JPS6253557B2 - - 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. improver,
Products containing antioxidants, surfactants, etc. are widely used. On the other hand, progress in rolling machinery equipment has been remarkable, and with the increase in the size of mills, rationalization and precision of the rolling process is required, such as reducing the number of passes, increasing rolling speed, and increasing the standard accuracy of rolled products. The conditions for rolling oils are becoming more severe, and palm oil and tallow-based rolling oils are no longer able to satisfy these conditions, but rolling oils that replace them are still being found. The current situation is that this is not the case. 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. (A) Aliphatic carboxylic acid or polycarboxylic acid having 12 or more carbon atoms. (B) A polycarboxylic acid ester having 4 or more carbon atoms each having at least one alkyl group having 11 or more carbon atoms and at least one carboxyl group in one molecule. An amide compound with at least one remaining amine group obtained by reacting at least one selected from the groups (A) and (B) with a polyamine, and the remaining amine group can react with the amide compound. This metal rolling oil is characterized by using a compound obtained by a reaction with a polycarboxylic acid having at least two carboxyl groups in the molecule. Examples of aliphatic carboxylic acids having 12 or more carbon atoms used in (A) of the present invention include lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid,
Saturated fatty acids such as behenic acid; unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, ricinoleic acid, arachidonic acid; Can be mentioned. Examples of polycarboxylic acids having 12 or more carbon atoms include Japanese acid, or so-called dimer acids and trimer acids obtained by polymerizing unsaturated fatty acids such as oleic acid and linoleic acid. Next, add at least 1 alkyl group and carboxyl group each having 11 or more carbon atoms in one molecule used in (B).
A polycarboxylic acid ester having 4 or more carbon atoms can be obtained by forming an ester from a polycarboxylic acid having 4 or more carbon atoms and a hydroxyl compound. Examples include esters of polyhydric alcohols having 1 or more hydroxyl groups and fatty acids having 12 or more carbon atoms, with at least one hydroxyl group remaining in the molecule, and alkylene oxide adducts of these. Examples of aliphatic alcohols having 12 or more carbon atoms include lauryl alcohol, myristyl alcohol, palmityl alcohol, oleyl alcohol, stearyl alcohol, and synthetic alcohols synthesized from olefin. Examples of polyhydric alcohol esters with at least one hydroxyl group remaining in the molecule include ethylene glycol monolaurate, propylene glycol monopalmitate, polyethylene glycol monooleate, glycerin monostearate, glycerin dilaurate,
Trimethylolpropane monopalmitate, trimethylolpropane distearate, sorbitol monolaurate, sorbitol dioleate,
Examples include, but are not limited to, sorbitol tristearate, pentaerythritol monopalmitate, pentaerythritol distearate, pentaerythritol trioleate, and pentaerythritol tetralaurate. Examples of polycarboxylic acids having 4 or more carbon atoms include dibasic carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, and itaconic acid, their acid anhydrides, trimellitic acid, and Examples include so-called dimer acids and trimer acids obtained by polymerizing unsaturated fatty acids such as oleic acid and linoleic acid. In addition, alkylene oxides include ethylene oxide,
Propylene oxide, butylene oxide, etc. are used. The polycarboxylic acid ester having at least 4 carbon atoms and having at least one alkyl group having at least 11 carbon atoms and at least one carboxyl group in one molecule used in (B) can be prepared by a conventional method using a polycarboxylic acid and a hydroxyl compound. It can be obtained by performing an esterification reaction, but at the end of the reaction, at least one carboxyl group always remains in one molecule of the polycarboxylic acid ester obtained, and at least one ester group and at least one Must possess an alkyl group with 11 or more carbon atoms. Furthermore, an ester of a polyhydric alcohol with at least one hydroxyl group remaining in the molecule that is part of the hydroxyl compound (B) and a fatty acid having 12 or more carbon atoms can also be obtained by a conventional esterification reaction. These esters are obtained by a dehydration esterification reaction between a carboxyl group and a hydroxyl group, and also by a transesterification reaction with a lower alcohol ester of a carboxyl group. An example of an ester production reaction between a polycarboxylic acid and a hydroxyl compound, and a polyhydric alcohol and a fatty acid having 12 or more carbon atoms is as follows: 1 mole of a hydroxyl compound or polyhydric alcohol, 0.5 to 5 moles of a polycarboxylic acid or fatty acid, An esterification reaction is carried out at 160 to 260°C for 2 to 15 hours in the presence of an alkaline catalyst such as caustic soda or caustic potash or an acidic catalyst such as hydrochloric acid, sulfuric acid, or para-toluenesulfonic acid under a nitrogen gas stream to obtain the desired result. An ester is obtained. In addition, when carrying out a transesterification reaction using lower alkyl esters of fatty acids (mainly methyl or ethyl esters), the reaction is carried out at 40 to 120°C using the above-mentioned alkaline catalyst or sodium methylate, and the desired reaction is carried out. Esters can be obtained. Next, at least one member selected from the groups (A) and (B) is reacted with a polyamine to form a polyamine containing at least one member in the molecule.
