JPS6358879B2 - - 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 an epoxy group It is a metal rolling oil characterized by using a compound obtained by reacting with a polyvalent epoxy compound having 2 or 3 epoxy compounds, and if necessary, extreme pressure additives, surfactants, antioxidants, etc. are added thereto. It is also possible to use it as 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 polyvalent epoxy compound having 2 to 3 epoxy groups to obtain a compound used in the metal rolling oil of the present invention. The reaction between AO adduct and polyepoxy compound is
It is obtained by adding 0.3 to 2 moles of a polyvalent epoxy compound to 1 mole of the AO adduct and reacting at 70 to 120°C. Examples of the polyepoxy compound having 2 to 3 epoxy groups in the present invention include ethylene glycol diglycidyl ether, glycerin triglycidyl ether, adipic acid diglycidyl ester,
Examples include succinic acid diglycidyl ester and polyethylene glycol diglycidyl ether. The compound obtained by reacting the above-mentioned AO adduct with a polyepoxy 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 if necessary, it can be used as a rolling oil. It is also possible to mix and use additives, surfactants, antioxidants, etc. The present invention will be further explained below with reference to Examples. The numbers in the examples indicate parts by weight. Synthesis Example 1 200 parts of lauric acid, 940 parts of hydrogenated castor oil with an iodine value of 2.5, and 11 parts of para-toluenesulfonic acid (hereinafter abbreviated as "PTSA") were added under a nitrogen gas stream.
Reacted at 140-160℃ for 8 hours, acid value 0.9, hydroxyl value
An ester having an average of 2 hydroxyl groups remaining in the molecule of 96.2 was obtained. An addition reaction of 580 parts of propion oxide to this ester was carried out in the presence of 2.3 parts of caustic potassium to obtain an AO adduct. Next, 174 parts of ethylene glycol diglycidyl ether and 2 parts of boron trifluoride etherate were added to the AO adduct and reacted at 80 to 90°C for 6 hours.
A compound with an acid value of 1.0 and a hydroxyl value of 57.5 was obtained. Synthesis example 2 568 parts of isostearic acid, 935 parts of castor oil,
15 parts of PTSA was reacted at 160 to 200°C for 6 hours under a nitrogen gas stream to obtain an ester having an acid value of 4.5 and a hydroxyl value of 38.2, with an average of one hydroxyl group remaining in the molecule. To this was added 2030 parts of propylene oxide in the presence of caustic potash. 250 parts of polyester glycol (MW=400) diglycidyl ether was added to the obtained reaction product to give an acid value of 1.6 and a hydroxyl value.
15.0 compound was obtained. Synthesis Example 3 568 parts of stearic acid, 939 parts of hydrogenated castor oil with an iodine value of 2.0, and 15 parts of PTSA were mixed under a stream of nitrogen gas to
The reaction was carried out at 180° C. for 6 hours to obtain an ester having an acid value of 2.0 and a hydroxyl value of 39.2, with an average of one hydroxyl group remaining in the molecule. An addition reaction of 880 parts of ethylene oxide to this ester was carried out in the presence of 3 parts of caustic potassium to obtain an AO adduct. Next, 232 parts of succinic acid diglycidyl ester and 2 parts of boron trifluoride etherate were added to 2351 parts of the AO adduct, and the mixture was reacted at 80°C for 6 hours.
A compound with a hydroxyl value of 30.0 was obtained. Synthesis Example 4 340 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 stream of nitrogen gas, and an average of 2 hydroxyl groups remained in the molecule with an acid value of 0.8 and a hydroxyl value of 90.0. An ester was obtained. An addition reaction of 1300 parts of ethylene oxide to this ester was carried out at 170 to 180°C in the presence of 3 parts of caustic potassium to obtain an AO adduct. Next, 130 parts of glycerin triglycidyl ether and 2 parts of boron trifluoride etherate were added to the AO adduct and reacted at 80 to 90°C for 6 hours to obtain a compound with an acid value of 0.4 and a hydroxyl value of 40.2. Synthesis Example 5 282 parts of oleic acid, 935 parts of castor oil, and 12 parts of PTSA were reacted at 150 to 180°C for 6 hours under a nitrogen gas flow.
An ester having an acid value of 1.1 and a hydroxyl value of 89.5 and having an average of two hydroxyl groups remaining in the molecule was obtained. An addition reaction of 264 parts of ethylene oxide to this ester was carried out in the presence of 3 parts of caustic potassium to obtain an AO adduct. Next, 258 parts of adipic acid siglycidyl ether and 2 parts of boron trifluoride etherate were added to this AO adduct, and the mixture was reacted at 80°C for 6 hours.
A compound with a hydroxyl value of 64.1 was obtained. Synthesis example 6 ricinoleic acid 300 parts, castor oil 935 parts, PTSA12
was reacted at 160 to 170℃ for 5 hours under a nitrogen gas flow,
An ester having an acid value of 1.1 and a hydroxyl value of 137.5 and having an average of 3 hydroxyl groups remaining in the molecule was obtained. Addition reaction of 440 parts of ethylene oxide to this ester at 160 to 170°C in the presence of 3 parts of caustic potassium,
Further, an addition reaction was carried out with 290 parts of propion oxide at 170 to 180°C to obtain an AO adduct. Next, ethylene glycol diglycidyl ether is added to the AO adduct.
Add 87 parts and 2 parts of boron trifluoride etherate, and heat at 80°C.
The mixture was reacted for 6 hours to obtain a compound with an acid value of 0.8 and a hydroxyl value of 55.4. Friction coefficient (μ) of Examples 1 to 6 of rolling oil having the composition shown in Table 1 using the compounds obtained in Synthesis Examples 1 to 6,
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 6 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

【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 × Width 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 then The rolling reduction ratio was calculated using the 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 6 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 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 polyvalent epoxy compound having 2 or 3 epoxy groups. Metal rolling oil.