Title of Invention

UREA GREASE COMPOSITION

Abstract Abstract UREA GREASE COMPOSITION The present invention aims to offer a urea grease composition which excels in noise performance, has long life at high temperatures and, further, also provides the basic performance of greases such as shear stability and heat resistance, as well as appropriate oil separation properties. The present invention provides a urea grease composition comprising; a diurea compound as shown by the General Formula (A) below; R11NHC0NHR12NHC0NHR13... (A), (where R11 and R13 are groups selected from the group consisting of hydrocarbon groups having from 6 to 20 carbons, at least one of R11 and R13is a dodecyl group and R'^ is a diphenylme thane group); and a diurea compound as shown by the General Formula (B) below: R2'NHCONHR22NHCONHR23.... (B), (where R21 and R23 are groups selected from the group consisting of hydrocarbon groups having from 6 to 20 carbons, at least one of R21 and R23 is an oleyl group, and R'22 is a diphenylmethane group).
Full Text

?-_::^ -^i^yi.:r'*->:j _ ^ — ^_^
This invention relates to novel urea grease compositions which excel in noise perfcrrrLanoe, have = long life at high temperatures and, further, also provide the basic performance of grease such as shear stability and heat resistance, as well as appropriate oil separation properties.
The foremost characteristic of urea greases using = urea compound as a thickener lies in their heat resistance and oxidative stability. Since greases which have a lubricating life at high temperatures several to ten or more times longer than the lubricating life of ordinary lithium greases have been developed, urea greases are now widely used today in many applications.
However, virtually all urea greases on the market have a poor noise performance and there are often situations where they cannot be used in many machines and apparatus where silence is nowadays required. The present situation is that the range of applications has become restricted.
electrical appliances, in order to ensure a comfortable and silent living environment, noise countermeasures are indispensable in equipment such as cleaners, washing machines, refrigerator compressors, air-conditioner compressors and fans, electric fans and fan heaters, dryers, exhaust fans and air purifiers. Low-noise greases which have superior noise performance are actively used in the bearing greases used in the rotating parts of these appliances.

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because cr r,-e ir.crBases Z5r~^razi^r~ =

"ignsT

rjtpu-s v.'hich, in ad.d.i.r-^c- ~o noise D3z:orrr.ar^oe.

are required by these domestic appliances, long life at the higher temperatures has become a very strong requirement, depending on the type of appliance. Greases which use urea compounds having superior noise performance as a thickener and which have long life are extremely effective and the development of better products is anticipated. Naturally, the basic performance of bearing grease such as shear stability (leakage resistance), stability at high temperatures and appropriate oil separation properties will be indispensable.
In the automobile industry, too, the requirement for silence has become stronger year by year. In particular, there has been thorough research into noise and its countermeasufes in high-quality saloon cars. Requirements for noise reduction in individual parts thereof are extrem.ely severe. Here, too, the requirement for high-quality greases with excellent noise performance for use in bearings has become stronger each year. Particularly m the case of bearings used in engine parts, long life at higher temperatures has become a very strong requirement. Greases which use urea compounds having superior noise performance as a thickener and which have long life are extremely effective and the development of better products is anticipated. Naturally, as with the above-mentioned greases for domestic electrical appliances, the basic performance of the bearing greases such as shear stability {leakage resistance), stability at high temperatures and appropriate oil separation properties will be indispensable.

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Rerer'sncss in ths "c^icr ^rt to '^^i^- ^zr^ — S'^s r^^^t'"'^ uO iiC j_3B T^roXjSr" 1^5 2_nc_"uci^ ^^Z.^T-^ _.ocmr;Sr4."os _^, -^ anci 3 due to the present applicani:.
Japanese Laid-open Pac&r.t 1-125655 -'1565; describes a thickener comnrising a mixture cf the diurea, corrpounds (i) and (ii) below as shown by the fcilowing general forrnulas:
ii) R"NHCONHR"NHCONHR'^ (ii) R^'^NHCONHR^VHCONHR-*
(where R"' is a diphenylmethane group, H."" and R"^ are each straight-chain or branched saturated alkyl groups having 8 carbons, R^^ is a tolylene group or a bitolylene group, and R^* and R^^ are each alkyl-substituted aromatic groups or halogen-substituted aromatic groups).
Japanese Laid-open Patent 2-77494 (1990) describes a thickener comprising a mixture of the above-mentioned diurea compounds (i} and (i1) where, in the above-mentioned general formulas (i) and (ii) , R'^^ is a bitolylene group, R^^ and R^^ each represent a straight-chain or branched saturated alkyl groups or unsaturated alkyl groups having 18 carbons, R^^ is a diphenylmethane group, and R^'* and R^^ are each straight-chain or branched satLiiatej alkyl grcups na"ing ?- c^^rbcns.
Japanese Laid-open Patent 5-17080 (1994) discloses a thickener comprising a mixture of the diurea compo".inds (i) and (ii) where, in the above-mentioned general formulas (i) and (ii), H*^ represents a tolylene group, R^'" and R^^ are each straight-chain or branched saturated alkyl groups or unsaturated alkyl groups having from 16 to 18 carbons, R^^ is a diphenylmethane group, and R^* and R^* are each straight-chain or branched saturated alkyl groups having 8 carbons.

I =^i^="=,ai=
describes a crease cc~positicri where, incs; thickener with a base oil containing an aikyldiphsnyl ether oil as an essential constituent, is a diurea compound where, in the above-mentioned general formula (i) , R ^ is an aromatic hydrocarbon group having from 6 to 15 carbons, R^'^ and R^^ are straight-chain alkyl groups having from S to 28 carbons, and the proportion occupied by said alkyl groups having 3 carbons in R' and R^^ is from 60 to 100% by mol.
Japanese Laid-open Patent 2-804S3 (19S0) (Page S, Table 2) describes a composition for use in tapered roller bearings where from 0.5 to 5% by weight of oxidation-modified polyolefin and/or acid-modified polyolefin is added to and mixed with a urea grease. Table 2 there shows urea thickeners using octylamine having 8 carbons, stearylamine (octadecylamine) having 18 carbons and MDI (diphenylmethane-4,4'-diisocyana-e) as raw materials, and it is demonstrated that the thickenets exhibited excellent effects such as mechanical stability, wet shear stability and pressure transferability.
Japanese Laid-open Patent 3-2-±353c 11391} describes a diurea compound where, in the above-described general formula (ij, R^^ is a 3,3 '-dimethyl-4,4'-biphenylene group and H^^ and R^'^ are a mixture of an alkyl group having from 3 to 18 carbons and an oleyl group. However, there have been drawbacks with this technique in that penetration has been poor and it has not been possible to obtain greases having a penetration of around 250 unless large amounts of thickener are employed, and the degree of oil separation under high temperatures hB.s he.en large.


^apsnese Laid-open ? = -ent -S-1S5€5^' ,'15 = 2; describes s^ LnTcrcvEo diu.rea'-""v'^e crr'^ass ■■ "^ '*f~z.'^'^ ~"" e diur™^ -'.~^e grease is made tc contain one or two cr more of an alkenyl succinimide, a tr.enal sale of an alkylbenzene sulphonic acid and a metal salii of pecrcleun: sulphcr-ic acid. It mentions that for the diurea-type grease it is possible to use diisocyanates and monoamines and that, for the monoamines, aliphatic amines such as stearylamine, and oleylamine and aromatic am.ines such as cyclohexylamine can t^'picslly be used. It discloses ~hat this grease has extremely good noise properties in comparison with greases of the prior art.
Further, examples of investigating production methods in order to improve the noise properties of urea greases can be found. For example, Japanese Laid-open Patent 2-4895 (1990) describes a production method for a urea grease in which noise properties have been improved by adding an isocyanate and an amine to a base oil, effecting a reaction at a temperature of from 60 to 120'C, performing a dispersion treatment on the resultant mixture of urea compound and base oil by using a kneading apparatus, and then heating up to between 150 and 130°C at a rate of temperature rise of from 0.5 Co 2°C/min.
Japanese Laid-open Patent 3-190996 (1991) describes a production method for a grease with excellent noise properties in which a base oil in which an isocyanate has been dissolved or dispersed and a base oil in which an amine has been dissolved or dispersed are pressurised m a reaction vessel, allowing them to react by impinging and mixing with each other or allowing them to react by increasing the pressure and introducing them to rotating mixing paddles.

