JPH01139694A - Lubrication oil - Google Patents

Abstract

PURPOSE:To provide a lubrication oil containing an esterified product derived from a specific polyol, a fatty acid and a dibasic acid, exhibiting high lubricity and high mill-cleaning property in the rolling of sheet steel and suitable for the plastic working of other metals. CONSTITUTION:The objective lubrication oil contains an esterified product derived from (A) a 2-6-hydric polyol (e.g., ethylene glycol, dipropylene glycol, neopentyl glycol, pentaerythritol or diglycerol), (B) preferably 6-30C straight- chain or branched-chain (un)saturated natural or synthetic fatty acid and (C) preferably 2-36C (un)saturated dibasic acid (preferably thiodiglycolic acid, dithiopropionic acid, phthalic acid, malic acid, etc.).

Description

Detailed Description of the Invention (Field of Industrial Application) The present invention relates to a nitrogen-containing esterified product 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, high lubricity and high 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 are broadly divided into those based on animal/vegetable oils (beef tallow, lard, soybean oil, rapeseed oil, palm oil, coconut oil, etc.) and those based on mineral oil. be done. In recent years, high-speed rolling, high-reduction rolling, and mill-clean rolling have been trending toward energy saving and improved production efficiency. Rolling oils that use animal or vegetable oils as base oils are suitable for high-load, high-speed rolling, but if the oil deposits on a cold-rolled steel plate are directly annealed without degreasing, the steel plate surface will be damaged during the annealing process. Causes stains. In other words, it has excellent lubricity but is unsuitable for mill cleanliness.

On the other hand, when cold rolling is performed using rolling oil with mineral oil as the base oil, no surface stains occur even if 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 fats and oils, fatty acids (capric acid, lauric acid, myristic acid, stearic acid, oleic acid, lylunic acid, etc.) or oil chemistry 73- November issue p, 695-70
Esters such as those listed in 5 (alcohol components include trimethylolpropane, pentaerythritol, 2
- Synthetic esters (monoesters, diesters, polyol esters, etc. using ethylhexyl alcohol, etc.) etc.
These oiliness improvers are added, but the amount of these additives is adjusted within a narrow range to the minimum necessary to maintain mill cleanliness. As mentioned above, various studies have been conducted on cold rolling oils that can simultaneously satisfy high lubricity and high mill cleanliness.
00, Japanese Unexamined Patent Publication No. 59-80498) Currently, there is no one suitable for both.

On the other hand, lubricants used for metal cutting and grinding include mineral oils, animal and vegetable oils, extreme pressure additives, surfactants, antifoaming agents, metal anticorrosives, antioxidants, preservatives, antifungal agents, etc. 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 condition that cutting and grinding oils must have is lubricity.

It must have cooling properties, rust prevention properties, and other incidental conditions such as foaming property, roughness on hands, 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 for Solving Problems 1) The present invention is a lubricating oil whose product is an esterification product of a polyol having a valence of 2 or more and 6 or less, a fatty acid, and a dibasic acid.

Polyols with a valence of 2 or more and 6 or less include ethylene glycol, diethylene glycol, propylene glycol,
Dipropylene glycol, butylene glycol, neopene glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol and its condensates diglycerin, diventaerythritol, etc. can be used. Furthermore, various polyether polyols obtained by adding ethylene oxide and/or propylene oxide to each of the above-mentioned polyols can also be used.

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, isooctylic acid, isodecanoic acid , isolauric acid, isomyristic acid, isopalmitic acid, isostearic acid, isoarachic acid, and other fatty acids having 6 or more carbon atoms. Natural fatty acids such as lanolin fatty acids, fish oil fatty acids, soybean oil fatty acids, coconut oil fatty acids, beef tallow fatty acids, and hydrogenated fatty acids thereof can also be used. 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.

