JP2604166B2 - Lubricant - Google Patents

Description

The present invention relates to an oxazoline compound excellent in lubricating oil, and includes rolling oil, cutting oil, grinding oil and drawing oil,
It can be used as metal plastic working oil such as press working oil or synthetic fiber spinning oil. In particular, in rolling of a thin steel sheet, it is excellent in high lubricity and high mill cleanability, that is, excellent in lubricity and direct annealing.

In addition, cold rolling and cutting and drawing of metals,
The present invention relates to a lubricating oil exhibiting excellent characteristics in metal plastic working such as press working.

(Prior Art) In recent years, the use conditions of lubricating oils have become severe with the rapid development of various machine industries, and excellent lubricating properties have been required.

Cold rolling oil used for thin steel sheet is made of animal or vegetable fats (tallow
Litter, soybean oil, rapeseed oil, palm oil, coconut oil, etc.) and those based on mineral oil. In recent years, energy saving, high-speed rolling with the improvement of production efficiency,
High-pressure reduction rolling and mill clean rolling are being pursued. Rolling oils using animal and vegetable oils as base oils are suitable for high-load, high-speed rolling.However, if the cold-rolled steel sheet is directly annealed without degreasing the adhering oil, the steel sheet surface in the annealing process Causes dirt. That is, it is excellent in lubricity but unsuitable for mill cleanliness.

On the other hand, when cold rolling is performed using a rolling oil using a mineral oil as a base oil, even if a cold thin steel sheet is directly annealed, surface contamination does not occur and the mill cleanability is excellent. However, it lacks high load and high speed rolling properties.

In general, rolling oils based on mineral oils are used to improve rolling lubricity, such as animal and vegetable fats and oils and fatty acids (capric acid, lauric acid, myristic acid, stearic acid, oleic acid, linolenic acid, etc.) or oil chemistry '73. Esters such as those described in the November issue, p.695 to 706 (where the alcohol component is trimethylolpropane, pentaneerythritol,
Oily improvers such as monoesters, diesters, and synthetic esters such as polyol esters with ethylhexyl alcohol, etc.) are added, but the amount of these additives is a minimum narrow range necessary to maintain mill cleanliness. Has been adjusted. As described above, various studies have been made on cold rolling oils which can simultaneously satisfy high lubricity and high mill cleanliness (for example, see JP-A-56-135600 and JP-A-
59-80498) Currently, there is no one suitable for both.

On the other hand, lubricants used for metal cutting and grinding are:
Mineral oil, animal and vegetable fats and oils, extreme pressure additives, surfactants, defoamers,
The composition is prepared by appropriately mixing a metal anticorrosive, an antioxidant, an antiseptic, an antifungal agent and the like according to the purpose. Cutting fluid is usually 10 with water
It is used by diluting it up to 100 times, but in some cases a water-insoluble cutting fluid is used.

The basic conditions for cutting and grinding oils are lubrication, cooling, rust prevention and other incidental conditions such as foaming,
It does not have rough hand, toxicity to humans or odor. Cutting and grinding fluids must have the above-mentioned performances in a well-balanced manner, even though the emphasis may differ depending on the purpose and conditions of use, but cutting and grinding fluids that can satisfy various conditions are not always sufficient. It is the current situation.

(Problems to be Solved by the Invention) The present invention provides a molecularly designed synthetic lubricating oil in order to impart excellent lubricating properties under the severer operating conditions of lubricating oils in recent years.

That is, it is a synthetic oil agent that has high lubricity and high stability, is hardly deteriorated by microorganisms, and hardly rots.

The present invention is a cold rolling oil for steel that contributes to the improvement of production efficiency such as energy saving and process saving.It is stable against heat and mechanical shear generated under high speed and high pressure, and has a chemical property such as oxidation, decomposition and polymerization. It is also stable to the reaction. In addition, it is easily volatilized without generating the thermal decomposition residue of the rolling oil in the annealing process,
It has both the cleanliness of the steel sheet surface (mill cleanness) and the high lubricity.

