JPS6252795B2 - - 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, 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. This metal rolling oil is characterized by using a polyamide obtained by reacting at least one member selected from the groups (A) and (B) with a polyamine. 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, neoacid, linear fatty acids obtained by the oxo method, and saturated fatty acids having a side chain at the α-position, etc. 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 is obtained by forming an ester from a polycarboxylic acid having 4 or more carbon atoms and a hydroxyl compound,
The hydroxyl compound is an ester of an aliphatic alcohol having 12 or more carbon atoms, an alkylene oxide adduct thereof, or a polyhydric alcohol having 2 or more hydroxyl groups, and a fatty acid having 12 or more carbon atoms. Examples include esters with one hydroxyl group remaining, and alkylene oxide adducts thereof. number of carbons
Examples of the aliphatic alcohol of 12 or more include lauryl alcohol, myristyl alcohol, palmityl alcohol, oleyl alcohol, stialyl 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, and trimethylolpropane. Monopalmitate, trimethylolpropane distearate, sorbitol monolaurate, sorbitol dioleate, sorbitol tristearate, pentaerythritol monopalmitate, pentalythritol distearate, pentaerythritol trioleate, etc. It is not limited to these. 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. Further, as the alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, etc. are used. Next, examples of polyamines that react with at least one selected from groups (A) and (B) of the present invention include ethylenediamine, propylene diamine, hexaethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenediamine. Examples include, but are not limited to, ethylenehexamine and the like. 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) is esterified by a conventional method from a polycarboxylic acid and a hydroxy compound. However, 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 carbon Must possess at least 11 alkyl groups. Furthermore, an ester of a polyhydric alcohol with at least one hydroxyl group remaining in the molecule which 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. An example of an ester production reaction between polycarboxylic acid (B) and an aliphatic alcohol having 12 or more carbon atoms, or a polyhydric alcohol and a fatty acid having 12 or more carbon atoms, is as follows: 1 mole of aliphatic alcohol or polyhydric alcohol , 0.5 to 4 moles of polycarboxylic acid or fatty acid at 160 to 260°C 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. ~
The desired ester is obtained by carrying out the esterification reaction for 15 hours. These esters can be obtained by a dehydration esterification reaction between a carboxyl group and a hydroxyl group, and also by a transesterification reaction of a carboxyl group with a lower alcohol ester. In addition, an example of the conditions for producing a polyamide obtained by reacting at least one member selected from the groups (A) and (B) with a polyamine is as follows: 1 mole of polyamine and 0.5 to 8 moles of (A), The desired polyamide is obtained by reacting with at least one selected from (B) under a nitrogen gas stream at a temperature of 140 to 260°C for 2 to 25 hours. In this reaction, all of the amine groups in the polyamine become amide, but some amine may remain. At that time, generally known treatments such as neutralization, quaternization, and amphotericization can be performed on the corresponding amine value using a treatment agent suitable for each treatment, if necessary. . These reaction products can be used as rolling oils as they are and have extremely high rolling performance; however, if necessary, they may be mixed with other lubricating oils, animal or vegetable oils, mineral oils, or may be mixed with extreme pressure additives, antioxidants, It can also be used by adding a surfactant or the like, and it can also be emulsified in water and used as an emulsion. The present invention will be explained in detail below using Examples. Synthesis Example 1 After reacting 790 parts of oleic acid and 103 parts of diethylenetriamine at 160 to 180°C under a nitrogen gas stream for 2 hours,
