JPH0227392B2 - MIZUKEIJUNKATSUSOSEIBUTSU - Google Patents

Description

[Detailed description of the invention]

The present invention relates to water-based lubricating compositions. Water-based lubricating compositions have attracted attention from the viewpoint of fire resistance, and recently, high-water content hydraulic fluids with high water content have been developed to save resources.
Water-based lubricating compositions are attracting attention from the perspective of environmental conservation, but they are also important in other applications such as press oils and cutting oils. It is difficult for water-based lubricating compositions to exhibit extreme pressure properties and lubricity, and the development of good extreme pressure additives is desired. An object of the present invention is to provide a water-based lubricating composition that does not have the above-mentioned drawbacks and has good lubricating performance by using an organic molybdenum compound. The composition of the present invention comprises a large amount of water and the general formula (In the formula, R ₁ and R ₂ are hydrocarbon groups having 1 to 18 carbon atoms that may be substituted with a hydroxyl group or an alkoxy group, and R ₁ and R ₂ may be the same or different.x,
y is a number from 0 to 4, and x+y=4. ) contains 0.05 to 30% by weight of the compound shown as an essential component. The compound of general formula () is known and can be obtained, for example, by the method described in Japanese Patent Publication No. 45-24562, Japanese Patent Publication No. 53-31646, etc. The compound of general formula () is effective if added in an amount of 0.05% by weight or more, but the effect does not improve much even if added in too large a quantity, so the use is limited to about 30% by weight, and in general, It is preferably used in an amount of about 0.1 to 5% by weight. Since the compound of general formula () is generally insoluble in water, it is used after being dispersed or solubilized in water using a suitable dispersant or solubilizer. Any suitable dispersant or solubilizer may be selected, but a method of emulsifying or solubilizing the polyhydroxy compound or its aqueous solution in the presence of a protein, a protein decomposition product, and/or a surfactant. It is preferable to use from the viewpoint of stability over time. The above-mentioned proteins used in this case include water-soluble proteins such as sodium caseinate, soybean protein,
Skimmed milk powder, whey powder, raw egg white, dried egg white, blood meal, meat meal, microbial protein, peptone, yeast extract,
Examples include albumin, lactalbumin, globulin, lactoglobulin, glutelin, pronumin, histamine, etc. As the protein decomposition products, those obtained by decomposing the above proteins using protease, acid, etc. can be used. Furthermore, various types of surfactants such as anionic, nonionic, cationic, and amphoteric surfactants can be used as the above-mentioned surfactants. Examples of anionic surfactants include soap N-acylamino acid salts, alkyl ether carboxylic acids, carboxylic hydrochloric acids such as acylated peptides,
For example, alkylsulfonic acids, alkylbenzenesulfonates, alkylnaphthalenesulfonates and their formalin condensates, dialkylsulfosuccinates, α-olefinsulfonic acids, N
- Sulfonic acid salts such as acylmethyl taurine, e.g. sulfuric acid ester salts such as sulfated oils, alkyl sulfates, alkyl ether sulfates, alkylarine ether sulfates, alkylamide sulfates, e.g. alkyl phosphates, alkyl ether phosphates; salts, phosphate ester salts such as alkyl allyl ether phosphates, and the like. Examples of nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene secondary alcohol ether, polyoxyethylene alkyl phenyl ether, ethylene oxide derivatives of alkylphenol formalin condensates, and polyoxyethylene polyoxypropylene block polymers. Ether type active agents such as polyoxyethylene glycerin fatty acid esters, polyoxyethylene castor oil and hydrogenated castor oil, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene