JPS62270693A - 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 polyepoxy 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 (hyrogenation 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 polyepoxy compd. having two or more epoxy groups. The compd. thus obtd. is incorporated as a main component to prepare a metal rolling oil.

Description

[Detailed description of the invention] 3. 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 sheets since ancient times, but instead, animal and vegetable oils such as beef tallow, pork fat, and hydrogenated Nagasu whale oil, mineral oils, or mixtures of these oils are used as base oils, and additives are added to them. , 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 passes, increasing rolling speed, 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 polyepoxy compound having at least two epoxy groups with a polyepoxy compound having at least two epoxy groups, and if necessary, extreme pressure additives and surfactants. 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 in which at least one hydroxyl group remains in the molecule, and alkylene oxide adducts thereof. 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 olefins. Examples of polyhydric alcohol esters having at least one hydroxyl group remaining in the molecule include ethylene glycol monolaurate, propylene glycol monopalmitate, polyethylene glycol monooleate, glycerin monostearate, glycerin dilaurate, and methylolpropane monopalmitate,
Trimethylolpropane distearate, sorbitol monolaurate, sorbitol dioleate, sorbitol tristearate, pentaerythritol monopalmitate, pentaerythritol distearate, pentaerythritol trioleate, pentaerythritol tetralaure-1, etc. However, 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 and linoleic acid. Examples include so-called dimer acids, trimer acids, etc. obtained by polymerizing unsaturated fatty acids such as. 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 at least one ester group and at least one carbon number of 11 or more must be present. must possess an alkyl group of

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 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.

A partial ester of castor oil with at least one hydroxyl group remaining in the molecule, or a partial ester of hydrogenated castor oil with at least one hydroxyl group remaining in the molecule, refers to a partial ester of castor oil with at least one hydroxyl group remaining in the molecule after esterification. It remains.

The above partial ester of castor oil or partial ester of hydrogenated castor oil is obtained by performing an esterification reaction between castor oil or hydrogenated castor oil and at least one selected from (A) and (B) using a conventional method. can get. To give an example of the reaction conditions, 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 2-25 at a temperature of 140-260℃ below
The desired partial ester is obtained by a time reaction. 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 alkylene 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 polyepoxy compound having at least two epoxy groups to obtain a compound used in the Kanai rolling oil of the present invention. The reaction between the C compound and the polyepoxy compound is obtained by adding 0.3 to 2 moles of the polyepoxy compound to 1 mole of the C compound and reacting at 70-120°C.

Examples of the polyepoxy compound having at least two epoxy groups in the present invention include ethylene glycol diglycidyl ether, glycerin triglycidyl ether, adipic acid diglycidyl ester, succinic acid diglycidyl ester, dimer acid diglycidyl ester, and polyalkylene glycidyl ether. Examples include glycidyl ether, triglycidyl ether of a glycerin alkylene oxide adduct, and the like.

These reaction products have high performance as rolling oil when used as is, but they can also be used by mixing with conventional rolling oil, and if necessary, extreme pressure additives, surfactants, and antioxidants may be added. It is also possible to use a mixture of the following.

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 1 282 parts of dimer acid, 935 parts of castor oil, and 12 parts of para-toluenesulfonic acid (hereinafter abbreviated as rPTsAJ) were reacted at 220 to 240°C for 16 hours under a nitrogen gas flow, resulting in an acid value of 16.8 and a hydroxyl value. An ester having an average of 2 hydroxyl groups remaining in the molecule of 92.0 was obtained.

Add 264 parts of ethylene oxide to this ester and add 2 parts of caustic potassium.
．． Compound C was obtained by addition reaction in the presence of 4 parts.

174 parts of ethylene glycol diglycidyl ether and 2 parts of boron trifluoride etherate were added to 1457 parts of the obtained C compound.
The mixture was reacted at 80° C. for 6 hours to obtain a compound having an acid value of 1.1 and a hydroxyl value of 66.5.

Synthesis Example 2 568 parts of isostearic acid, 935 parts of castor oil, PTS
Fifteen parts of A were reacted at 160 to 200° C. for 6 hours under a nitrogen gas stream to obtain an ester having an acid value of 4.5 and a hydroxyl value of 38.2, with an average of one hydroxyl group remaining in the molecule. This was subjected to an addition reaction with 2030 parts of propylene oxide in the presence of caustic potash. Polyethylene glycol (MW=400) diglycidyl ether 25
0 parts were added to obtain a compound having an acid value of 1.6 and a hydroxyl value of 15.0.

Synthesis Example 3 568 parts of stearic acid, 939 parts of hydrogenated castor oil with an iodine value of 2.0, and 15 parts of PTSA were mixed in a nitrogen gas stream at 150 parts of stearic acid.
Reacted at ~180°C for 6 hours, acid value 2.0, hydroxyl value 39
．． An ester having an average of one hydroxyl group remaining in the molecule of No. 2 was obtained.

Add 880 parts of ethylene oxide to this ester and add 3 parts of caustic potassium.
Compound C was obtained by carrying out an addition reaction in the presence of C. Next, C
2351 parts of compound and 23 parts of diglycidyl succinate
2 parts of boron trifluoride etherate were added thereto, and the mixture was reacted at 80°C for 6 hours to obtain a compound having an acid value of 0.8 and a hydroxyl value of 30.0.

Synthesis Example 4 939 parts of hydrogenated castor oil with an iodine value of 2.0, 792 parts of adipic acid monooleate, and 17 parts of PTSA were reacted for 8 hours at 140 to 160°C under a nitrogen gas stream to obtain a product with an acid value of 065 and a hydroxyl value of 58.2. An ester with an average of 1.2 hydroxyl groups remaining in the molecule was obtained, and then 1.
Compound C was obtained by addition reaction of 440 parts of ethylene oxide and 290 parts of propylene oxide at 60 to 180"C. Next, 87 parts of ethylene glycol diglycidyl ether was added thereto, and the reaction was carried out for 6 hours at 80 to 100"C. A compound having a value of 1.5 and a hydroxyl value of 86.0 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/rrl 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.

Table-1 Table-2 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 swing-hanging oil tester NU 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+nm X width 140mm Backup roll diameter 250mm x width 140mm Roll material Chrome steel Roll circumferential speed 30m/in Rolling material: 5PC-C Thickness 0.6mm x width 50mm x length 150mm Measuring method of rolling performance Two lines with an interval (t!I) were drawn, this was rolled, the interval (12) after rolling was measured, and the rolling reduction was determined by the following formula.

β2 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 comparison line in the figure indicates the results of the example.

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.
, using a compound obtained by reacting an addition reaction product obtained by further adding an alkylene oxide with a polyvalent epoxy compound having at least two epoxy groups. A metal rolling oil characterized by: