JP2007039570A - Water-containing lubricating oil composition and property stabilizer used in the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a property stabilizer such a pH stabilizer and a kinematic viscosity stabilizer which enables reduction of the maintenance of a water-containing lubricating oil over its long-term use and a water-containing lubricating oil composition having excellent property stabilization which contains the same. <P>SOLUTION: The water-containing lubricating oil comprises a urea compound. This urea compound exhibits pH stabilizing and kinematic viscosity stabilizing functions. By further incorporating morpholine or an alkylated morpholine into the water-containing lubricating oil, the pH stabilizing function and the kinetic viscosity stabilizing function are extremely superior. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a hydrous lubricating oil composition having good property stability and excellent flame retardancy over a long period of time, for hydrous lubricating oils such as a hydrous lubricating oil pH stabilizer and a kinematic viscosity stabilizer. It relates to the property stabilizer of

  Hydraulic equipment is widely adopted in the industry and contributes to productivity improvement. In these hydraulic devices, hydraulic fluid is used as a power transmission medium, but water-glycol based hydraulic fluids are used for disaster prevention in the vicinity of high-temperature heat sources and equipment that generates electric sparks. Various hydrous hydraulic fluids are used.

There is little change in the liquid property of the hydraulic fluid with respect to heat and shear, and it is desired to maintain the property within an appropriate range for a long period of time and to maintain the performance.
Water-glycol based hydraulic fluid has excellent performance, but in order to maintain its performance, the properties of the fluid such as pH, kinematic viscosity and preliminary alkalinity (JIS K2234) are controlled by replenishing the concentrate. It is common to use. For this reason, in the use of a water-glycol hydraulic fluid, it is a problem that labor and cost are required for maintenance and performance maintenance, and reduction of labor by extending the life of the fluid is required.

Examples of techniques for improving the performance of hydrous lubricating oil include polyoxyalkylene glycol diether compounds having a specific structure, polyoxyalkylene glycol monoether compounds having a specific structure, polyoxypropylene glycol monoether compounds having a specific structure, and fatty acids having a specific structure. Water-containing hydraulic fluid composition containing salt (see Patent Document 1), water-glycol flame-retardant hydraulic fluid containing a neutralized product of glycerol borate and base (see Patent Document 2), water structure having a specific structure Water-glycol flame retardant hydraulic fluid containing a reactive polyether (see Patent Document 3) and the like, and these inventions focus on sustaining lubricity and wear resistance.
Japanese Patent No. 3323490 Japanese Patent No. 2646308 Japanese Patent Laid-Open No. 7-23391

  The present invention has been made in view of the above-described state of the art, and includes a pH stabilizer and a kinematic viscosity stabilizer that can reduce maintenance over the long-term use of a hydrous lubricant. And a water-containing lubricating oil composition containing the same and having excellent property stability.

  As a result of intensive studies to solve the above problems, the present inventor has found that the urea-based compound has an excellent property stabilizing function such as an excellent pH stabilizing function and an excellent kinematic viscosity stabilizing function. The headline and the present invention were completed. Further, by blending a urea compound, a long-life water-containing lubricating oil composition has been completed.

That is, the present invention provides a hydrous lubricating oil composition comprising a urea compound.
The present invention also provides a water-containing lubricating oil composition that further comprises morpholine or alkylated morpholine in the water-containing lubricating oil composition.
The present invention also provides a water-containing lubricating oil composition containing a polyoxyalkylene polyol or an alkyl ether derivative thereof in the water-containing lubricating oil composition.

Further, the present invention provides the water-containing lubricating oil composition, wherein the polyoxyalkylene polyol is an ethylene oxide homopolymer, an ethylene oxide / propylene oxide copolymer, or a polyhydric alcohol with an ethylene oxide homopolymer, ethylene oxide, and The present invention provides a water-containing lubricating oil composition which is a compound obtained by adding a copolymer of propylene oxide or a copolymer of ethylene oxide and another alkylene oxide.
The present invention also provides the water-containing lubricating oil composition, wherein the polyoxyalkylene polyol is an ethylene oxide homopolymer or a random or block copolymer of ethylene oxide and propylene oxide. Is.

