JPS6121593B2 - - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to high quality lithium complex grease compositions with high extreme pressure properties, high dropping points, and long lubrication life.

Traditionally, lithium soap grease has been widely used due to its advantages such as relatively good heat resistance and water resistance, easy dispersion of soap into all types of lubricant bases, and reasonable price. has been used. However, in the case of lithium soap grease, when the operating environment and conditions reach high temperatures of 130°C or higher, the lubricating action of the grease deteriorates due to oxidative deterioration, which destroys micelles, reduces adhesion, softens, and increases oil separation.
It has the disadvantage of being lost quickly.

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 they tend to harden or become extremely soft after long-term use. There are drawbacks such as Moreover, it has drawbacks such as being extremely expensive, and its uses are naturally limited.

On the other hand, 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 in automobiles and the like are used in areas that are close to the heat source of an engine, the grease that lubricates the bearings is exposed to particularly high temperature conditions for a long period of time. In such cases, the grease needs to have sufficient high temperature resistance, durability, etc. Additionally, with the development of industry, machines are being operated under higher loads and harsher conditions, and lubricating greases that can withstand these conditions are needed. Currently, large amounts of extreme pressure additives are added to high-load greases in order to meet high-load conditions. However, extreme pressure additives generally have the disadvantage of polluting the environment and being corrosive. For example, among additives with good extreme pressure properties, those containing cadmium, antimony, etc. can no longer be used as poisonous substances. In addition, in terms of corrosion, chlorine-based extreme pressure additives tend to rust and corrode iron, copper, etc. at temperatures above 100°C. Many other extreme pressure additives have similar properties.

The purpose of the present invention is to meet the above-mentioned needs.
High temperature resistance, durability, water resistance, extreme pressure resistance (load capacity)
Our objective is to provide excellent high-quality lithium complex grease with the following characteristics.

The above purpose is to add base oil to the base oil as a thickening agent.
A lithium complex obtained by mixing and dispersing as essential components lithium soap of C ₁₂ - _{C 24} hydroxy fatty acids, lithium borate, and sodium borate, or 4 components in which potassium borate is further added to these three components. It was discovered that this could be achieved with grease, leading to the completion of the present invention. The grease provided by the present invention is most distinctive in that it has extremely high extreme pressure properties based on the combination of the above-mentioned specific three or four components, and at the same time has a high dropping point, which is an indicator of high temperature resistance. It is true.

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

Base oil: As the base oil used in the composition of the present invention, any oil having a known lubricating viscosity that has been conventionally used in lubricating oils can be used, and the most typical oil is a refined petroleum product. mineral oil, which is one of the mineral oils; α-olefin oligomers (e.g. viscosity 41.0cSt/37.8℃, viscosity index 130, pour point -60
Synthetic oils such as polyglycol oils, silicone oils, polyphenyl ether oils, halogenated hydrocarbon oils, and alkylbenzene oils can also be used alone or in combination with mineral oils. Can be used in combination.

Here, "oil having a lubricating viscosity" generally has a viscosity of about 2 to 500 cSt at 40°C, preferably about 20 to 500 cSt.
Refers to oil having a viscosity within the range of 200 cSt.

(a) Component: The lithium soap added to the base oil according to the invention is selected from lithium salts of _C12 to _C24 hydroxy fatty acids. The _C12 - _C24 hydroxy fatty acids used in the formation of such lithium salts are usually straight-chain saturated or unsaturated aliphatic monocarboxylic acids having hydroxyl groups in the molecule, and specifically include, for example, 2 -Hydroxydodecanoic acid, 2
-Hydroxytetradecanoic acid, 2-hydroxyhexadecanoic acid, 11-hydroxyhexadecanoic acid, ampretrichic acid, ricinoleic acid, ricinostearollic acid, 9-hydroxystearic acid, 10-hydroxystearic acid, 12-hydroxystearic acid, etc. among them those having 18 carbon atoms and hydroxyl group 9-,
Those bonded at the 10- or 12-position, especially 12-hydroxystearic acid and ricinoleic acid, are preferred.

Each of the above lithium salts of hydroxy fatty acids can be used alone, or two or more kinds can be used in combination. In addition, when forming the lithium salt from the above-mentioned hydroxy fatty acid, the hydroxy fatty acid can be reacted with lithium hydroxide not only in the form of a free acid but also in the form of a glyceride.

(b) Component: The second component added to the base oil according to the present invention is a lithium salt of boric acid. The lithium salt may be present in the form of monolithium borate, lithium metaborate, lithium tetraborate, lithium pentaborate, lithium perborate, etc., or a mixture of two or more thereof.

