JPH01139695A - Lubrication oil - Google Patents

Abstract

PURPOSE:To provide a lubrication oil containing an esterified product derived from a specific nitrogen-containing alcohol and a specific fatty acid and exhibiting high lubricity and high mill-cleaning property in the rolling of sheet steel and excellent characteristics also in the plastic working of other metals. CONSTITUTION:The objective lubrication oil contains an esterified product derived from (A) a nitrogen-containing alcohol of formula I or formula II (X1 and X2 are H or CH3; n is 1-5) [preferably N,N'-bis(2-hydroxyethyl)piperazine, N,N'-bis(2-hydroxypropyl)2-methylpiperazine, N-(2-hydroxyethyl)piperazine, N-(2- hydroxypropyl)2-methylpiperazine, etc.] and (B) a >=6C fatty acid.

Description

[Detailed description of the invention] (Industrial application field) The invention relates to nitrogen-containing esterified products with excellent lubricity, such as rolling oil, cutting oil, grinding oil, drawing oil, press oil, etc. It can be used as metal processing oil, metal plastic processing oil, synthetic fiber spinning oil, etc. Especially in rolling thin steel sheets, it has high lubricity and mill cleanliness, that is, excellent lubricity and direct annealing properties. In addition, the present invention relates to a lubricating oil agent that exhibits excellent properties in cold rolling of metals and metal plastic working such as cutting, grinding, drawing, and press working.

(Prior Art) In recent years, with the rapid development of various mechanical industries, the conditions under which lubricating oils are used have become more severe, and excellent lubricating properties have become required.

Cold rolling oils used for thin steel sheets include animal and vegetable oils, (beef tallow and
There are two main types: those that use pork fat, soybean oil, rapeseed oil, palm oil, coconut oil, etc. as a base oil, and those that use mineral oil as a base oil. In recent years, high-speed rolling, high-reduction rolling, and mill-clean rolling have been trending toward energy conservation and improved production efficiency. Movement・
Rolling oil that uses vegetable oil as a base oil is suitable for high-load, high-speed rolling, but if a cold-rolled steel plate is directly annealed without removing the oil adhering to it, it may cause surface stains on the steel plate during the annealing process. arise. In other words, it has excellent lubricity but is unsuitable for mill cleanliness.

On the other hand, when cold rolling is performed using a rolling oil based on mineral oil, no surface stains occur even when the cold thin steel sheet is directly annealed, and the mill cleanliness is excellent. but,
It lacks high load and high speed rolling properties.

In general, rolling oils based on mineral oils are made using animal/vegetable oils, fatty acids (capric acid, lauric acid, myristic acid, stearic acid, oleic acid, lylunic acid, etc.) or oil chemicals to improve rolling lubricity. 73-November issue p, 695-70
Esters as listed in 6 (synthetic esters such as monoesters, diesters, and polyol esters whose alcohol component is trimethylolpropane, pentaerythritol, 2-ethylhexyl alcohol, etc.)
These oils are used with the addition of similar agents, but the amount of these additives is adjusted within a narrow range to the minimum necessary in order to maintain milk cleanliness. As mentioned above, various studies have been conducted on cold rolling oils that can simultaneously satisfy high lubricity and high mill cleanliness.
5600. (Japanese Unexamined Patent Publication No. 59-80498) Currently, there is no one suitable for both.

On the other hand, lubricants used for cutting and grinding metals include mineral oils, animal and vegetable oils, extreme pressure additives, surfactants, antifoaming agents, metal anticorrosives, antioxidants, preservatives, antifungal agents, etc. depending on the purpose. The composition is made by appropriately mixing them. Cutting oil is usually 10% water.
It is used diluted to ~100 times, but in some cases a water-insoluble cutting fluid may be used.

The basic conditions that cutting and grinding oils must have are lubrication, cooling, rust prevention, and other incidental conditions, such as foaming, roughness, 11 toxicity to humans and animals, and no odor. Cutting and grinding fluids must have the above-mentioned performance in a well-balanced manner, although the emphasis differs depending on the purpose and conditions of use, but cutting and grinding fluids that can satisfy the various conditions are not always sufficient. This is the current situation.

(Problems to be Solved by the Invention) The present invention is a synthetic lubricating oil that has been molecularly designed to provide excellent lubricating properties as the usage conditions for lubricating oils have become more severe in recent years.

