JP2008074978A - Urea grease composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a urea grease composition excellent in the acoustic performance, having long life at high temperatures together with basic characteristics of grease such as shearing stability, heat resistance, moderate oil releasability and the like. <P>SOLUTION: The urea grease composition contains a diurea compound expressed by general formula (A): R<SP>11</SP>NHCONHR<SP>12</SP>NHCONHR<SP>13</SP>(wherein R<SP>11</SP>and R<SP>13</SP>express each a residue selected from the group comprising 6-20C hydrocarbon residues, but either one of R<SP>11</SP>or R<SP>13</SP>expresses a dodecyl residue; R<SP>12</SP>expresses a diphenylmethane residue) and a diurea compound expressed by general formula (B): R<SP>21</SP>NHCONHR<SP>22</SP>NHCONHR<SP>23</SP>(wherein R<SP>21</SP>and R<SP>23</SP>express each a residue selected from the group consisting of 6-20C hydrocarbon residues, but either one of R<SP>21</SP>or R<SP>23</SP>expresses an oleyl residue; R<SP>22</SP>expresses a diphenylmethane residue). <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a novel urea grease composition that has excellent acoustic performance, has a long life at high temperatures, and has the basic properties of grease such as shear stability, heat resistance, and appropriate oil release properties. is there.

The first excellent feature of urea greases containing urea compounds as a thickener is heat resistance and oxidation stability, and the lubrication life at high temperatures is several to tens of times longer than general lithium grease. Since greases having these have been developed, urea greases have been used in a wide range of applications today.
However, most commercially available urea greases have poor acoustic performance, and there are many situations where they cannot be used in many mechanical devices for which quietness is widely demanded in recent years. The current situation has been limited.

For example, household appliances such as vacuum cleaners, washing machines, refrigerator compressors, air conditioner compressors and fans, fans and fan heaters, dryers, ventilation fans or air purifiers have a comfortable and quiet living environment. Therefore, noise countermeasures are indispensable, and low-noise grease with excellent acoustic performance is positively used for bearing grease used in the rotating parts of these devices.
In addition to the acoustic performance, the demand for high-temperature and long-life has become very strong depending on the product due to the increase in temperature accompanying the downsizing of the device and higher output in addition to the acoustic performance. Grease using a urea compound with a long life and excellent acoustic performance as a thickener is very effective, and a better developed product is expected. Of course, basic performances such as shear stability (leakage resistance), high-temperature stability, and moderate oil separation properties, which are basic performances of bearing grease, are indispensable.

  In the automobile industry, the demand for quietness has been increasing year by year, and noise in high-end passenger cars has been thoroughly researched and taken countermeasures, and the demand for low noise in individual parts is extremely severe. Here too, the demand for high-grade greases with excellent acoustic performance for bearings that support rolling elements is increasing year by year. Especially for bearings used for engine parts, the requirement for high temperature and long life is also extremely high. Grease using a urea compound with a thickening agent that is strong against heat and has a long life at high temperatures and an excellent acoustic performance is very effective, and a better developed product is expected. Of course, basic performances such as shear stability (leakage resistance), high-temperature stability, and moderate oil release properties, which are the basic performances of bearing grease as well as the above-mentioned grease for home appliances, are indispensable. It is.

There are Patent Literature 1, Patent Literature 2 and Patent Literature 3 by the present applicant as literatures on urea grease relating to conventional acoustic characteristics.
In Patent Document 1, the general formula (I) R ³¹ NHCONHR ³² NHCONHR ³³
(B) R ³⁴ NHCONHR ³⁵ NHCONHR ³⁶
(Wherein R ³² is a diphenylmethane group, R ³¹ and R ³³ are each a linear or branched saturated alkyl group having 8 carbon atoms, R ³⁵ is a tolylene group or a bitolylene group, and R ³⁴ and R ³⁶ are each alkyl-substituted. A thickener comprising a mixture of the diurea compounds (a) and (b) represented by the following formula: an aromatic group or a halogen-substituted aromatic group.
In Patent Document 2, in the above general formulas (a) and (b), R ³² is a vitrylene group, R ³¹ and R ³³ are each a linear or branched saturated alkyl group or unsaturated alkyl group having 18 carbon atoms. , R ³⁵ is a diphenylmethane group, R ³⁴ and R ³⁶ are linear or branched saturated alkyl groups having 8 carbon atoms, and a thickener comprising a mixture with the diurea compounds (a) and (b) is described. ing.
In Patent Document 3, in the above general formulas (a) and (b), R ³² is a tolylene group, R ³¹ and R ³³ are linear or branched saturated alkyl groups or unsaturated alkyl groups having 16 to 18 carbon atoms. A thickener comprising a mixture of the diurea compounds (a) and (b) wherein R ³⁵ is a diphenylmethane group, R ³⁴ and R ³⁶ are linear or branched saturated alkyl groups having 8 carbon atoms Has been.

As a document relating to other acoustic characteristics, there is Patent Document 4, which includes a base oil containing an alkyldiphenyl ether oil as an essential component, and R ³² in the above general formula (A) as a thickener having 6 to 15 carbon atoms. R ³¹ and R ³³ are linear alkyl groups having 8 and 18 carbon atoms, and the proportion of the alkyl groups having 8 carbon atoms in R ³¹ and R ³³ is 60 to 100 A grease composition containing a diurea compound that is mol% is described.

  Patent Document 5 describes a composition for tapered roller bearings obtained by adding and mixing 0.5 to 5% by weight of oxidation-modified polyolefin and / or acid-modified polyolefin with urea grease. Urea thickeners based on octylamine, stearylamine (octadecylamine) having 18 carbon atoms and MDI (diphenylmethane-4,4'-diisocyanate) are shown, including mechanical stability, hydrous shear stability and pumpability It was shown that there was an excellent effect.

In Patent Document 6, R ³² is a 3,3′-dimethyl-4,4′-biphenylene group, R ³¹ and R ³³ are each an alkyl group having 8 to 18 carbon atoms and an oleyl group. A diurea compound consisting of a mixture is described. However, this technique has disadvantages such as poor consistency yield, and a grease with a consistency of around 250 cannot be obtained unless the amount of thickener is increased, and that the degree of oil separation at high temperatures is high.

