JPH0672230B2 - Lubricant - Google Patents

Description

TECHNICAL FIELD The present invention relates to a nitrogen-containing esterified product having excellent lubricity, such as rolling oil, cutting oil, grinding oil, drawing processing oil, and press processing oil. It can be used as a metal working oil, a metal plastic working oil, or a synthetic fiber spinning oil. In particular, when rolling thin steel sheets, it has excellent lubricity and high mill cleanliness, that is, excellent lubricity and direct annealability. In addition, the present invention relates to a lubricant that exhibits excellent properties in metal plastic working such as cold rolling and cutting, grinding, drawing, and pressing of metals.

(Prior Art) With the rapid development of various machine industries in recent years, the usage conditions of lubricating oils have become severe, and excellent lubricating characteristics have been required.

The cold rolling oil used for thin steel sheets is roughly classified into those based on animal and vegetable fats (beef tallow, lard, soybean oil, rapeseed oil, palm oil, coconut oil, etc.) and those based on mineral oil. To be done. recent years,
High-speed rolling, high-pressure reduction rolling, and mill-clean rolling are aimed at with energy conservation and improvement in production efficiency. Rolling oils that use animal and vegetable oils as base oils are suitable for high load and high speed rolling, but if directly annealed without degreasing the oil adhered to the cold-rolled steel sheet, the steel sheet will be used in the annealing process. Surface stains occur. 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 that uses mineral oil as a base oil, even if the cold-rolled steel sheet is directly annealed, surface contamination does not occur and the mill cleanness is excellent. But,
High load and lack of high speed rolling property.

In general, rolling oils based on mineral oils are used in order to improve rolling lubricity, animal and vegetable oils and fatty acids (capric acid, lauric acid, myristic acid, stearic acid, oleic acid, linolenic acid, etc.) or oil chemistry73- Esters listed in November issue p.695-706 (monoester, diester with trimethylolpropane, pentaerythritol, 2-ethylhexyl alcohol as alcohol component,
It is used by adding an oiliness improver such as a synthetic ester such as a polyol ester), but the addition amount of these is adjusted to the narrowest range necessary for maintaining the mill cleanliness. As described above, various studies have been made on cold rolling oils that can satisfy both high wettability and high mill cleanability at the same time (for example, JP-A-56-135600 and JP-A-59-8049).
8) Currently, there is no suitable one for both.

On the other hand, lubricating oils used for cutting and grinding of metals are mineral oil, animal and vegetable oils, extreme pressure additives, surfactants, defoamers, metal anticorrosives, antioxidants, antiseptic, antifungal agents, etc. depending on the purpose. The composition is appropriately mixed. Cutting fluid is usually 10 ~ 10
It is used by diluting 100 times, but depending on the case, a water-insoluble cutting fluid may be used.

The basic conditions that cutting and grinding oil must have are lubricity, cooling, rust prevention and other incidental conditions such as foaming,
It has no rough hands, animal toxicity, odor, etc. Even if the importance of cutting and grinding fluids differs depending on the purpose and conditions of use, the above-mentioned various performances must be provided in a well-balanced manner, but cutting and grinding fluids that can satisfy the various conditions are not always sufficient. is the current situation.

(Problems to be Solved by the Invention) The present invention is a synthetic lubricating oil that has been molecularly designed so as to have excellent lubricating characteristics in recent years under severe operating conditions of the lubricating oil.

That is, it is a synthetic oil agent that has high lubricity and high stability, is resistant to deterioration by microorganisms, and is resistant to decay.

INDUSTRIAL APPLICABILITY The present invention is a cold rolling oil for steel imparted to the improvement of production efficiency such as energy saving and process saving, which is stable against heat and mechanical shear generated at high speed and under high pressure, and chemicals such as oxidation, decomposition and polymerization. It is stable to reaction. Further, it easily volatilizes without producing a thermal decomposition residue of rolling oil in the annealing step, and has both a steel plate surface cleanability (mill clean property) and high lubricity.

On the other hand, in the case of cutting and grinding fluids, the present invention provides lubricity, cooling,
It is a synthetic lubricating oil that has excellent rust resistance, has no problems of foaming, rough hands, and animal toxicity and is resistant to decay.

(Means and Actions for Solving Problems) The present invention is a lubricating oil containing an esterification product of a diamine type tetraol represented by the general formula (1) and a fatty acid having 6 or more carbon atoms.

However, X: H or CH ₃ n: an integer of 1 to 3 R: an alkyl group having 2 to 6 carbon atoms, a phenyl group, or a cyclohexyl group. Synthetic ester oil agents referred to here are cutting / grinding oils, press working oils, and rolling oils. It can be widely used for various applications such as metal plastic working oil such as oil and mechanical lubricating oil. The cold-rolling oil for steel having the synthetic ester as the main component of the present invention has high lubricity and high mill-cleaning property, which enables rolling of thin steel sheets and direct annealing without degreasing of steel sheets. As a cutting and grinding oil, it has lubricity, cooling, and rust prevention.
In addition, it has excellent properties such as foamability, hand roughening, human animal toxicity, and odor.

