JPS62270694A - Metal rolling oil - Google Patents

Abstract

PURPOSE:To provide a metal rolling oil exhibiting excellent rolling performance, which is composed mainly of a compd. prepd. by adding an alkylene oxide to a partial ester of a castor oil having a residual hydroxyl group and then reacting the partial ester with a polyisocyanate compd. CONSTITUTION:A compd. selected from among a 12 C or higher aliphatic (poly) carboxylic acid and a partial ester of a 4 C or higher polycarboxylic acid having at least one 11 C or higher alkyl group and at least one residual carboxyl group of the polycarboxylic acid in its molecule is reacted with a castor oil (hydrogenation product) to prepare a partial ester of a castor oil (hydrogenation product) having at least one residual hydroxyl group in its molecule. An alkylene oxide is added to the partial ester. The adduct is reacted with a polyisocyanate compd. having two or more isocyanate groups. The compd. thus obtd. is incorporated as a main component to prepare a metal rolling oil.

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 a base, and additives, etc. Products containing oiliness 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 buses, increasing rolling speeds, and increasing the standard accuracy of rolled products. As a result, the conditions for rolling oils have become more severe, and although palm oil and tallow-based rolling oils are no longer able to satisfy these conditions, alternatives to these rolling oils 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) At least one alkyl group having 11 or more carbon atoms in one molecule, and at least one carboxyl group of the polycarboxylic acid remaining. A partial ester of a polycarboxylic acid having 4 or more carbon atoms, obtained by reacting at least one member selected from the group (A) and (B) with castor oil or hydrogenated castor oil, An addition reaction product obtained by further adding an alkylene oxide to a partial ester of castor oil or a partial ester of hydrogenated castor oil in which at least one hydroxyl group remains in the molecule (hereinafter referred to as "compound C") This is a metal rolling oil characterized by using a compound obtained by reacting a polyvalent isocyanate compound having at least two isocyanate groups with a polyvalent isocyanate compound having at least two isocyanate groups. It is also possible to mix and use additives, antioxidants, etc.

Examples of aliphatic carboxylic acids having 12 or more carbon atoms used in (A) of the present invention include saturated fatty acids such as lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, and behenic acid, oleic acid, linoleic acid, and linoleic acid. Examples include unsaturated fatty acids such as acids, ricinoleic acid and arachidonic acid, neo acids, and saturated fatty acids having a linear chain and a side chain at the α-position obtained by the oxo method.

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, the partial ester of a polycarboxylic acid having 4 or more carbon atoms having at least one alkyl group having 11 or more carbon atoms and at least one carboxyl group in one molecule used in (B) is a polycarboxylic acid having 4 or more carbon atoms. It is obtained by forming an ester with a hydroxyl compound, but the hydroxyl compound is a combination of an aliphatic monohydric alcohol having 12 or more carbon atoms, or a polyhydric alcohol having 2 or more hydroxyl groups and a fatty acid having 12 or more carbon atoms. Examples of esters include esters with one hydroxyl group remaining in the molecule, and alkylene oxide adducts of these. Examples of aliphatic alcohols with 12 or more carbon atoms include lauryl alcohol and myristyl alcohol. , palmityl alcohol, oleyl alcohol, stearyl alcohol, synthetic alcohols synthesized from olefins, etc. Polyhydric alcohol esters with at least one hydroxyl group remaining in the molecule include, for example, ethylene glycol monolaurate. , propylene glycol monopalmitate, polyethylene glycol monooleate, glycerin monostearate, glycerin dilaurate, trimethylolpropane monopalmitate,
Examples include trimethylolpropane distearate, sorbitol monolaurate, sorbitol dioleate, sorbitol tristearate, pentaerythritol monopalmitate, pentaerythritol distearate, pentaerythritol trioleate, pentaerythritol tetralaurate, 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, trimellitic acid, and oleic acid.
Examples include so-called dimer acids and trimer acids obtained by polymerizing unsaturated fatty acids such as linoleic acid. Further, as the alkylene oxide, ethylene oxide, propylene oxide, butylene oxide, etc. are used.

The 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 used in (B) is prepared by esterification using a conventional method from a polycarboxylic acid and a hydroxyl 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 there is always a small number of carboxyl groups (both one ester group and at least one carbon number). Must possess 11 or more alkyl groups.

An ester of a polyhydric alcohol with at least one hydroxyl group remaining in the molecule which is part of the hydroxyl compound of CB) 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 of a carboxyl group with a lower alcohol ester.

