JPS6358877B2 - - 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. It is characterized by using a compound obtained by reacting an addition reaction product obtained by adding an alkylene oxide to (hereinafter referred to as "AO adduct") and a diisocyanate compound having two isocyanate groups in the molecule. It is a metal rolling oil, and if necessary, animal and vegetable oils, mineral oils, extreme pressure additives, surfactants, antioxidants, etc. can be added thereto. 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 diisocyanate compound having two hydroxyl groups and two isocyanate groups of the AO adduct The compound obtained by reacting with has two or more ester bonds bonded in the molecule. Next, a compound obtained by reacting the AO adduct with a diisocyanate compound is synthesized by a conventional method by reacting the above AO adduct with a diisocyanate compound having two isocyanate groups in the molecule. Ru. That is, it is an addition reaction of a diisocyanate compound to the hydroxyl group bonded to the above-mentioned AO adduct. For example, the diisocyanate compound is reacted at a ratio of 0.3 to 2 moles with respect to 1 mole of the AO adduct at 60 to 100°C. The AO adduct is crosslinked with a diisocyanate compound,
"Produces a chain or network reaction product. Two isocyanate groups are added to the molecule used in the present invention."
Examples of diisocyanate compounds containing diisocyanate include methylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, naphthalene diisocyanate, methoxyphenylene diisocyanate, and biphenyl diisocyanate. The compound obtained by reacting the above-mentioned AO adduct with a diisocyanate compound has high performance as a rolling oil when used as it is, but it can be mixed with conventional rolling oil, animal or vegetable oil, mineral oil, extreme pressure additives, antioxidants, etc. It can also be used by adding a surfactant or the like. EXAMPLES The present invention will be explained in more detail below with reference to Examples. Synthesis Example 1 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, 1160 parts of propylene oxide was added at 160 to 180°C using 1.5 parts of potassium hydroxide as a catalyst. react, acid value
0.8, and an AO adduct with a hydroxyl value of 60.5 was obtained. Next, 5 parts of trimethylene diamine and 250 parts of 4,4'-diphenylmethane diisocyanate were added at 120°C, and after the addition was completed, the mixture was reacted at 80 to 90°C for 4 hours. The obtained compound had an acid value of 0.2 and a hydroxyl value of 4.5. Synthesis Example 2 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, ethylene oxide was reacted with 1 part of potassium hydroxide as a catalyst.
Addition reaction of 440 parts at 160 to 180°C, then addition reaction of 290 parts of propion oxide at 170 to 190°C,
An AO adduct with an acid value of 0.4 and a hydroxyl value of 146.2 was obtained. Next, 174 parts of tolylene diisocyanate and 2 parts of trimethylene diamine were added to the AO adduct, and after the addition was completed, the mixture was reacted at 80 to 90°C for 4 hours. The obtained compound had an acid value of 0.2 and a hydroxyl value of 40.9. Synthesis example 3 136 parts of pentaerythritol, 400 parts of lauric acid
1 part and 5 parts of sodium hydroxide under a stream of nitrogen gas.
After reacting at 180-190°C for 6 hours, 290 parts of propylene oxide was added at 170-180°C to obtain an AO adduct with an acid value of 0.8 and a hydroxyl value of 136. Next, 84 parts of hexamethylene diisocyanate and 2 parts of trimethylene diamine were added to this ester, and the reaction was carried out at 80 to 90°C for 5 hours to give an acid value of 0.5.
A compound with a hydroxyl value of 40 was obtained. Synthesis Example 4 After reacting 182 parts of sorbitol and 568 parts of stearic acid at 170 to 180°C under a nitrogen gas stream for 5 hours,
Using 2 parts of potassium hydroxide as a catalyst, 2200 parts of ethylene oxide was subjected to an addition reaction at 160 to 180°C, with an acid value of 1.2,
An AO adduct with a hydroxyl value of 75.7 was obtained. Next, 98 parts of methylene diisocyanate and 2 parts of trimethylene diamine were added to this AO adduct.
The reaction was carried out at ℃ for 5 hours. The obtained compound has an acid value of 0.9,
The hydroxyl value was 32.7. Synthesis Example 5 After reacting 134 parts of trimethylolpropane and 680 parts of behenic acid at 240 to 250°C under a nitrogen gas stream for 8 hours, 220 parts of ethylene oxide was added at 160 to 180°C using 1.6 parts of potassium hydroxide as a catalyst. react,
An AO adduct with an acid value of 1.8 and a hydroxyl value of 55.0 was obtained. This AO adduct is then treated with naphthalene diisocyanate.
105 parts and 2 parts of dimethylene triamine were added, and after the addition was completed, the mixture was reacted at 100 to 110°C for 4 hours. The obtained compound had an acid value of 1.0 and a hydroxyl value of 2.5. 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-based 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. Ta.
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.

【table】

[Table] 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 capacity test method Shell type high speed four ball friction tester rolling test method Rolling mill: Four-roll rolling mill 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 x 50mm x length 150mm Measuring method of rolling performance Rolling performance is measured by applying 50mm spacing (l ₁ ) to the steel plate before rolling. Two lines were drawn, the lines were rolled, the distance (l ₂ ) after rolling was measured, and the rolling reduction was determined using the following formula. 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 the drawing]

FIG. 1 is a rolling performance comparison diagram showing the rolling performance of Examples 1 to 5 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 diisocyanate compound having two isocyanate groups in the molecule.