On the other hand, in the case of cutting and grinding oils, the present invention is a synthetic lubricating oil which is excellent in lubricating properties, cooling properties and rust prevention properties, has no problems of foaming properties, roughening properties, human toxicity and is hard to rot.

(Means for Solving the Problems) The present invention relates to the following general formula (1):
A lubricating oil containing one or more oxazoline compounds satisfying any of (B), (C) and (D).

(A) R ₁ : alkenyl group having 5 or more carbon atoms, and R ₂ , R ₃ : CH ₂ OCOR (however, R: hydroxyalkyl group, hydroxyalkenyl group or phenyl group having 5 or more carbon atoms) (B) R ₁ : Hydroxy linear alkyl group or hydroxyalkenyl group having 5 or more carbon atoms, and R ₂ , R ₃ : CH ₂ OCOR or CH ₂ OH, H (R: alkyl group having 5 or more carbon atoms, alkenyl group, hydroxy An alkyl group, a hydroxyalkenyl group or a phenyl group) (C) R ₁ : an alkyl group having 5 or more carbon atoms, and R ₂ , R ₃ : CH ₂ OCOR (where R: a hydroxyalkyl group having 5 or more carbon atoms, or hydroxy Alkenyl group) (D) R ₁ : hydroxy branched alkyl group or phenyl group having 5 or more carbon atoms, and R ₂ , R ₃ : CH ₂ OCOR (where R: alkenyl group having 5 or more carbon atoms, hydroxyalkyl group) Or hydroxyalkenyl The lubricating oil referred to in the group) Here, cutting oil, grinding oil or drawing oil, those which can be press working oils, plastic working oils and machine lubricants such wide variety of applications of a metal such as rolling oil. The cold-rolling oil of steel containing oxazoline-based ester and oxazoline compound of the present invention as a main component has high lubricity and high mill cleanliness, and is capable of rolling thin steel sheets and directly annealing without degreasing the steel sheets. It is possible to provide lubricating, cooling and rust-proof properties as cutting oil and grinding oil, and has excellent properties without any problem in hand roughness, human animal toxicity, odor and the like.

Alkyl oxazolines represented by the general formula (1) generally include monoethanolamine, 2-methyl-2-amino-1,3-propanediol or 2-amino-2-hydroxymethyl-1,3-propadiol. It can be obtained by dehydration condensation with a monocarboxylic acid and a cyclization reaction.

As the monocarboxylic acid used in the above synthesis, saturated fatty acids having 6 or more carbon atoms, unsaturated fatty acids, hydroxy fatty acids, synthetic branched fatty acids and aromatic carboxylic acids include benzoic acid and salicylic acid.

Fatty acids include hexanoic, octanoic, decanoic, lauric, myristic, palmitic, stearic, arachinic, behenic, montanic, palmitooleic, oleic, erucic, ricinoleic,
Fatty acids having 6 to 30 carbon atoms, such as hydroxystearic acid, linoleic acid, linolenic acid, isooctylic acid, isodecanoic acid, isolauric acid, isomyristic acid, isopalmitic acid, isostearic acid, and isoarachinic acid are preferred. Lanolin fatty acids, fish oil fatty acids, soy oil fatty acids,
Natural fatty acids such as coconut fatty acid, tallow fatty acid and the like and hydrogenated fatty acids thereof can also be used. The reason why the fatty acid having 6 or more carbon atoms is limited is that an oxazoline-based ester product or an oxazoline compound with a fatty acid having less than 6 carbon atoms has a small improvement in the intended lubricity. On the other hand, the upper limit of the number of carbon atoms of the fatty acid is not restricted, but generally 30 or less carbon atoms are preferable as an industrially available range at low cost.

Further, the above monoethanolamine, 2-methyl-2
-Amino-1,3-propanediol or 2-amino-
2-hydroxymethyl-1,3-propanediol and monocarboxylic acid are used so that the synthesized oxazoline compound is a compound that satisfies any of the above conditions (A), (B), (C) or (D). It is important to use a proper combination.