The mixture was further reacted at 220 to 240°C for 6 hours to obtain a polyamide having an acid value of 18 and an amine value of 6. Synthesis Example 2 564 parts of dimer acid, 510 parts of stearic acid, and 146 parts of triethylenetetramine were mixed under a nitrogen gas stream for 200~200 parts.
The reaction was carried out at 240°C for 8 hours to obtain polyamide with an acid value of 16 and an amine value of 4.5. Synthesis Example 3 1700 parts of adipic acid monooleyl ester and 189 parts of tetraethylenepentamine were mixed under a nitrogen gas stream.
Reacted at 220-250℃ for 16 hours, acid value 16, amine value
Got 12.5 Amides. Synthesis Example 4 1110 parts of sebacic acid monolauryl ester, 423 parts of trimer acid and 189 parts of tetraethylenepentamine
The mixture was reacted for 25 hours at 200 to 240°C under a nitrogen gas stream to obtain a polyamide with an acid value of 24 and an amine value of 20. Synthesis Example 5 1024 parts of azelaic acid monobehenyl ester, 629 parts of adipic acid monooleylamide, and 146 parts of triethylenetetramine were mixed under a nitrogen gas stream for 200 to 200 parts.
The reaction was carried out at 240°C for 20 hours to obtain a polyamide with an acid value of 18 and an amine value of 12. Synthesis Example 6 1890 parts of a monoester of glycerin distearate and adipic acid and 103 parts of diethylene triamine were reacted at 160 to 220°C for 22 hours under a nitrogen gas stream to obtain a compound with an acid value of 26 and an amine value of 4. Synthesis Example 7 828 parts of monoester of ethylene glycol monolaurate and azelaic acid, ethylene diamine
60 parts were reacted for 16 hours at 200 to 240°C under a nitrogen gas stream to obtain polyamide with an acid value of 5.2 and an amine value of 6. Synthesis Example 8 3700 parts of monoester of 5 moles of ethylene oxide adduct of oleyl alcohol and adipic acid,
232 parts of pentaethylenehexamine was reacted under a nitrogen gas stream at 220 to 250°C for 16 hours to obtain a polyamide with an acid value of 13.0 and an amine value of 10. Synthesis Example 9 Propylene oxide of lauryl alcohol 10
Monoester of molar adduct and trimellitic acid
The acid value
16.5, a polyamide with an amine value of 13 was obtained. Synthesis Example 10 2340 parts of a monoester of an 8 mol ethylene oxide adduct of ethylene glycol monooleate and maleic acid and 103 parts of diethylenetriamine were reacted at 200 to 240°C for 16 hours under a nitrogen gas stream to reduce the acid value.
9.8, a polyamide with an amine value of 8 was obtained. Synthesis Example 11 Ethylene oxide of sorbitan triolate
Monoester of 20 molar adduct and dimer acid 2400
1, 282 parts of stearic acid, and 60 parts of ethylenediamine were reacted at 200 to 240°C for 20 hours under a nitrogen gas stream to obtain a polyamide with an acid value of 12.5 and an amine value of 15. The friction coefficient (μ) and pressure resistance of the rolling oils of Examples Nos. 1 to 11 with the compositions shown in Table 1 using the compounds obtained in Synthesis Examples 1 to 11 were measured, and the results were used as commercially available comparative examples. The results are shown in Table 2 along with the measurement results of tallow-based rolling oil. Further, the rolling performance test was conducted by applying a certain amount of Example Nos. 1 to 11 and commercially available tallow-based rolling oil to the rolling material as it was. The amount of oil attached to the rolled material is 1 for all Nos. 1 to 11 and tallow-based rolling oil.
g/ ^m2 . 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 was used. 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

【table】

【table】

[Table] Roll diameter 250 mm x width 140 mm Roll material Chrome steel roll peripheral speed 30 m/min Rolling material: SPC-C Thickness 0.6 mm x width 50 mm x length 150 mm Rolling performance measurement method Two lines with a distance (l ₁ ) 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 the rolling oils Nos. 1 to 6 of the present invention and the comparative example in terms of the relationship between rolling load and rolling reduction. Figure-2 shows the rolling oil of the present invention.
It is a rolling performance comparison diagram of Nos. 7 to 11 and a comparative example.

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. A metal rolling oil characterized by using a polyamide obtained by reacting at least one member selected from the groups (A) and (B) with a polyamine.