coiTiprised of a first orccess in which a T'ixturs -f fro~ 2 to 30% by weight of a urea compound where, in the above-mentioned general formula (i) , R^' and R'^ are sarurared alkyl groups having from 8 to 13 carbons ar,d R'^ is a tolylene group, a diphenylmechane grsup or a dimethyl biphenylene group, and from 98 to 701 by weight cf a base oil are heated to between 170 and 230'C to cause tihe urea compound to be completely dissolved in the base oil, and a second process in which, after the first process, cooling is effected at a rate of at least 5°C/min. In none of the above-mentioned Patient Documents 1 to 10 is there any description which specifically suggests the urea grease composition of this invention.
As described in. the above-mentioned patent documents, there are many examples where, for the isocyanate raw material, tolylene diisocyanate (TDI) or 3,3'-dimethyl-4,4'-biphenylene diisocyanate (TGDI) are used in order fco offer urea greases with excellent noise properties. Also, examples are given for production methods in which two or more different kinds of grease are mixed after a reaction process using a kneading apparatus or a high-pressure kettle so that there is no aggregation of the urea compound, and then hea^iing and dissolving the greases.
As the quantities of urea greases produced become greater and the demand for greases with superior noise properties intensifies in the market-place, cleaner working environments for production of ths greases and betner noise properties in the final commercial product are being sought.

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as a raw ".aCerial, in ccrplex rr^an'-fac^'-iring procedures cannot compete in the market-place.
And as regards grease manufacture, -^.oo, because of the increase in the quantities manufactured thereof, in is necessary to be even more careful in handling the TDI raw material [which is classified as a Class 2 Specified Chemical Substance under the Industrial Safety and Health Law), and in order to improve noise properties qualitatively, it is necessary to give consideration to reinforcing apparatus and extending manufacturing process times.
This invention provides a urea grease composition which excels in noise performance, has long life at high temperatures and, further, also provides the basic performance of grease such as shear stability and heat resistance, as well as appropriate oil separation properties.
Having taken careful cognisance of the problems and requirements in the marketplace, and by dint of thorough investigation and analysis, as well as intense research, of the scructural components cf urea thicksr.ing sgents in urea grease compositions, the inventors.have discovered that by limiting themselves to urea grease compositions incorporating certain specified urea thickening agents within the structural components of the urea, the result is an excellent urea grease composition which excels in noise performance, has long life at high temperatures and, further, also provides the basic performance of grease such as shear stability and heat resistance, as well as appropriate oil separation properties. They have thus arrived at this invention.

"n czrsr vcrds, zh^s ir.vszzici: prcviias = -rea rrease ccmposi-icr. cczz:zi.s-r.g-.
a diurea compound as showT; by the General ?crn-ul = (A) belc-w:
R^'NHCONKR^^NKCONHR^^ .... (A)
(where R^^ and R^^ are groups selected from the group consisting of hydrocarbon groups having from S to 20 carbons, at least one of R~~ and R'"^ is a docecyi group and R^^ is a diphenylmethane group) ; and. a diurea compound as shown by the General Formula (B) below:
R^'NHCONHR^^KHCONHR" .... (B) ,
(where R^' and R^^ are groups selected from the group consisting of hydrocarbon groups having from. 6 to 20 carbons, at least one of R^^ and R^^ is an oleyl group, and R^^ is a diphenylmethane group}.
Preferably the proportion occupied by );he dodecyl group in R''^ and R'^^ in the above-mentioned General ?ormula (A) is from 2 to 70% by mol and/or the proportion occupied by the oleyi group's) in F,'" and 5.""" m zne above-mennioned General Formula (3) is from 5 to 70% by mol.
Further it is preferred when a hydrocarbon group having from 6 to 2 0 carbons other than the dodecyl group (s) in R^' and R'^ in the above-mentioned General Formula (A) and/or a hydrocarbon group having from 6 to 20 carbons other than the oleyl group (s) in R^^ and R'^ in the above-mentioned General Formula (B) is an octyl group,



n-.enticned General rorrjjia (A) is irz-m

- ^ 5 DV

the proportion occupied by the cieyi group (s) in .-L'" and R'"^ in the above-mentioned General Fcrrnuls (3) is _rorQ s to 55% by mol, and the proportion occupied by the ocuyl group(s) in R^^, R-^ R^\ and R" is from IC to 90% by mol.
In a further aspect this invention provides a urea grease composition comprising:
diurea compounds as shovjn by the general fonrLulas:
(a) R^NKCONHR^NHCOi-IHR^
and
(b) R^NHCONHR^NHCONKR'
and, further, a diurea compound or compounds as shown by the general formulas:
(d) R^NHCONHR-NHCONHR^ and/or
(e) R'NHCONHR^NHCONHR(where R^ is a diphenyl methane group, R* is a hydrocarbon group having an octyl group as its main constituent, R^ is a hydrocarbon group having from 14 to 20 carbons and containing at least 20% by mol of oleyl group, and R* is a hydrocarbon group having a dodecyl group as its main constituent).
In an even further aspect this invention provides a urea grease composition comprising:

(b; R^NHCOl-THR^KTHCOl-THR" and
{C) R^NKCON~HR^NHCONHR^
and, further, a diurea coiTpound or compounds as shown by the general Eormulas;
{d) R^NHCOMKR VHCONHR' and/or
(e) R^NHCOKHR^NHCONHR' ,
(where R^ is a diphenyl methane group, R"^ is a hydrocarbon group having an octyl group as its main Constituent, R^ is a hydrocarbon group having from 14 to 20 carbons and containing at least 20% by mol of oleyl group, and R* is a hydrocarbon group having a dodecyl group as its main constituent).
Further this invention provides a urea grease composition comprising;
(i) a diurea compound as shown by the above-mentioned general formula (a); and
(ii) diurea compounds being diurea compounds Selected from the group comprising
CD the above-mentioned general formulas (b), (cj, (d) and (e)
(2) the above-mentioned general formulas (b), (c; and (d)
(3) the above-mentioned general formulas (b), (c) and (e),

the totality of diurea corr.pounds is irc:r, 20 to 3C% by moi .
Also, this invention provides a urea grease composition comprising:
a diurea compound as shown by the general forTiula:
(c) -R~NHC0NHR^NHC0NHR'
and, further, a diurea compound or compounds as shown by the general formulas;
(d) R-NHCONHR^NHCONHR' and/or
(e) R^NHCONHR^NHCONHR',
(where R^ is a diphenyl methane group, R^ is a hydrocarbon group having an octyl group as its main constituent, R" is a hydrocarbon group having from 14 to 2 0 carbons and containing at least 20% by mol of oleyl group, and R' is a hydrocarbon group having a dodecyl group as its main constituent).
In an even further aspect this invention provides a urea grease composition comprising:
diurea compounds as shown by the general formulas:
(c) R-NHCOKHR^NHCONKR^ and
(b) R^NHCOKHR^NHCONKR^
and, furz;her, a diurea compound or compounds as shown by the general formulas:

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: d; ?.A'?:ccNHR^>i:-:::c;.-:-:?/
and/or
{e) R^NKC0NHFr;j:~lC0:>n4R'-,
(where R^ is a diphenyl methane group, R^ is e hydrocarbon group having an octyl group as its main constituent, R^ is a hydrocarbon group Yiavinq from 14 to 20 carbons and containing st least 20% by mol of olsyl group, and R' is a hydrocarbon group having a dodscyl group as its main constituient) .
Also, this invention provides a urea grease Composition comprising:
(i) a diurea compound as shown by the above-mentioned general formula (c); and
(ii) diurea compounds being diurea com^pounds selected from the group comprising
(1) the above-mentioned general form.ulas (b) , (d) and (e)
(2) the above-mentioned general formulas (b) and (d)
(3) the above-mentioned general formulas (b) and fe) and the m-olar ratio of the diurea compound as shov,Ti by the above-raentioned general fcrmuia ,c> m relation "o the totality of diurea compounds is from 20 to 8C% by mol.
Corrpounds as shown by the above-mentioned General formula (A) may normally be prepared in accordance wiiih the reaction ecTiaCion beiowt [Formula 1]
OCN-R'^-NCO+R"NH3+R'^NH2 ->
R^^NHCONHR'-^NHCONHR^^ + R^^NHCONHR^^NHCONHR-^ + R^^NHCONHR^^NHCOirHR'^