The diamine-type tetraol of the general formula (1) is an alkylene oxide-added diamine-type tetraol obtained by adding a predetermined amount of ethylene oxide or propylene oxide to ethylenediamine, hexylenediamine, phenyldiamine, cyclohexyldiamine or the like. In particular, N, N, N ', N'-tetrakis (2-hydroxypropyl) ethylenediamine of X = CH ₃ , n = 1, R = C ₂ H ₄ is industrially available and inexpensive, It is advantageous as a lubricating oil for this purpose. The reason for using ethylene oxide adduct or propylene oxide adduct as tetraol here is that further alkylene oxide adducts such as butylene oxide adduct are industrially expensive and difficult to obtain, which is inconvenient for the lubricating oil of the present purpose. is there.

In the diamine type tetraol of the general formula (1), n is preferably in the range of 1 to 3, and when n is 4 or more, the molecular weight becomes large, and the lubricity decreases as the number of ether bonds increases. However,
The number of n shown here is an average number of moles, and in the case of an average of 3 moles, a distribution occurs in the number of moles of ethylene oxide or propylene oxide added, and there may be cases where n is 4 or more. That is, n is an average number, and the average number of moles is preferably 3 or less.

As fatty acids, hexanoic acid, octanoic acid, decanoic acid,
Lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, montanic acid, palmitooleic acid, oleic acid, erucic acid, ricinoleic acid, hydroxystearic acid, linoleic acid, linolenic acid, isooctylic acid, isodecanic acid , Isolauric acid, isomyristic acid, isopalmitic acid, isostearic acid, isoarachidic acid, and the like having 6 or more carbon atoms. Also lanolin fatty acid, fish oil fatty acid, soybean oil fatty acid, coconut oil fatty acid,
Natural fatty acids such as beef tallow fatty acids and hydrogenated fatty acids thereof can also be used. When a fatty acid having 5 or less carbon atoms is used, lubricity is poor.

On the other hand, although the upper limit of the carbon number of the fatty acid is not restricted, it is generally preferably 30 or less as the industrially inexpensive range.

The esterification reaction of the diamine type tetraol of the general formula (1) with a fatty acid can be carried out by a usual method in the absence of a catalyst or in the presence of a catalyst to synthesize the esterification product of the present invention, but the synthesis method is not particularly limited. Not something to do.

The diamine-type tetraol used as a raw material for synthesizing the esterification product of the present invention is a tetravalent alcohol,
Esterification reaction products with fatty acids can be obtained as monoesters, diesters, triesters, and tetraesters, but as the metalworking lubricating oil which is the object of the present invention, esterification products having an average diester or more are more preferable. .

Rolling oil, cutting and grinding oil, the synthetic ester of the present invention,
When used as a lubricating oil for metal plastic working such as drawing or pressing, an internal combustion engine lubricating oil, or a spinning oil agent for synthetic fibers, the synthetic ester alone may be used.
Further, it can be used as a mixture with other base oils such as mineral oils, animal / vegetable oils and commonly used existing synthetic esters. It is also possible to add an emulsifier to these depending on the purpose and use them as emulsion solutions. Further, by increasing the number of moles of the ethylene oxide adduct of the diamine-type tetraol of the general formula (1), a self-emulsifying oil can be obtained. It can also be used.

In addition, it can be used in combination with an emulsifier, a fatty acid, an antioxidant, a corrosion inhibitor, an antiseptic / antifungal agent, etc. which are commonly used as additives for practical lubricants.

When the synthetic ester compound of the present invention is used as a mixture with other base oils, the effect is recognized by the addition of 1% by weight or more, but the content should be 5% by weight or more, preferably 20% by weight or more. Therefore, the characteristics are stabilized. Hereinafter, an example of the ester synthesis method will be described.

Synthetic example 4 equipped with stirrer, thermometer, nitrogen gas injection pipe, water separator
Asahi Denka Kogyo Co., Ltd. quadrol (X = CH ₃ , n = 1, R = (CH ₂ ) ₂ ) 292 g and coconut oil fatty acid 840 g were charged in a _two- necked flask, and p-toluene was used as a catalyst. 2.2g of sulfonic acid was added, and xylene was used as a reflux solvent.
%, The mixture was stirred well and the mixture was allowed to react at 160-230 ° C. until the calculated amount of water had distilled off. The required time was 8 hours. After completion of the reaction, the catalyst was removed by washing with water, and xylene was subsequently distilled off under reduced pressure, followed by decolorization with activated clay to obtain a yellow liquid. The yield was 970 g and the acid value was 2.3 (Sample A). Hereinafter, a synthetic ester was produced by the same method.
The properties of the obtained synthetic ester are shown in Table 1.

(Example) Example 1 General characteristic test in metal plastic working The performance test results of the lubricating oil of the present invention are shown in Table 2 in comparison with the conventional one.

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

<Test by Bowden tester> Apply various test agents to the surface of low carbon steel plate and apply diameter to the oiled surface.
Press a 3/16 inch steel ball with a load of 3 kg (Hertz pressure 223 kg / m
m ^2), the friction coefficient of the coating oil back and forth sliding at a speed 4 mm / sec was measured number of slides to reach 0.15 (seizure resistance).