  Patent Document 7 describes an improved diurea grease in which a diurea grease contains one or more of alkenyl succinimide, metal alkylbenzene sulfonate, and metal sulfonate metal, and a diurea grease. As the grease, diisocyanate and monoamine can be used, and as the monoamine, an aliphatic amine such as stearylamine and oleylamine or an aromatic amine such as cyclohexylamine can be exemplified. It is disclosed that the acoustic properties are very good.

Furthermore, there are cases where manufacturing methods are being studied in order to improve the acoustic properties of urea grease. For example, in Patent Document 8, an isocyanate and an amine are added to a base oil, the reaction is performed at a temperature of 60 to 120 ° C., and a mixture of the produced urea compound and the base oil is dispersed using a kneader. Then, a method for producing urea grease is described which improves the acoustic characteristics of heating from 160 to 180 ° C. at a temperature rising rate of 0.5 to 2 ° C./min.
In Patent Document 9, a base oil in which an isocyanate is dissolved or dispersed and a base oil in which an amine is dissolved or dispersed are pressurized in a reaction vessel and subjected to collision-mixing to react, or the pressure is stirred while rotating. It describes a method for producing grease with excellent acoustic properties introduced into the wing and reacting.
Patent Document 10 discloses a urea compound 2 in which R ³¹ and R ³³ are a saturated alkyl group having 8 to 18 carbon atoms, and R ³² is a tolylene group, a diphenylmethane group, or a dimethylbiphenylene group in the above general formula (I). A first step of heating a mixture consisting of -30 wt% and base oil 98-70 wt% to 170-230 ° C to completely dissolve the urea compound in the base oil; A method for producing a low-noise urea grease comprising a second step of cooling at a speed is described. And the said patent documents 1-10 do not have description which suggests the urea grease composition of this invention concretely.

In order to provide a urea grease having excellent acoustic characteristics as described in the above-mentioned patent document, as a composition, isocyanate, which is a raw material, includes tolylene diisocyanate (TDI) and 3,3'-dimethyl-4,4'-biphenylene diisocyanate. There are many examples using (TODI). Examples of the production method include the use of a kneading apparatus and a reaction process using a high-pressure kettle to eliminate aggregation of the urea compound, and further mixing two or more kinds of different greases after heating and dissolving the grease.
As the production volume of urea grease increases and the demand for greases with excellent acoustic characteristics in the market increases, the production of greases requires a clean working environment and excellent acoustic characteristics for the final product.
Many users are demanding low-cost and high-performance greases, and the urea grease using TODI, which has a complicated manufacturing process and high raw material costs, cannot be competitive in the market.
With regard to grease production, due to the increase in production volume, it is necessary to be more careful in handling TDI (which is classified as the second category of specified chemical substances in the Industrial Safety and Health Act), which improves the quality of acoustic characteristics. Therefore, equipment reinforcement and extension of manufacturing process time must be considered.

Japanese Patent Laid-Open No. 1-139696 JP-A-2-77494 Japanese Patent Laid-Open No. 6-17080 Japanese Patent Laid-Open No. 3-28299 JP-A-2-80493 (page 6, table 2) JP-A-3-243696 JP 58-185893 A JP-A-2-4895 Japanese Patent Laid-Open No. 3-190996 Japanese Patent Laid-Open No. 3-231993

  The present invention relates to a urea grease composition that has excellent acoustic performance, has a long life at high temperatures, and has the basic properties of grease such as shear stability, stability at high temperature resistance, and appropriate oil release properties. is there.

  As a result of thorough investigation and analysis of the components of the urea thickener in the urea grease composition, the present inventors have accurately grasped the problems and demands in the market. Only for urea grease compositions combined with a specific urea thickener, it has excellent acoustic performance, long life at high temperature, shear stability, high temperature stability and moderate oil release The present inventors have found that an excellent urea grease composition having the basic performance of grease has been achieved, and have led to the present invention.