^_ :^ c:. J
Also, oompcunds as shcv.Ti by the abcve-ir.enticned General Formula (B) may be prepared ir. sirriiiar fashion to the compounds as shown by General Formula (A). [Formula 2]
0CN-R^--NC0+R^^NH2+R"NH2 ^
R^-NHCONKR^^NHCONHR^^ ^ R^NHCOIJHR-'^NKCONHR^- -R^^NHCONHR^^NHCONHR"
(where R^\ R^^ and R" ^re as described before) .
The compounds corresponding to the above-mentioned OCN-R^^-NCO and OCN-R^^-NCO are both diphenylmethane-d , 4 '-diisocyanate.
In order to introduce R^^ and R'^ in compounds of the aforementioned General Formula (A) , R^^NH^ and R'^'^^NHs are used, and in order to introduce R^'^ and R^^ in compounds of the aforementioned General Forrr.ula (B) , R^'NH; and R^NHa are used.
The invention is explained in detail below in relation to compounds of General Formulas (A) and (g) and general formulas (a) to (e) .
The dodecyl group and in particular n-dodecyl group in either of the aforementioned R^" and R^' imparts heat resistance to the urea grease and, by its presence, can extend the life of the urea grease at high temperatures. However, if both R'^ and R^^ are dodecyl groups, the noise performance is poor even though the heat resistance is good. Therefore, if either one of R^^ and R^^ is mad^ a dodecyl group, the other may be a hydrocarbon group of from 6 to 20 carbons, and preferably an oleyl group or an octyl group. Specific examples of raw materials which

supply d3de~/I groups preferably include straigr.t-chain
a mixture of a dodecylar'ine and clsyla-iine or oo-yla.-?.ina with diphenyimethane-4,4'-diisocyanate has sxcellsnt thermal stability and grease corrposicions using this are not apt to change at high temperatures, so that the effect on extending life is extremely large. The dodecyl group may occupy from 2 to 70% by mol, and preferably from 4 to 50% by mol, in respect of che tc^ral molar numijer of P/" and R'^ in the aforementioned General Formula (A).
At least one of the aforementioned R'^ and R'^ is an oleyl group and in particular an n-oleyl group. The presence of the oleyl group not only imparts excellent noise performance to the urea grease composition, but the adsorption properties of the urea grease composition in respect of the metal surfaces which form the sliding portions of machine parts become better, and so the lubricating properties are further improved. The oleyl group may occupy from 5 to 70% by mol, and preferably from 8 to 55% by mol, in R^'" and R^^ in the aforementioned General Form.ula (B) .
In this invention it is indispensable 'hat at least an oleyl group and a dodecyl group, particularly an n-dodecyl group, are incorporated in the diurea grease con^Josition, but preferably an octyl group, particularly an n-octyl group, is also incorporated.
If an oleyl group and a dodecyl group are added and an octyl group, particularly an n-octyl group, is further incorporated, it is appropriate if the proportion occupied by the dodecyl group in R^^ and R^^ in the aforementioned General Formula (A) is from 3 to 55% by mol, and further the proportion occupied by the olsyl

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occupied by the cctyi grcups in ?-"", R"^, R^" and ?.-^ is from 10 to 90% by raol.
Thickening agents encompassed by General Forr.ulas (A) and (B) which are characteristic of this invention may be used in the proportion such that they occupy from 20 to 100% by mol of the cotai thickening agent.
The thickening agents coTiprising diurea compounds as shown by the aforementioned General Formulas (A), ;B) and (a) to [e) may preferably be incorporated in the amount of from 2 to 30% by weight relative to the mineral oils or synthetic oils or mixtures thereof which form the lubricating oil. If the diurea compound'which is the thickening agent is less than 2% by weight relative to the mineral oils or synthetic oils or mixtures thereof which form the lubricating oil, the thickening effect becomes too small and the grease may become too soft, with the risk, for example, of leakage. If it exceeds 30% by weight, the grease may become too hard and its flow resistance increase, so that sufficient lubricating effect is not obtained in that the friction torque increases and ability to penetrate decreases. Also, -h^ cost increases.
For the lubricating base oils in iihis invention, those generally used as lubricating oils and base oils for greases may be used. They are not specially limited, but as examples mention may be made of mineral oils and/or synthetic oils and plant oils. Specific examples of synthetic oils are GTL-derived base oils (produced by the Fischer-Tropsch process), polyolefins such as a-olefin oligomers and polybutenes, polyalkylene glycols such as polyethylene glycol and polypropylene glycol.

trimsthylolpropane ester and pen-aer-ythritol ester perfluoroalkyl ethers, silicone oils and pol'^TDhenvi ethers, and as typical exarrples of plant oils men-ion -ay be made of castor oil and rapeseed oil. Exarr-ples may be given of using these base oils singly or in mixtures, but they do not limit the invention.
Also, it is possible further to add to the composition of the invencicr; additives such as anti¬oxidants and rust preventatives, oiliness agents and extreme-pressure additives, as well as anti-wear agents and solid lubricants or metal deactivators and polymers. For example, anti-oxidants include 2,6-di-tertiary-butyl-4-methylphenol, 2,5-di-tertiary-butyl-para-cresol, P,P'-dioctyldiphenylamine, N-phenyl-a-naphthylamine and phenothiazines. Rust preventatives include paraffin oxide, metal salts of carboxylic acids, metal salts of sulphonic acids, carboxylic acid esters, sulphonic acid esters, salicylic acid esters, succinic acid esters, Eorbitan esters and various amine salts. Oiliness agents and extreme-pressure addizives as well as anti-vjear agents include sulphurised zmc diai-<.yi aitniop.iosphates sulphurised zinc diallyl dithiophosphates dialkyl dithiocarbamates molybdenum dialjcyl organic complexes olefins triphenylphosphates> triphenylphosphorothionates, tricreaylphosphates, other phosphate esters and sulphurised fats and oils. Solid

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(DOl--='---"^--
j.yt£Crai^uorcrethylene) , tungsren disulohice a.r.c. graphite fluoride. Ketal deactivators in-lude N,\"'-di3alicylidene-l,2-Qiaminopropane, benzotriazole, benzoinidazole, benzothiazole and chiadiazole. As examples of polymers, mention may be made of polybutenes, polyisobutenes, polyisobutylenes, polyisoprenes and polymethacrylates.
By means of this invention it is possible to provide a novel urea grease composition which excels in noiae perforrrance, has long high-temperature life wich high dropping point, and, further, also provides che basic performance of greases such as shear stability and heat resistance, as well as appropriate oil separation properties. Examples
The invention is explained in detail below by means of examples and comparative examples, but nhe invention is in now way limited by these examples.
The abbreviations relating to the raw material constituents of the thickeners and the base oils used in the examples and comparative examples in Tables 1 to 5 below are as described next.
Isocyanate A is diphenylmethane-4,4'-diisocyanate, the molecular weight being 250.26.
Isocyanate B is tolylene diisocyanate, the molecular weight being 174.16.
For the amine raw materials:
Amine A is a straight-chain primary amine of average molecular weight 128.7 where the main constituent (at least 90%) is a saturated alkyl group of S carbons (industrial octylamine);