Dibasic acids include aliphatic dibasic acids such as oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, glutaric acid,
Adipic acid, pimelic acid, speric acid, azelaic acid,
Sebacic acid, decanedicarboxylic acid, dodecanedicarboxylic acid, tetradecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, eicosadecanecarboxylic acid, dimer acid and phthalic acid, cyclohexyldicarboxylic acid, malic acid, tartaric acid, and even sulfur-containing dibasic acids The acids thiodiglycolic acid, thiodipropionic acid, dithiodiglycolic acid, and dithiodipropionic acid can be used.

Although there are no particular limitations on the amount of each reaction compound for the ester compound of polyol, fatty acid, and dibasic acid, depending on the reaction molar ratio of polyol/fatty acid/dibasic acid, polyester may be formed and the viscosity may be too high. Otherwise, gelation may occur, and furthermore, if the average molecular weight becomes significantly high, the desired lubricity may be impaired, so the following reaction molar ratio is preferable.

Dihydric alcohol/fatty acid/dibasic acid = 2/1/1-2
/2/13-hydric alcohol/fatty acid/dibasic acid =2/2/
1-2/4/14 alcohol/fatty acid/dibasic acid-2
/2/1 to 2/6/1 Hexahydric alcohol/fatty acid/dibasic acid = 2/3/1 to 2/10/1 The esterification reaction is carried out in a conventional manner without a catalyst or in the presence of a catalyst to produce the ester of the present invention. However, the synthesis method is not particularly limited.

The synthetic ester oil mentioned here can be used for a wide variety of purposes, including metal plastic working oils such as cutting and grinding oils, press working oils, and rolling oils, and machine lubricating oils.

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

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 pressing, a lubricating oil for internal combustion engines, or a yarn-preventing oil for synthetic fibers, the synthetic ester can be used alone. It can also be used by mixing with other base oils (for example, mineral oils, animal/vegetable oils, and commonly used existing synthetic esters. Also, depending on the purpose, emulsifiers can be added to these and used as an emulsion liquid. You can also do it.

Furthermore, by increasing the number of moles of ethylene oxide adducts among various polyols, it can also be used as a self-emulsifying oil agent.

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 is observed when it is added in an amount 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
A Tulo flask was charged with 184 g of glycerin, 178 g of thiodipropionic acid, and 994 g of isostearic acid, and 2.6 g of P-toluenesulfonic acid was added as a catalyst.The mixture was heated to 160 to 230°C and the reaction was carried out until the calculated amount of water was distilled out. . The required time was 9 hours. After the reaction was completed, the catalyst was removed by washing with water, and the xylene was subsequently distilled off under reduced pressure, followed by decolorizing filtration using an activity enhancer to obtain a yellow liquid. The yield was 1130g and the acid value was 2.1.

(Sample H) Synthetic esters were produced in the same manner.

Table 1 shows the properties of the obtained synthetic ester.

(Example) Example 1 General property test in metal plastic working The performance test results of the lubricating oil of the present invention are compared with the conventional lubricant and are shown in Table 2.

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

Test using Bauden tester> The surface of a low carbon steel plate was oiled with various test agents, and a steel ball with a diameter of 3,716 inches was pressed against the oiled surface with a load of 3 kg at a Hertz pressure of 223 kg/ms'') and a speed of 4 am/ The number of sliding movements (seizure resistance) until the friction coefficient of the lubricant reached 0.15 was measured by reciprocating sliding with a see.

<Test using thermobalance> 35 g of the test material was placed in a platinum crucible and heated at a rate of 5°C per minute in a He atmosphere, and the heating temperature was measured when the test material in the crucible decomposed and was burnt out. did.

In the Bauden 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 that is easily plastically deformed is used.

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 lubricating oil composition and annealing properties of the rolling oil obtained when the rolling oil was used were evaluated.

