JPS58125795A - Lithium complex grease composition a having high dropping point - Google Patents

Abstract

PURPOSE:A rease composition having a high dropping point, improved oxidative stability, long life of lubrication, and extremely improved acoustic characteristics, obtained by dispersing respectively specific Li soap, Li salt, succinic acid imide- based dispersant, etc. into a base oil. CONSTITUTION:(A) Lithium salt consisting of Li salt of 10-34C fatty acid and/ or Li salt of 12-24C hydroxy fatty acid, (B) Li salt of aromatic oxycarboxylic acid and (C) a succinic acid imide-based dipsersant and/or a metal salt detergent as essential ingredients are uniformly dispersed into a base oil having lubricating viscosity, to give the desired grease. In a preferable blending amount, 5-20pts.wt. component A is blended with 0.1-10pts.wt. compoent B and 0.1- 5pts.wt. component C based on 100pts.wt. base oil.

Description

DETAILED DESCRIPTION OF THE INVENTION The invention relates to a lyticum complex grease composition '+9IJ of product t, which has high oxidation stability exceeding the dropping point S, long lubrication life and extremely good acoustic properties.

Traditionally, lyticum soap grease has been widely used due to its relatively good heat resistance and water resistance, the ease with which soap can be dispersed into all types of lubricant bases, and its reasonable price. [My friend. However, in the case of Lithiwum soap grease, if the environment and conditions for one use are high temperatures of 130℃ or higher, the micelles will be destroyed due to oxidative deterioration - the layering force will decrease 1
The disadvantage of 19% grease is that it rapidly loses its lubricating effect due to softening and increased oil separation.

Non-soap-based greases with extremely high dropping points and various complex greases have been developed as heat-resistant greases that compensate for these shortcomings, but the thickening agent hardens during long-term use. s Secretly softens. Moreover, it has drawbacks such as being extremely expensive, which naturally limits its uses. - The environment in which grease is used is becoming worse as mechanical devices become smaller and operating parts become faster. For example, when bearings for electrical components such as those used in automobiles are used in areas that are close to the heat source of an engine, the grease that lubricates the bearings is also exposed to high temperature conditions. In such cases, the grease must have sufficient high temperature resistance, durability, water resistance, etc.

Therefore, the above-mentioned lithium soap grease is also highly desirable due to the emergence of greases with excellent properties.

In order to meet the above-mentioned desire, it is an object of the present invention to completely improve the commonly used lithium greases, and in particular to
A high dropping point, which is an essential requirement under the operating conditions of 1% temperature of 50℃ or higher, and good stability of the thickening agent micelles at high temperatures, 1 good adhesion, etc. Our goal is to provide 1% quality lithium complex grease.

The above purpose is to mix into the base oil, lithium salts of fatty acids and/or hydroxy fatty acids and lithium salts of aromatic oxycarboxylic acids, and further as all essential components of a cono-monolyryl imide dispersant and/or a metal salt detergent. Achieved by dispersed lithium complex grease.

According to Japanese Patent Publication No. 54-2205, lithium soap containing hydrochloric acid, lithium salt of aliphatic acid, or monolithium boric acid, and oxycarboxylic acid such as aromatic oxycarboxylic acid are added to the lithium soap. It is disclosed that the acid Lithium Ix is used as an essential ingredient to prepare a high dropping point lithium soap grease. However, a grease with a high dropping point cannot be prepared from only two components: lithium soap of hydroxy fatty acid and solithium salt of aromatic oxycarboxylic acid.

This time, in addition to the above two ingredients, we added a succinimide dispersant and/or a kettle salt detergent as the fifth ingredient - a very high quality high dropping point lithium complex grease.
It was found that it could be edited.

According to the 14-sided invention, six components of F are added to the base oil, which is an oil having lubricating viscosity, namely (a) C10''
At least 141 lithium soaps selected from lithium salts of C34 fatty acids and CI 2-024 lithium fatty acids, (b) lithium salts of aromatic oxycarboxylic acids, and (C) succinimide-based dispersions. A high dropping point lithium complex grease composition is provided, which includes a lithium salt detergent and/or a pot Jr. J4 salt detergent as essential ingredients, uniformly mixed and dispersed therein.

Lithium compressor provided by Eri without invention.

The grease composition will be explained in more detail.

Base Oil: Base oils conveniently used in the compositions of the invention are mineral oils or synthetic hydrocarbon oils conventionally used in lubricating oils;
Synthetic oils such as synthetic ester oils or mixtures thereof. These devices generally have fJ2~ at 40°C.
5 oocst, preferably in the range of FJ 20 to 200 cst.

