JPH0794673B2 - Aqueous hydraulic fluid - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION This application is a continuation-in-part of patent application No. 374,157 filed March 3,1982.

The invention is particularly suitable for use in industrial hydraulic systems,
Improved high-water-based hydraulic fluid
lic fluid) is about.

The technology of power transmission by hydraulic fluid is well established.
Various incompressible liquids such as water and oil have been used as hydraulic fluids. Petroleum is superior to water as a hydraulic fluid in that it reduces wear on hydraulic components such as pumps, prevents the formation of rust, and has a higher viscosity than water, resulting in less liquid leakage. Unfortunately, a major drawback of oil is its flammability. Petroleum is also sensitive to the ingress of water into the hydraulic system in which it is used. Moreover, the disposal of spent petroleum hydraulic fluid poses an economic problem.

In recent years, "great wear resistance" due to low cost
Efforts have been made to create aqueous hydraulic fluids with good properties such as. Dithiophosphate (dithiophosphate)
an extreme pressure (EP) additive such as phosphate)
It is said that it should be included with the rsing agent). This is because such EP additives are almost insoluble in water. It has also been suggested to include various types of thickeners in the aqueous hydraulic fluid due to its inherently low viscosity. However, various such thickeners exhibit shear instability, which leads to a significant viscosity reduction of aqueous hydraulic fluids containing such thickeners.

SUMMARY OF THE INVENTION The present invention is oil-in-water.
The present invention relates to an emulsion type high viscosity, high-aqueous hydraulic fluid. The term "high-aqueous hydraulic fluid" is about 80% by weight
Or a composition comprising more than one water. In addition to water, the present invention includes (1) a polyether thickener as an essential component,
Includes (2) lubricity modifier, (3) dispersant, and (4) EP additive in all specified ratios.
Optionally, the hydraulic fluid of the present invention may include various emulsifiers, corrosion inhibitors, defoamers, coupling agents, freezing point depressants, etc., depending on the particular hydraulic system in which the hydraulic fluid is used. You can A concentrate (concen) that combines essential components of a hydraulic fluid and easily dissolves in water to form a hydraulic fluid.
trate) is preferable.

The high-aqueous hydraulic fluid of the present invention has excellent properties such as more stable viscosity characteristics, lower wear resistance and better lubricity as compared with the conventional aqueous hydraulic fluids.

To obtain a high-aqueous hydraulic fluid according to the present invention, about 120-1
Lubricity modifier and dispersant are mixed together at a temperature of 80 ° F (49-82 ° C), after which heating is stopped and EP additive is introduced into the mixture. Then water is added to obtain a uniform clear liquid. This clear liquor is mixed with a thickener and then more water is added to form a working fluid with the desired water content and viscosity. Optional components such as defoamers, corrosion inhibitors and the like may be added at any suitable time during liquid preparation.

Mixing the concentrate of the present invention with a considerable amount of water,
It is possible to produce a refractory hydraulic fluid that has excellent lubricity and wear resistance and has a stable viscosity. Even if the water concentration is 80% by weight or more, the hydraulic fluid of the present invention can be effectively used in a system including a vane pump, and the cost can be reduced by using it in place of standard hydraulic fluid.

Preferred Examples According to the present invention, (1) a polyether thickener, (2)
Provided are a high-aqueous working fluid consisting of a lubricity modifier, (3) a dispersant, (4) an EP additive and (5) water and a consulate capable of being diluted with water to produce such a working fluid. To be done. Conventional corrosion inhibitors, defoamers, metal deactivators and the like may be included in the composition. It has been proved that such a hydraulic fluid causes almost no decrease in viscosity during use.

Lubricity modifier The lubricity modifier used in the novel hydraulic fluid of the present invention includes:
Included are water immiscible liquids and water miscible, water-soluble or water-dispersible liquids, and mixtures thereof. These lubricity modifiers increase the lubricity of the hydraulic fluid and also act as plasticizers to prevent the formation of sticky deposits in the hydraulic system in which the hydraulic fluid is used. Moreover, high concentrations of water-miscible or water-dispersible liquids such as alkylene glycols, which are defined in more detail below, improve the fluidity and low temperature properties of hydraulic fluids.

The water immiscible liquid used as a lubricity regulator is
Aliphatic-, cycloaliphatic- and aromatic hydrocarbons; chlorinated hydrocarbons; mineral oils; dimethyl- and silicone oils such as methylphenylsilicone; vegetable oils, fish oils, fatty acids such as fatty acids, fatty alcohols and fatty acid amines Quality; condensation product of fatty acid and alkanolamine-these may be modified by phosphate-; ethoxylated fatty amide;
Includes organic esters such as di-2-ethylhexyl sebacate or azelate and trimethylolpropane tricaprylate; glycols and polyglycols; triallyl phosphates such as triisopropylphenyl phosphate; and liquids such as polyphenyl ether.

One group of preferred lubricity modifiers is synthetic hydrocarbon oils having a lubricious viscosity. Usually such oils are 100 ° F (37.8
Viscosity at 50 ℃ -700 Seybolt Universal second (SUS) range. Such synthetic hydrocarbon oils typically, made with a lower monoolefin by polymerizing in the presence of a suitable catalyst such as BF ₃ or AlCl _3. Examples of the lower olefin include ethylene, propylene, butylene and the like. Other synthetic hydrocarbon oils are poly-alpha-olefins and alkylbenzenes. Such synthetic hydrocarbon oils are sufficiently fluid at low temperatures.

