JPS61141794A - High-dropping point lithium complex grease composition improved in sound characteristics - Google Patents

Abstract

PURPOSE:A high-quality grease compsn. with a high dropping point, a prolonged lubrication life and good sound characteristics, prepd. by uniformly dispersing a lithium soap, a lithium salt and an imide succinate-base dispersant in a base oil comprising oil having lube viscosity. CONSTITUTION:At least one lithium soap selected from a lithium salt of 10-34C batty acid and a lithium salt of 12-24C hydroxy fatty acid, at least one lithium salt selected from a dilithium salt of 4-12C aliph. dicarboxylic acid and lithium borate, and an imide succinate-base dispersant are uniformly dispersed by mixing in a base oil comprising oil having lube viscosity. The oil having lube viscosity generally means an oil having a viscosity of about 2-500cSt at 40 deg.C. Stearic and oleic acids are pref. as a carboxylic acid used to form the lithium soap to be used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high quality lithium complex grease composition with a high dropping point, long lubrication life and very good acoustic properties.

Lithium soap grease with a high perfect score is generally called lithium complex grease, and several proposals have been made in the past (for example, U.S. Pat. No. 2,940,933).
Items 0 and 3, 2 2 3, 6 2 4,
JP-A-48-56203, JP-A-53-3708
(See Publication No. 2, Japanese Patent Publication No. 54-2205, etc.), but
These lithium complex greases have been thought to have poor acoustic properties due to the poor dispersibility of the gold maple salt used to form the lithium soap and the base oil in the base oil.

The object of the present invention is to provide a lithium complex grease composition that has significantly improved sound characteristics and a long sliding life without sacrificing the high dropping point properties of lithium complex grease. According to the invention, the purpose is to add a base oil consisting of an oil having a lubricating viscosity,
The following three components, namely +al Coo~C84 fatty acid lithium salt and CI
At least one lithium soap selected from lithium salts of 2-C24 hydroxy fatty acids [hereinafter referred to as atomic acid components] +hl C4-C1 at least one selected from dilithium salts of aliphatic dicarboxylic acids and lithium salts of boric acid
Seed lithium salt [hereinafter referred to as blFi5L] and (cl polymer viscosity index agent, succinimide dispersant and/or metal salt detergent [hereinafter referred to as 1cI component]) are uniformly mixed and dispersed as essential components. It was discovered that something could be done by doing this, and the present invention was completed.

Hereinafter, the lithium complex grease composition provided by the present invention will be explained in more detail.

Group γ1): As the base oil conveniently used in the composition of the present invention, any known oil containing lubricating viscosity that has been conventionally used in lubricating oils can be used, and the most representative ones are Mineral oil, which is one of the refined petroleum products, includes alkali, ester oils [e.g. diester oils such as dioctyl azelate, and tetraesters such as pentaerythritol ester of aliphatic monocarboxylic acid (e.g. pentaerythritol tetraamyl ester)] oil], poly-α-olefin oligomers (e.g., viscosity 41.Ocst/37.8°C, viscosity index 130,
Synthetic base oils such as octene-1/decene-1 copolymers having a pour point of -60 DEG C. and a flash point of 223 DEG C.) can also be used alone or in combination with mineral oils.

Here, "oil with lubricating viscosity" generally means 40℃
about 2 to 500 Cδt1 preferably about 20 to 20
Refers to oils having a viscosity within the range of 0 cst.

(a + acid component The lithium soap added to the base oil according to the present invention is et
selected from lithium salts of o-C14 fatty acids and lithium salts of CI2-C24 hydroxy fatty acids. C + o = Csa fatty acids used in the formation of such lithium salts include, for example, capric acid, undecanoic acid, lauric acid, myristic acid, palmitic stearic acid, arachidic acid, behenic acid, lignoceric acid, cerotic acid, montanic acid. , saturated or unsaturated higher aliphatic monocarboxylic acids such as melisic acid, oleic acid, elaidic acid, erucic acid, seamarinic acid, gadolenic acid, gondolaic acid, linoleic acid, lylic/acid, among which the number of carbon atoms is 16 to 22 carboxylic acids, particularly stearic acid and oleic acid, which are the most preferred carboxylic acids. In addition, C+ t~C74 hydroxy fatty acids are usually linear saturated or unsaturated aliphatic monocarboxylic acids having a hydroxyl group in the molecule, and specifically, for example, 2-hydroxydodecane,
2-hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, 11-hydroxyhexadecanoic acid, ambretic acid, ricinoleic acid, ricinostearolucic acid,
Examples include 9-hydroxystearic acid, 10-hydroxystearic acid, 12-hydroxystearic acid, etc.
Among these, those having 18 carbon atoms and those having a hydroxyl group bonded to the 9-110- or 12-positions are preferred, particularly 12-hydroxystearic acid and ricinoleic acid.

