JPH0244874B2 - KOHANNOREIKANATSUENYU - Google Patents

Description

[Detailed description of the invention]

(Field of Industrial Application) The present invention is a highly lubricating rolling oil that has excellent friction coefficient and pressure resistance under high pressure and high speed rotation, and at the same time, it can be annealed after rolling without going through electrolytic cleaning or other cleaning process. , No stains will be generated on the surface even if annealed as is. That is, it relates to a cold rolling oil for steel sheets that has excellent mill cleanliness. (Prior art) The cold rolling oil used when cold rolling thin steel sheets is based on animal or vegetable oils (beef tallow, lard, palm oil, coconut oil, etc., all of which have a triglyceride structure). It is broadly classified into those using mineral oil as the base oil. In recent years, with the improvement of production efficiency such as energy saving and process saving, high reduction rolling, high speed rolling, and mill clean rolling are becoming popular. 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 annealed without degreasing, the steel plate will be damaged during the annealing process. Causes surface stains. In other words, oils and fats having a triglyceride structure have excellent lubricity, but are unsuitable for mill clean properties (direct annealing properties). On the other hand, when rolling oil with mineral oil as the base oil is used for cold rolling of steel sheets, it does not cause surface stains even when cold thin steel sheets are directly annealed, and has excellent mill cleanliness. Poor rolling rate 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, linolenic acid, etc.) or oil chemistry '7311 to improve rolling lubricity. Oiliness improver for esters (synthetic esters such as monoesters, diesters, polyol esters, etc. whose alcohol component is trimethylolpropane, pentaerythritol, 2-ethylhexyl alcohol, etc.) as published on pages 695 to 706 of the Monthly issue. However, the amounts added are 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 simultaneously satisfy high lubricity and mill cleanliness (for example, Japanese Patent Application Laid-Open No. 135600/1982 and Japanese Patent Laid-open No. 80498/1983), but there are sufficient studies. The current situation is that the performance has not been reached. (Problems to be Solved by the Invention) The present invention is a cold rolling oil for thin steel sheets that contributes to energy saving, process saving, and improved production efficiency, and is stable against heat and mechanical shear generated under high speed and high pressure. in,
It is also stable against chemical reactions such as oxidation, decomposition, and polymerization. In addition, during the annealing process, it produces less thermal decomposition residue of rolling oil than triglycerides and is easily volatilized, providing both surface cleanliness and high lubricity for the steel sheet. (Means for Solving the Problems) The present invention provides a steel whose main components are synthetic esters, oils and fats obtained from the body of fish belonging to the family Prunidae, hydrogenated products thereof, and/or higher fatty acids or higher alcohols that are hydrolyzed products of the above-mentioned oils and fats. This cold rolling oil has high lubricity and high mill cleanliness, and enables rolling of thin steel sheets and effective annealing of cold rolled steel sheets without degreasing. The synthetic ester referred to in the present invention is a diester compound that has been molecularly designed and synthesized for such a purpose. In recent years, synthetic esters have been used as rolling oil additives or as base oils, but few of the synthetic esters currently used in cold rolling oils have been synthesized for this purpose, and are used in engine oils and hydraulic oils. In many cases, synthetic esters are selected from existing synthetic esters used as hydraulic oils or other lubricants, and synthetic esters are not able to fully satisfy both high lubricity and high mill cleanliness. The synthetic ester of the present invention is used for cold rolling oil.
That is, it has the characteristics of both high lubricity and high mill cleanliness, and has the following molecular design. general formula However, R, R': alkyl having 5 or more carbon atoms,
Alkenyl, hydroxyalkyl, hydroxyalkenyl group. X: Ethyl, propyl, isopropyl, butyl and isobutyl group n = 1 to 95% of the fatty acid, glycol ether, and esterification product represented by an integer of 1 or more, oil and fat extracted from the body of each fish of the family Prunidae, and its hydrogen additives or/
and cold rolling oil for steel sheets, characterized in that it contains 1 to 95% of higher fatty acids or higher alcohols that are hydrolyzed products of the oils and fats. ' is derived from natural products such as hexanoic acid, octylic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, palmitoleic acid, oleic acid, erucic acid, ricinoleic acid, 12-hydroxy It consists of fatty acid residues containing one or more of stearic acid and synthetic resin acids such as isooctylic acid, nonanoic acid, isolauric acid, isomyristic acid, isopalmitic acid, isostearic acid, and isoaracic acid. X is ethyl, propyl, isopropyl,
Selected from butyl, isobutyl groups, etc. Glycols used in the present invention include ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, isopropylene glycol, dipropylene glycol, diisopropylene glycol, polypropylene glycol, polyisopropylene glycol,
butylene glycol, isobutylene glycol,
Dibutylene glycol, diisobutylene glycol, polybutylene glycol, polyisobutylene glycol, etc. can be used. In addition, in the present invention, the number of carbon atoms in R and R' in general formula (1) is set to 5 or more because an ester compound having less than 5 carbon atoms does not improve the lubricating oil when cold rolling a steel plate. It's for a reason. On the other hand, general formula (1)

