JP2015147867A - lubricating grease composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a lubricating grease composition excellent in rust-prevention properties and water repellency.SOLUTION: There is provided a lubricating grease composition which is obtained by blending an oxazoline compound and a metal sulfonate in a grease base material composed of a base oil and a thickener, wherein the amount blended of the oxazoline compound is in the range of 0.4 to 3.5 wt.% based on the whole weight of the grease, the amount blended of the metal sulfonate is in the range of 0.4 to 3.5 wt.% based on the whole weight of the grease and the total amount of blending of the oxazoline compound and the metal sulfonate is preferably in the range of 0.9 to 6.5 wt.% based on the whole weight of the lubricating grease composition.

Description

  The present invention relates to a lubricating grease composition, and more particularly, to a lubricating grease composition having excellent rust resistance and water resistance.

  In recent years, lubricating grease has been used in various industrial fields such as steel, automobiles, general machinery and precision equipment in emerging markets such as Russia, Brazil and Southeast Asia. For this reason, lubrication grease is required to cope with high-temperature and high-humidity environments and salt mud water in areas where roads are not paved.

  If water is mixed in, the lubricity is deteriorated and the grease is often softened and leaked, resulting in poor lubrication.

  At the same time, rust prevention characteristics are required in view of rusting of parts due to mixed water, use of equipment in coastal areas, and generation of rust during overseas transportation of parts.

  Therefore, it is necessary for the grease to have both excellent antirust and water resistance functions even when mixed with water.

  Patent Document 1 discloses a technique in which metal salicylate and an alkyl methacrylate copolymer are blended with metal soap grease to suppress softening when mixed with water.

  Moreover, in patent document 2, the technology which improves rust resistance by mix | blending a specific two types of thickener with a specific ratio, and improving water resistance and pumpability, and also mix | blending a rust preventive agent. It is disclosed.

JP 2009-256444 A JP 2007-070461 A

  However, Patent Document 1 does not have a rust preventive function, and the rust preventive function according to Patent Document 2 does not reach the currently required function.

  Then, this invention makes it a subject to provide the lubricating grease composition which is excellent in rust prevention property and water resistance.

  Other problems of the present invention will become apparent from the following description.

  The above problems are solved by the following inventions.

1. Oxazoline compound and metal sulfonate are blended with grease base material consisting of base oil and thickener,
The blending amount of the oxazoline compound is in the range of 0.4 to 3.5 wt% with respect to the total grease weight, and the blending amount of the metal sulfonate is in the range of 0.4 to 3.5 wt% with respect to the total grease weight. A lubricating grease composition.

  2. 2. The lubricating grease composition as described in 1 above, wherein the total amount of the oxazoline compound and the metal sulfonate is in the range of 0.9 to 6.5 wt% with respect to the total weight of the lubricating grease composition.

  3. 3. The lubricating grease composition according to 1 or 2 above, wherein the weight ratio of the oxazoline compound to the metal sulfonate is oxazoline compound / metal sulfonate = 80/20 to 20/80.

  4). The base oil contains at least one selected from mineral oil, synthetic hydrocarbon oil, ester synthetic oil, ether synthetic oil, or glycol synthetic oil. Lubricating grease composition.

  5. 5. The lubricating grease composition as described in any one of 1 to 4 above, wherein the thickener contains at least one selected from metal soaps, composite metal soaps, and urea compounds.

  According to the present invention, it is possible to provide a lubricating grease composition that is excellent in rust resistance and water resistance.

  Embodiments of the present invention will be described below.

  The lubricating grease composition of the present invention is obtained by blending an oxazoline compound and a metal sulfonate with a grease base material composed of a base oil and a thickener.

  By blending an oxazoline compound and a metal sulfonate as a rust preventive agent, it is possible to provide a lubricating grease composition that is excellent not only in rust prevention but also in water resistance.

<Base oil>
As the base oil, it is preferable to use at least one base oil selected from mineral oil, synthetic hydrocarbon oil, ester synthetic oil, ether synthetic oil, and glycol synthetic oil.

  One of these base oils may be selected, or two or more base oils may be used in combination.