The above-mentioned lithium salts of aliphatic monocarboxylic acids or lithium salts of hydroxyaliphatic monocarboxylic acids can be used alone, or two or more of them can be used in combination.

In addition, in forming the lithium salt, the carboxylic acid can be reacted with lithium hydroxide not only in the form of the free acid but also in the form of its glyceride.

(bl component: The second component added to the base oil according to the invention is 04-C
+2 months selected from dilithium salts of aliphatic dicarboxylic acids and lithium salts of boric acid. Examples of the aliphatic dicarboxylic acids 04 to C+ used for forming the dilithium salt include succinic acid, glutaric acid, adipic acid, speric acid,
Examples include pimelic acid, azelaic acid, dodecanedioic acid, sebacic acid, etc. Among them, those having 6 to 10 carbon atoms, particularly adipic acid, sebacic acid and azelaic acid, are preferred. It is also possible to use lithium salts of boric acid, in particular lithium metaborate, lithium tetraborate, lithium pentaborate, lithium perborate, instead of or in combination with the silium salt (b15+i, min). .

(Cl component: The CL component is a component that promotes fine dispersion of the above-mentioned (at acid component and (BL component) into the base oil, which is blended into the base oil according to the present invention. In this method, a polymer viscosity index improver, a succinimide dispersant, and a metal salt detergent are used alone or in combination of two or more.

The polymer viscosity index improver (Viscosity Ind.
exImproverl generally has an average molecular weight of about 100
0 to about 1,500,000, preferably about 2,000 to about 300,000, oil-soluble [(i.e., a polymerized ornament that is soluble in base oil,
It is used to reduce the temperature dependence of the viscosity of lubricating oil, and any oil that has been conventionally used for this purpose can be used, and the following are typical examples: It is as follows.

(1) Polyisobutylene, with an average molecular weight of 1.0
Those within the range of 00 to 300,000.

(21 Homopolymers and copolymers of two or more methacrylic acid C2-C+s alkyl esters, especially those with an average molecular weight within the range of 20,000 to 1.500.OOO.

(3) 04-Cps alkyl ester of methacrylic acid and the following formula (% formula %) In the formula, R is a hydrogen atom or a methyl group, and X is a polar group, such as -Co(X:H2C)l, -K)C) 1. Copolymers with (meth)acrylic monomers such as CH260R', where R/ represents an alkyl group of 01 to C8, and n is an integer of 1 to 8, especially average molecular weight is 2
Those within the range of 0,000 to 1.5oo, ooo.

(4) 1 of C1-C,8 alkyl ester of acrylic acid
species or (co)electrocombinants of two or more species, especially with an average molecular weight of 20
,000 to 1.500.000.

(Hydrogenated product of 51 styrene-butadiene covehicle, especially one with an average molecular weight of 20.00 to 250.0 OL) and a styrene content of 25 to 70% by weight.

+61 hydride of styrene-imprene copolymer,
In particular, those having an average molecular weight in the range of 20,000 to 250,000 and a styrene content of 20 to 65% by weight (71 ethylene/-propylene copolymer, especially those having an average molecular weight in the range of 20,000 to 250,000) Among these, those with an ethylene content of 10 to 50% by weight.

) Esterified or amidated products of styrene/-maleic acid copolymer.

(91 polyethylene, especially those with an average molecular weight of s, oo).

~300.000 things.

Among the oil bath polymer compounds described above, those suitable for use in the present invention are methacrylic acid methyl ester polymers having an average molecular weight of 00,000 to 300,000, and methacrylic acid methyl ester having an average molecular weight of 80,000 to 80,000.
160,000 styrene-butadiene copolymer hydride, average molecular weight 80,000-160,000 styrene-imbrene copolymer hydride, average molecular weight 80,000-160,000 ethylene-
These include propylene copolymers and mixtures thereof.

Among those that have the effect of dispersing sludge in oil, polybutenyl succinate r1 obtained by the reaction of polybutene and maleic anhydride! It refers to a dispersant synthesized by a reaction between an anhydride and a polyamine, and specifically includes those represented by the following formula.

ho""~, /""-vH In each of the above formulas, AI is C5o-Ct. . In the polyimbutenyl group, p is an integer of 2 to 8, and q is an integer of 1 to 8.

Furthermore, metal salt detergents that can be used for 1g of 1C are organic i &
It refers to compounds consisting of compounds, and includes sulfonates, phenates, phosphonates, and salicylates represented by the following formulas.