Water immiscible lubricity modifiers may actually include naturally occurring hydrocarbons such as either paraffinic or naphthenic mineral oils. Such mineral oil is
It has a viscosity of 50-700 SUS at 100 ° F (37.8 ° C).
The preferred mineral oil for use in the hydraulic fluid of the present invention is 100 ° F.
It is a naphthenic light lubricating oil with a viscosity of 80-200 SUS at (37.8 ℃). A particularly preferred oil of this type is 100 at 100 ° F.
It has a viscosity of ~ 150 SUS.

Another group of preferred lubricity modifiers are the condensation products of fatty acids and alkanolamines. These water-dispersible products can be prepared by reacting a fatty acid or a fatty acid ester with an alkanolamine in a temperature range of 100 to 150 ° C. to remove condensed water or alcohol. The molar ratio of fatty acid or ester to amine ranges from about 2: 1 to about 1: 3. Optionally, a small amount, for example 0.01 to 0.05 mol of phosphoric acid may be present during the reaction.

The fatty acids used to make the condensate should generally contain from 7 to 22 and more preferably 12 to 18 carbon atoms. It may be saturated or unsaturated, or a mixture of both. Therefore, as a fatty acid suitable for forming a condensate, heptanoic acid, caprylic acid, petergonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, behenic acid (be
henic acids) are included. The preferred fatty acid reactant is a mixture of stearic acid and oleic acid.

Alkanolamines found to be useful in forming the condensate include ethanolamine, isopropanolamine, N-methylethanolamine, diethanolamine, dipropanolamine, diisopropanolamine and triethanolamine. A particularly preferred alkanolamine is diethanolamine.

Another group of preferred water soluble or dispersant lubricity modifiers are ethoxylated fatty amides, amines, alcohols and vegetable oils. These fatty alkyl groups are usually 7-22
More preferably 12 to 18 carbon atoms should be included. Such alkyl groups include heptanoyl, caprylyl, nonanoyl, capryl, lauryl, myristyl, stearyl, oleyl, and behenyl. Such lubricity regulators may consist of fats derived from vegetable oils such as palmitin-, coconut-, castor-rapeseed, soybean-, corn-, peanut-, sunflower oil and the like. Alternatively, such fats may be derived from animal fats such as tallow, lard, fish oil and the like.

The degree of ethoxylation of these water-soluble / dispersible lubricity modifiers should be 1 to 20 moles, more preferably 4 to 6 moles of ethylene oxide per mole of fatty acid amide, amine, alcohol or vegetable oil. .

A preferred group of water soluble lubricity modifiers is represented by the structural formula RO (Cn
H _2n O) _x H having alkylene and polyalkylene glycols; wherein R is hydrogen or an alkyl group containing 1 to 10 carbon atoms, n is an integer from 2 to 6, and x is 1 to 70. Is an integer. Alkylene glycol is
Includes ethylene- and propylene glycol and their higher homologues-such as ethylene- and dipropylene glycol. The preferred alkylene glycol is ethylene glycol.

Suitable water-miscible or water-dispersible polyoxyalkylene glycols include polyoxyethylene-, polyoxypropylene-, poly (oxyethylene, oxypropylene) glycols having a molecular weight of about 200 to about 4,000.
These polyglycols may or may not be capped at the tip with a lower alkyl group containing 1 to 10 carbon atoms. The minimum weight percentage of oxyethylene in poly (oxyethylene, oxypropylene) glycol is about 20.
Must be on the order of%. A particularly preferred polyglycol is poly (oxyalkylene-oxy-1,2-propylene) glycol monobutyl ether having a molecular weight of about 1,500 to about 4,000.

Generally, the lubricity modifier is about 0.50 to about 20% by weight of the hydraulic fluid.
Will occupy. The preferred hydraulic fluid of the present invention is 1.0 to 1
Contains 0% order of lubricity modifier.

Thickener The polyether thickener used in the hydraulic fluid of the present invention is
A relatively high molecular weight polyoxyalkylene compound, also referred to herein as a polyether polyol. This is α
-May be capped with olefin oxide. The thickener is water-soluble or at least water-dispersible. A preferred thickener is an alpha-olefin capped-polyoxyethylene-polyoxypropylene block copolymer containing 1,2-propylene oxide groups on the order of about 20-35% by weight.

Preferred as polyether thickeners useful in the aqueous hydraulic fluids of this invention are two normally liquid polyether polyols. Both types are obtained by reacting ethylene oxide with at least one lower alkylene oxide having 3 to 4 carbon atoms and an active aqueous compound. However, in one thickener, this active hydrogen compound is a fatty acid alcohol having two or more hydroxyl groups in the molecule, and in other types of thickeners, it has 4 to 30 or more, more preferably fatty acid groups. Is 12
It is an aliphatic monohydric alcohol containing up to 18 carbon atoms. These polyether polyols, which in either instance are hetero- or block copolymers, are capped by reaction with alpha-olefin oxides having from about 12 to 30, more preferably 12 to 18 aliphatic carbon atoms. Moreover, these thickeners in which the active hydrogen compound is a diol or polyol may be used in uncapped form only if they have a sufficiently high molecular weight. So at least 7,000 such uncapped polyether polyols
It must have a molecular weight of 0 and can have a large molecular weight of 75,000. Preferred uncapped polyether polyols of this type are about 10,000 to 3
It has a molecular weight of up to 0,000.

If the copolymer thickener in which the active hydrogen compound is a diol or polyol is capped by reaction with an α-olefin oxide, its molecular weight is on the order of 7,000 to 15,000, more preferably about 12,000 to 14,000. Must be in range. In both cases, i.e., the polyether polyol has a relatively high molecular weight of 20,000 or more, or a relatively low molecular weight of, for example, about 15,000 or less, the weight percentage of ethylene oxide groups is on the order of 25% to 80%. Must. More preferred is when the copolymer contains about 20% to 35% 1,2-propylene oxide groups.