There are no restrictions on the upper limit of the number of carbon atoms and the number of n in [Formula], but the number of carbon atoms should be 29 or less, and the number of n should be within the range that is generally available industrially at low cost.
30 or less, preferably 20 or less. If it becomes larger than this, the molecular weight of the compound will increase or it will solidify, and it cannot be used alone as a rolling oil, and even if it is used in combination with other base oils, it will have a negative effect on annealing properties. Therefore, in order to obtain a rolling oil that satisfies both lubricity and annealing properties, the number of carbon atoms in R and R' in formula (1) is preferably 29 or less, and more preferably n=20 or less. An example of the method for synthesizing the ester compound of the present invention from fatty acid and glycol is shown below.
The present invention is not limited to this method, and other conventionally known synthesis methods, such as the acid chloride method, can also be used. Reference examples of synthesis will be described below. 2.2 mol of isooctylic acid in a 4-necked flask equipped with a stirrer, thermometer, nitrogen gas blowing tube, and water separator.
Polyethylene glycol (average molecular weight 600) 1 mol
0.2% of the total charge amount of para-toluene sulfonic acid was added as a catalyst, and 5% of the charge amount of xylene was used as a reducing solvent and stirred well.
The reaction was carried out at ℃ until the calculated amount of water accumulated in the water separation tube. The required time was 8 hours. After the reaction was completed, the catalyst was removed by washing with water, and unreacted isooctylic acid was distilled off at 160° C. and 3 torr, followed by decolorization using activated clay to obtain a yellow liquid. The yield was 88%, the acid value was 0.2, and the saponification value was 123. Synthetic esters were produced in a similar manner using different types of fatty acids and glycols. Table 1 shows the properties of the obtained synthetic ester compound.

【table】

[Table] * Molar ratio In the present invention, the fishes of the family Aperidae are orange-colored fish called ratfish with a total length of 30 to 40 cm that mainly live in the deep sea near Cape Town, South Australia, New Zealand, etc. Hoplostethus atlanticus, H. mediterraneits, H. gilchristi, H. intermedius (English name: Saw belly), sandpaper filament. It is also known as Sandpaper fish and Orang roughy. The fat and oil extracted from this fish body (hereinafter referred to as ratfish oil) is orange in color and has a composition as shown in Table 2. As shown in Table 2, wax ester is the main component of rattufi oil, and wax ester is mainly composed of monoesters consisting of monoene fatty acids and alcohols having 18 to 24 carbon atoms and one double bond. There is. As can be seen from its composition, rathui oil is
It does not have a triglyceride structure like the animal/vegetable fats and oils normally used in rolling oil, but is a wax ester consisting of monoene fatty acids and alcohols, and is fluid at room temperature compared to commonly used animal/vegetable fats and oils. It has a low point and has excellent workability and thermal stability.

[Table] By hydrogenating the ratfish oil used in the present invention, the fish oil odor is eliminated and the lubricity and linear annealing properties are improved compared to non-hydrogenated ratfish oil, which is more preferable. Hydrogenation of the Latuffii oil used in the present invention can be carried out as necessary, but when the amount of hydrogenation exceeds 90%, it becomes a hard solid at room temperature, so it can be used as an additive, but it can be used alone. Therefore, it can no longer be used as rolling oil. Therefore, when using Ratufi oil as rolling oil, the hydrogenation rate is 5 to 89%.
A range of is preferred. The acid value, saponification value, and iodine value of Latuffii oil due to the difference in the amount of hydrogen added are
Shown in the table.

[Table] Higher fatty acids and higher alcohols can be obtained by hydrolyzing Latuffii oil by saponification, lipase decomposition, etc., and these can be used as lubricants. Table 4 shows the compositions of the main higher fatty acids and higher alcohols contained in the wax ester of rathui oil.

