JPS6358199B2 - - 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 phosphoric acid or A metal rolling oil characterized by using phosphoric acid ester or its salt obtained by reaction with phosphoric anhydride, and if necessary, extreme pressure additives, surfactants, antioxidants, etc. It is also possible to use them in combination. The aliphatic 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, arachidic acid, and behenic acid, oleic acid, linoleic acid, linolenic acid, and ricinoleic acid. and 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. A major feature of the present invention is that the AO adduct obtained above has at least one hydroxyl group remaining in each molecule, and the hydroxyl group of this AO adduct reacts with phosphoric acid or phosphoric anhydride. By doing so, two or more molecules of the AO adduct combine with phosphoric acid to form a phosphoric acid ester. Phosphate esters can be obtained by reacting AO adducts with phosphoric anhydride or phosphoric acid.
It is obtained by reacting 0.1 to 2 mol at 60 to 110°C for 2 to 6 hours. When phosphoric acid is used, it can be obtained by reacting at 120 to 150° C. for 2 to 6 hours under a nitrogen gas stream. The phosphoric acid ester thus obtained contains monoesters, diesters, and triesters of phosphoric acid, and if the AO adduct used to produce the phosphoric acid ester has two or more hydroxyl groups remaining, The esterification reaction between the ester having the group and phosphoric acid occurs in a chain or network form to produce a phosphoric acid polyester, and the phosphoric ester used in the present invention contains such a polyester. These phosphoric acid esters are used as salts by neutralizing residual acid groups, if necessary. Examples of salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, and compounds for obtaining salts of organic amines or their derivatives include ammonia, monoethanolamine, diethanolamine, and triethanol. Examples include amines, linear alkylamines having 1 to 18 carbon atoms, triethanolamine stearate, and morpholine. By this neutralization, the hydrophilicity of the reaction product can be appropriately adjusted depending on the conditions of use, and the polarity of the reaction product can also be adjusted to control the adsorption to metal surfaces. These phosphoric acid esters or salts thereof have high performance as rolling oil when used as is, but
It can be used by mixing it with conventional rolling oil, and if necessary, it can also be used by adding extreme pressure additives, antioxidants, surfactants, etc. EXAMPLES The present invention will be explained in more detail below with reference to Examples. The numbers in the examples indicate parts by weight. Synthesis Example 1 935 parts of castor oil, 282 parts of oleic acid, and 12 parts of para-toluenesulfonic acid (hereinafter abbreviated as "PTSA") were reacted at 150 to 180°C for 6 hours under a nitrogen gas stream to determine the acid value. 1.2, an average of 2 in a molecule with a hydroxyl value of 90.0
An ester with the remaining hydroxyl group was obtained. This ester is followed by ethylene oxide 264
An addition reaction was carried out at 180 to 200°C in the presence of 3 parts of potassium hydroxide to obtain an AO adduct. Furthermore, add 71 parts of phosphoric anhydride to the AO adduct at 70 to 80℃.
The reaction was carried out for 4 hours to obtain a compound having an acid value of 55.0 and a hydroxyl value of 15.0. This phosphoric acid ester was neutralized with triethanolamine, and a 1% aqueous solution of it was prepared.
Adjusted pH to 7.0. Synthesis Example 2 939 parts of hydrogenated castor oil with an iodine value of 2.0, 200 parts of lauric acid, and 11 parts of PTSA were mixed under a stream of nitrogen gas at 140 parts to 140 parts.
The reaction was carried out at 160° C. for 8 hours to obtain an ester with an oxidation rate of 1.0 and a hydroxyl value of 95.0, with an average of 2 hydroxyl groups remaining in the molecule. To this ester, 580 parts of propylene oxide was added to 180 parts of potassium hydroxide in the presence of 2.3 parts of potassium hydroxide.
Addition reaction was carried out at ~200°C to obtain the AO adduct. 71 parts of phosphoric anhydride was added to the obtained AO adduct at 60 to 70°C and reacted for 5 hours, resulting in an acid value of 60.0 and a hydroxyl value of 10.0.
The phosphoric acid ester of was obtained. This phosphoric acid ester was neutralized with triethanolamine stearate, and the pH of its 1% aqueous solution was adjusted to 7.0. Synthesis Example 3 940 parts of hydrogenated castor oil with an iodine value of 2.5, 568 parts of stearic acid, and 15 parts of PTSA were placed under a stream of nitrogen gas.
The reaction was carried out at 160 to 170°C for 6 hours to obtain an ester having an acid value of 1.8 and a hydroxyl value of 39.8, with an average of one hydroxyl group remaining in the molecule. This ester was then subjected to an addition reaction with 880 parts of ethylene oxide in the presence of 3 parts of potassium hydroxide at 160-170°C to obtain an AO adduct. Furthermore, add 36 parts of phosphoric anhydride to the AO adduct at 70 to 80℃.
The reaction was carried out for 4 hours to obtain a compound with an acid value of 35.0 and a hydroxyl value of 2.8. This phosphoric acid ester is neutralized with sodium hydroxide, and the pH of the 1% aqueous solution is
Adjusted to 7.0. Synthesis Example 4 935 parts of castor oil, 340 parts of behenic acid, and 13 parts of PTSA were reacted at 170 to 180°C for 6 hours under a nitrogen gas flow,
An ester having an acid value of 0.8 and a hydroxyl value of 43.2 and having an average of two hydroxyl groups remaining in the molecule was obtained. This ester was then subjected to an addition reaction with 1300 parts of ethylene oxide in the presence of 3 parts of potassium hydroxide at 170-180°C to obtain an AO adduct. Furthermore, add 71 parts of phosphoric anhydride to the AO adduct at 70 to 80℃.
and reacted for 4 hours, acid value 32, hydroxyl value
Compound 20.4 was obtained. This phosphoric acid ester was neutralized with dicyclohexylamine, and a 1% aqueous solution was prepared.
Adjusted pH to 7.0. Synthesis Example 5 935 parts of castor, 300 parts of ricinoleic acid, and 12 parts of PTSA were reacted at 160 to 170°C for 5 hours under a nitrogen gas stream to form an average of 3 hydroxyl groups in a molecule with an acid value of 1.1 and a hydroxyl value of 130.0. The remaining ester 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. Furthermore, add 71 parts of phosphoric anhydride to the AO adduct at 70 to 80℃.
The reaction was carried out for 4 hours to obtain a compound having an acid value of 42.1 and a hydroxyl value of 56.0. This phosphoric acid ester was neutralized with monoethanolamine, and a 1% aqueous solution of it was prepared.
Adjusted pH to 7.0. 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 as a comparative example along with the measurement results of tallow-based rolling oil.

【table】

【table】

[Table] 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. I went to The amount of oil adhering to the rolled material was 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. 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 rolling test method Rolling mill: Four-roll rolling mill Work roll diameter 150 mm x width 140 mm Backup Roll diameter 250mm x width 140mm Roll material Chrome steel roll circumferential speed 30m/min Rolling material: SPC-C Thickness 0.6mm x width 50mm x length 150mm Measuring method of rolling performance 50mm intervals (l ₁ ) on 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 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; It is characterized by using a phosphoric acid ester or a salt thereof obtained by reacting an addition reaction product obtained by further adding an alkylene oxide to a partial ester of hydrogenated castor oil with phosphoric acid or phosphoric anhydride. Metal rolling oil.