The diol used in the reaction as an active hydrogen-containing compound may be glycols such as ethylene glycol, diethylene glycol, and higher glycols.
The diol may contain oxyalkylene groups. Typical of the polyols used as active hydrogen compounds are glycerol, polyglycerol, trimethylol propane.

In producing these polyether polyols,
A mixture containing ethylene oxide and lower alkylene oxide in a liquid phase in which a suitable catalyst is uniformly dispersed,
Obtained by intimate contact with the diol- or polyol-source compound. As the catalyst, sodium and potassium hydroxide are preferable. The reaction is carried out at temperatures on the order of 50-160 ° C.

Such polyether polyols in which the active hydrogen compound is a diol and methods for their preparation are described in US Pat. No. 2,425,
No. 845, the disclosure of which is incorporated herein by reference.

As described above, the polyether polyol containing a diol or a polyol can be used as it is, or may be capped with α-olefin oxide before use. Advantageously, substantially small amounts of capped polyols--whether containing diols or polyols as active hydrogen-containing compounds or aliphatic monohydric alcohols--are provided in comparison to uncapped polyols. It can be used to make hydraulic fluids of different viscosities. Thus, for example, in the working fluid of the present invention, it was found that 4.8 parts by weight of the capped thickener produced a working fluid having a viscosity of 190-200 SUS at 100 ° F. Even with 12.5 parts, only a viscosity of 75-80 SUS can be obtained (see Examples I and II below).

The α-olefin oxide used to modify or cap the polyether polyol as described is about
Those containing 12 to 30, more preferably about 12 to 18 aliphatic carbon atoms, or mixtures thereof. . The amount of α-olefin oxide required to obtain the desired thickener is about 1-20% by weight of the total weight of the capped thickener.

The capping reaction is carried out by adding the α-olefin oxide to the polyether polyol (liquid) and heating the mixture at a temperature of about 50-90 ° C for about 1-2 hours depending on the batch size. It is desirable to make the polyether polyol as anhydrous as possible before adding the α-olefin oxide.

The second type of preferred thickener is a hetero- or block of ethylene oxide, which is a lower alkylene oxide, and an aliphatic monohydric alcohol containing 4 to 30 and more preferably 12 to 18 aliphatic carbon atoms. Copolymer is still 12 ~
It is capped with α-olefin oxide containing 30 aliphatic carbon atoms. Such thickeners and their methods of manufacture are disclosed in US Pat. No. 4,288,639, the disclosure of which is incorporated herein by reference.

Typical of the preferred monohydric alcohols for reaction with ethylene oxide and lower alkylene oxides are butyl alcohol, capryl alcohol, lauryl alcohol, myristyl alcohol, stearyl alcohol, cetyl alcohol and behelyl alcohol.
The reaction is a well-known alkaline oxyalkylation catalyst-
Done with strong bases such as sodium and potassium hydroxide. The reaction can also be carried out in the presence of an inert organic solvent. Examples of such solvents are aliphatic hydrocarbons such as hexane and heptane; aromatic hydrocarbons such as benzene and toluene; chlorinated hydrocarbons such as ethylene dichloride. The reaction temperature is 50 as described above.
It is on the order of ~ 160 ° C.

The latter method for producing a polyether polyol is well known to those skilled in the art. More details on the preparation of lower alkylene oxide heterocopolymers are disclosed in US Pat. No. 3,829,506, which is incorporated herein by reference. Additional information on preparing block copolymers of lower alkylene oxides can be found in US Pat. No. 3,535,307. This is also inserted here by reference.

Polyether polyols in which the active hydrogen compound is an aliphatic monohydric alcohol may be capped with α-olefin oxide as described herein above.

The molecular weight of the capped thickener discussed at the end of the above is about
7,000 to 15,000 range, more preferably 12,000 to 14,000
Must be in the range.

Other polyether polyols which are capped and serve as thickeners according to the present invention and their preparation are described in U.S. Pat.
No. 5,755, No. 3,036,118, No. 3,595,924, No. 3,706,714
And 3,829,505; and British Patent 950,844 and
No. 1,228,561. The disclosures of some of these are incorporated herein by reference.

In the hydraulic fluids of the present invention, the thickener will generally be from about 1.5 to about 15
Account for weight percent. This amount depends on the particular thickener used and the viscosity desired for the hydraulic fluid. The capped thickener as described above has a greater thickening than the uncapped thickener. Therefore, if a capped thickener is used, the working fluid of the present invention having a desired viscosity can be provided in a smaller amount.

The hydraulic fluid preferably contains an average of about 2-6% capped thickener, and 10-15% uncapped thickener. By using the preferred amount of thickener, the hydraulic fluid is
It will have a viscosity in the range of about 50 to about 200 SUS at 100 ° F.

Dispersants Useful dispersants included in the hydraulic fluids of the present invention are alkenyl-
Succinic anhydride or-succinic acid and a water-soluble active hydrogen compound-one example of which is a dialkylalkanolamine-is the reaction product. These dispersants are particularly useful for dispersing oil soluble EP additives such as zinc dialkyldithiophosphate in aqueous liquids. In this aqueous liquid it acts as an antiwear component and gives EP properties.