  Examples of the mineral oil include paraffinic and naphthenic oils.

  Examples of the synthetic hydrocarbon include poly α olefin, ethylene α olefin oligomer, and polybutene.

  Examples of the ester-based synthetic oil include ester oils such as diesters, polyol esters, and aromatic esters. Examples of the ether synthetic oil include alkyl diphenyl ether.

  Examples of the glycol-based synthetic oil include polyethylene glycol and polypropylene glycol.

  In consideration of the influence on the resin and rubber, it is preferable to use a synthetic hydrocarbon oil, but it is not particularly limited in the present invention.

<Thickener>
As the thickener, at least one selected from metal soaps, composite metal soaps, and urea compounds can be used.

  Examples of the metal soap system include Li soap, Ca soap, aluminum soap, and among them, Li soap can be preferably used.

  Examples of Li soaps include aliphatic monocarboxylic acids having 12 to 24 carbon atoms and / or lithium salts of aliphatic monocarboxylic acids having 12 to 24 carbon atoms containing at least one hydroxyl group. A lithium stearate salt or a lithium stearate salt can be preferably used.

Examples of the method for preparing Li soap include the following methods.
By mixing a predetermined amount of base oil, 12-hydroxystearic acid and lithium hydroxide, performing a saponification reaction by heating and stirring at about 80 to 130 ° C. in a mixing and stirring vessel, heating and stirring to the melting temperature, and then cooling. Then, a gel material mixed with base oil and Li soap is prepared.
Then, after adding various additives and stirring, a lubricating grease composition can be prepared through a roll mill or a high-pressure homogenizer.

  Examples of the composite metal soap system include Li composite soap, Ca composite soap, Ba composite soap, etc. Among them, Li composite soap and Ba composite soap can be preferably used.

  Li complex soap includes (a) two or more types of lithium-based complex soaps, or (a) component aliphatic monocarboxylic acids and (b) aliphatic dicarboxylic acids having 2 to 12 carbon atoms or diesters thereof. And lithium-based composite soaps with at least one of C7-24 aromatic monocarboxylic acids or esters thereof.

Examples of the method for preparing the Li composite soap include the following methods.
A base oil, 12 hydroxystearic acid and lithium hydroxide are mixed in a predetermined amount in a mixing and stirring vessel, heated and stirred at about 80 to 130 ° C. to carry out a saponification reaction, and further azelaic acid is mixed in a predetermined amount at about 80 to 200 ° C. The mixture is heated and stirred, lithium hydroxide is added thereto, and the mixture is cooled to produce a gel substance in which the base oil and the Li composite soap are mixed.
Then, after adding various additives and stirring, a lubricating grease composition can be prepared through a roll mill or a high-pressure homogenizer.

  Examples of the Ba complex soap include complex soaps of aliphatic dicarboxylic acid and monoamide carboxylic acid.

Examples of the method for preparing the Ba composite soap include the following methods.
Base oil, sebacic acid and carboxylic acid monostearylamide are mixed in a predetermined amount in a mixing and stirring kettle, heated and stirred at about 80 to 200 ° C., barium hydroxide is added thereto, and cooled, so that the base oil and Ba composite are mixed. Create a gel-like substance mixed with soap.
Then, after adding various additives and stirring, a lubricating grease composition can be prepared through a roll mill or a high-pressure homogenizer.

  Examples of the urea compound include diurea compounds, triurea compounds, tetraurea compounds, polyurea compounds, and the like, and diurea compounds are preferably used.

Specific examples of urea compounds include those represented by the following general formula.
Formula R ′ (NHCONHR) nNHCONHR ″
In the formula, R represents a divalent aromatic hydrocarbon group. R ′ and R ″ each represent a monovalent C6-C24 aliphatic saturated or unsaturated hydrocarbon group, alicyclic hydrocarbon group or aromatic hydrocarbon group. N is an integer and n = 1 is a diurea compound. , N = 2 is a triurea compound, n = 3 is a tetraurea compound, and n = 4 or more is a polyurea compound.

