JPS6358880B2 - - 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. At least one hydroxyl group in the molecule obtained by reacting an aliphatic carboxylic acid having 12 to 22 carbon atoms with castor oil or hydrogenated castor oil.
An addition reaction product (hereinafter abbreviated as "AO adduct") obtained by further adding an alkylene oxide to a partial ester of castor oil or a partial ester of hydrogenated castor oil in the form of a remaining isocyanate group. A metal rolling oil characterized by using a compound obtained by reacting with a diisocyanate compound having two compounds, and if necessary, extreme pressure additives, surfactants, antioxidants, etc. are mixed therein. It is also possible. The fatty acid carboxylic acids having 12 to 22 carbon atoms used in the present invention include saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachic acid, behenic acid, oleic acid, linoleic acid, linolenic acid, ricinoleic acid, Examples include unsaturated fatty acids such as arachidonic acid. Next, an aliphatic carboxylic acid having 12 to 22 carbon atoms is reacted with castor oil or hydrogenated castor oil obtained by hydrogenating castor oil, so that at least one hydroxyl group remains in the molecule. to obtain a partial ester of castor oil in the form or a partial ester of hydrogenated castor oil. Partial esters of castor oil with at least one hydroxyl group remaining in the molecule or partial esters of hydrogenated castor oil are those with at least one hydroxyl group remaining on average in the molecule after esterification. It is something to do. The above partial ester of castor oil or partial ester of hydrogenated castor oil can be obtained by carrying out an esterification reaction between castor oil or hydrogenated castor oil and an aliphatic carboxylic acid having 12 to 22 carbon atoms in a conventional manner. To give an example of the reaction conditions, the number of moles of aliphatic carboxylic acid is determined and used in the reaction so that at least one hydroxyl group remains in the molecule per mole of castor oil or hydrogenated castor oil. For example, castor oil or hydrogenated castor oil 1
Add 1 to 2 moles of aliphatic carboxylic acid per mole, and heat at a temperature of 140 to 260℃ under a nitrogen gas flow for 2 to 25 hours.
The desired partial ester is obtained by a time reaction. The number of hydroxyl groups remaining in the partial ester molecule is calculated from the hydroxyl value. Next, an alkylene oxide is added to this partial ester compound to obtain an AO adduct. The addition reaction of alkylene oxide to this partial ester compound is also carried out by a conventional method. Examples of the alkylene oxide used here include ethylene oxide and propylene oxide, and these alkylene oxides may be added alone or in a random or block manner, and the number of moles added is The amount is from 2 to 100 mol, preferably from 3 to 60 mol. The AO adduct obtained as described above is reacted with a diisocyanate compound having two isocyanate groups to obtain a compound used in the metal rolling oil of the present invention. The reaction between the AO adduct and the diisocyanate compound is obtained by adding 0.3 to 2 moles of the diisocyanate compound to 1 mole of the AO adduct and reacting at 60 to 100°C. Examples of the diisocyanate compound having at least two isocyanate groups in the present invention 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 also be used by mixing with conventional rolling oil, or extreme pressure can be added if necessary. A surfactant, a surfactant, an antioxidant, etc. can also be used in combination. The present invention will be explained in more detail with reference to Examples below. The numbers in the examples indicate parts by weight. Synthesis Example 1 284 parts of stearic acid, 935 parts of castor oil, and 12 parts of para-toluene sulfonic acid (hereinafter abbreviated as "PTSA") were placed in a reactor and reacted at 150 to 180°C for 6 hours under a nitrogen gas flow to react with the acid. An ester having an average value of 1.0 and a hydroxyl value of 89.5 and having an average of 2 hydroxyl groups remaining in the molecule was obtained. Ethylene oxide 264 to this ester
1 part was subjected to an addition reaction at 180 to 200°C in the presence of 3 parts of caustic potassium to obtain an AO adduct. Further AO adducts
Add 3 parts of trimethylene diamine and 98 parts of methylene diisocyanate to 1464 parts to give an acid value of 0.8 and a hydroxyl value.
Compound 3.6 was obtained. Synthesis Example 2 200 parts of lauric acid, 940 parts of hydrogenated castor oil with an iodine value of 2.5, and 11 parts of PTSA were mixed under a nitrogen gas stream to yield 140 to 170 parts of lauric acid.
