JPS5938295A - Water/glycol-base hydraulic oil - Google Patents

Abstract

PURPOSE:The titled hydraulic oil excellent in metal wearing resistance and biotreatability, which is prepd. by incorporating ethylene glycol and/or propylene glycol, a specified polyoxyalkylene derivative, oleic acid and an additive. CONSTITUTION:10-50wt% ethylene glycol and/or propylene glycol, not more than 15% total of polyoxyalkylene derivatives such as propylene oxide of average MW of 10,000-200,000 with 0.1-1wt% polyoxyalkylene derivative of phosphoric acid of the formula [wherein R1 is alkyl or alkylaryl; R2 and R3 are each H or R1O(-CH2CH2-O)n-], 1-20wt% oleic acid and not more than 10.0wt% additive such as a rust preventive, e.g., morpholine, antioxidant, e.g., benzotriazole, sequestering. agent, e.g., sodium gluconate, or pH adjustor, e.g., KOH, are dissolved in water.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a water-glycol type hydraulic oil, particularly a water-glycol type hydraulic oil having high lubricity and waste liquid treatment properties.

Water-glycol type hydraulic fluids are widely used as hydraulic fluids due to their superior flame retardancy, controllability, and relatively low cost. However, conventional water-green oil type hydraulic fluids lack metal wear resistance, and as a result, oil) and soil equipment wear out the friction parts of the equipment.
Instead, metal powder produced by wear gets mixed into the hydraulic oil, causing occasional troubles such as accelerated clouding and deterioration of the hydraulic oil itself. In addition, conventional water-grind oil type hydraulic fluids have the advantage of extremely good affinity for water, so when treating waste fluids, they diffuse infinitely into water, making waste fluid treatment extremely difficult. The situation is troubling.

SUMMARY OF THE INVENTION The first object of the present invention is to provide a water-glycol type hydraulic fluid with excellent metal wear resistance. IJU is equipped with a hydraulic oil that is suitable for treating cattle, such as activated sludge treatment.

The water-glycol type hydraulic fluid of the present invention contains glycol, a polyoxyalkylene derivative, and water as main components.
The Gly:1-al type hydraulic oil is characterized by containing a polyoxyalkylene derivative of phosphoric acid as a part of the polyoxyalkylene derivative.

In the water-grid type hydraulic oil of the present invention, metal wear resistance is improved by avoiding the inclusion of a polyoxyalkylene derivative of phosphoric acid in a part of the polyoxyalkylene M conductor. In addition, the glycol is limited to ethylene glycol, polyethylene glycol, or a mixture thereof, and the blending ratio is 10-50% by weight (hereinafter, % means a small amount %), and the polyoxyalkylene of phosphoric acid is derivatives to 0
．． 1% or more, and the total polyoxyalkylene derivative is 1% or more.
Oleic acid is limited to 1 to 20%, additives such as rust preventive agents, oxidation preventive agents, and metal ion sequestering agents are limited to 10% or less.
By assuming that the remainder is water and the total fft is 100%, the COO value of the hydraulic oil itself is 400,000 P1F, and the removal rate by biological treatment can be 70% or more.

In the water-glycol type hydraulic oil of the present invention, firstly, the polyoxyalkylene derivative used as a thickener includes a polyoxyalkylene derivative of phosphoric acid. Here, the term "polyoxyalkylene derivative" refers to one in which the polyol-1-nidial-4-lene chain moiety, which is a constituent unit, is composed of an A-oxy'brene unit or a higher oxyalkylene unit. A-oxy, an alkylene higher than ethylene A quinoid; It is necessary to
In addition, in order to provide hydraulic oil with a viscosity of 1 minute even with a small amount, it is preferable that the molecular weight is large, and the average molecular weight is 10,000 to 2.
Something around 0,000 is good. Further, it is preferable to limit the total blending ML of the boria-11 dialkylene derivative to 15%. This is because polyoxyalkylene derivatives are extremely difficult to treat with microorganisms, and their presence is not very desirable in waste liquid treatment.

The polyoxyalkylene derivative of phosphoric acid contained as a part of the polyoxyalkylene derivative provides the hydraulic fluid of the present invention with metal wear resistance f9! -JJ.