That is, the first of the present invention is the following general formula (A)
R ¹¹ NHCONHR ¹² NHCONHR ¹³ (A)
(In the formula, R ¹¹ and R ¹³ are groups selected from the group consisting of hydrocarbon groups having 6 to 20 carbon atoms, but one of R ¹¹ and R ¹³ is a dodecyl group, and R ¹² is Diphenylmethane group)
And a diurea compound represented by the following general formula (B)
R ²¹ NHCONHR ²² NHCONHR ²³ (B)
Wherein R ²¹ and R ²³ are groups selected from the group consisting of hydrocarbon groups having 6 to 20 carbon atoms, but at least one of R ²¹ and R ²³ is an oleyl group, and R ²² is diphenylmethane. Base)
The urea grease composition characterized by containing the diurea compound shown by these.
In the second aspect of the present invention, the proportion of dodecyl group in R ¹¹ and R ¹³ in the general formula (A) is 2 to 70 mol% and / or in R ²¹ and R ²³ in the general formula (B). The urea grease composition according to claim 1, wherein the proportion of oleyl groups is 5 to 70 mol%.
A third aspect of the present invention is a hydrocarbon group having 6 to 20 carbon atoms other than the dodecyl group in R ¹¹ and R ¹³ in the general formula (A) and / or R ²¹ and R in the general formula (B). The urea grease composition according to claim 1 or 2, wherein the hydrocarbon group having 6 to 20 carbon atoms other than the oleyl group in No. ²³ is an octyl group.
In the fourth aspect of the present invention, the proportion of the dodecyl group in R ¹¹ and R ¹³ in the general formula (A) is 3 to 55 mol%, and the oleyl group in R ²¹ and R ²³ in the general formula (B) ratio from 5 to 55 ^mol% occupied, about ^{R 11, R 13, R 21} , a urea grease composition according to claim 3, wherein the ratio of octyl group in ^{R 23} is 10 to 90 mol%.
The fifth aspect of the present invention is
General formula (a) R ¹ NHCONHR ² NHCONHR ¹
(B) R ³ NHCONHR ² NHCONHR ³
And a diurea compound represented by the general formula (d) R ¹ NHCONHR ² NHCONHR ⁴
And / or (e) R ³ NHCONHR ² NHCONHR ⁴
(Wherein R ² is a diphenylmethane group, R ¹ is a hydrocarbon group mainly composed of an octyl group, R ³ is a hydrocarbon group having 14 to 20 carbon atoms and containing 20 mol% or more of an oleyl group, and R ⁴ is a dodecyl group. (The main component is a hydrocarbon group.)
The urea grease composition characterized by containing the diurea compound shown by these.
The sixth of the present invention is
General formula (a) R ¹ NHCONHR ² NHCONHR ¹
(B) R ³ NHCONHR ² NHCONHR ³
(C) R ¹ NHCONHR ² NHCONHR ³
And a diurea compound represented by the general formula (d) R ¹ NHCONHR ² NHCONHR ⁴
And / or (e) R ³ NHCONHR ² NHCONHR ⁴
(Wherein R ² is a diphenylmethane group, R ¹ is a hydrocarbon group mainly composed of an octyl group, R ³ is a hydrocarbon group having 14 to 20 carbon atoms and containing 20 mol% or more of an oleyl group, and R ⁴ is a dodecyl group. (The main component is a hydrocarbon group.)
The urea grease composition characterized by containing the diurea compound shown by these.
The seventh of the present invention is
(I) a diurea compound represented by the general formula (a),
(Ii) (1) General formulas (b), (c), (d) and (e)
(2) General formulas (b), (c) and (d)
(3) General formulas (b), (c) and (e)
A urea containing a diurea compound composed of a diurea compound selected from the group consisting of, and having a molar ratio of the diurea compound represented by the general formula (a) to the total diurea compound of 20 to 80 mol% The present invention relates to a grease composition.
The eighth of the present invention is
Formula (c) R ¹ NHCONHR ² NHCONHR ³
And a diurea compound represented by the general formula (d) R ¹ NHCONHR ² NHCONHR ⁴
And / or (e) R ³ NHCONHR ² NHCONHR ⁴
(Wherein R ² is a diphenylmethane group, R ¹ is a hydrocarbon group mainly composed of an octyl group, R ³ is a hydrocarbon group having 14 to 20 carbon atoms and containing 20 mol% or more of an oleyl group, and R ⁴ is a dodecyl group. (The main component is a hydrocarbon group.)
The urea grease composition characterized by containing the diurea compound shown by these.
The ninth of the present invention is
Formula (c) R ¹ NHCONHR ² NHCONHR ³
(B) R ³ NHCONHR ² NHCONHR ³
And a diurea compound represented by the general formula (d) R ¹ NHCONHR ² NHCONHR ⁴
And / or (e) R ³ NHCONHR ² NHCONHR ⁴
(Wherein R ² is a diphenylmethane group, R ¹ is a hydrocarbon group mainly composed of an octyl group, R ³ is a hydrocarbon group having 14 to 20 carbon atoms and containing 20 mol% or more of an oleyl group, and R ⁴ is a dodecyl group. (The main component is a hydrocarbon group.)
The urea grease composition characterized by containing the diurea compound shown by these.
The tenth aspect of the present invention is
(I) a diurea compound represented by the general formula (c);
(B) (1) General formulas (b), (d) and (e)
(2) General formulas (b) and (d)
(3) General formulas (b) and (e)
A urea containing a diurea compound composed of a diurea compound selected from the group consisting of the diurea compound and having a molar ratio of the diurea compound represented by the general formula (c) to the total diurea compound of 20 to 80 mol%. The present invention relates to a grease composition.

（Ｒ^１１、Ｒ^１２、Ｒ^１３は前記のとおりである。）
また、一般式（Ｂ）で示される化合物も一般式（Ａ）で示される化合物と同様にして下記の反応式により製造することができる。

（Ｒ^２１、Ｒ^２２、Ｒ^２３は前記のとおりである。） The compound represented by the general formula (A) can be generally produced by the following reaction formula.

(R ¹¹ , R ¹² and R ¹³ are as described above.)
Further, the compound represented by the general formula (B) can also be produced by the following reaction formula in the same manner as the compound represented by the general formula (A).

(R ²¹ , R ²² and R ²³ are as described above.)

It is diphenylmethane-4,4′-diisocyanate that corresponds to the OCN—R ¹² —NCO and OCN—R ²² —NCO.

In order to introduce R ¹¹ and R ¹³ in the compound of the general formula (A), R ¹¹ NH ₂ and R ¹³ NH ₂ are used, and R ²¹ and R ²³ in the compound of the general formula (B) are introduced. For this, R ²¹ NH ₂ or R ²³ NH ₂ is used.

  The present invention is described in detail below in relation to the compounds of general formulas (A) and (B) and general formulas (a) to (e).

The dodecyl group, particularly the n-dodecyl group in any one of R ¹¹ and R ¹³ contributes to the heat resistance of the urea grease, and its presence can extend the life of the urea grease at a high temperature, When both R ¹¹ and R ¹³ are dodecyl groups, the heat performance is good, but the acoustic performance is poor. Therefore, any one of R ^{11 and} R ¹³ is a dodecyl group, and the other is a hydrocarbon group having 6 to 20 carbon atoms, preferably an oleyl group or an octyl group. A specific raw material for supplying the dodecyl group is preferably linear primary dodecylamine. A diurea thickener synthesized from a mixture of dodecylamine and oleylamine or octylamine and diphenylmethane-4,4'-diisocyanate has excellent thermal stability, and the grease composition using the same is difficult to change at high temperatures and has a long life. It is very effective in extending Dodecyl group, the total number of moles of ^{R 11} and ^{R 13} in the general formula (A), 2 to 70 mol%, preferably not occupy 4-50 mol%.

At least one of R ²¹ and R ²³ is an oleyl group, particularly an n-oleyl group. The presence of the oleyl group provides the urea grease composition with excellent acoustic performance, improves the adsorptivity of the urea grease composition to the metal interface that is the sliding part of the machine part, and improves the lubricity. The oleyl group occupies 5 to 70 mol%, preferably 8 to 55 mol% in R ²¹ and R ²³ in the general formula (B).