In the sulfonate formula, A2 and A'' are each a hydrogen atom or 08 to C3
o represents an alkyl group, Ar represents a benzene ring or a naphthalene ring, and M' represents an alkaline earth metal such as Ca,
Ba or Mg, and M' is alkaline, e.g. Na
, is Li.

(In the 1117 eneto formula, A3 represents an 04~eta alkyl foundation, Ml is an alkaline earth metal, such as CaXHa or Mg,
X is 1 or 2.

(llil phosphonate In the formula, A4 represents a C5° to C200 polyimbutenyl group, and Ml represents an alkaline earth metal, such as Ca, Ha
, Mg.

(tv+ In the salicylate formula, A5 represents a C8-C21 alkyl group, and Ml is an alkaline earth metal, such as Ca, Ha.

Represents Mg.

Among these metal salt detergents, calcium sulfonate,
Calcium phenate, calcium phenate, magnesium salicylate, etc. are suitable.

The grease composition of the present invention contains (al,
It can be produced by uniformly mixing and finely dispersing the three components (bl and (C).
The blending amounts of the three components, all (bl and (cl), in the base oil are not arbitrary and vary depending on the type of each component, but it is generally advantageous to use them in the following proportions per 100 parts by weight of the base oil. ( Preferred ranges are in parentheses.) A+ component: 2 to 40 parts by weight (5 to 30 parts by weight) (bl
Ingredients: 0.05-20 parts by weight (0.5-10 parts by weight) l
Cl component: 0.01 to 10 parts by weight (0.1 to 5 parts by weight)
Moreover, it is particularly preferable to use the component -) and the component (ra) in the following molar ratio within the above ratio range, in a concave circle.

(al component/(b11 molar ratio=0.5~)0, especially 1
~5 In addition to the above three components ial, (bl and (cl), the grease composition of the present invention may contain other conventional lubricating oil additives, such as rust inhibitors (e.g. oxidation paraffin, aminoimidacyline, barium dinonylnaphthalenesulfonate, etc.), antioxidants (e.g. 2,6-ditertiarybutyl-4-methylphenol, hephenyl-α-naphthylamine, octylated diphenylamine, etc.), extreme pressure Agents (eg, zinc naphthenate, lead naphthenate, fats and oils, tricresyl phosphate, etc.) may also be present in commonly used amounts.

The grease of the present invention can be produced, for example, as follows: Add and dissolve 1 g of (c) to the base oil, add to it the fatty acid or hydroxy fatty acid used to make component (c) lithium soap, and heat at 70°C. After melting at a temperature of ~80°C, add lithium hydroxide in an amount approximately equivalent to the fatty acid or hydroxy fatty acid at 80° to 90°C to form soap,
' to 150°C to dehydrate. Next, after adding dicarboxylic acid or boric acid to form component (b), it is cooled to a temperature of 80'' to 100°C, and approximately equivalent amount of lithium hydroxide to the dicarboxylic acid or boric acid is added. Then, heat and pressurize again and dehydrate again at 40° to 150°C. After dehydration is completed, heat to 195° to 215°C.

Then, it was left to cool at 175° to 193°C, and at the same temperature it became approximately 0.
Keep warm for ~40 minutes and cool under a breeze.

The lithium complex grease composition provided by the present invention as described above has a very high dropping point, very good acoustic properties, and has a long lubrication life, making it an extremely high-performance grease. be. In addition to the above properties, the inventive grease composition using a lithium salt of boric acid as a component has even higher extreme pressure properties.

Therefore, the grease composition of the present invention is suitable for lubricating bearings used in electric motors within a few seconds.
It is also very suitable as a grease for wheel bearings and ring bearings, which have an integrated bearing axle structure among automobile parts. Furthermore, since the grease composition of the present invention has excellent acoustic properties, it hardly emits any noise even when there is an antiphase in a bearing ring such as a near conditioner. A comfortable environment? can give.

Next, the present invention will be further explained by way of implementation.

Example 1 Refined mineral oil (paraffin base, viscosity index: 102, pour point knee 15°C, kinematic viscosity: 44.9 centistokes at 37.8°C, 6.4 centistokes at 98.9°C)22
33.5,9, hydride of styrene-butadiene copolymer (average molecular weight: approximately 130,000. styrene/content: 5
1300 g of a 10% solution of the above purified mineral oil (9 wt. let

Next, lithium hydroxide 38.5! ! Add a hot water bath solution (95℃ 130c19) in which the
After stirring for 0 minutes, heat steadily while applying pressure, stir at approximately 145°C for approximately 15 minutes under 8 mouth pressure (approximately 2.5 to 2.8 to 9/(7)2), and then pressurize while dehydrating. Return to normal pressure.