This phosphoric acid polyoxyfluorine 1:lene M conductor becomes a part of the polyoxyalkylene derivative, dissolves uniformly in the hydraulic oil, and plays a role as an extreme pressure lubricant. Note that the polyoxyalkylene derivative of phosphoric acid refers to a compound having a phosphoric acid group and a polyoxyalkylene chain portion. The blending amount of the polyoxyalkylene derivative of phosphoric acid is preferably 0.1% or more, more preferably 0.5% or more in the total hydraulic oil. Incidentally, the larger the amount is, the better, but about 1% is sufficient. Therefore, considering economic efficiency, the blending amount of the polyoxyalkylene derivative of phosphoric acid is 0.
．． It is about 1-1%. As the polyoxyalkylene derivative of phosphoric acid, a phosphorus ester of the general formula (1) % formula % (1) polyoxyalkylene]--ter is preferable. (1) In formula 1, 1 is an alkyl kite or alkylaryl group R2, R3 is hydrogen or R+ O(-C
I-121-12) There is n-C.

Glycols used as fluidizers or viscosity modifiers for hydraulic fluids are limited to clay, propylene glycol, or mixtures thereof, and the composition ratio of By taking ~50%, it becomes a hydraulic oil with a biological treatment property of 1. Based on the fact that ethylene glycol and propylene glycol are very good compared to other diethyl glycols, dipropylene glycols, etc., IC discovered that it was possible to improve the waste liquid treatment properties of hydraulic oil by limiting the use of glycols to propylene glycols.
A preferred blending amount is 35% to 50%.

By limiting the fatty acid used as the oiliness improver to Δleic acid and by setting the blending amount to 1 to 20%, the waste liquid treatment f[ is improved.

This means that the decomposition rate of acid in activated sludge is
Other fatty acids can be used more quickly, including Aleic acid (・
Second, it was discovered that the decomposition rate of glycols by activated sludge is also accelerated. In addition, a more preferable blending ratio of secondary leic acid is 1 to 10%.

In addition, additives such as rust preventive agents, oxidation preventive agents, and metal ion sequestrants should be contained at 10% F or more, thereby improving waste liquid treatment properties. Regarding rust preventives and antioxidants, it is preferable to use as few amounts as possible from the perspective of waste liquid treatment.
The hydraulic oil C of the present invention is more preferably about 0.1% to 5.0%.

Examples of rust inhibitors include morpholine, benzoic acid, cyclohexylamine, and triethanolamine; examples of antioxidants include benzotriazole, mercap-1benzimidazole, and mercap]-benzodeazole; and examples of sequestering agents include [ D1Δ, D King) Δ, gyrate inhibitors such as tritrium gluconate, and P(-1 regulators) such as caustic potash and caustic soda can be used in the same manner as in the past.

The water-glycol type hydraulic oil of the present invention has almost the same performance as conventional water-glycol type hydraulic oil in terms of viscosity, viscosity index, PH, foaming degree, corrosion resistance, and rust prevention properties as a hydraulic oil. Show. For example, the wear scar diameter of the four-ball wear test used as an indicator of metal wear resistance is different from the conventional one. It is about 20% smaller than that of . In addition, by limiting the other components of the hydraulic fluid, it is possible to demonstrate waste liquid treatment properties (C01).
The value may be less than or equal to 40'DI-'PM. This value is 25 to 50% lower than that of conventional water-grill type hydraulic oil. Further biological treatment J
! Considering that the COD removal rate of conventional general hydraulic oil is about 30 to 40%, the COD removal rate of biological treatment is 60%.
The degree of improvement is C.

By using the water-glycol type hydraulic oil of the present invention, metal wear in the hydraulic system in which this hydraulic oil is used is reduced, and the durability of mechanical equipment is improved. In addition, a regular coagulation treatment device is added to the general activated sludge treatment device.Leader 4
J makes it possible to sufficiently reduce the COD value. Therefore, even in factories with strict regulations, waste liquid can be disposed of in -1 minute) 1! is possible. In addition, by using ethylene glycol, propylene glycol, and A-leic acid, and minimizing the amount of morpholine and benzotriazole, toxicity is reduced and safety and hygiene are improved.

This will be explained below using examples.

The water-glycol type actuation elongation of the two scales shown in Table 1, △ and B, of the present invention was adjusted. For reference, the compositions of conventional water-glycol type hydraulic fluids C, [), and E for Class 311t are shown in Table 1. Here, the amount of water added is 4
Standardized to 0%.