In the present invention, it is indispensable that the diurea compound contains at least an oleyl group and a dodecyl group, particularly an n-dodecyl group, but preferably includes an octyl group, particularly an n-octyl group. is there.
In the case of further containing an octyl group, particularly an n-octyl group in addition to the oleyl group and the dodecyl group, the proportion of the dodecyl group in R ¹¹ and R ¹³ in the general formula (A) is 3 to 55 mol%, Further, in the general formula (B), the proportion of oleyl groups in R ²¹ and R ²³ is 5 to 55 mol%, and the proportion of octyl groups in R ¹¹ , R ¹³ , R ²¹ , and R ²³ is 10 to 90 mol. % Is suitable.

  The urea thickener contained in the general formulas (A) and (B), which is a characteristic diurea compound of the present invention, can be used at a ratio of 20 to 100 mol% in the total thickener.

  Thickeners composed of the diurea compounds represented by the general formulas (A), (B) and (a) to (e) are 2 to 30 with respect to mineral oil, synthetic oil or mixed oils which are lubricating base oils. It is preferable to make it contain by weight%. If the diurea compound, which is a thickener, is less than 2% by weight relative to the base oil, mineral oil or synthetic oil, or a mixture thereof, the thickening effect is small and the grease becomes too soft and leaks. When the amount exceeds 30% by weight, the grease becomes too hard, the flow resistance increases, the friction torque increases, and the intervention property decreases, so that a sufficient lubricating effect cannot be obtained. Also, the price will increase.

  As the lubricating base oil in the present invention, those generally used as a lubricating oil or a base oil for grease can be used. The material is not particularly limited, and examples thereof include mineral oil and / or synthetic oil and vegetable oil. Specific examples of synthetic oils include polyolefins such as α-olefin oligomers and polybutene, polyalkylene glycols such as polyethylene glycol and polypropylene glycol, diesters such as di-2-ethylhexyl sebacate and di-2-ethylhexyl adipate, and trimethylolpropane. Typical examples of vegetable oils include polyol esters such as esters and pentaerythritol esters, perfluoroalkyl ethers, silicone oils, polyphenyl ethers, and the like include castor oil and rapeseed oil. These base oils may be used alone or in combination, but these do not limit the invention.

In addition, an additive such as an antioxidant, a rust inhibitor, an oily agent, an extreme pressure agent, an antiwear agent, a solid lubricant, a metal deactivator, and a polymer can be further added to the composition of the present invention.
For example, as an antioxidant, 2,6-di-tert-butyl-4-methylphenol, 2,6-di-tert-butylparacresol, P, P′-dioctyldiphenylamine, N-phenyl-α-naphthylamine And phenothiazine. Examples of the rust inhibitor include oxidized paraffin, carboxylic acid metal salt, sulfonic acid metal salt, carboxylic acid ester, sulfonic acid ester, salicylic acid ester, succinic acid ester, sorbitan ester, and various amine salts. Oily agents, extreme pressure agents and antiwear agents include zinc sulfide dialkyldithiophosphates, zinc sulfide diallyldithiophosphates, zinc sulfide dialkyldithiocarbamates, zinc sulfide diallyldithiocarbamates, sulfurized dialkyldithiophosphates molybdiene sulfide, diallyldithiophosphate molybdate sulfide, sulfurized Examples thereof include dialkyldithiocarbamate molybdate, diallyldithiocarbamate molybdate, organic molybdate complex, sulfurized olefin, triphenyl phosphate, triphenyl phosphorothioate, tricresin phosphate, other phosphate esters, and sulfurized fats and oils. Examples of the solid lubricant include molybdenum disulfide, graphite, boron nitride, melamine cyanurate, PTFE (polytetrafluoroethylene), tungsten disulfide, and graphite fluoride. Examples of the metal deactivator include N, N′-disalicylidene-1,2-diaminopropane, benzotriazole, benzimidazole, benzothiazole, thiadiazole and the like. Examples of the polymer include polybutene, polyisobutene, polyisobutylene, polyisoprene, and polymethacrylate.

  According to the present invention, a novel urea grease composition having excellent acoustic performance, a high drop point, a high temperature and a long life, and having the basic properties of grease such as shear stability, heat resistance and appropriate oil release properties. Could be provided.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention in detail, this invention is not limited at all by these Examples.

Abbreviations relating to the raw material components of the thickener and the lubricating base oil used in the following Tables 1 to 5, Examples and Comparative Examples are as follows.
Isocyanate A is diphenylmethane-4,4'-diisocyanate and has a molecular weight of 250.26.
Isocyanate B is tolylene diisocyanate and has a molecular weight of 174.16.
As a raw material for amines,
Amine A is a linear primary amine (industrial octylamine) having an average molecular weight of 128.7 mainly composed of a saturated alkyl group having 8 carbon atoms (90% or more).
Amine B is a linear primary amine (industrial oleylamine) having an average molecular weight of 255.0 mainly composed of an unsaturated alkyl group having 18 carbon atoms (70% or more).
Amine C is a linear primary amine (industrial dodecylamine) having an average molecular weight of 184.6 mainly composed of a saturated alkyl group having 12 carbon atoms (90% or more).
Moreover, the 100 degreeC kinematic viscosity of the mineral oil shown in an Example and a comparative example is 10.12 mm < ² > / s,
Synthetic oil A is a poly α-olefin oil having a kinematic viscosity of 12.70 mm ² / s at 100 ° C.
Synthetic oil B is an alkyl diphenyl ether oil and has a kinematic viscosity of 12.69 mm ² / s at 100 ° C.
In addition, a, b, c, d, and e in the column of mol% of the thickener described in Examples in Tables 1 to 4 are respectively
(A) R ¹ NHCONHR ² NHCONHR ¹
(B) R ³ NHCONHR ² NHCONHR ³
(C) R ¹ NHCONHR ² NHCONHR ³
(D) R ¹ NHCONHR ² NHCONHR ⁴
(E) R ³ NHCONHR ² NHCONHR ⁴
(In the formula, R ² is a diphenylmethane group, R ¹ is a hydrocarbon group having 6 to 10 carbon atoms mainly composed of an octyl group, and R ³ is a hydrocarbon group having 14 to 20 carbon atoms and containing 20 mol% or more of an oleyl group. R ⁴ is a hydrocarbon group mainly composed of an n-dodecyl group.)
The urea compound represented by these is shown.
Further, a and b in the column of mol% of the thickener described in Comparative Example of Table 5 represent the above-described compounds described in Examples of Table 1 to Table 4, and f, g, h, i and j are respectively ,
(F) R ⁴ NHCONHR ² NHCONHR ⁴
(G) R ¹ NHCONHR ⁵ NHCONHR ¹
(H) R ³ NHCONHR ⁵ NHCONHR ³
(I) R ⁴ NHCONHR ⁵ NHCONHR ⁴
(J) R ¹ NHCONHR ⁵ NHCONHR ⁴
(In the formula, R ⁵ is a tolylene group, R ¹ is a hydrocarbon group having 6 to 10 carbon atoms mainly composed of an octyl group, and R ³ is a hydrocarbon group having 14 to 20 carbon atoms and containing 20 mol% or more of an oleyl group. R ⁴ is a hydrocarbon group mainly composed of an n-dodecyl group.)
The urea compound represented by these is shown.