<Test by Thermobalance> 35 mg of the test agent was placed in a platinum crucible and heated at 5 ° C. per minute in a He atmosphere, and the heating temperature at the time when the test agent in the crucible was decomposed and burned down was measured.

In the Bowden test, the actual plastic working conditions are made as close as possible, and the test temperature is set to 200 considering the heat generated by plastic deformation.
C., and the steel plate used is a mild steel plate that 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 flaws and the tool life.

Further, in a test using a thermobalance, it can be said that the higher the burning temperature of the test agent, the better the heat resistance.

Example 2 Rolling Lubricating Oil A mineral oil or palm oil used as a base oil of a practical rolling oil is blended with an emulsifier, a fatty acid, an antioxidant and the like which are commonly used as additives, and a synthetic ester which is the rolling oil of the present invention. The rolling oil composition obtained at that time was evaluated for lubricity and annealing.

Emulsion rolling is a two-high rolling mill Rolled material (spcc) 1.2 x 20 x 200 mm, oil content 3%, bath temperature 50
Rolling lubricity was evaluated by measuring the rolling load at a rolling reduction of 40% under the condition of ° C. Regarding the anneal property, several tens of steel sheets that had been rolled with the test emulsion solution were stacked, then fixed with narrow steel strips and annealed in a small annealing furnace.

The heating conditions during annealing are as follows: HNX gas (H ₂ : 5%) 120 ml / min, heating to 600 ° C. at a heating rate of 10 ° C./min.
It was kept at 00 ° C for 1 hour and then left to cool. After that, a cellophane tape was attached to the surface of the steel sheet, surface deposits were collected, and the adhered material was attached to white paper to visually determine the degree of stain, and the steel sheet surface cleanliness was evaluated. The test results are summarized in Table 3, and the symbols in the table are the same as those in Table 1.

Example 3 Cutting and Grinding Oil Cutting oils containing the substances of the present invention in Table 4 (Sample Nos. 1 to 4)
The results of the durability test and the four-ball lubricity test α model lubricity test of Sample Nos. 5 and 6 are commercially available cutting oils.

Example 4 Aqueous cutting oil Table 5 shows an aqueous cutting oil containing the substance of the present invention (Sample No. 7-
11) was prepared and diluted with sterilized water to 5% by weight to prepare a test solution.

The 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 diamine-type tetraol of the present invention and a fatty acid has far superior lubricating properties and stability to conventional lubricating oils, and is a rolling oil, a hydraulic oil, and cutting / grinding. It can be used as various industrial lubricating oils such as oil, lubricating oil for plastic working, lubricating oil for internal combustion engine, and synthetic fiber spinning oil.

For example, unlike the case where existing synthetic ester is used as a cold rolling oil or used as an additive, compared with the case where conventional palm oil is used as a base oil due to the improvement of rolling lubricity of steel sheets. It brings about energy and resource saving effects such as reduction of power cost. Further, it is also excellent in annealing property, normal electrolytic degreasing can be omitted, and equipment cost can be reduced.

Further, it has excellent lubricity with respect to cutting and grinding oils and can be a high-performance oil agent that can sufficiently satisfy various usage conditions such as odor and stability.

In addition, in terms of machining lubrication, sufficient lubrication is guaranteed even under severe conditions such as high-speed machining, enabling smooth machining and efficiency.

It is possible to prevent the product quality from deteriorating due to insufficient lubrication such as seizure flaws, and to prevent tool wear and damage.
Improve product quality and greatly extend tool life.

The power required during processing is reduced, and many excellent effects such as resource saving and energy saving are further promoted.

Continuation of front page (51) Int.Cl. ⁵ Identification number Office reference number FI Technical indication location C10N 40:24 Z 8217-4H (72) Inventor Hiroyuki Goto 1-3 chome, Chiwaka-cho, Kanagawa-ku, Yokohama Seiyu Oil Co., Ltd. (56) References JP-A-58-21488 (JP, A) JP-B-45-14447 (JP, B1) JP-B-57-27157 (JP, B2)

Claims (5)

[Claims] 1. A lubricating oil containing an esterification product of a diamine type tetraol represented by the general formula (1) and a fatty acid having 6 or more carbon atoms. However, X: H or CH ₃ n: an integer of 1 to 3 R: an alkyl group having 2 to 6 carbon atoms, a phenyl group or a cyclohexyl group 2. A diamine type tetraol represented by the general formula (1) is N = N, N ', N'-tetrakis (2-hydroxypropyl) in which X = CH ₃ , n = 1, R = C ₂ H _4. ) The lubricating oil according to claim 1, which is ethylenediamine. 3. The esterification product has 6 carbon atoms based on 1 mol of the diamine-type tetraol represented by the general formula (1).
The lubricating oil according to claim 1, wherein the above fatty acids are esterified at an average ratio of 2 mol or more. 4. The lubricating oil according to claim 1, wherein the lubricating oil is a cold rolling oil for steel plates. 5. The lubricating oil according to claim 1, wherein the lubricating oil is a metal cutting oil, a metal working oil such as a grinding oil, a drawing oil or a press working oil, and a metal plastic working oil.