In other words, it is a synthetic oil that has high lubricity, high stability, is resistant to deterioration by microorganisms, and is resistant to spoilage.

The present invention is a cold rolling oil for steel that contributes to improving production efficiency such as energy saving and process saving. It is also stable against reactions. In addition, it is easily volatilized during the annealing process without producing any thermal decomposition residual aroma of rolling oil, and has both steel plate surface cleanliness (mill cleanliness) and high lubricity.

On the other hand, in the case of cutting and grinding fluids, the present invention has lubricating properties, cooling properties,
It is a synthetic lubricant that has excellent rust prevention properties, has no problems with foaming, roughness on hands, toxicity to humans and animals, and is resistant to spoilage.

(Means and effects for solving the problems) The present invention mainly consists of an esterification product of a nitrogen-containing alcohol represented by the general formula (1) and (2) and a fatty acid having 6 or more carbon atoms. It is a lubricating oil.

X.

However, x, 2 H or CH8 It can be used for various purposes.

The cold rolling oil for steel containing synthetic ester as a main component has high lubricity and high mill cleanliness, and enables rolling of thin steel sheets and direct annealing of steel sheets without degreasing, and furthermore, Lubricating and cooling properties as a cutting and grinding fluid,
It has excellent properties such as rust prevention, foaming property, roughness, toxicity to humans and animals, and odor.

As the nitrogen-containing alcohol of general formula (1), N N'-bis(2-hydroquinethyl)piperazine, N N'-bis(
2-hydroxypropyl)piperazine, NN'-bis(
2-hydroxyethyl)2-methylpiperazine; NN'
-bis(2-hydroxypropyl)2-methylpiperazine, nitrogen-containing alcohol of general formula (2), N-(2
-Hydroquinethyl)piperazine>, N-(2-hydroxypropyl)piperazine, N-(2-hydroxyethyl)2-methylpiperazine, N-(2-hydroxypropyl)2-methylpiperazine are commercially available. The lubricating oil is advantageous for this purpose because it is easy to use and inexpensive. The reason for using an ethylene oxide adduct or a propylene oxide adduct as the polyol is that higher alkylene oxide adducts, such as butylene oxide adducts, are industrially expensive and difficult to obtain, making them inconvenient for the purpose of lubricating oil. .

Nitrogen-containing alcohol of general formula (1) or (2), where n is 1
The range of 5 to 5 is preferable, and when n is 6 or more, the molecular weight increases and the lubricity decreases as the number of ether bonds increases.

However, the number n shown here is the average number of moles, and when the average number is 3 moles, there is a distribution in the number of moles added of ethylene oxide or propylene oxide, and there may be cases where n is 6 or more. In other words, n is just an average number, and the average number of moles is preferably 5 or less.

Fatty acids include hexanoic acid, octanoic acid, decanoic acid,
Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, montanic acid, palmitoleic acid, oleic acid, erucic acid, ricinoleic acid, hydroxystearic acid, linoleic acid, lilunic acid, inoctylic acid, indecane A fatty acid having 6 or more carbon atoms such as inlauric acid, inmyristic acid, inpalmitic acid, instearic acid, and inarachic acid. In addition, lanolin fatty acids, fish oil fatty acids, soybean oil fatty acids, coconut oil fatty acids, beef tallow fatty acids, and hydrogenated fats ['V! It is also possible to use natural fatty acids such as

When a fatty acid having 5 or fewer carbon atoms is used, the lubricity is poor.

On the other hand, the upper limit of the number of carbon atoms in the fatty acid is not regulated, but it is generally preferable that the number of carbon atoms is 30 or less as it can be obtained industrially at low cost.

The esterification reaction between the nitrogen-containing alcohol of general formula (1) or (2) and the fatty acid can be carried out without a catalyst or in the presence of a catalyst to synthesize the esterified product of the present invention. The law is not particularly limited.

In the case of general formula (2), esterification and amidation may be carried out simultaneously depending on the reaction molar ratio of fatty acids.

It is preferable that the lubricant for this purpose is mainly composed of an esterified product, but it may be one in which both an esterified product and an amidated product are reacted.