For example, the synthetic oil has a viscosity of 41. Ocst740℃
, a polyalpha-olefin rubber such as octene-1/decene-1 with a viscosity index of 150, a flow point of -60°C, and a flash point of 223°C; Acid esters: Hindered ester oils such as trimethylolpropane furylic acid ester and pentaerythritol caproic acid ester can be used. Various synthetic oils such as polyglycol oil, silicone oil, polyphenyl ether oil, halonized hydrocarbon oil, and alkylbenzene oil can also be used.

6- (a) Growth: Lithium salt of C10-034 fatty acid and Cl11-02
4 Hydrococonut fatty acids are selected from 1 grave. Capric acid, undecanoic acid, lauric acid, myri7ic acid, palmitic acid, stearic acid, arachidic acid, behenic acid are used for the formation of lithium salts. 1g, lignoceric acid, cerotic acid, montanic acid, melisonic acid, olei/a-+
1 rydan 1g% Erka 1 lead) Somarinic acid, gadolenic acid, gondwaic acid, linoleic acid 1 Saturated or unsaturated higher fatty acids such as lyrinic acid and their glycerides have a richness rl, and the number of carbon atoms is 16 to 1. 22 are preferred to sometimes preferred, and examples include Irf, Albatic acid, stearic acid, oleic acid, and elaidic acid.

C12-C24 hydroxy fatty acids are usually straight-chain saturated or unsaturated aliphatic monocarboxylic acids having a hydroxyl group in the molecule, specifically, for example, ricinoleic acid, 2-hydrochloride, etc. Citric acid, 2-hydroxytetradecanoic acid, 2-hydrocyhexadecanoic acid, 11-hydrocyhexadecanoic acid, ambretric acid, ricinoleic acid 1, ricinosunarolic acid, 9-hydroxystearic acid, 10 -Hydroxystearic acid, 12-hydroxystearic acid, etc., among which the number of carbon atoms is 1
Preference is given to those having 8 atoms and those in which the hydroxyl group is bonded in the 9-110- or 12-positions to 112-hydroxystearic acid and ricinoleic acid.

The above-mentioned lithium salts of higher fatty acids or lithium salts of hydroxy fatty acids can be used alone or in combination of two or more or more. In order to form lithium salts from the aliphatic or hydroxy fatty acids mentioned above, the fatty acids or hydroxy fatty acids can be reacted with lithium hydroxide not only in the form of free acids but also in the form of glycerides.

Component (b): According to the invention, the second component added to the base oil is a lithium salt of aromatic oyazocarboxylic acid. The aromatic oxycarboxylic acid used for convenience is preferably of the type represented by the following formula 1, where R represents a hydrogen atom, a hydroxyl group, an alkyl group, or a lower alkoxylic acid group. For example, p-oxybenzoic acid, salicylic acid (0-oxybenzoic acid) = 9-2-oxy-4-hexyl i-benzoic acid, m-oxybenzoic acid, 2.5-oxybenzoic acid Acid (r), 21
6-dioxybenzoic acid (γ-resornoic acid), 4-oxybenzoic acid and 3-methoxybenzoic acid 11n are added. Salicylic acid is suitable for this purpose. Note that the hydroxyl group (OH) in the lithium salt may exist in a free form or in the form of OLi.

(C) Components: The six components that can be distributed to the base oil according to the invention are components that promote the fine division of the above-mentioned components (a) and (b) into the base oil. However, in the invention, succinimide dispersants and metal salt detergents can be used alone or in combination of two or more.

The phosphoric acid imide dispersant that can be used as component (Q) in the present invention is one of the ones that have the effect of dispersing sludge in normal engine oil (obtained by the reaction of polyptene and maleic anhydride). (1) A pardoner produced by the reaction between polybutenyl succinic anhydride and a polyamine, specifically, the one shown by the following formula is said to be effective.

(II) 11- (TV) (VI) [In each of the above formulas, Al represents a C1° to ctoo polyisobutenyl group, p is an integer of 2 to 8, and q is an integer of 1 to 8. ] -12- Furthermore, the concomitant salt detergent that can be used as component (C) is the sedimentation of degraded products of 1. Among the additives that prevent or suppress the occurrence of harmful substances and keep the inside of the engine clean, it means those that are organic admixtures. Explode.

(1) In the sulfonate formula, A2 and AI I are seven atoms and the father is C, 1
~0. . represents an alkyl group, 1 ArtfX represents a benzene ring or naphthalene ring, M
1 is an alkaline earth metal such as Oa, Ba or Mg; M2 is an alkali metal such as Na5K%L1.