(c) Component: The third component added to the base oil according to the present invention is the sodium salt of boric acid. This sodium salt may also exist in the form of sodium orthoborate, sodium diborate, sodium metaborate, sodium tetraborate, sodium pentaborate, sodium octaborate, etc., or a mixture of two or more of these. Note that the lithium salt of boric acid as the component (b) and the sodium salt of boric acid as the component (c) may be used in the form of separate single salts, or as a composite metal lithium-sodium salt of boric acid. It can also be used in the form of salts or mixed metal salts. Of course, the latter composite metal salt or mixed metal salt can be used as a component that simultaneously fulfills the roles of component (b) and component (c).

(d) Component: The fourth component added to the base oil according to the present invention is a potassium salt of boric acid. The potassium salt may also be present in the form of potassium orthoborate, potassium diborate, potassium metaborate, potassium tetraborate, potassium pentaborate, potassium octaborate, etc., or a mixture of two or more of these.

In addition, the lithium salt of boric acid as the component (b), the sodium salt of boric acid as the component (c), and
Potassium salts of boric acid as component (d) may be used in the form of individual salts, or may be used in the form of lithium-sodium-potassium complex metal salts or mixed metal salts of boric acid. can. The latter mixed metal salt can be used as a component that simultaneously fulfills the roles of component (b), component (c), and component (d).

Preparation of grease composition: The grease composition of the present invention contains three components (a), (b), and (c) or (a), (b), (c),
It can be produced by uniformly mixing the four components (d) and finely dispersing them. At that time
The amount of each component (a), (b), (c), and (d) in the base oil is not strict and varies depending on the type of each component, but in general, the proportions below are per 100 parts by weight of the base oil. (within a suitable range).

(a) Component: 2 to 40 parts by weight (5 to 20 parts by weight) (b) Component: 0.05 to 20 parts by weight (0.1 to 10 parts by weight) (c) Component: 0.05 to 20 parts by weight (0.1 to 10 parts by weight) ) (d) Component: 0.05 to 20 parts by weight (0.1 to 10 parts by weight) The grease composition of the present invention contains the above (a), (b) and (c).
In addition to the three components or the four components (a), (b), (c) and (d), if necessary, ordinary lubricating oil additives, such as
Antioxidants (e.g. 2,6-ditertyabutyl)
(4-methylphenol, N-phenyl-α-naphthylamine, octylated diphenylamine, etc.), rust inhibitors (e.g. paraffin oxide, aminoimidazoline, calcium dinonylnaphthalenesulfonate, barium dinonylnaphthalenesulfonate, etc.) are usually used. It can also be added in the amount shown.

Next, a general method for producing the grease of the present invention will be described.

In the grease of the present invention, a hydroxy fatty acid to form component (a) is added to a base oil and dissolved at a temperature of 70 to 80°C. Next, lithium hydroxide in an amount approximately equivalent to the hydroxy fatty acid is added at 80 to 90°C to produce soap. Then let it cool down a little to 70-80℃
Then, add boric acid to form component (b), and add approximately equivalent amount of lithium hydroxide. moreover,
Add boric acid to form component (c), and add about an equivalent amount of sodium hydroxide or both sodium hydroxide and potassium hydroxide. In addition,
Here, the entire amount of boric acid may be added at once, and then lithium hydroxide and sodium hydroxide or both sodium hydroxide and potassium hydroxide may be added. After that, heat and pressurize to 140℃.
Raise the temperature to ~150°C and start dehydration when it reaches 140-150°C. Once dehydration is complete, the temperature will be 195-220℃.
Heat to temperature, then cool to 175-193°C, maintain at that temperature for 10-40 minutes, and cool.

The lithium complex grease composition provided by the present invention as described above has a very high dropping point and long lubrication life, which are indicators of high temperature resistance, and has high extreme pressure properties, and is extremely effective as a grease. It is of high performance.

The present invention will be further explained below with reference to Examples.

Note that lithium hydroxide used in Examples and Comparative Examples is a monohydrate, and potassium hydroxide and sodium hydroxide are each anhydrous salts.