The alkenyl-succinic anhydride or succinic acid with which the active hydrogen compounds are reacted is prepared by reacting maleic anhydride with long-chain α-olefins in a conventional manner. The olefin is maleic anhydride (or maleic acid) and a temperature of 150.
Reacted at ~ 250 ° C, the amount of olefin used is at least stoichiometrically equivalent to the maleic anhydride reactant.
Preferred olefin reaction products have a chain of sufficient length to obtain a succinic anhydride reaction product having a molecular weight on the order of 500 to 2,000, more preferably about 800 to 1,200, and most preferably about 1,000. It is polyisobutene.

For other reactants, it is an active hydrogen compound, which may be an alkylalkanolamine having the formula: Where R is hydrogen or an alkyl group containing 8 to 24 carbon atoms, R ^I is hydrogen or (C ₂ H ₄ O) _x H or (C ₃ H ₆ O) xH, and R ^II is R or R ^I , And x is an integer from 1 to 50. A particularly preferred alkaline alkanolamine reactant is diethylethanolamine.

Alkenyl-succinic anhydride or other active hydrogen compounds that react with succinic acid have the structural formula:

HO (Z) yOR ^III HO (Z) yR ^IV or Where Z is (C ₂ H ₄ O) or (C ₃ H ₆ O), R ^III is an alkyl group containing 8 to 20 carbon atoms, and R ^IV is Or, SR ^III and R ^V are R ^I or an alkyl group containing 1 to 4 carbon atoms, and y is an integer of 3 to 10. R ^III is
In the C _{8 to} C ₉ alkyl group, y is preferably 5.

The alkenyl-succinic anhydride or -succinic acid is reacted with the active hydrogen compound at a temperature of about 50-250 ° C, more preferably 60-150 ° C, for a time sufficient to obtain the desired reaction product, usually 1-6 hours. . The relative amounts of anhydride and active hydrogen compound may vary somewhat, but it is preferred to use 2 moles of such compound per mole of anhydride for complete reaction of the anhydride.

In order to properly disperse the EP additive and other water-insoluble components in the aqueous phase of the working fluid, the working fluid should contain about 0.5 to about 5.0%, preferably 1 to 3% dispersant.

Extreme Pressure (EP) Additives The extreme pressure (EP) additives used in the hydraulic fluids of the invention are dithiophosphates or dithiocarbamates, each having the following structural formula.

Here, R ^V is an alkyl group containing 4 to 16 carbon atoms, more preferably 4 to 10 carbon atoms, phenyl or naphthyl, and X is hydrogen, amine, ammonium, substituted ammonium compound,
Metals of Groups I and II of the Periodic Table, namely alkali metals such as sodium, potassium or lithium, usually alkaline earth metals such as magnesium or calcium, Group II transition metals such as manganese, zinc (especially zinc Preferred)-, antimony, or Mo ₂ S ₂ O ₂ , and a is an integer of 1 or 2.

The dithiophosphate may be prepared by reacting alcohol with phosphorous pentasulfide at a temperature of 40 to 120 ° C. for 1 to 4 hours.

The typical alcohol used in this reaction is n-butyl,
It is a common alcohol such as n-heptyl, n-octyl, n-decyl and n-dodecyl alcohol. Suitable branched chain alcohols include 2-methyl-1-pentanol, 2-ethyl-1-hexanol and 2,2-dimethyl-1-octanol.

It is also possible to react organic- or inorganic bases with dithiophosphates to form EP additives for inclusion in the working fluid. Ashless dithiophosphates can be obtained by reaction with non-metallic bases such as amines, ammonia and substituted ammonium compounds. Reaction with metal oxides or hydroxides produces ashed dithiophosphates. This is usually preferred because of its properties.

The most commonly used metals are the metals of Groups I and II of the Periodic Table, namely the alkali metals such as sodium, potassium and lithium and the alkaline earth metals usually magnesium or calcium, and the Group II transition metals. Especially zinc, which is particularly preferred. Metals are generally used in the form of oxides or hydroxides for reaction with dithiophosphates.

Reaction of dithiophosphates with bases is generally 75-150 ° C.
At a temperature of 1 to 4 hours.

EP additive is in an amount of about 0.125-1.25%, more preferably 0.5-
There should be an amount of 0.75%.

Dithiocarbamates are well known compounds and are generally obtained by reaction of the appropriate amine with carbon disulfide.

Optional Additives In addition to the above essential components and water, the hydraulic fluid may also contain other substances-emulsifiers, corrosion inhibitors, defoamers, coupling agents, etc.

Suitable emulsifiers are those which range from 3 to 20 (Hydrophile-Lipophile-Balance) (HLB) (published by ICI United States, Inc. (1976) "HLB system"). (See Chapter 1). Examples of such emulsifiers are ethoxylated alkylphenols or alkylamines in which the alkyl group contains from 14 to 24 carbon atoms and the number of ethoxy groups is between 3 and 10. Long chain - for example, C ₈ -C ₁₈ alcohol be coemulsifier (co-emulsif
ier) used as. The hydraulic fluid is such an emulsifier
Although it may be included up to 1.5%, the preferred amount of emulsifier is from about 0.45 to 1.2%.

Small amounts, for example up to 0.5%, of various silicone defoamers are included in the working fluid, as well as small amounts-for example up to 0.1% of various corrosion inhibitors-for example benzotriazole and toltriazole. As vapor phase corrosion inhibitors, various water soluble alkylalkanolamines of the type used to react with succinic anhydride to form the aforementioned dispersants can be used. If not included as a lubricity modifier, the freezing point can be lowered by addition of a sufficient amount of freezing point depressant such as ethylene glycol to prevent freezing at the temperatures encountered during use.