The present invention also provides a property stabilizer for a water-containing lubricating oil containing a urea compound as an active ingredient.
The present invention also provides a pH stabilizer for a water-containing lubricating oil containing a urea compound as an active ingredient.
The present invention also provides a kinematic viscosity stabilizer for a water-containing lubricating oil containing a urea compound as an active ingredient.

  The water-containing lubricating oil composition of the present invention is excellent in property stabilizing properties such as pH stabilizing properties and kinematic viscosity stabilizing properties, and can reduce maintenance during long-term use. In addition to the water glycol-based hydraulic fluid, the water-containing lubricating oil composition is the same for W / O emulsion type and O / W emulsion type hydraulic fluid, rolling oil, forging oil, drawing oil, cutting oil, and the like. The effect can be expected.

The urea compound used in the present invention is a compound having a urea bond skeleton represented by the formula: = NCON =, and includes various compounds having the urea bond skeleton.
Preferable urea compounds include compounds having a structure represented by the general formula (1).

(Wherein R ^{1 to} R ⁴ represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, an aromatic-aliphatic hydrocarbon group, or an aromatic group, and the aliphatic hydrocarbon group, aromatic- In the aliphatic hydrocarbon group or aromatic group, an oxygen atom, a nitrogen atom, a sulfur atom, or a phosphorus atom may be bonded between carbon-carbon bonds, and R ^{1 to} R ⁴ may be the same. And may be different, or R ^{1 to} R ⁴ may be bonded to each other to form a ring structure.)

In the general formula (1), typical examples of the substituent substituted with the aliphatic hydrocarbon group, the aromatic-aliphatic hydrocarbon group or the aromatic group include an alkyl group, a hydroxyl group, an alkoxyl group, and an acyloxyl group. , Alkoxycarbonyloxyl groups, carbonyl groups, allyl groups, amino groups, oxo groups, nitro groups, cyano groups, and halogen atoms. Only one type of substituent may be used, or two or more types may be used. The number of substituents is not particularly limited, but is preferably 1 to 3.

The aliphatic hydrocarbon group includes a linear or branched, saturated or unsaturated aliphatic hydrocarbon group. A saturated aliphatic hydrocarbon group is an alkyl group and an unsaturated aliphatic hydrocarbon group may be mono- or poly-unsaturated and includes both alkenyl and alkynyl groups. The number of carbon atoms of the aliphatic hydrocarbon group is preferably 40 or less, more preferably 18 or less, and particularly preferably 7 or less.

Preferred alkyl groups having 1 to 18 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, and neopentyl. Group, tert-pentyl group, 2-methylbutyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, ethylbutyl group, n-heptyl group, 2-methylhexyl group, n-octyl group, isooctyl group, tert- Octyl group, 2-ethylhexyl group, 3-methylheptyl group, n-nonyl group, isononyl group, 1-methyloctyl group, ethylheptyl group, n-decyl group, 1-methylnonyl group, n-undecyl group, 1,1 -Dimethylnonyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group n- hexadecyl group, n- heptadecyl group, n- octadecyl group and the like,

Preferred alkyl groups having 1 to 7 carbon atoms include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group. Group, tert-pentyl group, 2-methylbutyl group, n-hexyl group, isohexyl group, 3-methylpentyl group, ethylbutyl group, n-heptyl group and 2-methylhexyl group.
Examples of the C1-C18 alkyl group substituted with a hydroxyl group include 2-hydroxyethyl group, 3-hydroxypropyl group, 4-hydroxybutyl group, 5-hydroxypentyl group, 6-hydroxyhexyl group and the like. It is done.