{industrial oleylamine) ,- and
Amine C is a straight-chain crirrarv amine cf average molecular weight 184.6 where the main constituent {ac least 90%) is a saturated alkyl group of 12 carbons (industrial dodecylamine).
Also, the kinetic viscosity at 1GG=C of the rr.ineral oil s'ncMn in the ex&rvples and cory.parative examples is 10,12 mrti'/s, while synthetic oil A refers no a pclv-a-olefin oil, the kinetic viscosity being 12,70 mm^/s at 100°C and synthetic oil B refers to an alkyldiphenyl ether oil, the kinetic viscosity being 12.69 mm^/s at lOCC.
a, b, c, d and e in the thickener mol% columns given in Tables 1 to 4 each denote urea compounds that can be expressed by:
(a)- R-NHCONHR^NHCONHR^
(hi R^KHCONHR^NHCONHP.^
(c! R-^:HCO^JHRn^'HCONKR^
(d) R^NHCOiraR^NHCONHE'
(e) R^NHCONHR^NHCONHR'
(where R^ is a diphenylmethane group, R^ is a hydrocarbon group of from 6 to 10 carbons having an octyl group as its main constituent, R^ is a hydrocarbon group having from 14 to 20 carbons and containing at least 20% by mol of oleyl group, and R^ is a hydrocarbon group having an n-dodecyl group as its main constituent).
Also, a and b in the thickener mol% column for the comparative examples given in Table 5 denote the above-

- - O -
the exa~.ples given in Tables 1 "o 4 sach ieno:;e urea compounds that can be expressed by:
it) R^iraCDlffiR^KHCONHR'
(g > R^NKCONHR^NHCOl-THR^
(h) R^NHCONHR^NHCONHR^
(i) R'NHCONHR^^CONHR'
{j ) R-NHCONHR^NHCONHR*
(where R^ is a tolylene group, R^ is a hydrocarbon group of from S to 10 carbons having an oc^yl group as its main constituent, R^ is a hydrocarbon group having from 14 LO 20 carbons and containing at least 20% by mol of oleyl group, and R* is a hydrocarbon group having an n-dodecyl group as its main constituent)-
Tests on the properties of the examples and comparative examples were carried out by the following methods -
1. Penetration: JIS K2220
2. Dropping point: JIS K2220
3. Oil separation: JIS K22ZC Method 3, conditions being lOC^C and 24 hours.
4. Noise test: Measured by the method of Japanese Patent 53-2357 (1978) .
5. Shell roll: ASTM D1631
6. Bearing life test: ASTM D3335
Greases of this invention were obtained by
synthesising urea compounds, the thickening agents, in lubricating base oil using the proportions shown in Tables 1 and 2, and by blending in additives.

- -JO -
ccr.stinuent A (diphenylmethane-4 , 4 ' -ciiisccyanate; were fed into a closed prctor-.-pe grease kercle apparatus, =nd ^his was heated, while agitating, tc cC Z. A-iir.e .-. (industrial octylamine) which was constituent 31 and which had been mixed in lubricating base oil was added and reacted with constituent A. Urea compound 'a' as sho'rfn by the formula
(occyl) -NKCONH- (diphenylmethane) -.*JHCONH- (cctyi; was obtained. The contents rose to apprcxinateiy SCC through the heat of the reaction. That temperature was maintained for 10 minutes and then amine B (industrial oleylamine) which was constituent B2 and which had been mixed and dissolved in lubricating base oil in advance was fed into the kettle and reacted with the remainder of isocyanate A which was constituent A. Urea compound 'b' as shown by the formula
(oleyl)-NHCONK-(diphenylmethane)-NHCONH-(oleyl) was obtained. After agitating for 5 minutes, amine A (industrial octylamine) and amine B (industrial oleylamine) which were constituent 33 and which had been nixed and dissolved in lubiicaciug base oi.^ ii"_ a^iv^r-ce were fed into the kettle and reacted with the remaining isocyanate A which was constituent A. Urea compound 'c' as shown by the formula
(octyi)-NHCONH'(diphenylmethane)-NHCONH-(oleyl) was obtained. Then, after agitating for 5 minutes, amine A (industrial octylamine) and amine C (industrial dodecylamine) which were constituent B4 and which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle and reacted with the

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(octyi; -NHCOKTH- Jdiphenyimeth^ne) -i^-ICON--:- ■cocecyl) was obtained. After again agitating for 5 minutes, amine B (industrial oleylamine) and amine C Cindustrial dodecylamine) which were constituent B5 and which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle and reacted with the remainder of isocyanate A which was constituent A. Urea compound 'e' as shown by the formula
(oleyl)-NHCONH-(diphenylmethane)-NECOKH-(dodecyl) was obtained. Then after quickly restarting heating, the temperature v;as raised to 170°C and that temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 3 0 minutes, cooling began, and at 125°C during the cooling process, 1.0% by mass, as an extraneous proportion, of octyldi phenyl amine, which is an ant i-oxidant, v;as added to the grease. After allowing further cooling to 30°c, the grease was treated in a chree-roll mill to give the grease of Example 1. Example 2
Lubricating base oil and isocyanate A which was constituent A (diphenylmethane-4,4'-diisocyanate} w^re fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to SO°C. Amine A (industrial octylamine) which was constituent Bl and which had been mixed in lubricating base oil was added and reacted with constituent A. Urea compound 'a' as shovn by the formula
(octyl)-NHCONH-(diphenylmethane)-NHCONH-(octyl) was obtained. The contents rose to approximately SC^c through the heat of the reaction. That temperature was


was fed into chs kettle and reacted wizh the re-r.ainder of isocyanate A which was constituent A. Urea coniDound 'b' as shown fay the formula
(oleyl)-NHCONH-(diphenylmethane)-NHCONH-(oleyl) was obtained. After agitating for 5 minutes, amine A (indusrrial cctylaraine) and amine B I'industrial oleylamine) which were constituent 33 and v/hich had been mixed and dissolved in lubricating base oil in advance were fed into the kettle and reacted with the remaining isocyanace A which was constituent A, Urea compound 'C as shown by the formula
(octyl)-NHCONH-(diphenylmethane)-NHCONH-(oleyl) was obtained. Then, after agitating for 3 minutes, amine A (industrial octylamine) and amine C (industrial dodecylamine) which were constituent B4 and which had been mixed and dissolved in lubricating base oil in advance were■fed into the kettle and reacted with the remaining isocyanate A which was constituent A. Urea compound 'd' as shown by the formula
(octyl)-NHCONH-Idiphenylmechane)-KHCCNH-idodecylj was obtained. Then after quickly restarting heating, the temperature was raised to ITO-'C and that temperature was maintained for approximately 3 0 minuces to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125°C during the cooling process, 1.0% by mass, as an extraneous proportion, of octyldiphenylamine, which is an anti-oxidant, was added to the grease. After allowing further cooling to 30°C, the grease was treated in a three-roll mill to give the grease of Example 2.

- 23 -

:-=s= ci_ =r:n L=cc--=r_='= .-. -A.-.ich va =
constifjent A (diphenylmethane-4 , 4 ' -dii30cyar_5.te) were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to SO = C. Ainine A (industrial octylamine) which was constituent 31 and which had been mixed in lubricating base oil v;as added and reacted with constituent A. Urea compound 'a' as shown by the formula
(octyl)-NHCONH-(diphenylmethane)-NHCOira-(octyl) was obtained. The contents rose to approximately 80°C through the heat of the reaction. That temperature vjas maintained for 10 minutes and then amine B [industrial oleylamine) which was constituent B2 and which had been mixed and dissolved in lubricating base oil in advance was fed into the kettle and reacted with the remainder of isocyanate A which was constituent A. Urea compound 'b' as shown by the formula
(oleyl) -NHCONH- (diphenylmethane) -I-3HC0NH- (oleyl) was obtained. After agitating for 5 minutes, amine A (industrial octylamine) and amine B (industrial oleylamine) which were constituent B3 and which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle and reacted with the remaining isocyanate A which was constituent .^. Urea compo-und 'c' as shown by the formula
(octyl)-NHCONH-(diphenylmethane)-NHCONH-(oleyl) was obtained. Then, after agitating for 5 minutes^ amine B (industrial oleylamine) and amine C (Industrial dodecylamine) which were constituent B5 and vjhich had been mixed and dissolved in lubricating base oil in advance were fed into the kettle and reacted with the