In order to limit transport and storage costs, it is preferred to first make a water-dilutable concentrate and add to it an appropriate amount of water to obtain a working fluid. Such a concentrate may have the composition shown in Table 1 below.

I Table component General amount Preferred amount Lubricity modifier 5-40 10-20 Thickener 5-20 12-18 Dispersant 5-20 10-15 EP Additive 1-10 2-6 Water Remaining Remaining When making the liquid, the oil soluble lubricity modifier, if any, the dispersant and the EP additive are mixed together and
Heat at 130-150 ° F (54.4-65.6 ° C) for 30-45 minutes. Various optional additives such as corrosion inhibitors, defoamers, emulsifiers, etc. are added to the water miscible lubricity modifier (if any) heated to 150-160 ° F (65.5-71.1 ° C). Otherwise, any such additives may be added directly to the mixture containing the oil soluble lubricity modifier and the EP additive. The two mixtures are then combined without heating, water is added and the mixture is mixed for 45-60 minutes to form a translucent liquid containing 35-45% water. This mixture is then combined with an appropriate amount of thickener and water to produce a working fluid with the desired water content-usually above 80% -and viscosity.

In order that the invention may be better understood, a few examples are set forth herein. This is for illustration only and does not imply that the scope of the invention is limited to this detail.

Example II A hydraulic fluid of the present invention having the composition shown in the table was prepared by the method described below.

II component weight% (a) Reaction product of polyisobutenyl succinic anhydride (average MW 1000) and diethyl ethanolamine 1.17 (b) Amide ¹ 0.9 (c) EP additive ² 0.38 (d) Polyglycol ³ 0.5 (e) Increase Sticky agent ⁴ 12.5 (f) Diethylethanolamine 0.5 (g) Additive ⁵ 0.06 (h) Water Remaining Note 1. About 1.5 mole of diethanolamine is present in the presence of about 1 mole of stearic acid, oleic acid mixture and about 0.03 mole of phosphoric acid. Phosphoric acid-modified condensate obtained by reacting under the following conditions 2. Zinc dialkyl (C ₄ -C ₁₀ ) dithiophosphate Note 3. Monobutyl ether of poly (oxyethylene-oxy-1,2-propylene) glycol (MW1500- 4000) Note 4. Poly (oxyethylene (75%)-oxy-1,2-
Propylene) glycol (MW25,000-30,000) Note 5. Benzotriazole and silicone defoamer Component (a) 23.3 parts by weight, component (b) 18.0 part, and component (c) 7.5 part are mixed and mixed at 130 to 150 ° F (54.4
~ 65.6 ° C) for 30-45 minutes. 1.2 parts of the additive, component (g), was dissolved in 10.0 parts of component (d) which had been heated to 150-160 ° F (66-71 ° C). The two mixtures were combined; the heat was removed and water was added in an amount to give 40% by weight of the final mixture. Mix the resulting batch for 45-60 minutes to obtain a uniform translucent liquid.

5 parts by weight of the translucent liquid prepared as described above are combined with 12.5 parts of diethylethanolamine, component (f) and water is added to bring the total amount of all substances to 100%. The generated hydraulic fluid has an initial viscosity of 75-80 SUS at 100 ° F (37.8 ° C).
Is.

Example II The following pump test was performed with the hydraulic fluid of Example I.

Table III Test conditions Pump Vickers V-104-C-10 Vane pump Pressure psi 800 (56Kg / cm ² ) Speed rpm 1200 Output (theoretical) gpm 7.5 Storage temperature ° F 115-120 (46-49 ° C) Filter size, micron 10 Test result Test # 1 Test # 2 Ring wear loss mgs 1678 244 Blade wear loss mgs 5 3 Total wear loss 1683 247 Wear rate mgs / hr 12.2 5.5 Viscosity loss% 2.3 5.6 Duration time 138 45 Example III IV The hydraulic fluid of the present invention having the composition was prepared by the following method.

IV component weight% (a) Reaction product of polyisobutenyl succinic anhydride (average MW1000) and diethylethanolamine 1.17 (b) Amide ¹ 0.9 (c) EP additive ² 0.38 (d) Polyglycol ³ 0.5 (e) Increase Viscosity agent ⁴ 4.5 (f) Diethylethanolamine 0.5 (g) Additive ⁵ 0.06 (h) Water Remaining Note 1. Diethanolamine about 1.5 moles about 1 mole about 1 mole
Phosphoric acid obtained by reacting with about 1 mol of a mixture of stearin and oleic acid in the presence of 0.03 mol of phosphoric acid
Modified-condensation product, Note 2. Zinc dialkyl (C ₄ -C ₁₀ ) dithiophosphate Note 3. Monobutyl ether of poly (oxyethylene-oxy-1,2-propylene) glycol (MW 1500-4000) Note 4. Capped with poly (oxyethylene (75%)-oxy-1,2-propylene) glycol (MW 12,000 to 15,000) Note 5. Benzotriazole and silicone defoamer Component (a) 23.3 parts by weight, component (b) 18.0 parts and 7.5 parts of component (c) are mixed, and 130-150 ° F (54.4
~ 65.6 ° C) for 30-45 minutes. The additive, component (g), 1.2 parts was dissolved in 10.0 parts of component (d) which had been heated to 150-160 ° F (65.6-71.1 ° C). The two mixtures were combined; the heat was removed and water was added to 40% by weight of the final mixture.
I added the amount so that The resulting batch was mixed for 40-60 minutes to obtain a uniform translucent liquid.

