More than 3 yuan of polyhydric alcohol a1；

2 yuan of carboxylic acids, carbon number 18～22 the unsaturated fatty acids of the carbon number 36～44 containing at least 75 mass % Polymerization reaction mixture and by the polymerization reaction mixture hydrogenate obtained by least either mixture b1 in mixture； And

The monohydric alcohol c1 represented with following formulas (1),

Formula (1)：R-OH