JPS633919B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to 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. In addition, some methods of improving lubricity during rolling include precoating phosphate ester-based extreme pressure additives (Japanese Patent Laid-Open No. 53-135860), and adding solubilized rolling oil (Japanese Patent Laid-Open No. 135860). 50-60671) have also been proposed, but when these alkyl ethoxylate phosphate esters and fatty acid ethoxylate phosphate esters are used, they both have high pressure resistance and excellent extreme pressure properties, but have low oiliness. Therefore, it has the disadvantage of a high coefficient of friction. 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 lubrication 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. Group (A) is castor oil or hydrogenated castor oil (hereinafter referred to as "hydrogenated castor oil"); (Group B) is castor oil with alkylene oxide added or hydrogenated castor oil with alkylene oxide added (C ) group is a castor oil derivative obtained by esterifying a part of the hydroxyl group of (A) or (B) with a fatty acid having 12 or more carbon atoms (group D) has an alkyl or alkenyl group having 11 or more carbon atoms A castor oil derivative obtained by an esterification reaction between a carboxyl group of a dicarboxylic acid monoester obtained from a hydroxy compound and a dicarboxylic acid and a part of the hydroxyl group of (A) or (B). The main component is a phosphoric acid ester or its salt obtained by the reaction of at least one member selected from the four groups (B), (C), and (D) with phosphoric acid or phosphoric anhydride, and as it is, Alternatively, the present invention relates to a metal rolling oil characterized in that animal and vegetable oils, mineral oils, surfactants, extreme pressure additives, etc. are mixed therewith as required. The hydrogenated castor oil in the present invention can be obtained by hydrogenating castor oil in a conventional manner. Castor oil to which alkylene oxide has been added or hydrogenated castor oil to which alkylene oxide has been added can be obtained by adding alkylene oxide to castor oil or hydrogenated castor oil by a conventional method. As the alkylene oxide, one having 2 to 3 carbon atoms is added in an amount of 2 to 100 moles. Furthermore, a castor oil derivative (hereinafter referred to as castor oil derivative (C)) obtained by reacting (A) or (B) with a fatty acid having 12 or more carbon atoms can also be obtained by a generally known esterification reaction. That is, the castor oil derivative (C) used in the present invention can be obtained by a dehydration esterification reaction between a hydroxyl group bonded to (A) or (B) and the above fatty acid, or by a reaction between (A) or (B) and the above fatty acid. It can also be obtained by transesterification with lower esters. However, the essential condition for this castor oil derivative (C) is that at least one hydroxyl group remains in the molecule of the castor oil derivative (C) at the end of the reaction, and 1 mol of (A) or (B) Against the above fat
It is obtained by reacting 0.5 to 2 moles. The fatty acids having 12 or more carbon atoms used to obtain the castor oil derivative (C) of the present invention include saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, neoacids, and Examples include side chain saturated fatty acids such as the obtained fatty acids, and unsaturated fatty acids such as oleic acid, linoleic acid, linolenic acid, arachidonic acid, and ricinoleic acid. Next, (A) is added to a dicarboxylic acid monoester obtained from a hydroxy compound having an alkyl or alkenyl group having 11 or more carbon atoms and a dicarboxylic acid.
The castor oil derivative obtained by reacting or (B) (hereinafter referred to as castor oil derivative (D)) is a castor oil derivative.
Similarly to (C), it is obtained by reacting 1 mole of (A) or (B) with 0.5 to 2 moles of the above dicarboxylic acid monoester, and the castor oil derivative (D) has at least 1 mole in the molecule. It is an essential condition that hydroxyl groups remain. In addition, the dicarboxylic acid monoester used to obtain the castor oil derivative (D) is a compound obtained by reacting a hydroxy compound having an alkyl or alkenyl group having 11 or more carbon atoms with a dicarboxylic acid at a molar ratio of 1:1. It has one carboxyl group. Examples of hydroxy compounds having an alkyl or alkenyl group having 11 or more carbon atoms include lauryl alcohol, palmityl alcohol, cetanol,
Stearyl alcohol, oleyl alcohol, ethylene glycol oleate, propylene glycol laurate, propylene glycol stearate, polyethylene glycol palmitate, polyethylene glycol oleate, glycerin stearate, sorbitol laurate, sorbitol oleate, pentaerythritol stearate, etc., and these The dicarboxylic acids include succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid,
Examples include so-called dimer acids obtained by polymerizing dibasic carboxylic acids such as itaconic acid and unsaturated fatty acids. The phosphoric acid ester used in the present invention includes the above (A),
It is synthesized according to a conventional method by reacting at least one compound selected from the four groups of compounds (B), (C), and (D) with a phosphorylating agent such as phosphoric acid or phosphoric anhydride. The phosphoric acid ester thus obtained contains phosphoric acid mono- and ditriesters, and further contains the above-mentioned (A), (B),