The synthetic ester of the present invention can be used as rolling oil, cutting/grinding oil,
When used as a lubricating oil for metal plastic processing such as drawing or press working, an internal combustion lubricating oil, or a yarn-preventing oil for synthetic fibers, the synthetic ester can be used alone. It can also be used in combination with other base oils, such as mineral oils, animal/vegetable oils, and commonly used existing synthetic esters. Depending on the purpose, an emulsifier can be added to these to use as an emulsion liquid, or by increasing the number of moles of the ethylene oxide adduct with the element-containing alcohol of general formula (1) or (2), It can also be used as a self-emulsifying oil.

It can also be used in combination with other commonly used additives for practical lubricants, such as emulsifiers, fatty acids, antioxidants, corrosion inhibitors, preservatives and anti-mold agents.

When the synthetic ester compound of the present invention is mixed with other base oils, etc., the effect can be seen with addition of 1% by weight or more, but the content should be 5% by weight or more, preferably 20% by weight or more. The characteristics become stable. An example of an ester synthesis method is shown below.

Synthesis example 4 equipped with a stirrer, thermometer, nitrogen gas blowing pipe, and water separator
NN'-bis(2-hydroxyethyl) in a Tulo flask
Piperazine 3487 and coconut oil fatty acid 7562 were charged, 2.27 g of p-toluenesulfonic acid was added as a catalyst, and 5% of the charged amount was added with xylene as a refluxing solvent.The mixture was stirred well and heated to 160-230°C for the calculated amount. The reaction was carried out until water was distilled out. The required time was 6 hours.

After the reaction was completed, the reaction mixture was washed with water to remove the catalyst, and then xylene was distilled off under reduced pressure, followed by decolorizing filtration using activated clay to obtain a yellow liquid. The yield was 945 and the acid value was 2.1 (sample A).A synthetic ester was produced in the same manner.

The properties of the obtained synthetic ester are described in Section 18. It is shown in Table 2.

(Actual Case) Actual Example 1 General Characteristic Test in Metal Plastic Working The performance test results of the lubricating oil of the present invention are compared with the conventional lubricating oil and are shown in Table 2.

The friction coefficient and seizure resistance were measured using a Pauden tester, and the heat resistance was measured using a thermobalance.

Test using Bauden testing machine> The surface of a low carbon steel plate was coated with various test agents, and a steel ball with a diameter of 3/16 inch was pressed against the coated oil with a load of 3 kg at a Hertzian pressure of 223 kg/r1j) and speed. The number of sliding movements (seizure resistance I!!E) until the friction coefficient of the lubricant reached o, 15jc was measured by sliding back and forth at 4 g/sec.

<Test using thermobalance> 351n9 of the test material is placed in a platinum crucible and heated at 5"C per minute in a He atmosphere, and the heating temperature is measured when the test material in the crucible decomposes and burns out. did.

In the Bowden test, the actual plastic working conditions are approximated as much as possible, and the test temperature is set at 20°C, taking into account the heat generated by plastic deformation.
The temperature is 0°C, and a mild steel plate is used, which is easily plastically deformed.

The friction coefficient corresponds to the power required during actual machining, and the seizure resistance corresponds to the occurrence of seizure defects and tool life.

Furthermore, in a test using a thermobalance, it can be said that the higher the burnout temperature of the test material, the better the heat resistance.

Example 2 Rolling lubricating oil Practical Rolling oil Mineral oil or palm oil used as the base oil is blended with emulsifiers, fatty acids, antioxidants, etc. that are commonly used as additives, and synthetic esters that are the rolling oil of the present invention. The lubricity and annealing properties of the resulting rolling oil composition were evaluated.

Emulsion rolling is performed using a two-roll rolling mill, and the rolled material (
apcc ) 1.2 x 20 x 200 g was measured for rolling load at a rolling reduction of 40 inches under the conditions of an oil concentration of 3% and a bath temperature of 50° C. to evaluate rolling lubricity. Regarding annealing properties, tens of steel plates rolled with the sample emulsion liquid were stacked together, fixed with a narrow copper band, and annealed in a small annealing furnace.

The heating conditions during annealing were HNX gas (H: 5%) 1
In an atmosphere of 20 ml/min, the rising speed fxo°C/m
The mixture was heated up to 600°C as an inlet, kept at 600°C for 1 hour, and then allowed to cool. Thereafter, a cellophane tape was attached to the surface of the steel plate, and the surface deposits were collected and attached to white paper to visually determine the degree of contamination, and the cleanliness of the steel plate surface was evaluated. The test results are summarized in Table 3, and the symbols in the table are the same as in Table 1.