In the △ hydraulic oil of the present invention, 40% but[1pyrene glycol] and 12.0% polyoxyalkylene derivative
, the above <1> as a polyoxyalkylene derivative of phosphoric acid
0.5% of polyoxyalkylene phosphoric acid ester in which R+ in the formula ) is decanol alcohol was used. In addition, 5% A-leic acid was used as the fatty acid. 8 of the invention product
The hydraulic oil of D3 contains 20% ethylene glycol, 20% propylene glycol, and 40% glycols.
It is said that Regarding polyoxyalkylene derivatives in Table 1 and D, diethylene glycol and di[1-pyrene glycol] are used as glycols. In addition, F, which is a conventional hydraulic fluid, is converted into glycol, -I
-tylene glycol and pyrene glycol are used, but the total amount thereof is 30% (20%).
．． 5%, whereas the conventional ones are 27%, 15%, and 22%. Furthermore, conventional hydraulic fluids C, D, and F do not contain polyoxyalkylene derivatives of phosphoric acid. Furthermore, in the hydraulic fluid of the present invention, the amount of rust inhibitors such as morpholine and cyanide acid is 1%, whereas in the conventional product, it is 2.4%.
~2.6% is added. Furthermore, benzotriazole is added in an amount of 0.2% in the hydraulic fluid of the present invention, but in conventional hydraulic fluids, it is added in an amount of 0.3 to 0.4%. E
In the case of the present invention, DTΔ and other additives are also 0.
1% conventionally, about 0.2% is added later.

Next, the properties of these hydraulic fluids are shown in Table 2. In Table 2, J3 has specific gravity, color, viscosity, viscosity index, reserve alkalinity, moisture, Pl-1, degree of foaming, corrosion resistance of copper plate,
Rust prevention property, friction coefficient, wear scar diameter, BOD value, and COD value were measured. The coefficient of friction and the diameter of the wear scar were measured using a Soda four-ball tester under the conditions of a rotational speed of 20 Or, a pixel of 9 m, and a maximum pressure of 5 kg-f/cm2 for a holding time of 20 minutes.

In addition, the BOD value Table 2 shows the biochemical oxygen demand and shows the percentage of activated sludge that can be treated by biological treatment, and the higher the BOD value, the easier the biological treatment is. There is. In addition, the test method for each item is described in the notes.

As is clear from Table 2, the hydraulic oils △ and B of the present invention are compared with the conventional hydraulic oils C, D, and [, and the ratio ■, color, viscosity, The viscosity index, reserve alkalinity, water content, l) l-1, degree of foaming, corrosion resistance of copper plate, and rust prevention property are almost the same. Furthermore, the hydraulic oils Δ and B of the present invention are different from the conventional hydraulic oils C and D.
, [compared to [], the friction coefficient and wear scar diameter are the same or slightly smaller even though the polyoxyalkylene derivative content is smaller. Furthermore, the BOD values of the conventional hydraulic oil were 358,000, 21,000, and 398,000, whereas the BOD values of the hydraulic fluid of the present invention were 566,000, 557,000, and 500,000. This shows a very high value. On the other hand, the COD values of the conventional ones are 590,000, 720,000, and /16,000, which are all over 400,000, while the COD values of Kikomei's are 380,000 and 390,000.
What's going on with h and /IO million? As described above, the hydraulic fluid of the present invention has a COD value as low as 401j or more, and exhibits bioprocessability.
With COD [30D value reversed, waste liquid disposal]! I! Bamboo is improving. In addition, the waste liquid containing 0.5% hydraulic oil with a value of +301) was drained into the test liquid, poured into activated sludge, and then MLSS
(Mixed l 1 quarSuspended
3olid) was adjusted to 2700 ppm, and an activated sludge treatment test was conducted. Activated sludge treatment test 0 in 4T Figure 1
．． i's Cot) draw the curve. From FIG. 1, 50% of G and I of the hydraulic oils Δ and B of the present invention are decomposed after 48 hours of treatment time, and even after that, the decomposition progresses gradually, and after 120 hours of elapsed time, about 50% of G and I are decomposed. It can be seen that 75% has been decomposed. Conventional product E also has relatively poor decomposition by activated sludge, but even after +3 after 120 hours, the decomposition rate is about 55%, and compared to the present invention's Δ, [3, biological treatment Sex is not good. In addition, regarding conventional C and D hydraulic fluids, they are not decomposed into activated sludge.
The F liquid treatment is difficult. Furthermore, Table 3 of the hydraulic oil of the present invention 1) Test liquid: 1601 2) Liquid fi: 47-50°C 3) Pump discharge amount: 17.51 /win4) Discharge J
I:210k(]・f/cm' ON:3sec
QFI-: 1sec5) Motor rotation speed: 1800v
, p, m6) Operating time: 210 kO-f/cm2 (7) for the five types of hydraulic oils A, [3 and used as reference, C, l), and E (7) using a test device to the high-pressure pump unit 1. , and tested whether it was compatible with hydraulic equipment. The results are shown in Table 3.