- -iLh. -
r=_.a.iruin3 isocyanace A which was c^nstii-uen" A. Vrea
was obtained. Then after quickly rescartir.c: heading, ^he temperature was raised to 170°C and that temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125°c during the cooling process, 1.0% by T7,ass, as an extraneous prcpomicn, of octyldiphenylamine, which is an anti-oxidan-, was added to the grease. After allowing further cooling to aO°C, the grease was treated in a three-roll mill to give the grease of Example 3. Example 4
Lubricating base oil and isocyanate A which was constituent A (diphenylmerhane-4,4'-diisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heating, while agitating, to 60°C. Amine A (industrial octylamine) which was constituent Bl and which had been mixed in lubricating base oil was added and reacted with constituent A.. Urea compound 'a' as shown by the forn-iula
(octyl)-NHCONH-(diphenylmethane)-NHCONH-(octyi) was obtained. The contents rose to approximately SCC through the heat of the reaction. That temperature was maintained for 10 minutes and then amine B (industrial cleylairiine) which was constituent B2 and which had been mixed and dissolved in lubricating base oil in advance was fed into the kettle and reacted with the remainder of isocyanate A which was constituent A. Urea compound 'b' as shown by the formula

- 25 -
(industrial octylsmine; and amine C (industrial dodecylamine) which were constitueni: B4 and which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle and reacted wirh the remaining isocyanate A which was constituent A. Urea compound 'd' as shown by the formula
(occyl)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl) was obtained. After again agitating for 5 minutes, amine B (industrial oleylamine) and amine C (industrial dodecylamine) which were constituent 35 and v-hich had been mixed and dissolved in lubricating base oil in advance were fed into the kettle and reacted with the remaining isocyanate A which was constituent A. Urea compound 'e' as shown by the formula
(oleyl)-NHCONH-(diphenylraethane)-NHCONH-(dodecyl) was obtained. Then after quickly restarting heating, the temperature was raised to 170°C and that temperature was maintained for approximately 3 0 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125°C during the cooling process, 1,0% by mass, as an extraneous proportion, of octyldiphenylamine, which is an anti-oxidant, was added to the grease. After allowing further cooling no SO=C, the grease was treated in a three-roll mill to give the grease of Example 4. Example 5
Lubricating base oil and isocyanate A which was constituent A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to SO°C. Amine A (industrial octylamine) which was constituent Bl and

- ^c -wr.i::h had been -ixed in lubricating base cil was added
(octyl) -NKCOfffl- (diphenylmethane) -KTiCOirH- (ocryl) was obtained. The contents rose to approximately 30=c through the heat of the reaction. That temperature was maintained for 10 minutes and then amine B (industrial oleylamine) which was constituent B2 and which had been mixed and dissolved in lubricating base oil in advance was fed inside the kettle and reacted with the remainder of isocyanate A which was constituent A. Urea compound 'b' as shown by the formula
(oleyl)-NHCONH-(diphenylmethane)-NHCONH-(oleyl) was obtained. Then, after agitating for 5 minutes, amine A (industrial octylamine) and aniine C (industrial dodecylamine) which were constituent B4 and which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle and reacted with the remaining isocyanate A which was constituent A. Urea compound 'd' as shown by the formula
loc^yl)-NHCONH-(diphenylmethane)-NHCONH-(dcdscyl) was obtained. Then after quickly restarting heating, the temperature was raised to 170=C and that temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125°C during the cooling process, 1.3% by mass, as an extraneous proportion, of octyldiohenylamine, which is an anti-oxidant, was added to the grease. After allowing further cooling to 8Q=>C, the grease was treated in a three-roll mill to give the grease of Example 5.

- 27 -
-l-obricatmg base oil and isocyanate A which was constituent A (diphenylTnethane-4 , 4 '-diisocyaria-e) were fed into a closed prototype grease kentle acoaratus, and this was hea-ed, while agitating^ to SO^C. AT^ine A (industrial octylamine) which was constituent Bl and which had been mixed in lubricating base oil was added and reacted winh constituent A. Urea cornpound 'a' as shown by the formula
(octyl)-NHCONH-(diphenylmethane)-NKCONH-(octyl) was obtained. The contents rose co approximately 30=C through the heat of the reaction. Thai: temperature was maintained for 10 minutes and then amine B (industrial oleylamine) which was constituent B2 and which had been mixed and dissolved in lubricating base oil in advance was fed inside the kettle and reacted with the remainder of isocyanate A which was constituent A. Urea compound 'b' as shown by the formula
(oleyl)-NHCOKH-(diphenylmethane)-NHCONH- loleyl) was obtained. Then, after agitating for 5 minutes, amine B (industrial oleylamine) and amine C (industrial CQdecylar:7lr.e,' which had bssn rrSx^d and dissolved in lubricating base oil in advance were fed into the keiitle and reacted with the remainder of isocyanate A which was constituent A. LTrea compound 'e' as shown by the formula
(oleyl)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl! was obtained. Then after quickly restarting heating, the temperature was raised to 170^0 and that temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125°C during the cooling process, 1.0% by mass, as an extraneous proportion, of

:a -
^=-y-diph=n.yla:r.ins, which is an ar.ci -cxid=n- , was aided
the grease •. Lubricating base oil and isocyanate A which was Constituent A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heated, vjhile agitating, to 60 = C. Arp.ine A (industrial cctylamine) which was constituent Bi and which had been mixed in lubricating base oil was added and reacted with constituent A. Urea compound 'a' as shown by the formula
(octyl)-NHCONH-(diphenylmethane)-NHCONH-(octyl) was obtained. The contents rose to approximately 80°C through the heat of the reaction. That tempe:!:ature was maintained for 10 minutes and then amine B (industrial oleylamine) which was constituent B2 and which had been mixed and dissolved in lubricating base oil in advance was fed into the kettle and reacted with the remainder of isocyanate A which was constitueni: A. Urea compound 'b' as shown by the formula
(oleyl! -NHCONK- (diphenylmeiihanej -Kl-CONH- voleylj was obtained. Then, after.agitating for 5 minutes, amine A {industrial octylamine) and amine C {industrial dodecylamine) which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle and reacted with the remaining isocyanate A which was constituent A. Urea compound 'd' as shown by the formula
(octyl)'NHCONH-(diphenylmethane)-NHCONH-(dodecyl) was obtained. Then after quickly restarting heating, the temperature was raised to llCC and that temperature was maintained for approximately 3 0 minutes to complete the

_ oo .

g -.nc .crTLoerature icr
reacticn. After rr^intainirj


process, 1.0% by mass, as an extraneous proportion, of octyldiphenylamine, which is an anti-oxidan^, was ad~ed to the grease. After allowing further cooling to SO°C, the grease was treated in a three-roll mill to give the grease of Exainple 8. Example 9
Lubricating base oil and isocyanate A which was constituent A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to 60^C. Amine A (industrial octylamine) and amine B (industrial oleylamine) which had been mixed and dissolved in lubricating base oil in advance were added from a hopper and reacted with isocyanate A. Urea compound 'c' as shown by the formula
(octyl)-NHCONH-(diphenylmethane)-NKCONH-(oleyl) was obtained. The contents rose to approximately 80°C through the heat of the reaction. That temperature was maintained for 10 minutes and then amine B (industrial oleylamine) which had been mixed and dissolved in l',ii;'^ic~ti"^" base oil in ^■^^Vc^nce wa^ fec^ ^n^o the kettle from a hopper and reacted with the rerrainder of isocyanate A. Urea compound 'b' as shown by the formula
(oleyl)-NHCONH-(diphenylmethane)-NHCONH- (oleylj was obtained. After further agitating for 5 minutes, amine A (industrial octylamine) and amine C (industrial dodecylamine) which had been mixed and dissolved in lubricating base oil in advance vjere fed into the kettle from a hopper and reacted with the remaining isocyanate A. Urea compound 'd' as shown by the formula