Example 3 Cutting oil containing the substance of the present invention as shown in Table 4 (sample heights 1 to 4)
The sample height of 5.6 indicates the commercially available cutting oil.

Note 1) Condition after 14 days O: No change △: Slightly grayish-black Note 2) Condition after 14 days ○: No putrid odor △: Slightly putrid odor 8E3) 400 m/! of each sample solution! was placed in a sterilized 500 m flat-bottomed flask and cultured with shaking at 30°C for 14 days (rotation speed: 15 rpm).

After that, a part of the sample was taken out silently and the number of fungi was measured.
At the same time, pH measurements, changes in appearance, and odor were observed. Furthermore, the rust overpainting performance was also observed.

A-=Measured by plate counting method using potato dextrose agar medium supplemented with antibiotics (chloramphenicol and tetracycline).

Note 4) Rust prevention was observed using the cast iron chip method. That is, about 159 dry-cut steel chips (F
C-25, 8-12 mesh) in a bedding dish (inner diameter 60
ttrm), about 25 rnl of the sample solution was added thereto, and after shaking thoroughly, it was allowed to stand for about 4 minutes. Next, the sample liquid was removed by a decanting method, and the state of rust generated on the Petri dish was examined over time.

Note 5) Measured using a Soda pendulum type friction tester.

Note 6) Tested using a Soda four-ball tester using the step load method (0,5 kg) at 200 rpm.

Example 4 Water-based cutting oil containing the present invention substance in Table 5 (Sample I41
1L7-11) was prepared and diluted with sterilized water to give a weight of 5%, which was used as a test solution.

Tests shown in Table 6 were conducted using the formulation examples shown in Table 5.

(Effects of the Invention) The synthetic ester compound obtained from the nitrogen-containing alcohol and fatty acid of the present invention has far superior lubricating properties and stability compared to conventional lubricating oils, and is suitable for rolling oil, hydraulic oil, cutting/grinding oil, etc. It can be used as various industrial lubricating oils such as 11"IL3 for metal plastic working, JA oil, lubricating oil for internal combustion engines, and spinning oil for synthetic fibers.

For example, using existing synthetic ester as cold rolling oil,
Also, unlike those that are used as additives, it improves rolling lubricity for steel plates, resulting in energy and resource savings such as power cost savings compared to conventional use of palm oil as base oil. . In addition, it has excellent annealing properties, making it possible to omit the usual electrolytic degreasing and reducing equipment costs.

As for cutting and grinding oils, it has excellent lubricity and can be a high-performance oil that fully satisfies various usage conditions such as odor and stability.

In addition, sufficient lubrication is guaranteed even under harsh conditions such as high-speed machining, making machining smoother and more efficient.

This prevents deterioration in product quality caused by insufficient lubrication, such as seizure defects, and also prevents tool wear and breakage, improving product quality and greatly extending tool life.

This produces many excellent effects, such as reducing the power required during processing and further promoting resource and energy conservation.

Procedural amendment /,7 1986! April 4th

Claims (5)

[Claims] (1) Lubricating oil containing an esterification product of a nitrogen-containing alcohol represented by general formula (1) or (2) and a fatty acid having 6 or more carbon atoms ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (1) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...(2) However, X: H or CH_3 X_2: H or CH_3 n = integer from 1 to 5 (2) General formula (1) is NN'-bis(2-hydroxyethyl)piperazine, NN-bis(2-hydroxypropyl)piperazine, NN'-bis(2-hydroxyethyl)2-methylpiperazine, NN'- The lubricating oil according to claim 1, which is bis(2-hydroxypropyl)2-methylpiperazine. (3) General formula (2) is N-(2-hydroxyethyl)piperazine, N-(2-hydroxypropyl)piperazine, N-(2-hydroxyethyl)2-methylpiperazine, N-(2-hydroxypropyl) The lubricating oil according to claim 1, which is 2-methylpiperazine. (4) The lubricating oil according to claim 1, wherein the lubricating oil is cold rolling oil for steel plates. (5) The lubricating oil according to claim 1, wherein the lubricating oil is a metal cutting oil/grinding oil or a metal plastic working oil.