(II) Phenate 0-M-0 where AI is 04-01. represents an alkyl group, M is an alkaline earth metal, such as Oa, Ba or Mg;
is 1 or 2.

(fil) In the phosphonate formula, A4 represents Oso~01, 0 polyisobutynyl foundation, and 1M represents alkaline earth gold such as Oa, Ba,
It is Mg.

(Iv) Salicylate OH In the formula, All represents an 08-C2□ alkyl group, and 1M represents an alkaline earth metal, such as oa, Ba, or Mg.

Among these detergents, lucium sulfonate, calcicum phenate, lucium sulfonate, 9-musalicylate, and musalicylate are preferred.

Preparation of Grease Composition: The uninvented grease composition contains (a) in the base oil described above;
F can be produced by uniformly mixing all three components (b) and (Q) and finely dispersing them.

At that time, the ratio of the six components (a), (b), and (C) to the base oil is not strict and varies depending on the type of each component, but it is generally as follows per 100 parts by weight of base oil. It is advantageous to use proportions (within a preferred range).

(a) Component = 11 to 40 parts by weight (5 to 20 parts by weight) (g) Component: [1,05 to 20 parts by weight ([11 to 20 parts by weight]
10th weight part) (Q) Ingredient? 0.01 to 10iii parts (o1 to 5 parts by weight) In addition, it is particularly preferable to use component (a) and component (b) in the following molar ratio within the above ratio range = component (a)/ ω) Component molar ratio −α5~
10. % range from 1 to 5.

The non-invention is that the grease composition contains the above (a), (b) and (
In addition to the three components C), other ordinary lubricating oil additives such as antioxidants (e.g. 2,6-
ivy-butyl-4-methylphenol 1N-phenyl-α-naphthylamine, octylated diphenylabane, etc.], rust inhibitor 111: oxidized nografine, aminoimidacillin, barium dinonylnaphthalenesulfonate, etc.), extreme pressure Agents (e.g., naphthenic zinc, lead naphthenate, sulfurized oils and fats, tricresyl phosphate, etc.) can also be distributed in the amounts normally used. Next, a general method for producing the grease of the present invention will be described.

The uninvented grease is prepared by adding the entire component (C) to the base oil, and then adding the fatty acid or hydroxy fatty acid for forming the component (a), and allowing it to dissolve at a temperature of 70 to 80°C. Next, lithium hydroxide in an amount approximately equivalent to the fatty acid or hydroxy fatty acid is added at 80 to 90°C to produce soap. Next, it was cooled a little and heated to 170 to 80°C, and all of the aromatic carboxylic acid that would form component (b) was added thereto, gradually warmed to the skin, and heated to 80 to 90°C in an amount approximately equivalent to the aromatic carboxylic acid mentioned above. of lithium hydroxide. Heat this
Raise the temperature to 145 to 150°C while applying Zll pressure, 14
When the temperature reaches 517-150°C, complete dehydration begins. Once dehydration is complete, heat the blade to 195-220°C and then heat to 175-220°C.
Cool to 193°C, maintain at that temperature for 10-40 minutes, and cool.

The above-mentioned Lyticum complex grease composition provided by F has a very high dropping point, very good acoustic properties, and has a long lubrication life, making it an extremely high-performance 91 grease. be. Therefore, the inventive grease composition is suitable for the lubrication of bearings used in, for example, S electric motors, and is also very suitable as a grease for wheel bearings of automobile parts with an integral structure of the hair ring axle. Are suitable. Furthermore, the uninvented grease composition '1521 has extremely low noise characteristics, so when used in bearings such as near conditioners, it emits almost no noise and provides a comfortable environment. can be given.

Hereinafter, the present invention will be further explained based on a practical example.

Case 1: Refined mineral oil (rough-in paste, viscosity index 102, pour point -15°C, kinematic viscosity 44.9 cst at 37.8°C.

6.4 C3t at 9 & 9°C) 252 L 2 f %
:' Succinimide (A) (Note 1) 30f and 12-
Add 270f of hydroxystearic acid to a 5 ton crepe and heat to 80°C for 60 to 40 minutes while stirring.
to completely dissolve all 12-hydroxystearic acid.

(Note 1) Succinimide (A) Al: 0,2 to C〒6 polyisopnyl group Average molecular charge: 2302 (assuming that Hokusumi is possessed) Total refined mineral oil 1
00 parts by weight dissolved in 110 parts by weight.

A hot water solution (95°C) in which lyticum hydroxide 3F3.51 was dissolved in 300 t"f, with stirring, 90
Hold at ℃ for 5-15 minutes. Then cooled to 75℃,
Hot water m liquid (95℃) in which salicylic acid 49.8F is dissolved
Float at 300r and stir to dissolve.