5 parts by weight of the translucent liquid prepared as above were combined with the thickener, component (e), 4.8 parts and diethylethanolamine, component (f), 0.5 parts, and the total amount of all materials was 100.
Water was added so that it became%. The resulting hydraulic fluid had an initial viscosity of 190-200 SUS at 100 ° F (37.8 ° C).

Example IV The following pump test was performed with the hydraulic fluid of Example III.

Table V Test conditions Pump Vickers V-104-C-10 Vane pump Pressure psi 1000 (70.3Kg / cm ² ) Speed rpm 1200 Output (theoretical) gpm 7.5 Storage temperature ° F 120 (49 ° C) Filter size, micron 10 Test result Test # 1 Test # 2 Ring wear loss mgs 1871 885 Vane wear loss mgs 35 15 Total wear loss 1906 900 Wear rate mgs / hr 20.7 20.0 Viscosity loss% 6.2 2.6 Duration 92 45 Example V VI having the composition shown in Table The working fluid of the present invention was prepared by the following method.

VI component weight% (a) Dispersant ¹ 1.06 (b) Hydrocarbon oil ² 0.80 (c) EP additive ³ 0.34 (d) Polyglycol ⁴ 5.0 (e) Thickener ⁵ 5.0 (f) Additive ₆ 0.03 (g) diethylethanolamine 0.38 (h) fatty alcohols 0.23 (i) water balance Note 1: polyisobutenyl succinic anhydride (average MW 1000) and ethoxylated (3-10 ethoxy) fatty (C ₁₂ -C ₂₄₎ amine.

Note 2. Polybutene (viscosity −400SUS, 100 ° F (37.8 ° C)) Note 3. Dialkyl (C _{2 to} C ₁₀ ) zinc dithiophosphate Note 4. Poly (oxyethylene-oxy-1,2-propylene) glycol (MW1500 ~ 4000) monobutyl ether Note 5. Capped with poly (oxyethylene (75%)-oxy-1,2-propylene) glycol (MW25,000-30,000) Note 6. Benzotriazole and silicone defoamer Component (a) 21.2 parts by weight and component (b) 16.0 portions were mixed and heated to 130-150 ° F (54.4-65.6 ° C) for 45-60 minutes. The heat was removed, 6.7 parts of component (c) and 7.5 parts of component (g) were added and the mixture was heated for 30-45 minutes. Additive, component (f), 0.9 parts to 150-160 ° F (65.
It was dissolved in 4.5 parts of component (h) heated to 6 to 71.1 ° C. The two mixtures were combined. Water was added in an amount to give 43.2% by weight of the final mixture. Mix the resulting batch for 45-60 minutes to obtain a uniform translucent liquid.

5 parts by weight of the translucent liquid prepared as above are combined with the thickener, component (e), 5 parts and polyglycol component (d), 5 parts so that the total amount of all the materials becomes 100%. Was added water. The resulting working fluid has an initial viscosity of 150-250 SUS at 100 ° F (37.8 ° C).

Example VI The following pump tests were performed with the working fluid of Example V using the same type of test pump and the same test conditions as in Tables IV and V.

Example VII A working fluid of the present invention having the composition shown in Table VIII was prepared by the following method.

VIII Surface component weight% (a) Reaction product of polyisobutenyl succinic anhydride (average MW1000) and diethylethanolamine 1.27 (b) Amide ¹ 1.0 (c) EP additive ² 0.5 (d) Polyglycol ³ 2.19 (e) Increase Thickener ⁴ 12.0 (f) Diethylethanolamine 0.5 (g) Additive ⁵ 0.06 (h) Water Remaining Note 1. About 1.5 mol of diethanolamine to about mol
Phosphoric acid-modified-condensation product obtained by reacting with about 1 mol of a mixture of stearic and oleic acid in the presence of 0.03 mol of phosphoric acid Note 2. Dialkyl (C ₄ -C ₁₀ ) zinc dithiophosphate Note 3. Poly (oxy) Monobutyl ether of ethylene-oxy-1,2-propylene) glycol (MW 1500-4000) Note 4. Poly (oxyethylene (75%)-oxy-1,2-
Propylene) glycol (MW25,000-30,000) Note 5. Benzotriazole and silicon defoamer 10.0 parts by weight of the translucent liquid prepared as described above is a thickener,
Component (e), 12.0 parts and diethyl ethanolamine,
Combined with component (f), 0.5 parts, water was added in an amount to bring the total of all ingredients to 100%. The generated working fluid is 100 ° F (37.8
The initial viscosity was 70 to 75 SUS.

Example VIII The following pump test was conducted using the hydraulic fluid of Example VII.

IX Table Test conditions Pump Vickers V-104-C-10 Vane pump Pressure psi 1000 Speed rpm 1200 Output (theoretical) gpm 7.5 Storage temperature ° F 125 ~ 140 (51.6 ~ 60 ° C) Filter size, micron 10 Test result Test # 1 Test # 2 Ring wear loss mgs 85 113 Blade wear loss mgs 91 1 Total wear loss 94 114 Wear rate mgs / hr 0.36 0.95 Viscosity loss% 1.4 3.8 Duration hr 264 120 Working Example IX Working fluid of Working Example V Pump test.

X Table Test conditions Pump Vickers V-104-C-10 Vane pump Pressure psi 1000 Speed rpm 1200 Extrusion rate (theoretical) gpm 25 Storage temperature ° F 120 (49 ° C) Filter size, micron 25 Test result Test # 1 Test # 2 Ring wear loss mgs 300 100 Blade wear loss mgs 4 6 Total wear loss 304 106 Wear rate mgs / hr 0.99 0.34 Viscosity loss% 3.5 14.8 Duration hr 308 308 Example X XI A working fluid of the present invention having the composition shown in the table was used. It was prepared by the following method.