Examples of the alkyl group having 1 to 18 carbon atoms substituted with an alkoxyl group include 2-methoxyethyl group, 2-ethoxyethyl group, 3-methoxypropyl group, 3-ethoxypropyl group, 4-methoxybutyl group, 4- An ethoxybutyl group, 2- (2-methoxyethyl) ethyl group, etc. are mentioned.
Typical substituted alkyl groups include alkoxymethyl groups, alkoxyethyl groups and alkoxypropyl groups, or acyloxymethyl groups, acyloxyethyl groups and acyloxypropyl groups such as pivaloyloxymethyl groups.
Preferred alkyl groups include unsubstituted alkyl groups, alkoxyalkyl groups, hydroxyalkoxyalkyl groups, polyhydroxyalkyl groups, hydroxypolyalkyleneoxyalkyl groups, and the like. As used herein, “acyl” includes both carboxylates and carbonates, and thus acyloxy-substituted alkyl groups include, for example, alkylcarbonyloxyalkyl.

Preferable examples of the aromatic-aliphatic hydrocarbon group include aralkyl groups having 7 to 26 carbon atoms.
The aralkyl group having 7 to 26 carbon atoms is preferably one composed of an alkyl group having 1 to 6 carbon atoms and an aryl group having 6 to 20 carbon atoms. Examples of the alkyl group having 1 to 6 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, n-hexyl group, A cyclopropyl group, a cyclobutyl group, a cyclohexyl group, etc. are mentioned, As a C6-C20 aryl group, a phenyl group, a naphthyl group, etc. are mentioned. Of the aralkyl groups having 7 to 26 carbon atoms, a benzyl group, a phenethyl group, and a 9-fluorenylmethyl group are preferable, and a benzyl group and a fluorenylmethyl group are particularly preferable.

The aryl group of the aralkyl group has 1 to 6 carbon atoms such as an alkyl group having 1 to 6 carbon atoms, a methoxyl group, an ethoxyl group, an n-propoxyl group, an n-butoxyl group, an isobutoxyl group, and a tert-butoxyl group. 6 may be substituted by a substituent such as an alkoxyl group, a hydroxyl group, an amino group, a nitro group, a cyano group, a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, or a carboxyl group. The number of substituents is not particularly limited, but is preferably 1 to 3. As such a substituted aralkyl group, a 2-methylbenzyl group, a 3-methylbenzyl group, a 4-methylbenzyl group, and a 4-methoxybenzyl group are preferable.

Preferable examples of the aromatic group include an aryl group having a phenyl ring and a monocyclic 5- to 7-membered heteroaromatic ring, and particularly an aryl group having a phenyl ring. The aromatic group may be substituted with a substituent. Among these, an aryl group having 6 to 20 carbon atoms is preferable.
Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group and a naphthyl group. For example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, C1-C6 alkyl group such as n-pentyl group, n-hexyl group, cyclopropyl group, cyclobutyl group, cyclohexyl group, etc., methoxyl group, ethoxyl group, n-propoxyl group, n-butoxyl group, isobutoxyl group, Even if it is substituted by a substituent such as a C1-C6 alkoxyl group such as a tert-butoxyl group, a hydroxyl group, an amino group, a nitro group, a cyano group, a halogen atom such as fluorine, chlorine, bromine or iodine, or a carboxyl group Good. The number of substituents is not particularly limited, but is preferably 1 to 3.

Preferable specific examples of the compound of the general formula (1) include, for example, urea, methylurea, 1,2-dimethylurea, 1,3-dimethylurea, trimethylurea, tetramethylurea, ethylurea, 1,2-diethylurea, , 3-diethylurea, 1-methyl-2-ethylurea, alkylureas such as 1-methyl-3-ethylurea, phenylureas such as phenylurea and diphenylurea, allylureas, acetyleneureas, imidazolidones, caffeine And ureasols. Of these, urea, methylurea, ethylurea, 1,3-dimethylurea, 1,2-dimethylurea, and caffeine are more preferable, and urea, methylurea, and ethylurea are particularly preferable.