sorbitol fatty acid esters, etc. Ether ester type active agents such as polyoxyethylene glycol Examples include ester-type activators such as fatty acid ester, fatty acid monoglyceride, sorbitan fatty acid ester, and sucrose fatty acid ester; nitrogen-containing activators such as fatty acid alkanolamide, polyoxyethylene fatty acid amide, polyoxyethylene alkylamine, and alkylamine oxide; It will be done. Further, examples of cationic surfactants include alkylamine salts, quaternary ammonium salts, benzalkonium salts, benbitonium chloride, and pyridinium salts, and examples of amphoteric surfactants include carboxybetaine types, sulfobetaine types, and amino acid surfactants. Examples include carboxylic acid salts, imidazolinium betaine, lecithin, etc. In addition, fluorine-based surfactants,
Silicone surfactants and the like can also be used. In the above-mentioned emulsification or solubilization method, the above-mentioned surfactant may not be used, and it is preferable to use a substance selected from proteins and protein decomposition products such as sodium caseinate. Further, examples of the polyhydroxy compound include dihydric alcohols such as propylene glycol,
Trihydric alcohols such as glycerin, sugar alcohols such as sorbitol and mannitol, monosaccharides such as glucose and fructose, disaccharides and trisaccharides such as sucrose, maltose and galactose, higher oligosaccharides, and starch by hydrolysis. Various invert sugars, starch syrup,
Dextrin, high fructose sugar, syrup, honey,
Jams etc. can be used. As the liquid polyhydroxy compound, one selected from the above-mentioned polyhydroxy compounds that is liquid at room temperature, such as propylene glycol, glycerin, etc., can be used. Regarding the usage ratio of each of the above components used to emulsify or solubilize the compound of the general formula (), one or more components selected from the group consisting of proteins, protein decomposition products, and surfactants may be used. It is 0.005% or more (the same below weight basis), preferably 0.05% or more, particularly preferably 0.05 to 5%, based on the total amount of the polyhydroxy compound or water, and the polyhydroxy compound is
30% or more, preferably 40% or more, for example 100% when using a liquid polyhydroxy compound
It is possible to get close. When attempting to emulsify or solubilize the organic molybdenum compound represented by the general formula () of the present invention by the above method, if the organic molybdenum compound has a high melting point and emulsification or solubilization is difficult, an appropriate solvent may be used. What is necessary is to dissolve and emulsify or solubilize. Usable solvents include those that are incompatible with the hydroxy compound, such as chlorine-based and ester-based solvents such as dioctyl phthalate, diisodecyl adipate, dioctyl adipate, chlorinated paraffin, and chlorinated fatty acid. By adding and mixing proteins (degraded products), surfactants, polyhydroxy compounds, or even water to the above-mentioned organic molybdenum compound or a substance to be solubilized consisting of it and a solvent, organic molybdenum emulsified or solubilized in water can be obtained. A compound is obtained, which can be mixed with water to obtain the composition of the present invention. An emulsifying or solubilizing agent containing the above proteins, etc.
The mixing ratio of the organic molybdenum compound or a mixture of the organic molybdenum compound and the solvent is about 1 to 4 (weight ratio) of the latter, but the latter may be increased as long as gelation does not occur. The composition of the present invention may contain thickeners (for example, cellulose-based, gum-based, chitosan-based, alginic acid-based, alkali metal salts thereof, esterified products, ethoxylated products, amines, polyols, etc.) to the extent that the effects of the present invention are not impaired. Polyoxyalkylene polyols (e.g., tallow amine, cyclohexylamine ethoxylates, polyoxyalkylene glycols or urethane modified products thereof, etc.), rust inhibitors (amines, carboxylates, etc.), corrosion inhibitors (benzotriazole, mercapto, etc.) benzotriazole,