- J J -icctyi} -N>:cc*-r?-:- (diphenylrriethar.s; -'-THCC*;?;- 'dodec".-l"
dodecylarpLine) which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle from a hopper and reacted with the remainder of isocyanate A which was constituent A. Urea compound 'e' as shown by the formula
(oleyl) -MHCCtJK- (dipher.ylmethar_e^ -m-iCC-lTA- (dodecyl) was obtained." Then after quickly restarting heating, the temperature was raised to 170°C and that temperature was maintained for approximately 3 0 minutes to complete the reaction. After maintaining the temperature for 3 0 minutes, cooling began, and at 125°C during the cooling process, 1,0% by mass, as an extraneous proportion, of octyldiphenylamine, which is an anti-oxidant, was added to the grease. After allowing further cooling no SO^C, the grease was treated in a three-roll mill to give the grease of Example 9. Example 10
Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to 60°C- Amine A (industrial octylamine) and amine B (industrial oleylamine) which had been mixed in lubricating base oil were added from a hopper and reacted with isocyanate A. Urea compound 'C as shown by the formula
(octyl)-NHCONH-(diphenylmethane)-NHCONH-(oleyl) was obtained. The contents rose to approximately 80=^0 through the heat of the reaction. That temperature was maintained for 10 minutes and then amine B {industrial oleylamine} which had been mixed and dissolved in


i-^jrrreating i;ase oil ir_ advance v.-as fed into the kett"'e

isocyanate A. Urea compound 'b' as shown by che forrcula
{oieyl} -NHCONH- (diphenylmethane) -NHCOtn-:- (oleyl) was obtained. After agitating again for 5 minutes, axine A (industrial octylamine) and amine C {industrial dodecylamine) which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle from a hopper and reacted with the remaining isocyanate A. Urea compound 'd' as shown by the formula
(octyl) -HHCONH- {diphenylmethane) -I-JHCOKM- (dodecyl) was obtained. Then after quickly restarting heating, the temperacure was raised to 170°C and that temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125'C during the cooling process, 1.0% by mass, as an extraneous .proportion, of octyldiphenylamine, which is an anti-oxidant, was added to the grease. After allowing further cooling to 80°C, the grease was treated in a three-roll mill to give the grease of Example 10. Example 11
Ti ;ta-W ta-V-^ l-T;;—,J->^,^ ^y-,— ^^,-w"+--^^-,—,j^ i^V. i"ij -^—. IT'- ^ ^ i~^ 1 ti '»
lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to 60°C. Amine A (industrial octylamine) and amine B (industrial oleylamine) which had been mixed in liibricating base oil was added from a hopper and reacted with the isocyanate A. "Urea coir.pound 'c' as shown by the formula

- ^^ -
' = z-yi: -irHCONK- (diphenvl-etr.5.r-s: -:,"H~0>r-:- rlevl





maintained for 10 minutes and then amine B (industrial oleylamine) which had been mixed and dissolved in lubricating base oil in advance was fed into the kettle from a hopper and reacted with the remainder of isccyanate A. Urea compound 'b' as shovm by the iormula
[oleyl) -NHCONK- (diphenylmeiihane) -WHCONH- (oleyl; v;as obtained, .^.fter agitating again for 5 minutes, amine B (industrial oleylamine) and amine C (industrial dodecylamine) which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle from a hopper and reacted with the remaining isocyanate A. Urea compound 'e' as shown by the formula
(oleyl) -NHCO^fH- (diphenylmethane) -NHCONH- (dodecyl) was obtained. Then after quickly restarting heating, the temperature was raised to 170°C and that temperature was maintained for approximately 30 minutes to complete the reaction. After m.aintaining the temperature for 3 0 minutes, cooling began, and at 125=C during the cooling process, 1.0% by mass, as an extraneous proportion, of octyldiphenylamine, which is an anti-oxidant, was added to the grease. After allowing further cooling to SQ°C, the grease was treated in a three-roll mill to give the grease of Exam.ple 11. ExamDle 12

Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to SO^C. Amine A (industrial octylamine) and amine B (industrial oleylamine) which had been mixed in lubricating base oil were added from a

- 33 -
as sr.ovn c-y Tine lorrnu^a
(octyl) -NHCONH- Jdiphenylmechane) -N:H:CCN>:- (olevi;. was obtained. The contents rose co aoprcxiir:ately S" -T through the heat of the reaction. That te-perature '^-as maintained for 10 minutes and then amine A (industrial octylamine) and amine C (industrial dodecylaraine) which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle from a hopper and reacted with the rem.ainder of isocyanace A. Urea compound 'd' as shown by the formula
(occyl)-KHCOKH-(diphenylmethane)-NHCGl^H-(dodecyl) was obtained. After agitating again for 5 minutes, amine B (industrial oleylamine) and amine C (industrial dodecylamine) which had been mixed and dissolved in lubricating base oil in advance were fed into the ketitle from a hopper and reacted v/ith the remaining isocyanate A. Urea compound 'e' as shewn by the formula
(oleyl)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl) was obtained. Then after quickly restarting heating, the temperature was raised to 170°C and that temperature was maintained for approximately 30 minutes to complete the reaction. Ai^i^r ::.aintair.in3 zh" t:^mner?.ti'^° for " Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease kettle apparatus, and this was

- lA -

-i=3 ^ _c

ir.-s ag-z5uing, zo ~G=C. Aniir.e A mdustria:.

bsei.: —ixed in lubricating base cil were addsii frc~. a hopper and reacted with isocyanate A. Urea coFpo-.ind 'c' as shown by the formula
(octyl)-NHCONH-(diphenylmethane)-NKCONH-(oleyl) was obtained. The contents rose to approximately aO°C through the heat of the reaction. That temperature was maintained for 10 minutes and then amine A (industrial octylamine) and amine C (industrial dodecylamine) which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle from a hopper and reacted with the remainder of isocyanate A. Urea compound 'd' as shown by the formula
(octyl) -NHCONH- (diphenylmethane) -IJKCONH- (dodecyl) was obtained. Then after quickly restarting heating, nhe temperature was raised to 170°C and that temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125°C during the cooling process, 1.0% by mass, as an extraneous proportion, of cctyldiphenylamine, which is an anti-oxidant, was added to the grease. After allowing further cooling to 6J'C, the grease was treated in a three-roll mill to give the grease of Example 13, Sxample 14
Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to 60°C. Amine A (industrial octylamine) and amine B (industrial oleylamine) which had been mixed in lubricating base oil were added from a

- 35 -
(c:;tyl; -NHCONH- (diphenylmethane) -l.TiCONI-i- ;oIeyl) was obtained. The contents rose to approximatelv acc through the heat of the reaction. That te-peratiure was niainrained for iO minutes and then amine B (industrial oleylamine) and amine C (industrial dodecylarr.ine) which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle from a hopper and reacted with the remainder of isocyanate A. Urea compound 'e' as shown by the formula
(oleyl)-traCONH-idiphenylmechane)-NHCOIffl-(dodecyl) was obtained. Then after quickly restarting heating, the temperature was raised to 170°C and that temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125°C during the cooling process, 1,0% by mass, as an extraneous proportion, of octyldiphenylamine, which is an anti-oxidant, was added to the grease. After allowing further cooling to 80°C, the grease was treated in a three-roll mill to give the grease of Exan^le 14. Example 15
Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) which was constituent A were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to 60°C. Amine A (industrial octylamine) which had been mixed in lubricating base oil was added and reacted with isocyanate A. Urea compound 'a' as shown by the formula
(octyl)-NHCONH'(diphenylmethane)-NHCONH-(octyll was obtained. The contents rose to approximately 80°C through the heat of the reaction. That temperature was



_-_Lbricatir_g bass oil in advanc
and reacted with, the remainder of isocyanate A. Urea
cotTipoiind 'b' as shown by the formula
(oleyl)-NHCONH-(diphenylmethane)-NHCONH-(oleyl) was obtained. Then, after agitating for 5 minutes, an-.ine A [ir.d'j.strial octylamine) and amine C (industrial dodecylamine) which had been mixed and dissolved in I'obricating bass oil in advance were fed into the kettle and reacted with the remaining isocyanate A. Urea compound 'd' as shown by the formula
(octyl)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl) was obtained. Then after quickly restarting heating, the temperature was raised to 170°C and that temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125°C during the cooling process, 1.0% by mass, as an extraneous proportion, of octyldiphenylamine, which is an ar.ti-oxidant, was added to the grease. After allowing further cooling to 30°C, the grease was treated in a three-roll mill to give the grease of Example 15. Example 16
With the blending proportions shown in Table 4, lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) which was constituent A were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to eO^C. Amine A (industrial octylamine) which had been mixed in lubricating base oil was added and reacted with isocyanate A. Urea compound 'a' as shown by the formula
:= wd-a _e:i

