JPS6358875B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to metal rolling oil. Conventionally, palm oil has been used as a rolling oil for steel plates for a long time, but instead, animal and vegetable oils such as beef tallow, lard, Nagasu whale hardened oil, mineral oils, or mixtures of these oils are used as base oils, and additives and oil-based oils are used as rolling oils. Products containing improvers, antioxidants, surfactants, etc. are widely used. On the other hand, the progress of rolling machinery equipment has progressed significantly, and as mills have become larger, there has been a demand for rationalization and precision of the rolling process, such as reducing the number of passes, increasing rolling speed, and increasing the standard accuracy of rolled products. As a result, the conditions for rolling oil are becoming more severe.
Palm oil and tallow-based rolling oils are no longer able to satisfy this condition, but at present no alternative rolling oil has yet been found. The present invention aims to provide a rolling oil that has better rolling performance than conventional palm oil or beef tallow-based rolling oils and can satisfy the harsh rolling processes currently required. The rolling oil of the present invention is composed of the following. That is, a partial ester obtained by reacting a polyhydric alcohol with a monocarboxylic acid having an alkyl group or an alkenyl group having 11 to 21 carbon atoms, with at least one hydroxyl group remaining in the molecule. An addition reaction product obtained by adding alkylene oxide to (hereinafter referred to as "AO adduct")
This is a metal rolling oil characterized by using a compound obtained by reacting a dicarboxylic acid with a dicarboxylic acid, and if necessary, it may contain animal or vegetable oils, mineral oils, extreme pressure additives, surfactants, oxidation It is also possible to mix and use an inhibitor or the like. Examples of the polyhydric alcohol in the present invention include glycerin, polyglycerin, pentaerythritol, sorbitol, and trimethylolpropane. On the other hand, monocarboxylic acids that form partial esters with the polyhydric alcohol include lauric acid,
Examples include saturated fatty acids such as myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, and unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, and ricinoleic acid. At least one of these monocarboxylic acids,
Partial esters with polyhydric alcohols can also be synthesized by esterification reactions between monocarboxylic acids and polyhydric alcohols, but they can also be synthesized by transesterification between lower alkyl esters of monocarboxylic acids and polyhydric alcohols. Synthesis is also possible, and the present invention is not limited in any way by these synthesis methods. An example of an esterification reaction between a polyhydric alcohol and a monocarboxylic acid is polyhydric alcohol 1
mol and 0.5 to 5 moles of monocarboxylic acid are subjected to an esterification reaction at 160 to 260° C. for 2 to 15 hours in the presence of an alkaline catalyst or an acidic catalyst under a nitrogen gas stream. Examples of alkaline catalysts used here include caustic soda, caustic potash, and soda carbonate, and examples of acidic catalysts include hydrochloric acid, sulfuric acid,
Examples include para-toluenesulfonic acid. In addition, when using lower alkyl esters of monocarboxylic acids (mainly methyl or ethyl esters),
The target partial ester can be obtained by reacting at 40 to 120°C using sodium methylate or the like in addition to the above alkaline catalyst. Next, an alkylene oxide is added to the above partial ester to obtain an AO adduct. Examples of alkylene oxides that react with the hydroxyl groups remaining in the partial ester of the polyhydric alcohol include ethylene oxide and propylene oxide.
The seeds may be added randomly or in blocks, and the number of moles added (if 2 or more species, add them together) is 2 to 100 moles, preferably 3 to 60 moles.
It is a mole. A major feature of the present invention is that the AO adduct obtained above has at least one hydroxyl group in one molecule, and a dicarboxylic acid can be obtained by reacting the hydroxyl group of the AO adduct with a dicarboxylic acid. Acid esters have two or more ester bonds in their molecules. Next, the compound obtained by reacting the AO adduct with the dicarboxylic acid is synthesized by an esterification reaction between the hydroxyl group bonded to the AO adduct and the dicarboxylic acid in accordance with a conventional method. For example, it is obtained by reacting at 130 to 200° C. at a ratio of 0.3 to 2 moles of dicarboxylic acid to 1 mole of AO adduct, producing a reaction product in which the AO adduct is crosslinked with dicarboxylic acid. Examples of dicarboxylic acids used in the present invention include dibasic carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, and maleic acid, and their acid anhydrides. The compound obtained by reacting the above AO adduct with dicarboxylic acid has high performance as a rolling oil when used as it is, but it can be used as a rolling oil, mixed with conventional rolling oil, animal or vegetable oil, mineral oil, or with extreme pressure additives or antioxidants. It can also be used by adding agents, surfactants, etc. The present invention will be explained in more detail with reference to Examples below. Synthesis example 1 136 parts of pentaerythritol, 710 parts of stearic acid
After reacting for 6 hours at 200 to 240°C under a nitrogen gas stream, 2 parts of potassium hydroxide was added as a catalyst, and 440 parts of ethylene oxide was added at 160 to 180°C, resulting in an acid value of 1.7 and a hydroxyl value of 43.6. The AO adduct of was obtained. Add 73 parts of adipic acid and 8 parts of para-toluenesulfonic acid to the total amount of this AO adduct and heat at 150 to 160°C.
After reacting for a period of time, a compound with an acid value of 2.0 and a hydroxyl value of 10.0 was obtained. Synthesis example 2 106 parts of trimethylolpropane, 680 parts of behenic acid
After reacting 4 parts of sodium hydroxide at 240 to 250°C under a nitrogen gas stream for 8 hours, addition reaction with 220 parts of ethylene oxide at 160 to 180°C resulted in an acid value of 2.2,
An AO adduct with a hydroxyl value of 56.0 was obtained. Next, 68 parts of sebacic acid and 8 parts of para-toluenesulfonic acid were added thereto, and the mixture was reacted at 150 to 160°C for 8 hours to obtain a compound having an acid value of 3.2 and a hydroxyl value of 1.5. Synthesis Example 3 After reacting 182 parts of sorbitol and 400 parts of lauric acid at 170 to 180°C under a nitrogen gas stream for 4 hours, 1 part of potassium hydroxide was added as a catalyst, and 1540 parts of ethylene oxide was added at 180 to 190°C. React, acid value
0.6, and an AO adduct with a hydroxyl value of 105.1 was obtained. This AO
49 parts of maleic anhydride and 5 parts of para-toluenesulfonic acid were added to the total amount of the adduct and reacted at 200 to 210°C for 8 hours to obtain a compound with an acid value of 1.5 and a hydroxyl value of 35.0. Synthesis Example 4 After reacting 166 parts of diglycerin and 565 parts of oleic acid at 200 to 250°C under a nitrogen gas stream for 5 hours, 1.5 parts of potassium hydroxide was added as a catalyst, and 1160 parts of propylene oxide was reacted at 160 to 180°C. Addition reaction occurs with
An AO adduct with an acid value of 0.9 and a hydroxyl value of 59.8 was obtained. this
59 parts of succinic acid and 9 parts of para-toluenesulfonic acid were added to the total amount of the AO adduct and reacted at 180 to 200°C for 8 hours to obtain a compound with an acid value of 5.0 and a hydroxyl value of 15.2. Synthesis Example 5 After reacting 92 parts of glycerin and 300 parts of ricinoleic acid at 160 to 170°C under a nitrogen gas stream for 4 hours, 1 part of potassium hydroxide was added as a catalyst, and 440 parts of ethylene oxide was added at 160 to 180°C. Then, an addition reaction was carried out with 290 parts of propylene oxide at 170 to 190°C to obtain an AO adduct with an acid value of 0.4 and a hydroxyl value of 150.1. 188 parts of azelaic acid to the total amount of this AO adduct,
Add 5.6 parts of para-toluenesulfonic acid and heat to 180-200℃
The mixture was reacted for 10 hours to obtain a compound with an acid value of 6.2 and a hydroxyl value of 21.6. For Examples 1 to 5 with the compositions shown in Table 1 using the compounds obtained in Synthesis Examples 1 to 5, the friction coefficient (μ),
Pressure resistance was measured. The results are shown in Table 2 along with the measurement results for tallow rolling oil as a comparative example. In addition, rolling performance tests were conducted by applying a certain amount of rolling oil to the rolled material as it was for Examples 1 and 2, and by supplying it as a 5% concentration emulsion for Examples 3 to 5 and Comparative Examples. . The amount of oil attached to the rolled material was set to 1 g/m ² in all Examples 1 to 5 and Comparative Example. Test results are shown in rolling reduction ratio (%) and rolling load (ton)
The relationship between the rolling performance and the rolling performance is evaluated and shown in Figure 1. In addition, as a comparative example, tallow-based rolling oil shown in Table 1 was used. The test method regarding the lubrication performance of the rolling oil of the present invention is as follows. Friction coefficient (μ) test method Soda pendulum type oil tester N type load-bearing capacity test method Shell type high speed four-ball friction tester