Examples of the method for preparing the urea compound include the following methods.
A base oil, diphenylmethane diisocyanate, and octylamine are heated and stirred at 70 to 180 ° C. to react, and the temperature is raised and cooled to create a gel-like substance in which the base oil and the urea compound are mixed.
Then, after adding various additives and stirring, a lubricating grease composition can be prepared through a roll mill or a high-pressure homogenizer.

<Oxazoline compound>
As the oxazoline compound, 2-heptadecynyl-2-oxazoline-4,4-dimethanol, 2-heptadecyl-2-oxazoline-4,4-dimethanol, 2-alkyl-2-oxazoline-4,4-dimethanol, Examples thereof include 2-alkenyl-2-oxazoline-4,4-dimethanol, and 2-heptadecynyl-2-oxazoline-4,4-dimethanol can be preferably used among them.

  A commercial item can be used for an oxazoline compound, for example, "ALKATERGE-T" by ANGUS Chemical Company, etc. are mentioned.

  The blending amount of the oxazoline compound is preferably in the range of 0.4 to 3.5 wt%, more preferably 0.5 to 3 wt%, and still more preferably 0.5 to the total lubricating grease composition weight. ˜2 wt%.

  If the blending amount of the oxazoline compound is less than 0.4 wt% with respect to the total weight of the lubricating grease composition, the optimum rust preventive property is lacking, and if it exceeds 3.5 wt%, the water resistance is not preferred.

<Metal sulfonate>
In the present invention, the metal sulfonate refers to metal salts of various sulfonic acids.

  Examples of the sulfonic acid include aromatic petroleum sulfonic acid, alkyl sulfonic acid, aryl sulfonic acid, alkyl aryl sulfonic acid, and the like. More specifically, dodecylbenzene sulfonic acid, dilauryl cetyl benzene sulfonic acid, paraffin wax-substituted benzene sulfone. Examples include acids, polyolefin-substituted benzene sulfonic acids, polyisobutylene-substituted benzene sulfonic acids, naphthalene sulfonic acids, and dinonyl naphthalene sulfonic acids. Of these, aromatic petroleum sulfonic acid and dinonylnaphthalene sulfonic acid are preferred.

  Examples of the metal include various metals such as calcium, barium, magnesium, zinc, sodium, and lithium.

  Furthermore, as a metal sulfonate, you may use the composite_body | complex of these sulfonic acid metal salts and a carboxylic acid metal salt and / or a carboxylic acid ester metal salt.

  As the metal sulfonate in the present invention, calcium sulfonate, barium sulfonate, zinc sulfonate, sodium sulfonate, and lithium sulfonate can be preferably used, and calcium sulfonate, barium sulfonate, and zinc sulfonate are more preferable.

  Commercially available metal sulfonates can be used, such as “NA-SUL CA-1089” manufactured by KING as calcium sulfonate, “NA-SUL BSN” manufactured by KING as barium sulfonate, “NA-SUL” manufactured by KING as zinc sulfonate. ZS ”,“ NA-SUL SS ”manufactured by KING as sodium sulfonate,“ NA-SUL 707 ”manufactured by KING as lithium sulfonate, and the like.

  The blending amount of the metal sulfonate is preferably in the range of 0.4 to 3.5 wt%, more preferably 0.5 to 3 wt%, and still more preferably 0.5 to the total lubricating grease composition weight. ˜1 wt%.

  If the blending amount of the metal sulfonate is less than 0.35 wt% or more than 3.5 wt% with respect to the total lubricating grease composition weight, the water resistance is insufficient, which is not preferable.

<Blending amount>
The total amount of the oxazoline compound and the metal sulfonate is preferably in the range of 0.9 to 6.5 wt%, more preferably 1 to 5 wt%, and still more preferably, based on the total lubricating grease composition weight. Is 1.5 to 2.5 wt%.

  If the total blending amount of the oxazoline compound and the metal sulfonate is less than 0.9 wt% or more than 6.5 wt% with respect to the total weight of the lubricating grease composition, it tends to lack water resistance, which is not preferable.

  The weight ratio of the oxazoline compound to the metal sulfonate is preferably in the range of oxazoline compound / metal sulfonate = 80/20 to 20/80, more preferably 80/20 to 25/75, and still more preferably 80/20. It is in the range of ~ 65/35.