Example 1 Refined mineral oil (paraffin base, viscosity index 102,
Pour point -15℃, kinematic viscosity 44.9cSt at 37.8℃, 98.9℃
6.4 cSt) 2501.7 g and 270 g of 12-hydroxystearic acid are placed in the autoclave No. 5, and heated to 80° C. over 30 to 40 minutes while stirring to completely dissolve the 12-hydroxystearic acid. Next, a hot aqueous solution containing 38.5 g of lithium hydroxide (95
℃) and maintain at 90℃ for 5-15 minutes with stirring. It was then cooled to 75°C and diluted with boric acid 44.4
Add 300 g of a hot aqueous solution (95°C) in which g is dissolved and stir to dissolve. After stirring for 5 to 15 minutes, 250 g of a hot aqueous solution (95°C) containing 31.4 g of lithium hydroxide is added and stirred for 5 to 15 minutes. A hot aqueous solution (95℃) in which 44.4g of boric acid was dissolved while maintaining the temperature between 75 and 80℃.
Add 300g and stir to dissolve. After stirring for 5 to 15 minutes, an aqueous solution containing 9.6 g of sodium hydroxide (30
℃) and continue heating gradually while stirring. Heat slowly to 145-150°C over about 1-1.5 hours, pressurize, and when the same temperature is reached, open the autoclave and dehydrate at the same temperature for 15-25 minutes. Once dehydration is complete, the contents of the autoclave are heated to a temperature of 205-220°C, then cooled with stirring to 185-192°C, maintained at this temperature for 20-30 minutes, and then cooled further to approximately 160°C. Add 60g of antioxidant. Continue stirring for an additional 30-60 minutes until the temperature drops to about 85°C, then process with a Manton-Goring type homogenizer.

The properties of the grease composition thus obtained were as follows.

Stability ^*1 (immiscible) 254 (mixed 60 times) 258 Shell roll test ^*2 (100℃ x 5h) Before test: 127 After test: 153 Difference: +26 Dropping point (℃) ^*1 : 253 Oil separation degree ^*1 (100℃ x 24h): 2.9% Heated copper plate corrosion ^*1 (100℃ x 24h): Passed Shell 4-ball test ^*3 Fusion load: 356Kg Initial seizure load: 79Kg Average Hertzian load: 44.6Kg *1 JIS By K2220.

*2 Roll stability test based on ASTM D1831.

*3 According to IP239.

Example 2 In order to reduce the amounts of lithium borate and sodium borate in half in the grease prepared in Example 1, 22.2 g of boric acid to form lithium borate,
A grease composition was prepared in the same manner as in Example 1, except that 15.7 g of lithium hydroxide, 22.2 g of boric acid to form sodium borate, 4.8 g of sodium hydroxide, and 2566.5 g of refined mineral oil were used. Prepared. The properties of the obtained grease composition were as follows.

Stiffness (immiscible): 250 (mixed 60 times): 254 Shell roll test (100℃ x 5h) Before test: 125 After test: 142 Difference: +17 Dropping point (℃): >260 Shell 4-ball test Melting Load: 282Kg Example 3 In the method described in Example 1, lithium borate and boric acid to form sodium borate were combined and the total amount of 88.8g was added at once, and then approx.
A grease composition was prepared in the same manner as in Example 1 except that lithium hydroxide and sodium hydroxide were added simultaneously after stirring for 10 minutes.

The properties of the obtained grease composition were as follows.

Stiffness (immiscible): 256 (mixed 60 times): 263 Shell roll test (100℃ x 5h) Before test: 128 After test: 148 Difference: +20 Dropping point (℃): 254 Shell 4-ball test Fusion Load: 355Kg Example 4 In order to change the amount of lithium borate and sodium borate in the grease prepared in Example 3 to one and a half times, 133.2g of boric acid, 47.6g of lithium hydroxide, and 47.6g of sodium hydroxide were added. A grease composition was prepared in the same manner as in Example 3, except that 2436.3 g of refined mineral oil was used.

The properties of the obtained grease composition were as follows.

Stiffness (immiscible): 252 (mixed 60 times): 258 Shell roll test (100℃ x 5h) Before test: 126 After test: 149 Difference: +23 Dropping point (℃): 242 Shell 4-ball test Fusion Load: 355Kg Example 5 Refined mineral oil (paraffin base, viscosity index 102,
Pour point -15℃, kinematic viscosity 44.9CSt at 37.8℃, 98.9℃
2499.7 g of 12-hydroxystearic acid (6.4 cSt) and 270 g of 12-hydroxystearic acid were placed in the autoclave of Step 5, and heated to 80°C for 30 to 40 minutes with stirring.
Completely dissolve hydroxystearic acid. Next, 300g of a hot aqueous solution (95℃) containing 38.5g of lithium hydroxide was added, and the solution was heated at 90℃ for 5 to 15 minutes with stirring.
Maintain for minutes. Then cool to 75℃ and add boric acid.
Add 300 g of a hot aqueous solution (95°C) containing 44.4 g and stir to dissolve. After stirring for 5 to 15 minutes, add 250 g of a hot aqueous solution (95°C) containing 31.4 g of lithium hydroxide.
Add and stir for 5 to 15 minutes. A hot aqueous solution containing 44.4 g of boric acid (95
℃) and stir to dissolve. After stirring for 5 to 15 minutes, 50 g of an aqueous solution (30°C) containing 4.8 g of sodium hydroxide and 6.8 g of potassium hydroxide was added, and the mixture was gradually heated while stirring. Heat slowly to 145-150℃ over about 1-1.5 hours, pressurize, and when the same temperature is reached, open the autoclave.
Dehydrate at the same temperature for 15 to 25 minutes. Once dehydration is complete, the contents of the autoclave are heated to a temperature of 205-220°C, then cooled with stirring to 185-192°C, maintained at this temperature for 20-30 minutes, and then cooled further to approximately 160°C. Add 60g of antioxidant. Continue stirring for an additional 30-60 minutes until the temperature drops to about 85°C, then process with a Manton-Goring type homogenizer.