When the dehydration is complete, add 67.89 g of azelaic acid, gradually cool to about 90°C with stirring, and add 30 g of lithium hydroxide.
．． 2.9 was dissolved in a hot aqueous solution (95°C) 250, i" was added, and 145 to 15
Slowly heat at 5°C and apply pressure. When the same temperature is reached, open the autoclave and dehydrate at the same temperature.

After dehydration is complete, reduce the contents of the autoclave to 195~2
Heat to a temperature of 15 °C and then, with stirring,
Allow to cool to 192°C, maintain this temperature for 20 to 30 minutes, then allow to cool further, and when the temperature reaches about 160°C, add 60.9% of the antioxidant octylated diphenylamine, and stir for an additional 30 to 60 minutes. Once the temperature has dropped to about 80-85°C, it is treated with a Manton-Goring type homogenizer. The properties of the grease composition thus obtained were as follows.

Difference: +32 Dropping Point IC): 257 Grease Dust Sound Measurement Test **8 After 120 seconds: 92 (Average value of 5 measurements) * Roll stability test according to AS'I'M D18311C. Same below.

** Based on JIS K2220. Hereinafter, measurements were similarly made by the method described in Niki-Kiki Japanese Patent Publication No. 53-2357. Colleagues below.

Comparative Example 1 A grease composition was prepared in the same manner as in Example 1, except that 2533.5 g of refined mineral oil was used instead of adding the hydride of styrene-butadiene copolymer. The properties of the obtained grease composition were as follows.

Consistency (unmixed 1:246 (mixed 60 times J: 248 Shell roll test (100℃ x 5hr) difference: +
25 Dropping point T°C): 232 After 120 seconds of grease dust sound measurement test: 7534 (average value of 5 measurements) Examples 2 to 8 Each component shown in Table 1 below was treated with the same jaw as in Example 1. A grease composition was obtained. Their properties are shown in Table 1.
I will stop and write it down.

Note: Same as used in Example 1.

(21 average molecular weight approximately 10.2,000; styrene content 3
1% by weight (3) Average molecular weight approximately 260.00.0141 Average molecular weight approximately s, oo.

(51 average molecular weight approximately 130,000; ethylene content 30
Weight % +61 Same as that used in Example 1.

(7) Same as that used in Example 1.

Contains no.

Examples 9 to 21 Each component shown in Table 2A and Table 2B below was implemented mJ 1
A grease composition was obtained in the same manner as above. Their properties are listed in Tables 2A and 2B.

Note: A' = C5t to C76 polyimbutenyl base 11 mixed with 110 heavy duty bath'S to 100 heavy sunto of shoyu oil.

(2) Same as the one used in Implementation Criteria 1.

+31 Same as the one used in the first example.

110 parts by weight of +41 A'' = C52 to C16 polyimbutenyl group average molecular weight: 21?0 dissolved in 100 parts by weight of refined mineral oil.

160 parts by weight of polyisobutenyl group average molecular weight of A'==C, .~Cta: 1172 dissolved in 100 parts by weight of refined mineral oil.

A product obtained by dissolving 140 parts by weight of polyisobutenyl group average molecular weight of C5z to Cva: 304 to 140 parts by weight of Kozue's 00M.

(39 parts by weight of 71 dinonylnaphthalene/calcium sulfonate (formula below), 100 parts by weight of fully refined mineral oil) dissolved in a bath.

(81 Magnesium alkyl salicylate (formula below) (mixed alkyl group of L=C+o-C+a made from silk mineral oil)
30 parts by weight dissolved in 30 parts by weight.

(91 alkyl salicylic acid power, lucium (formula below) (R
==e,. ~ CI6 mixed alkyl group) refined mineral oil 10
35 parts by weight dissolved for 0 electric lamp parts.

Examples 22 to 25 and Comparative Example 2.3 Grease compositions were prepared by processing each component shown in Table 3 below using Example 1 and a colleague's expense. Their properties are listed in Table 3.
I will stop and write it down.

Note: Use the same composition as Example 9.

(21 average molecular weight) (72,000; styrene content 3
1% by weight.

Same as that used in (Example 31).

+41 Same as used in Example 1.

Claims (1)

[Claims] The following three components are added to the base oil, which is an oil having lubricating oil viscosity.
That is, (a) at least one lithium soap selected from lithium salts of C_1_0 to C_3_4 fatty acids and lithium salts of C_1_2 to C_2_4 hydroxy fatty acids, (b) dilithium salts of C_4 to C_1_2 aliphatic dicarboxylic acids and lithium salts of boric acid. A high dropping point lithium complex grease composition with improved acoustic properties, characterized in that at least one lithium salt selected from the following and (c) a succinimide dispersant are uniformly mixed and dispersed as essential components.