Among the four groups of compounds (C) and (D), when a compound with two or more hydroxyl groups remaining in its molecule is reacted with phosphoric acid or phosphoric anhydride, it becomes an ester having a hydroxyl group. The esterification reaction with phosphoric acid occurs in the form of a chain or network to produce polyesters of phosphoric acid, which contain such phosphoric acid esters. These phosphoric acid esters are used as salts by neutralizing residual acid groups, if necessary. Salts include alkali metal salts such as sodium and potassium, alkaline earth metal salts such as calcium and magnesium, salts of organic amines or their derivatives such as ammonia, monoethanolamine, diethanolamine, triethanolamine, and carbon atoms of 1 to 1.
18 linear alkyl amines, triethanolamine stearate, morpholine, etc. This neutralization allows the hydrophilicity of the reaction product to be appropriately adjusted depending on the conditions of use. Furthermore, this neutralization can also adjust the polarity of the phosphate ester and control its adsorption to metal surfaces. These phosphoric acid esters or their salts have extremely high rolling performance even when used directly as rolling oil, but if necessary, other animal or vegetable oils or fats,
Mineral oil, surfactant, and extreme pressure additives can be mixed and used. The present invention will be explained below with reference to Examples. Example 1 71 parts of phosphoric anhydride was added to 935 parts of castor oil at 60 to 70°C and reacted for 4 hours, resulting in an acid value of 84.7 and a hydroxyl value.
The phosphoric acid ester of 15.6 was obtained. This phosphoric acid ester was used to neutralize caustic soda, and the pH of the 1% aqueous solution was adjusted to 7.0. Example 2 Castor oil with 10 moles of ethylene oxide added
1,375 parts of phosphoric anhydride and 71 parts of phosphoric anhydride were reacted at 60 to 70°C for 4 hours to obtain a phosphoric acid ester having an acid value of 20 and a hydroxyl value of 50. This was neutralized with morpholine, and the 1% water
The pH was adjusted to 7.0 with an ethanol mixed solution. Example 3 941 parts of hydrogenated castor oil, 200 parts of lauric acid, and 11 parts of para-toluenesulfonic acid (hereinafter referred to as PTSA) were added.
The reaction was carried out at 120 to 160° C. for 8 hours under a N ₂ gas flow to obtain a castor oil derivative with an acid value of 1.0 and a hydroxyl value of 96.0. Add 71 parts of phosphoric anhydride to this castor oil derivative and add 60 to 70 parts of phosphoric anhydride.
C. and reacted for 4 hours to obtain a phosphoric acid ester having an acid value of 4.2 and a hydroxyl value of 9.0. This phosphoric acid ester was neutralized with triethanolamine stearate, and the pH of its 1% aqueous solution was adjusted to 7.0. Example 4 Stearic acid diglyceride succinate was obtained by reacting 100 parts of succinic anhydride with 624 parts of stearic acid diglyceride at 100 to 110°C for 4 hours under a _N2 gas stream. Next, 935 parts of castor oil and 15 parts of PTSA were added, and the mixture was reacted for 20 hours at 150-180°C under a stream of _N2 gas.
A castor oil derivative with an acid value of 5.0 and a hydroxyl value of 70 was obtained.
The above castor oil derivative was maintained at 70 to 80°C, and 71 parts of phosphoric anhydride was added. After the addition was completed, the reaction was further carried out at 70 to 80°C for 4 hours to obtain a phosphoric acid ester having an acid value of 60 and a hydroxyl value of 20. This phosphoric acid ester was neutralized with caustic soda, and the pH of the 1% aqueous solution was adjusted to 7.0. Example 5 Castor oil 935 parts, stearic acid 426 parts, PTSA12
react at 120-160℃ for 10 hours under _N2 gas flow,
A castor oil derivative with an acid value of 3.5 and a hydroxyl value of 62.0 was obtained. 42.6 parts of phosphoric anhydride is added to this castor oil derivative from 70 to 70 parts.
The mixture was added at 80°C and reacted for 4 hours to obtain a phosphoric acid ester having an acid value of 24.0 and a hydroxyl value of 12.4. This phosphoric acid ester was neutralized with diethanolamine, and the pH of the 1% water-ethanol solution was adjusted to 7.0. Example 6 1161 parts of hydrogenated castor oil to which 5 moles of ethylene oxide had been added, 282 parts of beef tallow fatty acid, and 14 parts of PTSA were reacted at 120 to 160°C for 8 hours under a stream of _N2 gas, resulting in an acid value of 2.0,
A castor oil derivative with a hydroxyl value of 96.0 was obtained. Add 113.6 parts of phosphoric anhydride to this castor oil derivative and add 70
It was added at ~80°C and reacted for 4 hours to obtain a phosphoric acid ester having an acid value of 46.0 and a hydroxyl value of 8.0. Neutralize this phosphoric acid ester with 2-ethylhexylamine, and adjust the pH of the 1% water-ethanol solution.
Adjusted to 7.0. Example 7 935 parts of castor oil, 184 parts of maleic acid monooleate
and 11 parts of PTSA at 150-180 °C under _N2 gas flow.
After reacting for 10 hours, a castor oil derivative with an acid value of 1.5 and a hydroxyl value of 92.6 was obtained. Add 70 to 80 parts of phosphoric anhydride to this castor oil derivative.
C. and reacted for 4 hours to obtain a phosphoric acid ester having an acid value of 36.5 and a hydroxyl value of 10.6. This phosphoric acid ester was neutralized with triethanolamine, and the pH of its 1% water-ethanol solution was adjusted to 7.0.
Adjusted to. Table 1 shows the phosphoric acid ester compounds of Examples 1 to 7.
It was subjected to rolling performance tests as a single unit or as a blended product. The friction coefficient (μ) and pressure resistance of rolling oil Nos. 1 to 7 were measured, and the results are shown in Table 2. For rolling oils Nos. 1 to 4, the oils were applied as they were to the rolled material, and for Nos. 5 to 7, the oils were applied as 15% emulsions for testing. The amount of oil adhering to the rolled material was set to 1 g/m ² for all Nos. 1 to 7. The results of the rolling property test are shown in Figure 1 as a rolling performance evaluation based on the relationship between rolling reduction (%) and rolling load (ton).