An example of an ester production reaction between a polycarboxylic acid and a monovalent hydroxyl compound, and between a polyhydric alcohol and a fatty acid having 12 or more carbon atoms is as follows. 0.5 to 5 moles of fatty acid are mixed with 160 to 5 moles of fatty acid under a nitrogen gas flow 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.
The esterification reaction is carried out at 60°C for 2 to 15 hours to obtain the desired ester. In addition, when carrying out transesterification 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, etc. to achieve the desired result. Esters can be obtained.

Next, at least one member selected from the groups (A) and (B) is reacted with castor oil or hydrogenated castor oil obtained by hydrogenating castor oil, so that at least one compound in the molecule is reacted. A partial ester of castor oil or a partial ester of hydrogenated castor oil in which the hydroxyl group of is retained is obtained.

Partial esters of castor oil with at least one hydroxyl group remaining in the molecule or partial esters of hydrogenated castor oil are those with at least one hydroxyl group remaining on average in the molecule after esterification. It is something to do.

The above partial ester of castor oil or partial ester of hydrogenated castor oil is produced by an esterification reaction between castor oil or hydrogenated castor oil and one or more selected from (A) and (B) by a conventional method. An example of the reaction conditions is that for 1 mole of castor oil or hydrogenated castor oil, at least 1 hydroxyl group in the molecule is
The number of moles of the compounds of groups (A) and (B) is determined so that the remaining compounds are used in the reaction. For example, to 1 mole of castor oil or hydrogenated castor oil, add less than 2 moles of a carboxyl compound if it is a partial ester of aliphatic carboxylic acid or polycarboxylic acid, or less than 1 mole if it is a dimer acid, and then 2-2 at a temperature of 140-260°C below
The reaction was carried out for 5 hours to obtain the desired partial ester. The number of hydroxyl groups remaining in the partial ester molecule is calculated from the hydroxyl value.

Next, alkylene oxide is added to this partial ester compound to obtain compound C. The addition reaction of fullkylene oxide to this partial ester compound is also carried out by a conventional method.

Examples of the alkylene oxide used here include ethylene oxide, propylene oxide, butylene oxide, etc., and these alkylene oxides may be added alone or in combinations of two or more in a random or block manner. The number of moles added is 2 to 100 moles, preferably 3 to 60 moles.

The compound C obtained as described above is reacted with a polyvalent isocyanate compound having a small number (both of which have two) of isocyanate groups to obtain a compound used in the metal rolling oil of the present invention.C
The reaction between the compound and the polyvalent isocyanate compound is obtained by adding 0.3 to 2 moles of the polyvalent isocyanate compound to 1 mole of the C compound and reacting at 60 to 100°C.

Examples of the polyvalent isocyanate compound having at least two isocyanate groups in the present invention include methylene diisocyanate, tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, nitrodiphenyl diisocyanate, diphenylmethane sulfone diisocyanate, nitrodiphenylmethane diisocyanate, diphenyl sulfone diisocyanate, naphthalene diisocyanate, Examples include fluorene diisocyanate, chrysene diisocyanate, methoxyphenylene diisocyanate, biphenyl diisocyanate, dimethoxybiphenyl diisocyanate, and triphenylmethane triisocyanate.

The obtained reaction product can be used as it is and has high performance as a rolling oil, but it can also be mixed with conventional rolling oil.

The present invention will be explained in more detail with reference to Examples below.

The numbers in the examples indicate parts by weight.

Synthesis Example 1 284 parts of stearic acid, 935 parts of castor oil, and 12 parts of para-toluenesulfonic acid (hereinafter abbreviated as rPTsAJ) were placed in a reactor, and reacted for 6 hours at 150 to 180°C under a nitrogen gas stream, resulting in an acid value of 1. An ester having an average of 2 hydroxyl groups remaining in the molecule with a hydroxyl value of 89.5 and a hydroxyl value of 89.5 was obtained.

Add 264 parts of ethylene oxide to this ester and add 3 parts of caustic potassium.
addition reaction at 180-200'C in the presence of
Compound C was obtained. Further, 3 parts of triethylene diamine and 98 parts of methylene diisocyanate were added to 1464 parts of Compound C to obtain a compound having an acid value of 0.8 and a hydroxyl value of 3.6.

Synthesis Example 2 Succinic acid monolauryl ester 283 parts and iodine value 2.0
939 parts of hydrogenated castor oil and 12 parts of PTSA were reacted at 220 to 240°C for 11 hours under a nitrogen gas stream, resulting in an acid value of 2.
5. An ester having a hydroxyl value of 92.0 and having an average of 2 hydroxyl groups remaining in the molecule was obtained. Compound C was obtained by addition reaction of 174 parts of propylene oxide to this ester in the presence of 7.4 parts of caustic potassium.