The properties of the examples and comparative examples in each table were performed according to the following test methods.
1. Consistency: JIS K2220
2. Dropping point: JIS K2220
3. Oil separation degree: JIS K2220B method, conditions are 100 ° C., 24 hours.
4). Acoustic test: Measured according to the method described in Japanese Patent Publication No. 53-2357.
5. Shell roll: ASTM D1831
6). Bearing life test: ASTM D3336

  According to the blending ratios shown in Tables 1 and 2, synthesis of urea compounds as thickeners was carried out in the lubricating base oil, and additives were blended to obtain the grease of the present invention.

Example 1
Lubricating base oil and component A isocyanate A (diphenylmethane-4,4′-diisocyanate) were placed in a sealed grease prototype kettle and heated to 60 ° C. with stirring. Add component B1 amine A (industrial octylamine) mixed with lubricating base oil and react with component A;
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (octyl)
The urea compound a shown by this was obtained. The content of the reaction rises to about 80 ° C. due to the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine B (industrial oleylamine) of component B2 previously mixed and dissolved in the lubricating base oil is placed in the kettle, Reacting with the remaining component A isocyanate A, the formula:
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. After stirring for 5 minutes, component B3 amine A (industrial octylamine) and amine B (industrial oleylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle, and the remaining component A isocyanate A and React,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound c shown by this was obtained. Next, after stirring for 5 minutes, amine A (industrial octylamine) of component B4 and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle, and the remaining isocyanate of component A React with A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound d shown by this was obtained. After stirring again for 5 minutes, amine B (industrial oleylamine) of component B5 and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil were put into the kettle, and the remaining isocyanate A of component A and React,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound e shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three-roll mill to obtain the grease of Example 1.

Example 2
Lubricating base oil and component A isocyanate A (diphenylmethane-4,4′-diisocyanate) were placed in a sealed grease prototype kettle and heated to 60 ° C. with stirring. Add component B1 amine A (industrial octylamine) mixed with lubricating base oil and react with component A;
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (octyl)
The urea compound a shown by this was obtained. The content of the reaction rises to about 80 ° C. due to the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine B (industrial oleylamine) of component B2 previously mixed and dissolved in the lubricating base oil is placed in the kettle, Reacting with the remaining component A isocyanate A, the formula:
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. After stirring for 5 minutes, component B3 amine A (industrial octylamine) and amine B (industrial oleylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle, and the remaining component A isocyanate A and React,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound c shown by this was obtained. Next, after stirring for 5 minutes, amine A (industrial octylamine) of component B4 and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle, and the remaining isocyanate of component A React with A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound d shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was processed with a three-roll mill to obtain the grease of Example 2.

Example 3
Lubricating base oil and component A isocyanate A (diphenylmethane-4,4′-diisocyanate) were placed in a sealed grease prototype kettle and heated to 60 ° C. with stirring. Add component B1 amine A (industrial octylamine) mixed with lubricating base oil and react with component A;
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (octyl)
The urea compound a shown by this was obtained. The content of the reaction rises to about 80 ° C. due to the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine B (industrial oleylamine) of component B2 previously mixed and dissolved in the lubricating base oil is placed in the kettle, Reacting with the remaining component A isocyanate A, the formula:
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. After stirring for 5 minutes, component B3 amine A (industrial octylamine) and amine B (industrial oleylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle, and the remaining component A isocyanate A and React,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound c shown by this was obtained. Next, after stirring for 5 minutes, component B5 amine B (industrial oleylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle, and the remaining component A isocyanate A React with
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound e shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three-roll mill to obtain the grease of Example 3.

Example 4
Lubricating base oil and component A isocyanate A (diphenylmethane-4,4′-diisocyanate) were placed in a sealed grease prototype kettle and heated to 60 ° C. with stirring. Add component B1 amine A (industrial octylamine) mixed with lubricating base oil and react with component A;
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (octyl)
The urea compound a shown by this was obtained. The content of the reaction rises to about 80 ° C. due to the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine B (industrial oleylamine) of component B2 previously mixed and dissolved in the lubricating base oil is placed in the kettle, Reacting with the remaining component A isocyanate A, the formula:
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. Next, after stirring for 5 minutes, amine A (industrial octylamine) of component B4 and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle, and the remaining isocyanate of component A React with A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound d shown by this was obtained. After stirring again for 5 minutes, amine B (industrial oleylamine) of component B5 and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil were put into the kettle, and the remaining isocyanate A of component A and React,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound e shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three-roll mill to obtain the grease of Example 4.

Example 5
Lubricating base oil and component A isocyanate A (diphenylmethane-4,4′-diisocyanate) were placed in a sealed grease prototype kettle and heated to 60 ° C. with stirring. Add component B1 amine A (industrial octylamine) mixed with lubricating base oil and react with component A;
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (octyl)
The urea compound a shown by this was obtained. The content of the reaction rises to about 80 ° C. due to the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine B (industrial oleylamine) of component B2 previously mixed and dissolved in the lubricating base oil is placed in the kettle, Reacting with the remaining component A isocyanate A,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. Next, after stirring for 5 minutes, amine A (industrial octylamine) of component B4 and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle, and the remaining isocyanate of component A React with A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound d shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three-roll mill to obtain the grease of Example 5.