  The content of the urea compound may be appropriately selected, but is preferably 0.005 to 1.0% by mass, more preferably 0.01 to 0.5% by mass, and particularly preferably 0. 0.03 to 0.3% by mass. When the content is small, there is a problem that a sufficient addition effect cannot be obtained. When the content exceeds 1.0% by mass, the addition effect corresponding to the addition amount cannot be obtained, which is not preferable.

The above content varies depending on the inclusion of other additives and the like within the above range, but the water-containing lubricating oil composition containing the urea compound is JIS K2514 (Lubricating Oxidation Stability Test Method) " In the life evaluation test using the test equipment specified in the section (Rotating cylinder type oxidation stability test method), it is possible to select an addition amount that reduces the amount of change in pH, kinematic viscosity, or preliminary alkalinity before and after the test. The test conditions of this test are, for example, the amount of test solution: 80 g, catalyst; none, test temperature: 120 ° C., enclosed oxygen pressure: 620 kPa (@ 25 ° C.), test time: 12 Hr.
When the above test conditions are used, the pH change amount is ± 25% before and after the test, preferably ± 15%, particularly preferably ± 8%, or the 40 ° C. kinematic viscosity change amount is before and after the test. It may be added so that it is ± 25%, preferably ± 15%, particularly preferably ± 5%.
As described above, the urea compound exhibits excellent performance as a property stabilizer such as a pH stabilizer and a kinematic viscosity stabilizer.

The present invention is also a water-containing lubricating oil composition containing a urea compound that can obtain such test results.
The hydrous lubricating oil composition of the present invention can be applied to various hydrous lubricating oils, but can be suitably applied to water-glycol hydraulic fluids.
A hydrous lubricating oil such as a water-glycol hydraulic fluid contains water. Water content should just be 30-50 mass%. Examples of glycols contained in the water-glycol hydraulic fluid include glycols such as ethylene glycol, diethylene glycol, trimethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, hexylene glycol, and dihexylene glycol. The monoalkyl ether of these glycols is mentioned. These glycols may be used alone or in combination of two or more. Usually, it is preferable to use propylene glycol or dipropylene glycol. Content of glycols should just be 20-60 mass%, Preferably it is 25-50 mass%.

In the hydrous lubricating oil composition of the present invention, it is preferable to further blend morpholine or alkylated morpholine, and it is particularly preferable to blend alkylated morpholine. The urea-based compound and morpholine or alkylated morpholine can exhibit extremely excellent property stabilizing properties such as excellent pH stabilizing property and kinematic viscosity stabilizing property by interaction.
The alkylated morpholine is a compound represented by the following general formula (2).

（式中、Ｒ^５は炭素数１以上のアルキル基である。）

(In the formula, R ⁵ is an alkyl group having 1 or more carbon atoms.)

Although carbon number of the alkyl group in General formula (2) is 1 or more, the upper limit is preferably 5 or less, and more preferably 3 or less. If the alkyl group has a large number of carbon atoms, the solubility in the hydraulic fluid may be insufficient. Specific examples of the alkyl group include a methyl group, an ethyl group, and a propyl group, and a methyl group and an ethyl group are preferable.
The content of the morpholine and alkylated morpholine may be 0.01 to 5.0% by mass, preferably 0.05 to 3.0% by mass, and particularly preferably 0.3 to 1%. 0.5% by mass. When the content is less than 0.01% by mass, there is a problem that a sufficient addition effect cannot be obtained, and when it exceeds 5.0% by mass, an addition effect commensurate with the addition amount cannot be obtained.

In the water-containing lubricating oil composition of the present invention, any component that is usually used in a water-containing lubricating oil can be used except that the urea compound or the urea compound and morpholine or alkylated morpholine are blended.
In the hydrous lubricating oil composition of the present invention, it is preferable to add a thickener.
As the thickener, a water-soluble polyoxyalkylene polyol or an alkyl ether derivative thereof can be used. Specifically, water-soluble ethylene oxide (EO) homopolymer, EO / propylene oxide (PO) copolymer, polyhydric alcohol with EO homopolymer, EO and PO copolymer or EO and other Examples thereof include compounds obtained by adding a copolymer with an alkylene oxide (for example, 1,2-butylene oxide, tetrahydrofuran, α-olefin oxide, etc.), or alkyl ether derivatives thereof. 1-4 are preferable and, as for carbon number of the alkyl group in the alkyl ether group in this alkyl ether derivative, 1-3 are especially preferable.