[Table] General formula of the present invention However, R, R': alkyl having 5 or more carbon atoms,
Alkenyl, hydroxyalkyl, hydroxyalkenyl group It contains 1 to 95% of a hydrogenated product of or/and a higher fatty acid or higher alcohol that is a hydrolyzate of rathui oil, but preferably 20 to 70% of synthetic ester and a hydrogenated product of rathui oil.
A mixing range of 20-70% is more preferred. When actually using the rolling oil of the present invention,
It can also be used alone as a rolling oil. It can also be used in combination with other base oils, such as mineral oils and animal/vegetable oils. It is also possible to add an emulsifier to these and use them as an emulsion. In addition, it can also be used in combination with fatty acids, antioxidants, corrosion inhibitors, emulsifiers, etc., which are commonly used as additives in practical rolling oils. When the rolling oil 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. As a result, the characteristics become stable. (Example) Next, the present invention will be described in more detail by referring to Examples. Example 1 A mixture of synthetic esters and hydrogenated rattuy oils shown in Table 1 and/or higher fatty acids or higher alcohols, which are hydrolysates of the oils and fats, can be used alone as rolling oil, and The rolling oil of the present invention can be used in combination with mineral oils, animal and vegetable oils that are generally used as base oils, or emulsifiers, fatty acids, antioxidants, corrosion inhibitors, etc. that are commonly used as additives in practical rolling oils. . Examples of cold rolling using rolling oils having these compositions will be described. The lubricity and annealing properties during cold rolling were evaluated by the following method. For evaluation of cold rolling lubricity, a 2.30 mm hot rolled pickled steel plate was used and cold rolled for 3 passes.
After degreasing a steel plate rolled to 1.20 mm, it was immersed in an oil bath in which each test oil was diluted to 5.0% with n-hexane, and stood for a certain period of time to evaporate the solvent and apply rolling oil uniformly and quantitatively. The steel plate thus prepared was subjected to cold rolling. The rolling load at a reduction rate of 45% was measured to evaluate rolling lubricity. In addition, the friction coefficient of each sample oil was determined using a Bowden friction tester (load: 1 kg, 100°C), and the lubricity of the rolling oil was evaluated. For evaluation methods regarding the annealing properties of rolling oil, please refer to
Approximately each sample oil was applied to the surface of a cold-rolled steel plate (80 x 100 x 0.8 mm).
An amount equivalent to 630 mg/m ² was dropped using a microsyringe, and a cold rolled steel plate of the same size was placed on top. After stacking several dozen steel plates in this way, they were fixed with narrow steel strips and the test plates were annealed in a small annealing furnace. The heating conditions during annealing were HNX gas (H ₂ : 5%) and a heating rate of 120 ml/min.
It was heated to 600°C at a rate of 10°C/min, 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 this was pasted on white paper to visually determine the degree of contamination, and the cleanliness of the steel plate surface was evaluated. The above are the evaluation results of the rolling lubricity when the mixed rolling oil of the synthetic ester and the hydrogenated product of Latphy oil shown in Table 1 of the present invention are used as they are, and the measurement results of the lubrication properties using the Bauden type lubrication tester. ,
Table 5 summarizes the test results when cold-rolled steel sheets were directly annealed while being rolled.
The symbol for G is the same as in Table 1.

[Table] Example 2 Mineral oil or refined beef tallow used as the base oil of practical rolling oil, emulsifiers, fatty acids, antioxidants, etc. that are commonly used as additives, and synthetic esters and latufi, which are the rolling oil of the present invention. Table 6 summarizes examples of rolling oil obtained by blending oil with hydrogen additives, and the lubricity and annealing properties of the same rolling oil. The symbols B to I in the table are the same as in Table 1. It is. For emulsion rolling, the rolled material (SPCC) 1.2 x 20 x 200 mm is rolled using a two-roll rolling mill with an oil concentration of 3.
%, and the rolling load was measured at a bath temperature of 50°C and a rolling reduction of 40% to evaluate rolling lubricity. Regarding annealing properties, several tens of as-rolled steel plates were stacked with the sample emulsion, fixed with a narrow steel strip, and annealed in a small annealing furnace. The annealing conditions are the same as in the case of using rolling oil alone in the previous example. The method for determining surface cleanliness is also the same.

[Table] (Effects of the invention) The rolling lubricating oil of the present invention improves the rolling lubricity of steel plates,
It has excellent annealing properties, enables high reduction rates and high speed rolling, greatly contributes to improved productivity, and can significantly reduce surface stains on the resulting steel plates.

Claims (1)

[Claims] 1. General formula However, R, R': alkyl, alkenyl, hydroxyalkyl, hydroxyalkenyl group having 5 to 29 carbon atoms; X: ethyl, propyl, isopropyl, butyl, and isobutyl group; It is characterized by containing 1 to 95% of an esterified product and 1 to 95% of a higher fatty acid or a higher alcohol that is an oil or fat obtained from a fish of the family Orientidae, a hydrogenated product thereof, or/and a hydrolyzate of the oil or fat. cold rolling oil for steel sheets. 2 R and R' in general formula (1) are hexanoic acid, octylic acid, decanoic acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, palmitooleic acid, oleic acid, erucic acid, Each fatty acid residue of ricinoleic acid, 12-hydroxystearic acid, isooctylic acid, nonanoic acid, isolauric acid, isomyristic acid, isopalmitic acid, isostearic acid, isoarachic acid, X is an ethyl or/and isopropyl group, n is 1 to The cold rolling oil for steel sheets according to claim 1, which is an integer of 20.