Examples 6 and 7
Lubricating base oil and component A isocyanate A (diphenylmethane-4,4′-diisocyanate) were placed in a sealed grease prototype kettle apparatus at the blending ratio shown in Table 2 and heated to 60 ° C. with stirring. Add component B1 amine A (industrial octylamine) mixed with lubricating base oil and react with component A;
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (octyl)
The urea compound a shown by this was obtained. The content of the reaction rises to about 80 ° C. due to the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine B (industrial oleylamine) of component B2 previously mixed and dissolved in the lubricating base oil is placed in the kettle, Reacting with the remaining component A isocyanate A, the formula:
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. Next, after stirring for 5 minutes, amine B (industrial oleylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are placed in the kettle and reacted with the remaining component A isocyanate A. ,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound e shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three-roll mill to obtain greases of Examples 6 to 7.

Example 8
Lubricating base oil and component A isocyanate A (diphenylmethane-4,4′-diisocyanate) were placed in a sealed grease prototype kettle and heated to 60 ° C. with stirring. Add component B1 amine A (industrial octylamine) mixed with lubricating base oil and react with component A;
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (octyl)
The urea compound a shown by this was obtained. The content of the reaction rises to about 80 ° C. due to the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine B (industrial oleylamine) of component B2 previously mixed and dissolved in the lubricating base oil is placed in the kettle, Reacting with the remaining component A isocyanate A, the formula:
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. Next, after stirring for 5 minutes, amine A (industrial octylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle and reacted with isocyanate A of the remaining component A. Let
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound d shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three-roll mill to obtain the grease of Example 8.

Example 9
Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) are placed in a sealed grease prototype kettle, heated to 60 ° C. with stirring, and mixed with amine A (industrial octylamine for industrial use). ) And amine B (industrial oleylamine) are added from a hopper and reacted with isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound c shown by this was obtained. The reaction temperature rises to about 80 ° C. due to the reaction heat, but is kept at that temperature for 10 minutes, and then amine B (industrial oleylamine) previously mixed and dissolved in the lubricating base oil is stuck into the kettle from the hopper and remains. React with isocyanate A,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. After further stirring for 5 minutes, amine A (industrial octylamine) and amine C (industrial dodecylamine) mixed and dissolved in the lubricating base oil in advance are put into the kettle from the hopper and reacted with the remaining isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound d shown by this was obtained. After stirring again for 5 minutes, amine B (industrial oleylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil were put into the kettle from the hopper and reacted with the remaining isocyanate A,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound e shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three-roll mill to obtain the grease of Example 9.

Example 10
Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) are placed in a sealed grease prototype kettle, heated to 60 ° C. with stirring, and mixed with amine A (industrial octylamine for industrial use). ) And amine B (industrial oleylamine) are added from a hopper and reacted with isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound c shown by this was obtained. The reaction temperature rises to about 80 ° C. due to the reaction heat, but is kept at that temperature for 10 minutes, and then amine B (industrial oleylamine) previously mixed and dissolved in the lubricating base oil is stuck into the kettle from the hopper and remains. React with isocyanate A,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. After further stirring for 5 minutes, amine A (industrial octylamine) and amine C (industrial dodecylamine) mixed and dissolved in the lubricating base oil in advance are put into the kettle from the hopper and reacted with the remaining isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound d shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three-roll mill to obtain the grease of Example 10.

Example 11
Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) were put into a sealed grease prototype kettle device at the blending ratio shown in Table 3, heated to 60 ° C. with stirring, and mixed with the lubricating base oil. Dissolved amine A (industrial octylamine) and amine B (industrial oleylamine) are added from a hopper and reacted with isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound c shown by this was obtained. The reaction temperature rises to about 80 ° C. due to the reaction heat, but is kept at that temperature for 10 minutes, and then amine B (industrial oleylamine) previously mixed and dissolved in the lubricating base oil is stuck into the kettle from the hopper and remains. React with isocyanate A,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. After further stirring for 5 minutes, amine B (industrial oleylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle from the hopper and reacted with the remaining isocyanate A,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound e shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three-roll mill to obtain the grease of Example 11.

Example 12
Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) are placed in a sealed grease prototype kettle, heated to 60 ° C. with stirring, and mixed with amine A (industrial octylamine for industrial use). ) And amine B (industrial oleylamine) are added from a hopper and reacted with isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound c shown by this was obtained. The content of the reaction rises to about 80 ° C. by the heat of reaction, but is kept at that temperature for 10 minutes, and then amine A (industrial octylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil. ) From the hopper into the kettle and reacted with the remaining isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound d shown by this was obtained. After further stirring for 5 minutes, amine B (industrial oleylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle from the hopper and reacted with the remaining isocyanate A,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound e shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three roll mill to obtain the grease of Example 12.

Example 13
Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) are placed in a sealed grease prototype kettle, heated to 60 ° C. with stirring, and mixed with amine A (industrial octylamine for industrial use). ) And amine B (industrial oleylamine) are added from a hopper and reacted with isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound c shown by this was obtained. The content of the reaction rises to about 80 ° C. by the heat of reaction, but is kept at that temperature for 10 minutes, and then amine A (industrial octylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil. ) In the kettle from the hopper to react with the remaining isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound d shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three roll mill to obtain the grease of Example 13.

Example 14
Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) are placed in a sealed grease prototype kettle, heated to 60 ° C. with stirring, and mixed with amine A (industrial octylamine for industrial use). ) And amine B (industrial oleylamine) are added from a hopper and reacted with isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound c shown by this was obtained. The content of the reaction rises to about 80 ° C. by the heat of reaction, but is kept at that temperature for 10 minutes, and then amine B (industrial oleylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil. From the hopper into the kettle and react with the remaining isocyanate A,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound e shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three roll mill to obtain the grease of Example 14.

Example 15
Lubricating base oil and component A isocyanate A (diphenylmethane-4,4′-diisocyanate) were placed in a sealed grease prototype kettle and heated to 60 ° C. with stirring. Add amine A (industrial octylamine) mixed with lubricating base oil and react with isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (octyl)
The urea compound a shown by this was obtained. The content of the reaction rises to about 80 ° C. due to the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine B (industrial oleylamine) previously mixed and dissolved in the lubricating base oil is put into the kettle and remains. React with Isocyanate A,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. Next, after stirring for 5 minutes, amine A (industrial octylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle and reacted with the remaining isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound d shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three roll mill to obtain the grease of Example 15.