When the synthetic ester of the present invention is used as a rolling oil, a lubricating oil for metal plastic working such as a cutting / grinding oil, a drawing oil, a pressing oil, an internal combustion engine lubricating oil or a synthetic fiber spinning oil, etc. It can be used alone. It can be used by mixing with other base oils, for example, mineral oil, animal and vegetable oils, and commonly used existing synthetic esters. Further, depending on the purpose, an emulsifier may be added to these and used as an emulsion liquid, or they may be used in combination with an antiseptic / antifungal agent and the like.

When the synthetic ester compound of the present invention is used as a mixture with another base oil or the like, the effect can be recognized by adding 1% by weight or more, but the content should be 5% by weight or more, preferably 20% by weight or more. This stabilizes the characteristics.

 Hereinafter, an example of a method for synthesizing an oxazoline compound will be described.

Synthesis Example 4 equipped with a stirrer, thermometer, nitrogen blowing tube and water separator
2 mol of lanolin fatty acid, 2-methyl-2
-Amino-1,3-propanediol (2 mol) was charged and the reaction was carried out in a xylene refluxing solvent at 180 to 260 ° C. until the calculated amount of water had flowed out. The required time was 7 hours. After the completion of the reaction, xylene was distilled off, then, after decolorization with activated clay, the clay was separated by filtration to obtain a target product symbol A712 g of a reaction product. The oxazoline compounds produced in the same manner are shown in Table 1 below.

(Example) Example 1 General property test in metal plastic working Table 2 shows performance test results of the lubricating oil of the present invention in comparison with those of a conventional lubricating oil.

The coefficient of friction and the seizure resistance were measured with a powder tester, and the heat resistance was measured with a thermobalance.

<Testing with a powder tester> Apply various test agents to the surface of a low carbon steel sheet and press a 3/16 inch diameter steel ball against the oiled surface with a load of 3 kg (Hertz pressure 223 kg
/ mm ² ), and reciprocated at a speed of 4 mm / sec to measure the number of sliding operations (seizure resistance) until the friction coefficient of the oiling agent reached 0.15.

<Test by Thermobalance> 35 mg of the test agent was put 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 was measured.

In the powder test, the test temperature should be as close as possible to the actual plastic working conditions.
The temperature is set to 0 ° C, and the steel sheet is also a mild steel sheet that is easily plastically deformed.

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

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 Mineral oil or palm oil used as a base oil of a practical rolling oil was blended with an emulsifier, a fatty acid, an antioxidant, etc., which are commonly used as additives, and a synthetic ester as the rolling oil of the present invention. The lubricating properties of the rolling oil-plastic obtained at the time of the annealing were evaluated for the annealing property.

Emulsion rolling is a two-high rolling mill, in which rolling material (spcc) 1.2 × 20 × 200 mm is measured under a condition of an oil concentration of 3% and a bath temperature of 50 ° C. at a rolling reduction of 40% to evaluate rolling lubricity. did. Regarding the annealing properties, several tens of steel sheets rolled with the test emulsion liquid were stacked as they were, fixed with a narrow steel strip, and annealed in a small annealing furnace.

Heating conditions during the annealing, HNX gas _{(H 2: 5%) 120ml} / min
In the atmosphere, the mixture was heated to 600 ° C. at a rate of 10 ° C./min, kept at 600 ° C. for 1 hour, and allowed to cool. Thereafter, a cellophane tape was adhered to the surface of the steel sheet, and the adhered substance on the surface was collected. The adhered substance was adhered to white paper, and the degree of contamination was visually determined to evaluate the cleanliness of the steel sheet surface. The test results are summarized in Table 3 and the symbols in the table are the same as in Table 1.

Example 3 Cutting Grinding Oil Table 4 shows a cutting oil containing the substance of the present invention (sample Nos. 1 to 4).
Sample Nos. 3 and 4 show the results of the durability test and the four-ball lubrication test α model lubrication test of 2). Commercial cutting oils are shown.

Note 1) Condition after 14 days ○: No change △: Slightly grayish black Note 2) Condition after 14 days ○: No rotting odor △: Some rotting odor Note 3) 500 ml flat bottom flask sterilized with 400 ml of each sample solution And shaking culture (rotation speed: 150 rpm) at 30 ° C. for 14 days.