  If the oxazoline compound is added in a weight ratio of more than 80/20 with respect to the metal sulfonate, it tends to lack water resistance and waterproofness, which is not preferable.

<Others>
Other substances may be added to the lubricating grease composition of the present invention as long as the effect thereof is not affected. For example, known antioxidants, extreme pressure agents, oiliness agents, viscosity index improvers and the like can be appropriately selected and added.

  Examples of the antioxidant include phenolic antioxidants such as 2,6-di-tert-butyl-4-methylphenol and 4,4′-methylenebis (2,6-di-tert-butylphenol), alkyldiphenylamine, Examples include triphenylamine, phenyl-α-naphthylamine, phenothiazine, alkylated-α-naphthylamine, and alkylated phenothiazine.

  Examples of extreme pressure agents include phosphorus compounds such as phosphate esters, phosphite esters, phosphate ester amine salts, sulfur compounds such as sulfides and disulfides, dialkyldithiophosphates, metal salts of dialkyldithiocarbamic acid, and the like. It is done.

  Examples of the oily agent include fatty acids or esters thereof, higher alcohols and polyhydric alcohols or esters thereof, aliphatic amines, and aliphatic monoglycerides.

  Examples of the viscosity index improver include polymethacrylate, ethylene-propylene copolymer, polyisobutylene, polyalkylstyrene, styrene-isoprene copolymer hydride, and the like.

  Examples of the present invention will be described. The present invention is not limited to the embodiments.

1. Preparation method of each lubricating grease composition <Preparation of Li soap-based lubricating grease composition>
The base oil shown in the table, 12-hydroxystearic acid and lithium hydroxide are blended in the amounts shown in the table, and the mixture is stirred and heated at about 80 to 130 ° C. in a mixing and stirring vessel, and stirred to the melting temperature. And then cooled. The resulting gel material was mixed with 1 wt% of an antioxidant and the compounds shown in the table as a rust inhibitor and stirred, and then passed through a roll mill or a high-pressure homogenizer to prepare a lubricating grease composition.

<Preparation of Ba complex soap-based lubricating grease composition>
The base oil shown in the table, sebacic acid and carboxylic acid monostearylamide were mixed in a mixing and stirring vessel, heated and stirred at about 80 to 200 degrees, barium hydroxide was added thereto, and the mixture was cooled. The total amount of barium composite soap was blended as shown in the table. The resulting gel material was mixed with 1 wt% of an antioxidant and the compounds shown in the table as a rust inhibitor and stirred, and then passed through a roll mill or a high-pressure homogenizer to prepare a lubricating grease composition.

<Preparation of Li composite soap-based lubricating grease composition>
The base oil shown in the table, 12-hydroxystearic acid and lithium hydroxide are blended in a predetermined amount in a mixing and stirring kettle, heated and stirred at about 80 to 130 ° C. for saponification reaction, and further azelaic acid is blended in a predetermined amount, The mixture was heated and stirred at about 80 to 200 ° C., lithium hydroxide was added thereto, and the mixture was cooled. The total amount of lithium composite soap was blended in the amounts shown in the table. The resulting gel material was mixed with 1 wt% of an antioxidant and the compounds shown in the table as a rust inhibitor and stirred, and then passed through a roll mill or a high-pressure homogenizer to prepare a lubricating grease composition.

<Preparation of urea compound lubricating grease composition>
The base oil shown in the table, diphenylmethane diisocyanate and octylamine were blended in the amounts shown in the table, and the reaction was conducted by heating and stirring at 70 to 180 ° C., and the temperature was raised and cooled. The total amount of urea compounds was blended in the amounts shown in the table. The resulting gel material was mixed with 1 wt% of an antioxidant and the compounds shown in the table as a rust inhibitor and stirred, and then passed through a roll mill or a high-pressure homogenizer to prepare a lubricating grease composition.