.'o::_yl -Kr.C-^'Si^.' ^dipher.yime-har-e, -KK::::?:.">:- "c-tvi;
cnrough the heat o£ the reac-ion. That temperature was maintained for 10 minutes and then amine 5 {induSTirial oleyia-Linsl which had been mixed and dissolved in lubricating base oil in advance was fed into the kettle and reacted with che rem^ainder of isocyanate A. Urea compound 'b' as shown by the formula
(oleyl)-NKCONH-(diphenylmethane)-KHCONH-(oleyl) was obtained. Then after agitating for 5 minuties, amine B (industrial oleylamine) and am.ine C (industrial dodecylamine) which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle and reacted with the remainder of isocyanate A which was constituent A. Urea compound 'e' as shown by the formula
(oleyl)-NHCONH-{diphenylmethane)-NHCONH-{dcdscyl) was obtained. Then after quickly restarting heating, the temperature was raised to 170°C and that temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125°C during the cooling process, 1.0% by mess, as an extraneous proportion, of ocnyldiphenylamine, whicn is an anti-oxidi;-".:-, --.as added to the grease. After allowing further cooling to SO^C, Che grease was treated in a three-roll mill to give the grease of Exanple 16, Examole 17
r I
Lubricating base oil (a mixture of a mineral oil and synthetic oil A) and isocyanate A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to 60°C. Amine A (industrial octylamine) which had been


■c.ztyl'i -•A'HCOKK- ■.diphenylmsthans) -I^THCOK"-:- foctyl ■ was obtained. The contents rose to approxi:r,ately 8G^c through the heat of the reaction. That teiaperature was maintained for 10 minutes and then amine 3 {industrial oleylamine) which was constituent B2 and which had been rriixsd and dissolved in lubricating base oil in advance was fed in-o the kettle and reacted with the remainder of isocyanate A.which was constituent A. Urea compound 'b' as shown by the formula
(oleyl)-NHCONH-(diphenylmethane)-NHCONH-(oleyl) was obtained. After agitating for 5 minutes, amine A {industrial octylamine) and amine C (industrial dodecylamine) v/hich had been mixed and dissolved in lubricating base oil in advance were fed into the kettle and reacted with the remaining isocyanate A which was constituent A. Urea compound 'd' as shown by the formula
(octyl)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl) was obtained. Then after quickly restarting heating, the temperature was raised to 170°C and that temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 3C minutes, cooling began, and at 125°C during the cooling process, l.G% by mass, as an extraneous proportion, of cctyldiphenylamine, which is an anti-oxidant, was added to the grease. After allowing further cooling to 80=c, the grease was treated in a three-roll mill to give the grease of Example 17. Example 18
Lubricating base oil (synthetic oil B) and isocyanate A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease kettle apparatus, and this

was heated, while agirating, zo 50°C. Airiine A (industrial waa added and reached wich isocyanate A. Urea ccmpcund
;octyl) -NI-iCClJH- ;:diphenyitr.ethar.e) -::>:CO: (oleyl)-NHCONH-(diphenylmethane)-NHCONH-(oleyl) was obtained. After agitating for 5 minutes, amine A (industrial octylamine) and amine C (industrial dodecylamine) which had been mixed and dissolved in lubricating base oil in advance were fed into the kettle and reacted with the remaining isocyanate A which was constituent A. Urea compound 'd' as shown by the formula
(octyl)-NHCONH-(diphenylmethane)-NHCONH-(dodecyl) was obtained. Then after quickly restarting hearing, the "srr.cerature v.'as raised to I'^O'^C ^nd that -emperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125'='C during the cooling process, 1.0% by mass, as an extraneous proportion, of octyldiphenylamine, which is an anti-oxidant, was added zo the grease. After allowing further cooling to 80°c, the grease was treated in a three-roll mill to give the grease of Example 18.

p.s^ ns-^ = -
l"-;bric=ting bsse oil and isccyanate A idichenvlTr.e 4,4 '-diisccyenate) were fed into a closed protozv-re grease kettle apparatus, and this was heated, while agitating, to 60°C. Arrdne A {industrial octylamine) which had been mixed in lubricating base oil was added from a hopper and reacted with isocyanate A. Urea compound 'a' as showTi by the formula
(octyl)-NHCONH-(diphenylmethane)-NHCOKH- (octyl) was obtained. The contents rose to approxirriazely SO'^C through the heat of the reaction. That temperature was maintained for 10 minutes and then amine C (industrial dodecylamine) which had been mixed and dissolved in lubricating base oil in advance was fed into the kettle from a hopper and reacted with the remainder of isocyanate A. Urea compound 'f' as shown by the formula
(dodecyj; -NHCOUH- (diphenylsnethane) -NHCONH- (dodecyl) was obtained. Then after quickly restarting heating, the temperature was raised to no°C and that temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125=C during the cooling process, 1.0% by mass, as an extraneous proportion, of octyldiphenylamine, which is an anti-oxidant, was added to the grease. After allowing further cooling to BOoc, the grease was treated in a three-roll mill to give the grease of Comparative Example 1. Comparative Example 2
Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to 6Q°C. Amine B (industrial

- il -
--=_■ -—^—r_e; wtLich. Xs:i D^er. mxxed ir. _'j^ric=zLr.o base oil
'jrea compound ' b' as shown by ths formula
(oleyl) -NTiCONH- (diphenylmethans) -NHCCN:-:- .^ol&yl: was obtained. The contemns rose ic approximately £0=0 through the hear of the reaction. That temperature was maintained for 10 minutes and then amine C (industrial dodecylamine) which had been mixed and dissolved in lubricating base oil in advance was fed into the kettle from a hopper and reacted with the remainder of isocyanate A. Urea compound 'f' as 3bov;n by -he for!T,ula (dodecyl) -NHCONK- (diphenylmethane) -rJHCONH- (dodecyl) was obtained. Then after quickly restarting heating, the temperature was raised to 170°C and that temperature was maintained for approximately 3 0 minutes to complete the reaction. After maintaining the temperature for 3 0 minutes, cooling began, and at 125°C during the cooling process, 1.0% by mass, as an extraneous proportion, of octyldiphenylamine, which is an anti-oxidant, was added to the grease. After allowing further cooling to 80°C, the grease was treated in a three-roll mill to give the grease of Comparative Example 2. wOT-oara L. I'.'B i:.xc;rrL"0-LB —
Lubricating base oil and isocyanate B izolylenediisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to 60°C. Amine A (industrial octylamine) which had been mixed in lubricating base oil was added from a hopper and reacted with isocyanate B. Urea compound 'g' as shown by the formula
(octyl)-NHCONH-(tolylene)-NHCONH-(octyl) was obtained. The contents rose to approximately 80°C through the heat of the reaction. That temperature was

- 42 -
maintained JJcr 10 minutes and then amine B (indust rial oleylamine) which had been mixed and dissolved in lubricating base oil in advance was fed into the kettle from a hopper and reacted with the remainder o£ isocyanate B. Urea compound 'h' as shown by the formula
(oleyl)-NHCONH-(tolylene)-NHCONH-(oleyl) was obtained. After agitating again for 5 minutea, amine A (industrial octylamine) and amine C (industrial dodecylamine) which had been mixed and dissolved jn lubricating base oil in advance were fed into the kettle from a hopper and reacted with the remaining isocyanate B. Urea compound 'j' as shown by the formula
(octyl)-NHCONH-(tolylene)-NHCONH-(dodecyl) was obtained. Then after quickly restarting heating, the temperature was raised to 170°C and that temperature was maintained for approximately 30 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125'C during the cooling process, 1.0% by mass, as an extraneous proportion, of octyldiphenylamine, which is an anti-oxidant, was added to the grease. After allowing further cooling to 60°C, the grease was treated in a three-roll mill to give the greaae of Comparative Example 3. Comparative Example 4
Lubricating baae oil and isocyanate B (tolylenedlisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to 50°C. Amine A (industrial octylamine) which had been mixed in lubricating base oil was added from a hopper and reacted with isocyanate B. Urea compound '9' as shown by the formula