3 parts of triethylenediamine and 4.4 parts of the obtained C compound
125 parts of 1-diphenylmethane diisocyanate was added and reacted to obtain a compound having an acid value of 0.8 and a hydroxyl value of 10.5.

Synthesis Example 3 939 parts of hydrogenated castor oil with an iodine number of 2.0, 282 parts of oleic acid, and 12 parts of PTSA were mixed under a nitrogen gas stream for 150 to 150 parts.
Reacted at 180°C for 6 hours, acid value 0.8, hydroxyl value 90.
An ester of 6' was obtained with an average of 2 hydroxyl groups remaining in the molecule. To this ester, 264 parts of ethylene oxide was added to 1 part of potassium hydroxide in the presence of 3 parts of potassium hydroxide.
Addition reaction was carried out at 80 to 200°C to obtain compound C.

This was then added with 3 parts of triethylenediamine and 4.4"-
12.5 parts of diphenylmethane diisocyanate
After the addition was completed, the reaction was carried out at 80 to 90°C for 4 hours to obtain a compound having an acid value of 0.5 and a hydroxyl value of 4.0.

Synthesis Example 4 624 parts of stearic acid diglyceride and 10 parts of succinic anhydride
0 part was reacted at 100 to 110° C. for 4 hours under a nitrogen gas stream to obtain stearic acid diglyceride succinate. Next, 935 parts of castor oil and 15 parts of PTSA were added, and the reaction was carried out at 140 to 160°C for 10 hours under a nitrogen gas stream.
A reaction product was obtained with an acid value of 1.2 and a hydroxyl value of 67.0, with an average of two hydroxyl groups remaining in the molecule. To this reaction product, 88% of ethylene oxide was added at 170 to 180°C.
0 part was subjected to an addition reaction to obtain compound C. Next, 2 parts of triethylene diamine and 50 parts of naphthalene diisocyanate were added to this, and the reaction was carried out at 90 to 100°C for 5 hours.
A compound having an acid value of 1.7 and a hydroxyl value of 2.5 was obtained.

The friction coefficient (μ) and pressure resistance of Examples 1 to 4 of rolling oils having the compositions shown in Table 1 using the compounds obtained in Synthesis Examples 1 to 4 were measured. The results are shown in Table 2 as a comparative example along with the measurement results of tallow-based rolling oil.

In addition, the rolling performance test was conducted by directly applying a certain amount of rolling oil to the rolled material for Example 1.2, and for Example 3.4.
And for comparative examples, tests were conducted by supplying the emulsion as a 5% concentration emulsion. The amount of oil adhering to the rolled material was set to 1 g/rd in all Examples 1 to 4 and Comparative Example.

The results of the test were evaluated as rolling performance based on the relationship between the rolling reduction ratio (%) and the rolling blade (ton), and are shown in Figure 1.

The test method regarding the lubrication performance of the rolling oil of the present invention is as follows.

Friction coefficient (μ) test method Deposition-type shaker type oil tester NII type load-bearing capacity test method Shell type high-speed four-ball friction tester Rolling test method Table-1 Table-2 Rolling machine Two-four-high roll rolling mill Workpiece Roll diameter 150mm x Width 140mm Backup roll diameter 250mm x Width 140mm Roll material Chrome steel Roll peripheral speed 30m/ll1in Rolling material: 5pc-c Thickness 0.6mm x Width 0n+m x Length 150mm Measuring method of rolling performance Before rolling Two lines with an interval (11) of 5 mm were drawn on the steel plate, the lines were rolled, the interval (12) after rolling was measured, and the rolling reduction was determined by the following formula.

z Also, 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 4 of the rolling oil of the present invention and a comparative example based on the relationship between rolling load and rolling reduction. The area south of the comparison line in the figure indicates the example fish. Patent applicant: Miyoshi Oil Co., Ltd. Figure-1

Claims (1)

Scope of Claims: (A) an aliphatic carboxylic acid or polycarboxylic acid having 12 or more carbon atoms, (B) having at least one alkyl group having 11 or more carbon atoms in one molecule, and a carboxyl group of the polycarboxylic acid. A partial ester of a polycarboxylic acid having at least 4 carbon atoms in which at least one group remains, and at least one member selected from the group (A), (¥B¥)¥, and castor oil or hydrogenated A partial ester of castor oil or a partial ester of hydrogenated castor oil obtained by reacting castor oil with at least one hydroxyl group in its molecule.
, and the addition reaction product obtained by adding alkylene oxide and at least two isocyanate groups.
A metal rolling oil characterized by using a compound obtained by reacting with a polyvalent isocyanate compound.