Example 16
Lubricating base oil and component A isocyanate A (diphenylmethane-4,4′-diisocyanate) were placed in a sealed grease prototype kettle apparatus at the blending ratio shown in Table 4, and heated to 60 ° C. with stirring. Add amine A (industrial octylamine) mixed with lubricating base oil and react with isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (octyl)
The urea compound a shown by this was obtained. The content of the reaction rises to about 80 ° C. due to the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine B (industrial oleylamine) previously mixed and dissolved in the lubricating base oil is put into the kettle and remains. React with isocyanate A,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. Next, after stirring for 5 minutes, amine B (industrial oleylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are placed in the kettle and reacted with the remaining component A isocyanate A. ,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound e shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three-roll mill to obtain the grease of Example 16.

Example 17
Lubricating base oil (mixture of mineral oil and synthetic oil A) and isocyanate A (diphenylmethane-4,4'-diisocyanate) were placed in a sealed grease prototype kettle apparatus and heated to 60 ° C. with stirring. Add amine A (industrial octylamine) mixed with lubricating base oil and react with isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (octyl)
The urea compound a shown by this was obtained. The content of the reaction rises to about 80 ° C. due to the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine B (industrial oleylamine) of component B2 previously mixed and dissolved in the lubricating base oil is placed in the kettle, Reacting with the remaining component A isocyanate A, the formula:
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. After stirring for 5 minutes, amine A (industrial octylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle and reacted with the remaining component A isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound d shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three roll mill to obtain the grease of Example 17.

Example 18
Lubricating base oil (synthetic oil B) and isocyanate A (diphenylmethane-4,4′-diisocyanate) were placed in a sealed grease prototype kettle apparatus and heated to 60 ° C. with stirring. Add amine A (industrial octylamine) mixed with lubricating base oil and react with isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (octyl)
The urea compound a shown by this was obtained. The content of the reaction rises to about 80 ° C. due to the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine B (industrial oleylamine) of component B2 previously mixed and dissolved in the lubricating base oil is placed in the kettle, Reacting with the remaining component A isocyanate A, the formula:
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. After stirring for 5 minutes, amine A (industrial octylamine) and amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil are put into the kettle and reacted with the remaining component A isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound d shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three-roll mill to obtain the grease of Example 18.

Comparative Example 1
Lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) were put into a sealed grease prototype kettle device at the mixing ratio shown in Table 5, heated to 60 ° C. with stirring, and mixed with the lubricating base oil. Add dissolved amine A (industrial octylamine) from hopper and react with isocyanate A,
formula,
(Octyl) -NHCONH- (diphenylmethane) -NHCONH- (octyl)
The urea compound a shown by this was obtained. The reaction temperature rises to about 80 ° C by the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil is stuck into the kettle from the hopper and remains. Reacting with the isocyanate A
formula,
(Dodecyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound f shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three-roll mill to obtain the grease of Comparative Example 1.

Comparative Example 2
Amine B (industrial oleylamine) mixed with and dissolved in lubricating base oil by adding lubricating base oil and isocyanate A (diphenylmethane-4,4'-diisocyanate) to a sealed grease prototype kettle, heated to 60 ° C with stirring Is added from the hopper and reacted with isocyanate A,
formula,
(Oleyl) -NHCONH- (diphenylmethane) -NHCONH- (oleyl)
The urea compound b shown by this was obtained. The reaction temperature rises to about 80 ° C by the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil is stuck into the kettle from the hopper and remains. Reacting with the isocyanate A
formula,
(Dodecyl) -NHCONH- (diphenylmethane) -NHCONH- (dodecyl)
The urea compound f shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three roll mill to obtain the grease of Comparative Example 2.

Comparative Example 3
Lubricating base oil and isocyanate B (tolylene diisocyanate) are placed in a sealed grease prototype kettle, heated to 60 ° C. with stirring, and amine A (industrial octylamine) mixed in the lubricating base oil is added from the hopper to add isocyanate. React with B,
formula,
(Octyl) -NHCONH- (Tolylene) -NHCONH- (Octyl)
The urea compound g shown by these was obtained. The reaction temperature rises to about 80 ° C. due to the reaction heat, but is kept at that temperature for 10 minutes, and then amine B (industrial oleylamine) previously mixed and dissolved in the lubricating base oil is stuck into the kettle from the hopper and remains. React with isocyanate B,
formula,
(Oleyl) -NHCONH- (tolylene) -NHCONH- (oleyl)
The urea compound h shown by this was obtained. Further, after stirring for 5 minutes, amine A (industrial octylamine) and amine C (industrial dodecylamine) mixed and dissolved in the lubricating base oil in advance are put into the kettle from the hopper and reacted with the remaining isocyanate B,
formula,
(Octyl) -NHCONH- (Tolylene) -NHCONH- (Dodecyl)
The urea compound j shown by these was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was processed with a three roll mill to obtain the grease of Comparative Example 3.

Comparative Example 4
Lubricating base oil and isocyanate B (tolylene diisocyanate) are put into a sealed grease prototype kettle, heated to 60 ° C with stirring, and amine A (industrial octylamine) mixed and dissolved in the lubricating base oil is added from the hopper. React with isocyanate B,
formula,
(Octyl) -NHCONH- (Tolylene) -NHCONH- (Octyl)
The urea compound g shown by these was obtained. The reaction temperature rises to about 80 ° C by the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil is stuck into the kettle from the hopper and remains. Reacting with isocyanate B,
formula,
(Dodecyl) -NHCONH- (tolylene) -NHCONH- (dodecyl)
The urea compound i shown by this was obtained. Thereafter, heating was resumed promptly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was treated with a three roll mill to obtain the grease of Comparative Example 4.