- 43 -
(octyl)-NHCONH-(tolyiene)-NHCONH-(octyl) was obtained. Thu contents rose to approxi^iately 80"C through the heat of the reaction. That temperature wfta maintained for 10 minutes and then amine C {industrial dodecylamine) which had been mixed and dissolved in lubricating base oil in advance was fed into the kettle from a hopper and reacted with the remainder of iaocyanate B. Urea compound 'i' as shown by the formula
{dodecyl}-NHCOOTI-{tolyiene)-NHCONH-(dodecyl) was obtained. Then after quickly restarting heating, the temperature waa raised to nO°C and that temperature was maintained for approximately 30 minutes to complete the reaction. After maivitaining the temperature for 3 0 minutes, cooling began, and at 125°C during the cooling proceaa, 1.0% by mass, as an extraneous proportion, of octyldiphenylamine, which is an anti-oxidant, was added to the grease. After allowing ■ further cooling to f30°C, the grease was treated in a three-roll mill to g:ive the grease of Comparative Example 4. Comparative Example 5
Lubricating base oil and isocyanate B (tolylenediisocyanate) were fed into a closed prototype grease kettle apparatus, and this was heated, while agitating, to 60°C. Amine B {industrial oleylamine) which had been mixed in lubricating base oil was added and reacted with isocyanate B. Urea compound 'h' as shown by the formula
{oleyl)-NHCONH-(tolyiene)-NHCONH-(oleyl) was obtained. The contents rose to approximately 80'=C through the heat of the reaction. That temperature was maintained for 10 minutes and then amine C (industrial dodecylamine) whj.ch had been mixed and dissolved in lubricating base oil in advance was fed into Che kettle

- 44 -
from a hopper and reacted with the remainder of isocyanate B. Urea compound 'i' as shown by the formula
(dodecyl) -NHCONII- {tolylene} -NHCONH- (dodecyl) was obtained. Than after quickly re.=7tarting heatiiiq, i:he temperature was raised to 170'^C and that temperature was maintained for approximately 3 0 minutes to complete the reaction. After maintaining the temperature for 30 minutes, cooling began, and at 125°C during the cooling procesa, 1.0% by mass, as an extraneous proportion, oJ: octyldiphenylamine, which is an anti-oxidant, was at^ded to the greaa&. After allowing further cooling to 80°c, the grease was treated in a three-roll mill to give the grease of Coinparative Example 5.











-50 -
.a
(where R11 and R13 are groups selected from the group consisting o£ hydrocarbon groups having from 6 to 2o carbons, at least one of R11 and R^' is a dodecyi group and R^^ ia a diphenylmethane group); and
a diurea compound as shown by the General Formula
(B) below;
R^^NHCONHR^^NHCONHR'^ .... (B) ,
[where R^^ and R^"* are groups selected from the group conaiBCing of hydrocarbon groupa having from 6 to 20 carbons, at least one of R^^ and R^^ is an oleyl group, and R^^ is a diphenylmethane group).
2. A urea grease composition according to Claim L,
wherein the proportion occupied by the dodecyl group in
R11 and R13 in the above-mentioned General Formula (A) is
from 2 to '70% by mol and/or the proportion occupied by
the oleyl group (s) in R21 and R13 in the above-mentioned
General Formula (B) is from 5 to 70% by mol.
3. A urea grease composition according to Claim 1 or 2,
wherein the hydrocarbon group having from 6 to 20 carbons
other than bhe dodecyl group in R21 and R13 in the above-
mentioned General Formula (A) and/or the hydrocarbon


U J.Mf. 1. w J
- 51 "
group having from 6 to 20 carbons other than an oleyl group in R^^ and n" in the above-mentioned General Formula (B) is an octyl group.
4. A urea greaae composition according to Claim 3,
wherein the proportion occupied by the dodecyl group
in R^^ or R^^ in the above-mentioned General Formula
(A) is from 3 to 55% by mol, the proportion occupied
by the oleyl group (s) in R^^ and R^^ in the above-
mentioned General Formula (B) is from 5 to 55% by
mol, and the proportion occupied by the octyl grovipra
in R^', l\", R^', and R" is from 10 to 90% by mol.
5. A uroa grease composition comprising;
diurea compounds as shown by the general
formulas:
la) R'-NHCONHR^NHCONHR^
and
;b) R^NHCONHR^NHCONHR^
and, further, a diurea compound or compounds as shown by the general formulas:
(d) R^NHCONHR^NHCONHR'^ and/or
(a) R^NHCONHR'NHCONHRS
(where R^ is a diphenylmethane group, R^ is a hydrocarbon group having an octyl group as its main constituent, R^ is a hydrocarbon group having from 1^ to 20 carbons and containing at least 20% by ;mol ol! an oleyl group, and R*" is a hydrocarbon group having a dodecyl group as its main constituent).
AMENDED SHEET

- 52 -
6. A urea qreaiBe composition according to Claim 5
further comprising:
a diurea compound as shown by the general formula:
(c) R^NHCONHR^NHCONHR^
7, A urea grease composition according to Claim 6
wherein the molar ratio of the diurea compound as
shown-by the above-mentioned general formula (a) in
relation to the totality of diurea compounds is from
20 to 80% by mol.
8 . A urea grease composition comprisJ.ng:
a diurea compound as shown by the general formula:
(C) R^NHCONHR^NHCONHR^
and, further, a diurea compound or compounds as shown by the general formulas:
(d) R^NHCONHR^NHCONHR^ and/or
(e) R^NHCONHR^NHCONHR(where R^ is a diphenylmethane group, R^ is a hydrocarbon group having an octyl group as its main constituent, R^ is a hydrocarbon group having from 14 to 20 carbons and containing at least 20% by mol of oleyl group, and R^ is a hydrocarbon group having a dodecyl group as its main constituent). 9. A urea grease composition according to Claim 8 additionally comprising;
a diurea compound as shown by the general formula:
AMENDED SHEET

- 53 ■
(b) R^NHCONHR^NHCONHR^
10. A urea grease composition according to Claim 9
wherein the molar ratio of the diurea compound as
shown by the above-mentioned general formula (c) in
relation to the totality of diurea compounds ia from
20, to 80% by mol.
11. Method of improving the noise perforinance, by using a urea grsase composition according to any one of the preceding Claims 1 to 10.
12. Use of the urea grease composition according to any one of the preceding Claims i to 10 for improving the noise performance.

AMENDED SHEET

Documents:

http://ipindiaonline.gov.in/patentsearch/GrantedSearch/viewdoc.aspx?id=O9PmaNxETWe618fArnR5vQ==&amp;loc=egcICQiyoj82NGgGrC5ChA==


Patent Number 269808
Indian Patent Application Number 1586/CHENP/2009
PG Journal Number 46/2015
Publication Date 13-Nov-2015
Grant Date 06-Nov-2015
Date of Filing 20-Mar-2009
Name of Patentee SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Applicant Address CAREL VAN BYLANDTLAAN 30, NL-2596 HR THE HAGUE
Inventors:
# Inventor's Name Inventor's Address
1 TANAKA, KEIJI 4052-2 NAKATSU, AIKAWA-CYO, AIKOU-GUN, KANAGAWA, AIKOU 243-0303
2 SHINODA, NORIAKI 4052-2 NAKATSU, AIKAWA-CYO, AIKOU-GUN, AIKOU, KANAGAWA 243-0303
3 KATOU, TETSUYA 4052-2 NAKATSU, AIKAWA-CYO, AIKOU-GUN, AIKOU, KANAGAWA 243-0303
PCT International Classification Number C10M115/08
PCT International Application Number PCT/EP07/60023
PCT International Filing date 2007-09-21
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 2006-256330 2006-09-21 Japan