Thereafter, a part of the sample was aseptically exchanged, the number of fungi was measured, and at the same time, pH measurement, change in appearance, and odor were observed.
Furthermore, the rust prevention performance was also observed.

The number of fungi was measured by a plate count method using a potato dextrose agar medium supplemented with antibiotics (chloramphenicol and tetracycline).

Note 4) The anticorrosion property was observed by the cast iron chip method. That is, about 15 g of dry-cut casting chips (FC
-25, 8-12 mesh) was collected in a Petri dish (about 60 mm in inner diameter), about 25 ml of a sample solution was added thereto, shaken sufficiently, and allowed to stand for about 4 minutes. Next, the sample liquid was removed by a tilt 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) The test was performed by a step load method (0.5 kg) at 200 rpm using a Soda type four-ball tester.

Example 4 Aqueous Cutting Oil Table 5 shows an aqueous cutting oil containing the substance of the present invention (Sample No. 5
To 7), and diluted with sterile 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 nitrogen-containing polyol and the fatty acid of the present invention has much better lubricating properties and stability than conventional lubricating oils, and is suitable for rolling oils, hydraulic oils, cutting and grinding oils. And lubricating oils for metal plastic working, lubricating oils for internal combustion engines, and various industrial lubricating oils such as synthetic fiber spinning oils.

For example, unlike those in which existing synthetic esters are diverted as cold rolling oils or as additives, the improvement in rolling lubricity of steel sheets makes it possible to use conventional palm oil as a base oil compared to conventional oils. Energy saving and resource saving effects such as reduction of power cost are brought. Also, it has excellent annealing properties, so that ordinary electrolytic degreasing can be omitted.

In addition, cutting and grinding oils have excellent lubricating properties, and can be high-performance oils that can sufficiently satisfy various use conditions such as odor and stability.

In processing lubrication, sufficient lubrication is ensured even under severe conditions such as high-speed processing, which enables smooth and efficient processing.

In addition to preventing product deterioration caused by insufficient lubrication such as seizure flaws, wear and breakage of the tool are also suppressed, thereby improving the product quality and greatly extending the life of the tool.

The power required at the time of processing is reduced, and many excellent effects such as further saving of resources and energy are produced.

────────────────────────────────────────────────── ─── Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical indication location C10N 40:22 40:24 (56) References JP-A-55-43080 (JP, A) US Patent 4224172 (US, A) French patent 2079970 (FR, A)

Claims (3)

(57) [Claims] (1) In the general formula (1), the following condition (A):
A lubricating oil containing one or more oxazoline compounds satisfying any of (B), (C) and (D). (A) R ₁ : alkenyl group having 5 or more carbon atoms, and R ₂ , R ₃ : CH
₂ OCOR (R: hydroxyalkyl group, hydroxyalkenyl group or phenyl group having 5 or more carbon atoms) (B) R ₁ : hydroxy straight-chain alkyl group or hydroxyalkenyl group having 5 or more carbon atoms, and R ₂ , R ₃ : CH ₂ OCOR or CH ₂ OH, H (R: alkyl group having 5 or more carbon atoms, alkenyl group, hydroxyalkyl group, hydroxyalkenyl group or phenyl group) (C) R ₁ : alkyl having 5 or more carbon atoms R ₂ , R ₃ : CH ₂ OCOR (where R: hydroxyalkyl group or hydroxyalkenyl group having 5 or more carbon atoms) (D) R ₁ : hydroxy branched alkyl group having 5 or more carbon atoms or phenyl group And R ₂ , R ₃ : CH ₂ OCOR (where R is an alkenyl group, a hydroxyalkyl group or a hydroxyalkenyl group having 5 or more carbon atoms) 2. The lubricating oil according to claim 1, wherein the lubricating oil is a cold rolling oil for a steel sheet. 3. The lubricating oil according to claim 1, wherein the lubricating oil is a metal working oil such as a metal cutting oil, a grinding oil, a drawing oil, a press working oil, and a metal plastic working oil.