Specific examples of the water-soluble polyoxyalkylene polyols include polyoxyalkylene glycol, polyoxyalkylene triol, polyoxyalkylene glycol monoether, polyoxyalkylene glycol diether and the like.
When using a copolymer of EO and another alkylene oxide, or a copolymer of EO and another alkylene oxide as an adduct to a polyhydric alcohol, the other alkylene oxide is preferably PO, The molar ratio of EO / other alkylene oxide is preferably 25/75 to 80/20. If the molar ratio of EO is too small, the solubility in the working fluid may be insufficient. Further, the addition mode of EO and other alkylene oxide copolymers may be random addition or block addition.

The average molecular weight of the water-soluble polyoxyalkylene polyols is preferably in the range of 3,000 to 20,000, more preferably in the range of 5,000 to 18,000. When the average molecular weight is lower than 3,000, the original thickening effect is small and it is necessary to increase the blending amount. Therefore, the blending ratio of glycols is relatively decreased and the solubility of the system is changed. Therefore, it is not preferable. On the other hand, if the molecular weight exceeds 20,000, the stability of the thickener against heat and shear may be impaired, and the change in properties when the thickener is decomposed is not preferred.
The content of the thickener may be 5 to 40% by mass, preferably 10 to 30% by mass.

The hydrous lubricating oil composition of the present invention preferably has a 40 ° C. kinematic viscosity of 19.8 to 74.8 mm ² / sec, particularly preferably 28.8 to 50.6 mm ² / sec.
The water-containing lubricating oil composition of the present invention includes a lubricant, a liquid phase rust preventive agent, a gas phase rust preventive agent, a metal deactivator, a pH adjuster, an antifoaming agent, a colorant, and other optional additives. Can be blended as needed.
Examples of the lubricant include saturated fatty acids such as myristic acid, palmitic acid, lauric acid and stearic acid, unsaturated fatty acids such as oleic acid, linoleic acid and linolenic acid, aromatic fatty acids and dimer acids. These fatty acids may be used alone or in combination of two or more.

  As the liquid phase or gas phase rust preventive agent, in addition to the alkylated morpholine which is an essential component of the present invention, morpholine, monoethanolamine, diethanolamine, triethanolamine, 3-amino-1-propanol, 1-amino-2- Propanol, 3-methoxypropylamine, 3-ethoxypropylamine, ethylenediamine, diethylenetriamine, cyclohexylamine, N-methylethanolamine, N-methyldiethanolamine, N-ethylethanolamine, N-ethyldiethanolamine, Nn-butylethanolamine Nn-butyldiethanolamine, dimethylethanolamine, diethylethanolamine, dibutylethanolamine, N- (β-aminoethyl) ethanolamine, 1,4-bis (2-hydroxyethyl) imidazo Emissions, hydroxyethyl piperazine, 2-methylpiperazine, 2,5-dimethylpiperazine, 2,6 organic amines and their derivatives such as dimethyl piperazine, and the like carboxylic acid alkali metal salt. These liquid phase or vapor phase rust preventives may be used alone or in combination of two or more.

  Examples of the pH adjuster include alkali metal compounds such as potassium hydroxide and sodium hydroxide in addition to those mentioned as the gas phase and liquid phase rust preventive agents. It is preferable to adjust the hydraulic fluid to a desired pH by blending these pH adjusters. If the pH is too low, the solubility of the lubricant present in the liquid is insufficient and there is a risk of sludge formation. On the other hand, if the pH is too high, the wear resistance of the hydraulic fluid may be reduced.