XI Table component weight% (a) Dispersant ¹ 2.50 (b) Hydrocarbon oil ² 1.50 (c) Diethylethanolamine 0.72 (d) EP additive ³ 0.65 (e) Fatty alcohol 0.42 (f) Additive ⁴ 0.23 (g ) ethylene glycol 2.50 (h) a thickener ⁵ 3.00 (i) water balance Note 1: polyisobutenyl succinic anhydride (average MW 1000) and ethoxylated (3-10 ethoxy) fatty (C ₁₂ -C ₂₄₎ amine * 2. Naphthenic mineral oil (viscosity to 100 SUS, 100 ° F) Note 3. Dialkyl (C _{4 to} C ₁₀ ) zinc dithiophosphate Note 4. Benzotriazole and silicone defoamer Note 5. Poly (oxyethylene (75%)-oxy-1,2-propylene) glycol (MW 12,000-15,000) capped with 1. Mix component (a) 38.5 and component (b) 14.0 and mix at 130-150 ° F. Heat to (54-66 ° C) for 45-60 minutes.
The heat was removed, component (c) 11.0 and component (d) 10.0 were added and the mixture was mixed for 30-45 minutes. 0.3 part of benzotriazole was dissolved in 6.5 parts of component heated to 150-160 ° F (66-71 ° C). The two mixtures were combined. 10.7 parts of water are added and the mixture is mixed for 45-60 minutes to obtain a uniform translucent liquid.

6.5 parts by weight of the translucent liquid prepared as described above was added to water 87.8
Part, ethylene glycol 2.5 parts, component (i) 3.0 parts, and silicone defoamer 0.2 parts. The mixture was mixed for 45-60 minutes until a uniform translucent product was obtained. The initial viscosity of the produced hydraulic fluid was 210 to 320 SUS.

Example XI A pump test was performed with the hydraulic fluid of Example X. in this case,
Except for the duration of the test, the same type of pump and the same conditions as in Tables IV and V were used. These test results are shown below in XI
Shown in Table I.

Example XII The hydraulic fluid of Example X was subjected to the following pump test. The test conditions used and the results are shown in Table XIII below.

XIII Table Test conditions Test conditions Pump Vickers 25V17 A Intra-vane pump Pressure psi 1000 (70.3kg / cm ² ) Speed rpm 1200 Output (theoretical) gpm 17 Storage temperature ° F 115-120 Filter size, micron 25 Example XIII The working fluid of Example X was used in Example I, except for the duration of the test.
A pump test was carried out using the same type of pump as X, X-table and the same conditions. The results of these tests are shown in the XII table below.

XIV table Test results Test No. # 1 # 2 Duration hr 1080 706 Ring wear loss mgs 50 100 Blade wear loss mgs 8 5 Total wear loss mgs 58 105 Wear rate mgs / hr 0.054 0.15 Viscosity: Initial (SUS @ 100 ° F) 310 240 Final (SUS @ 100 ° F) 183 267

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication C10M 137: 10) Z C10N 30:00 A 30:06 40:08 (56) References 56-34796 (JP, A) JP-A-57-14696 (JP, A) US Pat. No. 4288639 (US, A)

Claims (27)