The polyamine used here includes ethylenediamine, propylenediamine, hexaethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, etc., but is limited to these. It is not something that will be done. The above amide compound is composed of polyamine and (A), (B).
It is obtained by carrying out an amide reaction with at least one selected from among the above. To give an example of the reaction conditions, the number of moles of carboxyl compound is determined and used in the reaction so that at least one amine group remains in the molecule per mole of polyamine. For example, to 1 mole of ethylenediamine, add a carboxyl compound in an amount of 1 mole or less for lauric acid, or 0.5 mole or less for dimer acid, and react for 2 to 25 hours at a temperature of 140 to 260°C under a nitrogen gas stream. to obtain the desired Amide. The number of amine groups remaining in the amide molecule is calculated from the amine value. The reaction of the amide compound with at least one remaining amine group obtained as described above with the polycarboxylic acid is carried out as follows. 0.2 to 1 mole of amide compound to polycarboxylic acid
Add 2 mol and react at 160-240°C for 5-20 hours. Examples of polycarboxylic acids having at least two carboxyl groups in the molecule that can react with the amine groups remaining in the amide compound include the polycarboxylic acids having 4 or more carbon atoms used in the present invention (A) and (B), dimer Acids, trimer acids, etc. can be used. If amines remain in the reaction product obtained as described above, generally known treatments such as neutralization, quaternization, and amphotericization are carried out as necessary for the corresponding amine value. It can be used after carrying out the treatment using a treatment agent suitable for the treatment. These reaction products have extremely high rolling performance when used directly as rolling oil, but if necessary, they may be mixed with other lubricating oils, animal or vegetable oils, mineral oils, or added with extreme pressure additives, antioxidants, or interfaces. It can also be used by adding an activator or the like. The present invention will be explained in detail below using Examples. Synthesis Example 1 684 parts of behenic acid and 146 parts of triethylenetetramine were reacted at 200 to 240°C for 20 hours under a nitrogen gas stream,
An amide with an acid value of 24 and an amine value of 130 was obtained. Add 141 parts of sebacic acid to this amide and heat at 200 to 220℃.
After reacting for 10 hours, a compound having an acid value of 28 and an amine value of 9 was obtained. Synthesis Example 2 282 parts of dimer acid, 568 parts of stearic acid, and 189 parts of tetraethylenepentamine were mixed under a stream of nitrogen gas at 160 parts.
The reaction was carried out at ~220°C for 16 hours to obtain an amide with an acid value of 15 and an amine value of 85. Next, 95 parts of adipic acid was added to this amide and reacted at 160 to 220°C for 12 hours to increase the acid value.
21, a compound with an amine value of 7 was obtained. Synthesis Example 3 516 parts of palmitic acid, 382 parts of succinic acid monooleyl ester, and 189 parts of tetraethylenepentamine were reacted at 200 to 220°C for 12 hours under a nitrogen gas stream,
An amide with an acid value of 18 and an amine value of 85 was obtained. Next, 98 parts of maleic anhydride was added to this amide, and 180~
The reaction was carried out at 200°C for 10 hours to obtain a compound with an acid value of 20.0 and an amine value of 5. Synthesis Example 4 792 parts of adipic acid monooleyl ester and 103 parts of diethylenetriamine were mixed under a nitrogen gas stream at 220 parts
The reaction was carried out at ~240°C for 16 hours to obtain an amide with an acid value of 3.0 and an amine value of 50. Next, 1107 parts of succinic anhydride was added to this amide and reacted at 180 to 200°C for 15 hours.
A compound with an acid value of 8.5 and an amine value of 1 was obtained. The friction coefficient (μ) and pressure resistance of Examples 1 to 4 of rolling oils with the compositions shown in Table 1 using the compounds obtained in Synthesis Examples 1 to 4 were measured, and the results were used as comparative examples for tallow-based rolling oil. The results are shown in Table 2 along with the oil measurement results. In addition, the rolling performance test was carried out by directly applying a certain amount of rolling oil to the rolled material for Examples 1 and 2, and by applying rolling oil to the rolled material as it was for Examples 3 and 4 and Comparative Example.
Tests were carried out supplied as a % concentration emulsion. The amount of oil adhering to the rolled material was set to 1 g/m ² in all Examples 1 to 4 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). In addition, as a comparative example, tallow-based rolling oil shown in Table 1 was used.

【table】

【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 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 chart showing the rolling performance of Examples 1 to 4 of the rolling oil of the present invention and a comparative example based on the relationship between rolling load and rolling reduction. No. of the comparison line in the figure.
indicates the example number.

Claims (1)

[Claims] 1. (A) An aliphatic carboxylic acid or polycarboxylic acid having 12 or more carbon atoms. (B) A polycarboxylic acid ester having 4 or more carbon atoms each having at least one alkyl group having 11 or more carbon atoms and at least one carboxyl group in one molecule. An amide compound with at least one remaining amine group obtained by reacting at least one selected from the groups (A) and (B) with a polyamine, and the remaining amine group can react with the amide compound. A metal rolling oil characterized in that it uses a compound obtained by a reaction with a polycarboxylic acid having at least two carboxyl groups in its molecule.