Emulsion rolling uses a two-roll rolling core to roll the rolled material (
spcc) 1, 2 x 20 x 200 mm, the rolling load was measured at a rolling reduction of 40% under 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 (11”: 5%
) In an atmosphere of 120 mQ/min, the temperature increase rate was set to 10°C/
The mixture was heated to a minimum of 600°C, held 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 and grinding oil Cutting oil containing the substance of the present invention as shown in Table 4 (Samples Nα1 to 4)
) durability test, four-ball lubricity test α model lubricity test results are shown. Sample Na5.6 represents a commercially available cutting oil.

Note 1) After immersing a cold-rolled steel plate in sample oil, pull it out and leave it horizontally in a place near a window in the layer where it will not be exposed to direct sunlight, and check the condition! ! ! Inspection.

Note 2) The lubricity of the cutting oil according to the present invention was compared with that of a commercially available cutting oil by applying a load of 0.5 kg/aJ per minute at 220 rpm using a JIS K2519 four-ball tester.

Note 3) Using ASTM 02714 α model LFW-1 testing machine.

15 kg per minute at 300 rpm and 110°F3
The wear and seizure load of the test piece was measured when a load of up to 15 kg was applied.

Example 4 Water-based cutting oil containing the present invention substance in Table 5 (sample Nα7
~11) was prepared and diluted with sterilized water to obtain a 5% by weight binding test solution.

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

Note 1) Condition after 14 days 0: No change Δ: Slightly grayish black Note 2) Condition after 14 days 0: No rotten odor Δ: Slightly rotten odor Note 3: Rust resistance was observed using the cast iron cutting layer method. I did it. In other words, approximately 15g of dry-cut steel chips (
FC-25, 5-12 mesh) into a Petri dish (inner diameter 6
0 mm), add approximately 25 ml of sample to this,
After shaking thoroughly, the mixture 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 +) Measured using an Aida pendulum type friction tester.

The test was carried out by the step load method (0.5 kg) at 200 rpm using a pouring mouth type four-ball testing machine.

(Effects of the Invention) The synthetic ester compound obtained from the nitrogen-containing polyol 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 and grinding oil. lubricating oil for metal plastic processing, lubricating oil for internal combustion engines,
It can also be used as a lubricant for various industrial applications, such as a spinning oil for synthetic fibers.

For example, unlike existing synthetic esters that are used as cold rolling oil or as additives, the improved rolling lubricity of flII plates compared to conventional palm oil as base oil. This results in energy and resource savings such as power cost savings. It also has excellent annealing properties,
Ordinary electrolytic degreasing can be omitted, and equipment costs can be reduced.

Furthermore, as 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 severe conditions such as high-speed machining, making machining smoother and more efficient.

This prevents product quality deterioration caused by insufficient lubrication, such as seizure defects, and also prevents tool wear and damage.
Improve product quality and greatly extend tool life.

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

Procedural amendment 1986/1/'2-day

Claims (7)

[Claims] (1) A lubricating oil containing an esterification product of a divalent to hexavalent polyol, a fatty acid, and a dibasic acid. (2) Polyols with a valence of 2 or more and 6 or less are ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butylene glycol, neopentyl glycol, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, sorbitol, and condensation thereof. The lubricating oil according to claim 1, which is diglycerin, diglycerin, or diventaerythritol. (3) The lubricating oil according to claim 1, wherein the fatty acid is a linear or side chain, saturated or unsaturated natural or synthetic fatty acid having 6 to 30 carbon atoms. (4) The lubricating oil according to claim 1, wherein the dibasic acid is a saturated or unsaturated dibasic acid having 2 to 36 carbon atoms. (5) The lubricating oil according to claim 4, wherein the dibasic acid is any one of thiodiglycolic acid, thiodipropionic acid, dithiopropionic acid, phthalic acid, cyclohexyldicarboxylic acid, malic acid, and tartaric acid. (6) The lubricating oil according to claim 1, wherein the lubricating oil is cold rolling oil for steel plates. (7) The lubricating oil according to claim 1, wherein the lubricating oil is a metal cutting oil, a grinding oil, or a metal plastic working oil.