The reaction was carried out at .degree. C. for 8 hours to obtain an ester having an acid value of 0.9 and a hydroxyl value of 96.2, with an average of 2 hydroxyl groups remaining in the molecule. An addition reaction of 580 parts of propylene oxide to this ester was carried out in the presence of 2.3 parts of caustic potassium to obtain an AO adduct. 2 parts of trimethylene diamine and 87 parts of tolylene diisocyanate were added to the obtained AO adduct, and a reaction was carried out to obtain a compound having an acid value of 0.5 and a hydroxyl value of 32.8. Synthesis Example 3 939 parts of hydrogenated castor oil with an iodine value of 2.0, olein
282 parts and 12 parts of PTSA were heated to 150~ under nitrogen gas flow.
The reaction was carried out at 180° C. for 6 hours to obtain an ester with an average acid value of 0.8 and a hydroxyl value of 90.6, with two hydroxyl groups in the molecule and a remaining ester. Add 264 parts of ethylene oxide to this ester in the presence of 3 parts of potassium hydroxide to
The addition reaction was carried out at 200°C to obtain an AO adduct. Next, 3 parts of trimethylene diamine and 4 parts of trimethylene diamine were added to this.
125 parts of 4′-diphenylmethane diisocyanate
The mixture was added at 120°C, and after the addition was completed, the reaction was carried out at 80 to 90°C for 4 hours to obtain a compound with an acid value of 0.5 and a hydroxyl value of 4.0. Synthesis example 4 300 parts of ricinoleic acid, 935 parts of castor oil, PTSA12
part was reacted at 160 to 170°C for 5 hours under a nitrogen gas flow,
An ester having an acid value of 1.1 and a hydroxyl value of 130.0 and having an average of 3 hydroxyl groups remaining in the molecule was obtained. To this ester, in the presence of 3 parts of caustic potassium, 440 parts of ethylene oxide was subjected to an addition reaction at 160 to 170°C, and then 290 parts of propylene oxide was subjected to an addition reaction at 170 to 180°C to obtain an AO adduct. 3 parts of trimethylene diamine and 168 parts of hexamethylene diisocyanate were added to the obtained AO adduct to conduct a reaction, and the acid value
0.5, and a compound with a hydroxyl value of 26.0 was obtained. Synthesis Example 5 340 parts of behenic acid, 935 parts of castor oil, and 13 parts of PTSA were reacted at 170 to 180°C for 6 hours under a nitrogen gas stream to determine the acid value.
An ester having an average of 2 hydroxyl groups remaining in the molecule with a hydroxyl value of 0.8 and a hydroxyl value of 90.3 was obtained. An addition reaction of 1300 parts of ethylene oxide to this ester was carried out in the presence of 2 parts of caustic potassium to obtain an AO adduct. 3 parts of trimethylene diamine and 210 parts of naphthalene diisocyanate were added to the obtained AO adduct and a reaction was carried out to obtain a compound having an acid value of 0.4 and a hydroxyl value of 2.0. Friction coefficient (μ) of Examples 1 to 5 of rolling oil having the composition shown in Table 1 using the compounds obtained in Synthesis Examples 1 to 5,
The 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, in the rolling performance test for Examples 1 and 2, a certain amount of rolling oil was directly applied to the rolled material,
Further, in Examples 3 to 5 and Comparative Examples, tests were conducted by supplying the emulsion as a 5% concentration emulsion.
The amount of oil adhering to the rolled material was 1 g/m ² in all Examples 1 to 5 and Comparative Example. The test results are shown in Figure 1 as a rolling performance evaluation based on the relationship between rolling reduction ratio (%) and rolling force (ton).

【table】

[Table] 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 peripheral speed 30m/min Rolling material: SPC-C Thickness 0.6mm x Width 50mm x Length 150mm Measuring method of rolling performance 50mm intervals on the steel plate before rolling (l ₁ ) 2
A line was drawn, the line was 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 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 of castor oil in which at least one hydroxyl group remains in the molecule, obtained by reacting an aliphatic carboxylic acid having 12 to 22 carbon atoms with castor oil or hydrogenated castor oil; A metal rolling oil characterized by using a compound obtained by reacting an addition reaction product obtained by further adding an alkylene oxide to a partial ester of hydrogenated castor oil and a diisocyanate compound having two isocyanate groups. .