【table】

[Table] Rolling test method Rolling machine: Four-high roll rolling machine Work roll diameter 150mm x width 140mm Back-up roll diameter 250mm x width 140mm Roll material Chrome steel Roll circumferential speed 30m/min Rolling material: SPC-C Thickness 0.6mm × 50 mm × Length 150 mm Method for measuring rolling performance Draw two lines with a spacing of 50 mm (l ₁ ) on the steel plate before rolling, roll this, measure the spacing after rolling (l ₂ ), and use the following formula. The rolling reduction ratio was determined. Rolling ratio (%)=l ₂ −l ₁ /l ₂ ×100 Further, the rolling load (ton) at that time was measured using a load cell.

[Brief explanation of drawings]

FIG. 1 is a rolling performance comparison diagram showing the rolling performance of Examples 1 to 5 of the rolling oil of the present invention and a comparative example based on the relationship between rolling load and rolling reduction.

Claims (1)

[Claims] 1 A partial ester with at least one hydroxyl group remaining in the molecule obtained by reacting a polyhydric alcohol with a monocarboxylic acid having an alkyl group or an alkenyl group having 11 to 21 carbon atoms. A metal rolling oil characterized by using a compound obtained by reacting an addition reaction product obtained by adding an alkylene oxide with a dicarboxylic acid.