【table】

【table】

[Table] Commercially available tallow-based rolling oil was used as a comparative sample. The test method regarding the lubricity of the rolling oil for steel plates of the present invention is as follows. Friction coefficient test method Soda pendulum type oil tester N-type load carrying capacity test method Shell type high speed four ball friction tester Rolling test method Rolling mill: Four-roll rolling machine Work roll diameter 150mm Width 140mm Back-up roll diameter 250mm Width 140mm Roll material: Chrome steel Roll circumferential speed: 30m/min Rolling material: SPC-C Thickness 0.60mm x Width 50mm x Length 150mm Method of measuring rolling performance Two rolls are placed on the steel plate before rolling at intervals of 50mm (l ₁ ). A line was drawn, the line was 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]

The drawing is a rolling performance comparison diagram showing the rolling performance of Examples and Comparative Examples in terms of the relationship between rolling load (ton) and rolling reduction (%).

Claims (1)

[Scope of Claims] 1. Castor oil or hydrogenated castor oil as group (A); (B) castor oil with alkylene oxide added, or hydrogenated castor oil with alkylene oxide added; (C) as group (A). ) or a castor oil derivative obtained by esterifying a part of the hydroxyl group of (B) with a fatty acid having 12 or more carbon atoms.Group D is a hydroxy compound having an alkyl or alkenyl group having 11 or more carbon atoms and a dicarboxylic acid. A castor oil derivative obtained by an esterification reaction between the carboxyl group of a dicarboxylic acid monoester obtained from an acid and a part of the hydroxyl group of (A) or (B). The main component is a phosphoric acid ester or a salt thereof obtained by the reaction of at least one member selected from the four groups C) and (D) with phosphoric acid or phosphoric anhydride, and can be used as is or as necessary. A metal rolling oil characterized in that it is mixed with animal and vegetable oils, mineral oils, surfactants, extreme pressure additives, etc.