2. Details of base oil, rust inhibitor and antioxidant used in Examples <Base oil>
Poly-α-olefin A: 40 ° C. viscosity 18 mm ² / s (“DURASYN164” manufactured by Ineos Oligomers Japan)
Poly-α-olefin B: 40 ° C. viscosity 68 mm ² / s (“DURASYN170” manufactured by Ineos Oligomers Japan)
Paraffin-based mineral oil A: 40 ° C. viscosity 22 mm ² / s (“Super Oil N22” manufactured by JX Nippon Oil & Energy Corporation)
Paraffinic mineral oil B: viscosity at 40 ° C. of 141 mm ² / s (“Super Oil N150” manufactured by JX Nippon Oil & Energy Corporation)
Polyol ester: 40 ° C. viscosity 29 mm ² / s (“Unistar H-334R” manufactured by NOF Corporation)
Diphenyl ether: 40 ° C. viscosity 100 mm ² / s (MORESCO “MORESCO HILUB LB-100”)

<Rust preventive>
Oxazoline (2-heptadecynyl-2-oxazoline-4,4-dimethanol): “ALKATERGE-T” manufactured by ANGUS Chemical Company
Calcium sulfonate: “NA-SUL CA-1089” manufactured by KING
Barium sulfonate: “NA-SUL BSN” manufactured by KING
・ Zinc sulfonate: “NA-SUL ZS” manufactured by KING
・ Sodium sulfonate: “NA-SUL SS” manufactured by KING
Lithium sulfonate: “NA-SUL 707” manufactured by KING
・ Sorbitan monooleate: “Ionet S-80S” manufactured by Sanyo Chemical Industries
Aspartic acid derivative: “K-CORR 100A2” manufactured by KING
・ Zinc 2-ethylhexanoate: Nacalai Tesque ・ Oxidized paraffin metal salt: “OX-0851” manufactured by Nippon Seiwa Co., Ltd.
・ Sarcosine derivative: “SARKOSYL O” manufactured by BASF
・ Alkenyl succinic acid: "Sunhibitor 102" manufactured by Sanyo Chemical Industries

<Antioxidant>
In the examples, phenyl-α-naphthylamine (VANLUBE81 manufactured by Sanyo Chemical Industries) was used as an antioxidant.

3. Examples, Comparative Examples <Examples 1-8, 11, 12, 17-21, Comparative Examples 1-17, 21-23>
As described above <Preparation of Li soap-based lubricating grease composition>, the blending materials shown in the table were blended in the amounts shown in the table to obtain a lubricating grease composition.

<Examples 9, 10, 22-24, Comparative Example 18>
As described above <Preparation of Ba complex soap-based lubricating grease composition>, the blending materials shown in the table were blended in the amounts shown in the table to obtain a lubricating grease composition.

<Examples 13 to 16, Comparative Example 19>
As described in <Preparation of Li composite soap-based lubricating grease composition>, the blending materials shown in the table were blended in the amounts shown in the table to obtain a lubricating grease composition.

<Examples 25 and 26, Comparative Example 20>
As described above in <Preparation of urea compound lubricating grease composition>, the blending materials shown in the table were blended in the amounts shown in the table to obtain a lubricating grease composition.

4). Evaluation Method The obtained lubricating grease composition was evaluated for the following items, and the results are shown in Tables 1 to 4.

<Rust prevention evaluation>
About the obtained lubricating grease composition, the rust prevention test was done as follows based on DIN51802 (EMCOR test).
The specified self-aligning ball bearing (1306K) is filled with 10 g of the lubricating grease composition, attached to the Emco testing machine, and 30 ml of 7% saline is added to the testing machine, and then rotated at 80 rpm for 8 hours at room temperature. The time stop was repeated twice. Thereafter, after further operation for 8 hours, the system was left for 108 hours, and the rusting state of the bearing outer ring raceway surface was evaluated in 6 stages according to the following criteria.
0: No rusting 1: Very weak rusting (rusting within 3 points)
2: Weak rusting (rusting part is less than 1% of the surface)
3: Rusting (rusting part is 1% or more and less than 5% of the surface)
4: Strong rusting (rusting is 5% or more and less than 10% of the surface)
5: Very strong rusting (rusting is 10% or more of the surface)

<Water Resistance Evaluation 1 (Washing Water Resistance Test)>
About the obtained lubricating grease composition, the water-washing water resistance test was done based on JIS K2220.16: 2013.
Test temperature: 38 ° C
The amount of leakage of the rust preventive compounded grease was evaluated with respect to the leakage amount (wt%) of the grease composition not containing the rust preventive agent.
In the present invention, if the increase amount is less than 20, the water resistance is not lowered by the addition of the rust inhibitor, and it can be evaluated that the water resistance is good.