mercaptobenzothiazole, etc.), antifoaming agents (silicone-based, alcohol-based, etc.), colorants, water softeners (EDTA, etc.), or extreme pressure additives other than compounds of the above general formula () (e.g., chlorinated paraffin, chlorine, etc.) sulfurized fatty acids, sulfurized fats and oils, sulfurized esters, sulfurized olefins, phosphoric acid esters, phosphite esters, dithiocarbamic acid metal (zinc, iron, copper, etc.) salts, dialkyl (or allyl) dithiophosphate phosphonates, phosphinates, etc.), oily agents etc. can be added arbitrarily. The present invention will be explained below with reference to Examples. Production example 1 Sodium caseinate 2.5 parts (parts by weight, same below)
and 97.5 parts of glycerin were heated and mixed. A solution of 20 parts of [(C ₈ H ₁₇ ) ₂ NCS ₂ ] ₂ −Mo ₂ S ₂ O ₂ dissolved in 80 parts of dioctyl phthalate is mixed with this mixture under stirring to obtain a composition that can be emulsified or solubilized in water. I got something. This is referred to as composition (A). Production Example 2 5 parts of sodium dodecylbenzenesulfonate, 10 parts of propylene glycol, and 85 parts of glycerin were heated and mixed. To this mixture, 30 parts of [(C ₈ H ₁₇ ) ₂ NCS ₂ ] ₂ Mo ₂ S _1.5 O _2.5 dissolved in 70 parts of chlorinated paraffin CB-419 (manufactured by Asahi Denka Kogyo Co., Ltd.) was mixed under stirring. A composition that can be emulsified or solubilized in water was obtained. This is referred to as composition (B). Production Example 3 [(C ₈ H ₁₇ ) ₂ NCS ₂ ] ₂ Mo ₂ S _2.1 O _1.9 10 parts Dioctyl phthalate 40 parts Glycerin 49 parts Sodium dodecylbenzenesulfonate (2.5% aqueous solution) 1 part was vigorously stirred to form a composition. Obtained. This is referred to as composition (C). Production example 4 [(C ₄ H ₉ ) ₂ NCS ₂ ] ₂ Mo ₂ S _1.5 O _2.5 5 parts, dibutyl phthalate 45 parts, nonylphenol ethoxylate (EO addition moles 10, 5% aqueous solution) 5 parts, propylene glycol 45 The mixture was vigorously stirred to obtain a composition. This is referred to as composition (D). Production Example 5 A composition was obtained in the same manner as Production Example 3, except that 10 parts of [(C ₁₂ H ₂₅ ) ₂ NCS ₂ ] ₂ Mo ₂ S ₃ O ₁ was used as the organic molybdenum compound. This is referred to as composition (E). Production example 6 [(C ₁₈ H ₃₇ ) ₂ NCS ₂ ] ₂ Mo ₂ S ₁ O ₃ 10 parts, Z-sec-
A composition was obtained by vigorously stirring 10 parts of zinc hexyl dithiophosphate, 30 parts of dioctyl adipate, 48 parts of glycerin, and 2 parts of sodium dodecylbenzenesulfonate (2.5% aqueous solution). This is referred to as composition (F). Production Example 7 A composition was obtained in the same manner as Production Example 3 except that [(C ₅ H ₁₁ ) ₂ NCS ₂ ] ₂ Sb was used instead of the organic molybdenum compound of Production Example 3. This is referred to as composition (x). Examples Compositions (A) obtained in the above Production Examples 1 to 7,
Using (B), (C), (D), (E), (F) and (x), mix each component shown in Table 1 below to obtain water-based hydraulic oil (a), (b),
Obtained (c), (d), (e), (f), and (g). For these water-based hydraulic fluids, the Shell 4-bulb test (1500 rpm, 20 kg/
cm ² , wear marks measured for 15 minutes), vane pump test (Vitkers vane pump V-105C, discharge pressure 50
Kg/cm ² , shaft rotation speed 1200 rpm, 50 at liquid temperature 40℃
The amount of wear on the vane and cam ring was measured after the lapse of time. The results are shown in Table-2.

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Claims (1)

[Claims] 1. General formula (In the formula, R ₁ and R ₂ are hydrocarbon groups having 1 to 18 carbon atoms that may be substituted with a hydroxyl group or an alkoxy group, and R ₁ and R ₂ may be the same or different.
x and y are numbers from 0 to 4, and x+y=4. ) A water-based lubricating composition containing 0.05 to 30% by weight of the compound shown.