Comparative Example 5
Lubricating base oil and isocyanate B (tolylene diisocyanate) are put into a sealed grease prototype kettle, heated to 60 ° C with stirring, and amine B (industrial oleylamine) mixed and dissolved in the lubricating base oil is added from the hopper to add isocyanate. React with B,
formula,
(Oleyl) -NHCONH- (tolylene) -NHCONH- (oleyl)
The urea compound h shown by this was obtained. The reaction temperature rises to about 80 ° C by the heat of reaction, but is kept at that temperature for 10 minutes. Next, amine C (industrial dodecylamine) previously mixed and dissolved in the lubricating base oil is stuck into the kettle from the hopper and remains. Reacting with isocyanate B,
formula,
(Dodecyl) -NHCONH- (tolylene) -NHCONH- (dodecyl)
After that, heating was resumed quickly, the temperature was raised to 170 ° C., and the temperature was maintained for about 30 minutes to complete the reaction. After holding for 30 minutes, cooling was started, and at 125 ° C during the cooling process, octyldiphenylamine, an antioxidant, was added to the grease in an extraordinary amount of 1.0% by mass, and then allowed to cool to 80 ° C. The grease was processed with a three roll mill to obtain the grease of Comparative Example 5.

Claims (10)

The following general formula (A)
R ¹¹ NHCONHR ¹² NHCONHR ¹³ (A)
(In the formula, R ¹¹ and R ¹³ are groups selected from the group consisting of hydrocarbon groups having 6 to 20 carbon atoms, but one of R ¹¹ and R ¹³ is a dodecyl group, and R ¹² is Diphenylmethane group)
And a diurea compound represented by the following general formula (B)
R ²¹ NHCONHR ²² NHCONHR ²³ (B)
Wherein R ²¹ and R ²³ are groups selected from the group consisting of hydrocarbon groups having 6 to 20 carbon atoms, but at least one of R ²¹ and R ²³ is an oleyl group, and R ²² is diphenylmethane. Base)
The urea grease composition characterized by including the diurea compound shown by these. The proportion of dodecyl groups in R ¹¹ and R ¹³ in the general formula (A) is 2 to 70 mol% and / or the proportion of oleyl groups in R ²¹ and R ²³ in the general formula (B) is 5 The urea grease composition according to claim 1, which is ˜70 mol%. Carbon groups other than the dodecyl group in R ¹¹ and R ¹³ in the general formula (A) and / or carbons other than the oleyl group in R ²¹ and R ²³ in the general formula (B). The urea grease composition according to claim 1 or 2, wherein the hydrocarbon group of formula 6 to 20 is an octyl group. The proportion of dodecyl groups in R ¹¹ and R ¹³ in the general formula (A) is 3 to 55 mol%, and the proportion of oleyl groups in R ²¹ and R ²³ in the general formula (B) is 5 to 55 mol. %, R ¹¹ , R ¹³ , R ²¹ , R ²³ occupying a proportion of octyl groups is 10 to 90 mol%. General formula (a) R ¹ NHCONHR ² NHCONHR ¹
(B) R ³ NHCONHR ² NHCONHR ³
And a diurea compound represented by the general formula (d) R ¹ NHCONHR ² NHCONHR ⁴
And / or (e) R ³ NHCONHR ² NHCONHR ⁴
(Wherein R ² is a diphenylmethane group, R ¹ is a hydrocarbon group mainly composed of an octyl group, R ³ is a hydrocarbon group having 14 to 20 carbon atoms and containing 20 mol% or more of an oleyl group, and R ⁴ is a dodecyl group. (The main component is a hydrocarbon group.)
The urea grease composition characterized by containing the diurea compound shown by these. General formula (a) R ¹ NHCONHR ² NHCONHR ¹
(B) R ³ NHCONHR ² NHCONHR ³
(C) R ¹ NHCONHR ² NHCONHR ³
And a diurea compound represented by the general formula (d) R ¹ NHCONHR ² NHCONHR ⁴
And / or (e) R ³ NHCONHR ² NHCONHR ⁴
(Wherein R ² is a diphenylmethane group, R ¹ is a hydrocarbon group mainly composed of an octyl group, R ³ is a hydrocarbon group having 14 to 20 carbon atoms and containing 20 mol% or more of an oleyl group, and R ⁴ is a dodecyl group. (The main component is a hydrocarbon group.)
The urea grease composition characterized by containing the diurea compound shown by these. (I) a diurea compound represented by the general formula (a),
(Ii) (1) General formulas (b), (c), (d) and (e)
(2) General formulas (b), (c) and (d)
(3) General formulas (b), (c) and (e)
A urea containing a diurea compound composed of a diurea compound selected from the group consisting of, and having a molar ratio of the diurea compound represented by the general formula (a) to the total diurea compound of 20 to 80 mol% Grease composition. Formula (c) R ¹ NHCONHR ² NHCONHR ³
And a diurea compound represented by the general formula (d) R ¹ NHCONHR ² NHCONHR ⁴
And / or (e) R ³ NHCONHR ² NHCONHR ⁴
(Wherein R ² is a diphenylmethane group, R ¹ is a hydrocarbon group mainly composed of an octyl group, R ³ is a hydrocarbon group having 14 to 20 carbon atoms and containing 20 mol% or more of an oleyl group, and R ⁴ is a dodecyl group. (The main component is a hydrocarbon group.)
The urea grease composition characterized by containing the diurea compound shown by these. Formula (c) R ¹ NHCONHR ² NHCONHR ³
(B) R ³ NHCONHR ² NHCONHR ³
And a diurea compound represented by the general formula (d) R ¹ NHCONHR ² NHCONHR ⁴
And / or (e) R ³ NHCONHR ² NHCONHR ⁴
(Wherein R ² is a diphenylmethane group, R ¹ is a hydrocarbon group mainly composed of an octyl group, R ³ is a hydrocarbon group having 14 to 20 carbon atoms and containing 20 mol% or more of an oleyl group, and R ⁴ is a dodecyl group. (The main component is a hydrocarbon group.)
The urea grease composition characterized by containing the diurea compound shown by these. (I) a diurea compound represented by the general formula (c);
(B) (1) General formulas (b), (d) and (e)
(2) General formulas (b) and (d)
(3) General formulas (b) and (e)
A urea containing a diurea compound composed of a diurea compound selected from the group consisting of the diurea compound and having a molar ratio of the diurea compound represented by the general formula (c) to the total diurea compound of 20 to 80 mol%. Grease composition.