JPS635438B2 - - 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. 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. (A) group is castor oil or hydrogenated castor oil (hereinafter referred to as hydrogenated castor oil); (B) group is castor oil with alkylene oxide added or hydrogenated castor oil with alkylene oxide added (C) group 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.As group (D), a hydroxyl group having an alkyl or alkenyl group having 11 or more carbon atoms. A castor oil derivative obtained by an esterification reaction between the carboxyl group of a dicarboxylic acid monoester obtained from a compound and a dicarboxylic acid and a part of the hydroxyl group of (A) or (B). ), (C), and (D), and a reaction product obtained by the reaction with an isocyanate compound having two or three isocyanate groups in the molecule, as the main component, The present invention relates to a metal rolling oil that is used as it is or mixed with animal and vegetable oils, mineral oils, surfactants, extreme pressure additives, etc., as necessary. 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) For the above fatty acids
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 in the molecule. 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, and polyethylene glycol palmitate. , polyethylene glycol oleate, glycerin stearate, sorbitol laurate, sorbitol oleate, pentaerythritol stearate, etc., and those obtained by adding alkylene oxide to these hydroxy compounds,
Examples of dicarboxylic acids include dibasic carboxylic acids such as succinic acid, adipic acid, azelaic acid, sebacic acid, maleic acid, fumaric acid, and itaconic acid, and so-called dimer acids obtained by polymerizing unsaturated fatty acids. Next, the reaction product of at least one selected from the four groups (A), (B), (C), and (D) and the isocyanate compound is the reaction product of the above (A), (B), and (C). , (D) and an isocyanate compound having two or three isocyanate groups in the molecule according to a conventional method. That is, it is due to an addition reaction of an isocyanate compound to a hydroxyl group bonded to a compound of groups (A) to (D). 60 to 100 at a ratio of 0.3 to 2 moles
The compounds of groups (A) to (D) are crosslinked with an isocyanate compound to produce a chain or network reaction product. 2 isocyanate groups in the molecule used in the present invention
Or, as an isocyanate compound having three compounds, methylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate,
Nitrodiphenyl diisocyanate, diphenylmethane diisocyanate, nitrodiphenylmethane diisocyanate, diphenylmethane sulfone diisocyanate, diphenyl sulfone diisocyanate, naphthalene diisocyanate,
Examples include fluorene diisocyanate, glycerin diisocyanate, methoxyphenylene diisocyanate, biphenyl diisocyanate, dimethoxybiphenyl diisocyanate, triphenylmethane triisocyanate, and the like. The reaction product of at least one member selected from the above groups (A) to (D) and an isocyanate compound has extremely high rolling performance even when used as it is as a rolling oil, but if necessary, other products may be added. It is possible to use a mixture of animal and vegetable oils, mineral oils, surfactants, extreme pressure additives, etc. The present invention will be explained below with reference to Examples. Example 1 Castor oil with 3 moles of ethylene oxide added
1067 parts of stearic acid, 568 parts of stearic acid, and 16 parts of para-toluenesulfonic acid (hereinafter referred to as PTSA) were reacted at 150 to 180°C for 6 hours under a stream of _N2 gas to produce a castor oil derivative with an acid value of 1.4 and a hydroxyl value of 24.9. Obtained. This castor oil derivative contains 125 parts of 4.4' diphenylmethane diisocyanate and 3 parts of triethylene diamine.
The reaction product was reacted at 90° C. for 5 hours to obtain a reaction product with an acid value of 0.24 and a hydroxyl group of 1.1. Example 2 Castor oil with 50 moles of ethylene oxide added
Add 5 parts of triethylenediamine to 3135 parts and add 70 to 90 parts.
85 parts of 4.4' diphenylmethane diisocyanate was added thereto and reacted at 80°C for 5 hours to obtain a reaction product with an acid value of 0.28 and a hydroxyl value of 40.6. Example 3 Hydrogenated castor oil 941 parts, beef tallow fatty acid 282 parts,
12 parts of PSTA was reacted at 150 to 180° C. for 6 hours under a N ₂ gas stream to obtain a castor oil derivative having an acid value of 3.5 and a hydroxyl value of 72.0. 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 10 hours at 150-180°C under a stream of _N2 gas.
A castor oil derivative with an oxidation value of 5.0 and a hydroxyl value of 70 was obtained.
Add 5 parts of triethylene diamine to the above castor oil derivative and heat tolylene diisocyanate 87% at 70-90℃.
3.0 and reacted for 4 hours, acid value 3.0, hydroxyl value
12.5 reaction products were obtained. The reaction products of Examples 1 to 4 were subjected to a rolling performance test as shown in Table 1, either alone or as a blend. The friction coefficient (μ) and pressure resistance of rolling oils No. 1 to 4 were measured, and the results are shown in Table 2.

【table】

[Table] For rolling oil Nos. 1 and 2, the oil was applied as it was to the rolling material, and for Nos. 3 and 4, it was applied as a 15% emulsion and tested. The amount of oil adhering to the rolled material was set to 1 g/m ² for all Nos. 1 to 4. The results of the rollability test are shown in Figure 1 as a rolling performance evaluation based on the relationship between rolling reduction (%) and rolling load (ton). A 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 type pendulum type oil tester N-type load capacity test method Shell type high speed four ball friction tester rolling test method Rolling mill: Four-roll rolling mill 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 2 rolls are placed on the steel plate before rolling at 50mm intervals (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 In addition, 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 reaction product obtained by the reaction of at least one member selected from the four groups C) and (D) with an isocyanate compound having two or three isocyanate groups in the molecule, and can be used as it is or A metal rolling oil characterized in that animal and vegetable oils, mineral oils, surfactants, extreme pressure additives, etc. are mixed therein as required.