The properties of the obtained grease composition were as follows.

Stiffness (immiscible): 277 (mixed 60 times): 286 Shell roll test (100℃ x 5h) Before test: 139 After test: 153 Difference: +14 Dropping point (℃): 250 Shell 4-ball test Fusion Load: 355Kg Comparative Example 1 44.4g of boric acid to form lithium borate
A grease composition was prepared in the same manner as in Example 1, except that 2577.5 g of refined mineral oil was used instead of adding 31.4 g of lithium hydroxide. The properties of the obtained grease composition were as follows.

Stiffness (immiscibility): >500 Shell type 4-ball test Fusion load: 282Kg This is a fluid-like product with a stiffness of 500 or more and no grease form, and is completely useless as a grease. I don't have it.

Comparative Example 2 Boric acid 44.4 to form sodium borate
A grease composition was prepared in the same manner as in Example 1, except that 2555.7 g of refined mineral oil was used instead of adding 9.6 g of sodium hydroxide and 9.6 g of sodium hydroxide. The properties of the obtained grease composition were as follows.

Stiffness (immiscible): 246 (mixed 60 times): 236 Shell roll test (100℃ x 5h) Before test: 123 After test: 148 Difference: +25 Dropping point (℃): >260 Shell 4-ball test melting Load: 251Kg Comparative Example 3 44.4g of boric acid to form lithium borate
and 31.4 g of lithium hydroxide and 44.4 g of boric acid and sodium hydroxide to form sodium borate.
A grease composition was prepared in the same manner as in Example 1 except that 2631.5 g of refined mineral oil was used instead of adding 9.6 g. The properties of the obtained grease composition were as follows.

Stiffness (immiscible): 235 (mixed 60 times): 233 Shell roll test (100℃ x 5h) Before test: 117 After test: 165 Difference: +48 Dropping point (℃): 200 Shell 4-ball test fusion Load: 158Kg Comparative Example 4 360g of stearic acid to form lithium stearate instead of adding 270g of 12-hydroxystearic acid and 38.5g of lithium hydroxide to form lithium 12-hydroxystearate
and 54.4g of lithium hydroxide, and refined mineral oil.
A grease composition was prepared in the same manner as in Example 1 except that 2395.8g was used. The properties of the obtained grease composition were as follows.

Stiffness (immiscible): 238 (mixed 60 times): 272 Shell roll test (100℃ x 5h) Before test: 119 After test: 255 Difference: +136 Dropping point (℃): 197 Shell 4-ball test Fusion Load: 251Kg Comparative Example 5 The properties of a commercially available general-purpose lithium 12-hydroxystearate soap grease containing no extreme pressure additives were as follows.

Stiffness (immiscible): 272 (mixed 60 times): 273 Shell roll test (100℃ x 5h) Before test: 137 After test: 168 Difference: +31 Dropping point (℃): 180 Shell 4-ball test Fusion Load: 200Kg Initial baking load: 63Kg Average Hertzian load: 29.6Kg Comparative Example 6 The properties of commercially available lithium 12-hydroxystearate soap grease containing sulfide and lead compounds as extreme pressure additives were as follows. .

Degree of purity (immiscibility): 282 (mixed 60 times): 276 Shell roll test (100℃ x 5h) Before exam: 141 After exam: 180 Difference: +39 Dropping point (℃): 184 Ciel 4-ball test Fusion load: 355Kg Initial seizure load: 89Kg Average Hertz load: 47.8Kg

Claims (1)

[Scope of Claims] 1 A base oil consisting of an oil having lubricating viscosity is added with the following three components as thickeners: (a) lithium soap of C ₁₂ to C ₂₄ hydroxy fatty acids, (b) boric acid A high dropping point lithium complex grease composition having high extreme pressure properties characterized by uniformly mixing and dispersing a lithium salt and (c) a sodium salt of boric acid as essential components. 2 A base oil consisting of an oil with lubricating viscosity is added with the following four components as thickeners: (a) lithium soap of _C12 - _C24 hydroxy fatty acid (b) lithium salt of boric acid (c) boric acid A high dropping point lithium complex grease composition having high extreme pressure properties characterized by uniformly mixing and dispersing potassium salt of boric acid (d) as an essential component.