After stirring for 10-15 minutes, add lyticum hydroxide 31, Ot is M
Place the mixture in a heated water bath U (95°C) and gradually heat while stirring. Approximately 1-1.
5 hours of music and Yutsu<! Heat the autoclave to the same temperature, then fully open the autoclave and heat it to the same temperature.
Dehydrate for 25 minutes. After the dehydration is completed, heat the whole inside of the autoclave to a temperature of 195 to 205°C, then cool it to 188 to 192°C while sweating, maintain this temperature for 20 to 60 minutes, and then cool it further.
When the temperature reaches 0℃, apply 60 tons of antioxidant. 5 more
Stirring was continued for 0 to 60 minutes. Once the temperature reached about 80 to 85° C., the mixture was treated with a Manton-Goring type homogenizer. The properties of the grease composition obtained in this manner were as follows.

Chou♂ (1 unmixed oro): 239 (60 times #5 oro): 256 -20'- Shell roll test *2 (100℃ x 5h) Before test:
119 After test: 149 Difference: +30 Dropping point (℃):) 280 Oil separation degree *1 (100 x 24 h): 2.2% water resistance *
1 (3a℃X1h): 2.0% JIn hot copper plate corrosion *1
(1oo℃ x 24h): Zengaku Grease Dust Sound Measurement Test*
After 3120 seconds: 68 (average of 5 measurements) *4.

Functional life: 2540h *1 J Engineering S　K2220.

*2 Roll stability test based on As'I'M D1831.

*3 c9 measurement according to the method published in VCif publication No. 53-2557.

=21- *4 Life time according to ASTM D1741 B method.

Comparative Example 1 Instead of adding succinimide (A),
A grease composition was prepared in the same manner as in Example 1 except that Harisei Mineral Oil 2531.21 was used. The properties of the obtained grease composition were as follows.

Consistency (small item; 11): 278 (60 times i; day): 266 Seal 1 call test (100°C x 5h) before test = 13
9 After test: 176 Difference: +54 Dropping point (℃): 195 Grease dust sound measurement test After 120 seconds: 4114 (average of 5 measurements) Machine life: 1240 hours Actual pain examples 2 to 8, comparative example 213 A grease composition was obtained by treating each component shown in Table 2.1 below in the same manner as in Detailed Example 1.The properties of these components are summarized in Table 1.In addition, commercially available 12-hydroxy The results of stearic acid 9mm soap grease are described as Comparative Example 2.It was prepared in the same manner as in Example 1 except that refined mineral oil was used instead of adding ('') component 1 (0) component. The grease is described as Comparative Example 6.

Notes to Table 1 Al: Polyisobutanyl group of 052 to C76 Average molecular weight: 2170 110 parts by weight of total refined mineral oil were distilled into 110 parts by weight.

(2) ~O Al: C, ~076 polyisobutenyl group average molecular weight: 1172 160 parts per 100 parts of mineral oil.

Al5o, ~076 7-giri ingtinyl group average molecular ii: 1304 14040 parts by weight dissolved in 100 parts by weight of total refined mineral oil.

(4) Calcicum dinonylnaphthalene sulfonate (
A product prepared by dissolving 39 parts by weight of 100 parts by weight of N mineral oil.

(5) Magnesium alkylsalicylate (formula below)
(R: Fluorine 1+z group of Clo-Cl6) was dissolved in 60 parts by weight in 1 part of Iyusei Fumoto Oil 100 ji.

(6) Aruki Rusaritel Sentou Ruzokum (Fki E) (
R: C1o~0□6 alkyl group) 60 shifts per 100 parts by weight of refined mineral oil! @Bath-dissolved.

(7) Same as Example 1 for T-mail.゛ (8) Same as Example 1, made of gold.

27- Procedural amendment (voluntary) February 22, 1980 Director General of the Patent Office Shima 1) Haruki Tono■, Indication of the case 1981 11L! SA 6758 No. 2,
Name of the invention: 3-2-5 Omengaseki, 1-ku
Name Shell Oil Co., Ltd. (Name) 4. Agent Address: 107

Claims (1)

[Claims] The five components listed in 1F, which are not oils having lubricating viscosity,
(a) at least one lithium soap selected from CIo-0341 lithicum 1 and lithium salts of 012 to C24 hydrochlorinated fatty acids; (b) aromatic oxycarbonic acid; A high dropping point Lithium conglenox grease composition comprising a lithium salt, and (C) a succinimide-based dispersion and/or a bitter salt detergent uniformly distributed as all essential components.