Examples of the metal deactivator include benzotriazole compounds such as benzotriazole, tolyltriazole, 5-methylbenzotriazole, carboxybenzotriazole and alkali metal salts or amine salts thereof, mercaptobenzothiazole and alkali metal salts thereof. It is done.
Examples of the antifoaming agent include silicone compounds, and examples of the coloring agent include alcohol-based coloring agents and metal-based coloring agents.

Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not restrict | limited at all by these examples.
(Evaluation of hydraulic fluid)
Regarding the stability of the hydraulic fluid, the life was evaluated using a rotary cylinder type oxidation stability tester. This tester is defined in item 6 of “JIS K2514 (Lubricating oil oxidation stability test method)”. Evaluation was made based on changes in pH and kinematic viscosity of the solution after the test. The smaller the amount of change, the better the stability of the hydraulic fluid.
The test conditions are as follows.
Test solution volume: 80g
Catalyst; None Test temperature: 120 ° C
Enclosed oxygen pressure: 620 kPa (@ 25 ° C.)
Test time: 12 hours

(Examples 1 to 11)
The components shown in Table 1 and Table 2 were mixed at the blending amounts shown in Table 1 and Table 2 to prepare a water-containing lubricating oil composition. It evaluated by the said test using the prepared water-containing lubricating oil composition. The evaluation results are shown in Tables 1 and 2.
(Comparative Examples 1-2)
The components shown in Table 3 were mixed at the blending amounts shown in Table 3 to prepare a water-containing lubricating oil composition. It evaluated by the said test using the prepared water-containing lubricating oil composition. The evaluation results are shown in Table 3.

In Tables 1 to 3, thickeners, glycols, metal deactivators, and lubricants are shown below.
Thickener A is polyoxyethylene / oxypropylene glycol, a random copolymer having an EO / PO molar ratio of 75/25, and an average molecular weight of 15,000. Thickener B is polyoxyethylene / oxypropylene glycol, a random copolymer having an EO / PO molar ratio of 75/25, and an average molecular weight of 5,000. Thickener C is polyoxyethylene / oxypropylene glycol, a random copolymer having a EO / PO molar ratio of 50/50, and an average molecular weight of 1,750.

The glycols were dipropylene glycol, the metal deactivator was methylbenzotriazole monoethanolamine salt, and the lubricant was coconut fatty acid containing 48% lauric acid. Note that potassium hydroxide (KOH) was used as the alkaline agent.
About each Example and the comparative example, it adjusted so that 40 degreeC kinematic viscosity might be set to 48.0 mm < ² > / sec by 10.0 with the compounding quantity of an alkali agent, dipropylene glycol, and a thickener.

As shown in Tables 1 and 2, all examples according to the present invention showed excellent stability.

The water-containing lubricating oil composition of the present invention can suppress a change in pH for a long period of time, can also suppress a change in kinematic viscosity for a long period of time, and can reduce labor required for maintenance of the water-containing lubricating oil composition. Therefore, it is extremely useful in the field of hydrous lubricating oil.

Claims (8)

  A hydrous lubricating oil composition comprising a urea compound.   The water-containing lubricating oil composition according to claim 1, further comprising morpholine or alkylated morpholine.   The water-containing lubricating oil composition according to claim 1 or 2, comprising a polyoxyalkylene polyol or an alkyl ether derivative thereof.   Polyoxyalkylene polyol is ethylene oxide homopolymer, ethylene oxide / propylene oxide copolymer, or polyhydric alcohol with ethylene oxide homopolymer, copolymer of ethylene oxide and propylene oxide or ethylene oxide and other alkylene oxide. The water-containing lubricating oil composition according to claim 3, which is a compound obtained by adding a polymer.   The water-containing lubricating oil composition according to claim 3, wherein the polyoxyalkylene polyol is an ethylene oxide homopolymer or a random or block copolymer of ethylene oxide and propylene oxide.   A property stabilizer for a water-containing lubricating oil containing a urea compound as an active ingredient.   A pH stabilizer for a hydrous lubricating oil containing a urea compound as an active ingredient.   A kinematic viscosity stabilizer for hydrous lubricants containing a urea compound as an active ingredient.