[Claims] 1. An emulsion-type high-aqueous hydraulic fluid having oil in water, comprising (1) about 1.5 to about 15% of a polyether thickener and (2) about 0.5 to about 20%. A lubricity modifier,
(3) Alkenyl-succinic anhydride or a dispersant which is a reaction product of succinic acid and a water-soluble active hydrogen compound, about 0.5 to about 5.0%.
And (4) about 0.125 to about 1.25% of an extreme pressure additive comprising a dialkyl- or diallyl dithiophosphate or a dialkyl or diallyl dithiocarbamate, (5)
Hydraulic fluid, the remaining part of which comprises at least 80% water, said percentage being a weight ratio based on the total weight of the liquid. 2. The thickener is ethylene oxide and 3 to 3.
At least one lower alkylene oxide having 4 carbon atoms is reacted with at least one active hydrogen compound initiator to form a hetero or block copolymer, and this copolymer is further mixed with at least one α-olefin oxide. The hydraulic fluid of claim 1 which comprises a polyether polyol made by reacting with a polyol having a molecular weight of from about 7,000 to 15,000. 3. The hydraulic fluid according to claim 2, wherein the active hydrogen compound is a diol or a polyol. 4. The hydraulic fluid according to claim 2, wherein the active hydrogen compound is an aliphatic monohydric alcohol containing 4 to 30 carbon atoms. 5. A minimum of 1 wherein said thickener contains a diol or polyol, ethylene oxide and 3 to 4 carbon atoms.
Consisting of a polyether polyol made by reacting a lower alkylene oxide of a type to form a hetero or block copolymer, wherein the copolymer is approximately
Claim 1 having a molecular weight of 7,000 to 75,000
Hydraulic fluid according to the item. 6. The thickener reacts ethylene oxide and propylene oxide with a lower glycol or polyol to form a block copolymer, the copolymer further containing 12 to 30 aliphatic carbon atoms. consisting of a polyether polyol obtained by reacting with α-olefin oxide, said polyol comprising about 7,000 to 75,
A hydraulic fluid according to claim 2 having a molecular weight of up to 000. 7. The thickener is reacted with ethylene oxide / propylene oxide and an aliphatic alcohol containing 12 to 18 aliphatic hydrocarbons to form a block copolymer. 5. The hydraulic fluid of claim 4 which comprises a polyether obtained by reacting with an .alpha.-olefin oxide containing from 30 aliphatic carbon atoms, said polyether having a molecular weight of about 7,000 to 15,000. . 8. The hydraulic fluid according to claim 6, wherein the active hydrogen compound is ethylene glycol. 9. The lubricity modifier is an aliphatic hydrocarbon, an alicyclic hydrocarbon, an aromatic hydrocarbon, a mineral oil, a silicone oil synthetic hydrocarbon oil, a glyceride, a fatty alcohol, a condensation product of a fatty acid and an alkanolamine. , A group consisting of phosphoric acid-modified-condensation products of fatty acids and alkanolamines, ethoxylated fatty amines, glycols, polyglycols, ethoxylated vegetable oils, ethoxylated fatty amides, organic esters, triallyl phosphates, polyphenyl ethers and mixtures thereof. The hydraulic fluid according to claim 1, which is selected from the group consisting of: 10. The lubricity modifier is 100 ° F. (37.8 ° C.)
10. The hydraulic fluid of claim 9 comprising polybutene having a viscosity of about 400 SUS. 11. The hydraulic fluid according to claim 9, wherein the lubricity modifier is a phosphoric acid-modified-condensation product of a fatty acid and a dialkanolamine. 12. The lubricity modifier is 100 ° F. (37.8 ° C.)
10. The hydraulic fluid according to claim 9, which is a naphthene-based light lubricating oil having a viscosity of about 100 SUS. 13. The hydraulic fluid according to claim 9, wherein the lubricity modifier is ethylene glycol. 14. The lubricity modifier has a molecular weight of from about 1,500.
A hydraulic fluid according to claim 9 which is a monobutyl ether of up to 4,000 poly (oxyethylene-oxy-1,2-propylene) glycol. 15. The lubricity modifier comprises a mixture of phosphoric acid-modified-condensation products with fatty acids and dialkanolamines, and a mixture of poly (oxyethylene-oxy-1,2-propylene) glycol monobutyl ether. Hydraulic fluid according to claim 9. 16. The hydraulic fluid according to claim 9, wherein the lubricity modifier comprises a mixture of polybutene, polyglycol and fatty alcohol. 17. The hydraulic fluid of claim 9 wherein said lubricity modifier comprises a mixture of mineral oil, fatty alcohols and glycols. 18. A hydraulic fluid according to claim 9 wherein said lubricity modifier comprises a mixture of fatty alcohols and glycols. 19. The succinic acid-or succinic anhydride ester wherein the alkenyl group contains 16 to 30 carbon atoms.
With succinic anhydride or succinic acid, Wherein R is hydrogen or an alkyl group containing about 8 to 25 carbon atoms and R ^I is hydrogen, (C ₂ H ₄ O) xH, or (C ₃ H ₆ O) x
H, R ^II is R or R ^I , and x is a reaction product with an alkylalkanolamine, which is an integer from 2 to 50, the reaction product having a molecular weight of about 800 to 2,000. The hydraulic fluid according to item 1. 20. The succinic anhydride ester has a molecular weight of about 1,00.
20. The hydraulic fluid according to claim 19, which comprises a reaction product of polyisobutenyl succinic anhydride of 0 and diethylethanolamine. 21. The dispersant is an alkenyl-succinic anhydride or ester of succinic acid and ethoxylated castor oil.
The hydraulic fluid according to claim 1. 22. The hydraulic fluid according to claim 1, wherein the dispersant is succinic anhydride or an ester of succinic acid and an ethoxylated fatty amine. 23. The dispersant is succinic anhydride or succinic acid, and a structural formula HO (Z) yOR ^III HO (Z) yR ^IV or Where Z is (C ₂ H ₄ O) or (C ₃ H ₆ O) and R ^III is 8 to
An alkyl group containing 20 carbon atoms, R ^IV is 2. The hydraulic fluid according to claim 1, wherein SR ^III and R ^V are reaction products with R ^I or an alkyl group containing 1 to 4 carbon atoms and y is an integer of 3 to 10. . 24. The extreme pressure additive is a structural formula, Where R ^V is an alkyl group containing 4 to 16 carbon atoms,
Phenyl or naphthyl, X is hydrogen, amine, ammonium or substituted ammonium, sodium, potassium, lithium, calcium, magnesium, manganese or zinc,
The hydraulic fluid according to claim 1, wherein a is an integer of 1 to 2. 25. The hydraulic fluid according to claim 24, wherein the extreme pressure additive is zinc dialkyldithiophosphate. 26. The extreme pressure additive comprises from about 4 alkyl groups.
25. The hydraulic fluid of claim 24 which is a zinc dialkyldithiophosphate containing up to 10 carbon atoms. 27. An emulsion-type high-aqueous working fluid having oil in water, which comprises reacting (1) ethylene oxide, propylene oxide and a lower glycol or polyol to form a block copolymer, and further forming this block. It consists of a polyether polyol obtained by reacting the copolymer with an α-olefin oxide containing from about 12 to about 18 aliphatic carbon atoms, said polyether being a thickener having a molecular weight of about 12,000 to 14,000. 2 to about 6%
And (2) about 1 to about 10% of a lubricity control agent, and (3) a reaction product of polyisobutenyl succinic anhydride and diethyleneethanolamine, the reaction product having a molecular weight of about 1,000. About 3% and (4) alkyl groups are about 4 to
Zinc dialkyldithiophosphate containing about 10 carbon atoms About 0.
A hydraulic fluid comprising 5 to about 0.75% and (5) the balance water, said percentage being a weight percentage relative to the total weight of the liquid, said liquid comprising at least 80% by weight water.