<Water resistance evaluation 2 (hydrous four-ball test)>
The obtained lubricating grease composition was mixed with 15 wt% of distilled water, and in accordance with ASTM D4172, a high-speed four-ball test (test equipment: shell four-ball test, test piece: upper and lower test balls SUJ2 (steel) (1/2 inch) ), 20 grade, room temperature, 1200 rpm, 392 N, 60 minutes), and the wear scar diameter (mm) after the test was measured.
It can be evaluated that the smaller the value is, the smaller the deterioration of the lubricating grease composition function (wear resistance) when water is contained, and the better the water resistance.
In the present invention, if the value is less than 1.0, it can be evaluated that the water resistance is good.

5. Evaluation According to Examples and Comparative Examples 4 and 21 to 23, a lubricating grease composition having rust resistance and water resistance can be obtained by combining oxazoline and metal sulfonate as rust inhibitors in combination. I can confirm. Even if only one of them is blended, these effects cannot be obtained.

  Moreover, according to the results of Comparative Examples 12 to 20, it is clearly understood that as another compound used together with the oxazoline, water resistance cannot be obtained with a compound other than metal sulfonate.

  Furthermore, from Comparative Examples 1-3, 8, and 9, even if it is a combination of oxazoline and metal sulfonate, even if the total blending amount is too small, too much water lacks, especially when the blending amount is increased, It is suggested that the water resistance works in the direction of inhibition.

  Furthermore, from Comparative Examples 5 to 7, 10, and 11, the blending ratio of oxazoline and metal sulfonate is preferably oxazoline compound / metal sulfonate = 80/20 to 20/80, and exhibits water resistance and rust prevention effects. Can be confirmed.

  The lubricating grease composition of the present invention can be suitably used for bearings, gears, rubber seals, etc. that require rust prevention and water resistance. Specifically, the electric radiator fan motor, fan coupling, Rolling bearings, sliding bearings or gears for automobile accessories such as electric control EGR, electronic control slot valve, alternator, idler pulley, electric brake, hub unit, water pump, power window, sliding door, wiper, electric power steering, rubber seal It can be used for parts.

  In addition, control switches for automatic transmissions that require rust prevention, lever control switches, push switches and other electrical contact parts that require rust prevention and lubrication, the X-ring part of viscous couplings, and exhaust brakes O-rings, rubber seals, headlights, seats, ABS, door locks, door hinges, clutch boosters, two-part flywheels, window regulators, ball joints, clutch booster gears, sliding parts, fishing gears and automobile It can also be applied to rolling bearings, gear parts, and the like.

Claims (5)

Oxazoline compound and metal sulfonate are blended with grease base material consisting of base oil and thickener,
The blending amount of the oxazoline compound is in the range of 0.4 to 3.5 wt% with respect to the total grease weight, and the blending amount of the metal sulfonate is in the range of 0.4 to 3.5 wt% with respect to the total grease weight. A lubricating grease composition.   The lubricating grease composition according to claim 1, wherein the total amount of the oxazoline compound and the metal sulfonate is in the range of 0.9 to 6.5 wt% with respect to the total weight of the lubricating grease composition.   The lubricating grease composition according to claim 1 or 2, wherein the weight ratio of the oxazoline compound to the metal sulfonate is oxazoline compound / metal sulfonate = 80/20 to 20/80.   The base oil contains at least one selected from mineral oil, synthetic hydrocarbon oil, ester-based synthetic oil, ether-based synthetic oil, or glycol-based synthetic oil. The lubricating grease composition described. The lubricating grease composition according to any one of claims 1 to 4, wherein the thickener contains at least one selected from metal soaps, composite metal soaps, and urea compounds.