JPS6358876B2 - - 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 1 to 21 carbon atoms and having at least one hydroxyl group remaining in its 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 polyepoxy compound having two or three glycidyl groups in the molecule, and if necessary, animal or vegetable oil or fat. , mineral oil, extreme pressure additives, surfactants, antioxidants, etc. can also be used in combination. 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 similar monocarboxylic acid is as follows: 1 mole of a polyhydric alcohol and 0.5 to 5 moles of a monocarboxylic acid are mixed in a stream of nitrogen gas in the presence of an alkaline catalyst or an acidic catalyst. It is obtained by carrying out an esterification reaction at 160 to 260°C for 2 to 15 hours. Examples of the alkaline catalyst used here include caustic soda, caustic potash, and soda carbonate, and examples of the acidic catalyst include hydrochloric acid, sulfuric acid, and p-toluenesulfonic acid. In addition, when using lower alkyl esters of monocarboxylic acids (mainly methyl or ethyl esters), in addition to the above-mentioned alkaline catalyst, sodium methylate etc. are used to react at 40 to 120°C to form the desired part. Esters can be obtained. 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; The compound that is
It is synthesized by reacting the above AO adduct with a polyvalent epoxy compound having 2 to 3 glycidyl groups in the molecule. That is, it is due to the addition reaction of a polyvalent epoxy compound to the hydroxyl group bonded to the AO adduct, for example, at a ratio of 0.3 to 2 moles of the polyvalent epoxy compound to 1 mole of the AO adduct.
It is obtained by reacting at 70 to 120°C, and the AO adduct is crosslinked with a polyvalent epoxy compound to produce a chain or network reaction product. Examples of the polyepoxy compound having two to three glycidyl groups in the molecule used in the present invention include ethylene glycol diglycidyl ether, glycerin triglycidyl ether, adipate diglycidyl ester, and succinic acid diglycidyl ester. The compound obtained by reacting the above-mentioned AO adduct with a polyvalent epoxy 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, or used as an extreme pressure additive. It can also be used by adding antioxidants, surfactants, etc. EXAMPLES The present invention will be explained in more detail below with reference to Examples. Synthesis Example 1 After reacting 106 parts of trimethylolpropane and 680 parts of behenic acid at 240 to 250°C under a nitrogen gas stream for 8 hours, 1.6 parts of potassium hydroxide was added as a catalyst.
Add 220 parts of ethylene oxide at 160-180℃,
An AO adduct with an acid value of 2.2 and a hydroxyl value of 56.0 was obtained. Next, 83 parts of ethylene glycol diglycidyl ether,
Two parts of boron trifluoride etherate were added and reacted at 80°C for 6 hours to obtain a compound with an acid value of 1.2 and a hydroxyl value of 46.7. Synthesis example 2 136 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,
Add 440 parts of ethylene oxide at 160-180℃,
An AO adduct with an acid value of 1.5 and a hydroxyl value of 43.4 was obtained. Then ethylene glycol diglycidyl ether 87
part, add 1.2 parts of boron trifluoride etherate, 80
-100 for 4 hours to obtain a compound with an acid value of 0.5 and a hydroxyl value of 60.5. Synthesis Example 3 After reacting 182 parts of sorbitol and 564 parts of oleic acid at 160 to 170°C under a nitrogen gas stream for 2 hours, 1 part of potassium hydroxide was added, and 440 parts of ethylene oxide and 290 parts of propylene oxide were reacted at 180 to 190°C. An addition reaction was performed to obtain an AO adduct with an acid value of 0.4 and a hydroxyl value of 152. Next, 260 parts of adipic acid diglycidyl ester and 2 parts of boron trifluoride etherate were added to this.
React at 80-100℃ for 4 hours, acid value 0.2, hydroxyl value
105 compounds were obtained. Synthesis Example 4 After reacting 166 parts of diglycerin and 400 parts of lauric 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 1750 parts of propylene oxide was added at 160 to 180°C. , acid value 0.6,
An AO adduct with a hydroxyl value of 48.0 was obtained. Next, add glycerin triglycidyl ether 130 to the total amount of AO adduct.
parts, add 2.3 parts of boron trifluoride etherate, and add 80 parts of boron trifluoride etherate.
Reacted at ~90℃ for 6 hours, acid value 0.3, hydroxyl value 42.3
The compound was obtained. Synthesis Example 5 After reacting 92 parts of glycerin and 300 parts of ricinoleic acid at 160 to 170°C under a nitrogen 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 170-190
Add 290 parts of propylene oxide at °C to determine the acid value.
0.4, and an AO adduct with a hydroxyl value of 148.5 was obtained. then
Succinic acid diglycidyl ester in total amount of AO adduct
Add 230 parts and 1 part of boron trifluoride etherate,
Reacted at 80-90℃ for 6 hours, acid value 0.8, hydroxyl value
Compound 121.7 was obtained. 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 adhering 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 rolling performance and 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.

【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-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 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 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 polyvalent epoxy compound having two or three glycidyl groups in the molecule.