None of the hydraulic fluids tested had any particular abnormalities, and the invention product of the present invention, including B, did not generate sludge, and there was no abnormal wear in the pumps and valves. In addition, ΔJ of the present invention
Compared to conventional hydraulic oils C, D, and [3], hydraulic oils 3 and 3 showed good results, with less or less total wear and tear and part surface roughness. .

In addition, for reference, the composition of the hydraulic oil Δ of the present invention shown in Table 1 is taken as the basic composition, and all polyoxyalkylene derivatives are 12
．． 5%, and the phosphoric acid and 1 sual of polyA
Five types of hydraulic oils were prepared in a range of 5% and the friction coefficient and wear scar diameter were measured using the above-mentioned four-ball tester.

These values are shown in Figure 2. Figure 2 J: Friction coefficient LL
, polyol-1 dialkylene'' addition of needle phosphate ester ■ Nis, there is no change, about 0.7/1 ~
The value was about 0°75. However, it can be seen that the wear scar diameter sharply decreases as the addition of 1 sulfur phosphate to the polyoxycarbonate resin increases.

It has been revealed that the wear scar diameter becomes smaller when the amount of Nisdel phosphate added to the polyoxyalkylene 1-del in Figure 2 is 0.1% or more.

Further, the basic composition of the hydraulic oil △ of the present invention shown in Table 1 is used, and the polyoxyalkylene needle phosphate ester of the formula (1) has the aroma Chic alcohol stuff 3
A friction test was conducted using the four-ball tester described above. Figure 3 shows the diameters of these wear scars and the friction coefficients. For reference, the hydraulic oil to which polyoxyal 4: renyl nityl phosphate ester is not added is also compounded.
! Show c. From FIG. 3, it can be seen that the wear scar diameter does not change much even if the value of "l R+" shown in formula (1) of the polyoxyal 4: lentic acid phosphate ester is varied by +3.

[Brief explanation of the drawing]

Figure 1 is a diagram showing the relationship between COD and pouring time in an activated sludge treatment test using two types of hydraulic oil of the present invention and three types of conventional hydraulic oil, as shown in Example 1. Figure 3 is a diagram showing the relationship between the amount of phosphoric acid in polyoxyalkylene ether, the friction coefficient, and the wear scar diameter. This is a bar graph showing the relationship between wear scar diameter. No. 71 △, 1
3 is the hydraulic oil of the present invention, C, D, [ is the conventional hydraulic oil, respectively. One person for special V1 appearance Toyota Motor Corporation (Ri, Go (intercompany)
Representative of e-Ten Central Institute Co., Ltd. Patent attorney: Hirodo Okawa Patent attorney: Akito Fujitani Patent attorney: Akio Maruyama Figure 1 Elapsed time (Hr)

Claims (3)

[Claims] (1) In a water-glycol type hydraulic oil whose main components are a Grinylene derivative, Boria j=I Schiff) and water, poly(A21) of phosphoric acid is added to the polyoxyalkylene derivative. A water-glycol type hydraulic fluid characterized by containing a fulgylene derivative. (2) The polyoxyalkylene derivative of phosphoric acid has the general formula (
The hydraulic oil according to claim 1, which is polyA xyalkylene -thyl nisdel phosphate represented by 1). R2 / R+ O(-CI-42CH20) +l -P
(1) 11\0R3 (In the formula, RI is an argyl group or alkyl) noryl group,
R2, R3), hydrogen number rLR+ O(-C112C
LI 2-〇)0-. ) (3) Glycol consists of ethylene glycol, propylene glycol or a mixture thereof, and the blending ratio is 1
0-50% by weight, phosphoric acid polyoxyalkylene M conductor is 0.1% by weight or more, total polyoxyalkylene derivatives are 15% by weight or less, oleic M1-20% by weight, rust preventive, antioxidant, metal Additives such as ion sequestering agents 10
．． 0% or less, and the hydraulic oil according to claim 1, which has a total δt of 100% by weight with the remainder water.